Materials Sciences

in Space
A Contribution
to the Scientific Basis of Space Processing

Edited by
B. Feuerbacher, H. Hamacher
and R. 1. Naumann

With 199 Figures

Springer-Verlag
Berlin Heidelberg NewYork Tokyo
Prof. Berndt Feuerbacher
Dr.-Ing. Hans Hamacher
DFVLRe.V.
Institute for Space Simulation
Linder Hohe
5000 KOln 90, FRG

Dr. Robert 1. Naumann

NASA Marshall Space Flight Center
Space Science Laboratory
Alabama 35812, USA

ISBN-13:978-3-642-82763-1 e-ISBN-13:978-3-642-82761-7
DOl: 10.1007/978-3-642-82761-7
This work. is subject to copyright. All rights are reserved, whether the whole or part of the
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© by Springer-Verlag Berlin, Heidelberg 1986
Softcover reprint of the hardcover 1st edition 1986

The use of registered names, trademarks, etc. in this publication does not imply, even in the
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216113020-543210
Preface

t~icrogravity research, a new field originating from the accessibility of

space, has reached the age of adolescence. An impressive set of results
has emerged from the fi rst Space 1ab fl i ght, whi ch by now has been fully
evaluated. In view of this and the wealth of information available from
other space experiments, ground based research, and short-term microgra-
vity experiments in ai rp 1anes, rockets or fall towers, it was felt that
the time was ripe for a comprehensive review of the field.

The initiative of the US to build a permanent station in space, which

was soon followed by a European decision to join this venture, further
focussed attention onto microgravity materials sciences. This originates
from the interesting prospects of a commercial space uti 1ization, which
would heavily rely on the results of scientific or technical experiments
in space. From this point of view it also seemed timely and essential to
provi de prospective commerci a 1 users with the necessary i nformat i on on
previous experience, and more importantly, with a sound scientific basis
for space processing.

The aim of the present volume consequently is twofold, namely

- to stimulate new scientific experiments in space in order to expand

our knowledge gained from microgravity research, and

to provide industry with the information obtained from space experi-

ments sofar and to contribute to the scientific background for commer-
cial space utilization.

By its very nature, the field of microgravity research is multidiscipli-

VI

nary. Therefore, a number of experts in vari ous sci ent i fi c di sci p1 i nes
was selected to give authoritative views in the various chapters of this
volume. The book is written for a broad readership, including graduate
level students, research scientists, up to senior scientists in the
industrial management. Therefore , and in view of the multidisciplinary
aspect, th~ various contributions are not written for the specialist in
the field, but rather for the educated scientist or engineer working on
a different subject area.

The book is divided into four parts. The first three chapters serve as a
general introduction, including the particular aspects of gravity reduc-
tion. The second part focuses on the physical phenomena underlying
various space investigations. Here the fundamental background is summari-
zed, with special emphasis on those features that include an influence
of gravity. Reference to actual space experiments is made herE: only in
exeptional cases.

Speci fi c poi nts concerni ng hardware for space experiments are di scussed
in Part III. This is followed by a description of case studies and
results in the last part of the book. Here results of experiments
already flown in space are compiled in the various relevant fields,
emphasizing the typical approaches and problems in microgravity experimen-
tation. An attempt is made to be exhaustive in available results up to
Space 1ab 1, with a selection of important or characteri st i c future
experiments.

The editors express their thanks to all contributors to this volume,

and to the numerous people involved in the compilation of this text.
They are indebted to NASA, ESA, and the German Aerospace Research
Establishment (DFVLR) for invaluable support. Our special thanks go to
~·1rs.Dagmar Horwath for her indispensable help in the production of
this volume.

Berndt Feuerbacher
Hans Hamacher
Robert J. Naumann

Koln and Huntsville, September 1985

Contributors
Beysens, Daniel
Commissariat a L'Energie Atomique,
F-91191 Gif sur Yvette Cedex, France

Brown, Robert A.
Massachussetts Institute of Technology, Cambridge
MASS 01239, USA

Doreaus, Robert H.
Rensselear Polytechnic Institute, Materials Engineering Department,
Troy, NY 12181, USA

Elleaan, Daniel P.
NASA-Jet Propulsion Laboratory, 4800 Oak Grove Dr, Pasadena,
CA 91109, USA

Favier, Jean-Jacques
Commissariat a L'Energie Atomique, Centre d'Etudes Nucleaires,
F-38041 Grenoble, France

Feuerbacher, Berndt'
Oeutsche Forschungs- und Versuchsanstalt fur Luft- und Raumfahrt e.V.
Institute for Space Simulation, 0-5000 Koln 90, Fed. Rep. of Germany

Frohberq, Gunter
Technische Universitat Berlin, Joachimstaler Str. 31/32
0-1000 Berlin 15, Fed. Rep. of Germany

Gonfalone, Alain
European Space Agency, NL-2200 AG Noordwijk,
The Netherlands

Haaacher, Hans
Deutsche Forschungs- und Versuchsanstalt fur Luft- und Raumfahrt e.V.,
Institute for Space Simulation, 0-5000 Koln 90, Fed. Rep. of Germany
VIII

Haynes, J. Michael
University of Bristol, School of Chemistry, Cantock's Close,
Bristol, England BS8 1TS

Herlach, Dieter M.
Deutsche Forschungs- und Versuchsanstalt flir Luft- und Raumfahrt e.V.,
Institute for Space Simulation, 0-5000 Koln 90, Fed. Rep. of Germany

Hurle, Donald T.J.

Royal Signals and Radar Establishment, St. Andrews Road,
Great Malvern, Worc WR14 3PS,
United Kingdom

Langbein, Dieter
Battelle-Institute e.V., Am Romerhof 35,
0-6000 Frankfurt/Main, Fed. Rep. of Germany

Nauaann, Robert J.
NASA-Marshall Space Flight Center, Space Science Laboratory,
Alabama 35812, USA

Saba, Peter R.
Rheinisch-Westfalische Technische Hochschule Aachen,
Foundry-Institute, Intze-Str. 5,
D-5100 Aachen, Fed. Rep. of Germany

Snyder, Robert S.
NASA-Marshall Space Flight Center, Space Science Laboratory,
Alabama 35812, USA

Steinborn, Wolfgang
Deutsche Forschungs- und Versuchsanstalt flir Luft- und Raumfahrt e.V.,
Space Oepartment, 0-5000 Koln 90, Fed. R~p. of Germany

Stur., Jorg C.
Rheinisch-Westfalische Technische Hochschule Aachen,
Foundry-Institute, Intze-Str. 5,
D-5100 Aachen, Fed. Rep. of Germany
Walter, Hans-Ulrich
European Space Agency, 8-10 Rue Mario-Nikis,
F-75738 Paris, France
Contents
Part I: Microgravity Materials Sciences
1.J~oductLon. By B. Feuerbacher ................................... 3
1.1 The Space Utilization........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 5
1 .2 The Scientific Basis..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 Present State and Future Developments ........................... 9

2.H~to~cal Development. By R.J. Naumann ............................ 11

2.1 Motivation for Microgravity Experiments ......................... 11
2.2 First Experiments........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 13
2.2.1 Drop Tower and Aircraft Experiments ..................... 13
2.2.2 Apollo Experiments.................... . . . . . . . . . . . . . . . . .. 13
2.3 Skylab and Apollo-Soyus Test Project Experiments ................ 16
2.3. 1 Crystal Growth Experiments............ . . . . .. . . . . . . . . . . .. 21
2.3.2 Metallurgical Experiments ............................... 21
2.3.3 Electrophoresis Experiments ............................. 23
2.3.4 Skylab and Apollo-Soyus Experiments in Perspective ...... 24
2.4 SPAR Experiments.......................... . . . . . . . . . . . . . . . . . •. . .. 25
2.5 Creation of the Science Base .................................... 27

3.5~on ot W~e4~ne4~. By H. Hamacher ...................... 31

3.1 Free Fall: The Principle to Simulate Weightlessness ............. 31
3.2 Free Fall Trajectories........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 33
3.3 The Orbital Flight.............................................. 34
3.3.1 Atmospheric Drag..................... . . . . . . . . . . . . . . . . . .. 36
3.3.2 Solar Radiation Pressure................................ 39
3.3.3 The Extended Spacecraft ................................. 40
3.3.4 G-jitter ................................................ 44
3.4 Other Free-Fall Methods ......................................... 47
3.4.1 Sounding Rockets ........................................ 47
3.4.2 Research Aircrafts ............. ~ ......................... 48
3.4.3 Drop Tubes and Drop Towers .............................. 49
XII

Part II: Physical Phenoaena 53

4. Convection and 8ufk

T~an4po~, By R.A. Brown ...................... 55
4. 1 Bulk Fluid Flow................................................. 55
4.2 Scalings for Flow and Species Transport ......................... 59
4.3 Transport Phenomena in Directional Solidification ............... 70
4.4 Transport Phenomena in the Floating Zone ........................ 78
4.5 Drop Dynamics.................. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 80
4.6 Summary and Perspective................................ . . . . . . . .. 84

5. D~ffu4~on and A~omLc T~an4po~, By G. Frohberg ..................... 93

5.1 Thermodynamics of Irreversible Processes ........................ 95

5. 1 . 1 Phenomenological Equations.............................. 95
5.1.2 Diffusion ............................................... 96
5.1.3 Transport Effects...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 97
5.1.4 Influence of Gravity on Transport ....................... 100
5.2 Diffusion and Transport in Simple Systems ....................... 101
5.2.1 Reference System ........................................ 101
5.2.2 Simple Solutions of the Continuity Equation ............. 104
5.2.3 The Boltzmann-Matano Method ............................. 106
5.2.4 Experimental Methods and Problems ....................... 107
5.3 Theories of Diffusion Processes in Liquids ...................... 116
5.3.1 Diffusion and Viscosity ................................. 116
5.3.2 Quasicrystalline Models ................................. 117
5.3.3 Model of Critical Volume ................................ 117
5.3.4 Fluctuation Theory ...................................... 117
5.3.5 New Concepts and the Dynamic Structure of Liquid ........ 118
5.3.6 Theories of Transport Processes in Liquids .............. 119
5.3.7 Isotope Effect in Diffusion and Transport ............... 120
5.4 Influence of Diffusion on Related Experiments ................... 121
5.4.1 Solidification and Eutectic Alloys ...................... 121
5.4.2 Ostwald-Ripening ........................................ 124
5.4.3 Separation of Immiscible Liq~ids ........................ 124
5.4.4 Crystallization ......................................... 125
5.5 Conclusions ....................................................... 125
 XIII

6. Cap~ and Wettin~. By J.M. Haynes ........................... 129

6. 1 Surfaces ........................................................ 130
6 . 1 . 1 The Gibbs Model ......................................... 130
6.1.2 Determination of Surface Tension ........................ 133
6.1.3 Surface Tension and Other Properties .................... 134
6.2 Surface Tension of Solutions .................................... 137
6.3 Surface Tension of Solids ....................................... 138
6.4 Wetting and Spreading ........................................... 139
6.4.1 Contact Angles: Measurement and Character ............... 140
6.5 Capillarity ..................................................... 142
6.5.1 Hydrostatic Equilibrium ................................. 142
6.5.2 Diffusional Equilibrium ................................. 144
6.5.3 Capillary Stability ..................................... 145
6.6 Practical Conclusions ........................................... 146

7.SoliditLcatLon. By P.R. Sahm and J.C. Sturm ........................ 149

7.1 Objectives for Solidification Research Under Microgravity ....... 150
7.2 Solidification Front Dynamics ................................... 151
7.3 Complex Interactions of Different Transport Processes ........... 155
7.4 Gravity-Independent Convective Processes ........................ 157
7.5 Effect of Convection on Microstructure and Properties ........... 159
7.6 Towards Novel Materials and Technologies ........................ 166

By D.M. Herlach and B. Feuerbacher .... 168

8. Nucle.a.;t,Wn and tln.de/l.CooJ..i..n.r;.
8.1 Nucleation Theory ............................................... 169
8.1.1 .Clusters and Nuclei. .................................... 169
8.1.2 Homogeneous and Heterogeneous Nucleation ................ 173
8.1.3 The Nucleation Rate ..................................... 174
8.2 Nonequilibrium Solidification ................................... 176
8.2.1 Undercooling and Hypercooling ........................... 176
8.2.2 Thermodynamic Conditions ....... ! • . . • . • . . . . . . . . . • . . . . . . . • • 177
8.2.3 Influence of Solidification Ki~etics .................... 178
8.2.4 Microstructure Refinement ............................... 180
8.3 Experimental Approaches ......................................... 182
8.3.1 Rapid Cooling ........................................... 183
8.3.2 Amorphous Containment ................................... 184
XIV

8.3.3 Dispersion Techniques ................................... 184

8.3.4 Container less Undercooling .............................. 185
8.4 Microgravity Prospects .......................................... 187

9. ~ca1 Phenomena. By D. Beysens .................................. 191

9.1 Universality of the Critical Behavior. Scaling Laws ............. 19'2
9. 1 . 1 Broken Symmetry - Order Parameter ....................... 192
9.1.2 The Landau Free Energy .................................. 194
9.1.3 Scaling Laws. The Renormalization Group Approach .......• 196
9.1.4 Critical Fluid Dynamics ................................. 201
9.2 Non Equilibrium Phenomena ....................................... 203
9.2.1 Fluids Under Shear Flow: Change of Upper Critical
Dimensionali ty .......................................... 204
9.2.2 Phase Separation Process: Nucleation, Spinodal
Decomposi tion ........................................... 204
9.2.3 Ionic Conductivity Measurements ......................... 207
9.3 Finite Size Effects: Wetting and Prewetting Transitions ......... 208
9.3.1 In the 2-Phases Region: Wetting ......................... 209
9.3.2 In the 1-Phase Region: Prewetting ....................... 210
9.3.3 Near the Critical Point: The Critical Adsorption ........ 210
9.4 Gravity Dependence .............................................. 210
9.4.1 The Liquid-Vapor Transition ............................. 210
9.4.2 The Phase Separation Process ............................ 212
9.4.3 Wetting Layers .......................................... 212
9.4.4 The A-Point of Helium ................................... 212
9.5 Experiments Under Microgravity Conditions ....................... 213
9.5.1 Microgravity to Obtain a Bulk Critical Cell at the
Gas-Liquid Critical Point ............................... 213
9.5.2 Microgravity to Avoid Stratification .................... 217
9.6 General Conclusion .............................................. 222

Part III: Experiaental Hardware 225

10. Fwznace4. By W. Steinborn ........................................ 227

10.1 Special Requirements to Furnaces in Space Laboratories ........ 228
 xv

10.2 Review of Heating Techniques and Their Potential for

Space Furnaces ................................................ 231
a. Resistance Heating ...................................... 231
b. Electron Beam Heating ................................... 233
c. Inductive Heating ....................................... 233
d. Electrical Discharge Heating ............................ 234
e. Heat Pipe Heating ....................................... 234
f. Mirror Heating .......................................•.. 236
g. Direct Current Passage Heating .......................... 240
h. Laser Heating ........................................... 240
i. Microwave Heating ....................................... 241
k. Chemical Reaction Heating ............................... 241
10.3 Practical Spaceborn Furnace Configurations and Their
Characteristics ............................................... 241
a. Isothermal Heating Furnaces ............................. 242
b. Gradient Furnaces ....................................... 249
c. Zone Heating Furnaces ................................... 253
d. Universal Furnaces ...................................... 255
10.4 Peripheral Devices ............................................ 256
10.5 Future Trends in Space Furnace Development .................... 259

11. Fluid cxp~entA. By A. Gonfalone ............................... 266

11 . 1 Introduction .................................................. 266
11.2 Particular Characteristics of Fluid Instrumentation ........... 267
11.3 The 'Spacelab Facilities ....................................... 273
11.4 Concluding Remarks ............................................ 289

12. ContaUteM..e44 'P/l.OCe4-1.i..n.g. Techn.olo91J-.

By R.J. Naumann and D.O. Elleman ................................... 294
12. 1 Drop FaciIi ties ............................................... 295
12.1.1 The MSFC Drop Tubes .................................. 295
12.1.2 The JPL Drag-Free Drop Facility ...................... 299
12.2 Acoustical Levi tators ......................................... 300
12.2.1 Single-Axis Tuned Cavity Acoustic Levitator
Furnace .............................................. 300
12.2.2 Three-Axis Levitator ................................. 301
12.2.3 Single-Axis Interference Levitator ................... 302
XVI

12.3 Aerodynamic Levi tators ........................................ 306

12.4 Electromagnetic Levitators .................................... 307
12.5 Electrostatic Levitation ...................................... 309
12.6 Prospectus for Container less Processing ....................... 310

Part IV: Case Studies and Results 315

13. ~etal4 and Compo~it~. By J.J. Favier ............................ 317

13.1 Metallurgical Technologies .................................... 318
13.2 Test of Theories .............................................. 321
13.2.1 Eutectic Growth ...................................... 321
13.2.2 Directional Solidification ........................... 327
13.3 Elaboration of New or Improved Materials ...................... 331
13.3.1 Particle Redistribution .............................. 332
13.3.2 Systems of Interest .................................. 334
13.3.3 Skin Technology ...................................... 336
13.4 Characteristic Future Experiments ............................. 337
13.4.1 The "GETS" Experiment ................................ 337
13.4.2 The Mephisto Project: ................................ 337
13.5 Conclusions ................................................... 340

14. BinWL!I S!I~;terM wdh ~-wcib.i..J.i.;t!l C;ap in the LLq,uid S;ta;te.

By H. U. Walter ..................................................... 343
14.1 Binary Systems with Miscibility Gap in the Liquid State ....... 347
14.2 Minimum Free Energy Configurations ............................ 351
14.3.1 Simulation of Spinodal Decomposition and Growth
of Nuclei ............................................ 354
14.3.2 Nucleation ........................................... 354
14.3.3 Terrestrial Observation of the Early Stages of
Spinodal Decomposition and Nucleation ................ 357
14.4 Results of Microgravity Investigations ........................ 364
14.5 Conclusions ................................................... 374
 XVII

15. C/I.!j-<Jt.aJ. t;/l.owt.h. By D.T.J. Hurle .................................. 379

15. 1 Introduction .................................................. 379
15.2 Space Relevant Growth Techniques .............................. 380
15.2.1 Floating Zone Melting ................................ 380
15.2.2 Bridgman Growth ...................................... 383
15.2.3 Growth from Metal Solution by the Travelling
Heater Method (THM) .................................. 387
15.2.4 Growth from Aqueous Solution ......................... 390
15.2.5 Vapour Growth ........................................ 393
15.3 Discussion .................................................... 394
15.4 Future PotentiaL ............................................. 395
15.5 Conclusions ................................................... 398

16. Fluid DynwniC-<!. By D. Langbein ................................... 401

16.1 Capillarity ................................................. '.. 401
16.2 Stability ..................................................... 404
16.3 Microgravity Experiments on Liquid Bridges and Drops .......... 408
16 . 4 Dynamic Models ................................................ 409
16.5 Wetting and Spreading ......................................... 413
16.6 Interface Convection .......................................... 416
16.7 Microgravity Experiments on Interface Convection .............. 419

17. Themnoph!J-<lLcaJ. r/l.0pe/l.;tLeA. By G. Frohberg ........................ 425

17.1 Overview on Properties with Gravity Influence ................. 425
17.2 Design of Experiments for Reduced Gravity
(Diffusion and Atomic Transport) .............................. 429
17.2. 1 Container Design ..................................... 429
17.2.2 Temperature Control .................................. 433
17.2.3 Analysis of Diffusion Components ..................... 435
17.3 Diffusion Experiments in Space ................................ 436
17.3.1 Selfdiffusion in Zn (Skylab) ......................... 436
17 . .3.2 Solute Diffusion of Au in Pb (Apollo-Soyuz) .......... 437
17.3.3 Selfdiffusion in Sn (Spacelab-1) ..................... 438
17.3.4 Self- and Interdiffusion in Sn/In (01 Flight) ........ 441
17.3.5 Interdiffusion in Pb/Zn (01 Flight) .................. 441
17.3.6 Interdiffusion in Salt Melts (01 Flight) ............. 442
XVIII

17.4 Transport Experiments in Space ................................ 442

17.4.1 Thermotransport of Co in Sn (Spacelab-1 and 01) ...... 442
17.4.2 Thermotransport in AgI/KI (01 Flight) ................ 444
17.5 Summary and Outlook ........................................... 444

18. s;ilcv.J41Ul. By R.H. ·Doremus ......................................... 447

18. 1 Uses and Types of Glass ....................................... 447
18.2 Melting of Glass .............................................. 449
18.3 Glass Formation and Crystallization ........................... ~51
18.4 Diffusion ..................................................... 454
18.5 Bubbles ....................................................... 456
18.6 Processing of Glass in Low Gravity ............................ 458
18.7 Measurement of Properties of Glass in Low Gravity ............. 460
18 . 8 Summary ....................................................... 461

19. 5e~atLon TechnLqulUl. By R.S. Snyder ............................ 465

19.1 Electrophoresis ............................................... 466
19.2 Continuous Flow Electrophoresis on Earth ...................... 468
19.3 Continuous Flow Electrophoresis in Space ...................... 470
19.4 Isoelectric Focusing .......................................... 473
19 .5 Phase Partitioning ............................................ 477
19.6 Conclusions ................................................... 479

Index ................................................................. 483

Part I:
Microgravity Materials Sciences
1 Introduction
B. FEUERBACHER
Institute for Space Simulation, DFVLR, Koln, FRG

The development of space exploration and astronautics has undergone a

major change in scope duri ng the early ei ght i es. Thi sis quite apparent
from the avail abi 1ity of a new space transportation system, the space
shut t 1e, whi ch offers a 1arge cargo capabil ity to low earth orbits with
the novel features of full payload recoverability and nearly regular,
frequent servi ce. Along with thi s, a number of other aspects changed
more gradually and less apparent. The role of man in space has shifted
from a mainly technical piloting function to a much more active involve-
ment, including scientific tasks and interactive work in space. This is
ill ustrated by Fi gs. 1.1 and 1. 2, contrast i ng the rather clumsy appear-
ance of Astronaut Aldrin on the lunar surface during the Apollo 11
mission with the hands-on work of Payload Specialist Lichtenberg in the
shirt-sleeve environment of Spacelab during STS-9.

Fig. 1.1 Astronaut Aldrin on Fig. 1'.2 Payload Specialist

the Moon during Apollo 11 Lichtenberg working in Spacelab
during STS-9
4

On the other hand, products requi red only in small quanti ties, but of
high specific cost are likely candidates for space manufacturing. In
fact, the first space product available on the market, monodisperse
latex spheres, belongs to this category. These are precision polystyrene
microspheres of uniform size for a variety of applications, e.g. medical
microscopy calibration, which can be produced in space with improved
uniformity and in size ranges not achievable by ground processing (Fig.
1. 5) . They have been recogni zed as a cali brat i on standard by the US
Nat i ona 1 Bureau of Standards. There is a number of other candi dates of
space products in this category. McDonnell Douglas Aerospace Corporation
has demonstrated a several hundredfold increase in throughput in free-
flow electrophoresis in space, a process used to purify biomedical
products for pharmaceutical applications. Interesting prospects are also
seen in the crysta 11 i zat i on of speci ally taylored semi conductor compounds
for optoelectronic applications in communication technology or infrared
sensors.

Fig. 1.5 Spherical latex spheres

of uniform size lO~m in diameter
processed in space

The third step in the pyramid of Fig. 1.4 is the production of

comparison standards in space for the purpose of research redirection on
earth. Here the space mi crogravity envi ronment is utili zed to process
samples in an idealized way not readily accessible on earth. After
return to ground the samples are carefully investigated, and provided
nove 1 and commerci ally interest i ng proper t ies are found, di rected ground-
based research and development efforts ' are initiated to produce the
materials in an economic way on earth. Numerous experiments in the
present space mi crogravity programmes are designed along thi s 1i ne, many
of wh i ch are discussed in Part IV of this volume. One example may
illustrate this here. Littke [1.3 ) has grown protein crystals during the
 5

While scientific research always had a driving function in space explora-

tion, the goals were originally directed mainly towards an investigation
of space i tse 1f, rangi ng from the near earth envi ronment, the sun-earth
re 1at ions, the planetary system to the very 1imits of our uni verse. So
the scientific disciplines of astronomy, astrophysics and magnetospheric
research were dominating the scene. With the advent of Spacelab, a
laboratory specifically designed for scientific work in space, new
qualities of space flight were accessible, with a particular emphasis on
the availability of nearly vanishing gravitational acceleration for
extended times duri ng force-free orbital fl i ght. Thi s opened space as a
novel research tool to a number of usually earth-bound disciplines like
physics, chemistry, medicine, or biology. At the same time, a gradual
but drastic change could be observed in the technological and commercial
utilization of space flight. While in the early days the main impact of
space exploration on every days life on earth was seen in a technological
spinoff, the wide ranging impl ications in the field of communications
were soon recognized and utilized, leading to a substantial benefit and
economi c return. The same sequence of events occured in the area of
earth observations. Recently there are good indications for a similar
development in the microgravity disciplines.

1.1 The space utilization pyramid

We cannot expect the commerci a 1 uti 1 i zat i on of space mi crogravity to be

a rapid development. The action of gravity has always been a dominating
factor for life on Earth, so it is burned into our minds and thinking in
terms of absence of gravity is difficult. It is, however, wrong to
be 1 i eve that the commerci a 1 app 1 i cat i on of mi crogravity is a very recent
thought. In fact, a British patent was issued in 1782 to a merchant
named William Watts from Bristol, U.K., for the production of lead shot
by a free fall techni que. Thi s methode turned out to generate shot of
much better quality than previously available. In 1785 Watts built a
drop tower in Bri sto 1 (see Fi g. 1.3) and deepened a well, gi vi ng a total
fa 11 of 27.2 m [1. 1 1. Production of shot by thi s techni que was a great
commercial success and is still in use today.

In spite of this early example of microgravity utilization, the correspon-

ding development in space sofar was focused on the fundamental scientific
side. Of course, the ultimate test for the usefulness of such efforts is
6

Fig. 1.3 Engraving from 1872,

showing the first drop tower
used to produce spherical lead
shot by a free all technique.
This tower was built in Bristol
in 1785.

whether people are wi 11 i ng to pay for it. These two aspects are not
controversary but rather complementary, as can be illustrated by a
"pyramid scenario" of space utilization, Fig. 1.4. A mass production in
space, which forms the top of the pyramid, is only expected for a
product that is requi red in 1arge quant it i es and cannot be manufactured
on earth in an economi c way. Very few products of thi s ki nd can be
identified todate. One possible candidate is the growth of gallium
arsenide crystals with improved stoichiometry in space [1.21, a material
that can serve as the basi s for a new hi gh-speed semi conductor techno-
logy. The economi c feasi bil ity of such a process is still to be demon-
strated.

It em_ j;xamR~_~
!-1ass Productio-.!'.:....:.:in~S!:.pa:::c:::e=--_. _ _ -I~\---_ _ _ _ _~G~a ~.~l _____ _
High-Cost. Low-Volume Hormones
Products Latex Spheres
Comparison Standards Protein Crystals
19._r_R_e_s_earch Redirection Dispersion Alloys
Understanding of Silicon Crystals
Process Parameters Marangoni Convectio~
Fundamental Fluid Physics
Physics & Chemistry Critical Phenomena

Fig. 1.4 Space utilization scenario

 7

Spacelab 1 flight of a size and perfection sufficient for x-ray structure

analysis. Knowledge of the structure is a prerequisite for the synthesis
of proteins on earth, and consequently protein crystal growth in space
has generated lively commercial interest.

Under standi ng of pr.ocess parameters is another important goal in mi crogra-

vity space experimentation. The free fall environment allows to separate
gravity dependent process parameters from those not influenced by gravita-
tional forces, a distinction that in many cases is not possible on
earth. The results of such experiments may directly influence large-scale
earth-bound processes .. Here ori gi nates the i ncent i ve for steel compani es
or semiconductor industry, but also for scientific and technical institu-
tions to get involved in space microgravity programmes. This may be
exemplified by the experiment of Eyer and Nitsche [1.4] during Spacelab
1, investigating si 1icon crystal growth by the zone melting technique.
Their results indicated an unexpected large influence of surface-induced
Marangoni convection on doping inhomogenities, a finding that has signifi-
cant impact on ground-based silicon crystal growth methods.

The bas is of the space app 1i cat ions pyrami de of Fi g. 1. 4 is formed by

fundamental research in physics, chemistry, physico-chemistry and related
fi e1ds. A major part of the present volume is devoted to thi s topi c,
mainly concentrated in Part II. Fractions of the two adjacent levels of
the pyramid are also covered in Part III, so the contents of the present
book may be represented by the dashed triangle in Fig. 1.4.

1.2 The scientific basis

In the area of fundamental sciences, there are three different kinds of

incentives to consider experimentation in space. Those are

* investigation of phenomena which intrinsically are influenced by gra-

vity;

* access to novel measurement techniques that make use of the absence of

gravity to improve accuracy, observability, or detection limits;
8

* improved or novel processes possible only under reduced gravity.

On the atomic level there are few phenomena directly influenced by

gravity. The earth gravitat i ona 1 force on an atom is negl i gi b1e on the
scale of electrostatic intermolecular forces and even in comparison to
the relatively weak van-der-Waals interaction. Therefore we expect gravi-
tat i on-i nduced effects only under part i cul ar ci rcumstances, for examp Ie
near a bifurcation poi nt, where two forces are balanced, so a small
externa 1 force can determi ne the di rect i on of evo 1ut i on of the system,
or in a system near a critical point, where molecular assemblies can
grow to such a size that the gradient in gravity becomes comparable to
the coordinative intermolecular forces. The latter is discussed extensi-
vely in Chapter 9 of this volume.

Gravity becomes more conspi cuous on the macroscopi c scale. Here it is

responsible for the ubiquitous phenomena of bulk convection, sedimenta-
tion and buoyancy, and hydrostatic pressure. These effects, particul arly
important in 1i qui ds and gases, therefore are the subject of vari ous
investigations under gravity free conditions, as described in Chapters
4, 6 and 16.

Reduction of the gravitational acceleration gives access to a wide range

of novel measurement techni ques or ranges. Convection and sedimentation
are dominating transport of heat and matter in many systems. In space
other, weaker transport mechanisms are unveiled and become accessible to
observat ion. For instance, novel results on thermomi grat ion (Soret
effect) have been obtai ned on Space 1ab 1 (Ref. 1. 5, see also Chapter
5). Similar considerations prevail on the reduction of hydrostatic
pressure, which opens up new measurement possibilities in critical
systems. A typical example of a space experiment in this category can be
found in the field of containerless undercooling (Chapter 8). Here an
effect is studied that is not depending on gravity at all. However, the
absence of gravitational acceleration allows to position a sample free
of container walls and with very low di~turbing forces, so completely
new research avenues are opened to study nucleation, which are not
accessible on earth.
 9

A wide variety of processes can be identified that can only be performed

in space, or else can be improved in space compared to the corresponding
ground process. Examples are found in the fields of crystal growth,
separation techniques and the production of novel materials such as
metastable structures, glasses or glassy metals, alloys with new proper-
ties and compos ites not access i b1e on earth. Many of these aspects are
discussed in the present volume, particularly in the chapters of Part IV.

1.3 Present state and future developments

Microgravity materials and fluid sciences is beginning to develop into a

sound research field. After the early pioneering results of the Apollo
and Skylab aera, Spacelab has introduced a new dimension into space
experimentation, which is s.tarting to carry fruits. Parallel to Spacelab
and comparable flight opportunities like the International Microgravity
Laboratory (IML), i ntens i ve ground based research is in progress, suppor-
ted by short-term microgravity facilities such as airplane or rocket
flights or drop towers.

The present volume wi 11 present a number of resu lts of space and ground
experiments available todate. This stock of data experience is growing
at a rapid pace, and it is hoped that the discussion of scientific
phenomena in Part II will stimulate this expansion. In this way, a sound
scientific basis is established, which can serve as a solid foundation
for future commercial applications of microgravity in space.

This will be of particular importance under the aspect of the advent of

a permanent space station, whi ch wi 11 open up new prospects of space
utilization, with novel experimental possibilities and less restrictions
in operation time, resources and flexibility. In the space station era,
the microgravity utilization pyramid will evolve into a steady state
condition, with new ideas entering in the scientific base which selecti-
ve ly percolate upwards to the more app 1 i cati on ori ented stages. Here it
is important to stimulate an intensive int~raction between science and
industry. It is therefore essent i alto estab 1i sh strong research efforts
involving materials and processes in which there is intense technological
interest in order to provide sufficient information to industry on the
expected benefit of space process i ng to that they can make rat i ona 1
10

deci si ons regardi ng the busi ness aspects of a commerci a 1 space venture
0.6].

References

[1 .1 ] M. Hayne~, private communication. Thanks are due to the Bristol

City Archives for Fig. 1.2.

[1.2] H.C. Gatos, J. Lajowsk, L.M. Pawlowicz, F. Dabkowski, and C.-J. Li,
in Proceedi ngs 5th European Symposi urn "Materi a 1 Sci ences under
Mi crogravity", ESA SP-222, p. 221 (1984)

[1.3] W. Littke and C. John, Science 225, 203 (1984)

[1.4] A. Eyer, H. Lei ste and R. Nitsche in Proceedi ngs 5th European
Symposi urn "Materi a 1 Sci ences under Mi crogravity" ESA SP-222, p.
173 (1984)

[1.5] Y. Malmejac and J.P. Praizey, in Proceedings 5th European Sympo-

sium "Material Sciences under Microgravity" ESA SP-222, p. 147
( 1984)

[1.6] R. J. Naumann, "Mi crogravity Sci ence and App 1 i cat ions Program Des-
cription Document", NASA, February 1984.
2 Historical Development
R. J. NAUMANN
Space Science Laboratory
NASA Marshall Space Flight Center
Huntsville, Alabama 35812 U.S.A.

Summary
This chapter outlines the history of the U.S. Microgravity Science, and
Applications program from its beginning as strictly an applications program
aimed at developing space manufacturing processes for commercial use,
through its metamorphosis as a material science program, to its present
status as a mi crogravi ty sci ence program. Si gnifi cant fi ndi ngs of the
early flight experiments are summarized.

2.1 Motivation for Microgravity Experiments

In the conceptual years of space flight, it was recognized that the orbital
envi ronment was in many ways di fferent from that of Earth and that the
design and construction of spacecraft to operate in this environment would
be a formi dab 1e challenge. The pri mary envi ronmental factors that had to
be consi dered were the vacuum of space, energetic radi at i on from the Sun
and other sources, and the near absence of apparent gravitational effects
resulting from the free-fall condition of orbital flight. Of thesa
factors, the long exposure to a virtually zero-gravity environment is a
truly unique situation that cannot be duplicated or even approximated for
any length of time on Earth.

Interest in low-gravity phenomena began to evolve in the late 1950's from

several different disciplines. The behavior of fluids in the absence of
effective gravity was the object of a number of research efforts in order
to design propellant management systems and other fluid systems required by
the then emerging space technology. The development of spacecraft thermal
control systems that uti 1i ze change of phase of materi al s for heat storage
prompted questions concerni ng sol i difi cat i on phenomena in zero gravi ty.
The possibility of erection and repair of large structures in space by
brazing and welding raised issues concerning t~e flow of liquid metals when
dominated by capillary forces.

In considering the likely behavior of liquids and solidification processes

in the low-gravity environment of an orbital spacecraft, it was recognized
that thi s envi ronment mi ght be useful for a vari ety of uni que processes.
12

Obviously, buoyancy-driven convective flows would be eliminated or dras-

t i ca lly reduced. Thi s woul d all ow many processes such as crystal growth,
alloy solidification, combustion, and other chemical reactions to be
studied under diffusion-controlled conditions that are quiescent, easier to
control, and vastly simpler to analyze. Also, many secondary phenomena,
such as thermocapillary flows, electroosmotic flows, Stefan flows, Soret
diffusion, etc., could be studied without the complicating and sometimes
overwhelming effects of buoyancy-driven convection.

Sedimentation or Stokes settling is also virtually eliminated in the micro-

gravity environment. This allows fluids with multi-phase components to be
held in suspension more or less indefinitely. The most obvious application
of this aspect of the microgravity environment to materials processing
would be the solidification of systems with a liquid-phase miscibility gap
or with a di spersed second phase. Thi s may al so be useful for invest i-
gat i ng processes such as nucl eati on and growth phenomena, studyi ng systems
near their critical points, performing experiments to test various ripening
theori es, and invest i gat i ng the stabil ity of foams, fl ocs, and other di s-
persions. Of course, the lack of sedimentation also poses additional prob-
lems that must be dealt with, such as the removal of bubbles from a system.

The absence of hydrostatic pressure permits the shapes of 1i qui ds to be

dominated by surface tension. This should allow liquid bridges or molten
floating zones to be extended to the Rayleigh limit (length of the zone
equal to the circumference). One obvious application is the extension of
the float zone crystal growth process to materials that have too low a sur-
face tension to support a reasonable size zone in Earth's gravity. The ex-
tended zone length would also allow more area for heat input which could
result in better control of the temperature field in the vicinity of the
growth interface. It should be possible to obtain flatter isotherms, which
should result in less radial segregation, and steeper axial gradients,
which would provide more stability against interfacial breakdown and allow
higher growth rates and/or dopant concentration.

In the virtual absence of gravity, it is also possible to suspend droplets

or high temperature melts without physical contact. Some small controlling
force such as electrostatic, electromagnetic, or acoustic radiation pres-
sure is required to overcome the residua.l spacecraft accelerations and
maintain the position of the droplet or melt. This offers unique opportun-
 13

ities to process materials at high temperatures without a crucible. Since

many materials become highly corrosive above their melting points, this
technique may be useful for measuring thermophysical properties or for pro-
ducing ultrapure materials. Also, the elimination of heterogeneous nucle-
ation sites should allow melts to be deeply undercooled before solidifica-
tion. Such undercooling may have dramatic effects on the final microstruc-
ture of the solid. Metastable phases, inaccessible to equilibrium solidi-
fication, may be obtained in bulk samples. Amorphous phases may be ob-
tained in systems that do not ordinarily form glasses. It may also be pos-
sible to test various theories of homogeneous nucleation by using con-
tainerless techniques to eliminate heterogeneous nucleation sites.

2.2 First Experiments

2.2.1 Drop Tower and Aircraft Experiments
The drop towers at the Marshall Space Flight Center (MSFC) and at the Lewis
Research Center, along with aircraft such as the KC-135 flying ballistic
trajectories (illustrated in Figs. 2.1-2.4), were used extensively to pre-
dict the behavior of propellants in tanks during low-gravity coasting
periods. Equilibrium configurations and oscillations of liquids in par-
tially filled tanks were studied. Also, a number of experimental concepts
such as various levitation and position control techniques for later space
processing experiments were developed and tested in these facilities. A
small sample of uniformly dispersed monotectic alloy (Ga-50 AU Bi) was
prepared ina drop tower experi ment at the Marshall Space Fl i ght Center.
[1] Figure 2.5 illustrates the resulting microstructure.

2.2.2 Apollo Experiments

The first opportunities to perform long-duration experiments in low gravity
came with the Apollo lunar program. Several small "suitcase" experiments,
such as shown in Fig. 2.6, were added to the flight manifest on Apollo 14,
16, and 17 and were performed by the crew duri ng the trans-Earth coast.
The experiments consisted of a low temperature furnace to perform casting
experiments on model composite systems, a heat flow and convection experi-
ment, a pri mit i ve elect rophores is experi ment til test the concept of per-
forming electrophoretic separation of biological materials such as cells
and macromo 1ecul es in the absence of buoyancy-dri ven flows that 1i mit the
process on Earth, and a fluid pumping experiment to test different tech-
niques for achieving and maintaining phase separation of stored liquids
duri ng the drai ni ng and fi 11 i ng of storage tanks. The power and wei ght
14

DROP TOWER
DROP TOWn DETAILS

IILUlt"fTU
,,,"',,.s
'U
.., 'TI"we....
.."
fin nu. IU'SIIlfll

Fig. 2.1. Low-gravity drop tower facility

Fig. 2.2. Photograph of NASA KC-135 flying low-gravity trajectory

 15

....
10.1
14) WETEAS/SU.'ON D
.47' .. AQI

E ...
' .1

!:i
9'"
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S.l KILOMETERS

1-------
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14.5 KILOMETERS-----_ ..-j

so
S£a)NDS

Fi g. 2.3. Typical low-gravity trajectory flown by the KC-135 aircraft.

Reasonably low accelerations can be maintained for 20-30 sec .

Fig. 2.4. Low gravity inside a research aircraft. Packages may be

free-floated as shown here or bolted to the aircraft floor.
16

avail ab 1e for such experi ments great 1y 1i mited thei r capabi 1 i ty and the
scientific details that could be obtained from them. All the experiments
operated successfully but revealed the presence of more subtle non-
gravitational flows that needed further understanding before the micro-
gravity environment could be used to advantage.

Fig. 2.5. Microstructure of Ga-50 AU Bi solidified during free fall in

the MSFC drop tower (left) and the control sample sol idified under iden -
tical conditions except in normal gravity. The dark regions are the Ga-
rich particles in the Bi-rich matrix (light grey region).

Fig. 2.6. Apollo 14 heat flow and convection experiment apparatus

2. 3 Sky1ab and Apollo-Soyuz Test Project Experiments

Sky1ab offered the first opportunity to perform materials processing exper-
iments in a dedicated facility shown in Figs. 2. 7-2 . 10. The experiments
[2J consisted of welding and brazing investigations, a study of combustion
in a diffusion-controlled envi r onment, several solidification experiments
 17

Fig. 2.7. Science astronaut Owen Garriott at the

control console in Skylab

=ig. 2.8. The Skylab M512 materials processing facility. This

facility was l ocated in the mult i ple docking adapter section of
5kyl ab, and coul d be vented to space through the 4-i nch vacuum
line at the 1eft of the photograph. The work chamber featured
~lectrical connections and a universal mount designed to accommo-
jate the individual apparatus for each me l ting and solidification
~xperiment interchangeably.
18

Fig. 2.9. The Skylab M518 multi-purpose electric furnace system

Fig. 2.10. The Skylab M518 mUlti-purpose electric furnace

installed in the M512 materials processing facility
 19

i nvol vi ng all oys and composi tes, fi ve crystal growth experi ments, and an
unsuccessful attempt at containerless solidification. In addition, a group
of demonstration experiments were performed during the later portion of the
Skylab mission. These relatively simple experiments were conceived during
the mission and were performed with equipment available on Skylab. They
were intended to provide material for classroom use that demonstrated the
effects of virtual weightlessness. In fact, they also provided some
interesting scientific insights. For example, it was shown that a liquid
bridge simulating a molten floating zone could be extended to its theoreti-
cal Rayleigh limit (length equal to circumference) before it broke into two
individual droplets, but an unsuspected "jump-rope" instability developed
when the zone was rotated, as may be seen in Fig. 2.11. [3J This finding
could have important implications for later attempts to grow crystals in
space by the float zone technique.

Fig. 2.11. "Jump-rope" instability of a rotating liquid bridge discovered

during a Skylab demonstration experiment. The liquid is colored water sus-
pended between two socket wrench extensi ons mounted in camera brackets.
Thi sis an exampl e of an ersatz experiment put together by the crew usi ng
available onboard equipment.

The Apollo-Soyuz Test Project (ASTP) (shown in F?gs. 2. 12 and 2.13) offered
an opportunity to fly several new experiments as well as to refly several
of the Skylab experiments that had produced provocative results. [4J The
resources available to experimenters on ASTP (power, weight, and time) were
considerably less than on Skylab and constrained the types of experiments
that could be performed.
20

Fig. 2.12. Artist's concept of the ASTP flight. The Apollo Command and
Service Modules fitted with a special docking adaptor (left) are shown in
the process of docking with the Salyut spacecraft (right).

Fig. 2.13. Multi-purpose electric furnace used i n the ASTP

 21

2.3.1 Crystal Growth Experiments

In general, the solidification and crystal growth experiments performed on
Skyl ab and ASTP di d not produce spectacul ar results, but di d confi rm that
buoyancy-driven convective flows were sufficiently suppressed so that
diffusion-controlled conditions could be approached, as may be seen in Fig.
2.14. Several interesting scientific results were obtained. For example,
Witt et al. (MIT) produced very uniformly doped InSb, completely free of
the growth rate striations which occur in Earth's gravity because of -small
temperature oscillations resulting from convective flows. [5J This con-
fi rmed that the growth rate fl uctuat ions observed in many crystal growth
processes were indeed gravity related and could be eliminated in a micro-
gravity environment.

Walter, however, did observe growth striations in his doped InSb experiment
which was solidified in a quasi-containerless (pendant drop) process. [6J
It is possible that these growth stria resulted from unsteady Marangoni
(surface tension-driven) convection which can take place when free surfaces
are exposed to a thermal gradient.

Wi edemei er (RPI) grew Ge Te and GeSe crystals by chemi ca 1 vapor transport

usi ng i odi de vapor as the transport agent. The space-grown crystals were
somewhat 1arger with we ll-defi ned facets and si gnifi cant ly fewer defects
than the Earth-grown crystals. [7, 8J Thi s confi rmed the suppos it i on that
the more quiescent growth conditions in the microgravity environment could
produce superi or crystal s. However, a totally unexpected result was ob-
tained. The amount of material transferred from the source to the growing
crystals was as much as five times more than expected based on existing
models for diffusion transport and from ground-based experiments in a
convectively stable configuration. [9J Wiedemeier suggested that the
anomalous transport mi ght have been caused by heat released from chemical
reactions by chemical reactions taking place throughout the growth ampoule,
although the details of this explanation have not been completely worked
out. It became clear that our understanding pf chemical vapor transport,
even under the si mp 1 ifyi ng condit ions provi ded by a mi crogravity envi ron-
ment, was far from complete.

2.3.2 Metallurgical Experiments

Another intriguing result was obtained from an experiment by Larson
(Grumman Aerospace Corporati on) in whi ch MnBi rods were grown ina Bi ma-
22

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10.00' .....·,"'.. ,

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SA15

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... 1.0 U ... 1.1 ... '.6 '.1

ao
... , ... U I.l 1.0 0.. . . . . . . . D.J U
DISTANCE fiN) mR"NCI.'N)

Fig. 2.14. The results of Skylab's liquid zinc diffusion experiment are
shown above. All samples were processed, identically, those at left on
Earth, those at right on Skylab. The curv~s show the distribution of the
radioactive zinc atoms after melting and resolidification. All Earth
samples showed uniform distribution of 65Z n caused by convection and
diffusion in the melted metal (the upper left sample shows non-uniform
distribution caused by incomplete melting of the sample). The Skylab
samples indicate a 65Z n distribution attributed to pure diffusion in
excellent agreement with theoretical curves, thus allowing the determin-
ation of an average coefficient of diffusion of 4.28 x 10- 5 cm 2/s.
 23

trix by directionally solidifying a eutectic mixture of MnBi/Bi. The mag-

netic properties of the space-grown material were considerably different
from Earth-grown material using identical growth conditions. [10] In fact,
the low temperature coerci ve strength of the space-grown materi a1 was the
highest ever measured at the time for MnBi and approached the theoretical
limit. It was later shown that this difference resulted from finer rod
diameters in the space-grown sample which fortuitously happened to be close
to the optimum size for elongated, single-magnetic domains. [11] Why the
rod di ameter of the space-grown sample was different from the Earth-grown
samples is still not completely understood, but we now know that convection
plays a more important role in the solidification of some eutectic systems
than had been previously realized.

Various attempts to make uniform dispersions, either by dispersing a

second-phase material in a host matrix or by monotectic reactions, were not
generally successful because of a vari ety of unexpected agg1 omerati on or
phase separation mechani sms. The most successful of these attempts was
that of Takahashi (University of Tokyo) who took the precaution of coating
his SiC fibers with Ag before they were mixed with the Ag matrix material.
[12] Also, he incorporated a spring-loaded plunger in his cartridge to
accommodate the volume change during melting and reso1idification in order
to avoid any free surfaces in the melt. This apparently eliminated many of
the surface tension effects that caused agglomeration or expulsion of the
dispersed phase in other experiments.

Despite the early success of Lacy and Otto using the drop tube, several
attempts to produce in situ composites from systems with liquid phase mis-
cibility gaps (monotectic systems) in space resulted in massive phase
separation. Such systems will rapidly separate in Earth's gravity because
of density differences between the two liquid phases, but it has now become
apparent that there also exists significant non-gravitational effects.
These mechanisms involved a rich variety of interfacial effects that are
only now beginning to be understood, such as critical point wetting,
Ostwa1d ri peni ng, thermocapi 11 ary and other sutrface tens i on-dri ven flows,
and particle pushing at solidification interfaces.

2.3.3 Electrophoresis Experiments

Two electrophoresis experiments were flown on ASTP. A simple static column
device was developed by Allen et a1. (MSFC) and separated a variety of
24

samples including various ethyrocytes, lymphocytes, and fetal kidney cells.

[13J The samples were electrophoresed for a predetermined time and frozen
in place by means of a thermoelectric cooler for return to Earth. Although
several columns were lost because of minor equipment problems, it was
demonstrated that electroosmotic flows, which had plagued earlier space
electrophoresis experiments, could be controlled by suitable low zeta
potential coatings on the walls. Also, it was found by Barlow (then at
Abbott Laboratori es) that several sampl e bands of ki dney cells exhi bited
increased production of urokinase and other cell products, indicating that
it may be possible to separate kidney cells electrophoretically according
to their function. Attempts to duplicate these results using ground-based
continuous flow electrophoresis devices have only recently been successful
because of improvements in electrophoresis technology. These improvements
resulted primarily from studies of gravity influences on the flows in
electrophoretic chambers that were prompted by the Materials Processing in
Space program. Furthermore, some of the electrophoretic and selective
culturing techniques developed by Abbott Laboratories in conjunction with
this experiment has led to the commercial production of urokinase (Abbo-
kinase) for the treatment of thrombosis.

The second electrophoresis experiment consisted of a continuous flow device

developed by Hanning (Max Planck Institute for Biochemistry, Munich). The
purpose of the experi ment was to analyze the separat i on of vari ous ce 11
types in microgravity by using ultraviolet absorption analysis. No attempt
was made to collect and return the samples. Unfortunately, the high pres-
sure arc lamp, which served as the UV source, burned brighter than expected
in the convectionless low-gravity environment, and the detectors were
almost completely saturated; thus, little information could be obtained
about the separation.

2.3.4 Skylab and Apollo-Soyuz Experiments in Prespective

The materials processing experiments on both Skylab and ASTP were limited
by a number of factors. Si nce thi s WqS a new fi e1d of research, the
approach taken by many of the investigato~s tended to be somewhat Edisonian
in nature. In some cases, the decision to fly certain experiments came
late, and the flight schedule did not permit sufficient time for a thorough
ground-based development program. The available equipment was constrained
by power and weight. This was particularly critical in the crystal growth
experiments where the furnaces were limited in temperature and had inade-
 25

quate control of axial and radial thermal graidents which greatly affect
the stabil ity and pl anari ty of the growth interface. Al so, it was neces-
sary to use the simpler gradient-freeze technique for directional
solidification rather than the more conventional Bridgman-Stockbarger met-
hod in which the growing crystal is translated relative to the furnace. In
the gradient-freeze method, the low temperature end of the furnace is held
constant while the high temperature end is reduced in a controlled manner.
This has the result of accelerating the growth rate while reducing the
axial gradient, just the opposite of what is required to maintain a stable
interface ina heavily doped or all oy-type sol i d sol uti on semi conductor~
For thi s reason, these early space results were useful only for compari ng
processes carried out in space with those carried out in a similar process
on the ground. Generally, the space processed samples did not compare
f avorab ly wi th the best process that coul d be done on the ground, nor were
the results i ndi cati ve of the best that coul d be accompl i shed in space
using optimal equipment.

2.4 SPAR Experiments

The early Skylab and ASTP experiments should be regarded as a modest begin-
ni ng from whi ch we 1earned many important and, in some cases, unexpected
1essons. Unfortunately, the long hi atus in manned space fl i ght opportuni-
ties between ASTP and space shuttle precluded additional long-duration
space experiments in which samples could be readily recovered for analysis.
As an interim measure, a series of Space Processing Applications Rocket
(SPAR) flights were initiated. These flights, using Nike-boosted Black
Brandt rockets, coul d carry several small experi ment packages and provide
up to 5 minutes of free-fall time. A typical payload is illustrated in
Fig. 2.15. The restrictions on experiments that could be performed were,
of course, even greater than on the earl i er Sky 1ab and ASTP fl i ghts. How-
ever, the 10 SPAR fli ghts with some 40 experiments did provide opportuni-
ties to test new concepts and develop improved apparatus. Several of ex-
periments were conducted to assess various fluid flows in the microgravity'
environment. [14] Acoustic and electromagnetic levitation techniques were
developed to position samples for containerlesls processing. [15-17] The
influence of gravity on the structure of castings was thoroughly studied
with experiments at elevated gravity using a centrifuge and at reduced
levels using SPAR rockets. [18] An unexpected change in the spacing of
secondary dendrite arms was discovered in the samples solidified in low
gravity. [19] Additional data on mechanisms that produce phase separation
26

in monotectic systems were obtained, [20] and it was demonstrated that

massive separation from critical point wetting and spreading could be
avoided by selecting the crucible such that it was preferentially wet by
the host phase. [21]

Fig. 2.15. Typical SPAR payload

An improved directional solidification furnace was developed, and the un-

expected behavior of MnBi eutectic growth was studied using a series of
flights at different growth rates. It was confirmed that samples of this
material processed in low gravity have significantly smaller rod diameters
and spacings than samples grown under identical conditions in Earth gravi-
ty. [22] Figure 2.16 compares the results of low-gravity vs. unit-gravity
processed samples, and Fig. 2.17 shows the departure of the low-gravity
resul ts from the A V2 = constant re 1at i onshi p predi cted by the Jackson and
Hunt theory of eutect i c sol i difi cat ion. ~23] Subsequent experi ments on
Earth using strong magnetic fields to damp the convection produced results
similar to the flight experiments. [24] This is a peculiar result since
the Jackson and Hunt theory does not consi der convection, yet departures
from theory occur in the absence of convection. Recent results obtained on
Spacelab 1 add new insight to this interesting phenomenon. [25,26]
 27

GAOUHO-COHTAOl fl iGHT SAWlE

Fig. 2.16. Microstructure of MnBi-Bi eutectic solidified at 50 cm/hr on

Earth (left) and on a SPAR flight (right). The dark spots are the MnBi
rods in a Bi matrix (light background). The difference in the micro-
structure is quite apparent •

.;
z
o
;:::
"a:
~

in
o
"zU
f
SPAR VI
~ UNIT GRAVITY
o MICRO GR A VITY ___
01.0
a:
~
>- o VERTICAL DE ST ABILI Z ING SPAR IX
;;,; 6 VERTICAL STA BILIZING UN IT G RAV ITY
a HORIZONT A L MI CRO GRAV IT Y~
o MICRO GR AV ITY

1.0 10. 0
SOLIDIFICATION VELOCITY , V ( m
e /h )

Fig. 2.17. Plot of the rod spacing of MnBi rods in MnBi-Bi eutectic vs.
solidification velocity. Note the departure from the AV2 = constant law
in microgravity as the solidification velocity is increased.

2.5 Creat i on of the Science Base

The early space processing program was considerf d by NASA to be an applica-
tions program. Strong emphasis was placed on experiments that were
oriented toward products that could be manufactured in space. It was hoped
that sufficient improvements would be found in the space processed materi-
als so that private companies would be encouraged to develop commercially
viable space industries. The experiments performed on Skylab and ASTP
28

indicated that effects of processing in space are often subtle and can be
easily missed unless the right questions are asked, that the elimination of
gra vi ty-dri ven flows often reveals the presence of secondary flows that
must also be controlled, and that considerable attention must be given to
understanding what limits a process in Earth's gravity before maximum ad-
vantage can be taken of microgravity experiments.

This led NASA to place a high priority on developing an extensive ground-

based research program to serve as a science base for future flight experi-
ments. The primary purposes of this program are: (1) to explore and iden-
tify fruitful areas for microgravity research; (2) to understand how gravi-
tational effects limit certain Earth-based processes and how such limits
may be overcome, either by better control stratagems on Earth or by use of
the microgravity environment of space; (3) to understand how fluids will
behave in the microgravity environment considering residual accelerations
of the spacecraft as well as possible non-gravity-driven flows; (4) to ex-
plore the advantages of containerless processing and the limitations of
Earth-based techniques such as levitators, drop facilities, and aircraft;
(5) to develop centers of excellence where results obtained in space may be
compared to the best available Earth techniques; and (6) to develop the
necessary technology and apparatus for carryi ng out the vari ous space ex-
periments. Also the primary emphasis was shifted away from immediate
applications toward more fundamental scientific issues. The scope has been
broadened to include basic research in relativity, fluid mechanics, criti-
cal phenomena, cloud microphysics, combustion science, and biotechnology in
addition to materials science. Programs have also been established to
a 11 ow i ndustri al fi rms to conduct research of a propri etary natu re on a
joint endeavor basis with NASA in which the costs, risks, and benefits are
shared. [27]

References
1. Lacy, L.L.; Otto, G.H.: Electrical resistivity of gallium-bismuth
solidified in free fall. AIAA Journal 13 (1975) 219.

2. Naumann, R.J.; Herring, H.W.: Materiials Processing in Space: Early

Experiments. NASA SP-443 (1980).

3. Carruthers, J.R.: Studies of liquid floating zones on SL-IV, the

Third Skylab Mission. Proceedings of the Third Space Processing
Symposium, Skylab Results, NASA TM X-70252 (June 1974) II, 837.

4. Apollo-Soyuz Test Project, Summary Science Report. NASA SP-412 (1977).

 29

5. Witt, A.F. et a1.: Crystal growth and steady state segregation under
zero gravity: InSb. J. Electrochem. Soc. 122 (1975) 276.

6. Walter, H.U.: M560 growth of spherical crystals. Proceedings of the

Third Space Processing Symposium, Skylab Results, NASA TM X-70252
(June 1974) I, 257.

7. Wiedemeir, H.; Klaessig, F.C.; Irene, E.A.; Wey, S.J.: Crystal growth
and transport rates of GeSe and GeTe in microgravity environment. J.
Crystal Growth 31 (1975) 36.

8. Wiedemei r, H. et al.: Morphology and transport rates of mixed IV-VI

compounds in microgravity. J. Electrochem. Soc. 124 (1977) 1095.

9. Chandra, D.; Wiedemei r, H.: Chemical vapor transport and thermal

behavior of the GeSe-GeI4 system for different inclinations with
respect to the gravity vector: Comparison with theoretical and micro-
gravity data. J. Crystal Growth 57 (1982) 159.

10. Larson, D.J.: Zero-g processing of magnets (MA-070). Apollo-Soyuz

Test Project, Summary Science Report. NASA SP-412, I (1977) 449.

11. Pirich, R.G.: Characterization of effects of plane front solidifica-

tion and heat treatment on magnetic properties of Bi/MnBi composites.
IEEE Trans. Mag. MAG-16 (1980) 1065.

12. Takahashi, S.: Preparation of silicon carbide whisker reinforced

silver composite material in a weightless environment. 15th AIAA
Aerospace Sciences Meeting, Los Angeles, California, January 24-26.
1977 (AIAA Paper 77-195).

13. Allen, R.E. et a1.: Column electrophoresis on the Apollo-Soyuz Test

Project. Sep. Purif. Meth. 6 (1977) 1-59.

14. Schafer, C.F.; Fichtl, G.H.: SPAR I Liquid Mixing Experiment. AIAA
Journal 16 (1978) 425.

15. Wang, T.G., Saffren, M.M.; Elleman, D.D.: Drop dynamics in space.
Materials Sciences in Space with Applications to Space Processing, 52
(1977) 151-172 (Leo Steg, ed.), New York: AIAA.

16. Whymark, R.R.: Acoustic field positioning for containerless proces-

sing. Ultrasonics 13 (1975) 261.

17. Frost, R.F.; Chang, C.W.: Theory and applications of electromagnetic

levitation. Materials Processing in the Reduced Gravity Environment
of Space, 9 (1982) 71 (G.E. Rindone, ed.), Amsterdam: Elsevier Science
Publishing Co.

18. Johnston, M.H.; Griner, C.S.: The direct observation of solidifica-

tion as a function of gravity level. Met. Trans. 8A (1977) 77.

19. Johnston, M.H.; Parr, R.A.: The influence of acceleration forces on

dendritic growth and grain structure. Met. Trans. 138 (1982) 85.

20. Gelles, S.H.; Markworth, A.J.: Microgravity studies in the liquid-

phase immiscible system: Al-In. AIAA Journal 16 (1978) 431.
30

21. Potard, C.: Solidification of hypermonotectic Al-In alloys under

microgravity conditions. Materials Processing in the Reduced Gravity
Environment of Space, 9 (1982) 543 (G.E. Rindone, ed.), Amsterdam:
Elsevier Science Publishing Co.
22. Pirich, R.G.: Studies of directionally solidified eutectic Bi/MnBi at
low growth velocities. Met. Trans. 15A (1984) 2139-2145.
23. Larson, D.J.,. Jr.; Pi ri ch, G.; Sil berstei n, R.; deCarlo, J.; Busc£lmi,
C. Effect of applied magnetic field on directional solidification of
eutectic MnBi/Bi. Met. Trans. 15A (1984) 2155-2161.
24. Jackson, K.H.; Hunt, J.D.: Lamellar and rod eutectic growth. Trans.
AIME 236 (1966) 1129.
25. Favier, J.J.; deGoer, J.: Directional solidification of eutectic
alloys. European Symposium, Material Sciences Under Microgravity,
Results of Spacelab I, ESA SP-222 (1984) 127.
26. Muller, G.; Kyr, P.: Directional solidification of InSb-NiSb eutec-
tic. European Symposium, Material Sciences Under Microgravity,
Results of Spacelab I, ESA SP-222 (1984) 141.
27. Federal Register 44 (1979) 47650.
3 Simulation of Weightlessness

H. HAMACHER
Institute for Space Simulation, DFVLR, Koln, FRG

The phenomenon of gravitation is characterized by the mutual attraction of

any two bodies. The universal character of gravitation was first recognized
by Isaac Newton who found the well-known law for the attraction force F ac-
ting between two mass points or homogeneous spherical bodies

F = YMm/R2 (3.1)

M, m are the masses, y = 6.67.10- 11 Nm2kg- 2 the universal gravitational

constant and R the distance of the centers. The weight of a body of mass m
is related to the gravitational acceleration g of the earth by W= mg. As-
suming an ideally central gravitational field for the earth, Eq. (3.1)
yields for points outside the earth periphery

g (3.2)

g/go = (Re/R)2 (3.3)

where go = YMe/Re2 = 9.81 ms- 2 is the gravitational acceleration at the

earth surface, usually called 1 gravity or 19. Me = 5.97.1024 kg and
Re = 6.371.106 m are mass and mean equatorial radius of the earth, respec-
tively.

3.1 Free Fall: The Principle to Simulate weightl~ssness

It is one of the unique possibilities of the space flight that a freely

orbiting spacecraft offers a zero or virtually zero-gravity state to its
interior objects. This may be explained by the fact of orbital mechanics
that the gravitational force is balanced by the centrifugal force. But it
32

is important to note that this is a weightlessness relative to a reference

frame fixed to the spacecraft. If, for instance, a spacecraft has an alti-
tude of 400 km, the earth acceleration is only reduced by 12 percent versus
go to a terrestrial observer.

A more gener'al basis for discussing simulation of weightlessness is Ein-

stein's principle of equivalence. The mass m of a body may be determined
either by weighing W= mg'g (gravitational mass mg) or by measuring its ac-
celeration "a" due to a force F = mi' a (inertial mass mil. The equality of
mg and mi has been proved to an accuracy of 1.10- 11 • One conclusion is that
an observer can not distinguish whether he is in an uniform gravitational
field or in an accelerated frame of reference (principle of equivalence). A
system "1" being subject to a gravitational field characterized by 9 is
identical to a system "2" ~eing accelerated with il2 = -9 relative to an
inertial observer (Fig. 3.1). An inertial, i.e. force free system "3" is
achieved by a3rel = 9 of system "3" relative to system "2". This is identi-
cal to the situation that, in the gravitational, field a system "4" moves
with a4 = g, which is the free fall. Hence, all bodies within system "4"
appear to be weightless relative to a reference frame fixed to it. Hence, a
freely orbiting satell ite, a special case of a free fall system, is nn"ly

"1" "2"

Q1
g~ 77~;;g t
I

c3rel =9
c3abs=O
Equivalence

Fig. 3.1: Einstein's Principle of Equivalence Between a Gravitational Field

and an Accelerated System to Explain the State of Weightlessness for a Free
Fall ing Object.
 33

one of the possible methods to simulate weightlessness.

Weightlessness or zero gravity is an ideal state that, in practice, cannot

be accompl ished completely. None of the conditions made in the discussion
of the orbital flight can be met exactly. Deviations of the earth shape
from a sphere or the anisotropy of the earth density are reasons that g(R)
is only roughly represented by the Eqs. (3.2) and (3.3). Additionally, free
fall conditions cannot be realized exactly because of residual forces. The
atmosphere even at orbital altitudes exerts a slight drag force to a space-
craft. There are a number of other effects, inducing small gravity-like di-
sturbances inside a real spacecraft, acting in different directions, in
steady-state or transient form.

In the following sections methods to simulate weightlessness are des-

cribed. The discussion is mainly focused to the manned orbital flight and
to its charcteristic disturbing forces. This is followed by a brief des-
cription of other free fall methods and existing facilities.

3.2 Free Fall Trajectories

The path which a freely drifting object follows under the influence of the
earth's centered gravitational field depends on its total energy, given by

E = mv2/2 - ymMe/(Re + h) = const (3.4 )

Only in case of E < 0, i.e. if the kinetic energy is always smaller than
the potential energy, the object will remain earth bound, following an
elliptical trajectory with the center of the earth at one focus
(Fig. 3.2). A special case is the circular orbit (vo =vs) where the gravi-
tational force mg is balanced by the centrifugal force mVs2/R. If the ini-
tial tangential velocity Vo is sufficiently lower than vs' the resulting
ellipse will intersect the earth at a distance s, from the vertical of the
starting point A.-In case of s « Re , the earth'gravitational field can be
considered as being homogeneous, resulting in the well-known trajectory
parabola.

All types of trajectories have been appl ied to weightlessness simulation

methods. The 0 r bit a 1 flight offers the unique opportunity to simu-
34

Fig. 3.2: Free Fall Trajectories in

the Earth Gravitational Field

Elliptical
Orbit

late zero gravity without time limitations by trajectory kinematics. Mis-

sion durations achieved today range from days (Spacelab) to months (Skylab)
and even to years (Salyut).

Ballastic flights of sounding rockets and airplanes are examples for the
use of par abo 1 i c trajectories. Coast periods range from about 25
sec for the airplane KC-135 of NASA to 6 min for the Skylark rocket as used
in the German TEXUS Programme.

The s t r a i g h t fall is realized in drop facilities, usually consis-

ting of a tube which can be evacuated to minimize aerodynamic drag. Exis-
ting drop facilities range up to 145 m in height (NASA Lewis Research Cen-
ter) and 5.15 sec zero gravity duration.

3.3 The Orbital Flight

Consider a spacecraft freely drifting in a circular earth orbit with its

center of mass (CM) at an altitude h. The gravitational force mg is then
balanced by the centrifugal force mRws2.t Assuming a central gravitational
field, the orbital velocity vs and the arlgular velocity Ws follow from Eq.
(3.2) as

(3.5 )
 35

(3.6 )

where II = yM e = gR2 = goRe 2 = 3.98'10 14 m3s- 2 is the gravitational para-

meter of the earth 1). The residual ~g-environment as a result of distur-
bance effects and the finite dimensions of the vehicle may be grouped with
respect to its nature as follows.

- Due to various residual ext ern a 1 forces a spacecraft is not in a

freely drifting state. Atmospheric drag and solar radiation pressure give
rise to a nearly s tea d y - s t a t e acceleration of the eM. The
corresponding acceleration transfered to a particular object inside the
spacecraft depends on its coupling to the spacecraft structure.

- Additional t ran s i e n t external forces may result from opera-

tional activities, such as thruster firings for attitude control and
other orbital maneuvers. These forces in general exert also a torque to
the vehicle. Constant rotation of the vehicle produces a steady accelera-
tion and will induce for example rotational flow to a contained fluid
[ 3.1 J.

- The mass allocation inside a spacecraft in general changes due to the mo-
tion of mechanical parts, crew activities, etc., resulting in i n t e r -
n a 1 forces. These forces do not involve a momentum change to the space-
craft CM system. Impulses caused by internal forces are always compensa-
ted by equal and opposite impul ses, resulting in an exitation of the
flexibility modes of the spacecraft. The induced transient acceleration,
called g - j i t t e r, is characterized by a broad frequency spectrum.
Even though g-jitter may reach high peak values, the resulting displace-
ments of particles with respect to the CM are small because of its com-
pensated and random nature.

A spacecraft is an extended body, which is in general rotating around its

1) For h = 0 follows: vso = 7.91.10 3 ms- 1 and wo 1.24.10-3 s-1 with only
small liari ations if hiRe «1.
36

CM. For objects located out of the CM, gravity and centrifugal forces are
not balanced completely, resulting in a "tidal force". Additionally, the
movement of a mass point relative to the spacecraft will induce a pseudo
(Coriolis) force, if the reference frame is a non-inertial system.

- The oblateness of the earth and irregularities of its mass distribution

are reasons for the non-central field of the earth and for slight devia~
tions from the circular orbit. These perturbations will not influence the
effective gravity at the CM because it is still in free fall condition.
However, constrained mass points out of the CM will undergo acceleration.

This is only an incomplete list of disturbing effects acting in a real

spacecraft. In the following, those will be discussed with respect to their
magnitude and time behaviour, which are of major interest to material s
science experiments.

3.3.1 Atmospheric Drag

The orbital velocity Vs of a spacecraft is always in excess of the most

probable molecular speed urn of the residual atmosphere, ranging from
750 ms- 1 at 150 km to 1,200 ms- 1 at 450 km altitude (The 1976 Standard At-
mosphere). Thus, the momentum transfered to the spacecraft surface by mole··
cular collisions is highly directional and opposite to the spacecraft velo-
city vector. From a consideration based on the theory of free molecular
flow (with a mean free path large in comparison to a characteristic space-
craft dimension) the following relation for the drag can be derived

(3.7)

The drag coefficient Cd depends on the shape of the spacecraft and the type
of the molecular reflectance (e.g. diffuse or specular). p is the mean at-
mospheric density and Ap the spacecraft c~oss sectional area prOjected onto
the plane normal to the flight direction'. Values of 2~Cd~3.5 may be re-
garded as an appropri ate range, the lower 1imi t representi ng a diffusely
reflecting sphere and the upper limit a specular reflecting flat plate with
the free stream flow normal to the surface [3.2J. The acceleration .arising
from aerodynamic drag follows as
 37

(3.8)

where M is the vehicle mass . There is in general a harmonic time variation

of the vector ad with a cycl e given by the orbital period. The magnitude of
ad varies mainly with the diurnal change of and the al teration of Ap, re-
sulting from' rotation oJ the vehicle with respect to the orbital velocity
vector, if any. This also determines the directional change of ad' Due to
its low frequency, ad(t) may be considered as being quasi-steady in most
cases.

Figure 3.3 shows the dependency of ad versus altitude as predicted for the
Space Shuttle Orbiter (Space Transportation System STS). The plots are
based on values of Cd = 2 and M ~ 9'10 4 kg, as being typ i cal for Spacelab
as a Shuttle payload [ 3.3J. The flight mode in favour for conducting
~g-experiments is the Gravity Gradient Mode (GGM), an attitude in which the

STS is stabil i zed by the earth gravity gradi ent, with the wi ngs in the
orbital plane and the nose pointing outward from the center of earth. For
200 km, a level of ad: 10- 5 go is to be expected. Note the strong variation
of ad in the low altitude range. A change from 200 to 300 km will result in

Fig. 3.3: Prediction of Acceleration due to

Atmospheric Drag ad vs Altitude for the Space
Shuttle Orb i ter. M = 90 718kg. Cd = 2 [ 3.3J .

200 600 1000

Altitude [km]
38

a reduction of ad by about one order of magnitude. The other decisive para-

meter in Eq. (3.8) is the ratio of Ap/M, which is small in case of the STS
because of its tremendous mass. Quite higher Ap/M values have to be expec-
ted for free-flying experiment platforms where large areas of solar arrays
are needed. An example is the European Retrievable Carrier EURECA, which
will be launched for its first 6 to 9 month mission by early 1988 [3.4J.
R.E. Olson and J. Mockovciak [3.5J reported results of a study for an US-
Materials Experiment Module (MEM). Data of Ap/M are shown in Table 3.1. A
comparison yields values one order of magnitude higher for the two plat-
forms considered.

A possible way to compensate this is the choice of higher orbits. Figure

3.4 is a plot of ad versus altitude as predicted for EURECA I, taken from
Ref. [3.4J. This investigation also comprises predictions of the orbital
decay due to atmospheric drag and the influence of long time variations as
a consequence of changing solar activities.

Fig. 3.4: Prediction of Accelera-

tion due to Atmospheric Drag vs
Altitude for the Platform EURECA
[3.4 J.
600
<II [km]

-
"0
:::J
:.;:
<{

o 1 2 3 4
[10 6go J

Tab 1e 3.1 Comparison of Ap/M Values for Oifferent Carriers

EURECA I Ap/M = 2.0-10- 2 m2 /kg Ref. [3.4 J

MEM Ap/M = 1.8-10- 2 rn2/kg Ref. [3.5 J
STS Ap/M = 2.4-10- 3 m2 /kg Ref. [3.3 J
 39

A potential approach to cancel drag forces would be the application of the

"drag free satell ite" concept. It has been demonstrated on the US experi-
mental Navigation Satellite TRIAD I, launched in 1972 [3.5-3.7J. This con-
cept requires (1) an active thruster system to compensate external forces,
and (2) a tiny spherical "proof mass", located at the platforms CM and
freely floating in a 'sat~llite fixed cavity. The proof mass is then shiel:-
ded from any drag and is therefore in a free fall state. The relative posi-
tion of the proof mass with respect to the cavity is controlled to be con-
stant, causing the platform to follow the path of the proof mass. Residual
compensated accelerations due to impulses of the thrusters have been less
than 10-11 90 in case of TRIAD I.

3.3.2 Solar Radiation Pressure

Solar rotation acts as a pressure on surfaces exposed to it due to photon

momentum transfer. The direction is always opposite to the vector pointing
the sun. The magnitude of solar radiation pressure is given by

1+ S
Psr =-c
-E (3.9 )

where S denotes the surface reflectivity (0::: S::: 1), c the speed of 1i ght,
and E = 1.4 joule/(m2s) the solar constant [3.8J. For a perfectly reflec-
ting (S = 1) and a black body (S = 0) follow values of Psr = 9.33,10- 6 Pa
and 4.67.10-6 Pa, respectively.

The acceleration induced by solar radiation pressure is

(3.10 )

Ap has the analog meaning as in section 3.3.1. as r vanishes when the space-
craft enters the earth shadow. Estimations for asr for EURECA I, MEM and
STS, based on S = 1 and the Ap/M val ues given tn Table 3.1, are 1i sted in
Table 3.2. The levels are some orders of magnitude lower than the related
values of atmospheric drag.
40

Table 3.2 Acceleration due to Solar Radiation Pressure for S = 1

EURECA as r = 1.9·10-8 go
MEM a sr = 1.7·10-8go
STS asr = 2.3·10- 9go

3.3.3 The Extended Spacecraft

Consider a spacecraft in circular orbit (Fig. 3.5) with the frame of refe-
rence (x, y, z) originating in the CM and oriented such that the xz-plane
is in the plane of orbit and the z-axis in the direction of the radius vec-
tor R. The angular velocity vector wof the frame of reference is supposed
to be parallel to &is. The position vector r indicates the momentary loca-
tion P of the object under consideration.

z Fig. 3.5: Nomenclature for the

P Frame of Reference Fixed to the
Spacecraft CM.
~-:h=-~C~/,"~bital Plane
R -.. .

The relation between the total accelerati6ns a of P and aCM is given by

(3.11)

where ac = 2 wx ~ is the Coriolis acceleration and arel the acceleration of

P relative to CM. By using Eq. (3.3) and restricting this discussion to the
 41

important case of the GGM (ws = w= const) we obtain

(3.12)

where (.) denotes differentiation with respect to time, ad acceleration due

to drag and ah acceleration induced by coupling forces between the object
in question and the frame of reference. This may be the hydrodynamic resi-
stance a particle experiences in a fluid or the levitation force acting on
a sample in a positioning device.

Expanding R/l into a power series in terms of x, y, z and considering only

linear terms, separation of Eq. (3.12) into components yields

x ahX + lad I - 2wz

y a hy - w2y (3.13)
z ahz + 2wx + 3w 2 z

Drag forces other than those resulti ng from the atmosphere are di sregar-
ded. The vector ad is then oriented in the -x-direction. Equation (3.13)
shows that the moti on in y-di rect ion is decoupl ed from the other compo-
nents.

In case of ah'" 0, a resting object (it = z = 0) experiences the drag acce-

leration ad in the positive x-direction as expected. The forces acting in
y- and z-direction are proportional to the displacement y and z, respecti-
vely. The y-component is restoring, whereas the z-component is repelling
with three times the gradient of the y-direction. For an altitude of h =
300 km this gradient becomes

z = 3w 2 = 4.1,10- 7 go/m (3.14 )

Thus, in case of Spacelab, where z ~ 2.5 m may be regarded as a characte-

ristic distance from the eM, z ranges in the order of 10- 6 go. For the
planned Space Station, however, values of 10- 5 go are to be expected unless
care will be taken, for instance such that the microgravity experiment mo-
dules will be arranged along of the x-axis.
42

As a comparison, in case of an inertial hold of the frame of reference, the

gradient along the vector R will be only 2/3 of the magnitude given by
Eq. (3.14).

In case of a freely floating and initially resting particle (ah 0),

Eq. (3.13) has the solution

x = Xo - (3/2) adt2 - 6z o (wt - sin wt) + (4ad/w2)(1 - cos wt)

y = Yo cos wt (3.15 )
z = (2ad/w2 )(wt - si n wt) + 4zo [1 - (3/4) cos wtJ

t = 0: x= xo, y = Yo, z = zo
X= Y= z = 0
Solutions of Eqs. (3.15) for two particles A and B, initially resting at
the CM and at (xo = Yo = 0, Zo = 10 m) respectively, are depicted in
Figures 3.6 and 3.7. It may be seen that despite of ad the particles will
finally move in the -x-direction due to Coriolis and tidal forces. Figures
3.7 show the x- and z-components vs time. The behaviour during the initial
phase may be described by the first terms of the power expansion of Eqs.
(3.15 )

x - Xo = (ad/2) t 2 - zo(wt)3 + ••• (3.16 )

z - Zo = (3/2) zo(wt)2 + (ad/3) wt 3 + (3.17)

As follows from Fig. 3.7a, the motion of particle A is well approximated by

the first term of Eq. (3.16) (straight lines) within the initial 7 minu-
tes. It holds also for particle B in case of ad ~10-5 go. This is the ap-
proach of constant linear acceleration, i.e. neglecting tidal and Coriolis
forces. The motion of particle B in z-direction (Fig. 3.7b) is well des-
cribed by the first (tidal) term of Eq. (3.17) within the time phase depic-
ted, if ad ~ 10- 6 go. Only in case of lalfger ad values, the higher terms.
become effective. The magnitude of the first term of Eq. (3.17) is propor-
tional to the initial value Zo and vanishes therefore for Zo = O. The move-
ment of particle A is well approximated by the second term within the time
phase considered.
 43

Fig. 3.6: Trajectories of Parti-

cles A and B for Various Values
of Atmospheric Drag Acceleration
ad. Acting in -x-Direction. The
Initial Velocity is Zero. Alti-
tude h = 300km. Gravity Gradient
Mode.

10
--x
[m) a -10

102
Fig.3.7a: x-Components vs Time of
tt the Example Fig. 3.6

10
(min)

-A
--- B
10-1
102
--
x
10 [m] I 10-1 ICf2

Fig. 3.7b: (z-zo)-Components vs

Time of the Example Fig. 3.6
44

For further discussions of free drifting point trajectories see Refs. [3.9J
and [3.10J.

3.3.4 G-J itter

The equations of motion derived in the previous section by transformation

to the CM fixed frame of reference are appropriate to analyse such proces-
ses which are mainly affected by orbital induced disturbances. Its charac-
teristic time scales are of the order of the orbital period. The class of
g-j itter di sturbances are, in contrast to that, characteri zed by time
scales being some orders of magnitude smaller, and by its inherent local
and statistical nature. This distinctioJ] justifies to superimpose orbital
and g-jitter induced disturbances, the g-jitter being the irregularly fluc-
tuating contribution to the local acceleration fiel d. For a comprehensive
analysis see Ref. [3.11J.

Ampl itude and frequency of the g-jitter vector depend in a complex way on
the vibration behaviour of the spacecraft structure, the location of the
experiment under consi derati on, and type and 1ocat i on of the vi brati on-
generating sources. Origins of g-jitter are thruster firings for orbital
and attitude control maneuvers, the operation of auxiliary spacecraft
equipment and scientific experiments, and in case of manned systems the
crew activities, etc. Crew motion induced g-jitter have been studied exten-
sively in Skylab with the result that, for instance, astronauts can produce
significant disturbance inputs to the spacecraft attitude control system.
Total forces up to 400 N were exerted during soaring activities [3.12J. The
Skylab data, analysed and summarized in Ref. [3.13J, have been appl ied to
predict the g-jitter peak values of the Spacelab-1 mission for various
types of motion and for the two locations: Pilot Stand and Materials
Science Double Rack (MSDR) [3.14J. Remarkable features of the data given in
Table 3.3 are the high ~g-levels when comparing with the levels induced by
atmospheric drag and tidal acceleration, gi~en in the previous sections for
this very payload.
 45

4.8 ,..---.,.----,.---.,.----,---,-.---..... Fig. 3.8: Time History of the

Acceleration Response at the
Control Center Rack as Measured
[ 103go ] I----II--I---I-----if---I----l within the Space1ab Engineering
Model [3.15J.
at 1.6
o
-1.6

-
-4.8 \---1 -_ 1 ....---1-_1....---1----1
o 0.5 [sec] 1.5
t

5~----------------------~
Fig. 3.9: Spectral Distribution
of the Acceleration Response
shown in Fig. 3.8

10,..----~----.,.---~
Fig. 3.10: In-Flight Measure-
+a x ment Results of the Sl-1 Mis-
sion. The Spike Patterns Shown
[10-3~t--_..-I--_-I----l Were Caused by the Operation of
the Metri c Camera and Are the
Components Along the Longitudi-
o I....JWJJJ.IdWWIJIII1II nal Axis (x-Axis) [3.16J
10
-ax

O~---'-----'-----I
o 6 12
46

Table 3.3 Predicted Crew Motion Induced ~g-Levels at Pilot Stand and
Materials Science Double Rack (MSDR) of SL-1 in 10- 4 go [3.14J.

Event Pilot Stand MSDR

min/max min/max

Deep breathing 0.1/1. 5 0.1/1.3

Coughing 0.7/1.4 0.6/1.2
Sneezing 2.1/3.3 1.8/2.8
Crouch and stand 3.8/5.2 3.2/4.4

As an example for g-jitter induced by auxiliary equipment and experiment

operation, results of an investigation performed for the German D1-Spacelab
Mission will be discussed briefly. The g-jitter spectral distribution has
been measured on ground within the Spacelab Engineering Model at different
locations under on-orbit operational conditions [3.15J. Figure 3.8 shows
the ampl itude-time function at a certain location inside Spacelab (Control
Center Rack) for the case of a fully activated Spacelab without any inte-
grated experimental hardware. The signal shows a randomly fluctuating beha-
viour. The corresponding spectrum in the range between 0 and 100 Hz (Fig.
3.9) has a maximum of 4'10- 4 go at 60 Hz. Small intensities were observed
in the regions below 20 Hz and above 130 Hz.

A1thoug.h the characteri sti cs of g-j itter depend strongl y on the parti cul ar
system investigated, the examples discussed may give an order of magnitude
impression for the levels to be expected in a manned system. They also show
the effectiveness of certain operational and design precautions.

For a final scientific analysis, the actual in-flight data of the ~g-envi­
ronment has to be known. Microgravity measurements have been performed for
the Material Science Double Rack (MSDR) Experiments during the SL-1 Mission
[3.16J. Peak values in the +x, -x, +y, -y, +z, and -z directions have been
recorded every second during the operational time of the MSDR. As an exam-
ple, Fig. 3.10 shows g-jitter caused by the operation of the Metric Camera
(Experiment 1 EA 033). Regular spike patterns were generated in all direc-
tions as a result of the film transport with a frequency of 0.1 Hz. The
strongest effect was dominant along the longitudinal axis (x-axis) of
Spacelab, in which the film transport occured. One of the conclusions of
 47

the analysis is that the g-jitter level of SL-1 was, with the exception of
Orbiter trim burns for altitude adjustment, mainly determined by disturban-
ces caused by the payload itself.

3.4 Other Free-Fall Methods

The increasing microgravity research has led also to the application of si-
mulation methods other than the orbital flight: the use of sounding
rockets, aircrafts and drop tubes or towers, each having unique experimen-
tal capabilities. Although these methods offer relative brief pg-periods,
they contribute si gnifi cantl y to the advancement of mi crogravity research
and serve frequently as precursors to experiments to be performed ultimate-
ly in orbital fl ight. In certain cases, however, they are al so means for
conducting research in parallel and complementary to orbital missions.

3.4.1 Sounding Rockets

A typical rocket mission fl ight profile to simulate weightlessness is shown

in Fig. 3.11. During the launch phase, the vehicle is stabilized by ekter-
nal fins, inducing a spin about the longitudinal rocket axis. The coasting
phase is reached at an altitude of 90 km where aerodynamic forces are suf-

300 ,-----------1
[km]

200

-«
~
:J
:.;:::
100
VPayload Separation
o-Despin Parachute
'Tip Eject Deployment
L -_ _ ____ ____ __ ____
/ )mpact
o
~ ~ ~ ~ ~~

200 400 [sec] 840

Time

Fig. 3.11: Flight Profile of a Black Brant Vc Sounding Rocket as Used in

the SPAR Project.
48

ficiently low, after the despin of the rocket, ejection of the nose cone
and separation of the payload from the booster. Durations of periods with
~g-levels smaller than 10- 4 go achieved are 4 minutes 20 seconds in the
U.S. Space Processing Applications Rocket (SPAR) Project and 6 minutes in
the German sounding rocket program TEXUS (Technologische Experimente unter
Schwerelosigkeit) [3.17, 3.18J. The ~g-level, mainly determined by atmos-
pheric drag, rest spin, attitude control maneuvers and operational distur-
bances, compares favourably with that of a manned orbital system. As all
example, ~g-values registered along the longitudinal axis during SPAR IX
ranged between -0.10 and +0.17,10- 4 go' the positive direction being paral-
lel to the flight vector [3.19J. The payload will begin its re-entry into
the atmosphere typically between 6 and 8 minutes after liftoff. Recovery of
the payload is achieved by parachutes, which are deployed at an altitude of
about 5 km. The maximum acceleration can reach up to 50go during the re-
entry phase and 12go during liftoff (TEXUS 11). An example of a sounding
rocket payload is shown in Fig. 2.15 (SPAR).

Sounding rocket missions, in summary, are powerful and cost effective tools
to prepare and to develop more complex and more costly experiments for or-
biting laboratories. The safety requirements are drastically lower than
those for Shuttle missions and the lead times are short. Considerable expe-
rience has been gained with experimentation on sounding rockets in the
course of the SPAR and TEXUS programmes. Although little information is
available, similar efforts have been aChieved in the USSR using rockets to
allow coasting periods of 10 minutes duration D.201

3.4.2 Research Aircrafts

The use of an experimental aircraft to fly parabol ic trajectories offers

periodes of 15 to 60 seconds in free-fall during a climb and dive maneu-
ver. Main advantages of these method is the access of the experimentor to
the experiment during the ~g-period and the number of parabolas which can
be performed in a single flight.

Figure 2.3 shows the flight characteristics of the NASA four engine air-
craft KC-135 [3.21J. A low-g period of approximately 25 seconds can be at-
tai ned duri ng each maneuver, a seri es of up to 40 parabol as is normally
performed during one flight of two to three hours duration. The ~g-level
 49

achievable depends on the mechanical coupling of the particular experiment

to the aircraft structure. Best val ues are reached when the experimental
setup is released motionless at the beginning of the coasting phase to
drift freely within the aircraft bay (Fig. 2.4). Levels of 10-3 go or even
lower can be achieved by this method. Figure 3.12 shows the g-history ob-
tained in a fixed setup during one parabola.

Fig. 3.12: Residual Accelera-

tlon Measured in a Fixed Setup
During the Coasting Phase of
the NASA Aircraft KC-135
(Courtesy of J. Straub, Tech-
nische Universitat MUnchen)

10-3 -.............------.---r-...-----'-"I
10 [s~J 20
o
-
.1....-1

3.4.3 Drop Tubes and Drop Towers

Drop tubes and drop towers allow to simulate weightlessness on ground.

Although they offer free fall periods of the order of few seconds, test
frequencies are of the order of one or several tests per day, depending on
the complexity of the facility and the particular experiment.

Drop tubes allow re-solidification of uncontained material samples during

the free-fall, heated to the liquid phase befo.re dropping. The tubes are
evacuated to reduce the atmospheric drag. The maximum mass of a particular
material solidifying during the drop phase in an evacuated tube, depends on
its melting temperature and thermal properties. For some materials, solidi-
fication occurs only when high inert gas pressure is used to increase heat
loss by convection and conduction. However, in these cases microgravity
conditions no longer apply. But is has been shown that for various pro-
50

cesses the containerless nature is significant rather than the microgravity

conditions (Chapter 8, [3.22J).

A 100 meter drop tube is in operation at NASA-Marshall Space Flight Center,

Alabama, providing 4.6 seconds of free fall duration (Fig. 12.1). The tube
can be evacuated to a pressure of about 1 x 10- 4 Pa, resulting in residual
accelerations down to the 10- 6go range, depending on the mass and size of
the sample. At the end of the free fall phase, the samples are decelerated
and caught in a fixture having a foil inner layer. The facility is equipped
with various melting devices for melting samples up to 3500 0 C (Fig. 12.2).
Temperature detectors are installed along the tube for recording the tempe-
rature history during the free-fall.

Another type of drop tube has been developed at Jet Propulsion Laboratory,
Pasadena, California. Atmospheric drag is eliminated by forcing air through
the tube downward with 19o acceleration by means of a suction fan mounted
at the lower end (Fig. 12.6). The cross-sectional area varies inversely
with the square root of the di stance from the upper end of the tube. The
contour design includes also a correction for the boundary layer displace-
ment thickness. The g-level for this 13.7 m tube can be pre-selected be-
tween 10- 6 and 19o •

Drop tower facilities are charcterized by a drop capsule, allowing to ac-

commodate large experimental packages. Aerodynamic drag is either compensa-
ted by providing auxiliary thrust or by evacuating the drop tower. Drop
towers exist at NASA-Centers, one of which having a free-fall height of 89
m allowing 4.3 seconds of microgravity and a maximum mass of the test
package of 204 kg (Fig. 2.1). The ~g-level achievable ranges from 10- 2 to
1O- 5 go •

References

[3.1 J R.J. Naumann; Proc. NASA Workshop (m Spacecraft Dynamics as Related

to Laboratory Experiments on Space, NASA Conf. Publ. 2199 (1979),
p. 63
[3.2] J.E. Ladner, G.C. Ragsdale, Earth Orbital Satellite Lifetime, NASA
TN 0-1995 (1964)
 51

[3.3 J NASA/ESA Space1ab Payload Accomodation Handbook, Main Vol., Issue 1,

Revision 7 (1982)
[3.4 J D. Eilers; Mikrogravitationsbedingungen orbita1er P1attformen.
DGLR-Jahrestagung, MUnchen, 17.-19. Oktober 1983
[3.5 J R.E. Olson, J. Mockovciak, J. Spacecraft, 18 (1981), p. 141
[3.6 J Staff of Space Dept. Johns Hopkins Univ. / Guidance and Control Lab
Stanford Univ.; J. Spacecraft, 11 (1974), p. 637
[3.7 J B. Lange; AIM J., 2 (1964), p. 1590
[3.8 J R.E. Smith; D.K. Weidner; Space Environment for Use in Space Vehicle
Development, NASA TM X-53 (1968), p. 798
[3.9J H.F. Bauer; ZfW 6 (1982), p. 184
[3.10J B.S. Perrine; Proc. NASA Workshop on Spacecraft Dynamics as Related
to Laboratory Experiments on Space, NASA Conf. Pub1. 2199 (1979),
p. 137
[3.1fl R.F. Gans; Proc. NASA Workshop on Spacecraft Dynamics as Related to
Laboratory Experiments on Space, NASA Conf. Pub1. 2199 (1979), p. 96
[3.1~ B.A. Conway; T.C. Hendricks; A Summary of the Sky1ab Crew/Vehicle
Disturbances Experiment T-013, NASA TN D-8128 (1976)
[3.1~ M.C. Ku11as; Handbook on Astronaut Crew Motion Disturbances for Con-
trol System Design, NASA Ref. Pub1. 1025 (1979)
[3.1~ NASA, Space1ab Mission One: Integrated Payload Requirements Docu-
ment, NASA-MSFC Doc. No. JA-010, Revision D (1981)
[3.15J D. Eilers, et a1; Vibrationsmessung und -entstorung fUr Space1ab-
Experimente der D1-Mission, Final Report ERNO PRV-TB-l/1-81 (1981)
[3.16J W. Hamacher; U. Merbo1d; Proc. AIAA Shuttle Environment and Opera-
tions II, 85-7026-CP (1985), p. 228
[3.17J Y. Ma1mejac; H.U. Walter; Materials Science Research with Sounding
Rockets, ESA MAT (79) 5 Rev. 1 (1980)
[3.18J Handbook for Space Processing Sounding Rocket Science Payloads,
NASA-MSFC M-EH-75-2 (1975)
[3.19J Space Processing Applications Rocket (SPAR) Project, SPAR IX Final
Report, NASA TM 82 549 (1984)
[3.2ill V.S. Avduyevsky (Editor); Scientific Fou~dations of Space Manufac-
turing, MIR Publishers, Moscow (1984)
[3.2fl JSC Reduced Gravity Aircraft Users Guide, NASA JSC-17 385 (1981)
[3.2~ R.J. Bajuzick; N.D. Evans; W.H. Hofmeister; M.B. Robinson; Proc.
Second Symposium on Space Industrialization, NASA Conf. Pub1. 2313
(1984), p. 243
Part II:
Physical Phenomena
4 Convection and Bulk Transport
ROBERT A. BROWN

Department of Chemical Engineering and

Material& Processing. Center
Massachusetts Institute of Technology
Cambridge, Massachusetts

Probably the most alluring prospect of performing experiments

in a low-gravity environment is the ability of freeing an
experiment from the action of the earth's gravity, which although
constant and of known direction, has pronounced effects on
the processing of fluids and gases. The most important effects
of gravity are the impossibility of levitating a fluid mass
isolated from solid surfaces and the consequences of
buoyancy-driven-convection caused by gradients of temperature
and concentration in the fluid. It was recognized over a
decade ago that the large reductions in gravity possible aboard
an orb i tal spacecraft will remove these two effects and lead
to new experiments and, possibly, to the development of new
methods for processing materials. In conjunction with the
enormous interest in experimental research in a low-gravity
environment, many new analyses have been reported that add
to the understanding of transport phenomena both on earth
and in space relevant to the design and intepretation of these
experiments.

4.1 Bulk Fluid Flow

The aims of this chapter are to review many of these

theoretical developments and to lay the groundwork for the
more specific discussions that follow in this volume. The
presentation focuses on the mechanisms for fluid motion listed
in Table 4.1. Most of these mechanisms are present in systems
on earth and in outer space. Only buoyancy-driven flows are
suppressed in a low-gravity environment.
56

Table 4.1. Mechanisms for Bulk Fluid Motion.

Mechanism Effective Damping Relevant Systems

I. Free Oscillations viscosity Drop dynamics

driven by surface and containerless
tension processing

II. Surface-tens ion-driven viscosity, Drop dynamics

flows caused by gradients impurities and containerless
of temperature and/or processing
concentration along a
meniscus

III. Buoyancy-driven flows viscosity All systems

caused by gradients of wi th bulk fluid
temperature or
concentration in bulk fluid

IV. Forced convection caused viscosity All systems

by relative motion of with solid
solid boundaries boundaries

V. Convection caused by viscosity Systems with

density change with evaporation,
change-of-phase condensation,
and solidification

Thenonlinear flow transitions from laminar to time-periodic,

and finally chaotic convection caused by increasing buoyancy
forces are well documented on earth, as are the detrimental
effects on materials processing bf the resulting spatially
and temporally irregular convection. For example, time-periodic
and chaotic oscillations caused by natural convection in
solidification systems lead directly to dopant striation in
the final solid product [4.1]. Experiments in low-gravity
 57

have confirmed that the transitions leading to time-periodic

convection are not present [4.2J. Experimental and theoretical
studies also have confirmed that surface-tens ion-driven (thermo-
capillary) flows can be as or more intense than buoyancy-
driven motions in many of the small-scale experimental systems
used in space experiments. Moreover, similar sequences of
transitions from laminar to chaotic convection driven by surface-
tension gradients have been demonstrated in experiments, both
on earth and in space. Eliminating these flows is one of
the major challenges for development of nearly convectionless
materials processes in low gravity.
Other, seemly weak sources of relative motion of fluids
that are masked by natural convection in terrestrial experiments,
become apparent in space. Bulk motion caused by localized
heating of moving, compressible gases and by the density
differences associated with phase changes are examples that
must be considered. Although both mechanisms usually lead
to weak flows, they are nevertheless important when they are
the sole source of fluid motion.
The possibility of levitating drop, bubbles, and liquid
shells for long per iods of time has lead to renewed interest
in the fluid dynamics of isolated fluid masses, especially
as it relates to the theories for the dynamics of raindrops
[4.3] and for the fissioning of an atomic nucleaus [4.4J.
The availability of experimental facilities capable of continuously
recording drop dynamics has become especially important with
the discovery of regular [4.5] and stochastic [4.6] oscillations
of drops on timescales that are long compared to the oscillation
frequency of the drop. Experiments on liquid shells, a bubble
captured inside a drop, are being studied to understand the
dynamics for forming concentric-walled spherical shells for
fuel targets in laser-fusion experiments [4.7J. Recently,
weakly nonlinear analysis has predi9ted dynamic centering
of a bubble inside an inviscid drop [4.8]. Levitation also
has important applications in physical property, e.g. viscosity
and surface tension, measurements for high-temperature corrosive
liquids, such as semiconductor and metal melts. Inducing
free oscillations of levitated drops (Mechanism I in Table
58

4.1) of the material and measuring the oscillation frequency

and damping rate can be used to determine the surface tension
and viscosity of the melt, if the axisymmetric capillary waves
induce the dominant flow inside the drop. Thermocapillary
motion (II) and buoyancy-driven convection (III) cause bulk
motion in these experiments on earth and make the interpretation
of the data almost impossible.
Eliminating buoyancy-driven convection also removes a
major mechanism for convective mixing in materials processing
operations and reduces the transport of heat and species to
control either by molecular diffusion (conduction or diffusion)
or by convection driven by one of the other mechanisms listed
in Table 4.1. The importance of convective transport relative
to molecular diffusivity is measured by a Peclet number as

(4 •1)

where V* is a characteristic velocity for convection, L * is

a length scale for the gradient of the species, and D is the
molecular diffusivity. The relevant velocity scale is the
one associated with the dominant mode of convection in the
region of the flow where the species gradient is being determined.
Diffusion dominates for low Pe and the gradients can be estimated
from the species profile for the diffusion controlled process.
Thin boundary-layers of the species form at high Peclet number.
Then the variation of the species is confined to these layers
which scale as a function of Pe. One of the most important
contributions of research in the last decade has been the
identification of flow regimes for low and high Peclet numbers
in various materials processes. This progress is particulary
important with respect to flow fields driven by temperature
and concentration gradients which are affected by convection.
Some of these results are reviewed in Sections 4.3 and 4.4,
with respect to heat and mass transport in the directional
solidification and floating zone crystal growth processes.
The results summarized in Section 4.3-4.5 compose only
a small fraction of the large literature on transport phenomena
relevant to materials processing in a low-gravity environment.
 59

The topicS have been chosen to emphasize several important

issues in transport phenomena in the absence of gravity that
are generic to many systems not mentioned here because of
lack of space.

4.2 Scalings for Flow and Species Transport

Understanding the precise roles of each of the mechanisms

for flow and the resulting effects on heat and mass transport
involves solving the appropriate boundary-value-problems composed
of the conservation equations for mass, momentum, energy and
species in the geometry of interest. The usual approach is
to write the differential forms of the conservation laws for
these quantities in terms of dimensionless variables scaled
to be vary between zero and unity. For the variations in
the dependent variables (e.g. velocity, concentration, and
temperature) to satisfy this criterion, the scalings must
identify the dominant transport mechanisms in each conservat-
ion law. For particular choices of the scales, dimensionless
group arise in the equations and boundary conditions; the
relative magnitudes of individual transport mechanisms are
estimated by comparing the sizes of the groups. Instead of
presenting the transport equations in the general form necessary
to encompass all the mechanisms listed in Table 4.1, the discussion
focuses only on the dimensionless groups. These are listed
in Table 4.2 in terms of the thermophysical properties and
characteristic scales given in Table 4.3.

Tab Ie 4.2. Dimensionless groups appearing in mathematical

descriptions of transport processes.

Group s Based on Thermophysical ProEerties

Schmidt Number Viscous Diffusivity
Species Diffusivity
Sc . _v_
D
Prandtl Number Viscous Diffusivity
Heat Diffusivity
Pr .. _v_
a
GrouEs Based on Partic.ular Geometry

Thermal Peclet Convective Heat Transport V* L *

Number Pet -
Diffusive Heat Transport a
60

Convective Species Transport * *

Solutal Peclet V L
Number Diffusive Species Transport Pes - - D -

Reynolds Number Convective Momentum Transport V* L *

Viscous Momentum Transport Re \}

Thermal Grashof Buoyancy Force

Number Viscous Force !.IT

Thermal Buoyancy Force

Rayleigh
Viscous Force
Number

Solutal Grashof Buoyancy Force

Number Viscous Force Gr s '" !.Ic

Solutal Buoyancy Force

Rayleigh Ra '" Gr • Pr
Viscous Force s s
Number

Thermal Force due to Surface- * !.IT

a(daldT)L
Marangoni Tension Gradient Mat'" p\}2
Number Viscous Force
Solutal Force due to Surface-
Marangoni Tension Gradient
Number
Viscous Force
Groups Arising from Boundary Conditions

Biot Number Heat Loss by Convection hL *

Bi
Conduction in Bulk k
~ *3 *
Radiation Heat Loss by Radiation EaT L
Number Conduction in Bulk
R ~---;--
k

Gravitational Gravitational Force on

gL *2 !.Ip
Bond Number Meniscus Bo '"
g a
Surface Tension Force

Rotational Centrifugal Force on

Bond Number Mensicus Q2L*3!.1e
Bo '"
Surface Tension Force r a

Capillary Viscous Force on

Mensicus *
Number U
Ca '"
Surface Tension Force a
 61

Crissipation Variation of Surface

Number Tension Force (daldT)tlT
Mean Surface Tension Cr t" a
Force
Cr .. (daldc)tlc
s (J

The groups listed in Table 4.2 are divided into three

categories, depending of the relevance of the shape of the
domain and the conditions specific on velocity, temperature,
and species along the boundaries of the fluid. The groups
formed purely from thermophysical properties are listed first.
The Schmidt (Sc) and Prandtl (Pr) numbers are ratios of molecular
diffusivities. Important distinctions in the transport behavior
of gases and liquids are made by examining these ratios.
Prand tl numbers vary ing between ex tremely large values (O( 1 0 2-1 0 3))
for highly viscous, poor conducting polymeric liquids, to
near uni ty (O( 1)) for low molcular weight gases at room temperature
and pressure, and to low values (0(10- 1 -10- 2 )) for metallic
conductive liquids. The Schmidt number for species transport
varies between the large values (O( 1 0 2 -10 3 )) typ ical for conducting
and non-conducting liquids alike to unity for gases at atmospheric
pressure.
The second category of dimensionless group includes those
that specify ratios of transport mechanisms in bulk fluids
and which depend on the size and shape of the geometry. Several
flow domains that will be discussed in this chapter are shown
in Fig. 4.1. The Peclet numbers for heat and mass transport
are primary examples of this type of dimensionless group.
Both are ratios of convective to diffusive transport, and
depend on the magnitudes of the velocity field V* and the
length scale for the diffusive gradient L*. The appropriate
choices of the velocity and length scales for evaluating these
numbers are not always obvious. The primary fluid motion
may be driven by any of the mechanisms listed in Table 4.1.
Furthermore, non-uniformities in the boundary conditions may
cause different driving forces to dominate in specific regions
of the fluid. The choice of the appropriate length scale
is no less difficult. The first guess is the length scale
62

for the system, e.g. the size of the container for the fluid.
However, the thickness of the boundary-layers in temperature,
species concentration, and velocity that form when large Peclet
and Reynolds numbers are predicted by this method are the
appropriate length scales for highly convected fields. The
sizes of these layers depend on the magnitudes of the dimensionless
groups [4.9].

Table 4.3 Thermophysical properties and characteristic

scales used for forming dimensionless groups.

Symbol Definition

c* Characteristic Concentration Scale

L * Characteristic Length Scale
T * Characteristic Temperature Scale
V* Characteristic Velocity Scale
o* Characteristic Value of Interfacial Tension
LIT Characteristic Temperature Difference
lIc Characteristic Concentration Difference
lip Characteristic Density Difference Across a Meniscus
a Thermal Diffusivity
K Thermal Conductivity
D Molecular Diffusivity
h Heat Transfer Coefficient
v Momentum Diffusivity ~/p

~ Newtonian viscosity
p Mass Density
£ Emissivity
g Acceleration of Gravity
o Stefan-Boltzmann Constant
8t Coefficient of Thermal Expansion, see eq. (4.3)
Sc Coefficient of Solutal Expansion, see eq. (4.4)
o Interfacial Tension
do/dT, Rate of Change of Interfacial Tension with
do/dc Temperature and Concentration

In many circumstances it is appropriate to express the

Peclet numbers as products of a" ratio of diffusivities (either
 63

the Prandtl or Schmidt number) multiplied by the Reynolds

number, 1. e.

Pet:l Pr Re Pes :I Sc Re (4.2)

Then increasing convective transport is identified with the

increasing influence of inertia in the flow. At large Re
boundary-layers form in all three field variables and the
relative thicknesses of these layers depend on the magnitudes
of Pr and Sc; this situation has been analyzed for simple
geometries with both forced and natural convection [4.9].
Boundary-layers may form in the temperature and species
concentration even at low Re because of small molcular
diffusivities; in these cases the length scale for the boundary-
layer is partially decoupled from the scale for the flow.
This situation is particularly important in materials processing
in low-gravity because, with the exception of surtace-tension-
driven-convection, the fluid motions are slow enough that
inertial forces are unimportant. Even so, the high Schmidt
numbers for liquids cause these flows to dominate the transport
of species in many applications; examples of this phenomena
are qescribed in Sections 4.3 and 4.4.
The magnitude of the fluid motion is set by the strength
of the dominant driving force relative to the damping action
of viscosity (see Table 4.1). Dimensionless groups which
scale this ratio for buoyancy-driven and surface-tens ion-driven
flows are given in Table 4.2. The descriptions of buoyancy-
driven and surface-tens ion-driven flows encompassed by these
dimensionless groups are related to the linear approximations
given below for the dependence of the density and interfacial
tensions on temperature T and concentration c:

p p* [1 - Bt(T - T* ) + Bc(c -c * )J , (4.3)

a .. a* [1 + (daldT)(T - T*) + (daldc)(c - c*)] (4.4)

64

where the symbols are defined in Table 4.3. Such expressions

are not particularly useful for liquids with a maximum in
the density or for prediction of extremely large changes in
either p or a where the linear approximation may be poor.
The Grashof and Rayleigh numbers both scale the relative
importance of buoyancy to viscous forces in free convection,
although they arise when different scalings are used for the

Figure 4.1 Sample flow geometries discussed in this chapter.

TCOLD

(a) Vertical cylinder

heated from below.

qeO

H
TCOLD !
L

qeO

(b) Thin two-dimensional slot heated

from the side.
 65

Figure 4.1 (cont inued) .

(c) Thin two-dimensi0nal

slot with free
TCOLD
surface and
heated from the side.

q=O

d) Bridgman-Stockbarger crystal (e) Floating zone crystal

growth system. growth system.

fEED ROO

MELTING
INTERFACE
MENISCUS

SOLI OF ICATION
INTERFACE

CRYSTAL

V,
66

velocity and pressure fields. Traditionally, the Rayleigh

number is used for flows driven primarily by destabilizing
vertical (with respect to gravity) temperature or concentration
fields and the Grashof number is used for systems with lateral
gradients (perpendicular to the direction of g). The vertical
cylinder heated from the bottom (Fig. 4.1a) and the slot heated
from the side (Fig. 4.1b) are examples of these two situations.
Natural convection in systems with purely vertical gradients
begins at a critical value of Rat or Ras as an instability
from a static fluid and evolves into a finite amplitude pattern.
Increasing the driving force leads to nonlinear transitions
in the flow that change the spatial pattern, e.g. from axisymmetric
to three-dimensional for flow in a cylinder heated from below
[4.10]. Time-periodic motions begin at higher specific values
of the Rayleigh number and persist until the flow becomes
chaotic as demonstrated in many experiments; for examples
see [4.10-4.13J. It is the transition to time-periodic and
chaotic convection that plague the microscopic homogeneity
of semiconductor crystals grown from the melt [4.2J.
Prediction of these flow transitions by numerical solution
of the conservation equations is extremely difficult because
of the highly convected character of the flows and the myriad
of flow states with different symmetries that must be accurately
computed. Multiple steady and time-periodic axisymmetric
flows have been computed for idealized flows, such as the
cylinder heated from below [4.14,4.15J; transitions to steady
three-dimensional motions have been predicted by several
calculations [4.10,4.16J. The onset of time-periodic and
chaotic convection has not been computed for the cylindrical
geometry, but has been analyzed for natural convection in
an idealized two-dimensional layer heated from below [4.17J.
Perfect alignment of vertical temperature gradients is
difficult to achieve on earth with a constant acceleration
vector and impossible to maintain in space, where the dominant
direction may change with time depending on its orign. Lateral
temperature gradients cannot be supported by a hydrostatic
pressure field and thus must cause fluid motion no matter
what the magnitude of the temperature difference. When these
 67

gradient are small with respect to an unstable vertical gradient

(i.e. when the temperature field is nearly vertical) the effect
of lateral gradients can be viewed as an imperfection to the
steady flow states and transitions that exist for perfectly
vertical alignment [4.18]. The sharp transitions in Rayleigh
number in the flow present without the lateral gradients are
smeared into gradual changes as Rat is increased.
Flow driven primarily by lateral temperature gradients,
such as the horizontal cavity shown as Fig. 4.1b, cannot be
viewed in terms of the flow transitions present for a system
with only vertical gradients. The motions driven by lateral
gradients are weak for low values of Grashof number and represent
a momentum balance of only viscous and bouyancy forces. The
buoyancy forces are determined by the tempera ture (or solute)
distribution in the liquid, which is set by conduction and
convection. Approximations to these flows are computed in
terms of a Taylor series expansion in powers of Grt and are
especially useful for analysis of flows in low-gravity with
boundary conditions simple enough that the resulting linear
problems can be solved in closed form [4.19]. Boundary layers
form with high values of either Grt or P r and complicate the
analysis. Nonlinear transitions to time-periodic and chaotic
flows are also present, as have been identified in experimental
[4.20] and computational [4.21] reports for natural convection
in low Prandtl number fluids. Closed form analysis of the
flow is available for the case of a rectangular section so
thin (H/L « 1) that the velocity and temperature fields in
most of the channel are almost one-dimensional and the turning
flow is confined to regions near the ends that are the same
size as the channel height H. The details of the flow and
species transport in these end regions are crucial when the
analysis is use to describe transport in processes occuring
in these corners, as is the case in horizontal growth of crystals
from the melt; see [4.21]. Asymptotic and numerical solutions
for the buoyancy-driven flow caused by a temperature gradient
in the limit (H/L) « 1 were presented in refs. 4.22 and 4.23.
Hart analyzed the basic flow [4.24] and its stability [4.25]
for fluids with low Pro
68

The combined influence of buoyancy differences due to

temperature and concentration gradients can alter the flow
patterns and flow transitions in many experimental systems
and are receiving considerable attention; see the review paper
by Chen and Johnson [4.26]. These effects are just beginning
to be investigated with respect to specific situations arising
in materials processing, such as the directional solidification
systems shown in Fig. 4.1d [4.27-4.29]; these results are
discussed in Section 4.3.
Flows driven by surface-tension differences caused by
temperature variations can develop transitions to time-periodic
and chaotic convection similar to the buoyancy-driven motions
described above. These motions are particulary detrimental
to low-gravity experiments and so have recieved a great deal
of attention. When the temperature gradient is perfectly
vertical to the mensicus motion begins at a critical value
of the thermal Marangoni number [4.30,4.31]. The more typical
situation involves imposed temperature gradients along the
mensicus which drive flows for any value of fiT. Such a gradient
exists in the slot with a free surface shown in Fig. 4.1c
and in the floating zone (Fig. 4.1 e). Closed-form analysis
of surface-tens ion-driven flows is possible when the motion
is either slow [4.32,4.33], i.e. Mat« 1, or nearly one-dimens-
ional, as is the case for long two-dimensional [4.34] and
axisymmetric [4.35]. The long slot has been used as a model
system for understanding thermocapillary motions. Long axi-
symmetric cylindrical surfaces are not good models for the
floating zone which has an aspect ratio of about unity. Further-
more, long zones cannot exist because of the Rayleigh instability
which breaks the cylinder in drops; see [4.36] for a discussion
of this instability.
The evidence for the transitions to time-periodic motion
in floating zones is presented in Section 4.4. Theoretical
understanding of these oscillations is limited to the analysis
of two-dimensional shear waves on the surface of a long slot
[4.37,4.39]. The important prob lem of understanding the supression
of thermocapillary motion by the deposition of surfactant
materials on the surface of a liquid has been addressed by
 69

Homsy and coworkers [4.40,4.41] for the flow in a slot. Chun

has shown experimentally [4.42J that the thermocapillary motion
can be conf ined to the surface of a cylindrical meniscus by
superimposing rigid rotation on the bulk fluid; Smith has
presented an analysis for this situation in the limit of large
rotation rates [4.43J.
The shape of a liquid/fluid interface is set by surface
tension, by the fluid motion in both phases adjacent to the
interface, by gravity, and by the wetting conditions along
any three-phase contact curves between liquid, fluid, and
connecting solid surfaces. When flows are present the interface
may deform to comphensate for the non-uniform viscous and
dynamic pressure forces on it. Most theoretical and numerical
analyses are for geometries where the mensicus can be approximated
as a coordinate surface in a separable orthogonal coordinate
system and assume that the underlying flow causes little deflection
of the interface. The last assumption is indicated mathematically
when the Capillary number (Ca) is small (small viscous forces)
and the flow is weak or almost uni-directional (small inertial
forces); see [4.40,4.41,4.44J for examples of these assumptions.
Deflections of the surface due to gravity (as measured
by BOg), rotation (Bo r ), and changes of the capillary pressure
caused by temperature and concentration variation along the
surface (Cr) are usually ignored when the flows are computed.
Large deformations of even static interfaces are possible
on earth and in space experiments, as shown by the calculations
for the shapes of small-scale floating zones in Section 4.4.
These deflects influence the flow. Even when the surface
defection is small, dynamic interactions between the mensicus
and the flow may be partially responsible for transitions
to three-dimensional and time-periodic motions, as suggested
by Komantani et a1. [4.45J for surface-tension-driven flow
in a model floating zone. Analyses are needed that account
for these effects.
Levitation experiments in low-gravity make possible the
detailed study of surface deformations of static and oscillating
drops. Drop oscillations induced by deformation of the surface
are an example of motion driven by an unbalanced capillary
70

pressure distribution, so that exact description of the surface

shape is essential for understanding the motion. Important
theoretical results are summarized in Section 4.5 along with
the available experimental data.

4.3 Transport Phenomena in Directional Solidification

The most important consequence of convection in materials

processing applications is its relationship to mixing of species
and hence to the distribution of material in the final product,
as has been well documented in directional solidification
of semiconductor materials in systems similar to the Bridgman-
Stockbarger furnace shown as Fig. 4.1d. In the absence of
convective mixing the concentration field for a solute or
dopant in the melt will be essentially one-dimensional, decaying
exponentially from a value of calK at the melt/solid interface
to Co far away, where K is the equilibrium partition coefficient
for the solute at the melt/solid interface defined as
K ~ Csolid/Cmelt- The regimes of convective transport for
a solute with low diffusivity (high Sc) are displayed in Fig. 4.2
for a typical directional solidification system. Here the
abcissa is a measure of the intensity of the flow. In the
vertical Bridgman crystal growth system, convection caused
by temperature differences and the solute profile adjacent
to the interface mixes the solute and leads to a non-uniform
concentration distribution across the solidification interface.
This variation is only smoothed away when the convection is
intense enough to form a thin mass-transfer boundary layer
adjacent to the interface.
Burton et ale [4.46] classified the effect of mixing
in melt crystal growth in terms of an effective segregation
coefficient Keff measured as the ratio of the concentration
of the solute in the crystal at the interface (neglecting
solid diffusion) to a constant concentration of solute assumed
to be present in the bulk of the melt; i.e.,

(4.5)
 71

Crystal growth which is convectionless except for the uni-

ax ial mot ion caused by the mov ing sol idi fica t ion fron t corresponds
to Keff = K. In this case, solute rejected (K <1) at the
interface only effects the concentration of the melt on the
length scale of the diffusion gradient O(D/V g ), where Vg is
the growth rate. Crystals with constant concentration can
be grown as long as the ampoule is sufficiently long to account
for the transients introduced at the start of growth [4.47].
Introducing convective mixing of the bulk melt lowers Keff
(for K < 1)' In the limit of rapid convection throughout
the entire melt, the bulk concentration of solute responds
instantly to the partitioning at the interface and the
concentration of the Crystal changes continuously throughout
the crystal growth; this limit was described first by Scheil
[4.48]. Time-periodic and chaotic convection begin at critical
values of the Rayleigh number and lead to periodic and chaotic
back-melting of the melt/solid interface and to axial (in
the direction of growth) bands of non-uniform solute
concentration. Directional solidification in a low-gravity
environment removes the continuous axial variation of the
concentration caused by convective mixing, as demonstrated
by the experiments of Witt et al [4.2] and the subsequent
analysis of Favier [4.49].
Numerical calculations reported in [4.28,4.50,4.51] show
the transition from diffusion-controlled crystal growth at
low convection levels to the boundary-layer limit when the
convection is intense, but laminar. The effectiveness of
the mixin~ is characterized in these reports by the maximum
difference in solute concentration across the solidification
interface as a function of Rayleigh number or flow intensity.
Representative calculations from [4.51] are shown in Fig. 4.3
and are taken from analysis of the growth of gallium-doped
germanium in the Bridgman-Stockbarger System designed by Wang
!
[4.52]. Results are shown for crystal growth velocities ranging
between 2 and 8 ~m/sec.
72

Figure 4.2 Influence of flow transitions on solute segregation.

I
NO STEADY TIME-PERIODIC CHAOTIC I TURBULENT
CONVECTION LAMINAR I
I
I
PURELY AXIAL RADIAL REGlLAR IRREGULAR I
HEAT TRANSFER TEMPERATURE BACKMELTING, BACKMELTING, I
BY CONDLCTION GRADIENTS RESOLIDFICATION RESOUDIFICATIONI
I
I
I
FLOW
MASS TRANSFER WEAK AXIAL UNEVEN I
STATES DIFFUSIOI CONVECTIVE COMPOSITION AXIAL I
LIMITED MIXING STRIATIONS STRIATIONS I
I
I
I
RADIAL
I
DOPANT ~':~~ATQ I
SEGREGATION LESS RADIAL
SEGREGATION

Rocl Roca Roc3

DIMENSIONLESS TEtlf£RATURE GRADIENT IRol

The nonzero value of fJ.c when bulk convection is absent corresponds

to segregation induced by curvature of the soldification inter-
face. An important feature of Fig. 4.3 is the maximum in
segregation for intermediate values of Rat. The height and
location of the maximum is a function of the flow pattern
in melt, and thus the thermal characteristics of the furnace.

Axisymmetric isotherms, and streamlines are shown in

Fig. 4.4 as computed for the growth of gallium-doped germanium
used in the calculation shown in Fig. 4.3. The calculations
shown are for thermal Rayleigh numbers corresponding to
gravitational accelerations of O.lg (Rat lx107) and 1xl0- 3 g
lx10 5 ) ; more details are available in [4.51J. The
isotherms are shown for the entire melt/crystal/ampoule system;
the streamlines are only appropriat~ in the melt. The ampoule
is made of boron nitride which has a thermal conductivity
intermediate between melt and cry tal phases of germanium.
 73

Figure 4.3. Variation of max imum difference in solute concentration

across the melt/solid interface as a function
of flow intensity measured by Rat. Results are
for simulation of gallium-germanium crystal growth
in the Bridgman-Stockbqrger furnace of Wang [4.52].
Experimental data for earthbound experiments of
Wang are shown as the data points (e).

100r----------------------------------,

z
~ 80
r
«
C!)
w
0:: 60
C!)
w
en
...J 40
«
0
«
0:: 20

~
0
---

0
104 105
RAYLEIGH

The discontinuity in the thermal conductivities at the

melt/crystal/ampoule junction leads to large radial temperature
gradients there, as identified in the conductiive heat transfer
analysis of Jasinsky [4.53]. A second set of large radial
gradient is introduced at the junction of the adiabatic region
with the hot zone of the furnace; Chang and Brown [4.50]
first showed that these gradients can drive very intense
convection.
The flow field at the lower convection level is composed
of the almost vertical streamlines corrsponding to the uni-
axial crystal growth velocity and two slowly rotating toroidal
cells driven by the radial temperature gradients discussed
above. Increasing the gradiational acceleration increases
the intensity of the cells, effectively compressing the growth
streamlines into a thin diffsuion layer adjacent to the
74

melt/crystal interface. The isoconcentration contours of

gallium corresponding to the two thermal Rayleigh numbers
shown in Fig. 4.4 are displayed in Fig. 4.5. At Rat = 1x10 5

Figure 4.4 Isotherms and streamlines for Bridgman-Stockbarger

grDwth of gallium-doped germanium in the furnace
of Wang. Streamlines are shown for gravitational
accelarations corresponding to O.001g and O.1g '.
The temperature field is unchanged by the increase
in convection level and is shown on the left.

STREAMLINE

\fmaa •
9,87 110- 5

MELT -r--

...
u
>-
INTE R FACl. __ ~ m

:*
c::::=::::::::riffi
If)
0
Ii; UJ

~%
;:;::::.
Z
CRySTA'---- _
WI
~--+4l
0
N
~f.

~
ffi.
.~J
~

tltmin :
-6 .70110- 6

t t INTERFACE
 75

the curves of constant composition are approximately flat,

thereby indicating very little influence of bulk convection
on the solute field. The intersection of isoconcentration
lines with the melt/crystal interface indicates radial dopant
segregation across the crystal.

Figure 4.5 Contours of constant gallium concentration for

the flow fields shown in Fig. 4.4. The concentration
is scaled with the average value in the crystal
divided by K.

Concen Ir a ti on CONCENTRATION
RAT =I x 10 5
ROT = I x 10 7
6c = 1.80
6c =1.197

f-
f-
a
:I:
a I-
:I:
f-

3.38 w
z
o
N

U
I-
<{
2.84 In
<{

o
<{

t 17.24
76

Figure 4.6 Axial concentration profiles for gallium along

the centerline of the melt for three values of
Rat. Results are from the simulations of gallium-
doped germanium crystal growth in the furnace
of Wang.

15'.--------------------,
g
(.)
zl2
o
I-
«
0::9
I-
Z
lLJ
(.)
ZS
o
(.)

lLJ
~:3
...J
o
CI)

o~--~--~--~~--~--~
o .2 .4 .S .8 1.0
DIMENSIONLESS DISTANCE FROM INTERFACE

The gallium concentration at the higher Rayleigh number

shows the effects of moderate mixing in both the convection
cells. The composition in the upper cell is constant and
the solute field in the lower field is beginning to develop
a core with constant composition. The solute levels in the
two cells are connected by a diffusion layer located approximately
half way between the cell centers. This two-cell structure
of the solute field is more apparent from the plot of the
axial concentration in the melt along the centerline of the
ampoule, shown in Fig. 4.6 for several values of Rat. It is
clear from these results that the simple idea of a uniform
bulk concentration used in the definition of Keff fails in
crystal growth systems with only l~minar convective mixing.
A totally uniform bulk concentration only exists when the
melt is stirred between cells by temporal fluctuations in
the flow.
It is important to note from the experimental data shown
 77

on Fig. 4.4 that the earthbound system of Wang produces radial

segregation on the portion of the curve corresponding to intense
convection. Performing the identical experiment in a low-
gravity environment may produce crystals with larger radial
segregation, if the mean acceleration level in space is not
sufficiently low to push the segregation behavior to the diffusio.n
controlled portion of the curve.
Introducing the effect of a non-dilute solute on the
density of the melt alters the convection in the melt, espeqially
near the melt/crystal interface where the solute gradient
is largest. Coriell et al. [4.27] and Hurle et al. [4.54]
have analysed the onset of thermosolutal convection driven
by a vertical destabilizing solute profile in the presence
of a stabilizing vertical temperature gradient. Mcfadden
et al. [4.29] have computed steady-state and time-periodic
finite amplitude convection evolving from the critical value
of Ra s • Radial temperature gradients caused by imperfections
in the furnace design,such as described above, cause thermally-
driven flows that distort the solute profile. These flows
are shown in [4.55] to be imperfections (in the sense described
in Section 4.2) to the motions analyzed in [4.29]. Although
no clear experimental evidence exists for the effect of thermo-
solutal convection in directional solidification, the crystal
growth experiments reported by Bourret et al. [4.56] do show
intense (nearly perfect) mix ing in a small-scale system with
a destabilizing solute field.
Favier and coworkers [4.57,4.58] have used the stabilizing
effects of the solute profile in GeSi growth to damp convection
and obtain crystal growth near the maximum in the radial
segregation curve on earth. Simulations ·of convection and
segregation in this system [4.51] suggest that diffusion-controlled
growth can be obtained in solidification of this alloy in
a low-gravity environment.
The summary of transport phenomena in directional
solidification has not touched on the interaction of convection
with the macro- and microscale morphology of the melt/crystal
interface. This subject has been reviewed recently by Glicksman
et al. [4.59]. Of particular interestarecalculations[4.60,4.61]
78

and experiments [4.62J that demonstrate direct coupling between

the melt/crystal interface shape and the convective flow pattern.

4.4 Transport Phenomena in the Floating Zone

Much of the interest in meniscus shape and stability

and in thermocapillary-driven flows in a low-gravity environment
has focussed on understanding the transport processes relevant
to the floating zone method (see Fig. 4.1e) as a technique
for containerless solidification of corrosive materials.
Here a polycrystalline rod of material is pulled through a
circumferential heat source, e.g. a radiative heater or an
electron beam. A molten zone forms just ahead of the heater
and is resolidified into a single crystalline rod along the
stern of the heater. The shape of the melt is determined
by the interactions of heat transfer in the melt, solids and
ambient which sets the length of the molten zone and the shapes
of the bounding melt/solid interfaces, and by surface tension
which holds the mensicus in place against gravity and dynamic
forces (viscous stress and dynamic pressure).
Considerable analysis of the shape and stability of static
[4.37,4.63J and rigidly rotated [4.37,4.64J has been reported
for a zone formed between two inert cylindrical rods. Although
these calculations have identified a myriad of interesting
effects, many of which that have been examined experimentally,
they ignore the fundamental coupling between heat transfer
in the zone with its length and shape. Duranceau and Brown
[4.65J have developed a thermal-capillary model that couples
heat transfer in the melt and solid by conduction with the
determination of the shape of the zone. Sample results for
the growth of a one centimeter radius silicon crystal are
shown in Fig. 4.7 for several different values of the gravitational
Bond number (G BOg) and a specific heater temperature profile.
Increasing the gravitational acceleration causes the mensicus
to sag, thereby reducing the surface area of the interface
and the amount of heat transfered by radiation to the zone.
The length of the zone shrinks, effectively reducing the mensicus
 79

deformation from the amount that would be predicted if the

length remained constant. For zero acceleration, no translation
rate (V g = 0) and a symmetric heater profile, the mensicus
shape should be symmetric about the center of the heater profile.
fhe deformation of the zone caused by gravity breaks the symmetry
of both the zone shape and temperature field, as shown b~y.

the isotherms plotted in Fig. 4.7. The loss of symmetry is

significant when considering the

Figure 4.7. Shapes and temperature fields for one centimeter

radius floating zones of silicon predicted by
the thermal-capillary model in [4.65]. Zone shapes
are for different values of the gravitational
Bond number G'" BOg (see Table 4.2). The value
G = 3.5 corresponds to crystal growth on earth.

AMBIENT
TEMPERATURE
G=O.O G= 1.75 G=3.5 DISTRIBUTION

8co (zl

8 m =1.5
IT =1.0

8:'=0.2

patterns expected by either buoyancy- or surface-tension-driven

convection. The applicability of the conduction-dominated
80

thermal-capillary model has been partially verified by comparison

with experiments by.Kern [4.66J.
Analysis of convection and dopant segregation in floating
zones has been limited to studies of steady, axisymmetric,
convection caused by differential crystal rotation [4.67-4.69J,
and buoyancy- and surface-tension-driven convection [4.70J.
The evolution from the uni-axial convection produced by crystal.
growth to intense laminar convection with boundary-layers
of solute along the solidification interfaces is documented
in [4.67J and is qualitatively similar to the path discussed
in Section 4.3.
Experimental measurements of the flow and temperature
fields in floating zones both on earth [4.71,4.72J and in
space [4.73J have demonstrated the transition from steady
to time-periodic and chaotic motion. The onset of time-periodic
convection has been documented to be as an azimuthal wave
that travels around the circumference of the liquid zone [4.72J;
the frequency of the wave depends on the zone size. No theoretical
predictions are available that describe the fluid mechanics
of this traveling wave and an analysis of this instability
as a function of zone shape and the mode of heating is the
outstanding problem in understanding thermocapillary motion
in the floating zone.

4.5 Drop Dynamics

The dynamics of liquid drops held together by surface

tension, and some with electrical charge have been of theoretical
and experimental interest since Plateau [4.74J first used
rotating drops held in a neutrally buoyant liquid as models
for the shape of a rotating heavenly body bu assuming that
the attractive forces of surface'tension in his experiment
.)
would mimic the gravitational attraction of solar-sized bodies.
Fentometer-sized liquid drops with electrical charge and rigidly
rotating have also been postulated as models from heavy atomic
nuclei and used in model calculations for nuclear fussion
[4.4], The large number of theoretical analyses of the shapes
 81

and dynamics of these drops have been performed with little

experimental confirmation because of the difficulties of levitating
drops on earth. Available data has been obtained either on
drops in free fall for times of order of a few seconds [4.7]
or liquid/liquid systems where the drop is made neutrally
buoyant in an outer surrounding liquid [4.75]. Although long

Figure 4.8 The change in the oscillation frequency for a

two-lobed motion with increasing amplitude o~
oscillation as measured by the axis ratio of the
maximum prolate shape. The asymptotic results
of [4.77] (solid curves), numerical calculations
of Foote ( A ) and Alonso ( + ) , and experimental
results of Trinh and Wang [4.76] ( . , R=O.49cm;
0 , R=O.62 cm) are shown;

3
~:
I '"
fI
~
-0-05
~
iJ' o
Ii
".,.

S':-::----:-'-:-._L~~',~~
Jl
_5 - 0-10--
tl,

~
0-1

1-0 1-2 1-4 1-0 1-8 2-0

Axis .... Iio al maximum prolale shape (L/W)

durations are feasible in the second system, the results are

clouded by the more complex fluid mechanics caused by the
viscous interactions of the two fluids.
Wang an~ coworkers have studied the dynamics of an uncharged
drop immersed in a neutrally-buoyant liquid [4.75,4.76.]
Tsamopoulos and Brown compared the me~sured frequencies of
oscillation as a function of the amplitude of the deformation
with the results of a weakly nonlinear analysis of inviscid
oscillating drops and bubbles [4.77]. The results of this
comparison are shown in Fig. 4.8, along with results of several
numerical simulations of viscous [4.78,4.79] drop oscillations.
The agreement between the asymptotic results and the measurements
82

is satisfying, especially considering the analytical nature

of the analysis. Furthermore, the asymptotic results for
drop oscillations plotted in Fig. 4.8 are indistinguishable
from the numerical results of Benner [4.80] for solution of
the same problem.
The weakly nonlinear analysis has been extended to included
electrical charge for a conducting drop [4.5]. An analysis
valid to the first order in the amplitude of the oscillation
uncovered resonant motions of drops for particular values
of the electrical charge where two axisymmetric modes of
oscillation have the same linear frequency. Then the nonlinear
evolution of the drop involves both modes which interact on
a long timescale compared to the basic linear frequency. The
details of the evolution depend on the initial deformation
of the drop. Resonance occurs for a charged invsicid drop
between the four- and six-lobed oscillations at the dimensionless
charge value Q ~ Q1 [3211/3]1/2 scaled with [0411EmR3]-1/2,
where Em is the permittivity of the surrounding medium and
R is the radius of the equivalent spherical drop. The evolution
of the oscillation of a charged drop with Q Q1 is shown
in Fig. 4.9 for initially 4-lobed disturbance; the timescale
is scaled with the reciprocal of the frequency of the linear
oscillation. In less than three cycles the oscillation has
evolved from a 4-lobed to a 6-lobed form. The drop will
continuously exchange energy between these two modes if components
of both modes are present in the initial condition.
The dynamics becomes even more complex when non-axisymmetric
modes are included in the initial disturbance. Natarajan
and Brown [4.6] have shown that an uncharged drop perturbed
to have 5-lobe and 8-lobed (a pair of resonant modes) non-
axisymmetric deformations will wander stochastically about
all possible three-dimensional configurations
, on a long timescale
compared to the natural frequepcy of oscillation. This
dynamics constitutes one of the simpliest physical systems
for observing chaos in fluid mechanics. Low-gravity experiments
present the opportunity to observe this feature.
Acoustic [4.81] and electrostatic [4.82] levitation systems
/"
are ~oth available for positioning drops in a low-gravity
 83

Figure 4.9 Shapes of drops initially perturbed by a 4-lobed

deformation with Q = Q, as a function of time.

T T
(a) I=i .. (b)

eb
If-

y y
0 0

-I -II--
1<1.

-2 -2
-2 -I 0 2 2 0
x x

T T
I=t" (c) 1 = 1ftr (d)

m
1-

y 0 y 0 I-- -

-I II--
1<1.

-~~2----~----~-----~--~ -2 I I I
2 -I ox 2

1= 'i>r (e) 1 =1j1r (fJ

m
1- -

y 0 y 0 I--

-I I 1<1.

-~~2------~I----~O~---+----~ -2 I I I
-2 -I o
x x
84

environment. Understanding the dynamics of charged drops

is especially important for electrostatic levitation because
of the interaction of the electrical field with the drop shape
[4.83]. The maximum drop size that can be suspended in an
electric field is set by the Rayleigh limit for the bursting
of the drop at which point the electrostatic stress overwelms
the surface tension [4.84]. In the dimensionless units of
charge introduced above this limit is Q Qc = 4/n. Tsamopoulos
~

et al. [4.85] have studied the dynamics of drop breakup for

a drop with charge near Qc and have shown that it is also
controlled by slow evolution leading to prolate shapes and
then to rapid break up.
The fluid mechanics of the centering of a bubble inside
an inviscid liquid shell by inducing oscillations of the shells
has also been understood as a long timescale, nonlinear interaction
of oscillation modes [4.8] and has been observed in experiments
[4.86].

4.6 Summary and Perspective

The low-gravity environment of outer space was first

thought to be a panacea for fluids experimentation and materials
processing. Over a decade later the role of eliminating gravity
in specific systems is much clearer and its promise is not
quite so clear cut. It is a unique environment for suspending
fluids without contact with solid and will lead to new experiments
not feasible on earth. The major difficulty comes with the
desire to create convectionless processes with temperature
and concentration gradients. The considerable experimental
and theoretical effort that has gone into understanding directional
solidification has demonstrated that experimental systems
(both the hardware and the materials to be processed) can
be designed so as to eliminate .buoyancy-driven convection
in a system with a gravitiational acceleration of one-thousandth
of the value on earth. This is a realistic goal for use aboard
an orbital spacecraft. Poorly designed small-scale crystal
growth systems and attempts to grow larger crystals, as the
power becomes available, will result in crystals with increased
 85

radial segregation of dopants and impurities because of the

weak nonuniform mixing that will be present in these systems.
Optimi~ation of hardware for use in space is essential if
significant increases in the quality of the product are to
be obtained.
The time-periodic and chaotic flows characteristic of
confined systems with temperature and solute gradients on
earth can be removed in space. Similar flow transitions driven
by surface-tension gradients in systems with a free surface
are not automatically surpressed. Elimination of these transitions
is necessary before containerless processing from a nearly
convectionless melt is a reality. Moreover, the increased
importance of liquid wetting in "contained" systems at low-
gravity may create free surfaces where none are expected from
ground-based tests. Surface-tension flows make exist in any
system where the liquid is not forced to wet the walls of
the container.
No simple method is available for reducing surface-tension-
driven flows. Introducing a surface-active film to surpress
the surface-tension gradients pollutes the melt. Rigid rotation
of the fluid only forces the convection to the interface.
Applied magnetic fields for electrically conducting liquids
have been used to surpress the transition to time-periodic
convection in crystal growth systems on earth and will have
the same effect in space; however, such large field strengths
are needed to totally eliminate convection that this is not
a viable option for creating convectionless processes in either
environment.

Acknowledgement

The author is grateful to the Mi;crogravity Sciences and

Applications Program of the National Aeronautics and Space
Administration and to the National Science Foundation for
their support.
86

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 87

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88

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Morrish, K.A.: Thermosolutal convection during directl,onal
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4.31 Scriven, L.E.; Sternling, C.V.: On cellular convection

driven by surface-tension gradients: effects of mean
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4.32 Harriott,G.M.: Fluid flow and mass transport in a small

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4.33 Da-Riva, 1. ;Pereira, E.A.: A regular perturbation approach

to surface tension driven flows. Acta Astronautica 9
(1981) 217-224.

4.34 Sen,A.K.; Davis, S.H.: Steady thermocapillary flows in

two-dimensional slotsJ. Fluid Mech. 121 (1982) 163-18"6;

4.35 Xu, J.J.; Davis, S.H.: Liquid bridges with thermocapillarity.

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4.36 Ungar, L.H.; Brown, R.A. :The dependence of the shape

and stability of captive rotating drops on multiple
parameters. Phil. Trans. R. Soc. Lond. (1982) A306
347-370.

4.37 Smith, M.C.; Davis, S.H.: The instability of sheared

liquid layers. J. Fluid Mech. (1982) 121 187-206.

4.38 Smith, M.C.; Davis, S.H.: Instabilities of dynamic thermo-

capillary liquid layers. Part 1. Convective instabilites.
J. Fluid Mech. 132 (1983) 119-144.

4.39 Smith, M.C.; Davis, S.H.: Instabilities of dynamic thermo-

capillary liquid layers. Part 1. Surface-wave instabilites.
J. Fluid Mech. 132 (1983) 145-162.

4.40 Homsy, G.M.; Meiburg, E.: The'effect of surface

contamination on thermocapillary flow in a two-dimensional
slot. J. Fluid Mech. 139 (1984) 443-459.

4.41 Carpenter, B.; Homsy, G.M.: The effect of surface

contamination on thermocapillary flow in a two-dimensional
slot. Part 2. Partially contaminated interfaces. J. Fluid
Mech. 155 (1985) 429 -439.
 89

4.42 Chun, C.-H.: Marangoni convection in floating zone under

reduced gravity. J. Crystal Growth 48 (1981) 600-616.

4.43 Smith, M.K.: Thermocapillary and centrifugal-buoyancy-

driven motion in a rapidly rotating liquid cylinder. J. Fluid
Mech. (1985) in press.

4 • 44 H a I" I" i 0 t t, G. M.; B I" own, R. A.: F I ow i n a d iff ere n t i all y

rotated cylindrical drop at low Reynolds. number. J. Fluid
Mech. 126 (1983) 269-285.

4.45 Kamotani, Y.; Ostrach, S.; Vargas, M: Oscillatory thermo-

capillary convection in a simulated floating-zone
configuration. J. Crystal Growth 66 (1984) 83-90.

4.46 Burton, J.A.;Prim, R.C.; Slichter, W.P.: The distribution

of solute in crystals grown from the melt. J. Chem.
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4.47 Bourret, E.D.; Derby, J.J. Brown, R.A.: Dynamics of

Bridgman-Stockbarger growth of non-dilute binary alloys.
J. Crystal Growth 71 (1985) 587-596.

4.48 Scheil, E.: Bermerkungen zur Schicktkristallbilbung. Z.

Metallk. 34 (1942) 70-72.

4.49 Favier, J.J.: Initial transient segregation during

unidirectional solidification of a binary alloy in a
furnace with thermal damping. J. Crystal Growth 49 (1980)
373-380.

4.50 Chang, C.J. Brown, R.A.: Radial segregation induced

by natural convection and melt/solid interface sha~e
in vertical Bridgman growth. J. Crystal Growth 63 (1983)
343-364.

4.51 Adornato, P.A.; Brown, R.A.: Convection and segregation

of dilute and non-dilute binary alloys: Effect ampoule
and furnace design. J. Crystal Growth (1985) submitted.

4.52 Wang, C.A.: Crystal growth and segregation in vertical

Bridgman configuration. Ph.D. Thesis, Cambridge: Massachusetts
Insitute of Technology 1984.

4.53 Jasinski, T.J.: Thermal analysis of the vertical Bridgman

semiconductor crystal growth technique. Ph.D. Thesis,
Cambridge: Massachusetts Institute of Technology 1982.

4.54 Hurle, D.T.J.; Jakeman, E.; Whe~ler, A.A.: Hydrodynamic

stability of the melt during solidification of a binary
alloy. Physics Fluids 26 (1983) 624-626.

4.55 Adornato, P.M.; Brown, R.A.: Petrov-Galerkin methods

for natural convection in directional solidification
of binary alloys. J. Computat. Physics (1985) submitted.
90

4.56 Bourret, E.D.; Derby, J.J.; Brown, R.A.; Witt, A.F.:

Segregation effects during growth of pseudo-binary systems
with large liquidus-solidus separation. Acta Astronautic
11 (1984) 163-171.

4.57 Rouzaud, A.; Favier, J.J.: A comparative study of thermal

and thermosolutal convective effects in vertical Bridgman
crystal growth. Part I Experimental Results. J. Crystal
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of thermal and thermosolutal convective effects in vertical
Bridgman crystal growth. Part I Theoretical Analysis.
J. Crystal Growth (1985) in press.

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of rlows with the crystal-melt interface. Ann. Rev. Fluid
Mech. (1985) in press.

4.60 Davis, S.H.; Muller, U.; Dietsche, C.: Pattern selection

in single component systems coupling Benard convection
and solidification. J. Fluid Mech. 144 (1984) 133-151.

4.61 Chang, C.J.; Brown, R.A.: Natural convection in steady

solidification: finite-element analysis of a two-phase
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1-27.

4.62 McFadden, G.B.; Coriell, S.R.; Boisvert, r.F.; Glicksman,

M. E.; Fang, Q. T.: Morphological stabili ty in the presence
of fluid flow in the melt. Metall. Trans A15 (1984) 2117-
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liquid zones. J. Colloid Interface Sci. (1977) 60 126-136.

4.64 Brown, R.A.; Scriven, L.E.: The shape and stability of

captive rotating drops. Philos. Trans. R. Soc. Lond (1980)
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4.65 Duranceau, J.L.; Brown, R.A.: Thermal-capillary analysis

of small-scale floating zones: steady-state
calculations. J. Crystal Growth (1985) submitted.

4.66 Kern, E.L.: Microgravity Si zoning investigation. NASA

Report, NAS8-34920, 1984.

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by differential rotation in a solall floating zone. J. Crystal
Growth 69 (1984) 589-604. I

4.68 Harriott, G.M.; Brown; R.A.: Flow in a differentially

rotated cylindrical drop at mode·rate Reynolds number. J. Fluid
Mech.144 (1984) 403-418.
 91

4.69 Kobayashi, N.; Wilcox, W.R.: Computational studies of

convection due to rotation in a cylindrical floating
zone. J. Crystal Growth 59 (1982) 616-624.

4.70 Clark, P.A.; Wilcox, W.R.: Influence of gravity on thermo-

capillary convection in floating zone melting of silicon,
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4.71 Chun, Ch. -H: Experiments on steady and oscillatory temperature

distribution in a floating zone due to the Marangoni
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4.72 Preisser, G.; Schwabe, D. ;Scharmann; A.: Steady and

oscillatory thermocapillary convection in liquid columns
with free cylindrical surfaces. J. Fluid Mech. 126 (1982)
545 -56 7,

4.73 Schwabe, D.; Preisser, G.; Scharmann, A.: Verification

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9 (1982) 265-273.

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des liquides soumis aux seules forces moelculaires.
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of small-amplitude drop oscillations in immiscible liquid
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4.77 Tsamopoulos, J.A.; Brown, R.A.: Nonlinear oscillations

of drops and bubbles. J. Fluid Mech. 127 (1983) 519-537.

4.78 Foote, G.B.: A numerical method for studying simple drop

behavior: simple oscillations. J. Computat. Physics 11
(1973) 507-530.

4.79 Alonso, C.T.: The dynamics of colliding and oscillating

drops. In Proc. into colloq. on drops and bubbles.
Pasadena: Jet Propulsion Laboratiry 1974.

4.80 Benner, R.E.: Equilbria, stability, and bifurcati'ons

in fluid physics. Ph.D. Thesis, University of Minnesota
1983.

4.81 Jacobi, N.; Croonquist, A.P.; Elleman, D.O.; Wang; T.G.:

Acoustically induced oscillation and rotation of a large
drop in space. In Proc. 2nd into colloq. on drops and
bubbles. D. H. Le Croissette (ed.) Pasadena: Jet Propulsion
Laboratory 1981.
92

4.82 Davis, R.E.; Ray, A.K.; Single aerosol particle size

and mass ~easurements using a electrodynamic balance. J.
Colloid Interface Sci. 75 (1980) 566-576.

4.83 Adornato, P.M.; Brown, R.A.: Shape and stability of

electrostaticall-y levitated drops. Proc. R. Soc. Lond. A389
(1983) 101-117.

4.84 Rayleigh, J.W.S.: On the equilibrium of liquid conducting

masses charged with electricity. Phil. Mag. 14 (1882)
184-186.

4.85 Tsamopoulos, J.A.; Akyllas, A.; Brown, R.A.: Dynamics

of charged drop breakup. Proc. R. Soc. Lond. (1985)
in press.

4.86 Lee, M.C. Feng, I.; Elleman, D.D.; Wang, T.G.; Young,
A.T.: Generation of a strong centering force in a sub-
millimeter compound droplet system. In Proc. 2nd into
colloq. on drops and bubbles. D.H. Le Croissette (ed.)
Pasadena: Jet Propulsion Laboratory 1981.
5 Diffusion and Atomic Transport

G. FROHBERG
Technische Universitat Berlin, FRG

Diffusion is a common phenomenon in gases, liquids and solids. The diffu-

sion coefficient, describing these processes, is typically of the order of
1 cm2/s for gases, 10-5 cm2/s for liquids and normally lower than 10-8cm2/s
for solids. Diffusion in gases, of lower practical interest in the field of
material science, is well understood in terms of the kinetic gas theory. On
the other hand, much experimental and theoretical interest is concentrated
on diffusion in solids and in this field many new and fine tools have been
introduced in diffusion investigations in the last decades.

As a result, our knowledge of diffusion in solids is well established

([5.1J- lS.5 ]). But, to be more precise, this is only true for crystalline
solids, while our knowledge about noncrystalline solids is as limited as it
is about liquids. This obviously corresponds to some deficiency in even the
most modern theoretical methods to handle more complicated structural pro-
blems as the disordered state (e.g. liquids and glasses) by appropriate
statistical methods. It is also reflected by the fact that for crystalline
solids diffusion in disordered concentrated alloys is much less understood
than in dilute alloys.

Another reason for the limited knowledge about diffusion processes in

liquids is related to the experimental problrm of accuracy in measuring
diffusion in such systems. In the case of am\llrphous solids, these struc-
tures are related to a deviation from thermal equilibrium, and normally it
is difficult to define the magnitude of this deviation. In liquids, mea-
surements are hampered by cons i derab 1e and uncontro 11 ab 1e contributions
from different types of convection to the atomic diffusion process. On the
other hand, many problems in modern material science are related to diffu-
sion controlled processes in the liquid state just ahead of the solidifica-
94

ti on front. Hence there is a growi ng demand for a better understandi ng of

the diffusion mechanism in the liquid state.

Unfortunately a large contribution to diffusion-like mixing processes in

liquids is known to arise from gravity, which cannot be eliminated in
ground experiments for time spans beyond a few seconds. Hence quite natu-
rally a major part of material science experiments in space is concerned
with investigations of diffusion controlled processes in the liquid state
[5.6J. Some of them are basic experiments on diffusion, where the extraor-
dinary chance is used to get reliable diffusion data on the pure atomic
diffusion process, unperturbed by gravity driven convection. One of the ob-
jectives of such fundamental experiments is to compare these data with the
different theories of liquid diffusion, which up to now cannot be scruti-
ni zed due to alack of accurate data from ground experiments (see Sect.
5.3).

With the modern understanding of the liquid diffusion mechanism as a pro-

cess of collective atomic motions, there are some theoretical approaches
under discussion that imply direct contributions of gravity to the intrin-
sic atomic diffusion, arising from thermodynamic density fluctuations in
the liquid (Subsect. 5.3.5). Compared to the contributions from gravity-
driven macroscopic convections, the density fl uctuations are expected to
contribute by "microscopic convections", which might not be separable from
the collective motions on the atomic scale.

Another way to get. information about the diffusion mechanism in 1iquids is

the analysis of the isotope effect, provided the results of space experi-
ments are sufficiently accurate (Subsect. 5.3.7). This way has been proved
very successfully in the case of solids.

Finally, transport experiments may al so give information about the diffu-

sion mechanism, but this information is in most cases restricted to quali-
tative arguments, because it always includes an additional unknown trans-
port parameter, which has to be separated using the experimental results.
From theory very little is known about the transport parameters in liquids
([5.7], [5.8J and Sect. 5.1.3 and 5.3.6).

As a quite practical result of diffusion experiments in space and the ex-

pected knowledge about the diffusion mechanism, it will be possible to give
 95

the temperature dependence of the diffusion coefficient very accurately and

to understand and recalculate the pseudo-diffusion contributions resulting
from other effects, especi ally from gravity. But the mai n effect woul d
result in a better understanding of all diffusion-controlled processes as
e.g. the solidification process of alloys.

5.1 Thermodynamics of Irreversible Processes

5.1.1 Phenomenological Equations

Diffusion and atomic transport processes arise due to deviations from

thermodynamic equilibrium, hence the theory of thermodynamics of irrever-
sible processes is applicable. In a system of n components there are always
n+1 generalized forces Xi and conjugate generalized fluxes Ji (i=l, ••• ,
n+l), for which the following phenomenological equations hold (see [5.1J,
[ 5. 7] , [5. 9 J, [5. 10 J, [5. 11 J) :

Ji =z(k=l, ••• ,n+l} Lik • Xk for i=1, ••• ,n+1. (5.1 )

In the general case, Ji, Xi and Fi are vectors and Lik is a second drder
tensor, but in isotropic substances such as liquids, Lik is a scalar quan-
tity and the scalar product in Eq.(5.1} reduces to a real product.

Forces and fluxes are called "conjugate", when they satisfy the relation

z ( i =1, ••• , n+ 1) J i • Xi = s T, (5.2)

where s is the density of entropy production and T the absolute tempera-

ture. As a standard set of fluxes and forces, Ji has the meaning of a par-
ticle current density and Xi is the total force on a particle, given by

i=l, ... ,n. (5.3)

Fi is the real effective force on the particle during migration and ~i the
chemical potential of the particle. For i=n+1=q, J q is the heat flux den-
sity and

Xq - (vT }/T (5.4)

96

is the conjugate thermodynamic force. Obviously. Lqq/T is the heat

conductivity. In the presence of a magnetic field of intensity Bm. the
On sager relations take the form

i .k=l ••••• n+1. (5.5)

Since in general ~i is a function of all concentrations Ci (particle den-

sity) of the components. the gradients of the concentrations appear in the
generalized forces Xi:

Xi = Fi - Vi vp - Hi vT - ~(k=l ••••• n) ( d~i/ dCk) vCk (5.6)

Vi (d~i/d p) (5.7)

Hi = (d~i/dT) - ~i/T (5.8 )

Vi and Hi are partial molar volume and enthalpy. respectivly (5.7). p is

the pressure. Contributions from concentration gradients to the fluxes are
called "diffusion fluxes". those from direct forces Fi or vp or VT are
termed "transport fl uxes". because the fi rst type is rel ated to a random
walk of the particles. while the latter type is characterized by a drift
movement.

The phenomenological coefficients Lik depend only on the thermodynamic

variables p.T.C1 •••.• Cn and external fields but not on the forces. at least
in a first linear approximation. Equations of the type (5.1) hold for any
natural coordinate system of all diffusing particles in a volume element
(for other systems see Sect. 5.2.1). The value of Lik hence depends upon
the coordinate system.

5.1.2 Diffusion

As defined in the preceeding section. the case with all Fi=O. p=const. and
T=const. gives pure diffusion fluxes in Eq. (5.1). Using (5.6) we get

Ji = - ~(k=l •••.• n) Dik VCk. where (5.9)

(5.10 )
 97

are the diffusion coefficients of the system. In principle, it would be im-

possible to do diffusion experiments on the ground, since Fi=Mi .,g (Mi= mo-
lecular mass) and hence not zero (see 5.1.3). But it is easy to show that,
at least under laboratory conditions, the influence of Fi is small and can
be neglected. This is not necessarily true for processes in large dimen-
sions (e.g. atmosphere, if there were no convection). Another question is,
whether there is any influence of gravity acting as an external field on
the Lik or the Dik' This will be dicussed in 5.1.4 and together with the
different theories in 5.3; (compare also Chapter 17). For experimental re-
sults and further details see e.g. [5.3J, [5.5J, [5.7J, [5.12J).

5.1.3 Transport Effects

Pure transport fluxes occur in Eq. (5.1) in all cases complementary to dif-
fusion, i.e. all vCi=O but not all of Fi, vp, v T vanishing. This will be
discussed in the following sections.

Chemical Diffusion

It seems contradictory to discuss chemical diffusion in the context of

transport effects, but when speaking of diffusion as a process of random
walk of the particles, of course relative to a suitable reference system
(normally the center of mass system CMS of all particles in a volume ele-
ment), that should be only true for the case of selfdiffusion. In chemical
diffusion, the chemical concentration gradient produces real forces, which
are different for the components and hence the individual CMS's of the va-
rious components are drifting relative to each other. If, in a two compo-
nent system, 0'1 is the self-diffusion coefficient of component 1 in the
alloy (in CMS1) and D'c1 is the chemical diffusion coefficient of the same
component (in CMS), then

(5.11 )

is the flux of atoms 1 according to the drift velocity vI (velocity of CMS1

relative to CMS). The chemical force can be related to the thermodynamic
factor m1 and is proportional to
98

m1 - 1 = a1n(f1)1 a1n(N1), (S.12 )

where f1 is the activity coefficient of component 1 and N1 the mole frac-

tion (S.7). Chemical diffusion coefficients in liquids are normally mea-
sured in the center of volume system, CVS (see S.2.1). In summary, chemical
diffusion according to the definition given in S.1.2 is a diffusion pro-
cess, but incl udes transport contributions. For experimental results and
more details see e.g. [S.3J, [S.12J.

Thermotransport

This type of particle transport, sometimes named "thermodiffusion", "ther-

momi grati on" or "Soret-effect", ari ses from a temperature gradient in
(S.l):

Ji - - (Liq - E(k=l, ••• ,n) Lik Hk vT/T

(S.13)
=- Qi Ci Bi vT/T

Here the reduced heat of transport Qi and the particle mobility Bi are in-
troduced. Bi is defined by the drift velocity Vi resulting from force Fi:

(S.14 )

In two-component systems, Bi may be expressed by the diffusion coefficient

Di:

(S.lS)

fTi is the transport correlation factor [S. 7J, and kb the Boltzmann con-
stant. From an atomistic point of view, ~i results from scattering of pho-
nons and electrons at the migrating particle, giving a true transport force

Fi = - Qi nIT. (S.16 )

A discuss·ion and experimental results for liquids can be found in [S.7].

 99

Electrotransport

Also named "electrodiffusion", "electromigration" and "Haeffner effect" (in

the case of se lftransport), thi s effect ari ses from an external el ectri c
field E in the liquid. Therefore, only charged particles give a direct
field force

Fi = zi e E, (5.l7)

where (zi e) is the true charge of particle i (e.g. in ionic salts), and e
is the elementary charge. In the case of metals, the electrons must be
treated as an additional component i. This gives rise to cross terms Lie
and Lik in (5.l), which can be described by a pseudo-charge (zei e), resul-
ting from scattering of electrons (n = e) at the moving charged particle.
Hence the total force is

Fi = (zi + Zei) e E = zeffi e E. (5 .18 )

(Zeffi e) is called the effective charge of particle i. Analogous to (5.l3)

we obtain

Ji = Ci Bi zeffi e E (5.l9)

For more details see [5.7J and [5.8J. A theory for zeff in liquids will be
discussed in Sect. 5.3.6.

Transport in Pressure Gradients

If all gradients in Eq. (5.6) vanish except v p, the particle fluxes in

(5.1) are given by

Fi E{k=1, ••• ,n) Lik Vk vp

(5. 20 )
- Veffi Ci Bi vp,

where Veffi is the effective transport volume of component i, of the order

of one atomic volume. In solids Veff is approximately the partial molar
volume (relaxation volume in the case of a vacancy or an interstitial)
100

[5.13 J. The effect shoul d be al ways present in experiments on the ground,

but it is normally small, except for experiments in a centrifuge. In an
acceleration field g we have

'Vp = pg ,P (ENiMi)/(ENiVi) (5.21)

where P is the density.

Transport by Gravity

The gravitational acceleration g (or any other acceleration) directly

enters the equations as an external force

Fi = Mi g, (5.22 )

where Mi is the mass of the moving particle. But normally there is also a
pressure gradient in an acceleration field, which according to (5.21) and
(5.20) contributes to the force at the particle. Using Veffi=Vi, from the
equations above we get

Ji = Ci Bi (Mi/Vi -P ) Vi g, (5.23)

which means that components with higher density than the mean are drifting
in the direction of g, the others in the opposite direction.

5.1.4 Influence of Gravity on Transport Processes

The preceeding relations show that the only way by which gravity directly
enters the phenomenological equations (5.1) is by gravitational transport
Eq. (5.22) and (5.23). The magnitude of , this term will usually be small.
Hence, a significant influence of gravit~ is only possible through a change
of the diffusion coefficients or similar quantities with g. But no informa-
tion about the extent of such an influence can be drawn from (5.1). This
can only be done from theories involving the diffusion mechanism (see
Sect. 5.3).
 101

5.2 Diffusion and Transport in Simple Systems

To simplify notations while discussing gross features, the following dis-

cussions will be limited to two component systems, which is the most impor-
tant case in diffusion experiments. In this case, the total particle con-
centration Co is

(5.24)

Hence, if we take V1, V2 constant as a first approximation:

(5.25 )

i.e. there is only one independent concentration gradient.

5.2.1 Reference Systems

Common Reference Systems

The phenomenological equations (5.1) are normally derived in the center of

mass system CMS. Here a relation for mass fluxes holds:

E (i=l, ••• ,n) Mi Ji = 0 (5.26)

Thus the fluxes are not independent [5.9]-lS.1l], [5.7]. There are n rela-
tions between the Lik:

E (k=l, ••• ,n) Lik Mk = 0 (5.27)

For n=2 this yields

(5.28 )

Therefore

(5.29)
102

(5.30)

(5.31)

In experiments on liquid diffusion where the shape of the liquid is fixed

by a capillary, the diffusion is measured relative to the "center of volume
system CVS", which is defined by

(5.32)

Vi Ji are the volume fluxes. Then, if we denote the corresponding Lik by

"Lvik and Di by "Dvi":

. (5.33)

(5.34 )

Obviously the mole fluxes Jvi in CVS are not equal in general and are dif-
ferent from those in CMS.

If Vl=V2 then (5.32) is equivalent to the definition of the "center of par-

ticles system CPS", often used in solids

(5.35)

In this case, if we denote the corresponding Lik by "Lpiko Di by "Dpi":

(5.36)

and Lpll = Lp22 (in CPS). (5.37)

Theoretical considerations in crystalline solids mostly refer to the "lat-

tice system LS", which is a local system 1 ike CMS but with the origin and
 103

the axes fixed to the local lattice. In an experiment, indentation markers

are often used to fix these systems at different locations. The "partial
diffusion coefficients" for example are measured in this system. Unfortu-
nately, there is no equivalent system in liquids, except in the quasi cry-
stalline model (see 5.3.2) where it could perhaps be possible to define
such a system. Since in a system like LS restrictions of type (5.27);
(5.32) and (5.35) do not exi st, there are two independent diffusion
coefficients in LS compared to only one in CMS, CVS, CPS. It is still an
open questi on, whether diffusi on in 1 i qui ds cannot be descri bed by two
independent diffusion coefficients [5.14J. The problem could perhaps be
sol ved by defi ni ng an "envi ronment system ES", fi xed to a "mean surroun-
ding" of the migration particle (atom), as an equivalent to the lattice in
a solid. Such a system has to be definitely different from CMS, which of
course also represents a type of surrounding of the migration atom. The ex-
perimental problem is how to realize such a coordinate system. For efforts
to solve this question compare Chapter 17.

Transformation between Reference Systems

If the description of diffusion and transport processes is to be changed

from a coordinate system a to another b, where a is moving with a velocity
v relative to b, the forces and fluxes for component i in the two systems
are rel ated by

(5.38)

The transformation of diffusion coefficients and other parameters is then

to be derived from the definitions of the systems. For example, if a is the
environment system ES and b=CVS, then from (5.32) we get

(5.39 )

(5.40 )

i.e. there is only one diffusion coefficient in CVS, which is called

"interdiffusion coefficient D12" of components 1, 2 and normally measured
in interdiffusion experiments. In the case of solids, ES is identical with
LS, so l5.40) gives the velocity of marker movement (LS) relative to CVS.
104

This velocity corresponds to the drift of vacancies in the lattice as a

consequence of different partial diffusion coefficients and is known to
produce the "Kirkendall effect". Again, in the picture of the "quasi-cry-
stalline model", (see 5.3.2), a Kirkendall effect might exist in liquids,
too. Of course, the typical void production, which sometimes is observed in
solids, will not appear in liquids. Equation (5.40) clearly demonstra,tes
that the existence of a Kirkendall effect in liquids again depends upon the
existence of an environment system ES with two different diffusion coeffi-
cients.

Since CMS, LS and ES are local systems, i.e. their validity is restricted
to the location where they are defined, such systems are unsuitable for a
description of the diffusion process by the continuity equation (Fick's
second 1aw) :

IJ· Jfi + a Ci/at = Si (5.41)

where Si is the source of particles of type i, cOllJ1lonly zero. Hence an "end

face system FS" is used, fixed to one end of the sample. Here Jfi is the
flux relative to FS and the solution of the differential equation (5.41) is
related to the corresponding diffusion coefficient Dfi in FS. Consequently,
the analysis of concentration profiles yields diffusion coefficients Dfi'
which then have to be transformed to the desired system, say CMS. As poin-
ted out above, CVS usually is equivalent to FS, at least in most liquid
diffusion experiments. Sometimes another definition of FS is more suitable,
as e.g. in the case of the Boltzmann-Matano method (see 5.2.3).

Accordi ng to (5.38) true transport forces remai n unchanged when changing

the coordinate system. But since Bi changes with Di' Eq. (5.15), the trans-
port contributions to Ji have to be transformed by the same procedure.

5.2.2 Simple Solutions of the Continuity E~uation

Most experiments on diffusion are arranged to allow only one-dimensional

diffusion (along, say, the x-axis). In the case of selfdiffusion and dilute
solute diffusion, moreover the diffusion coefficient will be constant. Then
the most frequently used "thin layer" diffusion in hal f-space or double
half-space samples (see fig. 5.1a,b)
 105

20
H
I~
,.
X x
Fig. 5.1a: Half-space sample, Fig. 5.1b: Double half-space sample
layer at x = 0 layer at x = o.

will be described by the following solution of (5.41) (5.25):

Ci (x,t) = (Coi d/'; 1[ Dfi t ) exp (- x2/4 Dfi t) (5.42 )

where Coi is the initial concentration in the layer and t diffusion time. d
is the (small) layer thickness in the case of Fig. 5.1a and half the thick-
ness in the case of Fig. 5.1b. With transport forces in the double half-
space sample, the whole concentration profile of (5.42) is drifting with a
velocity v according to (5.14), since (5.41) has the form

(a/ax)(Dfi (aCi/ax) + Ci v) + aCi/at = 0 (5.43)

and can be transformed to the type without transport terms by the transfor-
mation x'=x-v t, t'=t, provided v= const.

Transport experiments are often carried to steady state conditions. The

time required can be estimated from

(5.44)

L is the length of the diffusion or transport zone [5.7J.

Interdiffusion experiments are commonly done with a double half-space

sample, the halves beeing different alloys. Then, in the case of constant
Dfi=D12, the profile is given by
106

Ci(x,t} = Ci(+oo,O} + (Ci(-oo,O}-Ci(+oo,O» erfc(x//4 D12 t}/K (S.4S)

with K=2. The same formula, but with K=l, represents the solution for
Ci(O,t}=C(-oo,O}=const. (constant concentration at x=O). In the case of con-
centration dependent 012, the Boltzmann-Matano method must be applied (see
S.2.3 and [S.lS]).

Equations (S.42) and (S.4S) only apply if the diffusion zone has not yet
touched the ends of the sample. Otherwise, instead of (S.4S) with K=l,
C1(O,t)=Cib and Cic=Ci(+oo,O}, L length of sample,

(4/1T) l:(n=O ••• oo} sin «2n+1) 1Tx/2L} exp (-(2n+1) q} (S.46 )

with q = ,f. ° t/4L2

or for the mean concentration Cmi in the sample

(S.47)
(8/,f.) l: (n=O ••• oo) exp (-(2n+1) ;. ° t/4L2}
S.2.3 The Boltzmann-Matano Method

If in a diffusion experiment the boundary conditions can be expressed in

terms of a variable u=x/It, then the solution of the continuity equation is
only a function of u. The diffusion coefficient 012, even if it is a func-
tion of the concentration Ci' may be deduced from Ci(X} by

Ci
012(Ci} - (1/2t) (dx/dCi) f x dC~ (S. 48)
Cia

provided dCi/dx=O for Ci=Cia, i.e. far away from the diffusion zone
[S.lSJ. For a typical 1 iquid interdiffusion experiment in a capillary with
the double hal f-space sample as just described, the above conditions
apply. Then Cia is the concentration at the sample end with x=-L/2, Cib
 107

that at the end with x=L/2. It is very important to use equations (5.46)
only in a coordinate system where the origin is defined by

Cib
f x dCi = 0 (5.49)
Cia

which, in the case of liquid diffusion, usually should be equivalent to FS

and CVS. Hence the measured diffusion coefficient is identical with D12·

The Boltzmann-Matano method is also applicable to the boundary condition

Ci(O,t)=const=Cia and Ci(x,O)=Cib, where of course (5.49) is not valid and
not necessary, since the boundary at x=O must be known.

5.2.4 Experimental Methods and Problems

Experimental Methods

The experimental liquid d i f f u s ion techniques may be characte-

rized by the boundary conditions established in the experiment, and perhaps
additionally by a special type of technique. Three methods have mainly been
employed in the past decades [5.16J. In all cases vertical capillaries are
used with a small temperature gradient of about 0.1 deg/cm directed upwards
to minimize thermal convection.

The "capi 11 ary-reservoi r techni que" has been most extens ivel y used. Here a
vertical capillary, some cm in length and about 0.5 to 2 mm in diameter, is
filled with material of composition c (fig. 5.2). The bath will be modera-
tely stirred to guarantee composition b at the upper end (x=O) of the capi-
llary. Composition c typically represents pure component 1 with a tracer 1*
for selfdiffusion, tracer 2 for solute diffusion, or an alloy 1/2 for in-
terdiffusion. Composition b then consists of pure 1 for self- and solute-
diffusion and another alloy 1/2 for interdiffusion. If C2 (or C1 respec-
tively) is the component diffusing out of the capillary, then C2 at the
upper end is kept at the constant concentration C2b of the bath. The diffu-
sion coefficient has to be calculated from the mean value Cm2(t) of C2(x,t)
in the capillary by using (5.47), or from the concentration profile C2(X,t)
by using (5.46), in an iterative procedure. Equation (5.45) with Ci(_oo )=
C2b, Ci(+oo)=C2c=C2(x,0) and K=l may be used instead of (5.46), if the dif-
108

fusion zone has not yet touched the lower end of the sample. In all cases
D2 must be constant. If D2 varies with C2, the Boltzmann-Matano method is
appl icable too, but because of the "end effect", it is difficult to define
the Matano-interface (x=O), since (5.49) is not valid in this case. A prob-
lem is the convection in the upper part of the capillary. The accuracy has
been reported to be no better than 10% [5.16J, even in the best experi-
ments.

Coi. ((-co)

Fig. 5.2 Fig. 5.3a Fig. 5.3b Fig. 5.4

The "long capillary technique" [5.16J avoids most of the problems mentioned
above by using a long (5-20 cm) vertical capill ary, where the diffusing
component 2 (or 1*) will be placed as a thin layer at one of the ends of
the sample (at the lower end if of higher density, fig. 5.3a) for self- or
solute-diffusion. The upper and lower halves of the capillary are filled
with different compositions 1/2 for interdiffusion experiments (fig.
5.3b). The constant diffusion coefficient can be calculated from the con-
centration profile by using (5.42) or (5.45), respectively. Concentration
dependent D-values can be obtained by applying the Boltzmann-Matano method
to the configuration shown in fig. 5.3b. The long capillary technique gives
results of higher accuracy, but there al'e still flow problems resulting
from thermal expansion and the vol ume change at the melting point, when
heating up and cooling down the sample.

The "shear cell technique" tries to reduce convection anslng from volume
changes by dividing the capillary into several sections (5 ... 50 "discs"),
which, at the end of the experiment but still in the 1 iquid state, are
 109

sheared agai nst each other to cut the sampl e before cool i ng down [5.16],
(fig. 5.4). There are, of course, strong convections from shearing, but
their effect is 1imited to neighbouring cell s. Hence it is necessary to
measure the mean concentration in each cell. Local methods of analysis and
thus the study of radial distributions or wall effects are not possible. On
the other hand, corrections for thermal expansion are not necessary. The
boundary condi ti ons may be the same as for the capi 11 ary-reservoi r tech-
nique or the long capillary technique. The shear cell technique yields the
best accuracy in ground based experiments (lowest error some %).

In spite of the improvements in the measurement techniques described above,

where errors and convective contributions to diffusion are reduced to a mi-
nimum, there is a remainder of influence from gravity-driven convection,
which cannot be eliminated completely in experiments on the ground. Hence
the onl y way to avoi d gravity- induced contri buti ons to the measured val ue
of the diffusion coefficient is to use the fairly new microgravity tech-
nique, first used by Ukanwa [5.17J in a Skylab flight and later in the
first Spacelab flight [5.18J. These and other experiments are described in
Chapter 17.

In t ran s p 0 r t experiments (on the ground) the experience of the

diffusion techniques is used with typical modifications [5.7]. For example,
in a "thermotransport experiment" the design of the capillary has to gua-
rantee vanishing radial heat flow from or to the sample. This is especially
important for the ends of the sample, where a well defined contact between
the heat source and the heat sink must be established. Since the tempera-
ture gradient is choosen upwards, it may happen that convection in an expe-
riment on the ground can not be avoided, if 02 of the havier component 2 is
negative, i.e. 2 is enriched at the hot end ([5.19J and section 17.4.1).
With the large temperature gradients applied free surfaces must be elimina-
ted to avoi d Marangoni -convect i on, whi ch even may occur from rough capi 1-
lary walls. It is very likely that in the past ,the importance of Marangoni-
convection has not been recognized in diffusio~ and especially in transport
experiments. This situation has changed as a result of diffusion research
in space.

In electrotransport experiments it is desirable to avoid any temperature

gradi ent along the sampl e axi s whi ch is diffi cult to real i ze. The results
must be corrected for thermotransport, which is not a serious difficulty.
110

Very restrictive problems arise from electroosmosis and magneto-hydrodyna-

mic stirring. Their contributions to the effective diffusion coefficient
are

(5.50 )

(5.51)

where je is the electric current density, dc the capillary diameter, Pe the

specific resistivity, aos the electroosmotic mobility, 0 the atomic diffu-
sion coefficient, n the viscosity, con the effective conicity of the capil-
lary and Kmhd=4.42·1Q10 A4 cm2 s4/g2 (see [5.7J). Hence, compared with
other wall effects contributing mainly at low diameters, there is only a
small intervall of dc val ues where measurements are possible, if any. The
capillary must be of insulating material and the internal surface very
smooth and of constant diameter. In an experiment on the ground, the trans-
port direction should be choosen to produce the higher density at the bot-
tom.

There are two methods used for transport experiments. With the "i nstati 0-
nary method" the transport parameter can be calculated from the transported
material, provided the mobility Bi of component i is known and, in the cen-
tral part of the sample (at x=O say), there is no concentration gradient in
the originally homogeneous liquid (Ci=Cio). Then from (5.41), (5.13),
(5.19)

xe
f (Ci - Cio) dx = Ji t with (5.52 )
o

Ji - Qi Ci Bi \if /T for thermotransport,

Ji zeffi e Ci Bi E for electrotransport.

X=xe defines the end of the sample, E is the electric field. Ji is taken at
x=O, i.e. Ci=Cio and VCi=O.

With the "stationary method", experiment time fitting (5.44), :lCi/at 0

and hence from (5.9), (5.41), (5.13), (5.19), if (5.15) is valid,
 111

Ji = - Di \lCi + Ci Bi Fi = 0, where (5.53 )

Ci = Ai exp (zeffi e U/kb T f Ti) (5.54)

Ci = Ai exp (Qi/kb T fTi) (5.55 )

for e1ectrotransport or thermotransport, respecti vel y. The constant Ai is

determined by

L
f Ci dx = Ci 0 L (5.56 )
o

where L is the length of the sample. In (5.54), T=const. is assumed, and in

all cases zeffi, Qi=const, which may be only a rough approximation. For
more detail s, especially in the case of self-transport, see [5.7J, [5.8],
[5.34J.

Influence of Macroconvection

As indicated, the main problem in the analysis of liquid diffusion experi-

ments on the ground arises from the fact that the total mixing process in
the 1iquid - interpreted as diffusion - is the sum of several contribu-
tions, and only one of these is the atomic diffusion process, described by
a diffusion coefficient D.

Another contribution is produced by gravity-driven convections as a result

of density gradients in the liquid, which normally originate from tempera-
ture gradi ents or concentrati on gradi ents. The spati a1 extension of the
corresponding convection modes is comparable to the size of the diffusion
cell and hence of macroscopic dimensions. The cpntribution to the total ef-
fective diffusion coefficient Deff from such lacroscopic convections will
be described by Dmac , but it is quite clear that Dmac may strongly depend
on the location within the diffusion cell and hence even on the method of
analysing the diffusion profile. With a local analysis - e.g. by an elec-
tron microprobe - the existence of contributions from macroconvections can
be detected from typical deformations of the isoconcentration lines, while
with the sectioning technique this information cannot be drawn from the
112

mean values of the diffusion coefficient at the cross-section of the cell.

If in a vertical capillary of diameter de there is a radial temperature
difference ~Tr between the axis and the capillary wall, then the mean value
of Dmac can be estimated from (5.21).

Dmac = 0.01 Yv pg de ~Tr/n (5.57)

withyv the volume expansion coefficient. The corresponding heat flj.lx per
em capillary is approximately

(5.58 )

where Ais the thermal conductivity. Using actual values for tin and dc =lmm,
Dmac =D/100, we find ~T r=lOm< and jq=20mW/cm, i.e. the condition of small
errors from Dmac is difficult to realize.

Of course experimenters try to minimize temperature gradients and to adjust

unavoidable density gradients close to the gravitational vector, but it
seems to be impossible (compare also 17.2) to eliminate them completely.
For example, during solidification or melting the heat of melting Hm must
be transported to the heat sink. As Hm is produced at the solidification
front in the sample, the temperature profile is strongly distorted towards
the capillary wall and the corresponding radial temperature difference ~ Tr
produces a mean contribution Dmac according to (5.57.). Dmac is reduced
with lower solidifi.cation times, but then ~Tr is enlarged. The product is
approximately constant and the contribution can be estimated from

(5.59)

with L the length of diffusion zone. For Sn and typical val ues dc =2mm,
L=lcm we get Dmac /D e ff=10%. For other melts with lower viscosity and lower
thermal conductivity Dmac may be even larger. Of course, (5.59) only re-
f
presents an order of magnitude estimate.! To lower the effect of Dmac ,
smaller dc-values may be choosen, but then wall effects interfere with the
measurements.
 113

Wall Effects

Since it has become good laboratory practice to use small capillaries in

liquid diffusion experiments, there has been a discussion about wall
effects, which - in analogy to surface and interface diffusion in solids -
exist and give rise to a lower or accelerated diffusion coefficient Dsfii
the immediate neighbourhood of the capillary wall [5.16J. The wall effect
is expected to have a typi ca 1 i nfl uence on the shape of the i soconcentra-
tion surface similar to the case of macroconvections or Marangoni-convec-
tion. According to ~.20J, the mean thickness dw of the special diffusion
zone near the wall is of the order of 0.01 ~m, but this depends on the type
of diffusion mechanism acting. According to experimental results, dw should
be in the order of dw=O.lmm, but the origin of this effect is not at all
clear. The mean contribution of the wall effect to Deff depends upon the
capillary diameter dc

Dwall = 4 dw (Os - D)/dc (5.60 )

If dc=lmm, dw=lmm, and we take Ds=O as an extreme case, Deff will be reduc~
ted by 40% compared to D.

Marangoni Effects

A contribution similar to the gravity-driven macroconvection arises from

the Marangoni-effect. By definition there is a shear stress at the free
surface of a liquid given by

+
't' = Vy (5.61)

where y is the surface energy of the liquid. The same equation holds for an
interface between two liquids, where y is the i~terface energy. As a conse-
quence there is a velocity gradient at the sur~ace or interface determined
by

(5.62 )

where na' nb are the viscosities and ~a, Vb the velocities of interfacing
liquids a and b, while ~ is the vector normal to the surface pointing from
114

a to b. Many investigators in the field of liquid diffusion have overlooked

or underestimated these effects in the past. Fortunately, in many experi-
ments free surfaces were absent, at least in the neighbourhood of the dif-
fusion zone (see e.g. capillary reservoir technique etc. [S.16J and chapter
17.2.1). The resulting macroscopic convections according to (S.62) are in-
dependent from the gravitational acceleration and hence also effective in
space experiments. With restrictions similar to those on Dmac , Marangoni-
contributions to Deff can be described by Dmar •

Two cases will be discussed here. If in a horizontal capillary the liquid

sample (length Ls) has free surfaces at both ends and there is a small tem-
perature gradient along the sample, then the whole liquid column moves (if
d( ycosB)/dT < 0) to the hot end with a velocity

Vc = (dc/8 Ls n ) t.(y cosB) (S.63)

where B is the contact angl e between the walland the 1i qu i d and t,( y cosB)
the difference of ycosB between the hot and the cold end. This yields a
contribution to Deff of approximately [S.21J

(S. 64 )

where Lc is the travel distance and td the diffusion time. For Sn with
Ls=SOnm, dc=lnm, Lc=Snm, td=SOOOS we get vc=2nm/s and Dmar =S.lO- Scm2/s,
i.e. of the order of D.

In a different case, the ends of the column may be in good contact with the
capillary wall, but a portion Ks of the lateral surface may be free. Then
there will be a flow with a mean velocity vm at that surface, and in the
opposite direction at the axis

vm = Ks t. yd c /8 Ls n (S. 6S)

where t.y is the difference of y-values between hot and cold end, correspon-
ding to a temperature (or concentration) difference t.Tc (t.C). For Sn with
dc=lnm, Ls=SOnm, Ks=O.S we get vm=lnm/s, which means total mixing in usual
diffusion times. For small values of Ks (good contact between capillary and
melt, smooth surface), a contribution to Deff has been estimated [S.21J
 115

(5.66 )

With the above values and D=2.10- 5cm2/s and Ks=O.Ol we get a contribution
Dmar=3.10- 5cm2/s, i.e. of the order of D. Hence Ks must be less than 0.001
to rule out Marangoni-c~nvections.

It seems to be widely accepted that a Marangoni-effect cannot appear at so-

lid surfaces, because the shear stress according to (5.61) will be compen-
sated by reaction forces from the wall. But assuming the interface energy
distributed over some atomic layers, shear stresses will also exist in the
vicinity of the wall and this will produce a flow of the liquid within some
atomic layers [5.22] .In contrast to the usual Marangoni-effect and the
corresponding law (5.61), this sec 0 n d 0 r de r Mar a n go n i -
e f f e c t is characterized by a certain velocity vo ' which appears very
close to the wall and will vary towards the interior of the liquid accor-
ding to the laws of hydrodynamics. From the principles above, the velocity
Vo has been calculated [5.22]:

Vo = (ay/aT) (do/n) (vT)s (5.67 )

with do the effective thickness of the liquid zone at the wall, where the
interface energy is distributed, and (vT)s the temperature gradient paral-
lel to the interface. For Sn with (v T)s=lK/cm and do=10- 7cm we get
vo=0.06mm/h. This is of course several orders of magnitude lower than the
velocities from the common Marangoni-forces and hence may indeed be neglec-
ted usually. But with respect to diffusion processes, which al so imply
small velocities, Vo may contribute considerably to the diffusion coeffi-
cient. With the figures above and 10h diffusion time (250 0 C), the liquid
will drift at the wall (and in the opposite direction at the axis) about
lmm, whil e the mean diffusi on di stance is about 15mm. In thermotransport
experiments, where much higher temperature gradients appear, the second or-
der Marangoni effect may be 1arger than the; dri ft due to the transport
force. For example, with aT/ax=lOOK/cm the drift distance amounts to lOcm,
which is often more than the capillary-length.

Accuracy and Representation of Diffusion Data

The problem of measurement accuracy in diffusion experiments has already

116

been discussed above. In ground experiments, the standard deviation ranges

from several % to several 100%, while in space experiments 0.5-1.5% appear
to be typical. Since there is no generally accepted theory of liquid diffu-
sion up to date, the different existing theories fit nearly all experimen-
tal data equally well or bad. Experimenters therefore mostly use a repre-
sentation of their data in the form of an Arrhenius-function, well known
from solid diffusion

D = Do exp(- Hd/kb T) (5.68 )

with Hd activation enthalpy of diffusion, Do preexponential factor and kb

the Bol tzmann constant. It is surpri sing that temperature dependences as
different as reported for the different theories in 5.3, should fit such a
simple function, but this is easily understood from the innaccuracy of the
data and the fact that in most cases data were only measured within rela-
tively small temperature regions (for a survey and specialized articles see
( [5.23J-[5.26J).

According to a recent analysis of self-diffusion data for Sn obtained in

space, a very accurate dependence of D'V T2 was found [5.27J, which favours
the fluctuation theory of Swalin

D = A Hv T2 (5.69)

where Hv is the enthalpy of evaporation and A a constant derived from the

interaction potential of the atoms ([5.28J and sec. 5.3.4).

5.3 Theories of Diffusion Processes in Liquids

5.3.1 Diffusion and Viscosity

An early theoretical approach relates the atomic diffusion coefficient D to

the viscosity n according to Stokes law

D = kb T/6 1T ra n (5.70)

with ra the radius of the diffusing atom. Several refinements have been in-
troduced in this formula, yielding an additional factor in the order of 1
[5.7J, [5.29J, [5.30J. This relation is of course only useful if the visco-
 117

sity is known.

5.3.2 Quasicrystalline Models

Stimulating results of pair-correlation analysis in liquids indicate that

at least some nearest neighbour shells of an atom in a liquid are arranged
similar to those in a solid. This led to the conclusion that atomic move-
ment in a liquid must overcome a potential barrier by thermal activation,
similar to the diffusion mechanism established in a solid [5.31J. Subse-
quent theori es therefore i ncl uded an equati on of type (5.70), [5.7 J. The
factor T in this equation makes it questionable whether D or n can be des-
cribed by a simple Arrhenius-equation (5.68).

5.3.3 Model of Critical Volume

The excess volume of a liquid compared to a solid is assumed to be

distributed uniformally. Allowing for fluctuations, there will be a certain
probability to concentrate the excess volume into a certain critical volume
Vc. Now a diffusive movement of a neighbouring particle is possible, a
process comparable to the vacancy movement in solids. In this model, which
is similar to the quasicrystalline model, the diffusion coefficient is
given by [5.7J, [5.31J

(5.71)

with gc a geometrical factor, vk the kinetic velocity of the particle, Vf

the free volume per atom and Yk a factor between .5 and 1. Since vk 'U IT
and Vf increases with T, the temperature dependence is somewhat different
to that predicted by the quasicrystalline model.

5.3.4 Fluctuation Theory

The basis of this theory is the same as for the model of critical volume,
but no critical value of excess volume is assumed to be necessary [5.28J.
Thus the particles can move without threshold by fl uctuations of the free
vol ume. Assuming elementary diffusion steps involving about 10 atoms, the
118

result of the theory is given by Eq. (5.69) with

(5.72)

and a the parameter in the exponent of the Morse potential function. An-
other form of Swalins formula is

D (3 Z2 kb2/96 h Hv a) T2
or (5.73)
D = (Z2 kb2/8 h Kf) T2

where Z is the coordination number in the liquid, h Planck's constant and

Kf the binding force constant between the atoms [5.7], [5.16J, [5.24J,
[5.28J. The values of D derived from the above equations fit relatively
well the experimental values except in some cases. The reason for these
discrepancies may be explained by experimental problems (convection contri-
butions included) and the uncertainty in the atomic force parameters. Accu-
rate self-diffusion experiments in space have recentl y given evi dence for
the T2 dependence [5.27J. It is interesting to note that, starting from a
similar basis, a D ~ T dependence has been derived [5.32J.

5.3.5 New Concepts and the Dynamic Structure of Liquids

Theories on liquid diffusion based on pure statistical physics were not so

successful so far and consequently are not discussed here. This is probably
due to the difficulty in describing the diffusion process within the frame-
work of autocorrelation functions, as diffusion occurs not only by the
movement of single atoms relative to their surrounding, but also by a col-
lective motion of larger atom assemblies. Computer simulations using large
numbers of atoms indicate long range movements additionally to movements on
the atomic scale. Starting from this the idea was born that the entity of
all particle movements in a liquid may be considered as a superposition of
ring vortices characterized by their radius Rv and the velocity ~a at their
axis. Hence there will be a distribution function for the number of
vortices [5.33J.

+ 3 +
dN = f(va, Rv) d (va) dR v (5.74 )
 119

within the intervals d3 (Va ), dR v• The corresponding lifetime being T (va,

Rv ), the elementary diffusion distance will be of the order of -la T and
thus

D = ff(fd/ 6) f(va,
-+
Rv) va2 T d3 (va
-+ )
dR v (5.75 )

where fd characterizes the correlation between particles in the vortex. The

problem is to define the type of distribution function, i.e. whether there
are only contributions from Rv-values of atomic order or also long-range
parts. If the latter is true, the wall effect is easily explained: near
the wall, the distribution function is cut off for Rv greater than the dis-
tance from the wall and hence Dis lowered. On the other hand, contribu-
tions from atomic sized Rv-values appear to be important, since in alloys
the selfdiffusion coefficients of the components may be very different.

In the picture of 1iquid diffusion given here, fl uctuations of density or

temperature on a microscopic or atomic scale could introduce "microconvec-
tions", driven by gravity. The vortices arising from these would have a
distribution function of their own, which will have to be added to that of
the diffusion process, but it woul d probably be impossible to distinguish
between the two contributions. Hence the "intrinsic diffusion coefficient",
measured in a ground experiment, would be the sum of an "atomistic diffu-
sion coefficient D" and a "microconvective gravity contribution Dg"

Dintr = D + Dg (5.76 )

No work on this problem is known to the author todate, but his own estimate
of the above effect using several models indicate a Dg far too small to be
detectable. Hence up to this moment no mechanism is known which could pro-
duce a significant contribution of microconvections. It is conceivable that
observed differences between results from ground and space experiments ori-
ginate from sources other than Dg•

5.3.6 Theories of Transport Processes in Liquids

Similar to the case of diffusion there are different theories for liquid
"electrotransport". In the quasicrystalline picture the formula derived for
solids applies [5.7J
120

zeffi = zi - za (aPe/aNi)/ Pe (5.77)

with zi the valency of atom i, za the mean valency in the 1iquid, and Pe
the specific resistivity. But there are problems to relate these values to
the measurable quantity zeff12 in CVS (see 5.2.1). Assuming all atoms in a
liquid in the activated state we obtain with tne molar volume V [5.7J

(5.78)

For "thermotransport" in 1 iquids a theoretical approach on the basis of

phonon scattering exists:

(5.79)

where 01, 02 are the scattering cross-sections for phonons, Vi, V2 the par-
tial molar volumes and Cs is the velocity of sound [5.7J. The problem here
is the knowledge of values for 01, 02.

Taking al so into account the contribution from scattering of electrons,

then for dilute component 1 and Vi = V2:

012 =AT + B T2 (5.80)

Here Pe has to be written as a function of the Fermi-energy EF [5.34J.

No theories exist for transport in a pressure gradient, while transport by

gravity can be described in a simple way, see Eq. (5.22).

5.3.7 Isotope Effect in Diffusion and Transport

I n the case of selfdiffusi on the mobil i ty of ali ght isotope shoul d be a

1ittl e greater than that of a heavy isotope, because of the difference in
the kinetic velocity. An isotope effect E therefore be defined as [5.7J
 121

(5.81)

where 1,2 refer to the different isotopes. In solids, E is known to give

information about the correlation factor, a quantity typical for the type
of diffusion mechanism acting. In liquids, a similar information may be ob-
tained [5.35J

E = p-1 (1 + p/q)-l , (5.82)

where p is the number of atoms migrating relative to a number q of atoms in

the elementary diffusion event. In the case p=l and q=l, E takes its maxi-
mum value of unity, which means "no collective motion". The only experi-
ments on the ground have been performed on Li [5.7J, because of the large
relative mass difference. The resulting E-value was close to unity, but the
data are somewhat questionable from the inherent inaccuracy of ground expe-
riments. The more accurate space experiments on Sn [5.27 J yiel ded E-val ues
between 0.4 and 0.7 at temperatures between 260 and 9000C. Quite reaso-
nable, this indicates some collective motion at lower temperatures, but re-
ducing at higher temperatures.

In transport experiments it is normally assumed that the observed differ-

ence in the transport fluxes originates from the different mobilities ac-
cording to (5.15). Different isotope masses should however have different
scattering cross sections for phonons and electrons, so the transport para-
meters Qi and zeffi should also differ. For more details see [5.7J, [5.8J.

5.4 Influence of Diffusion on Related Experiments

5.4.1 Solidification and Eutectic Alloys

Close to a moving solidification front in an alloy there are usually con-

centration gradients imposed by the partitiol1 coefficients at the boun-
dary. Under steady state conditions with constaht velocity Vs of the moving
boundary and constant temperature gradient, the concentration profile of a
component i at the liquid side can be expressed as a function of the dis-
tance x from the boundary [5.36J

C(x) = Co (1 + ko (1 - ko)exp(- vs x/Deff» (5.83)

122

with Co the concentration in the liquid reservoir, and ko the partition

coefficient, all parameters of course depending on i. The thickness of the
diffusion zone is ds=Defflvs (fig. 5.5). With macroconvection present, a
considerable part of the diffusion zone may be swept away. Hence the
concentration steadily rises in the liquid and is always lower in the
solid, so no steady state will be reached. If microconvections appear near
the boundary as a result of the concentration gradients and perhaps
nonvertical temperature gradients, these may raise Deff by the amount
Dmico Hence in solidification on the ground

Deff(9) = D + Dwall + Dmic + Dg (5.84 )

while in space we have (see 5.2.4 and 5.3.5)

(5.85 )

First experiments in space have verified relation (5.85). Deff(9) was found
about 10% (Zn/550 0 C, Sn/260 0 C) to 60% (Sn/800 0 C) higher than Deff(O)
[5.17J, [5.18J. Thus the diffusion zone ds is smaller in a space experi-
ment, steady state conditi ons provi ded. Thi s may have qual itati ve conse-
quences. If in solidification on the ground vT and Vs were choosen to avoid
undercooling, i.e.

(5.86 )

it may well happen that in space under the same thermal conditions (5.86)
will not hold for Deff(O) (fig. 5.5). Here ml is the slope aT/aN of the li-
quidus line in the phase diagram (N=molar fraction), V partial molar volume
and Vo the mean molar volume. If now the undercooling in the diffusion
front is too large (or not allowed by the liquid), the solidification front
is no longer stable.

With large macroconvections present, i.e. in the nonsteady state, the dif-
fusion profile is similar to (5.83) but with a smaller value ds ' because ds
is now limited by convections. Using (5.83) as an approximation this can be
described by a lower D eff (g), if the convections result from gravity.
I

Hence, compared with the same experiment in space, we may have in contrast
to (5.85):
 123

c(x)
Cl

,
a.
ISd
Jd
b
Co - - - - "'\.- - - - Q...
'<' Cliqu.
b
solid liquid \. 'K
\.
, Q.

Fi g. 5.5: Solidification Fig. 5.6: Dendritic growth Fig. 5.7: Lamellar

eutectic

D' eff(g) < D' eff(O) • (5.87)

In the case of dendritic solidification upon constitutional supercooling a

remarkable feature is the spacing Sd of the dendritic tips. There is as yet
no satisfactory quantitative theory describing the spacing off the eutectic
point, but we may use here the formulas derived for eutectics, where the
situation is quite similar, fig. 5.6 [5.36J. Here Sd'V .; Defffvs, so we con-
clude that Sd in a space experiment is lower than in a ground experiment,
provided (5.85) is valid (near steady state). In the case of (5.86) the
contrary may be true.

For eutectic alloys, as mentioned, the following relation has been derived
for the periodic distance of the lamellae (fig. 5.7)

(5.88)

crab is the interface energy between phases a anp b, Te , Ce eutectic tempe-

rature and concentrati on, and Hm heat of mel ting [5. 36J. The structure
therefore is finer in space than on ground, near-steady-state conditions
provided. This has clearly been demonstrated in space experiment [~.37J, on
an InSn/Ni Sb eutectic at 500 0 C, from which we concl ude 0eff(O) about 15%
smaller than Deff(9), in good agreement with the other findings. An oppo-
site result of a space experiment on A13Ni/Al [5.38J indicates strong con-
124

vections in the corresponding ground experiment.

5.4.2 Ostwald-Ripening

Assume a melt consists of two immiscible liquids a and b with different,

compositions of components 1 and 2, and phase b is in the form of small
droplets with different diameters. Then the larger droplets will grow on
cost of the smaller ones. The largest droplet will grow approximately ac-
cording to

(5.89 )

where Cl o and C20 are concentrations in a [5.39J. The diffusion coefficient

determines the speed of growth, i.e. the ripening process is expected to be
slower in space than on the ground. However, the effect of gravity on the
process will be much larger than expected from the discussed changes in
Deff. Equation (5.89) assumes, droplets not moving against each other,
which may be true in space (if there are no Marangoni-forces), but normally
not on the ground, because of the different densities of the phases [5.6J.

5.4.3 Separation of Immiscible Liquids

Cooling a melt with immiscibility gap from the homogenous region into the
gap, droplets of phase b appearing in a will grow according to

R(t) = Kr 1Deff t (5.90 )

where Kr is determined by the ratio of concentration differences in a and b

[5.40J. Again the same argument holds as in the preceding section: the
growth velocity is expected smaller in space, but a larger effect arises
from the difference in segregation dynami cs. Si nce coagu1 ati on has been
shown to take place also in space, a reasonable explanation invokes Maran-
gon; - forces, whi ch may be active because of concentrat; on grad; ents and
temperature gradi ents along the interfaces (see [5.6 J).
 125

5.4.4 Crystallization

There are three interesting features in the process of crystall i zation :

the growth velocity. the maximum size. and the quality of the crystal pro-
duced. In many cases quality and size are correlated. because the density
of defects built in during crystallization determines the quality. but also
determines long-range order and such the growth limitation of a single cry-
stal. Defects may be created by built in foreign molecules (or atoms) and
the related distorsions of the crystal. Especially in the case of an inho-
mogeneous distribution of built in impurity atoms. the lattice distorsions
may be large. This usually arises from convection. while diffusion zones
without convection are smooth and hence the distribution of impurity mole-
cules is more homogeneous. Impurities may hinder crystallization also by
adsorpti on on terraces. si nce crysta 11 i zat i on often is a comp1 i cated pro-
cess of coupled diffusion mechanism. In a first step the molecule is adsor-
bed on a terrace, then it diffuses along the terrace to a ledge andfina11y
along the ledge to a kink. where it contributes to the growth. If anywhere
on this way the admo1ecule is hindered to migrate, the growth velocity
slows down. This enlarges the chance to develop more new nuclei, i.e. more
but smaller crystal s will grow. Larger molecules may themsleves produce
distortions of the crystal. In the ordering process at the surface. there
are often several ways of sticking with only small differences in stacking
energy. Hence the molecule needs a quiet surrounding to find the lowest
energy position, which again may be hindered by convections. The influence
of convection on the growth velocity is not so easy to understand. In a
space experiment it was shown that protein crystals grow 30 ••• 1000 times
larger in space than on the ground and the growth velocity was also en-
hanced considerably [5.41J. In the case of such large molecules it is sus-
pected that a preformation of structured molecule assemblies ahead of the
sol idification front enhance crystal growth. but only if these are not
broken up by convections. For further experiments see [5.6J.

5.5 Conclusions

Gravity was shown to have a significant influence on diffusion processes in

liquids and hence all diffusion controlled mechanisms in melts are influen-
ced by gravity. Our present experimental knowledge about diffusion in space
is limited, but early results indicate that diffusion processes are gene-
126

rally about 10 to 50% slower in space. Neither the atomic diffusion mecha-
nism, even if extended to somewhat larger collective motions, nor macrocon-
vections as from buoyancy or Marangoni-forces may be the origin, although
the latter are often present, but not counted among the diffusion proces-
ses. It is s~pposed that there are contributions to the diffusion process
on a microconvective scale, present in space as well as on the ground,
which are strongly influenced by gravity, but the mechanism is not at all
clear up to now.

5.6 References
[5.1] Adda, Y.; Phil ibert, J,; "La diffusi on dans 1es sol ides"
Presses Universitaires, Paris, 1966
[5.2J Manning, J.R.; "Diffusion Kinetics for Atoms in Crystals"
Van Nostrand, Princeton, New Jersey, 1968
[5.3J Jost, W.; "Diffusion in Solids, Liquids,Gases"
Academic Press, New York, 1960
[5.4J Aaronson, H.I.; "Diffusion". American Society for Metals, Metals
Park, Ohio, 1973
[5.5J Sherwood, J.N.; Chadwick, A.V.; Muir, W.M.; Swinton, F.L.;
"Diffusi on Processes". Gordon and Breach, London, 1971
[5.6J ESA; "Results of SPACELAB-1". 5th Europ. Symp. on Material Science
under Microgravity, E1mau 1984. ESA, Paris, 1984
[5.7] Wever, H.; Frohberg, G.; Adam, P.; "E1ektro- und Thermotransport in
r4etallen". Joh. Ambrosius Barth, Leipzig, 1973
[5.8J Pratt, J.N.; Se110rs, R.G.R.; "E1ectrotransport in Metals and
Alloys", Trans. Tech., Riehen, 1973
[5.9J De Groot, S.R.; "Thermodynamics of Irreversible Processes"
North-Holland Publishing, Amsterdam, 1963
[5.10J Haase, R.; "Thermodynamik der i rreversi b1en Prozesse"
Steinkopff Verlag, Darmstadt, 1963
[5.11J Knof, H.; "Thermodynamics of Irreversible Processes in Liquids"
Vieweg Verlag, Braunschweig, 1966(;
[5.12] N.N.; "Diffusion Data" (Journal). Trans. Tech., Aedermannsdorf
[5.13J Frohberg, G.; phys. stat. sol. (b) 48, 243 (1971)
[5.14] Alexander, K.F.; Physica XXI, 446 (1955)
[5.15J Crank, J.; "Mathematics of Diffusion". Clarendon Press, Oxford, 1956
 127

[5.16] Nachtrieb, N.H.; "Selfdiffusion in Liquid Metal s" in Proc. Int.

Conf. on "Properties of Liquid Metal sU. Editors: Adams, Davies,
Epstein; Taylor &Francies, London, 1967
[5.17] Ukanwa, A.O.; M558, Proc. III. Space Processing Sym. Skylab Results
(1979), MFSC, Alabama, p. 427
[5.18] Frohberg, G.; Kraatz, K.H.; Wever, H.; "Selfdiffusion of Sn112 and
Sn124 in Liquid Tin" in "Results of SPACELAB-1" (see 5.6)
[5.19J Malmejac, Y.; Praizey, J.P.; "Thermomigration of Co in Liquid Tin"
in "Results of SPACELAB-1" (see 5.6)
[5.20] Fixman, M.; J. Chern. Phys. 29 (3), 540 (1958)
[5.21J Frohberg, G.; unpublished research in relation to 3.18
[5.22] Frohberg, G.; "Second Order Marangoni Effect", to be published
[5.23] Lodding, A.; Lagerwall, T.; "Atomic Transport in Solids and
Liquids". Proc. Europhys. Conf. at Marstrand/Sweden, 1970. Verlag
Z. f. Naturforschung, Tubingen, 1971
[5.24] Adams, P.O.; Davies, H.A.; Epstein, S.G.; "The Properties of Liquid
Metals". Taylor &Francies, London, 1967
[5.25J Evans, R.; Greenwood, D.A.; "Liquid Metals, 1976". Inst. of Physics,
Bri stol, 1977
[5.26] Shimoji, M.; "Liquid Metals". Academic Press. London, 1977
[5.27J Kraatz, K.H.; Frohberg, G.; Wever, H.; "Selbstdiffusion von Snl12
und Sn124 in schmelzflussigem Sn". Contribution at the Conference
of "Deutsche Gesell schaft fur Metall kunde", Stuttgart, 1985
[5.28] Swalin, R.A.; Acta Met. 7, 736 (1959)
[5.29] Walls, H.A.; Upthegrove, W.R.; Acta Met. 12, 461 (1964)
[5.30] Edwards, J.B.; Hucke, E.E.; Martin, J.J.; Met. Rev. 13, 1 (1968)
and Met. Rev. 13, 13 (1968)
[5.31J Eyring, H.; Ree, T.; Proc. US Nat. Acad. Sci. 47, 526 (1961)
[5.32] Reynik, R.J.; Trans. Met. Soc. AIME 245, 75 (1969)
[5.33J Frohberg, G.; "Vortex Theory of Diffusion in Liquids", under in-
vestigation, to be published
[5.34] Balourdet, M.; "Contribution a 1 'etude des mechanismes de thermo-
diffusion dans les metaux et alliages liquides". Thesis, Universite
de Grenoble, 1976
[5.35J Klemm, A.; J. Chern. Phys. 60, 237 (1963)
[5.36J Chalmers, B.; "Principles of Solidification". John Wiley & Sons,
New York, 1964
128

[5.37] Muller, G.; Kyr, P.; "Directional Solidification of InSb-NiSb

Eutectic" in "Results of SPACELAB-1" (see 5.6)
[5.38] Favier, J.J.; de Goer, J.; "Directional Solidification of Eutictic
Alloys" in "Results of SPACELAB-1" (see 5.6)
[5.39] Wagner, C.; Z. Elektrochem. 65, 581 (1961)
[5.40] Langbein, D.; "Theoretische Untersuchungen zur Entmischung nicht
mischbarer Legierungen". BMFT-FG-W81-004
[5.41] Littke, J.; John, C.; "Protein Single Crystal Growth under Micro-
gravity" in "Results of SPACELA8-1" (see 5.6)
6 Capillarity and Wetting

J. M. HAYNES

SCrool of Chemistry,
university of Bristol,
Cantock's Close,
Bristol BSS ITS, England.

Interfacial phenc:.rrena, originating at boundaries between phases, have a

profound influence on the behaviour of matter. The excess of energy
associated with the existence of an interface gives rise to the force of
surface tension, which results in a general tendency for conterminous
phases to adjust the areas of their ccmron boundaries, either to a
rnin:imJrn or to a rraximum, the first representing stable hydrostatic
equilibrium, and the second unstable. Extremization of this excess
energy may also lead to a redistribution of material CC>IIpOnents in the
inrrediate vicinity of an interface - the phenarenon of adsorption. The
curvature of interfaces imposes a IlEchanical equilibrium condition which
implies, in turn, an influence on the chemical potential of material
CC>IIpOnents in the system. Here again, equilibria may be stable or
unstable. In systems involving active material transport,
nan-equilibriurn (i1enanena can be of major interest.

Terrestrially, such surface-controlled phenomena are usually in

competition with the action of gravity, and equilibrium requires some
carpound minimization of the two effects. Ccmronplace exarrples are the
familiar shapes of pendent liquid drops suspended from a solid surface
(Fig. 16.1), and the stability limit - reached when gravity overcomes
surface tension which produces the IlEtronanic regularity of a
dripping tap.

In the absence of gravity, surface phenarnena becane dominant: not only

do taps not drip, but suspensions do not sediment, and gradients of
surface tension can drive significant fluid HCMS which, on Earth, may be
imperceptible. The consequences for materials sciences in space - and,
indeed, for everyday matters of practical life in space can be
profound and (despite the simplification reSUlting from elimination of
gravity) sometiIlEs surprising.

The relative magnitudes of capillary and gravity forces are expressed in

diItEnsionless form by the Bcod 11llIliJer:
/!3
Bo " cr d to t1f (6 .1 )
130

where ~ and A! are, respectively, the interfacial tension and density

difference between adjoining fluid phases, S is the gravitational
acceleration and d a characteristic length of the system. Evidently,
the Bond number can be maximized not ooly by reducing g but also by
reducing Af (Plateau's method) or by reducing cl (study of small
systens) • Thus, there are alternative nethods of studying systens in
which gravity forces are negligible, though for practical reasons they
are not always applicable to problens of interest.

'!his chapter will review the structure of phase boundaries and the
resultant interfacial phenarena of relevance, and will discuss the
influence of gravity on interfacial equilibrium and stability, with
particular reference to space naterials processing.

6.1 Surfaces

In five of the six possible pairwise canbinations of solid, liquid and

vapour, two contenninous phases will share a cormon boundary or
interface. (Gases, being always miscible, cannot form interfaces between
one another.) Whereas a molecule within the bulk of such a phase
experiences a force resulting fram the presence of neighbouring molecules
which, when tine-averaged, is isot::ropic, this is no longer true in the
vicinity of the phase boundary. Here, the different chanical
constitution and ,density of natter characterizing the phase on the other
side of the boundary gives rise to an anisotropic field which produces,
on a scale carrnensurate with the range of intermolecular forces, a
locally non-uniform density of natter, of energy, and of entropy. Thus,
interfaces which appear visually to be perfectly sharp discontinuities
at the level of the wavelength of light have, in fact, a relatively
gradual and continuous transition at the molecular level. '!he molecular
organization within this non-uniform region - which is, of course, such
as to minimize the excess free energy associated with its existence
- is generally not well known. Attempts to calculate it, either by the
nethods of statistical mechanics or by Monte Carlo simulation, have
enjoyed rather limited success.

6.1.1 '!he Gibbs Model

A formalism developed by Gibbs [6.1] cirCUllllTents this difficulty. In the

Gibbs model (Fig. 6.1), each bulk phase is inagined to continue with
uniform densities of natter, energy and entropy right up to a cc:mron
boundary (the Gibbs dividing surface or GOO) at which the properties
change abruptly. The excesses (or deficits) qf matter, energy and
entropy possessed by the real system in ccrrparison with the model are
 131

GDS

x
Fig. 6.1 The Gibbs model of the interfacial region. )( is the local
density of an extensive property such as energy, entropy or material
concentration, and i
is a distance perpendicular to the interface. The
cross-hatched and dotted areas represent, respectively, positive and
negative contributions to the surface excess of X associated with the
given location of the GDS.

then attributed, as surface excess quantities, to this dividing surface.

Such an excess would be proportional to the difference between the shaded
areas in Fig 6.1.

The drawback of such a model is that the magnitudes of the surface excess
quantities ( and even their sign) depend criticall y on the precise
location of the GDS, which, being confined to a region of molecular
dimensions, is altogether beyond any possibility of experimental
accessibility. This difficulty is overcame by selecting a location for
the GDS which makes one of the surface excesses (usuall y the excess
density of the major carponent) equal to zero. The GDS now has a precise
(though unknown) location, and all the other surface excess quantities
are now defined with equal precision. It turns out that this is
sufficient to guarantee a perfectly self-consistent account of the
equilibrium thermodynamic and mechanical properties of interfaces [6.2].
It also transpires that such relative surface excesses are linked with
physically measurable properties like the sur~ace tension, through the
Gibbs equation [6.1, 6.2]:

: (6.2)

Here, a subscript 1 external to a bracket indicates a relative surface

132

excess quantity defined in terms of a GOS which makes the surface excess
concentration of ccnponent 1 equal to zero. s'" is the surface excess
entropy, and r; is the surface excess concentration of the i-th
component and r' its chanical potential, there being c components in
all. Particularizing the Gil::bs equation to the isothermal variation of
surface tension with catp:>sition in a perfect two-component solution,

(6.3)

shCMing that the quantity (r2.)1 is m:Xiel-independent, since it can be

evaluated from experiment.

It can also be shCMn [6.2] that the surface excess of free energy per
f
unit area of interface, tl'" , is given by:

= (6.4)

The second term on the right is generally non-zero in any system of more
than one component, whatever the choice of GOS. It is therefore
incorrect (except for pure liquids at equilibrium) to identify the
surface tension with the surface free energy per unit area, despite the
fact that the two quantities are diJrensionally equivalent. Moreover,
another surface energy can be defined as the change in total energy U
of the system as the interfacial area A is changed at constant
temperature T and total volume V. It can be shown [6.3] that

(~) :; ~(do-) (6.5)

d ,
Tv 'OT VA
I

Evidently, the term "surface energy" must be used with caution if

ambiguity is to be avoided.

Surface tension, on the other hand, defined as the force necessary to

extend a surface by unit area, is a pUltely experimental quantity, though
in practice its determination may be hampered not only by errors of
neasurerent of the usual kind, but in sane cases by whether the extension
is perforrred as an equilibrium operation (Le. constant density of
rnolecules in the surface) or not (Le. analogous to the stretching of a
rubber membrane). This distinction will be referred to again later.
 133

6.1.2 Determination of Surface Tension

M:thods of rreasuring surface tension of liquids may be classified in

various ways, according to whether they are static, quasi-static or
dynamic, according to the extent to which they are independent of contact
angle, and according to whether they are, in principle, exact c:>r
empirical. Table 6.1 classifies several oc:mnon methods in this way:
the listing is not exhaustive, and anits methods of mainly historical
interest. There are also several variants \\'Ort:hy of mention: the
Wilhelmy plate method can be modified to include measurenent of the
surface tension force on semi-subrerged bodies ofaxisynuetric shape (in
which case the S1lElll empirical correction for edge effects on a
rectangular plate becares unnecessary), and ring detachment methods can
also be extended to bodies of other shapes. The Langrruir trough is used
exclusively in studies of insoluble m::>nolayers on liquid surfaces. In
the three quasi-static methods, the rate of strain of the surface is, to
sorre extent, under exper:inental control, though they are not always
well-suited to dynamic surface tension studies.

M:thod A B C

Capillary rise s cos ex

Sessile/pendent drop shape s none ex
Drop weight qs emp
Drop volume qs emp
wilhelmy plate s cos (ex)
Ring detachment qs slight emp
langrruir trough s none ex
Spinning drop s none ex
Oscillating jet d none ex
Capillary waves d none ex

In column A, the letters s, qs and d indicate whether the

rreasurernent is static, quasi-static or dynamic. Column B
describes the contact-angle dependence of the method
concerned, and in column C, ex and emp distinguish methods
that are exact fran th<;>se r~ring empirical corrections.
The indication (ex) sigmfies that a S1lElll empirical
correction may be necessary.

Table 6.1 Classification of methods of measuring surface tension

It is interesting to note that alm::>st all of the methods involve directly

a balance between capillary and gravitational forces, and therefore
134

hecare inapplicable as the Born number terns to large values. This not
only makes it difficult to rreasure surface tension in microgravity, but
also raises severe obstacles to the terrestrial measurement of
interfacial tension between liquids of very similar density.

Exper:i.nental details of the methods listed in Table 6.1 and a discussion

of the principles involved will be found elsewhere [6.4]. Same typical
values of surface and interfacial tensions are given in Table 6.2. It
should be emphasized that these data relate to rigorously clean systems.
The phenorrenon of adsorption, whereby trace quantities of surface-active
irrpurities can produce a dramatic reduction of surface tension, is in
practice one of the principal i.rrpediments to the establishment of
accurate data.

Substance liq/vapour liq/water

Water 72.75
Benzene 28.88 35.00
Hexadecane 27.46 53.77
Dodecane 25.44 52.90
Octane 21.69 51.68
Mercury 476 375
NaNO 117
RbNO 105
CsNO 97

Table 6.2 Values of surface and interfacial tension. (Data for fused
salts at 623K; others at 293K)

6.1.3 Surface Tension and Other Properties

The surface tension of pure liquids always decreases with increasing

terrperature, indicating a positive surface excess entropy. The sane is
usually (but not universally) true for liquid/liquid interfacial
tensions.
The value tends ultimately to zero as a critical point (or in the case of
rrulticatp:)nent systems a consolute temperature) is approached, and
several cammon empirical expressions for the variation with temperature
are of the form

(6.6)

where T(. is the critical tarperature.

 135

For example, the expression

= (6.7)

(where "'A. 'and "'3 a~e molar volumes of liquid and gas respectively)
represents the surface tension of many camon liquids Oller a wide
terperature range, with the constant ~ having a value of about 2.1 x 107
J K -I An alternative approach based on the principle of
corresponding states, yields:

: 4-4 )( 10
-7 -~(l
Tc. "'"c.
--T)'y', (6.8)
1;

\'rl.th t1' in N m-I and '1Ft.. in ml mole _I. Experimental data for various
substances are plotted according to E!q9ation (6.8) in Fig. 6.2. The
correlation is only moderately good for ,-~. < 0.8.

The parachor, P, defined as

p = 0' y* ~ ""L / (...,~ - '\1'~) (6.9)

we find that
Thus, differentiating Fqn. 6.,
is found empirically to be a temperature-independent quantity for many
substances. with respect to temperature,

1 d.o- -4oG-
a- ciT
= (6.10)

where ti is the volumetric coefficient of expansion of the liquid. In

Table 6.3, the quantity -(d,rr/tJ.T)/tl-q'
is given for various substances, and
is seen to lie fairly close to the expected value, with the notable
exception of water.

The parachor has additional usefulness in the! fact that it is additive,

in the sense that the constituent elements, bhemical groups and bonds of
a molecule have their own parachor equivalents, fran which, by summation,
the parachor of the whole molecule can be calculated. This enables the
surface tension of unknCMl'l materials to be predicted awroximately.

Far fran the critical point, the surface tensions of pure liquids are
relatively insensitive to the effects of pressure and (for radii above
about 5 nrn) of curvature. Close to the critical state these effects are
expected to become increasingly significant, as the ccrrpressibility and
136

1·0
+\ g 0
()
H:z.O
MeOH
e
+\g.
r~o

Q t;.H",

• Nz.o

Q >< Xe
e
+ ~j.j"
%
0
0
0
0
() 0
1·0 ()0
~ ()
crv.. . 10'1
()
I..

Fig.b.2. Experimental surface tension data plotted according to the

reduced equation (6.8) • The curve! represents the theoretical
prediction. Sources of data: critical tenperatures and volumes fran'
International Critical Tables; surface tensions from the sarre source,
except for ethane and nitrous oxide [A.J. Leadbetter, D. J. Taylor and B.
Vincent, Canadian Journal of Chemistry 42, 2930 (1964)], and xenon
[A.J. Leadl::etter and H.E. Thanas, Trans. Faraday Soc. 61, 10 (1965)].
 137

the thickness of the interfacial region both increase. Elq:er.imental

data are, ha.7ever, extrenely sparse.

Substance T/K _{drr/tAT)/ot rr

Water 293 10.09
Methanol 293 3.35
Ethanol 293 4.39
BenZene 293 3.69
xenon 163 3.52
Ethane 150 4.08

Table 6.3 Relation between thennal coefficients of surface tension and

of volune expansion - test of Eqn. 6.10
6.2 Surface Tension of Solutions

'!he Gibbs equation, in the fann of Eqn. 6.3, shCMS that if a solute is
positively adsorbed at the solution/air interface then the surface
tension of the solution decreases with increasing solute concentration.
(The converse lehaviour is shown l:y aqueoos solutions of simple ionic
salts, which are negatively adsorbed and therefore increase the surface
tension. ) The nolecular constitution of a solute nay le such as to ' give
very strong adsorption, as with hydrocarbon chains with polar end-groups
(such as CH!(CH,)... N(CHsh +, CHl(CHl.)"SOJI in aqueous solution, or with
non-netals dissolved in netals. '!he resultant decrease in surface
tension at low concentration may le dramatic, and such solutes are said
to be surface active. Sate representative data are ShCMn in Fig. 6.2.

Surface activity usually arises fran cxmq:letition IEtween lyophilic

(i.e. tending to dissolve) and lyepholic behaviour in the solute
nolecule. If the solute and solvent actually reach a miscibility limit
at a particular concentration, then a second liquid phase may form. '!he
interfaces IEtween the two liquids and letween each of them and the
surrounding air may then adept the equilibrium configuration dictated by
Neumann's Triangle (see Eqn. 16.3). '!his i'iO the three-fluid analogue of
Young's equation (Eqn 6.14 belCM). HCMever,iif the condition

. (6.ll)

is net (where conp:>nent 3 is air), tren the second liquid will spread
spontaneously over the surface of the first. Even when this dces not
occur, the 1/3 interface nay contain a 1IalCIID1ecular layer of component
2. Such a monolayer behaves as a two-dinensional phase, olEying an
138

equation of state, and may show discontinuous phase transitions with

change of temperature or of concentration.

If a solute is relatively slowly-diffusing, its solutions may take an

appreciable time to reach their equilibrium surface tension. The
resultant time-dependent (or dynamic) surface tension, which can be
studied by several of the methods listed in Table 6.1, may l:e inportant
in Sale practical contexts, and can give rise to significant fluid
notions. For example, wb:!n a drop of l:enzene is placed on the surface of
water, the initial (dynamic) surface tensions at the three interfaces
ol:ey the inequality (6.11) alDve, and rapid spreading occurs. Later,
however, as mutual saturation occurs and the surface tensions approach
their equilibrium values, c:rjs falls l:elow the sum of D"j:z. and 0""u' and the
benzene retracts spontaneously to form a floating lens. Many similar
cases are known ~ the resulting macroscopic flows can l:e regarded as a
partiCUlar case of Marangoni convection (see Section 6.5.3 below, am
Chapter 16).

6.3 Surface Tension of Solids

Although solid materials may posses a surface tension according to the

thernodynamic definition
'dF""
( (6.12)
)A )TVI

it cannot be measured by the techniques nonnally applied to liquids, for

which a freely nobile surface is required. Indeed, the lack of surface
nobility in solids makes it extremely difficult to perform the operation
inplied q. the awe definition, in which the surface is extended at
constant atan-density in the interfacial region. In practice, such an
extension will more probably proceed at constant numlller of atans in the
surface - a situation more reminiscent of the pure dynamic surface
tension of liquids and will in any case induce bulk strain in the
solid as well. The same lack of mobility also implies that a solid
surface must quite often exist in a non~librium state.

The surface tension of the melt can be measured as a function of

temperature and extrapolated back to the solidification point but
this does not take account of the structural change accanpanying the
phase change, which \IIOuld l:e expected to affect the surface tension.
Methods have been devised based on the extension under load of thin
wires, aloove the Tanmmn temperature (~2.T,/3) at which sane degree of
nobility awears~ another method is based on measurements of dihedral
 139

angles between grain boundaries in alloys. The results cannot, however,

De taken with oonfidence.

Despite this, various facts point to the operation of a solid surface

tension and to its iIrportant consequences. For instance, crystals gra.m
slowly and under careful control often show a remarkable unifonnity of
habit, presumably in response to the so-called WUlff equilibrium
condition:

(6,13)

where O'i. is the surface tension of the i -th crystal face and t", its
perpendicular distance fran the centre of mass. (This corresponds to
the tendency of fluid interfaces to minimize their area, but the area of
each crystal face now bears a weighting inversely proportional to its
surface tension.) Again, the tendency of large crystals to grow at the
expense of snall ones (as in Ostwald ripening of precipitates) appears as
a oonsequence of the solid surface tensim, and the saretines dramatic
nodifications of crystal habit seen in the presence of surfactants
illustrate the sensitivity of solid surface tension to adsorption •.
Finally, the wettability of solids by liquids, a topic of encnrous
practical illlportance, involves solid surface tensions. 'Ibis is discussed
in the next section.

6.4 Wetting and spreading

An interface kletween two fluids nay be observed to neet an adjacent

sm:xlth solid surface in a characteristic angle of, , the contact angle
, which is characteristic of the three phases ooncerned.
A total energy mirWnization [6.5] (or, less rigorously, a resolution of
forces parallel to the solid surface) leads to YCJllIl9's equation as a
oondition for equilibrium:

:. ,,.
cr + 0-:...1 cos of, (6.14)

It has been sha.m

[6.6] that this condition is unaffected even i f the fluid interface is
distorted by a gravitational field. MoreolTer, the contact angle itself
is wholly detennined within a suhnicrosccpic region where each of the
three phases is within intenrolecular force range of the other two; the
oontact angle is therefore independent of the presence or absence of a
gravity field, whose potential varies only slowly with position.
140

Even though the two solid surface tensions occurring in Young's equation
are essentially unmeasurable, there is no a priori reason to expect that
their difference, Oj3 - 0\1. ' must lie in the range: 02:3' even though
oos~ Il\USt lie between +1 and -1. When, as often happens, ,(, = 0, we
Il\USt therefore suppose that

(6.15)

'Ihus, Young's equation beo:rnes an inequality when" = 0" (or 180°), and
one of the fluids is then said to spocead spontaneously on the solid,

totally displacing the other fluid.

6.4.1 Contact Angles: Measurarent and Olaracter

Several experimental techniques are available for the determination of

contact angles. The angle can be directly observed from a profile
photograph of a sessile drop, or by optical gonia:netry at the three-phase
line. In a variant of this rrethod, the angle of inclination of a plane
solid surface passing through a fluid interface is varied until the
latter appears perfectly flat right up to its junction with the solid;
the contact angle through the lower fluid then equals the inclination of
the solid surface to the horizontal. The gea:netry of axisymmetric
sessile drops has been thoroughly studied, enabling the contact angle to
be deduced from observations of the volurre and rnaxiIrurn height (or
alternatively volume and equatorial diameter) of such drops.

'!he quantity 02.\ oos,", can be rreasured directly from the surface tension
force on a partially-submerged vertical solid body (e.g. a rod or a thin
plate), after appropriate correction for buoyancy. '!his is a variant of
the Wi lhelrny plate detachment method for measuring 02.., alone (Table 6. I)

Although the contact angle has been described above as a property

characteristic of the the two fluids and the solid ooncemed, in practice
it can be remarkably poorly-defined. Diffusional equilibrium should, of
course, be reached before rreasuranents ar~ m3de: the two fluids should
be mutually saturated, and the solid surface should be at adsorption
equilibrium with both, in order for the three surface tensions to reach
their equilibrium values. In the ccmnon case that one of the fluids is
air, it must be saturated with the vapour of the liquid, and the
solid/vapour interface must carry an equilibrium multilayer adsorbed
film. Furthenrore, as in all surface-chemical rreasurerrents, traces of
surface-active contaminants can produce very large .errors; the contact
 141

angle seems to be peculiarly susceptible in this regard. Even when

these precautions are taken, hCMeVer, experimental contact angles are
notoriously irreproducible, and frequently shcM marked hysteresis,
depending on the direction of previous notion of the contact line.

Contact angle hysteresis is usually ascribed [6.7) to microscopic

roughness and/or chemical heterogeneity of the solid surface.
Geanetrically, for Young's equation to apply, the solid surface must have
a continuous first derivative: i f the three-phase line is located at an
angular discontinuity, the two solid surface tensions are no longer
collinear and the contact angle is indeterminate within limits (Fig.
6.3) . A similar indeterminacy arises when the contact line encounters a
boundary between patches of solid surface differing in wettability. The
resultant canthotaxis (or "anchoring" of a fluid interface at a
geanetrical or chamical discontinuity on the solid surface) has been
utilized for fluid management in microgravity.

= (Dnt"ot ""'lIe)
~Ictvlb

Fig. 6.3 Canthotaxis at a sharp edge on the solid surface

Distinct from hysteresis of the static contact angle is the fact that
when the contact line is in motion the contact angle may show velocity
dependence [6.8), even at speeds as low as a few microns per second. In
nany instances the dynamic contact angle is of greater practical
importance than the static value, as in the kinetics of wetting and
spreading. Theoretical analysis encounters a non-trivial problem, in
that the shear rate in the fluid is required to approach infinity in the
three-phase region. The difficulty arises ih principle from the attempt
to apply continuum fluid mechanics to an essentially molecular-scale
phenomenon.

Despite all these difficulties, contact angles have been successfully

used to characterize solid surfaces through the concept of the critical
surface tension for wetting. It has been found "[6.9) that in many
cases a harologous series of liquids (e. g. aliphatic alcohols) will
142

form contact angles on a given solid that vary regularly with the
rorresponding liquid surface tensions. A plot of ros" against surface
tension (the wZismanw plot) is generally linear, and. the intercept at
ros cl = 1 gives the surface tension at which a liquid will just spread
spontaneously. Moreover, since the gradient -(d us "'lIAr) is usually
about 0.03 - 0.04, knowledge of the critical surface tension enables
rough predictions of contact angle for other liquids to be made ~ The
critical surface tension for wetting of a polymer appears to be a
reasonably well-defined characteristic of its chanical carp:>sition, ar:rl
values for many such materials have been reoorded (see, e.g., [6.10]).

6.5 Capillarity

Capillary statics is concerned with the hydrostatic ar:rl diffusional

equilibJ:ium of curved fluid interfaces, and with associated problems of
stability. In this context, "curved" means having a non-zero value of
the nean curvature, c:

c = +
(6.16)
mere ...., ar:rl""f. are the principal radii of curvature of the interface
(Le. the radii in two orthogonal planes normal to the surface at a
point, the planes being rotated until "'i and "Z achieve extreme values.)
By ronvention, for 1/v, sll and slv interfaces, a radius is given
positive sign if its associated centre of curvature lies in the denser
thase. For 1/1 interfaces, the radius is positive if its centre lies in
the direction of the axis of s~try, if there is one. In any other case
the sign must be decided arbitrarily and stated explicitly.

6.5.1 Hydrostatic Equilibrium

For mechanical equilibrium of a fluid interface, there must be a

difference in hydrostatic pressure, t. P , between the phases on either
side, as given by the Laplace equation:

= (6.17)

mere tr is the interfacial tension. '!he sense of the pressure

difference is always such that P increases when the interface is crossed
towards the centre of curvature of the smaller of 1j and i"',. •
 143

A few examples may clarify the situation. A spherical surface of radius

= ""'z. = ! ~ , with both centres of curvature coinciding with the
1"" has ...-;
sphere's centre am with C = ~2f"', '!hus, for a liquid droplet in a
gas, or a solid particle iJmersed in a gas or in a liquid, C. is
positive am the pressure is higher in the drop or particle. For a
vapour bubble in a liquid C is negative, and the pressure is higher in
the bubble than in the liquid. A part-sIi'terical meniscus is fonned
between air and a wetting liquid in a capillary: here, C is negative and
the pressure is reduced in the liquid hence the phenanenon of
capillary rise. For a cylindrical interface of radius .,.., "Ii =:!:.,.. and
=
""2.= dJ , am C = f /.". A plane interface has "fj = -rz. = 00 , and C = 0 •
An interface of saddle shape has"i and ~ of opposite sign. In the event
that -lj = - i"a, again (.. = 0: the surface, even though not plane,
nevertheless has zero mean curvature, and the pressure is the same in
both phases. (An exarrple is the catenoid - see Fig. 16.9.)

In a gravitational field a further condition of hydrostatic equilibrium

is that within a hCJlD9eneous fluid of density.f '

p = (6.18)

where '1 is the vertical height above the plane at which P equal ssome
fixed value Po. (Analogous equations describe behaviour in fields arising
from other gradients of potential, e.g. electrostatic, magnetic and cen-
trifugal.) Thus, if two phases separated by an interface differ in density
by Ap, the mean curvature of the interface will vary with,.: combining
eqns. 6.17 and 6.18, we have:

c :: (6.19)

where C = Co at the plane,) = O. If we take C =o(~-I), where d is a

characteristic· linear dinension of an interface, we see at once that
C tends to becare unifonn over the entirety of an interface when the
Bond number becares large (eqn 6.1) • Such surfaces of unifonn mean
curvature are tented hcmx:lastic. (For further details, see [6.11). )
'!he axisynmetric haroclastic surfaces are shown in Figs. 16. 5( a) to (c).
In addition, an infinity of non-axisyrrmetric hcmx:lastic surfaces can be
fomed, subject to nore arbitrary boundary conditions. Whereas the
axisyrrmetric cases can all be described in tenns of circular and elliptic
functions, the others are non-analytic and require recourse to n1lIlerical
nethods for their description.
144

6.5.2 Diffusional Equilibrium

Since chemical potential is a function of pressure, capillary phenanena

will affect such properties as vapour pressure and solubility. The
effect on vapour pressure is described by the Kelvin equation:

~ lk ~o (6.20)
"\1")-

where It is the gas constant, l' the vapour pressure of a liquid (of molar
volume "'l ) when the l/v interface has nean curvature c., and thet·
nonnal saturation vapour pressure when c.. = 0, both at the sarre
temperature T. When C is positive (e.g. liquid droplet), l' > 1'0 , and
vice versa. A sllnilar e~tion, applicable to solid particles in
solution, involves In sis" , where S is solubility: hence, small
particles are more soluble than larger. To treat a solid interface as
"fluid" in this way .implies the assunption that there is sufficient
mobility, through solution and recrystallization, for the solid surface
to achieve an equilibrium configuration.

The relative magnitudes of Laplace and Kelvin effects are shown in Table
6.5. It may be noted that Laplace effects are significant in a range of
moderate curvatures (of the order of r"";'or less) where Kelvin effects
are negligible. Moreover, in practice, Laplace equilibrium is achieved
by relatively rapid fluid flaw, whilst Kelvin effects involve diffusion
in the vapour or in solution. In most cases, and particularly for
liquids of law vapour pressure, Laplace equilibrium may be attained very
IlUlch more quickly than Kelvin equilibrium. This fact is significant in
considering questions of stability.

Relative vapour pressure (Kelvin) Laplace pressure/bar

r/nrn (bubble) (drop) (bubble or drop)
1 1 0
1000 0.9990 1.001 1.46
100 0.9891 1.011 14.6
10 0.897 1.115 146
1 0.337 2.968 1460

Table 6.5 Relative Magnitudes of Kelvin and Laplace effects (water,

291 K)
 145

6.5.3 capillary Stability

'!his problem is best illustrated by two examples. First, consider an

isolated liquid droplet in its vapour; its Laplace equilibrium sha~ is
spherical, which is the haroclastic shape rni.nimizing the interfacial area
for a given enclosed volurre. If the drop is defomed to an ellipsoid it
will revert spontaneously to its s};tlerical shape, driven by gradients of
hydrostatic pressure arising fram the non-uniform curvature of the
ellipsoid (Eqn. 6.17). It is therefore "Laplace stable". Acrording to
the Kelvin equation, hc:Mever, it exerts an enhanced vapour pressure in
inverse proportion to its size; thus, i f there exists another droplet of
different radius, the smaller drop will distil onto the larger, at an
ever-increasing rate, until the smaller drop has vanished. Such drops
are therefore "Kelvin unstable". The fact that relatively persistent

aerosols can be fomed illustrates the importance of the different rates

of Laplace and Kelvin processes.
A second exarrple is that of a cylindrical fluid colUIlU1. This too has a
positive curvature, becaning less positive as the cylinder grCMS in
diameter, and so is Kelvin unstable in the same way as the drop.
However, it is well-knCMn that it also becomes Laplace unstable When its.
length exceeds its circumference - the so-called Rayleigh instability.
Shorter rolUIlU1s are Laplace stable (or rretastable).

The stability conditions are best expressed in tenns of the effective

area, defined as

A~.ff = l6.21)

Which is related to the curvature by the Gauss equation:

= (6.22)

(A different nomenclature has been adopted in Chapter 16, where Eqn. 6.17
has been named the Laplace-Gauss equation.) The condition for Kelvin
stability is then

(0..1. A~.u/d.. V.t1.)~ > 0 (6.23)

and that for Laplace stability is

(ce A cf; ~ 5)v > 0 (6.24)

Where ~ is a variable describing the interface shape.
146

When a Laplace-stable interface is deformed fram its hemoclastic

a:mfiguration (in the absence of gravity), the resultant non-unifonnity
of curvature proouces gradients of hydrostatic pressure which drive it
back towards its original configuration, with a concomitant reduction in
interfacial area. When the stability limit is surpassed, hONeVer, any
transient non-unifonnity of curvature will drive the system tcMards a
new, more stable, configuration, even though the intermediate
non-equilibrium states may have a higher interfacial area than either the
initial or final states [6.12].

A static equilibrium fluid interface naturally exerts a unifonn surface

tension. If, hcMever, a transient non-unifonnity of surface tension is
induced (for example by gradients of temperature or of solute
concentration), instabilities of another kind can appear. The resultant
flOils are generally described as Marangoni convections, and are discussed
more fully in Chapter 16 (see also [6.11]).

6.6 Practical Conclusions

Surface and capillary phenomena are highly relevant to the behaviour of

fluids in microgravity, where the Bond number (F4n 6.1) tends to
infinity. This has important practical consequences for the very
operation of liquid-fuelled rocket motors in space vehicles, since in the
absence of external accelerations the propellants will occupy positions
in the fuel tanks that are dictated solely by capillary forces. The tank
no longer has a "bottom" at which to place the exit pipe, am
sophisticated propellant management devices are used to collect the fuel
at desired locations. Capillary phenamena are also relevant to the
everyday feeding and hygiene activities of astronauts.

In this volume we are more concerned with the lirplications for

materials processing in microgravity. For example, crystal growth by the
Czochralski and floating-zone techniques involve problems of wetting, of
capillary stability and of interfacial nOll. Wetting, being a molecular
phenanenon controlled by relatively short-range forces, is unlikely to be
affected by gravity forces. The capi~lary stability of axisymmetric
interfaces is well understood, thougl1 in ICM gravity even ICM rotation
speeds can proouce destabilizing centrifugal fields whose subtlety was
unsuspected before the early Skylab flights. Interfaces lacking axial
symmetry remain practically unexplored. Interfacial flOils of the
Marangoni type are nOll knCMn to assume often dominant :importance in
microgravity materials processing, but the fundamental physics is not
fully understood.
 147

~ further problem encountered in space flight is that the g-level is not

truly zero, neither is it constant. I t has been found that the unsteady
acoelerations arising fran microthruster firings, crew Il\OI1ements, etc.
("g-jitter") can produce disproportionate perturbations of fluid
behaviour. !obreover, for large liquid masses, for which both gravity and
capillary forces are' small, ,electrostatic effects can becane daninant,
with sanetimes surprising results [6.13).

Clearly, Imlch remains to be understood regarding the inplications of

capillarity for microgravity fluid behaviour. Fortunately, the very
space flights which engender these problems also offer opportunities for
practical research on their solution. '!be results to date are presented
and discussed in Chapter 16.

6.7 References

6.1 Gibbs, J.W. Collected WOrks (Dover Reprints, New York, 1961),
vol.I (esp. pp. 219 - 331)
6.2 Defay, R., Prigogine, I., Bellemans, A. and Everett, D.H.
Surface Tension and Adsorption (Longmans Green & Co., lDndon, 1966) .
6.3 Lord Kelvin (W. '!hanson) Phil. Mag. (4), 17, 61 (1859)
6.4 Adamson, A.W. Physical ChEmistry of Surfaces, 3rd. Etlition
(Wiley, New York, 1976)
6.5 Everett, D.H. and Haynes, J.M. Z. phys. Chan. 82, 36 (1972)

6.6 Johnson Jr., R.E. J. Phys. Chan. 63, 1655 (1959)

6.7 Blake, T.D. and Haynes, J.M. Frog. Surface Membrane Sci. 6,
125 (1973)
6.8 Blake, T.D., Everett, D.H. and Haynes, J .M. "wetting", SCI
!obnographs 25, 164 (1967)
6.9 Zisman, W.A. Advances in ChEmistry No. 43 (American Chanical
Society, Washington, 1964)
6.10 As reference [6.4), p.355
j

6.11 Haynes, J.M. Bull. Materials Sci", 4, 85 (1982)

6.12 Haynes, J.M. and Smith, J.S.L. Unpublished results,
University of Bristol, 1984
6.13 Allen, J. and Haynes, J.M. Unpublished observations fran
srS-5 mission, 1982
7 Solidification

P.R. SAHM and J.G. STURM

Foundry-Institute, Aachen Institute of Technology, FRG

Solidification on Earth is always linked to complex interactions of the va-

rious heat and mass transport processes. The amount of diffusive and con-
vective phenomena, especially in the vicinity of the liquid-solid inter-
face, take a strong influence on the microstructure and the resulting pro-
perties. Therefore a key of reproducible solidified microstructures at in-
creasingly higher levels of control is a better understanding of the inter-
actions between fluid mechanics and the liquid-solid interface.

In this context the solidification under micro-g opens up new challenging

perspectives as it allows the separation of the different gravity dependent
or independent phenomena.

Solidification front dynamics, second on the complexity scale of ~g-rele­

vant fluid related materials and life sciences [7.1], thus relies on
various interconnections encompassing several disciplines. Systematically
listed, they are

solid-liquid interface stability and morphology forming phenomena,

both concerning
o single phase and
o polyphase solidification,
s-l-interface interaction with discrete pa~ticles with
o gaseous, liquid or solid state of aggrtegate,
be they of
o own (= self-originating, i.e. nucleation in front of the solid-
liquid interface) or foreign phase.

In the wake of ~g-relevant research, solidification front dynamics have ge-

nerated discoveries describing convective dependent growth front morphology
150

effects including such concerning the engulfment of discrete particles. Se-

veral ~g-experiments have, meanwhile, also been performed and have deli-
vered first essential results.

7.1 Objectives for Solidification Research Under Microgravity

The central purpose of all sol idification-1 inked microgravity research is

an increase in our understanding of interactions between fluid mechanics
and the liquid-solid phase transition. This may be realized by separating
gravi ty- induced transport mechani sms such as buoyancy, sedimentati on and
natural convection from gravity-independent processes such as diffusion and
specific types of convection in order to study the contribution of single
mechanisms to the overall heat and mass transport and to the determination
of growth morphology (Table 7.1).

Table 7.1: Basic microgravity-re1evant effects which pervade nearly all.of

materials processing phenomena [7.2J.

Gravity-dependent transport process:

(1) Buoyancy and sedimentation induced by ~p (T,c)
(2) Natural convection induced by 6p(T) and ~p(c)

Gravity-independent transport processes:

(1) Convection caused by ~P1iquid-so1id ~ l/~Vm 1~
(2) Marangoni-convection induced by ~a(T) and ~a(c)
(3) Diffusion

~p = density differences
~a = surface energy differences
T = temperature
c = concentration
6p (T,c) = thermally and/or solutal1y induced density differences
~Vm = volume increment at the melting point
 151

7;2 Solidification Front Dynamics

The field of research called solidification front dynamics [7.3, 7.4, 7.5J
deals with the interaction between the solidification front and macroscopic
or microscopic convection which strongly affects the mass- and heat trans-
port processes, including the interaction with discrete particles present
at the solid-liquid interface.

Stability Criteria

The growth of a solid-liquid interface i.e. the adsorption of atoms on a

regular metallic crystal matrix is decisively related to diffusive heat
and, in the case of alloys, also to mass transport. Therefore a smooth and
planar interface is only stable up to critical values of the process para-
meters growth velocity and temperature gradient. Due to the solute rejec-
tion alloyed crystals tend to destabilized growth interfaces with increa-
sing growth velocities or decreasing temperature gradients.

To minimize the supersaturation or the related constitutional undercooling

in front of its interface the crystal increases its surface and becomes un-
stable. Cellular or dendritic growth occurs.

The stabi 1ity of an advanci ng sol i difi cati on front may be estimated when
using a well-known stabil ity criterion which phenomenologically connects
alloy with process parameters at the solidification front [7.6J:

(7.1)

with G = temperature gradient into the melt directly at the solidification

front, v = solidification front velocity, m = slope of the liquidus line,
Co = initial concentration, D = overall diffusion coefficient in the melt
and ko = the equilibrium partition coefficient. This equation is only valid
in the case of a diffusive regime in the melt and describes the critical
parameters for the destabilization of a planar interface (Fig. 7.1).
152

,=
-1ffi1ll-nTl~T TI - Ts .,u
-0
0
r:
(G/v)plan. (f)

Planar
.g.,

mnrl---- TI

---Ts
.S
.,
-0

U.,
> (G/v) ce 11 . C £
Cellular c (J)
::>
.,~ 0
a::
~--TI £
> (G/v)dend. --Ts
Dendritic
.,
() 0 <:> <;) C '" c> o---TI C; .,
-u
o c:P ~(;) o!> Q.,";, 0 c:;{o ::> 0
> (G/v) go.
1 b ¥'t.,
~----Ts ~

o-
IL .~
Globulitic

Fig. 7.1: There are only few basic types of solidification fronts to be
distinguished; the interaction of solid-liquid interface with discrete
particles will decide on particle engu1 fment conditions; different
(G/v)-va1ues are valid for the various morphologies; they decrease from
planar to equiaxed (= globu1itic).

Experimentally for every morphological transition (i.e. cellular to dendri-

tic) critical quotients of G/v can be determined.

The focus of interest is in the stabil ity of the sol idification front and
especially in the reasons for the onset of first instabilities. Therefore,
more advanced stability critieria have been developed in recent years. They
take into account a1 so the surface energy of the interface as well as the
pertubation frequencies (i.e. temperature fluctuations in the melt) at
which the interface may become morphologically unstable [7.7, 7.8J.

Boundary Layers at the Solidification Front

Due to the quality of an advancing solidification front to both reject so-

l ute and to extract 1atent heat, vari ous boundary 1ayers buil d up at the
growth interface. Their size extensions are strongly related to the diffu-
sivities of mass (D1), heat (al), and impulse (v1) transport (Fig. 7.2).
 153

ScI"" lq.,od Fig. 7.2: The three types of boundary

i layer ahead of an advancing solid-liquid

11 t~__ c-,-,- - - .

z
interface under simpl ifyi ng assumpti ons
(the subscript i indicates interface and
the subscript 1 bulk liquid):
(a) the solutal boundary layer is given
by
(a)
/).c

11~
- /).z

(b) the thermal boundary layer by

(b) ~T 1 /).T
- /).z z=o
:I
"1
!;
(c) the convective boundary layer by
I,
1 6I II-Ii
i
U '--f---t------
- /).Z z=o = ~
Distance from growth ftanl In real ity an interaction between these
layers takes place, and the analytical
description is much more complex.

These transport coefficients couple driving forces (i.e. the gradients in

front of the interface) and resulting fluxes. Table 7.2 shows the well-
known transport equations.

driving velocity gradient temperature gradient concentration/

~orce pressure gradient
I flux ~
impul se Newton's law
av
at= - - - 2 -
11 a2v
P ax
energy Fourier's law Dufour effect
aT a2T Dr (lIC)
- - = a --'2-
at ax
mass Soret effect Fick's
D~ (liT) aC
at

Table 7.2: Relation between driving force and flux at one dimensional
transport including the corresponding law and diffusivity.
154

Under convective conditions these equations, which govern only the diffu-
sive behavior, are no longer strictly applicable. As the convective fluid
flow is linked to heat transport, a rapid homogenisation in solidifying
mel ts occurs. The thickness 0T of the thermal boundary 1ayer ahead of the
solidification front. decreases with increasing fluid flow, see Figs. 7.Z
and 7.3. On the other hand, the temperature gradient at the solid-liquid
interface increases. Thus, convective fluid flow exerts a stabilizing in-
fluence on metallic solidification fronts, from a thermal point of view.

Besides the infl uence of the morphology the shape of the concentration
boundary layer determines the macroscopic segregation behavior. The stron-
ger the amount of convection the smaller the boundary layer and the more
the concentration distribution deviates from the initial composition (Fig.
7.3). This segregation behavior also plays a decisive role in crystal
growth processing of semiconductor materials. As one example, the origin of
striations in silicon crystal s belongs into this realm of considerations
(see section on single crystal growth). Here weightlessness offers the pos-
sibi 1ity to di stingui sh between the inf1 uence of surface tension gradient
induced Marangoni-convection and that of gravity-driven convection.

Fig. 7.3: Effect of convection on con-

centration profiles ahead of solid-
liquid (s-l) interfaces:
S-l ....toe.
(a) complete mixing by convection and
diffusion
~
c
OBv1
--- --------
ko'oB

(a) '0

(b) only diffusion, no convection

(c) diffusion and some convection/par-

tial mixing.
COB -- -~------
ko'vB / 6e
Note that ac-va1ues are different for 3
(c) ., Solid liquid cases.
 155

fhe effect of convection on the shape of the boundary layer can be

described by an effective distribution coefficient keff ~.~:

ko
keff = --------=------- (7.2)
ko + (1-k o ) exp (-voc/D)
which combines the natural distribution coefficient ko with the advance of
a real measured boundary 1ayer thi ckness Oc as defi ned in Fi gs. 7.3 and
7.4. If there is no convective mixing in the melt, Oc will be relatively
large and keff will tend towards unity. With complete mixing, 0 c tends to
zero and keff to ko • For partial mixing, such as illustrated in Fig. 7.3c,
keff varies between ko and unity. With this equation the influence of con-
vection on morphological stability (see Eq. 7.1) can be taken into account
[7.8 J.

In recent years both experimental and theoretical treatment of the trans-

port problem of solidification lead to new insights into the coupled beha-
vior of the different boundary layers.

7.3 Complex Interactions of Different Transport Processes

The overall density of a melt is dependent both to its temperature and to

its concentration. In the case of vertical directional solidification the
melt is superheated. This means a positive temperature gradient stabilizes
the density distribution. For all alloys with a solute having a higher den-
sity, i.e. copper in aluminum, the concentration enrichment in front of the
growing interface increases the density, and thus stabilizes the melt in
there.

In cases of less dense solute, i.e. magnesium in aluminum, the overall den-
s i ty profi 1e can become unstable due to the temperature
,
and concentrati on
distribution mix ahead of the interface. This Will give rise to the so cal-
led "thermosolutal" convection in the vicinity of the growth front. R.M
Sharp and A. Hellawell 1972 had hinted at such an effect on the basis of
experiments with Al-Mg alloys [7.9J.

Due to the strongly different diffusivities of mass and heat transport and
also the dependence on melt viscosity the theoretical treatment of the ari-
sing thermosolutal convection is a very complex fluid flow problem. A first
156

Fig. 7.4: (a) Stable and (b) unstable

density profiles generated by the inter-
action of the temperature and the con-
centration distributions ahead of an ad-
vancing solid-liquid interface; from
P.R. Sahm and A. Ecker 1984.

Fig. 7.5: Critical concentrations c;:*

of Sn in Pb delineate stability regimes
occuring as function of growth velocity
(with temperature gradient in the liquid
G1 = 200 Kcm- 1 as parameter); the full
concave curves represent the onset of
instabilities of convective character
for gravitational accelerations ge' 10-4
and 10- 6ge • The upper full line that
slopes downwards to the right represents
the onset of constitutionally related
morphological instabil ity; the nearly
parallel chain line labelledap/az = 0
represeryts the neutral density crite-
rion; S.R. Coriell et al. 1980.
 157

approach was delivered by S.R. Coriell in 1980 who numerically calculated a

stability diagram for the example of Pb-Sn alloys (Fig. 7.5) [7.10J. With
this analysis it was deduced that the critical concentration for the onset
of convection depends strongly on the gravity level. Therefore ~g-experi­
ments are very useful to cast new light on concepts so far developed.

Quantitative investigations on transparent model systems appear to be a

first step towards more quantitative monitoring of the influence of convec-
tion. Re1 ated experiments at 19 and under weightlessness are in prepara-
tion, for example by A. Ecker and P.R. Sahm 1985 [7.11J and S. Rex and
P.R. Sahm 1985 [ 7.12 J.

7.4 Gravity-Independent Convective Processes

Besides gravity dependent convective movements, which are buoyancy induced,

the advancing solidification front is subject to a microscopic, gravity-in-
dependent fluid flow towards itself (or away from itself, as the case may
be) termed solidification convection. It originates from the volume change
upon solidification and can be characterized as follows:

u (7.3)

in which u is the velocity of the solidification convection, Ps and p 1 the

densities in the solid and the liquid state respectively and v the solidi-
fication front velocity.

Little is known as yet concerning the effect of this type of convection on

the sol id-1 iquid interface. Experiments under microgravity using alloys
with well defined (i.e. positive, negative, and preferably, zero) volume
changes are desirable. A single-phase alloy with zero volume increment" Vm
would be an ideal test sample, P.R. Sahm and M. Rittich 1983, Fig. 7.6,
[7.131.

The solidification convection will specifically affect dendritic growth as

the three-dimensional flow perpendicular to the surface should somehow af-
fect solute distribution in between the growing dendrites.
158

vI ------- I --T-- J .
: Volune I~ement'
I of Alloys Solidi-

Vs lOY~ i 1 I tying with T-In-

terva l

~id----- -r-I--- ---

Ccxl.traction I I I :
I I I I
I I I I
I 1.1 I

: i: :
Tr Ts pi Tu T{OC]
(a) T,=Ts

7iI~~~~--~----~~-
liquid

(b) A ( (AVa, =0) (II

lQtOl(Jtc)! - tOZO

I I ~
so
_CIGMT . , . C'JfT .IIIIIUIUM
.-o4SMU.O IS to" "

I
IS to

I
,.

1.......-

~ ... I I ~ I ~
I I ~ I Y I

r
.~I I V IXI I IIII..
I
\
N
\1_1. .• 1
1
V~ I I 1''''-'\
".o • .....j

I"" CI
:,yt".J:
! I i •••• i i
I "'.1"
1

vi I I I I, ,..3"~
I

~a.ll I
I I I I I I I
I
I
•oo 1-4.•
V

(c) .. , I. .. ..
I rJ I
.IoTOMIC
.! . ,.
.'11 C,.T ........... " •
•\IoGe
I ..I to
-
Fig. 7.6: Upon solidification a (relative) volume change defined as
llV m = Vl - Vs/Vs occurs; lIV m may be ~ 0 (a); in addition, alloys solidi-
fying within a temperature interval II Ts_l will exhibit a locally varying
lIVmbehavior: an example for a single phase alloy with lIV m = 0 solidifying
dendritically is shown in (b); the well-known 2-phase (lIV m = OJ-alloys pre-
suppose violent compensating convective movement between the phases of op-
posite lIVm-sign (c), [7.14J.
 159

The temperature and concentration dependence of the surface tension can

lead to the second gravity independent type, i.e. to Marangoni convection,
particu1ary if "open surfaces" (i.e. melt-gas interfaces) are present. This
convection is one of the main processes disturbing pure diffusive heat- and
concentration fields in setups with free liquid surfaces (crystal growth,
welding, brazing).

7.5 Effect of Convection on Microstructure and Properties

According to figure 7.1, there are only a few basic types of crystalliza-
tion interfaces and their corresponding as-solidified microstructures. The
types shown in figure 1 not only pertain to single phase systems but also
to polyphase materials. Binary eutectics may be taken as typical represen-
tatives for polyphase solidification. Here in principle similar distinc-
tions apply as for single-phase alloys, figure 7.1.

I nstabi 1i ti es of p 1 a n a r s o l i d - 1 i qui d i n t e r f a -
c e s may cause the development of different morphologies of the
solidified material. Hence, there is considerable technological interest to
accurately understand the dependence of morphology on the individual
solidification parameters, including the effect of gravity-induced
convection. Eq.(7.1) provides critical G/v-numbers delineating transitions
between the various morphological regimes.

Ace 1 1 u 1 a r sol i d i f i c t ion front, which can be obtained

by decanting a melt during crystallization, shows an apparent similarity to
Benard convection cells as observed in fluid convection, fig. 7.7. In both
cases, temperature or concentration differences are the most likely causes
for the cellular structure. On the other hand, convection-induced concen-
tration changes within a single cell may change the melting point locally
in a simplified picture. This, in turn, may produce a hexagonal pattern
during sol idification, fig. 7. 7a. Experiments under weightlessness will
allow conclusions on the kind of connection between these effects, if there
is any, [7.15J, [7.16J.

Den d r i t i c g row t h determines, within a wide regime, the mi-

crostructure of technical alloys and consequently their properties, fig.
7.7. Therefore it is very important to know the growth conditions in de-
160

u
.~

+J
s...
"0
s::
Q)
"0

.0

Q)
u

s...
co
s::
co
~

0..

Fig. 7.7: Concentration peaks and valleys are measurable in front of

(quenched) cellular or dendritic solid-liquid interfaces (a); thus convec-
tion models may be visualized as follows (b): a macroscopic case A is de-
termined by perturbed solid-liquid interface; various types of cellular in-
terfaces, for example Al-Cu 0,4 shown in (c) may be connected with micro-
convective IlKlVements originating directly at the growth front; P.R. Sahm
and H.M. Tensi 1981; quenched interfaces from H.M. Tensi 1977, shown in
orientations parallel and perpendicular to growth directions; [7.1SJ,
[7.16J.
 161

tail. Studies deal ing with the steady state growth of a single dendrite
have already progressed to an advanced level, see for example, M.E. Glicks-
man 1981. The influence of gravity was impressively demonstrated by his ex-
periments using transparent model systems.

The goal of further investigations consists in unde r standing also the 'co-
operative" growth of arrays of dendrites, i.e. of entire dendritic growth
fronts, in order to predict the growth of adjacent dendrites and the asso-
ciated melt volume. Experiments under weightlessness could help to answer
such questions about the extent to which convective fluid flow plays a role
and also the extent to which it may be reproduced. As an example, figure
7.8 illustrates the effect of a change in dendrite orientation against the
flow direction of thermally induced convection in 19 [ 7.18].

~-
:
,
- - - - - - - -- - - -- - - - ... ,'-'" - ---',
\
i ,I
, "
t
I
'~
"
+
I
:
I

~:
I \ I
I "\ ,
\ , I
, ' /

Fig. 7.8: A crystall izing succinonitril-ethanol model alloy interface was

subjected to macroscopi c convecti on conditi ons; dendrite tips are observed
to bend against the convective flow vector [7.18J.

Lately, much attention has been attracted to ripening processes in the

mushy zone, i.e. the zone between liquidus and solidus temperature, within
dendritic arrays. It is expected that convection may have an effect on the
coarsening behavior (= ripening) and thus on dendrite arm spacings, which
so essentially determine the ensueing mechanical and physical properties of
castings.
162

E ute c tic sol i d i f i cat ion is also affected by gravita-

tionally induced transport processes. The lamellar spacing Ae and the
growth rate v are linked in most cases by the relationship

A2e v = C((D,m,cel. a( ct, B,m) •.• } (7.4 )

The constant C has been derived from first principles by K.A. Jackson and
J.D. Hunt in 1966 [7.19J. It is a function of the melt diffusion coeffi-
cient 0, the liquidus slope m at ce (= the eutectic composition), and, very
importantl y, of the interface energi es between the three i nvol ved phases
ct, Band m (=melt). As the constant in Eq.(7.4} is really a function of

vari ous gravity-di sturbed factors, in parti cul ar what concerns the diffu-
sion coefficient (see chapter on diffusion) and some system immanent para-
meters such as behavior of coupled zone eutectic growth, ~g may show cer-
tain effects on the microstructure [7.20J.

Convective transport processes are an important factor governing the deve-

lopment of cast macrostructure, fig. 7.9: The extent of their influence is
by no means clear as the solidification process in metallic melts does not
lend itself to direct observation. The transfer of results obtained from
transparent model melts, however, is only applicable in a restricted way.
So, for instance, no unequivocal answer has as yet been given to the
question of what may be the cause for the inner globulitic zone delineated
by the transition from columnar to e qui a xed grains, compare fig.
7.9. One possibility of answering this question involves the theory of con-
stitutional supercool ing. Following this theoretical approach, the melt
ahead of the solidification front undercools to such an extent that hetero-
geneous nucleation will occur ahead of the advancing sol id-l iquid inter-
face. Thi s requi res a fl at temperature profi 1e in the center of the cas-
ting, whiCh will be promoted by convective mixing.

Another theory considers dendrite tips r~molten or broken off by convection

and transported into melt regions where the thermal conditions allow an
equ i axed growth.

Solid-liqu d nterfaces i n t e r a c t with

par t i c u 1 ate mat t e r. Interactions of s-l-interfaces with
concl usions, be they gaseous, 1iquid or sol id, are of great significance
for the entire field of solidification [7.21J. An essential question to be
 163

Fig. 7.9: The classical ingot ma-

crostructure has been expl ai ned in
the following way: the outerfine-
grai ned zone (1) is formed on ac-
count of a high undercooling due to
the mold wall quenching effect;;
grain selection then takes place as
the grains with the optimal crystal-
lographic orientations prevail (2);
the inner globulitic part of the in-
got is due to arising from constitu-
tional supercooling nuclei which, in
turn, occur because of macroscopic
segregation into the i nterior (3);
the extent of the di fferent zones
zl,2,3 is strongly convection-depen-
dent.
1 = Chi ll zo ne
2 = Columnar zone
3 = Epi ax ed zone

Crystal

Fig. 7.10 : In order for a particle in front of a solid-liquid interface to

stay afloat, i.e. not to be engulfed by it, it is required that melt conti-
nuously flows into the "channel" formed between particle and s-l-interface;
the same condition may be visualized such that the convection velocity is
not equal along each of the l i nes of potent i al; physically this should re-
sult in a local change of growth front shape, similar to the effect to be
expected if heat conductivities of melt and particle are appreciably diffe-
ring; D. Langbein, 1981 [7.23 J.
164

answered in this context is: will the particles be engulfed by the crystal-
lization front or not, and, if engulfment occurs for a certain range of pa-
rameters, what are the critical values of those parameters. D.R. Uhlmann
and B. Chalmers (1964) in one of the first treatments of this subject in-
troduced a critical growth rate Vc which yields a measurable paramet.er for
deciding on engulfment or not, and thus describe corresponding mechanisms.

Introducing the engulfment problem fig. 7.10 sketches the physical back-
ground in a coordinate system moving with the solidification front (b) or
resting (a). It also points out the effect of different heat conductivities
between particle and melt on the local s-l-interface shape D.231

J. Potschke and K. Hohenstein (1982) [7.24J proposed a simple formulation

for Vc by

(7.5)

where C = a constant, /:,ao = ap S - ('1> 1 + as 1) with 1l = melt viscosity,

Ro = particle radius, jl =jl Ijll = ratio of particle-to-liquid heat conduc-
p
tivities, n = exponent. At speeds above Vc the particle would be engulfed,
below Vc it would be pushed away from the growth front. For particle sizes
below l~m even Brownian motion must be taken into consideration. Thus, it
is obvi ous that microconvecti ve movements and gravity woul d change condi-
tions from what is expressed by Eq.(7.5) as well. In that connection, al-
loys with /:,V m ~ 0 are expected to behave differently from alloys with zero
vol ume increment at the melting point (t:, Vm = 0) as concerns vc'

Weightlessness offers the possibility of studying the interaction between

particles and the solidification front in more detail. For example, the li-
miting conditions to push a particle ahead of the solid-liquid interface
instead of engulfing it can be determined, J. Potschke and K. Hohenstein
C7.24 1

Pot e n t i a 1 a p p 1 i cat ion s are linked to nearly all of the

discussed topics above. Table 7.3 summarizes regimes of ~g-relevant re-
search and possible improvements in materials and processes.

Di spers i on- hardened materi a1 s produced di rectly from the melt are of no-
table technological interest. Density differences between dispersed parti-
 165

Table 7.3: Relationship between ~g-re1evant research topics and application

oriented techno10~ies in metals and composites solidification
P.R. Sahm, 1982 17.251

regimes of application
~g-research topics

conventional processes possible new processes·

solidification front - ingot casting - improved single crys-

dynamics tal s of all sorts
- continuous casting
segregation phenomena - crystal growth - dispersoid materials
s-l interface i nter- - near net shape casting
actions with foreign
inclusions

immiscible alloys - continuous solidifi- - processing extremely

cation processes immiscible alloys
(A1-Pb) ..

nucleation, rapid - amorphous and partia1- - large volume amor-

solidification, 1y crystallized foils phous, metastable and
undercoo1ed melt lor fine-grained
alloys
- melt particularization - autonomous directio-
nal solidification

"large ingots" - container1ess melting - skin technology

and solidification
shape giving pro- - shape casting - improved microstruc-
cesses utilizing tures of various
spreading on sur- types
faces

numerical modelling - continuous casting - all solidification

with respect to op- technologies
timization and pre- - shape casting - system furnace-ingot
dictabi1ity or sample

development and con- - furnaces ~g-dedicated:

struction of special - diagnostics - furnaces
(dedicated) equip- - mixer and positioner - measuring equipment
ment - accelerometer - mixer
(g-leve1-monitors) - positioner
- accelerometer'
166

c1es and the melt lead to sedimentation effects on Earth so that the soli-
dified melt is not homogeneous with respect to the distribution of the par-
ticles within it.

In alloys with 1iqoid miscibility gaps, such as all monotectic systems,the

engulfment problem also exists in that the liquid droplets formed, as they
are hit by the advancing growth front, are either engulfed or pushed away.

7.6 Towards Novel Materials and Technologies

A short statement towards possible future applications both with respect to

improved or new materials and/or their technologies seems to be in order.
Table 7.3 lists the "conventional" Llg-research topics linking them to the
conventional materials technologies and some of their straightforward ex-
trapolations to modern technological aspirations. Such considerations
should increasingly include utilization of the customary materials proces-
ses which, however, may have to be staged into the Llg-environment of a pos-
sible future space station scenario.

It seems rather clear that improved microstructures (e.g. dispersoid al-

10ys), new processes (e.g. autonomous sol idification in combination with
skin technology), and a deepened interaction between process and hardware
(e.g. solidification and furnace design) will be but few of the "spin-offs"
of the Llg-era in materials science.

References
[7.1J P.R. Sahm, 1981: internal report at German Ministry of Research and
Development
[7.2J R. Jansen and P.R. Sahm, 1984: Mat. Scien. Enging. 65 199
! -

[7.3J P.R. Sahm, ed. 1981: "Erstarrungsfrlontdynamik", WORKSHOP Proc' s,

Foundry-Institute, Aachen Institute of Technology
[7.4J P.R. Sahm, 1982: in "Convective Transport and Instability Phenomena"
(eds. J. Zierep and M. Oertel jr.), Wiss. + Techn. Pub1., p. 515
[7.5J P.R. Sahm, ed. 1984: "Solidification and Fluid Dynamics in the
Earth's and the Sapce Laboratory", WORKSHOP Proc's, Foundry-Insti-
tute, Aachen Institute of Technology
 167

[7.6J W.A. Tiller. K.A. Jackson. J.W. Rutter. B. Chalmers. 1953: Acta
Met. 1 428
[7.7J J.A. Burton. R.C. Primm and W.P. Slichter. 1953: J. Chern. Phys •• 21
[7.8J W. Mullins. R.F. Sekera. 1964: Journal of Applied Physics. ~ 444
[7.9J R.M. Sharp and A. Hellawell. 1971: J. ~ryst. Growth. ~ 261
[7.10J S.R. Coriell. M.R. Cordes. W.J. Boettinger and R.F. Sekerka. 1980:
J. Cryst. Growth. 49 13
[7.11J A. Ecker and P.R. Sahm. 1985: in "The Scientific Objectives of the
D1-Mission" (D1-Brochure). exp't No. PK-HOL-04 (eds. P.R. Sahm and
R. Jansen). DFVLR Cologne
[7.12J S. Rex and P.R. Sahm. 1985: in "The Scientific Objectives of the D1-
Mission" (D1-Brochure). exp't No. MD-GFQ-02 (eds. P.R. Sahm and R.
Jansen). DFVLR Cologne
[7.13J P.R. Sahm and M. Rittich. 1983: Adv. Space Res. l103 (COSPAR Publ.)
[7.14J M. Rittich. 1985: Ph.D. Thesis. Foundry-Institute. Aachen Institute
of Technology. in print
[7.15J P.R. Sahm and H.M. Tensi. 1981: Adv. Space Res. 197 (COSPAR Publ.)
[7.16J H.M. Tensi. 1977: Maschmarkt. 83 7 (Oct. 7. 77)
[7.17J M.E. Glicksman. 1981. WORKSHOP Proc. "Solidification Front Dynamics"
(ed. P.R. Sahm) Foundry-Institute, Aachen Institute of Technology.
p. 75
[7.18J A. Ecker. 1985: Ph.D.-Thesis, FoundrY-Institute, Aachen Institue of
Technology, in print
[7.19J K.A. Jackson and J.D. Hunt, 1966: Trans. AIME 236 1129
[7.20J P.R. Sahm, 1977: Haus der Technik, Seminar Proc. No. 391, p. 33
L7.21J P.R. Sahm and H.U. Walter, 1980: in Proc. Vth ESA-PAC Symp. Europ.
Rocket and Balloon Programmes and Related Research (Bornemouth,
April 14-18, 1980) ESA Publ. No. SP-152, p. 509
[7.22J D.R. Uhlmann and B. Chalmers, 1964: J. Appl. Phys. 35 2986
[7.23J D. Langbein, 1981: Durchfilhrung von wissenschaftlichen Arbeiten ilber
Fremdteilchen vor einer Erstarrungsfront, Internal Report No. 9 51
022, Batelle Institute. Frankfurt/Main
[7.24J J. Potschke and K. Hohenstein, 1982: KRUPP Res. UB 003/82
= 7.25] P. R. Sahm, 1982: Keynote Statement in "Numeri ca 1 Modell i ng and Simu-
lation of Solidification Processes" (ed. P.R. Sahm), WORKSHOP Proc.,
Foundry-Institute, Aachen Institute of Technology
8 Nucleation and Undercooling

10.M. HERLACH and B. FEUERBACHER

Institut fur Raumsimulation

OFVLR, 0-5000 Koln 90

Nucleation plays an important role in many processes involving phase

changes, such as boiling, condensation, cloud formation, solidification,
defect formation etc. Even though it is not invoked in the formation of a-
morphous solid phases, nucleation dynamics is an essential ingredient into
our understanding of glassy solidification. Nucleation effects occur when-
ever the free energy of a phase formed in a transformation process becomes
size dependent, and they 1ead i nv ari ab 1y to the phenomenon of undercoo-
ling. The latter is a non-equilibrium process which gives access to areas
in the phase diagram not accessible to equilibrium systems.

For this reason, undercooling is a means to obtain metastable phases of ma-

terial s. Such metastables may have properties quite different from the
equilibrium phases, as known, for example, for graphite and diamond, two
modifications of carbon of which graphite is stable, while diamond is meta-
stable under all but extreme conditions. Another example of a metastable
phase is the amorphous form of metals, glassy metals. The understanding and
control of the nucleation therefore has the potential of leading to the
production of metastable materials of different and novel properties.

In nucl eati on theory, two di sti nctly different processes are consi dered
[8.~. Homogeneous nucleation asssumes that the constituents of the system
itself act as nucleation centers. On the other hand, heterogeneous nuclea-
tion relies on some foreign partner, such as an impurity or a wall, to ini-
tiate nucleation. While theoretical interest essentially focusses on the,
homogeneous process, in practice heterogeneous effects seem to dominate.

Any containment of a melt may obviously give rise to heterogeneous nuclea-

tion events at the wall s, which may lead to early nucleation and such to a
limitation of the achievable undercooling range. The microgravity available
 169

in space f1 ight lends itself as an environment to conveniently perform ex-

periments in containerless processing. eliminating one of the dominant
reasons for heterogeneous nucleation. It therefore allows to study the
nature of nucleation in more detail. to study the dynamics of the process
involved. and to access a larger range of metastable solid phases.

8.1 Nucleation Theory

In the following. we will give a short insight into the basic problems in-
volved in our understanding of the nucleation process. with special empha-
sis on its influence on the solidification transition. A phase change is
driven by a difference in free energy between the two phases. which forces
the system into the equil i bri urn phase at the temperature chosen. On the
other hand. nucleation sets up an activation barrier to be surmounted by
the phase, transition. such leading to undercool ing affects. In addition.
mobil ity considerations may influence the dynamics of the process. This
will result in a characteristic time and temperature dependence of any
transformation involving nucleation.

The first satisfactory theory of nucleation was given by Volmer and Weber
[8.2) who describe the nucleation of supersaturated vapour. This theory has
later been improved by Becker and Doring [8.3). who developed a kinetic
theory of nucleation. An extension of this theory to the phase transition
liquid - solid was undertaken by Turnbull and Fisher [8.4). In the follo-
wing we will develop the basic concept of this theory. first considering
homogeneous nucleation and then nucleation due to foreign phases within the
bulk or at the surface of undercooled melts. called heterogeneous nuclea-
tion.

8.1.1 Clusters and Nuclei

Consider a liquid with its essentially free motion of atoms. driven by tem-
perature. At any time atoms will approach each other statistically to dis-
tances comparable to the solid interatomic spacing, forming solid-like clu-
sters. However. as the temperature is above the melting point. these cl u-
sters will decay spontaneously. At the melting temperature TM• the free
energy of the solid (G s ) and liquid phase (G1) are equal, the two phases
170

being in thermodynamic equilibrium (Fig. 8.1). As we undercool the liquid

by an amount fl T = TM - T the free energy of the solid is lower by the
amount fl Gv• so we expect a spontaneous growth of the cl usters to form a
crystal. A negative free energy difference flG v therefore drives
crystallization.

>-
0'1
L..
Q.l
C
Q)

-
Q)
Q)
L..

I I
VI
.0 --1.1 T l-
.0 I
C)

TM Temperature

Fig.8.1. Temperature dependence of Fig.8.2. Free energy of formation

the bulk free energy of the solid of a nucleus as a function of its
and liquid phases radius

So far we have considered only the bulk contribution to the free energy
difference between solid and liquid. A cluster. however. implies an inter-
face between a liquid and a solid phase. described by an interface energy
a. which has to be taken into acccount in the free energy balance. The in-
terface energy is always positive and therefore acts as a barrier against
crystallization.

The free energyflG required to form a spherical cluster of radius r can now
be written as a sum of volume and surface contributions:

(8.1 )

This function is plotted in Fig. 8.2. showing separately the volume and
surface contributions flGv andflGs. respectively. 6G exhibits a positive ma-
 171

ximum of value 6G* at a critical radius r*, which forms an activation bar-
rier against crystallization and therefore is crucial for the undercooling
behaviour of a melt. For clusters of size below r* the surface-to-volume
ratio is large, so the surface contribution predominates. Such a cluster is
called an embryo, it is unstable and decays spontaneously. On the other
hand, a cluster larger than r*, termed a nucleus, can lower its free energy
by growing. Once it has grown beyond ro = (3/2) r*, it represents the
stable form of the system, so it will initialize crystallization.

The critical nucleus size r* can be obtained by differentiation of Eq.

(8.1):

(8.2)

The free energy barrier 6G* required to form a nucleus of critical size r*
is obtained by substituting (8.2) into (8.1):

(8.3)

It is of interest to obtain these quantities as a function of undercooling

of the melt. In a first approximation, the surface tension a can be assumed
independent of temperature in the undercool i ng range consi dered. For the
volume contribution to the free energy, Turnbull [8.51 has proposed a linear
approximation

(8.4 )

Here 6Hf denotes the heat of the fusion and 6T the undercooling TM- T •
With this we obtain

(8.5)

and r* = (8.6 )
172

~~r-----------------------------~
critical nucleus
Copper
Fig. 8.3. Critical nucleus
size: radius for copper as a function
0,.;'1.44·102 erglcm 2 of undercooling
AGy=AH,· ATITM
AH,=1.88 .1Q'Oerglcm3

E
....
~

---- -- ---
Lattice parameter
Cu: 3.61·1Q-8 cm

~-8'---__________--:':-::---:-:::-:-:-:-____----::-L--_ _--l
100 A TIKI - 200

Using experimental values of the (macroscopic) surface tension and the heat
of fusion, the temperature dependence of the critical nucleus size can be
calculated as shown in Fig. 8.3 for copper. The radius of a critical nucle-
us is seen to decrease continuously with undercooling ~T. At small ~T the
critical size is large, enclosing 106 to 10 7 atoms within the nucleus,
whereas at large undercooling the critical nucleus becomes very small, con-
taining only some hundreds of atoms. Apparently, questions arise on the va-
lidity of this simple theoretical approach at extreme undercooling values,
as a nucleus of a few hundred atoms cannot be treated by the thermodynamics
of macroscopic systems. In addition, the surface tension cr will become size
dependent as the radius of the nucleus approaches atomic scales [8.6]. On
the other hand, careful experimental results obtained at extreme degrees of
undercooling hold promise of leading to nfw information pertaining to the
microscopic properties of interfacial tension and cluster formation.
 173

B.1.2 Homogeneous and Heterogeneous Nucleation

With I1G*. the activation energy for the formation of a critical sized nu-
cleus. we can calculate the number of critical nuclei in a melt as

n* = Nk exp(-I1G*/kT) (B.7 )

Nk represents the number of equivalent sites. where nucleation can occur.

If Nk is equal to the number of atoms in the melt. i.e. each atom poten-
tially is a site for a nucleus. we have the case of homogeneous nuclea-
tion. fj,G* will then be represented by the form given in Eq. (B.3) for a
spherically shaped nucleus.

For the case of heterogeneous nucleation. Nk will be much smaller. repre-

senting wall sites or sites on catalytic particles within the melt. Hetero-
geneous nucleation sites will be active if they reduce the activation ener-
gy barrier against formation of a critical nucleus fj,G*. This barrier ari-
ses from the influence of the interface energy. so any change in interface
conditions introduced through an additional surface will have a dras~ic in-
fl uence.

Consider a cap-shaped cluster growing on an interface as illustrated in

Fig. B.4. Having the critical radius r = r*. the cap would be stable a-
gainst decay. except for its contact circle. which has a radius
r* sin -3 < r*. The cap can. however. be stabilized by surfaces forces as
shown in Fig. B.4 under the condition

-0'."
~
= 0'c;s + 0'I,c cos-3 (B.B)

where the subscripts c. 1 and s stand for cap (crystal nucleus). liquid.
and solid. respectively. This reduces the total volume required to form a
stable nucleus by the factor

f(-3) = 1/4 (2 - 3cos-3+ cos 3-3) ( B.9.)

whi ch is smaller than uni ty for any contact angl e below -3 = 1BOo. Conse-
quently the activati on barri er for heterogeneous nucl eati on is reduced by
the same factor
174

(8.10)

whi ch will 1ead to a corresponding decrease in achi evabl e undercool i ng

range, whenever heterogenous nucleation is active.

'. ,',. ,"'

Fig. 8.4. Heterogeneous nucleation:
stability of an embryo on a
','

"Liquid
substrate
:.: '

8.1.3 The Nucleation Rate

Assuming a nucleus of critical size will grow and induce crystallization by

addition of a single atom, the nucleation rate will take the form

I = n* dn/dt (8.11 )

where n* is the number of nuclei having critical size as given in Eq.

(8.2), and dn/dt is the rate of addition of a single atom from the melt.
The latter can be described as a diffusion controlled process, illustrated
in Fig. 8.5,

(8.12 )

with t,GA the activation energy for diffusive motion, Q a being proportional
to the number of atoms in contact with the nucleus, the atomic jump fre-
quency, and an accomodation coefficient.

0-0
Atom Nucleus
Fig. 8.5. Variation of free energy
for diffusive motion of an atom from
the liquid onto a nucleus
®;'s.7\ "
__ ~~._\J
Configuration
 175

rhe nucleation rate can therefore be expressed as a product of two exponen-

tial tenns:

(8.13 )

where~, Nk and /::"G* are depending on the nucleation process considered,

i.e. heterogeneous or homogeneous.

Of main interest in the present context is the variation of the nucleation

rate I as a function of temperature in the undercooling range T < TM• The
first tenn, describing the rate of addition of a single atom, decreases
monotonically with temperature, as the mobility of atoms in the liquid
phase becomes more and more impeded. On the other hand, the second factor
vanishes at the melting temperature, where the driving force /::"G v vanishes.
The activation barrier for critical nucleus formation will rapidly decrease
with increasing undercool ing and nucleation driving force /::"G v = Gs -Gl.
Therefore the number of critical sized nuclei will increase with decreasing
temperature, leading to a bell shaped curve for the nucleation rate as
shown in Fig. 8.6.

low Mobility high

high Number of nuclei low

ill
-0
0:::
c
Q
-0
~
U
::J
Z

exp(-llGA I k BT )

Temperature Tm

Fig. 8.6. Schematic temperature dependence of nucleation

rate, resulting from Eq. (8.13)
176

a.2 Nonequi1ibrium Solidification

An undercoo1ed melt represents a nonequi1ibrium system that has the poten-

tial to solidify into a nonequi1ibrium solid. Of course, the main interest
here is to control this process in such a way as to obtain a final solid
product of novel and interesting properties. The nature of the product is
determined by a competition between the kinetics of cooling and the kine-
tics of solidification, and by the thermodynamics of the system. The prope-
rties affected are the composition, homogeneity, and the structure, both on
a macroscopic and a microscopic scale.

a.2.1 Undercoo1ing and Hypercoo1ing

As a melt solidifies, the latent heat of fusion is released. This is, of

course, also the case for solidification from an undercoo1ed melt, with the
exception of amorphous solidification. The heat of fusion will, for small
degrees of undercoo1ing, heat the sample to the melting temperature, where
it will remain stationary until all material is transformed. Therefore only
the very fi rs t fract i on of the soli d wi 11 be soli difi ed under nonequ il i-
brium conditions, while the rest is transformed in a nominal equilibrium
process.

Apparently large degrees of undercoo1ing are required to ensure nonequi1i-

brium sol idification in the presence of reca1escence. Assuming adiabatic
conditions, this range can be defined by
TN
llHf :::: fc~ dT (a.14)
TN
where llH is the heat of fusi on, TN the nuc1 eati on temperature and c~ the
specific heat of the liquid. The values of TN for which inequality (a.14)
is satisfied is called the hypercoo1ing regime, with the equality holding
for the temperature of critical undercooling. In an alloy, critical under-
cool ing temperatures may be defined for various phases, as shown in Fig.
a.7. Undercooling to a temperature Tl will initilize solidification in the
a-phase. Reca1escence will bring the interface temperature into the two-
phase regime, where compositional partitioning takes place. In the hyper-
cooling regime, for recalescence temperatures TR below the solidus line Ts.
segregations solidification with uniform composites Co will occur [a.7].
 177

HYPOCOOLING HYPERCOOLING

T > TS

f
R

w
Q::
::::l T1
t-
<t:
Q::
UJ
Cl..
:L
UJ
t- SEGREGATED I-OMOGENEOUS IX

TIME ~ A TIME ____

%8 ~

Fig. 8.7. Illustration of hypocooling and hypercooling for adiabatic

solidification of theO(~phase. T1 and T2 are the respective undercooling
temperatures; TR designates the recalescense temperature

8.2.2 Thermodynamic Conditions

Undercooling can be a means to reach areas in the phase diagram not acces-
sible by equilibrium processes. Metastable crystalline phases can be soli-
dified in pure metals and alloys. In addition, the solubility of alloy sys-
tems can be extended beyond the equilibrium stability limits. This may lead
to the construction of "metastable phase diagrams" [8.8.-8.10).
CRITICAL
UNDERCOOLI NG

t.H= /s ci dT
T1 P

T1 HOMOGENEOUSCl
(EXTENDED SOLID
SOLUTION)
A TI ME _______

Fig. 8.8. Illustration of critical undercooling for adiabatic solidifi-

cation of theO(-phase with extended (metastable) solubility
178

The extension of solubility limits is illustrated in Fig. B.B. Assume we

can suppress B-nucleation either because, by chance, the lX-phase is the
more potent nucleation catalyst, or by intentionally introducing ~-nuclei
through a previous undercool ing cycle with reheating into the lX + 1 iquid
regime [B.7]. During undercooling, growth of the ~-phase occurs along the
extension of the lX solidus line as shown by the dashed line in Fig. B.B.
Provided the lX-phase can be undercooled to point Tl, critical undercooling
will result in a solid solution of a composition Co far beyond the equili-
brium solubility limit in the lX-phase.

An example for the solidification of a metastable crystalline alloy phase

is illustrated in Fig. B.9. Starting with a composition ca, sufficient
undercooling will result in a solid consisting of phase lX and the metasta-
ble phase l ' circumventing the formation of the stable B-phase. On the
other hand, pure l-phase may be sol i dified by undercool ing of a melt with a
composition within the range of the metastable phase, cb.

Fig. 8.9. Schematic illustration

of a possible reaction path for
primary phase catalysis of a
metastablet intermediate phase

I
/
"\
\
/ l \
I \

A B

B.2.3 Influence of Solidification Kinetics'

The final product of solidification following undercooling will depend on a

competitive infl uence of cool ing and sol idification dynamics. While the
cool ing rate is a parameter that can be controlled by the experimenter,
vari ous factors contribute to the time dependence of the crysta 11 i zati on
process •
 179

The steady state nucleation rate I derived in Section 8.1.2 is of limited

applicability to estimates on crystallization dynamics. In particular, con-
siderations concerning the growth of overcritical nuclei or crystallites
have to be taken into account. The kinetics of crystallization has been
calculated by Uhlmann [8.10-8.12], based on the work of Avrami [8.13], as-
suming constant crystal growth rate and nucleation rate with time. Defining
a certain volume fraction X as the limit of observable crystallization,
this may be expressed as

(8.15 )

where I is the steady state nucleation rate discussed above, u the rate of
advancement of the crystal 1 ization front per unit area, and t the time.
Based on this equation, socalled time-temperature-transformation (TTT)
curves can be constructed, an example of which is shown schematically in
Fig. 8.10.

A: homogeneous nucleation
Band C : heterogeneous nucleation
T of different activation energies
~"':;:,.-::..-- - T'
'- , -- -- C
" "',--':::-'- c
-'<- - ~~ -T';:"'~'l'-::: -
\ ',A
A

(cooling rate q )

quenched - in nuclei

Fig. 8.10. Temperature-Time-Transformation (TTT) diagram representing

different nucleation kinetics. The horizontal. position of the "nose"
corresponds to the number of potential nuclea·tion sites whereas its
width varies inversely to the activation energy to form critical clusters

In the TTT-diagram, the area inside the nose-shaped curve indicates the
region of observable crystallization. It is bounded by the melting
temperature TM and the glass temperature TG• Cooling curves can be plotted
as shown by the dashed lines. Their intersection with the TTT-curve
represents time and temperature of crystallization.
180

Different TTT -curves are possible corresponding to homogeneous nucleation

and various heterogeneous catalysts of different potency and size of ac-
tive area. This is indicated schematically in Fig. 8.10 by the curves
labelled A, B, and C. The time position of the nose is essentially deter-
mined by the number of active nucleation sites. Therefore we expect the
curve representing homogeneous nucleation to extend towards the smallest
time scal es. On the other hand, the wi dth of the TTT -curve is rel ated to
the inverse of the catalytic potency factor f (a) [8.9). Therefore, highly
potent heterogeneous nucleation centers will be reflected by a wide TTT-
curve like C in Fig. 8.10.

A significant feature of the TTT-curve is its ability to allow estimates of

. .
the relation between cooling rate and nucleation process and thereby the
~orm of the final phase obtained. With different cooling rates TA , Ta , and

Te , various nucleation processes can be selected, which may lead to differ-

ent phases of the final product. In particular, any cooling rate beyond Tx
wi 11 avoi d the regi ons of observabl e cry stall i zati on and wi 11 therefore
lead to a non-crystalline product, an amorphous or glassy phase.

8.2.4 Microstructure Refinement

The degree of undercooling prior to solidification has a marked influence

on the microstructure of the resulting solid products. In particular, high-
ly refined microstructures can be obtained by the process of rapid solidi-
fication. These are of special interest to materials sciences, as they hold
promise of improvements in mechanical properties such as strength, hard-
ness, and ductil ity, but al so in electric and magnetic properties, for
example reduction of electric conductivity and its temperature dependence,
softening of magneti c hysteresi s and the accompanyi ng losses, or prepara-
tion of "hard" superconductors with high critical magnetic fields (flux
pinning, Ref. 8.14).

Investigations of microstructural refinement have revealed a systematic de-

crease of grain size and dendritic arm spacing with increasing undercooling
on a variety of metallic systems [8.15-8.21). A number of materials exhibit
a stepwise decrease in grain size by about one order of magnitude, which
happens to occur at an undercooling around 6.T = 170 K. As an example, Fig.
8.11 shows the grain size of the invar alloy FeNi as a function of the de-
 181

gree of undercooling ~T [8.18]. For small ~T, the grain size remains nearly
unchanged until a critical value ~T* = 170 K is reached. Beyond 170 K, it
fall s abruptly within a small temperature range and then decreases slowly
with further undercooling. The rapid change in grain size at ~T* is often
accompanied by a disappearance of dendritic structure [8.18,8.19]. A com-
parable microstructure refinement to the grade shown here, with grain sizes
of a few micron, can otherwise be reached only by rapid quenching technolo-
gies [8.22].

Fig. 8.11. Grain size vs.

degree of undercooling in a
bulk undercooled melt
.l Fe-25%Ni
(Ref. 8.18)
• Fe-25%Ni-O.3%S

3-
'"
N
(f)

c:: 10 2
.-
~
l!l

-0

10
o 400
t.T. Degree of Undercooling (Oc)

Vari ous controvers i a1 approaches have been proposed to expl ai n the sudden
onset of microstructure refinement. One model relies on the rapid tempera-
ture increase due to recalescence [8.19]. Solidification following deep
undercooling is accompanied by a rapid release of the heat of melting,
which may lead to heating rates during the reyalescence phase in the order
of 10 3-10 6 K/s [8.23]. This heating process was suggested to be responsible
for the observed microstructure refinement by means of remelting of a pri-
mary dendritic structure, as the temperature locally rises near to or even
above the solidus temperature of the alloy. A semiempirical relation has
.
been found [8.21] between microcrystall ine grain size Land recalescence
heating rate T as

L2 • T= const. (8.16 )
182

In a different model, Horvay [8.24] has related the microstructure

refinement to a rapid increase in nucleation rate. With increasing
undercooling the crystallization velocity will increase (as long as we do
not yet reach the range of reduced atomi c mobil i ty). Now the growi ng
crystal usually will have a higher density than the liquid. With increasing
crystallization velocity the accompanying volume reduction can locally lead
to large negative pressures in the adjacent liquid, so cavitation may
occur. Collapsing cavities generate shock waves, which in turn might
include nucleation. This mechanism has been cited to interpret the
microstructure refinement of copper base alloy [8.25].

A number of additional experimental results are required to clarify the

underlying mechanism of microstructural refinement by undercooling. Acous-
tic measurements might be hel pful to clarify the role of cavitation or
cavity collapse during crystallization of an undercooled melt. On the other
hand, the influence of dendritic remelting on grain size could be clarified
by experiments that quench a melt at predefined levels of undercooling be-
fore or at the onset of spontaneous solidification. In both cases, observa-
tion of the recalescence process by means of high speed temperature mea-
surements could help to improve our understanding of the solidification
process through comparison with thermal modelling studies.

8.3 Experimental Approaches

Undercooling of metallic melts has been shown to be the key to various

novel products through the mechani sms of phase sel ecti on or mi crostructure
refinement. There are two distinctly different ways to achieve a high de-
gree of undercooling. Using very high cooling rates, such that the cooling
front propagates in the material with a velocity comparable to the crystal-
lization velocity, allows a control of solidification
,
kinetics. On the
other hand, cry stall i zati on can be constrai ned by i nfl uencing the nucl ea-
tion process, which is possible in case of predominant heterogeneous nuc-
leation. As shown in Subsect. 8.2.3, a removal of potential nucleation
sites leads to a shift of the respective temperature-time-transformation
curve along the time scale, so lower cooling rates lead to the same trans-
formation kinetics.
 183

8.3.1 Rapid Cooling

There are different techniques to achieve high cooling rates in the order
of 10 6-10 8 K/s by quenching the melt into the solid state [8.26]. The basic
pri nci pl e is to convert the 1i qui d very rapi dly from a droplet or jet into
a thin layer in contact with a substrate of high thermal conductivity. To-
date, two techniques are mainly in use. The socalled splat-cooling tech-
nique uses an anvil and piston arrangement, which can be rapidly moved by
either pneumatic pressure or electromagnetic forces. The sample is usually
melted in a levjtation coil in containerless state. When the melting pro-
cess is completed, the levitation force is switched off. The liquid droplet
falls through a light gate which initiates the anvil and piston mechanism.
The sample is quickly pressed into a splat of typically 20-80 ~m thickness
and 15-30 mm diameter. Due to these inherent limitations of sample dimen-
sions, the splat cooling technique is used mainly for basic research pur-
poses and for ultrapure sample preparation.

The second method employs a rapidly spinning copper wheel with typical sur-
face velocities of 2 km/min. The material to be quenched is melted induc-
tively in a crucible with a thin hole at the lower end. The melt is then
driven through the hole by gas pressure and spoutes out as a jet. At the
polished surface of the fast rotating wheel the melt is rapidly cooled in a
continous manner. The product of the melt spinning process is in the form
of thin ribbons of typical thickness of 20-60 ~m and up to 60 cm width.

These methods allow the application of extremely high cooling rates and are
standard processes for the producti on of metal sin the amorphous state,
even for commercial purposes. There are, however, a few points that have to
be taken into consideration. The low temperature at the melt-substrate
interface will lead to a large driving force for nucleation, which is en-
hanced by the fact that the substrate surface ltself can act as a heteroge-
neous nucleation site. The short time scales ihvolved can lead to a possi-
ble influence of transient effects in certain alloys [8.27], which are
neglected in the theoretical considerations given in Sect. 8.1. In addi-
tion, the preparation of metastable phases or microcrystalline solids by
these methods is limited to configurations of thin foils or ribbons. Such
limitations can be overcome by approaching the undercooling problem from
the other side, viz. using nucleation control methods rather than rapid
cooling.
184

8.3.2 Amorphous Containment

Assuming that heterogeneous nucl eati on at the interface to the contai ner
wall is the dominating process initiating solidification, one may try to
deactivate this catalytic nucleation site using inert walls. Walker [8.15]
developed a technique whereby the melt is kept in a container such that
it is separated from the crucible wall by a thin glassy coating consisting
of vitreous silica or similar glasses. This method has been further
improved by Kattamis et al. [8.17]. Using this technique, a considerable
enlargement of the undercooling range has been attained. Both pure transi-
tion metals and their alloy systems could be undercooled to large 6. T
values, e.g. up to 300 K in the case of Ni [8.28]. Such degrees of under-
cool ing are sufficient to investigate the microstructural refinement and
are close to the regime of hypercooling, which gives access to metastable
phases.

In a more recent experiment Turnball et a1. [8.29] reported the successful

preparation of a bulk metallic glass of the easy glass forming alloy Pd40
Ni40P20 of 1 cm3 in volume. Here the melt was embedded in a boron oxide
fluxing material and was cooled slowly with 1 K/s down to the glass tem-
perature, corresponding to an undercool ing of more than 6. T = 300 K. This
result is of particular interest because a critical cooling rate to avoid
crystallisation of 120 K/s has been calculated for this very alloy within
the framework of homogeneous nucleation theory [8.30]. Hence, the classical
nucleation theory seems to lead, at least in some cases, to an overestimate
of the homogeneous nucleation rate.

The melt fluxing method was the first successful technique to achieve deep
undercooling of large melt volumina. However, the detailed influence of the
coating material on the metallic melt remains unclear, at least concerning
the atomic processes at this interface. Moreover, the influence of
nucleation within the melt is still open, because only surface or interface
stimulated nucleation can be investigated.

8.3.3 Dispersion Techniques

The dispersion technique has been successfully applied in undercooling

experiments on a varity of different metals by Turnbull [8.31]. The method
 185

is based on a subdivision of the melt into small droplets. Assuming a

random distribution of heterogeneous nucleation sites within the melt, the
probability to find droplets free of any nucleation site will increase
rapidly as the droplet dimension approaches the average nucleation site
separation. For particle sizes of a few micron the solidification kinetics
is essentially determined by the "nucleus free" particles. Turnbull
concluded that in this case the limit of homogeneous nucleation may be
reached [8.32]. Investigations of a series of metallic elements yield in
this limit a maximum undercooling of roughlYilT::: 0.2 TM[8.33].

Recently Perepezko [8.34] combined the methods of particle subdivision and

amorphous containment by processing the subdivided samples not on a sub-
strate but in a liquid emulsion. Here mainly materials of low melting point
have been investigated. Surprisingly large degrees of undercooling have
been achieved in this way, in many instances twice those of earlier experi-
ments. A direct consequence of these results is the observation that the
limit of maximum undercooling by homogeneous nucleation apparantly is much
deeper than ilT = 0.2 1M. A careful analysi s shows that even those results
can be related to surface induced nucleation. So the hope exists thatex-
tended undercool ing might be possible by further reducing heterogeneous
nucleation processes.

8.3.4 Containerless Undercooling

One of the simplest techniques to perform containerless undercooling ex-

periments is the use of drop tubes. Recently this technique has been pro-
gressively utilized for nucleation studies in undercooled melts. Turnbull
et al. [8.35] used a short drop tube of about 1. 2 min 1ength to study the
undercooling behavior of PdSi droplets in a containerless state. This alloy
is a primary candidate for such investigations ,because the nucleation rate
is small compared to other metallic systems, so cooling rates of the order
of 10 4 K/s are sufficient to supress crystallization [8.36]. The melt of
the easy glass forming alloy Pd82Si18 was melted and dispersed to droplets
of 50-370 ~m in size. Depending on the droplet diameter d the droplets
solidified partly in a glassy state during the free fall. The fraction x of
gl assy dropl ets was then anal ysed. Fi g. 8.12 shows a di agram where xis
plotted versus d for Pd82Si18 droplets solidified in a drop tube filled
with Helium atmosphere. Assuming that the partition of glassy droplets was
186

x = exp[-(d/do)~J
0.8 Heterogeneous Volume
Nucleation
~
<[
x = eXP[-(d/d o)4.S]
G 0.6 Homogeneous Nucleation
oz _ x=exp[ -(d/d o)2]
B0.4
<[
Heterogeneous Surface
Nucleation
0::
u..
x 0.2
do =190 p.IT is used for
all three models

d DROPLET DIAMETER IN p'm

Fig. 8.12. The comparison of the drop tube results for Pd 82Si 18 with
the predictions of three nucleation models

free of heterogeneous nuclei, the measurements could be analysed with

respect to different nucleation processes. As can be seen from Fig. 8.12,
the results suggest dominant heterogeneous surface nucleation, which can be
related to oxidation processes at the surface. Similar results and
i ndi cati ons of surface oxi dati on i nfl uences have been found for ni obium,
undercooled in the 32 m drop tube at NASA [8.37].

Drop tube measurements suffer a problem in the determination of accurate

temperature-time profiles during solidification. This difficulty, along
with the surface contamination problem, can be overcome by using electro-
magnetic levitation techniques in an ultraclean environment. Now problems
are encountered here such as the sample stability against oscillations and
rotations [8.38] or temperature regulation [8.39], because the levitation
r.
force similtaneously is the heating sourc In spite of this, undercooling
experiments on Fe and Ni have been succes~fully performed [8.40,8.41] with
~T of 420 K and 480 K, respectively, thus extending the undercooling range

for these metals by a factor 1.5 compared to earlier results [8.33]. With
appropriate precautions against oxidation and other surface contamination,
enlarged undercooling levels have been achieved for other metals and alloys
by electromagnetic levitation, despite the large size of the sample
compared to those used in dispersion methods.
 187

8.4 Microgravity Prospects

~s shown in the preceding sections, nucleation is of fundamental interest

in the control of the liquid-solid phase transition and its consequence on
phase selection or microstructural refinement. Although nucleation
processes are qualitatively described within the classical nucleation
theory, many basic questions on nucleation in undercooled melts remain
open, concerning both the origin of heterogeneous nucleation at interfaces
and the quantitative calculation of nucleation rates as a function of
undercooling. A primary concern in an attempt to extend our insight into
the nature of the nucleation process is to strive for the limits of the
undercooling range. This implies reduction of heterogeneous nucleation as
far as possible. One of the most effective techniques to obtain extended
degrees of undercooling is containerless processing of melts in an
ultraclean environment. Investigations on undercooled liquids in
ultra-high-vacuum conditions and avoiding any contact with container walls
are strictly 1imited on the earth. While the electromagnetic levitation
technique looks promising at first glance, it is applicable only to metals
of high melting point, because levitation against earth gravity implies a
lower bound to the power absorption. As heat transfer takes place by
radiation only, the sample temperature cannot be lowered beyond a minimum
of about 1300 K. On the other hand, drop tower experiments are limited by
the short free fall time of a few seconds at most and a probl em in
obtaining accurate temperature-time profiles during the cooling period.

The microgravity environment offers a way out of this dilemma. Positioning

forces in a space laboratory are at least three orders of magnitude lower
than required on earth. This implies a lower boundary of unavoidable heat
input, so the samples can be held in position at much lower temperatures.
The low positioning forces lead to an additional advantage over. ground
levitation, which relates to undesirable fluid motions in the melt. Under
Ig conditions, the highly inhomogeneous levitatlon forces induce a violent
agitation of the 1iquid, which can result in disruption of the sample.
While the question of possible nucleation processes from fluid motion is
still open (dynamic nucleation), the quiescent state of a suspended liquid
in space certainly is preferable, with the extra benefit of lacking
convection or sedimentation effects in space.

With the possibility to achieve extended degrees of undercooling in an en-

188

vironment of controll ab le puri ty, a number of prospecti ve research areas

become accessible from microgravity experiments, including

- an improvement of our understanding of heterogeneous and homogeneous

nucleation processes;
- a delineation of the range of validity of present nucleation theory, par-
ticular for very large undercooling levels and thus small critical
clusters;
- extension of our knowledge on transformation kinetics over a wide range
of IJ.T;
- control of phase selection processes and metastable phase production;
- improved and controlled microstructural refinement.

From a more practical point of view, the possibility to process large quan-
tities of metallic alloys in an undercooled state opens new avenues to pre-
pare alloys of novel compositions and microstructural properties in stable
or metastable phases. Furthermore, the technique of liquid skin technology
[8.42] allows for production of material s in a predefined shape using
undercooling methods, such providing the possibility to obtain products
with novel properties in a form immediately ready for application.

References
8.1 J.W. Christian, The Theory of Transformations in Metals and Alloys
Part I, Pergamon Press (1975)
8.2 M. Volmer and A. Weber, Z. Phys. Chern. ~, 227 (1926)
8.3 R. Becker and W. Doring, Ann. Phys. 24, 719 (1935)
8.4 D. Turnbull and J.C. Fisher, J. Chern. Phys. 12, 71 (1949)
8.5 D. Turnbull, J. Appl. Phys. Q, 1022 (1950)
8.6 D.H. Rasmussen, M.R, Appleby, G.L. Leedom, S.V. Babu and R.J. Nau-
mann, J. Cryst. Growth 64, 229 (1983)
8.7 M. Cohen, B.H. Kear and R. t~ehrabian, in: Rapid Solidification
Processing: Principles and Technologies II, ed. by R. Mehrabian,
B.H. Kear and M. Cohen (Claitor's, Baton Rouge, LA,1980), p. 1
8.8 J.H. Perepezko and J.S. Paik, in: Proc. 29th Midwest Solid State
Conf.: Novel Materials and Techniques in Condensed Matter, ed. by
G. Crabtree and P. Vashishta (North Holland, N.Y. 1982), p. 57
 189

8.9 J.H. Perepezko, Y. Shiohara, J.S. Paik and M.C. Flemings, in: Third
Conf. on Rapid Solidification Processing: Principles and Techno-
logies (NBS, Gaithersburg, MD, 1982), p. 1
8.10 J.H. Perepezko, in: Int. Workshop: Nucleation - Rapid Solidification,
ed. by: P. Sahm (RWTH Aachen 1983), p. 9
8.11 D.R. Uhlmann, J. Non-Crystalline Solids Z, 337 (1972)
8.12 P.I.K. Onorato and D.R. Uhlmann, J. Non-Crystalline Solids, ~,
367 (1976)
8.13 M. Avrami, J. Chern. Phys. ~, 177 (1941)
8.14 W. Buckel, Supraleitung (Physik-Verlag, 1972)
8.15 J.L. Walker and G.R. St. Pierre, Interscience Publishers (N.Y.1961)
8.16 M.E. Glicksmann, Acta Met. Ii, 1231 (1965)
8.17 T.Z. Kattamis and M.C. Flemings, Trans. AIME 236, 1523 (1966)
8.18 T.Z. Kattamis and M.C. Flemings, Mod. Casting ~, 191 (1967)
8.19 T.Z. Kattamis, J. Cryst. Growth 34, 215 (1976)
8.20 G.D. Merz and T.Z. Kattamis, Met. Trans. 8A, 295 (1977 )
8.21 T.Z. Kattamis and S. Skolianos, in: Proc. 5th Int. Conf. on
Rapidly Quenched Metals, (WUrzburg 1984), p. 51
8.22 P.G. Boswell and G.A. Chadwick, Scripta Met. ll, 459 (1977)
8.23 M.C. Flemings and Y. Shiohara, Mat. Sci. Eng. 65, 157 (1984)
8.24 G. Horvay, ASME Proc. 4th US Nat. Congr. Appl. Mech. Part II
(New York 1962), p 1315
8.25 K. Lohberg and H. MUller, Z. Metallkde. 60, 231 (1969)
8.26 H. Beck and H.-J. GUntherodt, in: Glassy Metals I (Springer
Berlin, Heidelberg, New York, 1981), p. 1
8.27 C.V. Thompson, A.L. Greer and A.J. Drehman, in: Proc. 4th Int. Conf.
on Rapidly Quenched Metals, (Sendai 1981), p. 743
8.28 B. Lux, G. Haourand F. Mollard, Metall 3!"i, 1235 (1981)
8.29 H.\~.Kui, A.L. Greer and D. Turnbull, Appl. Phys. Lett. 45, 615
(1984)
8.30 H.A. Davies, in: Proc. 3rd Int. Conf. on Rapidly Quenched Metals,
(London, 1978), p. 1
8.31 D. Turnbull and R.E. Cech, J. Appl. Phys. Q, 804 (1950)
190

8.32 D. Turnbull, J. Chem. Phys. 20, 411 (1952)

8.33 see e.g.: B. Chalmers, Principles of Soli,dification (John Wiley
and Sons, New York, 1964)
8.34 J.H. Perepezko, in: Rapid Solidification Processing: Principles and
Technologies' II, ed. by R. Mehrabian, B:H. Kear and M. Cohen
(Claitor's, Baton Rouge, LA, 1980), p. 56
8.35 A.J. Drehman and D. Turnbull, Scripta Met. ~, 543 (1981)
8.36 M.- Naka, Y. Nishi and T. Masumoto, Proc. 3rd Int. Conf. on Rapidly
Quenched Metals (London, 1978), p. 231
8.37 L.L. Lacy, M.B. Robinson and T.J. Rathz, J. Cryst. Growth~, 47
(1981)
8.38 U. Essmann and H. Kiessig, Mat. Res. Bull. li, 1139 (1979)
8.39 D.M. Herlach, R. Willnecker and F. Gillessen, Proc. 5th Europ. Symp.
on Material Sciences under Microgravity (SchloB Elmau, 1984), p. 399
8.40 S.Y. Shiraishi and R.G. Ward, Can. Metal Quart. l, 117 (1964)
8.41 D.W. Gomersall, S.Y. Shiraishi and R.G. Ward, J. Austral. Inst. Met.
10, 220 (1965)
8.42 H. Sprenger, Proc. 5th Europ. Symp. on Material Sciences under
Microgravity (SchloB Elmau, 1984), p. 87
9 Critical Phenomena
D. Beysens
Service de Physique du Solide
et de Resonance Magnetique
CEN Saclay
91191 Gif-sur-Yvette Cedex, France

Critical Phenomena is a part of Physics which has de-

veloped rapidly over the last 15 years, as exempled by the
1982 Nobel price for Physics which was awarded to K. Wilson
for his major contribution in the field. Indeed the domain co-
vered by this field is very large. The concept of a 2 nd order
phase transition, which is detailed below. allows many diffe-
rent phenomena encountered near a transition to be considered
as being equivalent and so they can be formulated by the same
universal laws. This universality applies to both the physical
phenomena - not only critical points are involved but also
percolation. fractals. etc. - and the physical systems. Indeed
a very large number of physical systems, such as simple
fluids. binary· or multicomponent fluid mixtures,- including
metallic liquid mixtures··-, liquid crystals, microemulsions,
polymers, molten salt, alloys···. superfluid Helium, magnets,
ferroelectrics, etc. exhibit the same universal behaviors.
These systems can be classified into a few "universality
classes" • according to very simple criteria as we will see
below. In the following we will mostly deal with the "class"
of fluids.
To date only a very few exper~ments have been perfor-
med to study Critical Phenomena in a microgravity (~g) envi-
ronment. However ~g should be very helpful in removing the

I< See also D. Langbei n, chapter 16

1<1< See also H. V. Walter. chapter 14
1<1<1< See also J. J. Favier. chapter 13
192

very large hydrostatic pressure effects which occur near the

critical point of pure fluids, and also in inhibiting sedimen-
tation and convection during the phase separation processes.
It is our aim to show here why and how the universali-
ty can apply to Critical Phenomena and what universal beha-
viors are expected (parts 9.1 to 9.3)····, to analyse how far
microgravity is concerned (part 9.4), and review the present
and future experiments connected to microgravity (part 9.5).

9.1. UNIVERSALITY OF THE CRITICAL BEHAVIOR. SCALING LAWS.

9.1.1 Broken symmetry - Order parameter.

Critical phenomena appear near a transition, which can

be of different types. A very fruitful idea, the notion of
"broken symmetry", was introduced by Landau[9. 1] to classify
them. Indeed a transition is always connected to a change - a
breaking - of symmetry. A good example for our purpose is the
ferromagnetic-paramagnetic transition which occurs for Iron at
the Curie temperature. The para-phase at high temperature is
characterized by no magnetization (M=O), whereas the ferro--
phase at low temperature exhibits a spontaneous magnetization
(M=M+or M-~O). The magnetization M is associated with a change
of symmmetry between the more symmetric phase (M=O, T>Tc) and
the less symmetric one (M~O, T<Tc) it corresponds to the
notion of order parameter. The order parameter vanishes in the
disordered, more symmetric phase, and remains finite in the
ordered, less symmetric phase.
According to the variation of the order parameter at
the transition, two kinds of transition may occur
1) In a first order transition, the order parameter is
i
discontinuous at the transition. FQr instance, the solidifica-

**** This part makes reference to a review I presented at the

4th European Symposium on Materials Sciences under Microgravi-
ty, Madrid, Spain, 5-8 april 1983, (ESA SP-191, June1983) in
which more details can be found.
 193

tion of liquid water at o·c under normal pressure is of 1st

order, the order parameter bei ng the densi ty.
2) I n a second order transition, the order parameter
is continuous at th. transition. Examples of 2nd order transi-
tions are the liquid - gas transition at the critical density
Pc' wi th H=p-pc the order parameter (fig. 9. 1 a), or the liquid -
liquid transition of a binary mixture A + B at the top of the
coexistence (or miscibility) curve: the mixture is homogene-
ous for while it decomposes in two phases for T<Tc
(fig.9.1b). With Cc being the critical concentration,the order
parameter is H = c A- cc. A line of critical points is formed
when the pressure is varied in such a multicomponent system.
Note that when initially p ;o! Pc or cA;o! cc' the order
parameter becomes discontinuous at the transition, and the
transition is 1st order.

,st order 2nd order aspect T ,st order 2"d order aspect
T11--+_'-_P_h_a_s_e-+___R_e..::.9_io_n_--1
T,

Fig. 9.1a - Transition gas-liquid near the critical Fig. 9.1b- Transition fluict-fluid near the disso-
point. The J-phase region is above the lution critical point. Te is a function
coexistence curve. A 2 nd order transi- of pressure P and there exists aline of
tion occurs only for the critical den- cri tical point versus P. A 2 nd order
sity P::Pc' T} >Tc :p=pc' T" <Te : p=p+ transi tien occurs for c=cc· T 1>Tc :
or p-. L
c=C c . T2<Tc : c=c+ or C-.

Finally, the notion of the order parameter can be ext-

ended to a vectorial quantity with dimensionality n. For ins-
tance, the order parameter in the superfluid transition of
Helium is a vector of dimensionality n=2.
194

9.1.2 The Landau free energy

According to the above classification, the free energy

F of a system undergoiong a 2nd order phase transition will
show the following behavior as a function of the temperature
T (f i g. 9. 2)

F(T,H)

Fig. 9.2 - Free energy of a system undergoing a

2 n d order phase transition, accounting
for the Fig. 9.1 behavior.

F exhibits only one solution M=O. ( 9. 1 )

F exhibits 2 solutions M=M+ or M ( 9. 2)

The power expansion of F versus M and T near the transition

has to be an even power of M for symmetry reasons
A( T) 2 B( T) 4
F( T, M) + M +--M + ...
2 4
The values of M at equilibrium are obtained by minimizing F
~F
~M
= 0 = M [A( T)
2
+ B( T) . M + . . .
'
1 = 0

The conditions (9.1) and (9.2) will be satisfied if A( T) is an

odd function of T-T c and B( T) an even function
A(T) =a(T-T c ) + ... and B( T) = b +
So the Landau free energy can be written:

F (9.3)
 195

whose minima provide the behavior of M in both regions

(a)-
T ~ Tc M=Q
+
T < Tc M-= ±
b
1/2
(Tc-T)
1/2

The behavior of any property whi ch deri ves from th,e

free energy is therefore universal near a 2nd order phase
transition - at least asymptotically where the F - expansion
remains valid. Transitions which initially look very different
from each other such as the Curie point, the gas - liquid cri-
tical point, the liquid - liquid critical point, etc. will all
exhibit the same universal behavior.
The main properties deriving from M are the following:
i) The order parameter. Equi Ii bri um values of Mare
of
obtained by solving - = Q
OM
iil The isothermal susceptibility (Xl.
In a magnetic system submitted to an external field H,
the is defined as :
i sot :e:m(~j us:ep(~~ ~)i ~ ~ t ~
( 9. 4)
T OM T
In the Landau approximation of the free energy, the behavior
of the susceptibility becomes, for T>Tc
<
For a gas - liquid transition, the analogous
of the field H is the chemical potential difference [~-~c]' ~c

is the critical value of the chemical potential ~. The corres-

ponding parameter is termed the isothermal compressibility

X
p (~:L with P the pressure.

For a liquid - liquid transition, the field

H corresponds to the chemical potential difference between the

components (Al and (B), i.e [(~A-~B) - (~: - ~:)]. The

c
~A.B are the critical values of the chemical potentials of
the components, ~A and ~B . The susceptibility is the iso-
thermal osmotic compressibility
X
196

iii) The specific heat (C).

For magnetic systems the specific heat is derived from
the entropy (S) through
os
C = T OT
By expressing the entropy in terms of the free energy, one ob-
tains
OF
S
OT
= -
and C = - T
OT 2
From (eq. 9.3) one sees that the specific heat exhibit a jump
at Tc ' in the Landau framework.
The corresponding quantity for C in a gas - liquid
transition is the specific heat at constant volume (Cv) in a
liquid - liquid transition, it is the specific heat at ~­

tant pressure and concentration (C p . c ).

i v) Other quanti ties.
We will consider in the following the interfacial ten-
sion ( en between the two coexisting phases when T<T c . With A
the surface ~~ea between the 2 phases, 0' is defined as
0' =
OA
[9.2J
and exhibits a universal behavior when approaching Tc

9.1.3 Scaling laws. The Renormalization Group approach.

9. 1. 3. 1 Fluctuations of the order parameter.

Near Te the susceptibility diverges. The fluctuations of the
order parameter around its mean value, due to the thermal ex-
citations of energy k8T (k 8 is the Boltzmann constant), will
therefore become larger and larger and go to infinity at T c .
In fluids, the density or concentration is strongly coupled to
the refractive index, whose fluctuations near Tc will give
t
rise to the well known phenomenon of critical opalescence.
However the Landau theory neglects in F such fluctua-
tions (see eq. 9. 3 where no gradient terms are included), which
are expected to diverge at Te according to the same theory!
This seems to be not self-consistent, and local fluctuations
of the order parameter K(r) - r is the space variable - had to
 197

be includ1ed i: free l~e e~ergy (:.3~:

d 2]
F - Fe = d r 2" (T-Te)H (r) + 4" H (r) + 2" IVH(r) I (9.5)
Here v is v the sample volume. The coefficIent (d) has the di-
mension a length squared. One can define a generalized suscep-

tibility X( r) by generalizing eq. 9. 4 : dH( r) = Iv x( r) dH( r)

This definition means that x(r) is proportional to the ~­

lation function of the order parameter fluctuations

<SHIrl SH(o» = keT x(rl
The Fourier transform of x(rl - which can be experi-
mentally determined by neutron,X- ray or light scattering - is

I
often called the structure factor Xq

Xq = x(rl e iqr dr
APPlY.[~~~)_~ Fourier transform to eq.9. 5, and remembering that

X = --- ,one finds :

OH 2 T

wi t h T = 1.
One notes that in the limit q=O, Xq =
X. In the direct space
1 exp-r/t
x(rl ~ <SHIrl SH(ol> ~ - -------
d r
t is a typical length, called the correlation length
t = (dIal 1/2(T_T e )-V with v = 1/2. At T e , t diverges.

9.1.3.2 Failure of the Landau free energy-Upper critical

dimensionality.
Now that fluctuations of the order parameter are evaluated,
the problem of the self-consistence of the Landau theory can
be solved. The fluctuations of M can be neglected if for exam-
ple the ratio <SH2 >/H 2 remains finite when T~Te. A simple cal-
culation shows that this condition is fulfilled in a space of
<SH 2 > [T c -T)<1ll-4)/2
dimensionality D if ----- ~ ---- remains finite at
H2 Te
Te . This shows that it is only in a space of dimensionality
D>4 that the Landau theory applies. The dimensionality De=4 is
called the upper critical dimensionality.
The final result is that the Landau theory is n~t va-
lid in our "usual" D=3 space[9.4].
198

9.1.3.3. More exact results (Renormalization Group).

Scaling laws. Value of the critical exponents.
The fact that the Landau theory does not fit the experimental
results has been known for a long time. The basic reason is
that the order parameter M(r) is a quantity attached to a
small -but macroscopic- volume of size LD (D=3 in our space).
located at r. which is supposed to be at thermal equilibriu~

Such an order parameter requires that the correlation length

!:'<L. This is not possible close to Te where!:. diverges. The
underlying idea of the Renormalization Group approach[S.S] to
critical phenomena is to take into account fluctuations over
all scales L up to L~!:.. This modern point of view reproduces
systematicallY the main theoretical ideas on critical beha-
viors :
i) Universality. The behavior near Te will not be de-
pendent on the particular nature of the molecular interac-
tions. For instance. the calculations performed on the transi-
tion ferro-paramagnetism. with an Hamiltonian describing the
free energy. could be applied to a fluid mixture as well.
ii) Homogeneity of the critical properties. Homogenei-
ty is a generalisation of the Landau behavior. which enables a
critical physical quantity G to behave asymptotically close to
Te according to a power law with exponent A. the so-called
.. scali ng laws".
Thus the Renormalisation Group approach provides nume-
rical estimates of each universal part of the critical beha-
vior. such as the exponents. The results are valid only on
special trajectories[S.6]. Defining a reduced temperature
t = T-Te/Te we obtain

{: >0
0
G (V t-"
+
(critical isochore)

{:
< 0
G (V (-t)-" (coexistence curve) (9.6)
0

{: -" e
0
G (V H (cri tical isotherm)
;x! 0
trrajec- order par.- specific suscepti bi l i ty correlation structure Icorrelatio~ 'nterfacial

tory . . ter heat function factor length tension

M C X G( r) S( q) F. a'

+
C + + -
+ -y .
t>O 0 -'" ksTx =Cot < SH( r). SH( 0) >0: Xq= F.+=F.ot 0
ks
+ (T=1.240) ( v=O. 630)
A - 0< +
-t +Bc
or.
(or.-0.110)
H=O
- -r/E.
2.
C - -y e - - -
t<O B( -t)" -= ksTx =Cot X F. =c.ot
. a'=a'o( - t)
---
r1+"1 (1 +q 2 F. 2 )1-"1/2
~s ( v=O. 630)
( ~·O. 325) (T=1.240) ( v=O. 630)
A - 0< -
;;:-t + Bc
or.=O 110)
H=DoMS
1 c -./II!
lH#o t=O ksTx c = ('11=0.032) ~czF.oH -
( 8=4. 815)
- -y/llS -
L...-- --_. ~ ----- _._.-
SDo -
I
-'-----

Table 1.1. Sunr'larv of the principal behaviors.

The exponents S, 8, a, y, v .•. are universal, the amplitudes B, Do, A, C , s ... are non universal .. It exists
o 0
~

however universal relations between them (2-scale factor universality, ref[9.8-9.9]. kB is the Boltzmann constant, (0
(0
200

A universality class is thus formed. One can genera-

lize the notion of the order parameter, which can be a vector
with n components. The critical behavior will be the same in
any universality class defined by nand D, the dimensionality
of space.
The class of fluids is determined by D=3, n=1, and the
principal behaviors[S.7] are resumed in table 9.1.

9.1.3.4 Relations among amplitudes 2-scale factor

uni versali ty.
Universal combinations between the non universal amplitudes B,
C, e. o ... can be. demonstrated[s.a-s.s]. For instance, the
combinations
Re - A+C+/B2 0.059

or Rx - C+D o BS - 1 1.7 are universa1.

This has a nice consequence since only 2 independent amplitu-
des are independent - and therefore only 2 measurements allow,
in principle, all other quantities to be determined.

9.1.3.5 Correction and background terms.

If the behavior of the critical fluids'is well described by
the above scaling laws, it should be noted that this descrip-
tion is valid only asymptotically close to the critical point.
This region lies approximately within 0.1 K from Te' Further
away corrections-to-scaling terms in the free energy must be
accounted for[S.10]. This idea is simple to understand when
considering the influence of fluctuations. Far from Te fluctua-
tions are negligible and Landau type expbnents should be
found. If one considers[S.l1] the susceptibility written with
an "effective"exponent , ! X ~ t-yeff(t)
ef{f~~b : 'M!ff = 1.240
the limiting behavior is
t-«o 'eff

By expanding the critical properties not too far from Te' one
refinds the original Wegner expansions:
order parameter M = B( -tl i3( 1 +a~1 t A + ... l
 201

C A
specific heat t- cx (1+oc.a e t 6 + ... ) + Be
ks oc.
susceptibi l i ty ksT C o t- Y (1+a x t 6 + ... )

correlation length 1'. 1'. o t- (1+a t t 6 + ... )

Y

The exponent 6 = 1/2 is universal, leading to the universali-

ty of the ratios of the corrections, whose value is of order
unity[S.12 J.
The universal behavior is restricted to a region where
a correlation length can be defined, i. e. where 1'. is larger
than the intermolecular distances (a o ). Usually 1'.0 is found to
be in the same range as a o ' which allows the critical domain
to be defined as
IT - Tel ~ Te
Most usual fluids and fluid mixtures exhibit a critical tempe-
rature near room temperature, allowing a critical region as
large as 300K to be determined. Outside this range the proper-
ties of the systems could no longer be described in terms of
uni versali ty.
I nve rs ely, the non-critical properties remain as
"background" terms when the critical point is approached. Ac-
cording to the strength of the divergence (i. e. the value of
the critical exponent "II. in eq. 9. 6) and the respective values
of the critical (Go) and background (Bo) terms, the critical
behavior can be affected or not
G Got-~ + G+ aGt 6+ ... ) + Bo
For weak divergences, such as the specific heat diver-
g en c e wit h e x p 0 n en t ()(.= O. 1 1 , or for dynamic properties as
shown below, background terms are seen to have much influence.
The only solution to this problem is ,to approach Te as close
as possible. We will see that this is not always possible,
owing to the influence of the earth's gravity.

9.1.4 Critical fluid dynamics.

As done above for the static case, it is possible to

define dynamic scaling laws for the transport coefficients.
202

The theory is more delicate and the universality classes are

not so large as for the statics case. However, pure fluids and
binary fluids which exhibit similar equations of motion belong
to the same class[9.13].
Universal scaling laws can be defined near the criti-
cal point, however corrections-to-scaling are seen to be
large, especially for He. Whatever approach used, either the
Mode-Coupling approach or the Renormalization Group approach,
one shows that the formulation remains nearly the same[9.14].
Let us consider the transport coefficient u, which can
be a conductivity, a viscosity, etc. Its variation as a func-
tion of the correlation length can be written as :

The exponents x. and ware univers.ls, especially the

exponent w remains the same for any transport coefficient ~

w ~ 1 . The above behavior of U is complicated by a wavevector

(q) and frequency (00) dependence of the amplitudes So and A ••

In the limit of zero wavevector and frequency, the U-behavior

reduces to :

The amplitude Uo remains regular at T e , but may exhibit -as

does the viscosity- a strong temperature dependence. The term
is a correction term amplitude, with exponent 6 ~ v.
Universal ratios can be formed[9. 14-9. 15], as the
ratio R which enters the formulation of the decay rate of the
order parameter fluctuation or the ratios of the correction
amplitudes related to the and the order
parameter decay rate (a R )
R ~ 1.0

a ... /a R = 2 x1't
The principal transport coefficients which are acces-
sible by experiment have been reported in table 9.2 for the
gas-liquid and the liquid-liquid transition.
 203

Transition Thermal Mass Viscosity

Conductivity Conductivity

(xl\r) (XI\N) (x'l )

Liq-Vap 1 -1"\- x'll - 0.054 a )

Liq-Liq no di vergent 1 -1"\- x'l O. 064 b')

Table 9. 2 Exponents of transport coefficients as a function of

the viscosity exponent x'll.
a) From Mode Coupling ref[9.16]
b) From Renormalization Group ref[9.17]

When looking at table 1.2 one realizes that the know-

ledge of the exponent x'l is of prime importance to describe
critical dynamics. This exponent is very small and until now
it has not been well assessed, either experimentally or theo-
retically.
Fi nally, one notes that the intrinsic lifetime of
fluctuations ~i can be estimated as being in the reaL space
the diffusion time of a droplet of size (~) over the length
(~). Using the Einstein diffusion constant D=kBT/6'lt'11~, where 1"\
is viscosity,
(9.7)

9.2. NON EQUILIBRIUM PHENOMENA.

Non equilibrium phenomena near critical points are

particularly difficult to describe because of the necessity of
mixing statics and dynamics. They also involve very large
nonlinear processes. We will limit ourselves to 3 kinds of
phenomena which are important, either in their implications on
the transport coefficient measurements, the phase separation
processes, or technical implications.
204

9.2.1 Fluids under shear flow Change of upper critical

dimensionali ty.

A critical fluid can be taken out of equilibrium by

the introduction of a velocity gradient that we consider to
exist in the 3Vdirection. The shear rate is
80 = i)y
where V is the flow velocity. The shear flow can be produced
by a flow in a pipe, between 2 rotating disks or cylinders,
etc, i. e. each time an experiment involving a flow and visco-
sity is concerned. The fluctuations of the order parameter may
then be considerably modified. The fluctuations will resha-
ped like cigars, provided their lifetime ~i is sufficient to
Ufeel" the shear. This will occur for a deformation (~SO~i)

larger than the typical length ~, i. e. for

SO~i >1 (9.8)
~ i is a decreasing function of temperature (Eq.9.7), it means
the transition from "sphere" to "cigar" occurs close to Tc ;
Eq. (9.8) can thus be wri tten
or T < Ts
In this region the fluctuations are reduced in size, which
makes the Landau theory becomes again relevant[S.1B-S.1S].This
means that the upper critical dimensionality (see § 9.1.3.2)
Dc is no longer 4, but a value lower than 3. The exact value
is D c =2.4.

9.2.2 Phase separation process Nucleation, Spinodal

decomposi tion.

The study of the phase separation process has many im-

plications, especially in the prepairation of metallic disper-
sion alloys (see the chapters 13 by Favier and 14 by
Hal ter) . For a qualitative introduction l~t us consider the
Landau free energy. The susceptibility in the non stable re-
gion, inside the coexistence curve, can be deduced from
eqs. 9. 3-9. 4 :
 205

- 1
- X

x- 1 remains positive as far as (Te-T). M

2
< -a
3b
This condition determines a line which is homothetic to the c-o
existence curve; it is called the spinodal curve (Fig. 9. 3). The
region' between the coexistence and the spinodal curves is a
region of metastability (d 2 F/dM2 »0. Here supercooling occurs,
and nucleation is the usual mode of phase-separation. The re-
gion inside the spinodal curve, where the curvature (the sus-
ceptibi l i ty) is a region of instability. Phase
separation occurs via a spinodal decomposition process.

T
Ti ---------------
Te Metastable
Tf
Instable

- [oex. curve
\----'t-- Spinodal

Fig.9.3 Phase diagram of a binary system with miscibility gap.

Tbe spinodal line separates the region of metastability
from the region of instability.

Let us imagine that we perform a quench in a binary

fluid at M=O, from Ti to T f , into the unstable region (Fig. 9. 3).
The susceptibility x<O, and there is a growth of fluctuations.
However, fluctuations do not all grow with the same rapidity,
depending on their size (q-l). In fact, the growing rate is at

- 1
maximum for fluctuations of size qm J2 t.". In scattering
206

experiments[9.20-9.21],a well defined ring of radius Qm appears

after a Quench, and remains stable as long as hydrodynamic in-
stability -where gravity plays the fundamental role- remains
negligible [see fig . 9. 4J.

. .;. ~'~
. • .r'\'~
• .•,~~",,~,~.:
.. '

~-t.-fll..l'I
...
1"6' •
. ~r.~,.. .r.\\
. ',' ". .
- . ~~:. ., ,
4 ~ .. "
~~'". . . .' . '~.'f\'-
..
L~". . •
. , ,~
~
.:-,1." . .'. !'~';';'-.
, '; . '. '. .'
., ....,.
" 1

.....
...
::
• '.' ,

., .".'...;,.......,.,..-, .. . .
'~'."
-.. ~.~.~
'.
~.~
J '"
.....
. (t.. t

(1l.J:lJll.t"l II

Fig.9.4 - Typical ring structure of the light scattered by a bini

fluid undergoing phase separation near the critical poi
(Cyclohexane-Methanol mixture, 24.77 sec after a therr
qu~nch of T,-T c =-1mR. Tc~45', from ref[9.40]).

Sophisticated theories which account for the "modern"

theories of critical phenomena, as exposed above, lead to sca-
.
llng forms for t he produc t Qm~
e[9.22] . This product Qm~
e is ex-
pected to be a universal function of 8/~i' with 8 the time
after the Quench and ~ the intrinsic lifetime of fluctua-
tions . One distinguishes 2 differe ~ t types of behavior, depen -
ding on the time scales involved :
i) Short times: Diffusive behavior .
1/ 3
Qmc" (( (8/~i)
The Qm -variation corresponds to the Brownian diffusion of a
- 1 - 3
droplet of size 1:. ~ Qm with typical time
[see eQ. 9. 7 J.
 207

ii) Long times hydrodynamic behavior.

- 1
qmc. 0:: (8/..- i )
After a sufficiently long time interval, the fluctuations have
developed into droplets and the pressure related to the surfa-
ce tension has to be accounted for. Hydrodynamics applied to
- 1
these droplets naturally leads to a linear dependence of qm
on ti me assuming growth with a constant velocity (steady
state) .
The theory of such phenomena is complex and is presen-
tly being developed application to alloys is of great inter-
est and any further experimental information, especially with-
out gravity effects, will be of prime importance.

9.2.3 Ionic conductivity measurements.

As far as ionized liquids are concerned -mainly water-

anomalous behavior can be observed when an electric field is
applied. Conductance measurements are usually performed to
study such phenomena.
The initial motivation of the study of water near the
gas-liquid critical point is the enhanced corrosion which
occurs in boilers when the water is close to its critical
point (T c =374·C). Unless it is very pure, water contains ions
in solution; the fact that the isothermal compressibility di-
verges makes the electrostriction around an ion very
large. Thus the transport properties and the thermodynamic of
ions becomes anomalous. The conductance (J) of such a solution
exhibits strong anomalies near the critical point. Stokes law,
when applied to the migration of independent ions, should lead
to a Walden product (Jx'r[) independent of temperature. However
a large decrease of the Walden product is found in the region
where compressibility diverges, as through the ions were lar-
ger than expected. In fact, free ions can no longer be consi-
dered as independent, so the system may be regarded as consis-
ting of assemblies of densely packed molecules dissolved in
water of lower density[S.Z3].
Binary mixtures of which one component is water may
208

exhibit also a large decrease of conductance near the liquid--

liquid critical point, due to the interaction of charge car-
riers with the concentration fluctuations, -the order parame-
ter fluctuations[9.24].

9.3. FINITE SIZE EFFECTS WETTING AND PREWETTING TRANSITIONS

All the properties we have investigated above were

bulk properties. Systems were assumed to be of infinite spa-
tial extent. We will now consider the walls of the container.
The wall can be considered as an extra phase, so the 1-phase
region becomes a 2-phases region, and the 2-phases region is
changed into a 3-phases region. A wall (W) modifies the chemi-
cal potential at the surface and is therefore analogous to a
field for magnetic systems.
Let us consider (fig. 9. 5) a system with 2 components
or phases A and B and a wall W. For pure fluids A will be the
liquid, and B the vapor. For mixtures, A and B will be the
components, and W could be the vapor as well as the wall of
the contai nero

.
T

D-
A{T~W
-t [~W
-- ....~
~~
__-\-__
0', ",.
Id) --
_~~J~:~
I
/

..--
\ . j
I
\\
\
\
'\'
hTW\ U
Ie) I W{~: . Ib) e
------------
, T<TW ' U
[ la)

Fig. 9. 5 - Different wetting or adsorption regimes for pure or

bi nary fl ui ds.
 209

We assume A to be the component more highly attracted by W. Near

W a competition exists between the attraction of the wall and
the corresponding variation of the bulk chemical potential ~.

Several possibiliti.s of weak or strong adsorption will re~

suI t, according to the balance of energy, i. e. according to

the location of the system in its phase diagram (T, p) or (T, c):

9.3.1. In the 2-phases region Wetting.

Let the system be on the coexistence curve, where 2

phases of different composition coexist. Within ordinary gra-
vity conditions a meniscus separates the A-rich (A+) and B-
rich (B+) phases. This meniscus is bent near W with an angle
8 determined by the Antonov rule:
crA +a + cos 8 = crA +W - cr a + w

cr + + is the interfacial tension between the A+ and B+ phases.

A B
It obeys the power law (see Table 9.1)
cr + + C( t 2v
A a
+ , cr + are proportional to the density of the A+ and B+
A W B W
phases, respecti vely, i. e. for the di fference we obtai n

+ a+w
cr - cr C( M C( tP
A w
Therefore cos 8 varies with t as
cos 8 ex: Lf.I- ... ~ t - 1
i. e. it diverges at T e! A temperature Tw therefore exists
where cos 8=1 holds. From Tw to T e , the A+ -phase wets comple-
ll11L the wall. The transition from partial wetting (T>T w)
to complete wetting Ti>T>Tw) is called the wetting
transition[9.25J, which has experimentally been found to be of
1st order[S.26J.
In the complete wetting regime, the width of the A+
layer, located between the B + phase and the wall, depends on
the importance of gravity vs the interaction forces A-W ; es-
pecially the Van der Waals forces leads to a film thickness
( L) versus height (h) which should vary as
whereas one expects a logarithmic dependence when neglecting
the Van der Waals interactions[9.26J L C( Log h.
210

9.3.2 In the one-phase region Prewetting

The wetting transition is continued into the single-

phase region by a prewetting line (fig. 9. 5) which separates a
region of A-weak adsorption on W ("thin") from a region of A-
strong adsorption ("thick"). There is no clear cut separation
between the A-adsorbed film and the buik liquid, but rather a
concentration profile. The prewetting transition line is ex-
pected to be 1st order and should start tangentially at the
coexistence curve at the wetting transition (fig.9. 5).The line
should finish by a 2nd order transition.
Experiments with silica colloIds immersed in a binary
fluid[S.Z7] are connected to such phenomena.

9.3.3 Near the critical point Critical adsorption.

Because of the susceptibility divergence near the cri-

tical point, any perturbation of the chemical potential will
induce an order parameter perturbation on a length scale com-
parable to the correlation length (~). This leads to an ano-
malous adsorption[S.Z8]. The concentration profile of consti-
tuant A is universal. With Z the distance to the wall, the
excess concentration is expected[S.Z9] to vary as Z-~/· ~ Ii

9.4. GRAVITY DEPENDENCE.

We will now evaluate how gravity can interact with

critical phenomena. We will limit ourselves to fluids.

9.4.1 The liquid-vapor transition.

The susceptibility associated with the order parameter

-the density difference (P-P c )- is the isothermal compressibi-

110ty (_1 d P), which diverges at Te- Therefore, under ordinary

P dP
g-conditions, the fluid is compressed under its own weight and
 211

no longer remains at the critical density in the bulk (fig.9.6).

Then all measurements of the critical properties,
like susceptibility, correlation length, specific heat, order
parameter, order parameter decay time, viscosity, adsorption,
etc ... are rounded off and become meaningless close to Tc.

5 T-Tc=-0.025K 111
6 - 0.010 K (2)
- 0.005 K Il)
0.005 K 141
O.050K (5)
~p

IH (mm)

-5 5 4 l 2

Fig. 9. 6 - Temperature evolution of the density gradients vs

height H in a fluid near its critical point [from ref[9.30JJ.

Thermal conductivity (A) measurements also become

very delicate. The instability threshold is governed by the

liT.

Rayleigh number g

Here liT is the temperature difference set between plates at

the distance H Vo is the kinematic viscosity Vo =~/P and
DT A/PCp is the thermal diffusivity ratio. Near Tc. DT goes
to zero according to Tables 9.1 and 9.2 :
DT 0:: t" ( 9.9)
and even a very small gap liT will induce instabilities.
212

9.4.2 The phase separation process.

When a fluid system (gas-liquid or liquid-liquid) un-

dergoes a phase separation under earth gravity conditions, the
process is rapidly governed by convection. These convection
currents arise from the difference in density of the phases,
more exactly from the product :
g(p A+ - Ps+)· The final stage of the separa-
tion will reached as the denser phase is at the bottom of the
container, and the lighter at the top. Wetting forces may par-
tially modify this observation, as noted in § 9.3.1.
Due to this sedimentation process, late spinodal or
nucleation stages cannot be reached, which prevents a clear
understanding and a test of the mechanisms proposed for the
phase separation to be obtained; especially the role of in-
terfacial tension remains mostly hidden.

9.4.3 Wetting layers.

The wetting layer thickness is much g-dependent. A

simple way to understand that it will asymptotically vanish as
the critical point is approached is to consider the Laplace
radi us R :

Near Cj + + according to
A S
Table 9.1 : and

Therefore R will always gq to zero at Te ; the only

way to observe a larger wetting layer is to lower PAS or g.

9.4.4 The A - point of Helium

The A - point of He (T~~2. 17K) is a good example of a

very sharp 2nd order phase transition. However this transition
does not belong to the same universality class as the usual
 213

Critical Point in fluids. As a consequence the values of the

critical exponents are different. The A - point offers inte-
resting experimental possibilities:
The system is superfluid below the transition, making the
thermal relaxation times to be short.
- The isothermal compressibility diverges weakly, so the gra-
vity influence is weak.
It is why accurate data can be obtained on earth up to
reduced temperatures t=IT-TAI/TA~10-6. This limiting value is
mainly due to the hydrostatic pressure influence; experiments
in a 10- 4 g environment would allow reduced temperature up to
10-B to be obtained.

9.5. EXPERIMENTS UNDER MICROGRAVITY CONDITIONS

We will report shortly on the experiments already per-

formed in ~g and those planned in a near future. In addition,
some other experiments will be mentioned which, although not
strictly performed in ~g, are strongly connected with it.

9.5.1 Microgravity to obtain a bulk critical cell at the

gas-liquid critical point.

As stressed above (9.4.1) it is not possible to obtain a

sample critical in its bulk very near Tc under 1-g conditions,
the fluid beeing compressed under its own weight.
This part is concerned with proposals.

9.5.1.1 Specific heat at constant' volume in SF 6 .

[Nitsche-Straub-Lange, D1, ref[9. 31 JJ.
The specific heat Cv will be investigated near the critical
point of SF 6' A High Precision Thermostat (H-P-T)Calorimeter
has been developed, giving a thermal accuracy 0.1 mK or
better. The influence of the long relaxation times of the
thermal diffusivity would be accounted for by heating rates as
small as possible (10- 6 K.sec- 1 ). The investigated temperature
214

range is 10mK-300mK around the critical point( Te ~ 45.5° C).

9.5.1.2 Heat capacity near the A-point of He.
[Lipa, NASA proposal, ref[9.32]].
A new thermomet~r has been developped which uses a SQUID ma-
gnetometer as a detector. A sensitivity of 8T~10-9K has been
obtained near TA~2. 17K. The calorimeter contains 4 stages of
thermal isolation and includes a thermal shield which can be
controlled to within a few 10- 6 K. Inside, the final isolation
stage can improve the thermal regulation by two orders of ma-
gni tude.

9.5.1.3 Critical adsorption of SF 6 0n graphite.

[Findenneg, Eureca 1, ref[9.33]].
The H-P-T thermostat will be used to study the adsorption of
SF 6 on Grafoam- which is a graphite material similar to Gra-
foil but with much larger interlamellar distances, of the or-
der 100 to 300 A. Two or three near critical isochores a~e

investigated in the temperature range T - Te = 10mK - 15K.

The measurement method consists in comparing the volu-
me of a chamber (Vi) with Grafoam to the volume (V 2 ) of a re-
ference chamber. The volumes of the chambers are adj usted so
that the density ( Po) of both remai n constant during the expe-
riment. The adsorbed mass Ll.<Tm of the gas between the tempera-
tures T and T+Ll.T is gi ven by the volume change Ll.V i = - Ll.V 2 ,
i.e Ll.<Tm = P Ll.V i

9.5.1.4 Correlation length, Susceptibility and order

parameter of SF 6 . [Huijser-Michaels-
Trappeniers,Spacelab Eureca proposals,ref[9. 30]].
!
The isothermal compressibility and the correlation length of
SF 6 in the single-phase region will be studied by means of
light scattering techniques. As the order parameter fluctua-
tions are strongly coupled to the refractive index, they give
rise to a strong scattering of light near Te (see § 9.1.3.1).
From the intensity of the scattered and of the transmitted
light, the structure factor (see Table 9.1) can be obtained,
which allows both X and t to be determined simultaneously.
 215

In this experiment the sample is illuminated by laser

li ght, and the scattered intensity at various angles (from
-15° to 90°) is recorded via a photomultiplier and a photon-
counting system. Thee transmitted light is also detected.
The density, or order parameter, will be measured in
the 2-phases regi on through refracti ve. index measurements, as-
suming the Lorentz-Lorenz formula which connects the density
to the refractive index (n)

~oP + ..• ( 9. 10)

n 2 +2 3
Here ~o is the fluid polarisability.
In order to obtain a high accuracy, a special interfe-
rometer has been built. The interference pattern will be re-
corded by photographic means. A high precision thermostat is
needed, it has been specially designed for this experiment.
Note that in the 2-phases regions long equilibrium
times and wetting layers can produce unexpected effects. (see
below, § 9.5.2)

9.5.1.5 Decay rate of the order parameter fluctuations.

[Gammon, NASA proposal, ref[9.34JJ.
Light scattering techniques, as in the above proposal (see §
9.5.1.4), will be applied to investigate the order parameter
fluctuations in the single-phase region of Xenon. Here the dy-
namics of fluctuations are studied by means of photon correla-
tion spectroscopy. Two scattering angles will be used, and the
transmitted light will be recorded to determine the suscepti-
bility and the correlation length very close to Tc' Temperatu-
res will cover the range from 100mK t9 3~K - a resolution si-
milar to that of the thermostat.
In order to minimize the multiple scattering of light
due to the strong opalescence which occurs very near T c ' a
thin -100~m width- sample will be used, with a temperature hi-
story which can avoid wetting layers and the corresponding
density gradients.
216

9.5.1.6 Viscosity behavior.

Two distinct experiments are proposed
i) Viscosity of 3 He and 4 He along the critical iso-
chore. [Meyer-Behringer, NASA proposal, ref[9.35]J.
Of all the pure fluids, 3 He and 4 He show the largest influence
of the earth's gravity on their transport properties. Further-
more, the crossover effects are large, which implies that
measurements have to be done very close to Tc in order that
the power law behavior is clearly evidenced (see § 9.1.3.5).
Viscosity will be measured by means of a torsional os-
cillator filled with a 0.4mm fluid layer. whose damping will be
recorded. The measurement frequency can be ei ther 160 HZ or
3KHZ, which will allow the frequency dependence of viscosity
to be estimated. The influence of long relaxation times will
be also investigated.

ii) Viscosity very close to T c '

[Berg - Moldover, NASA proposal, ref[9.34JJ.
As above. a torsion oscillator is being developed to measure
the viscosity of fluids at moderate temperatures (0-100·C) and
pressures (0-10 MPa). The frequency used is very low (0.5 HZ)
so it remains small compared to the typical frequency of the
order parameter fluctuations. even close to Tc' ensuring that
no relaxation effects occur. In the same way a very low shear
- 1
rate ( O. 05 sec ) is needed to avoid the fluctuations from
being distorted. as indicated in § 9.2.1.

9.5.1.7 Thermal conductivity behavior in 3 He and 4 He

[Meyer. NASA proposal.ref[9. 35]J.
I

As noted above in § 9.4. 1.. the absence of gravity allows thermo-

gradient instabilities. related to the divergence of the iso-
thermal compressibility, to be avoided near Tc'
Here no frequency effects are to be dealt with. but
the experiment can become delicate because of the very long
relaxation times involved The thermal diffusivity (Eq. 9.9)
is vanishing as o CCtO. 63
T
 217

9.5.2 Hicrogravity to avoid convection.

This part is concerned with the study of phase separa-

tion in pure fluids and binary mixtures, and with the investi-
gation of wetting forces at the final equilibrium state. The
study of near critical ionized water will be also reported
since it is motivated by sedimentation phenomena. A few expe-
riments have already been performed in TEXUS sounding rockets,
which allow 6 min of a 10- 5 9 microgravity level. Also studies
on a binary fluid whose densities have been made very close to
each other have provided experimental microgravity simula-
ti ons.

9.5.2.1 Phase separation of pure fluids.

i) Phase separation and mixing of critical SF 6 .
[Lange-Straub, Texus 8 (1983), ref[9.36JJ.
Two samples of SF 6 at the critical density were observed by
means of a movie camera. The first cell, initially in the
single-phase region at the temperature Te + 500mK , was cooled
down to Te - 500mK in the 2-phases region during the ~g pe-
ri od, whereas the 2nd cell, initially in the 2-phases region
at the temperature T e -500mK, was heated into the single-phase
region to Te+500mK at the same time.
The results are the following
- Cooling down through Te : droplets formed which made
the cell completely opaque. No clear phase separation was
observed.
- Heating up through Te: no mixing was observed. This
surprising result can however be exp,lained by the fact that
both the heat diffusion time and the density relaxation time
tend to zero when approaching Te' This could cause severe li-
mitations to experiments in pure fluids very close to Te

ii) Phase separation of SF 6 .

[Klein-Wanders, D1, ref[9. 37 JJ.
Double exposure holograms allow the differential refractive
index distribution to be measured, and therefore the density
218

distribution to be determined, according to the Lorentz-Lorenz

formula (Eq. 9. 10). Three thermostated samples of SF 6 just
above, at, and just below the critical density will be placed
side by side in the Holographic Optics Laboratory HOLOP (cf
Chapter 11). The samples will be heated to T c +3K and then
cooled down below Tc' The heating and cooling period will last
3 hours, a period during which 30 double exposures holograms
will be taken. From these holograms the change in density dis-
tribution within the samples, as well as the time characteris-
tic of the phase separation and the 2-phases distribution,
will be determined.

9.5.2.2 Phase separation of binary fluids.

i) Phase separation of off-critical Cyclohexane-
Methanol [Langbein-Heide, Texus 7 (1983), Texus 9
(1984), ref[9.38JJ.
These experiments were conducted to investigate the Marangoni
convection due to the presence of thermogradients in the phase
separation process. Interesting results have been obtained,
especially it was found that only droplets of the minority
component were formed [Texus 7 5% weight methanol; Texus 9:
65% weight methanolJ. We will not discuss further such ex-
periments which are reviewed by Langbein in chapter 16 of
t hi s book.
ii) 1-9 separation of the isodensity mixture Cyclohe-
xane + deuterated Cyclohexane + Methanol.
[Beysens, ref[9. 39 J.
Adding a few percent weight of deuterated Cyclohexane to a bi-
nary mixture of Cyclohexane and Methanol allows the density of
the phases to be adjusted to be equal within 10- 6 g. cm 3 , while
the mixture remains a binary fluid with respect to the phase
separation and critical phenomena. Moreover, the critical pro-
perties are nearly identical to the Cyclohexane-Methanol sys-
t em [9.40J) .
A study of the phase separation at critical con-
centration has shown that spinodal decomposition occured even
in the very late stages. Macroscopic spinodal structures have
 219

been obtained (fig . 9 . 7) and the final equilibrium state of the

system is governed by the wetting forces, the Methanol-rich
phases wetting the container walls and surrounding the Cyclo-
hexane-rich phase.

Fig. 9.7 -Aspects of a 2cm diameter sample of a binary fluid

after a quench of 10mK below T c '
a) 2mn after t .he quench, with the isodensity system
(Cyclohexane + deuterated Cyclohexane + Methanol) in a
g=1 environment. Here g. 6p~1 0- 6 and structures are vi-
si ble.
b) 2mn after the quench, with the non isodensity system
(deuterated Cyclohexane + Methanol) in a ~g environment.
Here 9.~~10-8 and no stuctures are visible. [The
bubble is the vapor-phase] .

iii) Phase separation of a critical mixture of

",d""e,-,u"-t"-"-e..!.r-,a"-t"-"-e-,,d~_C"-'Z.y",,c,-,l,,--o=h,,,e,-,x,,"a,,,-,-,n",,e,---_..:.+__...,M,,,e,-,t"-,h=a.!cn,.,o=.l. [ Beys ens -
Guenoun-Perrot, Texus 11 (1985) ref[9. 41 JJ.
This experiment was designed to compare the results obtained
by an isodensity mixture in a 1 - g enviro ~ ment (see just above)
to the phenomena encountered in ~g .

A high precision thermostat was specially de-

si gned, which allows a thermal regulation to better than
0.25mK to be obtain. Visual observation by a movie camera and
CCD camera was made. The sample was a critical mixture of
deuterated Cyclohexane and Methanol, whi ch exhi bi ts the same
critical properties as the isodensity mixture of Cyclohexane +
deuterated Cyclohexane + Methanol but with a much larger den-
220

-3
sity difference ( ~O. 1g. cm ) .

The experiment was performed by quenching the

system at criticai concentration from the 1-phase region
(T c +5mK), into the 2-phase region (T c -10mK) and observing the
spinodal decomposition process. Although the evaluation of
these results is still in progress, the equilibrium times are
much longer than expected. ' No visib'le interfaces could be ob-
tained during the 6 mn duration of the experiment (fig. 9. 7).

iv) Phase separation of a critical mixture of Isobu-

tyric acid and Water. [Beysens-Legros, Parabolic
flight (1984) Beysens-Baudry, Space Shuttle
(1985), ref[9.42JJ.
This is a demonstration experiment performed in the Space
Shuttle (June 1985) by Baudry and still in evaluation . It has
been prepared during some seconds in a parabolic aircraft
ight by Legros (fig . 9. 8).

( a) ( b)

Fig. 9.8 - a) The flight sample of Isobutyric acid + water. The

isobutyric-acid-rich phase is coloured green; it wets
Teflon. The water-rich phase wets glass.
b) Photograph taken during a parabolic flight showing
the wetting layers.
 221

The Isobutyric acid + Water system has been cho-

sen because it meets the safety requirements for manned flight
and also because its critical temperature T c =30'C can be easi-
ly reached. The Isobutyric-rich phase was coloured green ~y

traces of Malachite. The experiment consisted first in the ob-

servation of the wetting layers, at room temperature, where
the system was in the 2-phases region. Then the cell was, hea-
ted by hand contact and stirred. The phase separation process
could be observed by letting the temperature of the cell drop
back to room temperature.

v) Nucleation and nuclear growth of a critical Isobu

tyri c aci d-Wa ter mi xt ure. [Klei n- Woermann-Hamacher-
Wanders, D2 proposal,ref[9. 43]J.
In this system where the pressure variation of the critical
point is particularly important, the jump from the 1-phase
region to the 2-phases region will be performed by a pressure
jump at constant temperature.
Holograms of the sample will be recorded, which
will enable a measurement of the particle density, the parti-
cle growth rate and the coagulation of the precipating phase
at different instants of the phase separation process.

vi) Phase separation processes in critical, near cri-

tical and off critical samples of Lutidine-Water.
[Beysens-Guenoun-Perrot, D2 proposal, ref[9.44]J.
Samples of Lutidine-Water at different concentrations will
be used to study the spinodal decomposition and nucleation
either close to the critical point, w~th critical and near
critical concentrations, or far from' the critical point,
on each side of the wetting transition temperature Tw'
Photographic images of the sample and the laser light scatte-
red at small angles will be recorded, together with the trans-
mitted light to detect the phase transition.
The Lutidine-Water system has been chosen be-
cause the wetting transition has already been determined on
ground. Moreover it exhibits an inversed coexistence curve
222

with a lower critical point Tc at 34°C, which facilitates the

thermal quenches in the 2-phases region.

9.5.2.3 Ionic solutions near the critical point of water

[Turner, Texus 10 (1984) - Texus 12 (1985), ref[9. 45JJ.
The aim of these experiments was to measure the conductance of
water solutions containing ions near the critical point
Tc = 374°C. Microgravity helps in maintaining a uniform salt
concentration (no sedimentation) also microgravity could
possibly allow to stabilize an emulsion in the 2-phases region
where conductivity could be measured, although, as we have no-
ted above, wetting phenomena may lead to a clear differentia-
tion of the phases.
Conductance measurement have been performed 3K above
Tc during the TEXUS 10 campaign. The experiment was complica-
ted by a preci pi tati on of salt just before launch. However it
has been assessed that the salt dissolution process in ~g Ls
nearly 4 times faster than under 1-g conditions. Also the con-
ductance has been found to be much lower than for the 1-g
measurements . A reflight of this experiment was done
(TEXUS 12) to assess these phenomena, but the results are not
yet available at this time.

9. 6. GENERAL CONCLUSION

Microgravity seems to be of great help for the highly

active field of critical phenomena, in preventing stratifica-
tions near the gas-liquid critical point and in avoiding
convections during the phase separation process of pure fluids
and mixtures. Whereas resultlJ of actually performed
experiments are scarce, numerous future investigations are
proposed which will allow a deeper understanding of the
physical concepts which are involved in the general area of
phase transitions and especially nucleation and growth,
spinodal decomposition, which are currently of great interest
in materials science.
 223

ACKNOWLEDGEMENTS
It is a pleasure to thank B. Feuerbacher,
G. H. Fi ndenneg , R. W. Gammon, R. Huijser, H. Klein,
D. Langbein, J.A. Li pa, H. Meyer, M. R. Holdover, J. Straub,
D. J. Turner , W. Wagner and D. Woermann, for useful
correspondence, comments, and for having sent their preprints
and reprints.

REFERENCES

9. 1 L. Landau and E. Lifshitz, "Statistical Physics"

( MI R, Moscow, 1967).
9.2. B. Widom, J. Chern. Phys . .1.1., 3892 (1965).
9. 3. L. S. Ornstein, and F. Zernike, Proc. Acad. Sci.
Amsterdam 1.2., 793 (1914).
9. 4. V. L. Ginzburg, Fiz. Tverd. Tela. £, 2 0 3 1 (1 96 0) .
9.5. K. G. Wilson and J. Kogut, Phys. Reports C12, 75
( 1974) .
9.6. M. E. Fisher, Rep. Prog. Phys. J.Q., 615 (1967).
see e. g. "Phase Transitions", ed. by M. Levy,
9.7 J. C Le Guillou and J. Zinn-Justin (Plenum Press,
New-York, 1982).
9.8. D. Stauffer, M. Ferer, M. Wortis, Phys. Rev. Lett.
29, 345 (1972).
9.9. C. Bagnuls and C. Bervillier, Phys. Lett.
107A, 299 (1985).
9. 10. F. J. Wegner, Phys. Rev. li, 4529 (1972).
9. 11 . C. Bagnuls and C. Bervillier, J. Phys. (Paris) Lett.
.12, L95 (1984).
9. 12. A. Aharony and G. Ahlers, Phys. Rev. Lett.
li, 7 8 2 (1 9 8 0) .
9. 13. P. C. Hohenberg and B.!. Halperin, Phys. Rev.
B13, 2110 (1976).
9. 14. D. Beysens, A. Bourgou and G. Paladi n, Phys. Rev.
A30, 2686 (1984).
9. 15. H. C. Burstyn and J. V. Sengers, Phys. Rev.
A27, 1071 (1983).
9. 16. J. K. Bhattacharjee and R. A. Ferrel, Phys. Rev.
A28, 2363 (1983).
9. 17. E. D. Siggia, B.!. Halperin and P. C. Hohenberg,
Phys. Rev. B13, 2110 (1976).
9. 18. A. Onuki, K. Yamasaki and K. Kawasaki,
Ann. Phys. Lli" 217 (1981).
9. 19. D. Beysens, H. Ghadamassi and B. Honcef-Bouanz,
Phys. Rev. 28A, 2491 (1983).
9.20. W.1. Goldburg, in "Scattering Techniques", ed. by
S. H. Chen, B. Chu and R. Nossal (Plenum Press,
New-York, 1981).
224

9. 21. N. C. Wong and C. M. Knobler, J. Chern. Phys. 69, 725

( 1978) .
9.22. see e. g. K. Kawasaki and T. Otha, Prog. Theor. Phys.
59, 362 (1978).
9.23. D. J. Turner, in Proc. 4th European Symposium on
Materiafs Processing under microgravity, Madrid
(1983) (ESA SP-191).
9.24. see e. g. J. Ramakrishnan, N. Nagarajan, Anil Kumar,
E. S. R. Gopal, P. Chandrasekhar and N. Ananthakrishna,
J. Chern. Phys. 68, 4098 (1978).
9.25. M. Moldover and J. Cahn, Sciences 207, 1073 (1980).
9.26. see e. g. the review by H. R. Moldover and J. W. Schmidt
Physica 12D, 351 (1984).
9.27. D. Beysens and D. Esteve, PhYs. Rev. Lett.
~, 21 23 (1 985) .
9.28. D. Beysens and S. Leibler, J. Phys. (Paris) Lettres,
il, L133 (1982) ; C. Franck and S. E. Schnatterly,
Phys. Rev. Lett. li, 763 (1982).
9.29. M. E. Fisher and P. G. de Gennes, C. R. Acad. Sci. Paris
287B, 207 (1978).
9.30. R. J. Huijser, A. C. Michels and N. J. Trappeniers, in
the same ref. as [9.23J.
9. 31. K. Nitsche, J. Straub and R. Lange, in Proc. 5th
European Symposium on Material Sciences under
Microgravity, Schloss Elmau (1984) (ESA SP-222).
9.32. J. A. Lipa, Proc. of Near Zero Conference,
Stanford (1983), to be published.
9.33. G. H. Findenneg, in the same ref. as [9.23J.
9.34. M. R. Moldover and R. W. Gammon, NASA contractor Report
CR 174637.
9.35. H. Meyer and R. P. Behringer,
NASA Proposal NAG4-379 (1984).
9.36. R. Lange and J. Straub, Internal Report (Technische
Uni versi tat MUnchen -L-A. fUr Thermodynami k) .
9.37. H. Klein and K. Wanders, AIAA Journal 20, 946 (1982)
9.38. D. Langbein and W. Heide, Adv. Space Res. !., 27 (1984)
9.39. D. Beysens, Proceed. of the 35th Congress of the
International Astronautical Federation, Lausanne 1984.
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9.40. C. Houessou, P. Guenoun, R.i Gastaud, F. Perrot and
D. Beysens, Phys. Rev. ll, (1985).
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9.43. H. Klein, D. Woermann, H. Hamacher and K. Wanders,
Private communication.
9.44. D. Beysens, P. Guenoun and F. Perrot, D2-proposal
[CEA Internal Report].
9.45. D. J. Turner, CERL Note, TPRDS/L/2802/N85 (1985).
Part III:
Experimental Hardware
10 Furnaces

WOLFGANG STEINBORN
Project Executive Department, DFVLR, Koln, FRG

Furnaces for Materials Processing in space as well as on the ground perform

according to one or more of the three heating principles:
Isothermic heating (for redistribution of components/dispersions/bub-
bles in a metallic matrix, nucleation and transport studies)
- Gradient heating (for directional solidification/Bridgman-Stockbarger-
crystall i zati on)
- Zone heating (for zone refinement/-crystallization)

The development of furnaces with suitable properties for industri al manu-

facturing or laboratory research on earth has a long tradition. With the
upcome of opportunities for the processing of materials under negligible
gravity in space laboratories it became necessary to develop adequate fur-
naces for applications aloft.

The present chapter describes the significant pecularities in design and

utilization of furnaces for the specific task of space experimentation and
processing.

The most challenging feature of space instrumentation is the antagonism

between the use of most advanced technology on one hand and exeptionally
long preparation periods, necessary to ensure the required high reliability
and to cope with the multifold interfaces in; the system, on the other
hand. Paragraph 10.1 is devoted to the typical technical and procedural
constraints associated with the development of hardware for space laborato-
ries. In paragraph 10.2 the spectrum of possible heating techniques is re-
viewed and discussed in the light of suitability for space applications.
This leads to paragraph 10.3 in which a survey of existing space furnaces
is given considering the respective international programmes on material s
processing. Representative models for the three heating principles or com-
228

binations of them are described exemplarily. In paragraph 10.4 special de-

vices out of the periphery of the furnaces which become of interest in con-
nection with the low g-experimentation, are discussed. Paragraph 10.5
closes the chapter with a prospect on future trends in space instrumenta-
tion for material s processing including an outlook to the projected space
station.

10.1 Special Requirements to Furnaces in Space Laboratories

In its almost 20 years history the development of low gravity experiment

hardware has been accompanied by the usual errors and difficulties which
occur in innovative work. The spaceborn constraints required the combina-
tion of know-how from both traditional furnace manufacturers or experienced
investigators and aerospace companies.

There are technical and procedural pecularities involved which do not occur
at all or to that extent in terrestrial construction, such as:
- Constraints due to the heavy mechanical loads induced by both the thru-
sters during ascent and the deceleration maneuvers during landing.
- Constraints resulting from the fact that space laboratories are nearly
closed systems in which only limited resources can be consumed and any
kind of pollution must be recycled.
- Constraints due to remote control and operation of the orbiting furnace.
- Constraints due to the different performance of components under weight-
less conditions.
- Constraints due to tight schedules and fixed launch dates.
- Constraints due to limited access to the flight hardware.

To overcome the mechanical load problem, and for volume and mass reduction,
mathematical models of furnaces and most?f the peripheral parts are esta-
b1 ished. Similarly the thermal conditioniil'lg of a furnace must be precisely
calculated and optima1ized with respect to the existing provisions for
cooling since dissipation of process heat constitutes a problem. In return
a decoup1ing of the furnace from external temperature variations can be ob-
tained. Such variations originate e.g. from the periodic transitions
through the earth shadow in a satellite mission.

Mathematical modelling being standard in payload development for space is

 229

now increasingly used also for terrestrial purposes. A major advantage is

that, once a model exists, the internal thermal behavior with respect to
the sample can al so be calculated and the layout optimal ized accordingly
(Fig. 10.1-1). All the new space furnaces in USA are thoroughly modelled
mathematically prior to construction (see exemplarily [10.lJ and ref's
therei n).

"",",UlI 1I1M11IIU

a) .
,. ..

:l--.------/\
~----'~~--~~~--~--'''----.

b)
\I
in
c)
't

""
100

! ... 1'-. ~
~

~ .",
I-
17
M
" 1 Il~-1
.... .... _....
~ ~f:: /'

'"
lOG
. 0;
"
,
" " . . .
I •

Fig. 10.1-1: Optimalization of a zone crystallization furnace with a finite

elements computer model by MBB-ERNO. Due to the symmetry of the profile on-
ly the left half is calculated. Part a shows the principal layout and re-
quired profile of the furnace which is designed for the travelling heater
growth of H91- xCd xTe. To maintain a constant x over length each of the 5
projected zones must be controllable individually. Part b shows the distri-
bution of knots representing heaters (20-22), ambient air (23) and insula-
tion (all others). Part c shows the calculated profiles for different hea-
ter powers and the correspondi ng heat fl ows for the heating elements (i n
Watt) in comparison with the required profile (Tsoll)'
230

Limited resources other than volume, mass carrying and heat dissipation ca-
pability are the electrical power, t~e total consumable energy, the access
to evacuation 1ines, the operational time since most space missions today
have a preset duration and, in manned missions, the crew disposition.

Power and energy savings are achieved by introducing intelligent electronic

control devices to reduce vain operation of the furnace, by exhausting ma-
ximum effi ci ency ranges of converters, by using good i nsul ati on and by
avoiding idle thermal masses, or, generally, by favouring economic heating
techniques over others [).0.2J. Similarly by adequate electronic means the
manual control by the crew can be minimized and, in combination with effi-
cient heating techniques the heatup and cool down times can be cut to make
efficient use of the limited mission time. Moreover as in space laborato-
ries there is normally a high integration density of furnaces and other
scientific equipment (The Materials Science Double Rack e.g. houses 7 faci-
lities each of which would, together with their periphery, require half a
terrestrial lab alone) the sequence of the experiments must be precisely
planned beforehand ("timelining") in a way that a most constant envelope of
power consumption, heat dissipation and crew activity is maintained.

Every kind of pollution in form of heat, evaporating gases or, here also of
importance, parasitic accelerations and electromagnetic radiations must be
controll ed si nce otherwi se they affect other experiments, or worse, in
manned mi ss ions, toxi c gases may escape into the 1ife supporting system.
Reduced safety protective means in unmanned orbiti ng 1aboratori es wi 11 in
the present state of technology be outbalanced by the expenses for automa-
tic control, robotics for sample and spare part exchange etc. It may, how-
ever, be expected in future missions, when sophistication of such devices
advances, that materials processing in space can increasingly be performed
wi thout man tendance. For whatever manned or unmanned mi ssi ons a remote
support by telemetry/telecommand from a grDund support centre,equipped with
adequate means for data processing and ei:pert teams of engineers and in-
vestigators, is indispensable for the operation of furnaces.

Procedural pecularities involved in the development of space hardware like

the "phased project planning" [10.3J or the optimalization of the necessary
number of identical models ("model philosophy" [1O.4J) will not be discus-
sed here.
 231

In summary a number of strange requirements distinguishes space from

ground engineering. The development not simply of a furnace but of a fur-
nace to perform in a complex system with limited resources and the need of
controlled removal or recycling of all process wastes has forced the engi-
neers to find new technological and procedural solutions. In this sence a
space laboratory is a suitable model case for the earth laboratory of the
future. Solutions for reduction of material and energy consumption, for
poll ution removal not by simply opening a window, for the advancement of
automatization and remote process control are here also of increasing im-
portance. Limited availability of space and resources on earth too will
lead to higher integration densities in conjunction with exact planning of
both effi ci ent process flows and di sposa1 of resources, i nc1 uding human
work.

10.2 Review of Heating Techniques and Their Potential for Space Furnaces

For the selection of a heating technique for a space furnace some specific
criteria apply. These include:
- flexibility in the composition of heat profiles, in temperature range,
sample materials and diameters (attraction of more users makes the expen-
sive space development more profitable)
good reproducabi1ity of results assuring precise comparison of space and
ground processes
- rapid heatup and cool down providing good exploitation of available time
in space
high efficiency in power conversion
low involvement of g-sensitive components (like wide gas volumes) causing
differences in performance between space and ground

Ten heating methods, reviewed in [10.2J under .'aspects of technical feasi-

bility, will be discussed here accordingly in the light of applicability
for the experiments.

a. Resistance Heating

The operating temperature range of a heater wire is given by its specific

Ohm resistivity which in turn varies with temperature. For metals like Tan-
232

talum the increase is by one order of magnitude over the interesting tempe-
rature range. Nevertheless Ta is a very widely ased heater material in
space furnaces since it is uncritical under safety aspects (low evaporation
and chemical reactivity with insulators, usually A1203)' The Ta and Alumina
combination can be used for temperatures up to 1800 0 C. Other uncritical
combinations are Rhodium or Platinum/Rhodium with different insulations for
the range below 1500 0 C. For temperatures above 1900 0 C only Tungsten or
Tungsten/Rhenium alloys in combination with Beryllia or Thoria can be used,
but those insulations introduce safety risks due to their toxicity so that
special provisions, like mUltiple containment, gas evaporization control or
others, which in turn could reduce the efficiency, must be foreseen.

Because space furnaces have to operate over long periods under restricted
access for maintenance, power supply control must also provide for compen-
sation of increasing resistivity due to degradation of the heaters through
chemical reactions with residual gases. Other undesired reactions are those
between heater and insulation leading to short circuits and overheating and
causing premature termination of furnace performance. Such negative effects
are normally avoided by electronic current limitation.

Special furnace setups will be presented in 10.3. It might be surprising

that the great majority of space furnaces (about 2/3) is using the rather
conventional resistance heating technique, yet, as will be seen from the
comparison with other techniques, it offers some unique advantages: Heating
profiles can be configured very flexibly by lining up several heating ele-
ments. The operational temperature ranges are very large. All this contri-
butes to a high variability in experimental application (multiuser facili-
ty!). Above all, since the heating system is in thermal equilibrium with
the sample, a good controllability and stability over length and time can
be achieved. Differences in performance under unit and low gravity (10.3)
are negligible. This is of extreme importance for a programme which like
materials processing in space is still in i;ts orientation phase so that the
effects of reduced gravity must be sounded out clearly, given only a small
number of avail abl e test opportuni ti es. Therefore a furnace performance
with good reproducability of results and little inherent artefacts is
necessary. In comparison with this advantage the relatively high thermal
inertia and related high time constants of resistance furnaces are of minor
significance and can be tolerated in many cases.
 233

b. Electron Beam Heating

This technique has reached a high development standard on earth in the past
25 years. Its appHcat,ions for welding, rapid alloy formation and high tem-
perature melting are well-known. Todate the sample geometry is not required
pointlike any more but can have the form of a rod of up to 40 mm in diame-
ter. Isothermal heating is accomplished by a sweeping beam. To improve ra-
dial homogeneity either the sample must be rotated or the beam spl it. The
target temperature is limited only by its own vapour pressure which should
not exceed 10- 3 mb (corresponding to 2800 0 C for a Tantalum cartridge).
Maximum power is about 1 kW.

The advantages of electron beam heating namely almost 100% efficiency, ra-
pid heatup and cool down are opposed by some disadvantages such as incomple-
te radial isothermicity, poor flexibility since quartz ampoules or unco-
vered samples with high vapour pressures cannot be used and the occurence
of high voltages (30 kV or more) with occasionally secondary electron emis-
sion and bremsstrahlung. This has restricted the method in space so far to
welding experiments [10.5J. However, a demonstration model is .under prepa-
ration for ESA [).0.6J (Fig. 10.2-1)

Fig. 10.2-1: Principal setup of an

electron beam heating furnace for
ABLENK~ space applications [10.6J
SYSTEM r"-=,~~---I.~

___ U c.onst.·
WXRMEscm tOE

ABSCIIJRHUNG

c. Inductive Heating

This method is widely used on earth for zone refinement and high quantity
production of 1arge di ameter semiconductors by Czochral sky crystal 1i za-
234

tion. For space application. however. the assessment is similar to b. The

advantage is a rapid heatup and cool down while insufficient thermal homoge-
neity over length (and also radially if the sample is misaligned). poor
flexibility due to its restriction to samples or cartridges with appropri-
ate conductivity. possible parasitic electromagnetic radiation. high power
demand (efficiency only 50%) and necessary cooling of the coil are the dis-
advantages. Czochralsky configurations in particular are impossible to de-
ploy in zero gravity. So far there is only one beneficial appl ication: in
combination with containerless levitation of the sample where the inductive
coil is used for both heating and supporting.

d. Electrical Discharge Heating

Heating by ion bombardment in gas discharge clouds with the sample car-
tridge being cathode and a surrounding cylindre being anode can only be
used for low temperature experiments. The reason is that the maximum power
density provided by the diode cathode principle is about 2 W/cm2.

Offering effective and rapid heating a higher flexibil ity of this method
vi a extension of the temperature range can only be achieved by magnetron
discharge. involving. however. high magnetic fields and a to date immature
technology. Vapour pressure limitations arise similarly to b. No space
applications are known.

e. Heat Pipe Heating

Heat pipes have long been in use in space for technological purpose. such
as temperature stabilization of heat radiators. since they guarantee reli-
ab 1e heat transport over long di stances qnd compl i cated paths. Therefore
they have been intensively investigated and advanced in the frame of space
programmes. For use in space furnaces their advantages have been discovered
only recently. They provide attractive characteristics that merrit conside-
ration as heating elements or temperature profile liners:
- Heat transport between source and si nk wi th a pl atform-type temperature
distribution along their walls providing an axial isothermicity of better
than 0-0.5 K/cm (0.5 K/cm for resistance heaters)
- High thermal stabil ity over time. With gas buffered heat pipes indepen-
 235

dence of variations in the heat source is achieved (Variable conductive

heat pipes, Fig. 10.2-2). With an active control of the gas reservoir
(active VCHP's) a precise indirect measurement and control of the tempe-
rature via the gas is possible.

Fig. 10.2-2: Working principle of a

tranlp)rt .lone I radiatar I ... buff.
gas buffered heat pipe (passive
_ti",
iiOl.. ion . . . dissipation
VCHP) and corresponding temperature
t t
+ distribution. The buffer gas ex-
pands and contracts with tempera-
ture thus increasi ng and reduci ng
•
heating ... the dissipation zone of the heat
pipe.
hut di"ipatlOn

Passive elements (exept active VCHP's) requlrlng no maintenance over long

1ifetimes (10,000 hours for temperatures $ 10000C, 1000 hours for tempe-
ratures from 1000 0 C to 2000 0 C)
- Heat trans~ort by capillary and diffusive forces assuring unchanged per-
formance under weightlessness (verified recently in a 16 hours test with
9 different types and geometries of NH3-filled, Aluminum or stainless
steel contained heat pipes [10.7J).

The positive profile lining effect of a he~t pipe is illustrated in

Fig. 10.2-3. For principle furnace arrangement~ usually tubular heat pipes
are chosen with the sample in the centre. One single heat pipe forms an
i sotherma1 furnace, two of di fferent temperature 1eve 1s (normally a Fixed
Conductance Heat Pipe with variable T for the hot end and a stable Passive
VCHP for the cold end) form a gradient furnace and two identical heat pipes
f1 ank i ng an i ntermedi ate small resistance ri ng heater form a zone furnace
(see 10.3).
236

Fig. 10.2-3: Axial temperature profile

and radial temperature homogeneity in a
tubul ar furnace with and without Heat
Pipe Liner

Despite these attractive features there are also some rather severe disad-
vantages for applications in space furnaces:
- No operations in excess of the rather small temperature range of a given
fluid/containment combination of a heat pipe are possible thus limiting
their flexibility for gradient freezing experiments or for different sam-
ple materials.
- They implicate safety risks because most of the working fluids are toxic
and are contained under high pressures (100 to 400 bar).
With active VCHP's again active elements would be introduced requring
maintenance and increasing the performance risk.

This explains why heat pipes have not been used more widely in the past. So
far only one furnace composed of two uncritical waterfilled copper-contai-
ned heat pipes for the temperature region of nooc has been flown [10.8J.
For future missions, however, there is presently a variety of heat pipe
furnaces under preparation in USA, France, Germany and Sweden.

f. Mirror Heating

High working temperatures can be achieved by focussing radiation from an

emitting source onto an absorbing sample. Theoretically the temperature of
the source should be reproducable in the focus (5,700 K for sun light,
2,600 K for a Tungsten filament). In practice the temperatures are much lo-
wer due to both the finite extension and heat losses by body conduction and
 237

secondary radiation of the sample. Nevertheless processing of high melting

oxide samples in radiation furnaces has been reported ~O.~.

In the years 1981 to 1984 several experiments were carried out to examine
possible influences of weightlessness to the performance of ha10gene lamps
(this lamp type had been proposed as best suited for space in earlier stu-
dies). They revealed ~0.10-10.12J, that the ha10gene cycle which is a dif-
fusive process, is not disrupted, but that the missing convective cooling
inside the lamp bulb, otherwise overlaid the ha10gene cycle, provokes a
higher filament temperature and, consequently, higher radiation intensity
for the same power setting. The effect amounts to between 8 and 15% and is
dependent on the diameter of the bulb.

Flight furnaces have been built after respective studies [10.13, 10.14J on
the basis of 2 or 1 ha10gene lamps whereby focussing of the radiation is
accomplished by means of closed rotational ellipsoids with the lamp located
in one and the sample in the other focus (other arrangements in the litera-
ture like ring radiators have not been considered for space furnaces). With
two 1amps the radi at i on is concentrated to the common focus of two i~ter­
secting e11ipsoides (Double ellipsoid mirror furnace, see 10.3).

The nature of heating by focussed radiation predestinates the method for

zone crystallization, but also gradient heating is possible, provided the
sample is aligned in the long axis of a monoe11ipsoid reflector and a pro-
file shaping tube is used (Fig. 10.2-4). The monoe11ipsoid furnace in the
configuration shown is attractive due to its simplicity, flexibility, radi-
ally isotropic heating and optimum efficiency. Model s for rocket f1 ight,
for Space1ab and for automatic operation on the EURECA satellite have been
developed. With the upcome of high power ha10gene lamps (1 kW) also higher
temperatures and larger sample diameters (e.g. 10 mm Silicon, M.P. 1420 0C)
became possible. A contraint is, that the samples must be supported in am-
poules (usually quartz) so that both ends cannoi be moved independently.

Recently possible improvements with respect to the axial T-profile have

been investigated. Since the samples have a finite radial extension the
upper section absorbs more radiation than the lower with the result that
there is a critical diameter (approx. 20 mm) at which the zone profile con-
verts into a gradi ent1 ike profi 1e. To reduce thi s effect an upward di s-
placement of the lamp off the focus by some millimeters [10.15 J or a devia-
238

A. B, C-e: KAU' AXES Ol"

Er.LlPSOID
F FOCUS

Fig. 10.2-4 Possible heating configurations with a monoell ipsoidal radia-

tion reflector, lamp in the upper focus, sample (in an ampoule) in the
lower. Part B exhibits the normally obtained zone profile, part C shows a
gradi ent profi 1e facil i tated by a bi sected i nconel profile shapi ng tube
around the sample (from an information sheet on the "Monoellipsoid furnace
ELLI II by A. Eyer and W. Steinborn)

tion from the ellipsoidal form of the reflector towards a paraboloid

[10.16J are proposed. However, these improvements cannot conceal the gene-
ral limitations of the mirror heating concept which have been experienced
meanwhile.

The principle advantages:

- flexibility in application with respect to shape and diameter of the sam-
ple and the high operational temperature range
- low thermal inertia providing short heatup and cool down times, especially
interesting for sounding rocket flights with only 6 minutes zero g-pro-
cessing time
- observability of the process
possibil ity of crucible-free processin~ either with uncontained 1 iquid
zones or with spherical samples in combination with a levitator

are outweighed by some severe disadvantages:

- heating properties are strongly dependent on the optical characteristics
of the sample, resp. the sample/ampoule configuration, which for most
cases are not known
 239

- low thermal inertia, figurating under advantages is at the same time a

great impediment: as the heating system is not in thermal equil ibrium
with the sample, temperature control is aggravated and can only be accom-
plished either invasively with thermocouples in the sample (unwelcome
since it affects crysta11 ization) or indirectly via radiation measure-
ments. The noninvasive measurement is principally of poor accuracy due to
the multifold reflections and radiation background in the furnace (see
aO.17], a study which marks the end of a long series of related studies
in which no definite solution could be found)
- temperature gradients and side plateaus cannot be controlled since they
depend on the heat dissipation of the sample which varies with the posi-
tion.

The deficiencies listed will even be enhanced if sunlight is used as radia-

tion source. One of the possible furnace concepts studied in the past
[10.18-10.20] is depicted in Fig. 10.2-5. The solar radiation, available
without attenuation by earth atmosphere, with a flux density of 1.35 w/m2
is collected by a parabolic concentrator with 2 m2 in cross section. This
area was estimated necessary to reproduce 1 kW inside the furnace. For the

Fig. 10.2-5: Basic concept of a so-

reflector lar heated furnace with two alter-
native sol utions for energy trans'-
COllector fer from collector to sampl e (from
aO.20 J)

tr1'lckiog
mechanism

receiver

heat storage

Energy
Tremter
heat transfer

light 9_. jde

energy feeder
exp~imental box

Fumace

sample

peripherl!ll supply units

240

further transport of the light, focussed by help of the Cassegrain princi-

ple, two solutions are suggested: the simpler one employs a light guiding
tube for di rect trans fer of radi at ion into the furnace whi ch shoul d here
ideally be a monoellipsoid mirror reflector. In the other solution an ener-
gy transformati on takes pl ace pri or to transport by conventi onal tech-
niques, be it a liquid loop or a heat pipe. This solution allows the intro-
duction of an energy storage device to bridge "shadow phases".

The periodic (90 minutes) passages through earth shadow which last about 30
minutes constitute a strong impediment to the realization of direct solar
radi ati on furnaces, at 1east for long durati on experiments. Constant sun
orbits are possible but generally outrouled as the launch expenses are too
high (polar orbits!) and general heat dissipation in the spacecraft is ag-
gravated. Other instabilities like changes in solar activity and drifts of
the satellite requiring very exact pointing shall only be mentioned here.

g. Direct Current Passage Heating

In this method the cartridge acts as furnace and is therefore passed by an

electric current. For electrically conducting samples the introduction of
an insulator between cartridge and sample material is reasonable which,
however, will thereby also reduce the heat flow to the sample. Without
this a power demand would result which cannot be supplied in space. Anyhow
the method is restricted to only one sample for which it is adapted, and,
since sample exchange is difficult. No space applications are known.

h. Laser Heating

Lasers provide relatively high power densi~ies (ruby lasers: 5x10 13 W/cm2,
compared to electron beams: 4x108 W/cm2) b~t the power conversion efficien-
cy is rather poor (10%) so that space applications so far are restricted to
small sample vol urnes (typically small spheres in containerless levita-
tors). The circumstance that optical properties of the sample are involved
(absorptivity of laser light) leads to further reduction flexibility and
applicability. A possible configuration for high temperature crystal growth
is proposed in [10.21J.
 241

i. Microwave Heating

This method is only applicable for dielectric materials such as organic

tissues, proteins et~. This kind of heaters is not considered here.

k. Chemical Reaction Heating

Two examples of the utilization of this method in space are reported

[10.22, 1O.23J. In order to impose minimum integrational and operational
efforts the experiments are designed in the form of autonomous closed
packages. Thus they can easily be carried and stowed on board and activated
if time is there. However, the exothermal chemical reactions used for heat-
up involve a safety risk. Therefore applications are restricted to very
singular experimental studies with poor control possibilities and small
sample volumes. In [10.23J the small growth ampoule is embedded in an "exo-
pack" which for protection is surrounded by several thick walled rigid me-
tal containers. These serve simultaneously as heat sink when the reaction
is terminated. The extent to which the sample is molten varies from experi-
ment to experiment so that reproducability is rather poor. However, basic
growth improvements accounting for low gravity processing have been obser-
ved.

10.3 Practical Spaceborn Furnace Configurations and Their Characteristics

The review of heating techniques under 10.2 shows that only few of them
have reached flexible applications as multiuser/multipurpose facilities
(i.e. resistance, mirror and recently heat pipe heating) whereas inductive,
electron beam and chemical reaction heating have found some singular appli-
cations. Concerning the relative abundance of the respective heating tech-
niques differences are not significant between 'space and earth except that
in the first generation of space furnaces mirr6r heaters find a larger re-
presentation which can mainly be attributed to their high efficiency,
transparency for observation (important to study 19/0g differences in situ)
and good exploitation of operation time due to rapid heating and cooling.

In this paragraph practical solutions resulting from the various attempts

to realize the three heating principles for the particular environment of
space laboratories are presented. Partly unconventional designs will be
242

found. It can also be seen that the space programme has stimulated innova-
tions which can be beneficially used also on earth.

Since the number of space furnaces amounts to more than 50 meanwhile it is

impossible to cover them all in the text of this chapter. Therefore the at-
tempt is made in Table 10-1 to register them completely (to the authors
knowledge), together with their most important characteristics, for the
sake of comparison. The Table 10-1 a to d is organized according to the
national and supranational space processing programmes in the world. Only
furnaces being in use for flight or in a high development state on the
basis of existing laboratory hardware have been incorporated (terminated
fl i ght programmes are not con s i dered) • Not inc 1uded are setups for very
singular experiments like exothermic packages (10.2), special modifications
of existing furnaces like the disk floating zone technique [10.24J, welding
arrangements ilO.5 J or reactors for protein crystall ization [1O.25J. Other
organic crystal growth facilities, the fluid experiment systems and the
levitation furnaces are included for completeness, but not discussed here
with reference to the following chapters. Part of the listed informaU·on
coul d be taken from [10.2 J, others were gathered from [10.26-10. 34J and by
personal communication.

Some interesting furnace models representing the respective heating princi-

ples, that have proven or give promise to useful performance in space will
be described in the following:

a. Isothermal Heating Furnaces

The "Isothermal Heating Facility" (IHF, No. E1 in Table 10-I) , one of the
facilities in the "Materials Science Double Rack" (MSDR), has demonstrated
performance in the Spacelab-1 Mission al1d is reflown in the D1 Spacelab
Mission. Fig. 10.3-1 shows a cross sect~on of the facility. The need to
minimize the total operation time and the power demand resulted in a twb
chamber concept allowing heating of one sample and cooling of another
simultaneously. To accomplish this, heater and cooler chamber can exchange
position by pulling them off the sample, rotating them by 180 degrees and
reinstalling them in place. This all takes place within a water cooled
dome. The two chamber design allows cool down times of only 5 minutes from a
process temperature of, say, 1300 0C to the prescri bed "touch temperature"
Table 10 -I a: Fumaces within the European Programmes (ESA and Member States)
~

.~ I g ..,'"
~
~ ~ :2 ~ !!! a
~ .~ ." C3~
1.i a~
E a: i3 E i I C C
:li! j ..,~
§ C
~E .§ .~
j ~ f2 ~ Iii a ""olf
II ~ o~ ~ ~ ~~ ~~ i3 E
II ~~ I ~-a is - :§ ~ ~~ !'! !!! i5 ~ :i I~
~ 8l E !'! ~ :g~ !'! ~
t9i! .S! ~ Co C is "C is
j :~ i ~ ~ 1l§ i" Ii ~ E til ~ ~ i E ""
::.~ ~.r i f Jj z '" ~§. i ~! ~ !l ~ ~ gj!!! ::'co ~ ~ 8l -6 ~!1
'" '" ::.
Isothermal Heating I Resistance 1. 40 TantaVstaln- Inert Gas 5 x 10-3 < 4 Thermo- Gradient Ves :~~~~I~:~ d~~g:r~I~~~~~~b~~~)~~
E1 Facility (IHF) (G) heater 1000/230 (1 cooling 100 less steel or 100 to. - 1820 50 couples - Insert (manually) metallic matrices, nucleation and
~ ~_ - Germany - (Tantal) chamber) carbrldgas Vacuum 0.25 transport studies
is Gradient Heating G Resistance 248 Quartz any 6 re's Yes Directional solidlfication/crystal-
E2 FaCility (GHF) 3 zones heater 8001250 3 31'S ampoules Vacuum 34 (nonma- ::5i 1470 100 for 3 - - (manually) lisation of metallic or
r--- ! i
B- i-France - IJP ctrlld. chanically) samples semiconducting systems
r--- .81.,..: Mirror Haeatlng Radiation 30 None or Inert Gas 10-4~01 700-17!0 light ,in- ,Eye, Yes Diverse zone crystallisation methods
E3 Ii!!
II Faclllty(MHF) Z from 2 haIo- 800/150 1 144 Quartz or 110 (rotation (absorption - tensity Video-or - (manually) of silicon or compound semiconductors
i-Germany - gene lamps ampoules Vacuum 0 to 20 RPM) dependent) meas. only stili camera
r--- I I High Temperature Resistance 8 5 Quartz Thermo Self- and interoiffuslon studies,
E4 ~a::a~~ (H1T} (0 heater 3001250 ~~= 110 capillaries vacuum 110 - ;$ 1870 - couPl~ - - No :~~:~I:nd other contribu1ions,

~ Gradl.nt Furnace wHh Resistance Stainless Quenching Ves

9 ArIH. 2 x 10-3 650 to 3 Thermo- I Solidification studies of metalsJ
E5 ~. Quenching (GFa) 2 zones heater 8001600 180 steel Mixture 140 to 1 1750 150 couples by water jet (manually) composites, Interface morphology
~ I.! is - G.nnany - (Rhodium) cartllidQes lOOK/sec
~ ::I!:I i Momoeilipsoid Mirror Z Radiation Zone and gradient crystallisation
E6
BJ :~) (G) ~~=- 3001100 ~1f3~~~nnd:U~~sonductors,
vapour Crystal (G) 2 15 Quartz 385 1.2 Thermo- Nucleation and crystal growth of HgJ2
E7 §~~ I Growth facility 2 zones ~!er/COppe 30 3 200 ampoules - - 10-4 to between couples - - - by sublimation under different
-i §..... - France - heat pipes 387 plateaus ampoule atmospheres
r--- ~ 1'1 SoIu1lon Crystal ~~ heate 76 x AI: 308 8 Crystal growth by coprecipitatlon
E8 iii 'S~ Growth Facllity :, ,_ O! G) Cupla!ed 15110 4 105 X charnbBr Argon - 10-4 to 5 Thermistors - - from aqueons and other solu1ions
- Denmark - '~Fortnn 235 walls 313

Crystal heat 308 4

Solutionfacility
Gmwth I 0, G) reslst.
Cuplated 1 I l0i8 ~~ "",:;'':-'
I """" I Air 10-4 I to Thermistors SeeE8
- DeMl8.rk - Fortnn walls 313
5 I X-ray transparent ~ 25 x Teflon 5 Online Studies of homogenlsatJon, decomposl-
E 10 ~ Fumace I graphite 514 1 10 x chamber Air - - ;$ 530 - Thermo-~:, - - tlon and t?sfWald ripening in
~_t
I ! $3 - Germany - filament 2 couples graphs monotectlC alloys
r--- ~I Three Zone Heat Pipe 3U su 9x 3 22 5 Quartz Vacuum any 670 Thermo- Epitaxial thin layers growth. bulk growth
En Furnace 10001100 1 3i5 ampoules orinertgas, 290 (nonme-- to 100 couples - - - of semiconductors, directlonal solidlfi-
i! 51... m::; ::::0
iti - Franc9 - ctrId pipes red, press. chanlcally) 1300 cation studies, alloys processing

.g 0 ~ MEPIUSTO 2~/cooIer Resistance 10 Quartz 10-6 Thenno- dem!ation of

~tudies sol~ants microsegregation,
<i1 l il _ France _ pa/ls,proIiIa
heatel 1000/500 3 760 ampoules vacuum 180 to ::i 1170 300 couples - Seilbeck - Interface stability and morphology,
9 strechabIe 10-3 measurement growth pertUrbatiOns, undercoollng

E 13 =:"-~ Z Resistance 4001150 1 20 Quartz J~ 200 7t ?;l (n!:~01 Thermo- _ _ _ TraveiHng heater growth of
~ _ Germany _ 5 zones heater 300 ampoules pressure
1ra1 1100 C:!j' couples Hg Cd Te

I\)
.j>.
w
'DIble 10 -I b: Furnaces within the European Programme (ESA and Member States) continued
~
t
~E' g
~§.
~ e~'E
~ ~~ a ~ ~j I I
~.3
a. ~ c ~ c7l e e i off
j ~; ~~ ~­
19 ~ Ii Ii
I '0 §
I II i ~i :aa ~-
.,,5
~~
e a. ~i I ~ ·r
j i1
I~ II ~i
i :!! ~ I~ ~~ II ~!I bi~ 8~ ~ ] ~i I I Ii J311 ~3~
I I Ii I
iI
700tomO Thermo- Stili Yes J Zone crystaNlsatlon of compound
from
Radiation
1halo- 1 3OOIf5O 1 20 1 Quartz 1 AIlJOn. I 10-4 absorption 20 samples Semiconductors DOing traveNlng heater
E 14 ~:~r.':~Fl"ld gone lamp 80 _cod 60 10 couples camera autamaticaJl or vapouritma methods
ampoules pressure 1 dependent
~ ~E Heat pipe gradient G 2 coaxial 20 10-3 Thenno-
li~1 fumacelorthe 2 Naheat 1 150 cartridge 100 10 .. 1320 100 couples - No SeeE2
III !i"l mul1Humece assembly zones pipes 10-1 I
~ MuHlpurposeiso1hennall IIG Resistance 20 Thenna- ~
I'i . 8 gmdlent Fumace!of MFA 2 zones heaters 180/90 1 100 90 .. 2070 400 couples See E 2
:E - France-
Rilsjs1ance 12 proces- 308
Solution growth (I,G) heaters, sed In cartridge 10-4 10 Thermistors SeeE8
E 17 1acNIty(SGF) Inco.,1 blocksof4 313
~ Th. TZM
Multlchember Raslstancoll000/20 I 4 12 Inert Thermo~ Gradient
I heater per Indap'1ly NI- 60 (1) .. 1720 30 couples Insert S"El
Furnace (G) 80 gas
- Gennony- (PtRhPt) chember c'tr1ld cortridges
4TC's Acoustic
Isothermal Furnace I Ras~COI 9001300 I 2 30 Inert per mixer. See E 1
heater per Indap'1ly cartridgas gas 40 (0.7) I .. 1470
- Germany- (G) 100 chamber Gmd.lnsert
(PtRhPt) chember c'tJtld
vacuum 0.03 4TC's Interface
10 TantaI
f. Gmdlent Furnace
- Gennony- 2 zones
Resistancol
heater
(Rhodium)
1000
I 3
Indep'ly
c'rild
293 cartrldgas or
inartgas
120 to
1
I .. 1720 75 per
chamber
Idemarcatiol SeeE2

Radiation Vacuum, 0.1101 1700tol770 Thermo- Video See E 6 plus

Monoellipsoid Minor z 20 Quartz I Grad.lnsert nucleation and undercooling studies
E21 Furnace from 1halo-I 1000/500 Air or 30 (Rotation absorption 50 couples downlink IIFdemarcatior
(G) 70 ampoules Inert gas 5 RPM) dependent using acoustic levitation
-Germony - gene lamp
~ II ""'''''''''.
Paraboloid Reflector Radiation 7001017701 Thermo- Interface
20 Quartz 50 .. 5 I absorption See E 3
Furnace from 1 halo- 70 ampoules couples Idemarcatlonl
- Sweden- gene lamp dependent

Double Ellipsoid Mirror 10 None or 700tol770 light I..

Radiation I 300 12 I absorption tensity Only static zone melting
Furnace from2pro- per Indep'Uy 20
Quartz Vacuum
Ilecloriamps chember c'rild ampoules dependent meas.only
E I~I
- sweden-
Radlotlon 700101770 Thermo- Rapid coo-
High temporature Alumina Nucleation I solidification studies
EE 24 Mlrrorfumace
- Sweden-
from 4 halo-
gene lamps
12 Crucible
absorption
dependent
couples ling In He
gas stream

Resistance 4 Stainless 1.5 4

~ Gradient Furnace G 8 stael vacuum 60 50 Thermo- SeeE 2
E25 heaters I 350 Indap'tIy 100
(nonme- I .. 1520
- Sweden- 2 zones (Pt,SN) c-trlld cartridges chanlcally) couples

'" Heat Pipe Isothennal 1 20 620 Thermo-

~ Furnace I coaxial 60/40 1 70 cartridge Vacuum 55 - to couples S"El
E28
I ~I - sweden - Kheatplpe 870 I I I I I I I
~ 'i Rapid heotlng Resistance 3 2500 Pure fotntetlon studies
E27 i " Furnace I heater 300 Indep'Uy crue:lble :~=- 1.5 mm' 1 absorption I I-I-I - I fabrication of metallic foams by
II _ Sweden _ W-fllamerrt .,rild depende~; rapid heating and cooling
II -
'ftIIble 10 -I c: Fumaces within the NASA programme
..,.
!'! 'E' g I
!! ~ I!! _
i~
i ¥
~ f §
j ~ ~
i 'c?I II!!"
'fi 'il ~ !'!
I; ! or~ ;
j li '0 Iii 8~ .§ 5 i ~ II!! i I oll ~ 11 ,g
'0 ~ Ai'S .ii .l!! co
'l!
.,
)j
jj .3 it ~i ii .~ i liTHjl'~~'g &i ~
:!il ~ ~::E ~
I!~'I'J ~I ~ ~
I"I~ lor I i ~e. I 8~ ~~ l~ < i~ iii
Source: Growth by Su~lmation and chem~1
Vopo,CrystalGmwIh 80 Quartz 37010390 Yes
Nl I""':" bel-I ResIstance 650 Air 1 em' 10-4 80 Thermo- IM~roscope transport of IR and 8-ray detectors
System (VCGS) WIlD 8OIIn:t heater 110 ampoule .... couples manually
!i ....... 31010350 "
__ (HgJ" PbSnTe)
(8) OptIcal
30 343
""""" Thermo- land schlJeren,i Yes Solut~n growth of organ~ CI)'StaIs,
=,,~mon1s _..... hoa1or 1000 grade glass 10-4 <8 manually studios of the growth process
Mlj -"'-I-nco 40 chamber
.... couples ~:k
and .... 315
RuldOlqlOlimont u 10 VId800r FtJndamontaJ studios In Ruld dynamics
N3 apparatus (FEA) 100 200
Yes studies of processes with Industrial appli-
""""'
,-... (STS41D) came... manually cations e.g. Float zone growth of Indium
- RockwoIt-
_IllS Eye
""".
~Ii Acousllcco_ _nco chember Inert Sphere Eye 3 axial IdoaJly ahaped spheres of glass,
Experiment systam (I) hoater, 180 63x63 None 890 acoustic No ceramic, metal, and solidification
gas ¢ 10 Video
(ACf5) tnconol x70mm' _tor process studios
Automated IlIroctIonaI ResIstance 4 8 vacullll 2xl0-4 Thermo- Intorfaco Directional solidification of low matting
N5 Solklllcatlon FtJmaco G 300 Ampoules or 100 to ::;;;400 50 No
~ ill (AIlSF)lDwlilmp._n hoa1ors ~'tIy 135 1nortgas 1
couples demarcation alloys. Interface stlHfl8S

Automated DI_naJ Resfstanco 4 8 vacuum 2xl0-4 470 to Therm0- Interface DIrectional solidification of metallic
N6 _nFUrnace hoa1ors 1175 Ampoolos or 100 to !nO 100 couples demarcation No a1~ and compos11os, semiconductors
(AIlSf)Hlghlilmp._. PtNICr ~ 135 Inert gas 1 and (low meI1lng) Insulalors
_Automated ......... 2 35 Quartz 2xl0-3 Thenno- Bridgman crystal growth of conpound
N7 DIroct1ona1SoIIdf1r:a1lon G .......... 500 Indop'1ly ampoules 120 to 1270 350 couples No semiconductors (Hg Cd Te) with well
FtJmaco (AAIISf) , - c'1r11d 250 10-1 controllec1gradlont profile
I .-- 1570 Undercoollng and nuclOailon studies
=.,.,=., IF Sphere Phofo- Ihoa1erslmul-l
N8 -,(I) Dfuctfon 1024 None ¢9 any sample Pyrometer I grapl1~ Ianeonly Praparat~n of amorphous and meta-
~ depondent Record levltator staba phases In metallic systems

Single axis acousI~ Resfstanco Chamber AIr .. Photo- Uniaxial 8 samples

N9 (I) hoa1or 3100/2e00 102xlO2 None ::;;; 1870 Pyrometer I graphic acoust~ bymanl- SooN 4
LevI1ato,~
SIC 1nortgas ~ _to,
hII x114mm' Record poIa1or

-P1Iposo G (I) IResIstance 20 any I 370 Therm0- Solidification of Immiscible al~

NtO _firmaco(GPllF) 32000s hoa1or I 1600 78 cartridge I HoIIum 70 OOnmB- to 100 couples No Bridgman and vapou, crystal growth
chanIcaIly 1170

MuItimnoFUrnace C8ranic any Thermo- 1_ Diverse zoning and Dlrsctfoal sotIdlflca-

Nil Ii! U IResIstance 25 400 nonme- ::;;;1570 100 tloncrysta1l_n_ofUW
- Gnrmman- 16 Zones hoa1ors I 1000/400 400 cartridge coopIos domarr:atIon
chanIcaIy compound semiconductors and ofhers
(8)
-6N
II . ..... and 10000 cartridge
Therm0-
couples Yes
EIoctroopIIaxIaI growth
ofGn AB from Gn sohrtlonwithAB
-MRA- '
-...
_ ....
• _ I 500 1 20 Quartz Inort 10to vapour Crystal ~h (PVT, CVl) of
N13 3_1- 2adjacorrt 10-4 :51170 Thermo- Yes (compound) semiconductors, studies
~ II Ji
==
:-m~
- RPt/Boelng - and saD1Iios
2xl00 ampoules gas 50 couples
o~
Imlcroscopni of cryotaIIIsatIon mechanisms.

*
Table 10 -I d: Furnaces within the Intercosmos and the Japanese Programmes
~
~E
~
g
~.§. ~
~ lE: :g,
~ :2 ~ ~ ~ii
~ .2- -;;- ag, ~ E 0:: ~'E i I
~ .E ~ e ~ :5 'E C E <21 ~ ~ .~
,. m ~~ ~ ~ ~ ~
-"off
:;;;0
~ ~ o
-i .. E ~ 8 = ~ E ~£ = ~
i~ ~ .ll :. ~ ,8
II d:. -'E ~
rl- j i '§
~ ~ = .8-§ .ii .!!! = ~ 1; ~
<21 ~1 ~o ~i ~ I 1;i '5 '§
E E ~ E
~jl
:lE~ ~.r I i
:t:
:t: _
i j §
z
i
:t: :lEB
.m
* J g~ Jd ~:!B. 8-~ :lE~
ilill i « I~ ~S~
i "" :lE
2x 10-2 470 9 Yes Semiconductor crystallisation
Kristal 21 Sleet Air 100 to to 50 ThefTTlO-
3001120 240 Cartridge (manually) Vapour and ·Brlgdman growth
- USSR- 3~~ IR~= 4x10-1 1370 couples

Resistance 5x1O-3 670 3 Yes Metallic Alloys, composite foams,

Splav(A1loy) 20 Cartridge vacuum 150 (nonme-- to 70 Thenno- lsothennai and directional
G Iheaters 5001300 175 (manually)
- USSR- 3 Zones Mo-ReflectOi chanlcally) 1260 couples solidification
g:Si' 470 Thenno~
Yes I Fabrication of larger quantities
~, Karund U Resistance 33 Air to 12 samples of compound semiconducting
13 - USSR- 3 Zones heaters 300 couples automatically crystal material
1520
~ 10-4 370 3 Integrated Yes Crystal growth by various zoning
t- KrIsIallsator/(CSK-l) U Resistance 16 ampoules
I
heaters 500/300 Air 100 to to 150 Thenno- Accelero- 19 samples and gradient methods. Glass, alloy
14 - CSR- 5 Zones 140 pousstainiess meter automatically and composite preparation
(PlRh) steel cartridge 6 1240 couples
--
Resistance 1 13.5 Thermo- Acoustic Yes low melting alloys, composites,
ContllousheatiOllJ I 11001300 (1 cooling Cartridge Vacuum 50 :iii 1570 - -
J1 Furnace (CHF) heater 50 I couples mixer manually foams
chaml:ler)

Large Isothermal Resistance 22 Thermo- Yes High melting alloys, composites,

J2 I 1100/950 1 Cartridge Vacuum 150 ;.$1870 - couples - manualily giasses.ceramlcs
Furnace (UF) heater 150
Ii:
~ Gradient Heating Resistance 10 mechani- Thermo- Acoustic Yes Directional solidification
J3 G 1100 1 Cartridge cally " 1520 60 couples - mixer manually Bridgman and vapour crystal growth
Furnace (GHF) heaters 110
J Radiation None or Inert Gas 3xlO-3to " 1770 Eye Yes Aoat Zone, Travelling Solvent,
Image Furnace 20 Quartz or 120 0.3, Rotation absorption -
J4 z from 2 1000 1 160 Camera's manually Crystal growth of semiconductors
OMF) lamps ampoules Vacuum 3to30RPM dependent

Radiation Uniaxial Ideally shaped spheres

Acoust~ levitation Sphere " 1770
absorption acoustic
J5 0) from halo- 1400 1 ~ 10 amorphons metals
Furnace (ALF) geneiamps dependent levitator
 247

of 45 0C for manual sample extraction. To avoid thermal stresses the cooling

can also be performed in two steps for which correspondingly two positions
in the cooling chamber are foreseen.

Fig. 10.3-1: Cross section of the Iso-

thermal Heating Facility (IHF) 10.35

While the heater chamber is under vacuum ( <10- 4 b) to avoid losses by heat
conduction the cooling chamber is flooded with Helium. The heater chamber
is isothermal to within 5 K over the whole length, the maximum temperature
being 1550 oC. The samples for isothermic experiments are enclosed in
Tantalum cartridges of 40 mm outer diameter, 100 mm length and 0.5 mm wall
thickness. This vol ume can al so be subdivided into several cavities, in
which e.g. samples of different material composition can be processed under
identical conditions. The sample holder is a tube of high thermal re-
sistance. Three to four thermocouples measuring ,
the temperature distribu-
tion in the sample are fed to the exterior. For thermic insulation between
sample and front vacuum flange a radiation shield, composed of several suc-
cessive Ta-foils interspaced by vacuum (superinsulation), is arranged
around the holder.

With a sl ight modification the furnace can be converted into a gradient

heater. As shown in Fig. 10.3-2 a "chill block" made of copper is introdu-
ced into the open end cone of the chamber and, for solidification, the hea-
248

ter/chill block configuration moved over the sample in the direction

indicated. The sample design of course is different from isothermic samples
in that the diameter is smaller (10 mm) and capillaries at the hot end are
foreseen as volume reserve for thermal expansion.

Fig. 10.3-2: Cross section of IHF heater

chamber and sample in the gradient con-
figuration [10.35J

Water
CocMlng -........,
Mohand
Haating ChambllrJChili Block

The control of the IHF is automatic to a high degree reducing crew inter-
vention in the nominal case to the exchange of samples. The typical process
times for the experiments vary from 30 minutes to 5 hours. The whole pro-
cess with all necessary steps (incl. chamber exchange, gas supply etc.) is
controlled by a software programme running in the central computer of the
MSDR. To determine the parameter set for the mission a number of runs for
each individual experiment (total number: 20) was executed in a ground mo-
del of the MSDR. The performance under weightlessness showed no significant
differences. The T-profiles measured during flight were in good agreement
with those determined previously on the ground (Fig. 10.3-3) an expression
that the control loops work satisfactorly. Only in the initial overshots in
the temperature of the heater, intended to accelerate heatup, sl ight in-
creases were noticeable (not shown) which can be attributed to missing con-
vection around the heater wires.

----. 'urnaco I.J Fig. 10.~-3: Flight/ground comparison of

floghlecp. temperature readings in the IHF (Experi-
- . sample temp
flighloxp. ment ES 309, from [10.35J)
II " " : sample temp.
grCMld expo
 249

For comparison, in Fig. 10.3-4 an isothermal furnace using a potassium heat

pipe is shown (E26 in Table 10-1). It allows temperatures from 350 to
600 0 C. As the furnace is concei ved for fl i ghts on soundi ng rockets, no
sample exchange is foreseen. The cavity dimensions are 20 and 70 mm. Iso-
thermicity over length is ± 1 K. Heatup is much slower than with the IHF.
To reach thermal eqilibrium at a preset T-level, 30 to 60 minutes prehea-
ting is necessary. This is not in conflict with the only 6 minutes flight
time since preheating can be executed before launch by means of an umbili-
cal from an external power supply to the payload. The weight of the furnace
is only 1.5 kg.

r------
~~:::
v,) cuc,; ;o" pump
conn('clI:tn
Fig. 10.3-4: Heat pipe isothermal
furnace for use in sounding rockets
[10.26 ]

r~"
11'1 :\11., 1101'1 C:ov~r
Mil r trll l*
HUllng tlt mtnt

HUI Pip.

MItl-K
insulat ion

Exttns ion spring

Insullil ion pCaln

Ma' lnll'

~~2~~~1c-- O. , ing
- 101.1011 plAI'
SIgnal conn'clion
POo/JItr conn. et,on
PC bOil:d 1.1011

b. Gradient Furnaces

As the purpose of gradient furnaces is directional solidification or Bridg-

man type crystallization, an important parameter is the ratio G/v (G: tem-
perature gradient, v: velocity with which t he solidification front pro-
ceeds). A definite value of G/v must be exceeded to render possible planar
solidification fronts which are usually desired. G is given by the tempera-
ture difference of at least two adjacent heating elements separated by a
thermal insulation. v can be realized in two ways: either by a gradual de-
crease of the high temperature level (gradient freezing) or by a mechanical
movement of furnace and sample relatively to each other. The latter alter-
nati ve is normall y chosen when hi gher temperatures and gradi ents are de-
250

sired [10.2J. For space laboratories it is of some concern, that the use of
a mechanical driving system constitutes the introduction of one more ac-
tive, maintenance requiring component and that, if the sample is moved re-
1ati vely to a fi xed furnace a mounti ng 1ength of about twi ce the sampl e
length in addition to the furnace must be foreseen for accommodation. Mo-
tion of the furnace, as realized in recent developments, is technically
more complicated, but saves one sample length and is, in addition, more be-
neficial from the low gravity standpoint since the sample remains quiet.

The first generation of space gradient furnaces, however, use the simpler
solutions of sample motion, as is the case for "Kristal" (I1 Table 10-I),
one of those furnaces with longest operational time in space, or of gra-
dient freezing as in the "Gradient Heating Facil ity" (GHF, E2) which flew
also as part of the MSBR. Accordingly the microprocessor controlled GHF
provides more flexibility in the configuration of T-profiles, has a steeper
T-gradient by virtue of superinsulation and allows simultaneous processing
of 3 samples [10.36J whereas both furnaces equal in the number of heaters
(3) and in the operational temperature ranges [10.37J.

As mentioned above the gradient furnaces of the second generation make use
of the advantages of mechanical motion of the entire or part of the heater
configuration over a stationary sample. Two different concepts are shown in
Figs. 10.3-5 and 10.3-6. Whereas in the "Gradient Furnace with Quenching
device" (GFQ, E5) a complex consisting of 2 heaters, insulation and the
cool/quenching zone is moved from left to right for solidification [10.38J
in the Mephisto furnace (E12) the right heater/cooler configuration is
mounted on a slider and can be driven towards its fixed counterpart (left).
In the GFQ the T-gradient for a given sample can be varied by a factor of
approx. 2.5 through an appropri ate compos iti on of the furnace atmosphere
(He 1 i urn, Argon, vacuum). The mutual i nfl uences of the different process
parameters incl. the interactions with sample and cartridges (here stain-
less steel) are discussed in [10.39J. Since the operation under gas pres-
sure allows no superinsulation a ceramic foam connected to Spacelab's ac-
tive water cooling loop has been selected for insulation. The GFQ is sche-
dul ed for fl i ght in Spacel ab 01 end of 1985 for studies of transport and
morphology phenomena in metallic solidification. As a multiuser facility it
requires man tendance for sample exchange. The whole process flows are con-
trolled by a microprocessor.
 251

1100 t rlOC]

Sample

Fig. 10.3-5: Cross section of the interior part of the GFQ with correspon-
ding T-profile (from [10.38J)

Fig. 10.3-6: Working principle of

the Mephisto furnace with T-profile
(from [10.27])

In the Mephisto furnace exceptionally high gradients are envisaged by coup-

ling the sample ends thermally with the 60 0 C heat sinks via a metallic film
[10.27 J. In addition superinsulation is used. The furnace is designated for
flight on an autonomous carrier (Materials Science Laboratory, MSL, 1986)
on which for the necessary heat release the carrier's liquid cooling loop
252

can be used. From temperature variations, induced by other facil ities or

sun/shadow changes, it will be decoupled by a special control system stabi-
1 izing the heat sinks to ± 0.25 K. The special arrangement which ensures
equal sample temperatures at both ends is aimed to facilitate measurements
of metallic undercooling at the solidification front via the Seebeck effect
in one of three samples processed in para 11 e1. Interface demarcation is
possible in a second sample, as well as accelerated cooling of the samples
alltogether by a rapid driving gear of 5 cm/s speed.

As indicated in 10.2 heat pipes have also been considered for application
in space gradient furnaces. As example of this very advanced furnace line,
Fig. 10.3-7 shows the Advanced Automated Directional Solidification Furnace
(AADSF, N71 [10.40J and Fig. 10.3-8 the Three Zone Heat Pipe Furnace
(TZHPF, Ell) [10.28 J. As Fi g. 10.3-7 indi cates, hi gh temperature gradients
are possible. The arrangement of the heat pipes is completely different in
both furnace versions. Whereas the AASDF consists of two adj acent tubul ar
heat pipes (Na-filled for the hot end and either Na or Hg filled for the
cold end) the TZHPF has 3 isothermal zones each heated by nine Na-heat
pipes of "pencil type" surrounding the sample. This design difference re-
sults from the originally different experimental intentions. Yet these fur-
naces, especially the one with 3 zones provide wide applications. The AADSF
was designed as a Bridgman crystall ization furnace and, presently, much
work is applied to improve its thermal behaviour in interaction with sample
and crucible to achieve planar solidification fronts. Furthermore magnetic
fields are applied to reduce convection as far as possible under unit gra-
vity [10.41, 10.42, 10.lJ. The TZHPF arose from the concept of furnace E7
(Table 10-1, see also 10.2) and is intended to reveal better flux control
for the epitaxial thin layers crystal growth from vapor. The elevated tem-
perature range wi th respect to E7 indi cates appl i cati ons for semi conduc-
tors.

Similarly to E7 the Vapor Crystal Growth System (VCGS, N1) flown in Space-
lab 3 in April 1985 is designed to produce crystals with low sUblimation
points (H912 ca. 114 0 C). Though little has been reported yet [10.43J the
furnace, having a seed crystal on a cold sting surrounded by a warmer am-
poule which holds the source material, and the possibility to reverse the
gradi ent if imperfect growth sets on (mi croscopi c observati on), has ob-
viously succeeded in growing a 1 cm3 well shaped crystal.
 253

a Fig. 10.3-7: The Advanced Automatic

Directional Solidification Furnace,
HI. Cd. "'"'0 T. V~ a: setup with two different T~level
tubular ~eat pipes arranged in
line, b: T-profile over sample
length (from [10.40J)

L-TYMCAL two ZONE

,,' FURN"C£

---

Fig. 10.3-8: The Three Zone Heat

Pipe Furnace in cross section with
corresponding T-profile, typical
for vapour epitaxi al growth (from
[ 1O.28J)

l.~

c. Zone Heating Furnaces

Floating zone solidification methods are, were applicable, very economical

in power consumption compared with other techniques since only a relatively
254

small volume has to be kept in the molten or gaseous state. It adds to this
economy if radiation heating with ellipsoidal mirrors (see 10.2) is used,
thus facilitating either larger sample diameters or higher process tempera-
tures in compliance with the limited resources in a space laboratory. The
Mirror Heating Facil ity (MHF, E3) as flown in Spacelab 1 (Fig. 10.3-9)
achieves by virtue of its fine polished, Au-coated reflecting surfaces a
15 mm molten zone in a 10 mm diameter Silicon rod (M.P. 1420 0C) with only
580 W lamp power (290 per halogene lamp). With higher powers (max. 600 W
per lamp) also 10 mm A1203 (M.P. 2045 0 C) could be molten. The samples can
be contained in transparent ampoules or containerless, the furnace atmos-
phere being vacuum or inert gas. For operation in excess of 150 Wper lamp,
however, a minimum gas pressure of about 10 mb is required for conductive
cooling of the lamp sockets. This value results from the relation between
mean displacement length of the gas molecules and the vessel dimensions. It
is also a reasonable upper limit since higher gas densities produce convec-
tion thereby complicating 19/0g comparisons.

Fig. 10.3-9: Design principle

furnace support
of the double ellipsoid Mirror
Heat i ng Facil ity (MHF, from
central shell
[10.44J)
sample
attochmentrod

melting zone

lamp common focus

sample

mirror ellipsoid

cooling pipe coil

In this context the question may arise whether the space vacuum can be used
directly for the evacuation of furnaces. In fact the vacuum quality is not
as good as could be assumed. First, the residual atmosphere in low earth
orbits amounts still to about 10-6 mb, second, there is much offgassing
around the platform and, third, the effective pumping speed is low so that
only prevacuum quality is disposable. This explains the ~existance of high
vacuum pump packages inside Spacelab (which ultimately, of course, evacuate
 255

to the outsi de through -well controll ed! - vent1 ines). The only furnace
known to evacuate directly through a 25 cm lock in the spacecraft wall is
"Sp1av" (I2) but, in spite of this large opening area, for reasonable vacua
long evacuation times are necessary, which would not comply with the short
duration of shuttle missions.
Recent developments show for zone furnaces too a return to resistance hea-
ter configurations better adaptable to the growth of compound semiconduc-
tors with complicated $toichometry (see e.g. E 13), where MHF and "ELLI"
furnaces (E 6, E 14, E 21) are at their limits (see 10.2).

d. Universal Furnaces
As the examples of Ell and E13 have demonstrated, furnace layout tends to-
wards more flexibility in the configuration of a T-profi1e. A mark is set
with the "CSK-1" or "Krista11isator" (14) which is under dedve10pment for
flight in the Sal jut station 1985/86 10.33. Like E13 it has 5 tubular re-
sistance heating segments. Thereby the formation of either 3 narrow or 2
wide zones of different temperature, independently controlled by a micro-
processor is possible over a range from 100 to 970 0C (Fig. 10.3-10). More-
over the furnace is equi pped wi th a mechani cal drive and an automati c
sample exchange mechanism for 19 samples in order to manage processing of
experiment series without crew intervention.
In the Grumman laboratories a 12 to 20 (later 50) zone furnace is under de-
velopment for use in directional solidification of eutectica and Bridgman
growth of compound semiconductors 10.46. The identical tubular resistance
heater segments are stacked up ina lternat i ng sequence wi th water cooled
insulator segments. One heater/insulator pair occupies 25 mm in length. The
sample diameter is also 25 mm. Each insulating segment is equipped with a
thermocoup 1e whi ch can be inserted to a depth in whi ch contact with the
sample wall is reached. The sample itself contains thermocouples as well.
This allows an overall sensing of the thermal conditions in the furnace.
The attractive features, that no mobile parts are involved and any indivi-
dual profile configuration, including crystallization under reversible gra-
dients can be realized, are obtained at the expense of a high demand in
power and cooling water. For the very sophisticated control of the furnace
a speci a1 software has been developed whi ch is runni ng on the company IS
Craycomputer. After further improvements in the electronic control and in
reducti on of water and power consumpti on the furnace is intended to be
mounted on a special carrier structure for flight in the Orbiter Cargo bay
by the end of this dekade. An application could be the production of magne-
tic materials or compound semiconductors like GaAs in space.
256

---~------ c-m----T------T--T-T.....C--
a ~ I
.
,I
-
\J I
--

t.. l __ .
- if. "'. -:-. -.. "'i- ll.'""'.#"" , -:->l.>L- - -~-~~~~
~ ~'!La.;.,.......I:'--.-Ill_ -. '-·zs.I-;";; :;-~-.",-.-:;;;- ;;;;;'-:;;;=V.~
D. ,r~

h c

Fig. 10.3-10: Principal layout (a) and achievable temperature profiles

(b-c) for isothermal, gradient or zone heating , measured with a
calibration sample in form of a stainless steel tube in the CSK-1 (from
[10.33J)

10.4 Peripheral Devices

The unique conditions for experimentation! in a gravity free environment

have stimulated the development and application of specific techniques in
the peri.phery of furnaces which are not so ubiquitous in terrestrial pro-
cessing. To these belong the containerless sample levitation and manipula-
tion techniques dealt with in chapter 12.
 257

Of particular i nterest is also the study of dynamics and morphology in the

vicinity of the fluid/solid interface of a material during growth or soli-
dification. One method commonly appl ied in space and ground furnaces to
preserve the momentary jnterface shape in directional solidification OJ'
Bridgman growth is demarcation by electric current pulses which makes use
of the Peltier cool ing effect. An alternative way has been chosen for the
GFQ-furnace (ES, Table 10-1) in which crystall ization in metal s will be
studied. Preservation of the interface morphology is achieved by rapid
freezing with a quenching device (Fig. 10.4-1). It consists of a ring with
nozzles from which water is ejected onto the sample cartridge. This quen-
ching ring is in mechanical connection with the cold end of the tubular
heater/cooler configuration described in 10.3. For quenching after a cer-
tain time of regular crystallization the whole configuration is shot pneu-
matically over the sample until the nozzle ring coincides with the actual
position of the solidification front. The introduction of acceleration com-

Fig. 10.4-1: Working principle of

a the GFQ quenchi ng devi ce (a) and
cooling characteristiscs obtained
for a 9 mm Al-sample in a stainless
steel cartridge 0. 5 mm wall thick-
ness (b) (from [ 10.38J)

b TrC)

735

- - - - Tliquidus

548 - - - - T solidus

o 1 2 3 4 5 6 7 8 9 I sec) [
Quenching slart
258

pensation by countermoving masses has long been discussed, finally the idea
was dropped because the measured impact is small and analyses reveal that
short impulses of low amplitudes will not trigger pertubations in confined
fluids. Cooling .rates of 160 K/sec in 9 Il1I1 Nickel and 50 K/sec in Aluminum
samples are possible (Fig. 10.4-1).

Since early experiments on binary metallic alloys with miscibility gap re-
vealed that demixing also occurs in zero gravity an acoustic mixing device
has been developed to counteract the (meanwhile understood) mechanisms of
dehomogenization in the liquid state (Fig. 10.4-2). Applied to the isother-
mal furnace (E19 in Table 10-1) it was successfully flown in TEXUS sounding
rockets several times and resulted, if, activated shortly prior to solidifi-
cation, in finer dispersions compared with ground reference tests [10.47].

Fig. 10.4-2: Design of the ultrasonic

I I
mixing system in comination with the
TEXUS isothermal furnace. The acoustic
transducer (1) f s connected vi a a wave
guiding system (2, 3) with the sample
cavity (4). This in turn will be cooled
from the opposite side with a cooling
finger (5) (from [10.47J)

An important contribution to the explanation of demixing mechanisms in mo-

notectic alloys was achieved with the in-situ observation of such a metal-
lic system by means of an X-ray transmission and photographic registration
during fl ight under weightlessness. All components of the furnace chamber
which held the Hg/Ga mixture in the liquid state (E10, Table 10-1) had to
be X-ray transparent. Flown on shuttle missions in 1982 and 1983 [10.48J
 259

this system marks the begin of the introduction of more in-situ diagnostics
of all kind into space experimentation in order to close the gap between
sampl e preparati on before 1aunch and sampl e analysi s after 1andi ng. The
latter gave sometimes rise to puzzling uncertainties since direct informa-
tion from the process under reduced gravity was lacking.

In the mean time the promissing use of online diagnostic techniques toge-
ther with space experimentation has been recognized and is augmenting.
Examples are the flight of holographic observation systems in the American
"Fluid Experiment System" combined with crystal growth in Spacelab 3 (April
1985) and in the German "Optiklabor" combined with crystal growth and fluid
science studies in Spacelab D1 (Nov. 1985) [1O.49J, or, technically
simpler, the photographic recording of the solidification of saltic melts
[10.50J in low gravity 1983.

10.5 Future Trends in Space Furnace Development

Future developments in materials processing instrumentation must be orien-

ted on the potential which is offered by the advent of permanent space
stations. Many of the limitations (see 10.1) will no more exist (short mis-
sion times) or be substantially reduced (contraints in volume, mass and
safety requirements). In this sense the conditions in an orbiting laborato-
ry will approach those we are used to from earth laboratories. Series of
experiments become possible in which following steps can be flexibly confi-
gured upon the results of previous steps. This leads to the necessity that
more facil ities for eval uation and process observation be avail able on
board. Two of them were adressed in 10.4, other diagnostic techniques of
interest for materials science could be:
- electron microscopy for structural studies
- X-ray diffractometry /topography for studi es of crystal formati on and
structures
- Laser-Doppler anemometry for surface motion studies
- pyrometry for undercooling/nucleation studies
- radioactive tracer detection for transport studies

Thus a large amount of basic investigations in fluids under weightlessness,

impeded so far by the various contraints and requiring a greater extent of
peripheral instrumentation, are waiting for execution.
260

For the furnaces themselves there is a trend away from the multiuser/multi-
purpose facilities which were well suited in the initial orientation phase
in which a broad spectrum of material s was screened for potential bene-
fits. Yet too many compromi ses had to be made and for the future hi gh de-
gree of "speciality of the materials to be studied or produced in space, de-
dicated facilities will be used. Easy and short access to the space station
for standard labortory or production equipment without extensive modifica-
tions must become reality. Since the effects of low gravity are small and
if an advantage in space by the time of the station is to be expected, the
instrumentation used must at least be competitive with the best standard
existing on earth. Examples of very advanced facilities have been given in
10.3. Other promissing material s processing devices of which very 1ittle
information is available, are under development by private companies for
eventual flight on future missions (e.g. a Low Temperature Vapor Crystal
Growth Furnace by 3M).

There are trends recognizable towards more automatic control or remote ope-
ration of processes from the ground ("telescience") since not always the
best experts can be flown to operate their equipment directly. Production
processes for which much experience already exists can be optimalized to
run without manual operation ("robotics", Fig. 10.5-1). It can be concluded
that by both,
- the stimul ati on of furnace improvements under space processi ng aspects
and requirements, and
- the ease of access for earth standard hardware to space laboratories,
a convergence in design between the two extremes will occur, resulting in
facilities of high technological standard.

Fig. 10.5-1: Prototype of an auto-

matic processing facility with 4
furnaces (front) and a magazine
with 35 samples
 261

Acknowledgements

The author wishes to thank H. Ahlborn, C. Barta, LA. Brown, R. Cadoret,

J.J. Favier, B. Feuerbacher, W. Herfs, D. Larson, J.C. Launay, R. Naumann.
G. Otto, H. Sprenger, H. Wiedemeier, A.F. Witt for the helpful discussions
which contributed to the comprehensiveness and correctness of the data
revealed in this chapter.

References
[IJ T. Jasinki, A.F. Witt
On the control of the crystal-melt interface shape during growth in a
vertical Bridgman configuration
[2J Advanced heating facility concepts for microgravity application
MBB-ERNO-Report under ESA-contract no. 4839/81/NL/HP, 1983 (and refe-
rences therein)
[3J Phased project planning guidelines
NASA-NHB 7121.2, 1968
[4J Studie zur Aufwandsoptimierung bei Satelliten- und Spacelab-Experi-
menten
Dornier-Report under BMFT-contract no. W78-34, 1978
[5J B.E. Paton et.al.
Special features of electron-beam welding and cutting apparatus and
processes for use in space
Avt. Svarka 3, 3-8, 1971
[6J MBB-ERNO-Report under ESA-contract
To be published in the ESA contractor reports
[ 7 J H. Koch, H. Losch
An European heat pipe experiment on the second flight of space
shuttle Challenger
Proc. 5th Int. Heat Pipe Conf., Japan May 1984
[ 8 J R. Cadoret
Mercury Iodide Growth
Spacelab I-Experiment No. ES 338, (1983,ireflown on Spacelab 3, 1985)
[9J K. Kitazawa, K. Nagashima, T. Mitzutani, K. Fueki, T. Mukaibo
A new imaging system utilizing a Xe arc lamp and an ellipsoidal
mirror for crystallization of refractory oxides
J. Cryst. Growth 39, 211-215, 1977
[10J A. Eyer, H. Walcher
Halogenlampenexperimente bei TEXUS IIIb
Final report for DFVLR, 1981
262

[11 J A. Sawaoka
Halogene lamp experiments in the Japanese sounding rocket programme
Private communication
[12J Halex experiment on shuttle flight STS41
Dornier-Report under ESA-contract no. 5/570/83/F/FC, to be published
[13J Towlson Consultants and Company
An arc image furnace for space applications
British Aircraft Corporation under ESA-contract no. SC/80/HQ, 1977
[14J A. Eyer, R. Nitsche, H. Zimmermann
A double ellipsoid mirror furnace for zone crystallization experi-
ments in Spacelab
J. Cryst. Growth 47, 219-229, 1979

[15J D. Langbein
Proc. of the 15th Jahrestagung der DGKK, Zeitschr. f. Kristallo-
graphie, Aachen 1984
[16J T. Carlberg
A preliminary report on floating-zone experiments with Germanium
crystals in a sounding rocket
Proc. 5th European Symposium on Materials Science under Microgravity
ESA-SP-222, 367-373, SchloB Elmau 1984
[17J R. Monti, G.P. Russo
Non intrusive methods for temperature measurements in liquid zones in
microgravity environments
Proc. 33rd Congress of Int. Astr. Fed., 145, 1982
[18J Solar energy concentrator system for crystal growth and zone refining
in space
Report by Lockheed under NASA-contract no. NAS8-30268, 1975
[19J Prospective study on the utilization of solar energy for the opera-
tion of Spacelab material science furnaces
Report by Societe Europeenne de Propulsion under ESA-contract no.
3787/78/F/FC, 1979
[20J Prospective study on the utilization of solar energy for the opera-
tion of Spacelab material science furnaces
Report by Dornier System under ESA-contract No. 3788/78/F/FC, 1979
[21] R. Beck
Crystal growth of oxides using a C02 laser
1st European Symposium on Materials ~cience in Space, Frascati 1974
[2~ Space processing for extended low-g testing
NASA-Report No. LASD-STT-73-005, 1973
[23J A.A. Chernov, S.N. Maksimovskii, L.A. Vlasenko, E.N. Kholina,
V.P. Martovitskii, V.L. Levtov
Growth of Germanium crystals with low dislocation density in a condi
tion of weightlessness
SOY. Phys. Crystallogr. 29/2, 1984
 263

[24J E.L. Kern, G.L. Gill

Microgravity Silicon zoning investigation
Mat. Proc. in space progr. tasks, NASA TM-82525, 1983
[25J W. Littke, C. John
Protein single crystal growth under microgravity
Science 225, 203-204, 1984
[26J R. Jonsson, S. Wallin, P. Holm
The microgravity research program in Sweden
AIAA, Proc. 6th Sounding Rocket Conf. Orlando/Fla., Oct. 1982
[27J G. Cambon, R. Barillot, F. Jamin-Changeart, J.J. Favier, Y. Malmejac,
J.P. Praizey
Mephisto: Research equipment for the study of solid/liquid interface
destabilization in metal alloys
Proc. 33rd Congress of Int. Astr. Fed. 164, 1982
[28J F. Jamin-Changeart, G. Cambon\ R. Barillot, J.C. Launay
Brief description of typical elements of a multifurnace assembly con-
cept accomodated on EURECA
Proc. 33rd Congress of Int. Astr. Fed. 166, 1982
[29J EURECA facility description
ESA-Doc. No. MG/AO/EUR-2, 1983
[30J Microgravity science and applications/experiment apparatus and faci-
1ities
NASA-Document, 1985
[31J J.P. Wilhelm
Industrial research opportunities in space: the case for advancing
electronic crystal technology
SRI-Report pres. at 17th Annual Electronics and Aerospace Conf.,
Sept. 1984
[32J L.L. Regel
Kosmicheskoe materialovedenie/seria issledovanie kosmicheskogo
prostranstva
Soviet academy of science report, 1984
[33J C. Barta, A. Triska, J. Trnka, L.L. Regel
Experimental facility for materials research in space/CSK-1
1984, submitted to J. Cryst. Growth
[34J (Japanese) material experiment laboratory (FMPT)
Handout on the occasion of the 2nd jOint ilapanese/ESA/DFVLR symposium
on microgravity research, 1985
[35J K. Wittmann
The Isothermal Heating Facility
Proc. 5th European Symposium on Materials Science under Microgravity
ESA-SP-222, 49-54, SchloB Elmau 1984
264

[36J G. Cambon, B. Castets, O. Boutemy, J.P. Gicquel, R. Aubron,

A. Boddaert, J. Benoit
Gradient Heating Facility behaviour
Proc. 5th European Symposium on Materials Science under Microgravity
ESA-SP-222, 115-119, 1984
[37J A.Y. Malinin, R.Z. Sagdeev, V.T. Khryapov, E.T. Solomin,
V.I. Seliverstov, Y.M. Zhelanni, A.F. Podolinni, D.V. Bocharov
Multipurpose apparatus "Crystal" for process experiments in space
Proc. 3rd European Symposium on Materials Science in Space,
Grenoble 1979
[38J Gradient furnace with quenching unit, technical description
Dornier System GmbH, 1984
[39J P. Behrmann, R. Benz
Heat transfer induced performance characteristics of gradient type
furnaces
Proc. 4th European Symposium on Materials Science under Microgravity
ESA-SP-191, 109-115, Madrid 1983
[40J S.L. Lehoczky, F.R. Szofran, B.G. Martin
Advanced methods for preparation and characterization of infrared de-
tector materials
Report under NASA-contract No. 8-33107, 1980
[41J A.F. Witt
The impact of space research on semiconductor crystal growth techno-
logy
Proc. Winter Meeting of ASME, 43-52, Boston 1983
[42J F.R. Szofran, S.L. Lehoczky
A method for interface control during Bridgman type crystal growth of
HgCdTe alloys
J. Cryst. Growth 70, 349-355, 1984
[43J NASA distributes Spacelab 3 payload for analysis following shuttle
1andi ng
Article in Aviation Week and Space Technology, May 13, 1985
[44J A. Eyer, H. Leiste, R. Nitsche
Crystal growth of silicon in Spacelab-1
Proc. 5th European Symposium on Materials Science under Microgravity
ESA-SP-222, 173-181, 1984
[45J H. Walcher, J. Baars
Private communication
[46J D. Larson
Private communication
[47J P.F. Clancy, W. Heide, D. Langbein
Sounding rocket flight test of an acoustic mixer by manufacture of a
lead-zinc emulsion alloy in microgravity
Proc. 4th European Symposium on Materials Science under Microgravity
ESA-SP-191, 99-104, Madrid 1983
 265

[48] H. Otto
Stability of metallic dispersions
Proc. 5th European Symposium on Materials Science under Microgravity
ESA-SP-222. 379-388. SchloB Elmau 1984
[49] Holographic interferometry near gas/liquid critical points
Proc. 5th European Symposium on Materials Science under Microgravity
ESA-SP-222. 323-325. SchloB Elmau 1984
[50] H. Klein. R. Nahle. K. Wanders
Metal-like solidification of a multiphase dispersion in lowgravit,y
during a space shuttle flight
z. Flugwiss. Weltraumforsch. 9/1. 14-20. 1985
11 Fluid Experiments
Alain GONFALONE

European Space Agency, Noordwijk

The Netherlands

11.1 Introduction

This chapter contains a brief description of techniques for

measuring fluid properties current in space. A selection of
instrumen~ representative of the latest technology are pre-
sented and briefly described. Some of these instruments have
already been flown. The scientific results that have been
obtained with them are reported by Langbein in Chapter 16 and
elsewhere [11.1], and will not be discussed here in any de-
tail.

Detailed reviews of materials--science experiments conducted

during the last decade can be fOMnd in Naumann [11.2] and
Seibert [11.3]. An updated survey has been edited by Dunbar
[11.4]. A technical assessment of the Fluid Facilities that
could be used by European scientists for future missions has
been published by Monti [ll.5, 11.6]. A concise description of
all instruments flown on Spacelab-3 has been given by Hill
[11.7] .
 267

11.2 Particular characteristics of fluid instrumentation

Fluid containment and manipulation is a novel and sometimes

problematical feature of fluid physics investigations con-
ducted under zero gravity. Most instruments are equipped with
devices for delivering fluids to an experiment chamber, where
they can be observed and submitted to various stimuli. Reser-
voirs and syringes are used to build up columns and to form
drops or bubbles. In some cases, undesirable mixing of liquid
and gaseous phase occurs, causing the liquid under study to be
contaminated by trapped gas bubbles (liquid gas separators
have been described in Reference (11.8]). When a fluid of high
purity is needed, or when cross-contamination has to be avoi-
ded, the fluids are often contained in closed experiment cells
equipped with their own transparent windows for visual obser-
vation.

The safe containment of toxic or flammable fluids is an addi-

tional constraint in a manned environment.

Silicone oils, which are for all practical purposes physiolo-

gically inert and which exhibit a wide range of viscosities
5
(0.5 to 10. cS), are commonly used as test fluids in space
experiments. Water, with additives to change its physical
properties, and in particular its surface tension, was used on
board Skylab to produce the first fluid columns in space
[ll.l].

Direct insertion of probes and sensors into fluids is the

easiest way to measure their properties. When the volumes in-
volved are small, the size of the sensor must be such as not
to alter the measurement itself or the dynamic properties of
268

the fluid being studied.

Optical techniques, which are non invasive and do not disturb

motions in the fluid, therefore play a dominant role in the
measurement of fluid parameters (Raat [11.9]). In certain
cases (flow visualisation), a combination of direct intrusion
(tracers) and remote sensing (light cut) is necessary. Optical
techniques are however limited essentially to transparent
fluids. The main fluid parameters to be studied and the asso-
ciated measuring techniques are as follows:

Density

An optical interferometer (Mach-Zehnder type for instance) is

commonly used to measure changes in refractive index. The
optical path of the light is split into two coherent beams
(the object and reference beams) which on recombination pro-
duce an interference fringe pattern that is directly related
to the variation in fluid density.

Holographic techniques can also be used, in which a reference

beam interferes with light scattered from the object. The
interference pattern, recorded directly on photographic film,
is called a 'hologram'. While conventional photography records
only amplitude and wavelength information, holography also
registers the phase content of the light. The interference
pattern recorded therefore includes retrievable three-dimen-
sional information about the object's physical attributes.

Two separate exposures of the test object at different times

allow interferometric measurements. In the case of fluids, the
first exposure records the undisturbed state, the second expo-
sure the disturbed state. These two exposures can either be
recorded on the same hologram (double-exposure holographic
interferometry) or on separate holograms (dual hologram inter-
ferometry). The latter technique has several advantages in
 269

terms of insensitivity to mechanical vibrations, and the

possibility to use Schlieren and shadowgraph techniques after
the test. Holographic interferometers are single-path devices
in that the object and reference waves travel through the same
object space. The two waves are temporally rather than spa-
tially separated, in contrast to classical interferometric
techniques. Test chamber windows of lesser optical quality may
therefore be used due to the cancellation of path-length
errors.

Shape

The shape or contour of a fluid volume is usually studied by

illuminating the fluid with a beam of white light, either
directly or as a bright background against which the fluid can
be visualised.
Holographic interferometry permits a quantitative evalua~ion

of the three-dimensional displacement or deformation of a

fluid's surface. The interference pattern of a doubly exposed
hologram contains the necessary information on the vector
displacement of surface points.

Flow

To visualise flow inside a liquid, a sheet-shaped beam of

light is used to illuminate a slice of the liquid to which
tracer particles, photochemical dyes, electrochemical dyes or
bubbles have been added.

Another method (Schlieren method) involves separating out

light rays which have not been deflected by density variations
by placing a sharp edge at the focal point of a lens system.
The Schlieren method records the first spatial derivative of
the density.

Fluid velocities can also be determined by laser doppler velo-

270

cimetry (anemometry), measuring the Doppler shift in the laser

radiation scattered from particles (naturally occurring or
artificially added tracers) in the flow.

Temperature

Thermocouples and thermistors are used for in-situ measure-

ments. An advanced technique involves thermal mapping with an
infrared camera, which acts as a scanning radiometer at in-
frared wavelengths, giving access to ranges of temperatures
between zero and a few hundred degrees centigrade with accu-
racies of better than one degree. This method is, however,
limited to surface measurements.

Although the absence of gravity is the factor that most af-

fects fluid behaviour in space, artificial stimuli are needed
to investigate particular properties:

Mechanical stimuli:

Liquid columns or liquid drops are submitted to a number of

mechanical perturbations to study their stability:

- rotation of the liquid bulk or counter rotation of the

two ends of a liquid column,
!
vibration of the liquid vo~ume
f
in order to study the
different modes of oscillation and their natural
damping,
- application of shear stresses by moving one end of a
liquid column away from the axis of symmetry.
Thermal stimuli:

Heaters are used to change the bulk temperature of a fluid in

order to induce phase changes, for example, or to mix two
components. Heat gradients are established to simulate crystal-
growth conditions, with the associated triggering of Marangoni
convection [see Chapter 16], or to control the progression of
a solidification front.

The heaters themselves are commonly made of resistive wires or

resistive layers spread on foils or insulating surfaces.
Cooling is usually achieved by conduction or radiation. When
active thermal control is required, Peltier elements that can
work either as refrigerators transporting heat from inside to
outside or as heat pumps transporting heat in the opposite
direction, are often used.

Acoustic stimuli:

Acoustic pressure is often used for sample positioning, and

this technique is described in detail by Naumann in Chapter
17. Ultrasonic stirring and mixing can be used to prepare
fluid dispersions (emulsion, bubble generation, particle
disaggregation and homogenisation).

Electrical stimuli:

There are three typical applications of electrical fields in

fluid-physics experiments:

Electrolysis: particles dispersed in a matrix liquid

of high electrical conductivity require large current
2
densities (0.1 A/cm ) at low voltages (10 V DC) for
deposition at the electrodes.
Electrophoresis: charged or polarised drops or
272

particles immersed in a liquid of moderate electrical

conductivity move through an electric field. The
different species can be separated extremely effi-
ciently, leading to the identification of new compo-
nents in mixtures.
contact less electrostatic manipulation: this appli-
cation is covered in Chapter 17.

Pressure stimuli:

A fluid pressure system is used to provide different operating

static pressures, depending on the vapour pressure of the
experiment fluid. Steep fluid pressure increases or reductions
can be required for the reduction or nucleation of gas bubbles
in a liquid, while variations in gas pressure may be necessary
in liquid/gas investigations.

A unifying feature of the various types· of instrumentation

described above is that all benefit from the attendance of
specialised scientists in space. There is, usually some means
of observing the ongoing phenomena, displaying physical para-
meters and adjusting the boundary or initial conditions. The
'Payload Specialist' or 'Science Astronaut', can often see the
fluid under investigation and images can be transmitted to
ground in parallel. A dialogue cab hence be established bet-
ween the astronaut and the scientist on the ground, who can
follow the progress of his experiment on a television screen
and participate in its direction. This kind of direct inter-
action is only possible with manned orbital laboratory like
Skylab and Spacelab. Spacelab is a shirtsleeve environment
installed in the cargo bay of the Shuttle.
 273

Most modern instruments have dedicated keyboards for repro-

gramming the progress of an experiment in real time, affor-
ding a certain amount of manual control to the Payload Specia-
list.

11.3 The Spacelab facilities

The Fluid Physics Module (FPM) is a multi-purpose facility

designed to permit the investigation of fluid shapes and fluid
motions in a microgravity environment.

~
v~ ID~
03
2
I
, ,/
,I
I

Fig. 11.1: Stability diagram for a liquid zone when

gravity effects are negligible. With the units selected
for the two axes the range in which a cylindrical column
is stable is delineated by a straight line; the column
breaks when its length is n times its diameter (courtesy
of I. Martinez [11.10].
274

The fundamental fluid physics problems that can be inves-

tigated with the FPM are:

- natural and enhanced liquid-bridge stability

- onset of surface-tens ion-induced convection
- interfacial forces
- drop coalescence.

By establishing a floating liquid zone between two parallel

coaxial discs, the behaviour of the liquid can be observed
when particular disturbances are applied. These disturbances
can be mechanical (rotation, vibration or lateral asymmetry),
thermal (heating), or electrical (voltage applied across the
zone). The zone in which a cylindrical column is stable is
indicated in Figure 11.1. The vertical axis represents the
volume contained between the two plates and the horizontal
axis is a parameter related to their separation distance.

By using suitable adaptors and containers, a variety of expe-

riments to investigate fluid motions induced by differences in
surface tension, bubble motion and fluid dynamic studies can
be carried out.

Description of the instrument:

The fluid-physics hardware consists of the FPM which is

mounted in a Space lab experiment rack, and a number of expe-
riment containers, fluid syringes and reservoirs.

The FPM is a precision apparatus fbr establishing a floating

liquid zone between two parallel co-axial discs. It is built
around an experiment chamber, which is fitted with two discs,
or end plates, which can be made to rotate at different speeds
in either direction. One disc, referred to as the front disc,
allows the injection of the operating liquid. The liquid can
be injected by combined automatic movements of the front disc
 275

and a reservoir or with an manually-operated independent

syringe which allows better control over the formation of the
zone.

Detailed descriptions of the FPM instrumentation have been

given elsewhere by Ceronetti [11.11] and Gonfalone [11.12,
11.13].

EXPERIMENT
/CHAMBER

,/
LAMP MIRRORS

RESERVOIR FRONT DISC REAR DISC CAMERA

TRANSLATION TRANSLATION/ ROTAT ION / CINE/

ROTATION VIBRATION / BRIEF

SHIFT

Fig. 11.2: Concept of the Fluid Physics Module.

Investigations can also be performed using closed containers,

which can be attached to one of the chamber's discs.

The experiment chamber" is complemented by four auxiliary

SUbsystems:
276

- A mechanical subsystem forming the supporting structure of

the FPM and made of magnesium alloy, which is ribbed for extra
strength and stability. The module is connected to telescopic
slides which enables it to be extracted from the rack.
- A monitoring subsystem for observing the fluid's external
shapes and motions, motions in a plane containing the axis of
rotation, and motions in a plane perpendicular to the axis of
rotation. Two 16 mm cine cameras can be used to record pheno-
mena of interest. In addition, a dedicated CCD video camera
can transmit images in real time to the investigator on
ground.
- An electronic control subsystem for controlling the FPM's
functions: namely disc rotation, rear disc vibration, displa-
cement of the rear disc and reservoir, heating, cine camera
operation and flash illumination.
- A cooling subsystem to reduce the temperature in the test
chamber sufficiently for manual intervention after investi-
gations requiring heating.

The dynamics of liquid drops has long been a subject of inte-

rest both for fundamental science as well as for various
applications in the meteorological and chemical sciences.
Although the shapes of drops submitted to particular excita-
tions have been widely described theoretically, very little
has yet been done in terms of experimental verification.

Trinh [11.14] and Wang [11.15] have developed a system to trap

a liquid drop at a stable position in an acoustic standing
wave in a resonant cavity. The static equilibrium shape of the
drop can be controlled by varying the magnitude of the acous-
tic radiation force. Depending upon the standing acoustic
wave, or the pressure intensity, a drop may be given the shape
 277

of a spheroid flattened at the poles, a spheroid lengthened in

the direction of the polar diameter, or a nearly perfect
sphere.

The main scientific objectives of the experiment first, con-

ducted on the Spacelab-3 flight, were to study the equilibrium
figures of a rotation drop (Fig. 11.3) and the large amplitude
oscillations of liquid drops in general.

The two experiments -rotation and oscillation- have been

chosen as the simplest tests representative of the entire
class of drop-dynamics experiments.

TOROIDAL

~
SHAPES
,\

\
LOBE STRUCTURES @] )

"
~ % :cp~
"

SYMETRICAL SHAPES

"--V-- ~ INCREASING ROTATION

Fig. 11.3: Shapes of rotating drops.

Description of the instrument:

The module consists of an acoustic chamber (nearly cube-

shaped, 20 cm each side) with three sources that generate
sound waves of variable frequencies and amplitudes in three
278

orthogonal directions. Three of the cube's walls are trans-

parent to permit illumination, image recording and viewing.
The sound waves are used to position, rotate and oscillate
water and silicone oil drops within the field of view.

In the microgravity environment of space, it is possible to

position and manipulate a free drop by applying small forces
that do not interfere with the process being studied. A sy-
ringe automatically injects liquid between two probes that
retract to leave a 'floating' drop of pre-determined size
inside the chamber. Sound waves of varying frequencies rotate
or oscillate the drop in view 01 the camera. The instrument is
designed to facilitate replacement of its major items of
auxiliary equipment, in order to ease repair and refurbishment
as well as the introduction of new equipment for special
investigations.

"FAR" WALL OPTIONS

• RETROREFLECTION WITH
COAXIAL ILLUMINATION
(1)FRESNEL LENS &MIRROR
(2)RETROREFLECT]VE SHEETING
• EDGE LIT DIFFUSING PLATE

FRESNEL CONDUCTIVE COAT INGS

LENS

MIRROR

Fig. 11.4: Schematic of the lighting system of the

Drop Dynamics Module (courtesy of T.G. Wang).
 279

The Fluid Experiment System is a facility specially designed

for conducting research into fluid phenomena, solidification,
chemical and biological processes.

On Spacelab-3, it was used by Lal [11.16] to develop a tech-

nique for solution crystal growth in a low-gravity environment
(see Aggarwal [11.17]). Variations in liquid density, solution
concentration and temperature around the growing crystal can
all be studied using a variety of techniques such as Schlie-
ren, shadowgraph and interferometric measurements.

Description of the instrument:

The instrument consists of a support module and an experiment

module. The support module services the functions common to
all FES experiments. It houses: the optical subassembly to
provide holographic recording (Fig. 11.5) and real time Schlie-
ren views of the experiment zone, the command and data system,
the thermal control for the experiment cell and the optics,
and the common diagnostics elements, such as accelerometers
and temperature probes. The role of holography as a major data
gathering system is described by Owen [11.18].
Each experiment is conducted in a dedicated cell, occupying a
maximum volume of about 1 liter and providing the heat-
exchange interface, stirring, thermal insulation, and thermal
gradients needed. Mechanisms for experiment initiation, such
as bubble-injection systems, crystal supports and mixing
devices, are all attached to the cell.
280

\
\
\
\
\ \ \

\\', ~ \
~ \ \ \
~ \ \ \

,-I-----/~
a: EXPERIMENT CELL
b: HOLOGRAPHIC FILM
c: LASER BEAM

Fig. 11.5: Path of the holographic laser beam within the

FES (courtesy of R.B. Lal).

On the Spacelab-3 flight, the system was adapted to the growth

of a triglycine sulfate crystal. A new technique for extrac-
ting the heat from a seed crystal through a semi-insulating
sting was established. The cell contained a seed crystal and a
solution of triglycine sulfate, which was heated at the start
of the experiment. The seed was then uncovered and the solu-
tion allowed to cool at a controlle4t rate in order to grow the
crystal. The desired temperature ne~r the growing crystal can
be maintained by changing the current direction in the thermo-
electric element attached to the 'sting' which then works as a
'cooler' or 'heater'.
 281

~HERMOMETER- - r-~
HEATER____

20 r pm

ST\~
IUL
\
•
~~
{J

"" -CRYS~AL

STIRRER -
SOLUTION

Fig. 11.6: Schematic of the groundbased apparatus for

triglycine sulfate crystal growth (Courtesy of R.B.
Lal).

The Holop uses an advanced optical technique to investigate

transparent media. Based on a holographic interferometer, it
permits three-dimensional reconstructipn of refractive-index
variations in a liquid volume and monitoring of the phenomena
associated with these changes.
282

On its first flight, Holop will be used to investigate four

different fluid problems (DFVLR Report [11.19]):
- Chemical waves in a liquid will be observed via the motion
of gaseous bubbles.
- Phenomena near the gas/liquid critical point will be stu-
died. The influence of disturbing phenomena like residual
gravity, fluctuations of forces, and thermostatic irregula-
rities will be assessed.
- Bubble motion induced by a temperature gradient will be
studied.
- The volume effects, i.e. shrinking or expansion, that usual-
ly accompany the solidification process will be investigated.

Description of the instrument:

The Holop is essentially a diagnostic unit on which different

test cells can be mounted to study changes in the characteris-
tics of a medium, in particular its density, composition,
refractive index, particle distribution, and velocity.

The Holop is accommodated in a Spacelab single rack. A mechani-

cal structure supports the optical elements, as shown in
Figure 11.7. A coherent light beam, generated by a He-Ne laser
(5 mW power), is spread to a diameter of about 60 mm. A beam
splitter provides the object beam, which passes through the
experiment cell, and the reference beam, which interferes with
it to provide the holographic image on film. A Hasselblad
camera has been specially modified for the purpose; the
objective has been removed, the ~perture has been opened up
for the reference beam, and all shatterable parts have been
removed for safety reasons. A simple plug-in interface allows
different cells to be mounted during the flight.
 283

ELECTRONIC BOX
HE.NE LASER

SHUTTER W1TH LENS

MIRROR 3

BEAM SPLITTER

CELL-BOX

CAMERA UNIT

Fig. 11.7: Holop configuration.

To set up an experiment, the Payload Specialist activates the

laser, installs the experiment cell, and loads the camera with
a film magazine. Thereafter, the experiment proceeds automati-
cally.

Scientific applications:

Under microgravity conditions, the primary mechanism governing

the motion of gas bubbles or liquid drops in a host liquid is
Marangoni convection. In such a two-component system, local
variations in interfacial tension at the drop or bubble inter-
284

face lead to convection in both media, as a result of which

the bubble or drop begins to move towards the warmer region
(Fig . 11.8).

:
F HOT
COLD

j:

Fig. 11.8: Flow patterns in a drop immersed in a host

liquid subject to a temperature gradient.

The Bubble, Drop and Particle Unit is designed to study such

drops, bubbles and particles in fluid matrices.
The prime objectives, summarised by Kingdon [11.20] and Napo-
litano [11.21], relate to:

bubble, drop and particle dynamics in liquid ma-

trices with non uniform temperature and concentra-
tion fields
- formation and dynamics off solidification fronts
- interactions between i~trusions and a solidifi -
cation front .

At a later stage the instrument will be adapted to the study

of the fluid dynamics of:
- intrusions
 285

- levitated sample
- solution growth
- electrophoresis
- life science experiments.

Description of the instrument:

The BDPU, which is currently in a pre-development phase,

consists of several modular elements that can be assembled as
illustrated in Figure 11.9 (Schawer [11.22). The service
module houses the data-acquisition subsystem and the power
conditioning and distribution subsystem. Depending on the
investigation in hand, it can be attached to one of several
optical modules, each of which consists of:

- a structural SUbsystem
- an optical diagnostic subsystem
- a three axis accelerometer package
with
holography,
interferometry,
light-section and
direct-illumination diagnostics.

A particular feature of the BDPU is the way in which the

experiment test cells can be plugged into the diagnostic
modules. Each experiment test cell consists of a basic struc-
ture, optical windows, heater and a volume/pressure compen-
sating device. A precision mechanism ~ositions the cell in the
optical path of the laser beam.

Each cell can be equipped with different stimUlating subsys-

tems to trigger the required perturbation(s). They can in-
clude:

- systems for fluid injection

286

- devices for drop and bubble generation (mechanical,

thermal, electrolytic or ultrasonic)
- systems for stirring and mixing
- systems for changing the operating pressure
- electrical voltage generators
- heaters and coolers.

Sensor data is transmitted via an interface to the service

module for data formatting and transmission to Spacelab's
Command and Data Management Subsystem (CDMS).

ELECTRONIC+
POWER CONDITIONING
MODULE

OPTICAL MODULES

Fig. 11.9: Modular concept of the Bubble, Drop and

Particle Unit (BDPU).

The BDPU will be ready for flight after 1988, and is seen as ~

potential payload element for future International Microgra-

vity Laboratory (IML) missions.
 287

Meteorologists and astrophysicists are interested in the

large-scale circulation of fluids under the influence of
rotation, gravity and heating.

The primary purpose of the Geophysical Fluid Flow Cell experi-

ments is to simulate the large-scale flows that occur natu-
rally in the atmospheres of rotating planets and in the inte-
riors of stars. In this investigation, Hart [11.23] and Toomre
[11.24] study three-dimensional fluid flows around a rotating
spherical body, with gravity forces scaled down to match
geophysical conditions.

Theoretical models of planetary circulations indicate 'that

planetary curvature plays an important role in the dynalltics of
rotating atmospheres because the two major constraints on the
flow rotation due to Coriolis forces and buoyancy due to
gravity vary with latitude.
This experiment contains the correct vector relationship
between the rotational vector and the gravitational body force
vector to simulate planetary characteristics, i.e. the resul-
tant body force is a maximum at the poles and a minimum at the
equator.

The density variation with altitude is simulated and the

different modes of instability or waves are studied as a
function of fluid viscosity, rotation ,
s~eed and gravity value.

The results of the simulation may reveal why Jupiter and

Saturn have axisymmetric cloud patterns, while the Sun seems
to have a preferred pattern of large eddies from pole to pole.

Description of the ins·trument:

288

The experiment hardware is designed to be installed near the

Shuttle's centre of mass, where gravity effects can be mini-
mised.

FILM ANNOTATION

VISIBLE STROBE

RONCHI RULING

SHUTTER ASSEMBLY

UV OPTICS

SPHERICAL CAPACITOR -----+---.::::p'\\--P~--~ UV STROBE

HIGH VOLTAGE TRANSFORMER

TURNTABLE

ROTATING HEAT EXCHANGER

Fig. 11.10: Main elements of the Geophysical Fluid

Flow Cell (GFFC) (courtesy of J.E. Hart).

The instrument consists of a stainless-steel hemisphere 2.4 cm

in diameter, surrounded by a sapphire hemisphere. The space
between the two hemispheres contains silicone oil. Sapphire is
transparent and is a good conductor of heat. It is therefore
possible to establish well-defined temperature gradients bet-
ween the two hemispheres and to take photographs of the inter-
vening fluid. The fluid has a dielectric constant which is
temperature dependent. Application of an electrical voltage
between the spheres produces an electric field and a radially
directed force similar to the gravity forces that act on
 289

oceans and atmospheres. A photochromic chemical dissolved in

the oil forms blue dye lines when bombarded by ultraviolet
light. By tracking the movement of the lines, it is possible
to track the fluid's motion and measure its velocity.

Figure 11.10 shows the main elements of the instrument and the
expected performance data is shown in Figure 11.11.

250 e ,;;; To';;; 500e

0 0 e .;:: i t. T : ,;;; 20 D e RADIAL
0 0 e ,;;; 10 T I';;; 20 0 e EQUATOR TO POLE
0';;; V ,;;; 10 KV (RMS)
HIGH VOLTAGE LEAD
0.01';;; n,;;; 3 RAD SEe- 1

Fig. 11.11: Technical performance specification for

the GFFC.

Different combinations of temperature, rotation speed and

voltages can be used to establish various levels of spherical
convection within the cell. The resulting flow rates and
thermal gradients are monitored by means of a camera posi-
tioned above the cell, viewing a quadrant of approximately
o
90 . Each film frame also records experiment status data and
the temperatures at various locations ~n the cell.

11.4 Concluding remarks

T.G. Wang has described the evolution of an instrument in the

following way:
290

"A question is posed, an experiment is conceived, an apparatus

is designed and built, and finally data are taken, results
assessed and conclusions drawn. However at every stage of this
process, concept, experimental techniques and apparatus are
modified to improve the value of the result. In many cases
intermediate results may suggest entirely new approaches, or
even modifications of the original purpose of the investiga-
tion".

Today's space instrumentation is in a rapid state of evolution

(Vreeburg [11.25]). The rudimentary set ups of the early days
for "look-and-see" type investigations have evolved into
sophisticated instruments similar to those used in ground-
based laboratories. Although mass, volume, power and crew time
are still expensive resources in space, it is no longer unu-
sual to employ equipment in space weighting more than one
hundred kilos, occupying in the order of a cubic metre, and
consuming hundreds of watts of power.

The possibility of repair offered by Spacelab also guarantees

some scientific return after every flight. Human intervention
will continue to be a major facet of instrumentation for new
investigations in which initiative and imagination are requi-
red when unexpected situations occur. Robotics will be used to
help the astronaut cope with hazardous conditions and to
provide remote control, and, automation will be used when a
long-duration space exposure, or series production of items is
required, for example on the Space Station.

References

11.1 Proceedings of the 5th European Symposium on Material

.Sciences and Microgravity: Results of Spacelab-l, Schloss-
Elmau, ESA SP-222, 1984.
 291

11.2 Naumann, R.J.; Herring, H.W.: Materials Processing in

Space: Early Experiments, NASA SP-443, 1980.

11.3 Seibert, G.: Processing and Manufacturing in Space,

ESRO SP-IOI (1974) 87-95.

11.4 Dunbar, B.J.: Material Processing in Space, Advances in

Ceramics, vol. 5, 1983.

11.5 Monti, R.: Review of the USA Fluid Science Facilities-

Objectives and Capabilities, ESA Contract 5853/84/F/FL, 1985.

ll.S Monti, R.: Fluid Science Facilities under Development

in Germany for Microgravity Experiments, ESA Contract
5853/84/F/FL, 1985.

11.7 Kelly Hill, C.: Spacelab Mission 3 Experiment Descrip-

tion, NASA TM-82502, 1982.

11. 8 Saunders, C.G.: A Hydrophobic-hydrophilic Zero Gravity

Liquid Gas Phase Separator, Space Engineering Meeting, Los-
Angeles, Calif., Society of Automotive Engineers, New-York,
1969.

11.9 Raat, J.: A Review of Techniques for the Measurement of

Fluid Properties in Material Science Experiments in Space, ESA
internal report, 1980.

11.10 Martinez, I.: Fluid Physics Utilisation Brochure,

ESA/Lamf. 1979.

]1.11 Ceronetti, G., Rovera, G.: The Fluid Physics Module: A

Contribution to Material Science and Physics in Space, ESA
SP-142 (1979) 137-147.
292

11.12 Gonfalone, A., Martinides, H.: The Fluid Physics

Module: New Possibilities and Applications. ESA SP-19l (1983)
95-97.

11.13 Gonfalone, A.: 1984, The Fluid Physics Module. A

Technical Description. ESA SP-222 (1984) 3-7.

11.14 Trinh, E., Wang, T.G.: Large Amplitude Free and Driven
Drop-shape Oscillations: Experimental Observations, J. Fluid
Mech. 122 (1982) 364-369.

11.15 Wang, T.G.: Progress in Container less Science and

Technologies. Manufacturing in Space. American Society of
Mechanical Engineers, New-York,(1984) 2152-2155.

11.16 Lal, R.B., Aggarwal, M.D., Kroes, R.L., Wilcox, W.R.:

A New Technique of Solution Crystal Growth. Phys. Stat. So~.

(a) (1983) 547-552.

11.17 Aggarwal, M.D., Lal, R.B.: Simple, Low-cost Reciproca-

ting Crystalliser for Solution Crystal Growth. Rev. Sci.
Instrum. 54(6) (1983) 772-773.

11.18 Owen, R.B., Kroers, R.L.: Holography on the Spacelab-3

Mission. Optics News (1985) 12-16.

11.19 DFVLR, Projekt HOLOP, Institut fur Raumsimulation,

Koln-Porz, W. Germany, 1984.

11.20 Kingdon, J., Gonfalone, A.: The Bubble, Drop and

Particle Unit: A Second Generation Fluid Physics Facility.
Adv. Space Research Vol. 4, No. 5 (1984) 91-94.

11.21 Monti, R., Napolitano, L.G.: The BDPU - A Microgravity

Fluid Sciences Facility. Proc. of 34th Congress of the Inter-
national Astronautical Federation, IAF, New-York, 1983.
 293

11.22 Schawer, J.: Study on a Drop and Bubble Unit. Final

Report, Executive Summary, ESA Contract no. 5503/83/F/FC,
1983.

11.23 Hart, J.E., Toomre, J., Gilman, P.: Theoretical and

Experimental Studies in Support of the Geophysical Fluid Flow
Experiment. NASA/MSFC FY-84 Atmospheric Processes Res. Rev.
(1984) 13-15.

11.~4 Hart, J.E.: Alternative Experiments Using the Geophy-

sical Fluid Flow Cell. Final Report, Colorado Univ. Boulder
Dept of Astrogeophysics, 1984.

11.25 Vreeburg, J.P.B.: Study on Equipment Requirements in

Support of Microgravity Fluid Physics Experiments. Final
Report, NLR TR 81115 U, ESA Contract no. 4668/81/NL/HP, 1985.
12 Containerless Processing Technology
R. J. NAUMANN
Space Science Laboratory
NASA Marshall Space Flight Center
Huntsville, Alabama 35812 U.S.A.
D. D. ELLEMAN
NASA Jet Propulsion Laboratory
4800 Oak Grove Drive
Pasadena, California 91109 U.S.A.

Summary
The vi rtua1 absence of hydrostatic pressure in a microgravity envi ronment
allows liquids to be confined solely by thei r surface tension and offers
the possibility of melting and solidifying materials without physical con-
tact. This "container1ess processing" eliminates contaminants that may be
introduced by the container or crucible and may be used to obtain ultrapure
materials. This is especially important for systems that are highly cor-
rosive in the melt. Elimination of container-induced nucleation also per-
mits melts to be deeply undercoo1ed before solidification. This offers the
possibility of studying homogeneous nucleation and solidification in under-
cooled melts. Such solidification can be extremely rapid and may produce
unique microstructures including metastable or amorphous phases in metals.
The range of gl ass formation may be extended in border1 i ne gl ass forming
systems, which may result in new glasses with unusual properties. Since
such glasses are formed from melts confined only by surface tension, they
will have perfectly spherical pristine surfaces, undamaged by grinding or
other shaping processes. It may also be possible to manipulate the melt to
form aspherica1 shapes, or to draw optical fibers from a container1ess
melt.
The dynamics of drops and bubbles may also be studied using container1ess
techni ques. Detail ed photographs of drop1 ets mergi ng were obtai ned ina
simple demonstration on Sky1ab. The drop dynamics module on Space1ab 3 is
dedi cated to a more e1 aborate set of experi ments to study the vi brat iona1
and rotational behavior of liquid droplets. The centering forces on a
bubble suspended in a droplet have also been investigated in a variety of
low-gravity experiments to the point where the role of droplet osci11~tions
are understood well enough to permi t the routine formation of thi n-wall ed
spherical shells up to a few millimeters in diameter that have a high de-
gree of concentri city. Such shell s have been used for fuel contai nment in
inertially confined fusion experiments [1] and are also finding a variety
of other uses. Fi na lly, the abil ity to suspend a hi gh temperature mel t
wi thout phys i ca 1 contact is usefu 1 for measu rement of hi gh temperatu re
thermophysica1 properties. Techniques ha~e been developed for independent
measurement of emissivity as a function .iOf temperature which permits the
determination of heat capacity, enthalpy, heat of fusion, etc. for metals
such as W, Mo, Nb, and other refractory materials. [2] Surface tension and
viscosity may also be determined without physical contact in low to mode-
rate viscosity samples by inducing oscillations in the melt and observing
their period and decay, or in high viscosity material by rotating of the
sample and measuring the distortion that results. [3]
There are a variety of techniques for container1ess processing that can be
used to some degree in Earth's gravity. These techniques consist of sus-
 295

pendi ng or levitating a specimen usi ng non-contact i ng forces such as gas

pressure from an acoustic field or air stream, or electric forces from an
electrostatic or electromagnetic field. Such techniques are limited to
sma 11 sampl es in Earth's gravity because the hydrostatic pressure must be
confined by surface tension, and distortions from sphericity are unavoid-
able. Also, the heating and cooling of the sample is generally not inde-
pendent of the levitation process. Free-fall facilities such as Marshall
Space Fli-ght Center's (MSFC) drop tube and Jet Propulsion Laboratory's
(JPL) aerodynamic drop facility avoid this difficulty, but the limited
free-fall distance restricts the sample to a size that can be solidified in
the ti me avai 1ab 1e. Neverthe 1ess, these techni ques have produced much
valuable information on containerless processing technology and serve as an
indispensible adjunct to microgravity experiments for testing new concepts,
screening prospective sample materials, and developing experimental proto-
col.
The use of the microgravity environment of an orbiting vehicle extends the
free-fall time more or less indefinitely and allows much larger samples to
be processed as well as close observation and manipulation of the sample
during processing. However, the small residual accelerations in an orbit-
ing vehicle require the use of some form of non-contacting positioning
force, similar to that used to levitate samples in Earth's gravity, to hold
the sample in the confines of its processing chamber for extended periods
of time.
The techniques and facilities for containerless processing, both in space
and on Earth, will be described in the remainder of this chapter.

12.1 Drop Facilities

12.1.1 The MSFC Drop Tube
The MSFC drop tube is a 25-cm-diameter stainless steel tube, approximately
100 m long, mounted vertically in the Dynamic Test Stand (see Fig. 12.1).
The tube may be evacuated to 10- 6 torr by six turbomolecular pumps
located at various stations. If additional cooling or a reducing atmos-
phere is desi red, the tube may be back-fill ed with mixtures of H2/He. A
bell jar at the top of the tube houses the device for sample melting. This
may consist of an electron beam heater, a resistance-heated "eye-dropper"
furnace, or an electromagnetic levitator.

In the electron beam heater, the sample is suspended from a wire or sting
of like composition and heated by bombardment from electrons generated from
a circular tungsten wire held at -8 kV relati~e to the sample. A toroidal
focussing grid is used to direct all emitted electrons to the sample (see
Fig. 12.2). As the sample melts, a pendent drop is formed which falls when
its weight exceeds the surface tension forces. The drop can also be de-
tached by mechanically pulling the sting sharply upward.

The 'resistance furnace provides an alternative method for sample melting

that can be used in an ambient or low pressure environment. The sample may
296

be deployed using the pendant drop on a sting technique, as in the electron

beam heater, or by squi rt i ng the melt through a small orifi ce ina quartz
(or other materi a1) tube
by applying a small burst
of He pressure. An e1ec-
t romagnet i c 1evi tator can
a1so be used for con-
tainerless melting of sam-
pl es. The sample is sus-
pended and heated by a
specially designed coil
which usually has to be
tailored to the size and
type of materi a1 of i nte-
rest. This can also be
used in an ambient or low
pressure environment (pro-
vided arcing can be avoid-
ed) and is well suited for
superheating and homoge- DETACIIMLE CATCHU
nizing samples that have
1i qu i d-phase regi ons of
immiscibility. Fig. 12.1. Schematic of the MSFC drop tube

SAMPLE
GROUND
WIRE

to'OI1
STANDARD
RESISTOR

GEARBOX

Fig. 12.2. Electron beam heater schematic for melting drop tube samples
 297

The amount of undercoo1ing obtained in a free-falling droplet is determined

by observing the reca1escence flash as the sample gives up its latent heat
during solidification. This is accomplished with three Si infrared detec-
tors looking down the tube. A typical signal is shown in Fig. 12.3. The
temperature just before reca1escence is determined from the calculated heat
loss from the time the sample was dropped until the observed time of re-
ca1escence. Undercoo1ings in excess of 500 K have been obtained with Nb
and Nb alloys. [4] Radiation becomes less efficient for ridding lower
temperature alloys of their latent heat and a low pressure gas is needed to
cause the sample to solidify in the 4.2-sec fall time. Cooling curves for
various pressures are shown in Fig. 12.4.

TYPICAL Si DETECTOR SIGNAL FOR DROP TUBE

,.
,.
,·,r--"'"

!24.0~~
jd3.o

~~!t:-----
~ ,~----------------------------------~---­
« .,

: c

Fig. 12.3. Detector signal showing the reca1escence flash from samples
solidifying in the drop tube. The top trace is a control sample that was
not melted. The two mi dd1 e traces show reca 1escence events at poi nt 3.
The bottom trace shows the current delivered to the sample from which the
time of drop detachment is derived.

Several interesting results have been obtained using the drop tube.
Droplets solidified from an undercoo1ed melt do not contain an internal
shrink cavity which is typical of a normally solidified droplet. When an
undercoo1ed droplet nucleates, dendrites grow rapidly through the melt and
shrinkage is accommodated by the interdendritic melt withdrawing from the
surface. Thi s 1eaves a roughened surface shown in Fi g. 12.5. In other
 I\)
S£M nUXIXI Of "" SINGLE CRYSTAlIDT0351
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2600
" \
\
\
2500 \
\
\
2400
~
_\
2300 "

2200

2100

2000

1900
~
1800

1700 L'__________~________~______~--J-----------L---------~

TIME !SECONDS)

Ie EDGE

Fig. 12.4. Calculated cooling curves for a 5-mm- Fig. 12.5. Scanning electron micrographs of
diameter Nb drop falling through He gas at various the surface of an undercooled Nb droplet that
pressures. The dotted lines indicate a velocity re- formed a single crystal. Note the dendritic
gime in which cooling is dominated by conduction. nature of the surface.
The hash mark indicates the transition to convective
cooling.
 299

studi es, amorphous PbSi Cu sampl es have al so been formed. [5J The meta-
stable A-15 phase of Nb3Ge has been formed but is apparently partially
destroyed by recalescence heating unless the sample is rapidly quenched.
[6J Collings found that oil quenching droplets of austenitic stainless
steels after undercooling in the drop tube will produce considerably more
of the metastable delta-ferrite phase than splat quenching. [7J A peculiar
mi crostructure was obtai ned in Ni A13 despite the fail ure to undercool the
material because of oxide formation. [8J The resulting droplets had highly
con vol uted su rfaces, and bul k densities are much 1ess than the parent
material. This effect is not yet understood.

12.1.2 The JPL Drag-Free Drop Facility

A uni que drop facil ity has been constructed at JPL for research on spheri-
cal shell formation. The facility has a cross sectional area that varies
as the inverse square root of the distance the sample has fallen as may be
seen in Fig. 12.6. Air is withdrawn with a blower at such a rate to con-
tinuously match the free-fall velocity of the sample.

Much has been learned about the

formation of spherical shells in FORCE-FREE DROP TOWER
ENTRANCE CROSSECTION
this facility. The molten mate- 0.6 x 0.6 m
rial which forms the wall of the
shell is extruded through an
annulus. Shells are formed by
Rayleigh instabilities in the
',:.,
cylindrical stream which may be
augmented by forced oscillations
13.1 m
of the nozzel driven by a piezo- FALL TIME • l6 sec

electric crystal. The fundamen-

tal mechanisms by which the bub-
b1e becomes centered have been
established theoretically, test-
ed experimentally in a Plateau
)~
tank, and are being applied in TERMINAL CROiSSECTION (I
0.23X0.23m~ -1 f_
this facility to produce spheri-
cal shells with uniformity of 1%
i!\ \ .
FAN
in both shell diameter and wall
thickness. [9J
Fig. 12.6. JPL aerodynamic drop facility
300

Such shells are finding a variety of interesting applications [10] other

than targets for inertial confinement fusion experiments, which motivated
much of the original research effort. The shells may be sintered or bonded
together by various epoxies to form very stiff, extremely lightweight
metallic or glass foam-like materials for use as structural members. Such
foams have excellent energy adsorbing qualities and are' promising as light
weight armor. The shells may be filled with a phase change material to
form a very effective insulating material. Such spheres can also be pumped
or circulated with a fluid to provide a stable thermal environment or to
transport large amounts of thermal energy.

The height of the drop facility is 3.6 meters. This provides 0.87 sec of
free fall, which is sufficient to solidify thin-walled glass or metal
spheres up to a few millimeters in diameter. In theory, larger drop facil-
ities of similar design could be constructed if larger spherical shells are
required, but since the length of such a facility depends on the square of
the time required, it may be more practical to produce larger shells in
space.

12.2 Acoustical Levitators

The use of acoustical forces to levitate or position samples for container-
less processing has received considerable attention. There are various
concepts for accomplishing this, but in each case the object is to provide
standing waves in some form of working fluid, usually a gas, such that one
or more pressure nodes exi st. These pressure nodes may be thought of as
energy wells. An object placed at such a node will experience a restoring
force if displaced by a small amount; hence, the object,will tend to remain
in the vicinity of the node. Acoustic positioning seems particularly well
suited to the processing of glasses since it is generally desirable to melt
glasses in an gaseous environment to maintain stoichiometry.

Maintaining stable levitation during heating and cooling of such samples,

however, has proved to be problemmatic. Several approaches to this problem
are described below.

12.2.1 Single-Axis Tuned Cavity Acoustic Levitator Furnace

It is possible to excite a cylindrical cavity with a single acoustic source
in such a manner as to produce one or more nodes or energy well s along the
axis. A hot-wall acoustic levitator furnace using this concept was devel-
 301

oped by Lierke (Battelle, Frankfort). The problem of maintaining resonance

conditions over the wide temperature range as the sample is melted and
sol ifified was approached by adjusting the gas composition so that the
average mol ecul ar wei ght increased with temperature in order to keep the
speed of sound constant. [11]

The device was flown on TEXUS-I. The sample apparently melted, but drifted
into the restraining cage during the flight before it solidified. No
further attempts have been made to test this concept.

12.2.2 Three-Axis Levitator

A three-axis acoustic levitator has been developed by Wang (JPL). Standing
waves of the fundamental frequency are produced ina rectangul ar cavi ty
usi ng th ree orthogonal dri vers to produce an energy well at the center of
the cavity. [12] The technique has several advantages: (1) equal pres-
sures are applied along each axis permitting liquid samples to maintain a
spheri ca 1 shape, (2) the sampl e may be rotated by varyi ng the phase angl e
between two of the dri vers, and (3) vari ous oscill atory modes may be ex-
cited in the sample by periodically varying the amplitude of one or more of
the drivers. Low-density solid, objects' can be levitated in unit gravity.
The devi ce has been flown several ti mes on SPAR rocket fl i ghts and the
ability to levitate and manipulate liquid spheres up to 2.5-cm-diameter has
been successfully demonstrated at ambi ent temperatures. Thi s techni que
forms the basis for the Drop Dynamic Module flown on Spacelab 3 to study
various phenomena in drops and bubbles.

A furnace version of this device, the Acoustic Containerless Experiment

System (ACES), has also been developed. The frequency is varied to main-
tai n resonance condit ions as the temperatu re changes. To protect the
dri vers from the hi gh temperatu res of the chamber, they are mounted away
from the chamber and coupled to the chamber through acoustic waveguides
into ports in the chamber walls as may be seen in Fig. 12.7. A low tem-
perature versi on of thi s devi ce whi ch operated at 650 °C was flown on
STS-ll, and a fl uori de gl ass sample was success full y melted but it con-
tacted the chamber wall before it sol i difi ed. A refl i ght opportunity has
not yet presented itself.

One limitation of this particular approach is the cooling rate. At present

the sample can only be cooled at the rate of a few degrees per minute
302

because nearly isothermal conditions must be maintained in the cavity which

means that the entire system must be cooled. Since glass formation, par-
ticularly in systems that are reluctant glass formers, requires rapid
quenching, methods must be found for increasing the quench rate. It may be
possible to maintain the walls at near ambient temperature and heat the
sample with radiant energy, but the thermal gradients in the levitating
medium may destroy the resonant conditions. Another possible solution
under consideration would be to translate the sample acoustically into a
cold chamber where it would be captured by another acoustic field. These
are technology issues that have not yet been tested.

A.C.E.S. FURNACE CANNISTER

--
LATI)C"UCTOfil
."""....NT
t""'''In."

Fig. 12.7. Acoustic Containerless Experiment System (ACES)

developed by JPL

12.2.3 Single-Axis Interference Levitator

A different approach to acoustic levitation has been taken by Whymark
(Intersonics Corporation). [13J This approach uses a fixed-frequency St.
Clair generator [14J to introduce high-frequency sound through a port in a
furnace with anechoci c wall s. Resonances are; avoi ded by appropri ate choi ce
of chamber dimensions. A reflector is introduced along or near the sound
axis and standing waves are generated by interference between the incident
and reflected wave. The first levitation node forms at A/4 from the re-
flector and other nodes are located at A/2 spacing along the acoustic axis.
The primary advantage of this approach is that the system is self-adjusting
 303

and does not require resonance to be maintained. As the temperature

changes, the sample simply moves with the nodal position along the acoustic
axis as the wavelength changes. Quenching is achieved by inserting a cage
of cold brass rods into the chamber and allowing the sample to radiate into
this heat sink.

The very strong axial sound pressures allow this system to levitate samples
in unit gravity. Sample size is limited to approximately A/2 diameter.
The levitation force is proportional to the sample volume; hence, the
samp1 e densi ty is the parameter that characteri zes the devi ce IS abil ity to
levitate. With the driver and reflector slightly dished to focus the sound
and by tuning the system by adjusting the reflector position relative to
the driver to maximize the standing wave intensity, samples of platinum (p=
21.4 gm/cm 3) have been levitated at ambient temperature. [15] Liquids,
however, prove more difficult. Only very small droplets of H20 (",1 mm
dia.) can be confined by their surface tension in the acoustic field.
Large drop1 ets are qui ck1y broken up. More vi scous 1i qui ds such as gly-
cerin can be levitated as may be seen in Fig. 12.8.

Fig. 12.8. Levitation of a glycerin drop in normal gravity. Note the se-
vere di stort i on produced by the combi nat i on of the acoustic pressure and
yravity.

As temperatu re increases, the 1evitat i on forces di mi ni sh approxi mate1y as

the inverse 5/2 power of temperature. [16] Thus, the ability of this tech-
304

nique to levitate at high temperatures in unit gravity is therefore quite

limited. Glass samples have been melted and levitated with difficulty at
600 ae, but this appears to be near the practical limit of this levitation
technique at ambient pressure.

The single-axis interference levitator has been flown on two SPAR rocket
flights and on STS-7. On the first SPAR attempt the sample drifted out of
the acoustic well just as it was beginning to melt. It appeared that the
acoustic field was much weaker than normal due to a small crack in the
driver. [17] On the second SPAR flight the sample was lost shortly after
melting. Again the sound field was observed to weaken dramatically but the
dri ver amplitude was normal. Subsequent invest i gat ion revealed that H20
adsorbs on the materi a 1 used for the sample insertion devi ce (whi ch al so
serves as the reflector) and that its insertion into the high temperature
cavity for the first time caused a considerable amount of H20 vapor to be
released. Since H20 is a good sound absorber, it was believed that this
weakened the sound field. [18J An automatic sample exchange mechanism was
added for the STS-7 fl i ght and the furnace components were baked-out and
stored under dry conditions to prevent the introduction of water vapor
duri ng sampl e i nserti on. Unfortunately, the brass cage jammed duri ng in-
sert i on and the camera ma lfuncti oned; hence, no meani ngful data coul d be
obtained from the experiment.

A major weakness in this approach is the large asymmetry in the axial vs.
radi a 1 restori ng force. The axi a 1 force is provi ded by the 1arge pressures
associated with the standing waves. The radial restoring force is essen-
tially the Bernoulli effect of the gas streaming past the sample. Recall
that a pressure node is also a velocity antinode. This force has been
measured in the laboratory and found to be roughly an order of magnitude
lower than the axial force. [l6J This weak radial force was responsible
for the sample loss on the two SPAR flights.

This strong axial pressure may be used to advantage in low gravity, how-
ever, by allowing fibers to be pulled frdm a suspended melt [19J as shown
in Fig. 12.9. Another advantage of the interference type levitator is that
additional reflectors may be introduced into the chamber and each reflector
will provide a levitation node. This allows molten drops to be moved
about, merged, or added to the primary melt as shown in Fig. 12.10.
 305

-t---

Fig. 12.9. Use of an interference levitator for containerless fiber pulling

Fig. 12.10. Two spheres suspended in acoustic levitator. The interference

between the reflected wave and the incident wave creates a stable pressure
node at V4 below the refl ector. as shown by the small sphere suspended by
the acoustic pressure. The ball s wi 11 remain suspended below the reflector
regardless of where they are moved within the acoustic field produced by the
driver at the bottom of the photograph. Two molten droplets in space may be
merged without physi ca 1 contact by si mply mavi ng thei r refl ectors together
as shown in the sequence. This would allow a melt to be replenished.
306

12.3 Aerodynamic Levitators

The use of Bernoull i forces to suspend a ball or other soli d objects ina
stream of air is a phenomenon known to virtually every child. This tech-
nique also has some utility as a technique for containerless processing on
Earth. [20-22] As with most levitation methods, difficulties begin when
the sample melts. By careful nozzel design and much patience, it has been
possible to levitate small spheres, melt them at high temperatures using a
C02 laser, and allow them to solidify without physical contact as may be
seen in the photographic sequence in Fig. 12.11.

However, this technique has not been particularly successful for extending
the glass-forming range of various reluctant glass formers. Apparently the
gas flow around the sample induces nucleation at very small undercoolings.
A similar problem may arise in attempting to use acoustic levitation for
producing difficult-to-form glasses. More definitive work is needed in
this important area of dynamic nucleation.

AIM .1.1 HVIUIIOH YIIH co, LASfR IIAflNG

Fig. 12.11. Containerless processing of oxides using an air-jet levitator

and external heating with a C02 laser
 307

12.4 Electromagnetic Levitators

Conductive samples may be levitated or positioned by Lorentz (JxB) forces.
The sample is placed in a suitably desi gned coil which is excited by radio
frequency (RF) current. Currents induced in the sample interact with the
magnetic field in the coil to produce forces which tend to move the sample
away from regions of high magnetic flux density. These currents also tend
to heat the sample, and in many cases this heating may also be used to melt
the sample. [23J

Si nce the induced forces can be qui te strong, it is easy to levitate si z-

able samples in Earth's gravity if sufficient power is available. The
amount of power required depends on the effective coupling between the coil
and sample which can be optimized by proper coil design. Molten samples
will of course be deformed by combination of surface tension, gravity, and
JxB forces. The limiting factor in the ability to levitate a melt is the
fact that the induced force must always be perpendicular to the B field.
Hence, the melt along the B direction is supported only by surface tension.
One of the main factors that limits the usefulness of electromagnetic levi-
tation for containerless processing of materials in Earth's gravity is the
inability to control the heating and cooling of the sample independently of
the levitation. Some control can be exercised by the coil design. The
sample heating is proportional to B2, whereas the levitation force is
proportional to VB. A typical coil design is shown in Fig. 12.12. The
coni ca 1 shape of the bottom wi ndi ng is chosen to increase the gradi ent of
the fi e 1d, hence its abil i ty to 1evitate. The reverse loop at the top
"caps" the magnetic bottle and prevents the sample from jumping out of the
coil as the current is increased. Controlling the current in the coil also
offers some control of the heating, but not always in the direction one
would intuitively expect. Depending on the sample and coil design, re-
ducing the current may actually increase the heating by allowing the sample
to fall deeper into the coil where the B field is larger. Introduction of
a quench gas is perhaps the best method for solidifying an electromag-
netically levitated melt.

Another limitation in the use of electromagnetic containerless processing

on Earth is the rather violent stirring that is produced in the sample by
the induced currents. Thi s st i rri ng may be benefi ci ali n homogeni zi ng
mel ts, but it may al so produce unwanted segregati on of second-phase com-
ponents and may possibly induce nucleation. [24J For example, Oran found
308

that the amount of undercooling that could be achieved was inversely depen-
dent on the current used to levitate the sample. [25J

Fig. 12.12. Typical coil for electromagnetically suspending and heatin9 a

sample in normal gravity. The coil is wound from Cu tubing through which
cooling water is circulated. Fiber glass sleeve insulation is placed over
the tube to prevent shorting.

Many of these limitations can be overcome by processing in a microgravity

envi ronment. Si nce the forces requi red to posit i on the sampl e are much
weaker than those required for levitation, the induced currents can be much
smaller; thus, independent control of heating and cooling can be ap-
proached. The amount of stirring in the sample can also be significantly
reduced; however, the amount of undercooling that can be achieved may still
be limited by the residual stirring. This may be particularly troublesome
if inductive heating has been used to melt the sample. Since most metallic
melts have low viscosities, the fluid motion may persist for some time
after the heating power is shut down and ': may induce premature rlUcleation.
,
Alternative heating methods or magnetic damping schemes should be con-
sidered for experiments whose objective is to achieve deep undercooling.

An electromagnetic levitator facil ity for use in microgravity has been

developed by General Electric. This device was used to melt and solidify a
 309

sampl e of Be with a di spersed phase of beryll i a on the SPAR II I rocket

flight. [26J A second flight on SPAR-IV failed to melt a sample of
Fe40Ni40P14B6 (METGLAS 2826) in the available time because the coupling
between the coil and sample was less efficient than predicted. The device
has recently been modified to fly on the Materials Science Lab carrier in
the space shuttl e payload bay. The modifi cat i on i ncl udes an automat i c
sample exchange mechanism and improved diagnostic measurements.

A more powerful electromagnetic levitator with auxillary electron beam

heating has also been developed by General Electric for use on Earth to
measure thermophysical properties of molten refractory materials. [27-28J
Improved values for heat capacity as a function of temperature have
recently been reported for liquid W, Ag, and Ga. [2J

12.5 Electrostatic Levitation

Electrostatic forces may also be used to levitate a charged sample. It is
well known that it is not possible to configure a static electric field so
that a charged particle would remain in static equilibrium. However, it is
possible to contain such a particle in a combined static and oscillating
electric field if the proper relations between the fields and the charge-
to-mass ratio of the particle are maintained. This is the principle behind
the quadrupole mass spectrometer. Small low-density particles have been
levitated between four rods in a quadrupole configuration. [29J The par-
ticles are charged inductively or sprayed with charge from a high-voltage
needle. Linear motion along the rails is controlled by electrostatic
grids. This technique lends itself nicely to multi-step container1ess pro-
cessi ng because the sample may be readily transported between process i ng
stations.

A sample may also be levitated and positioned in a single processing

chamber by placing it between four electrodes arranged in a tetragonal
manner as illustrated in Fig. 12.13. [30J The fields provided by the four
electrodes must be actively controlled by a c1psed loop system that senses
the posit i on of the sample and app 1i es the aippropri ate potential to the
electrodes to maintain the desired position.

The electrostatic levitation techniques have also found considerable appli-

cation on Earth for applying very uniform coatings and other processing of
sma 11 objects.
310

Fig. 12.13. Electrostatic levitation using a tetrahedral array of

electrodes with active control

12.6 Prospectus for Containerless Processing

Despite the considerable effort that has gone into developing microgravity
containerless processing technology, there are still many difficult and
perhaps unforeseen problems ahead. There simply have not been enough
fl i ght opportunities to develop these concepts into a matu re technology.
The limitations of containerless processing on Earth are well understood,
and it is unlikely that any new development will provide a significant
advancement in ground-based technology.

It is somewhat disturbing that some of the limitations that have been dis-
covered in Earth-based techniques may al so be limiting factors (although
perhaps less so) in microgravity processes. Of particular concern is the
increasing body of evidence that suggests that stirring, vibrating, gas
quenching, and practically any other disturbance to an undercooled melt
induces nucleation. We may very well find that homogeneous nucleation
cannot be achieved or even approached by either acoustic or electromagnetic
levitation even in a microgravity environment. If this is the case, one of
the major objectives for containerless prpcessing would not be achievable.
Perhaps it is time to consider alternate approaches to the problem of con-
tainerless positioning.

Robinson (MSFC) has suggested the possibility of simply allowing the sample
to free float in its processing chamber. [31] A key element to this tech-
 311

nique is the ability to deploy the sample without inducing any motion rel-
ative to the chamber. If this can be accomplished, free float times of 100
sec could be achieved in a 10-cm chamber in a 10- 6 g acceleration
field. This would be equivalent to a 50-km drop tube and should be suffi-
cient to solidify most samples of interest. Melting could be accomplished
by radiant heating or electron beam bombardment. The sample could be
positioned by two stings of sample material which are simultaneously with-
drawn after the sample melts. If necessary, any residual velocity could be
nulled by use of acoustical, aerodynamic, or electrodynamic force with
active position .control before the sample has cooled significantly.
References
1. Lee, M.C. et. al.: Application of microgravity and containerless
envrionments to the investigation of fusion target fabrication tech-
no logy. Materi a1s Process i ng in the Reduced Gravity Envi ronment of
Space 9 (1982) 95 (G. E. Ri ndone, ed.), Amsterdam: El sevi er Sci ence
Publishing Co.
2. Margrave, J.L.: Heat capacities of liquid metals above ·1500 K.
Materi a1s Process i ng in the Reduced Gravi ty Envi ronment of Space 9
(1982) 39 (G.E. RindQne, ed.), Amsterdam: Elsevier Science Publishing
Co.
3. Trinh, E.; Wang, T.G.: Large-amplitude free and driven drop-shape
oscillations: Experimental observations. J. Fluid Mech. 122 (1982)
315.
4. Lacy, L.L.; Robinson, M.B.; Rathz, T.J.: Containerless undercooling
and solidification in drop tubes. J. Crystal Growth 51 (1981) 47-60.
5. Steinberg, J.; Lord, A.E.; Lacy, L.L.; Johnson, J.: Production of bulk
amorphous Pbn.5Si 16.5Cu6 in a containerless low-gravity environ-
ment. Appl. Phys. Letters 38 (1981) 135-137.
6. Lacy, L.L.; Rathz, T.J.; Robinson, M.B.: Containerless undercooling
and solidification of bulk metastable Nb3Ge alloys. J. Appl. Phys.
53 (1982) 682-689.
7. Collings, E.W.: Magnetic studies of rapidly quenched stainless steel
alloys. Cryogenic Materials and Their Welding, Proceedings of the
International Cryogenic Materials Conference, Kiev, USSR, July 1984.
8. Ethridge, LC.; Curreri., P.A.; Kelley, M.: Results of the technical
exchange agreement between NASA and DuPont on the containerless drop
tube solidification of NiA13' NASA TM-86473, October 1984.
9. Lee, M.C.; Feng, I.; Elleman, D.O.; Wang, T.G.; Young, A.T.: Genera-
tion of a strong core-centering force: Submillimeter compound droplet
system. Proceedings of Second International Colloquium on Drops and
Bubbles, JPL Publication 82-7 (November 1981) 107.
10. Kendall, J.M.; Lee, M.C.: Wang, T.G.: Metal shell technology based on
hollow jet instability. J. Vac. Sci. Tech. 20 (1982) 1091.
312

l1. Lierke, I.G.: Hardware development and performance of an acoustical

positioning device. ESA Special Publication No. 114 (1976).

12. Wang, T.G.; Saffren, M.M.; Elleman, D.O.: Acoustic chamber for
wei ghtless positioning. AIAA Paper 74-155, 12th Aerospace Sciences
Meeting, January 1974.

13. Whymark, R.R.: Acoustic field positioning for containerless pro-

cessing. Ultrasonics 13 (1975) 251-261.

14. St. Clair, H.W.: An electromagnetic sound generator for producing·

intense high frequency sound. Rev. Sci. Instrum. 12 (1941) 50.

15. Oran, W.A.; Berge, L.H.; Reiss, D.A.; Johnson, J.L.: Method and
apparatus for shaping and enhancing acoustical levitation forces.
U.S. Patent 4,218,921, August 26, 1980.

16. Oran, W.A.; Berge, L.H.; Parker, H.W.: Parametric study of an acous-
tic levitation system. Rev. Sci. Instrum. 51 (1980) 626.

17. Naumann, R.J.; Oran, W.A.; Whymark, R.R.; Rey, C.: Postflight analy-
sis of the single-axis acoustic system on SPAR VI and recommendations
for future flights. NASA TM-82396, January 1981.

18. Rush, J.E.; Schafer, C.F.; Holland, R.L.: Analysis of SPAR VIII
single-axis levitation experiment. NASA TM-82447, September 1981.

19. Naumann, R.J.; Ethridge, E.C.: Containerless high purity pulliing

process apparatus for glass optical fibers. U.S. Patent Application
Sere No. 601130, 1982.

20. Oran, W.A.; Berge, L.H.: Containerless melting and solidification of

materials with an aerodynamic levitation system. Rev. Sci. Instrum.
53 (1982) 851.

21. Nordine, P.C.; Atkins, R.M.: Aerodynamic levitation of laser-heated

solids in gas jets. Rev. Sci. Instrum. 53 (1982) 1456.

22. Rush, J.E.; Stephens, W.K.; Ethridge, E.C.: Properties of a

constricted-tube air-flow levitator. Materials Processing in the
Reduced Gravity Environment of Space 9 (1982) 131 (G.E. Rindone, ed.),
Amsterdam: Elsevier Science Publishing Co.

23. Frost, R.T.; Chang, C.W.: Theory and applications of electromagnetic

1evitaat ion. Materi al s Processi ng in the Reduced Gravity Envi ronment
of Space 9 (1982) 71 (G.E. Rindone, ed.), Amsterdam: Elsevier Science
Publishing Co.

24. Johnson, W.C.; Kolter, G.R.; Tiller,W.A.: The influence of stirring

on the nucleation of tin and tin-pb alloys. Trans. AIME 227 (1963)
890.

25. Oran, W.A.: Containerless processing technology. Proceedings of

SAMPE, Cincinnati, Ohio (October 1983) 146.

26. Wouch, G.; Frost, R.T.; Pinto, N.P.; Keith, G.H.; Lord, A.E., Jr.:
Uniform dispersion of BeO particles in Be casting produced in rocket
free fall. Nature 274 (1978) 235.
 313

27. Wouch, G.; Okress, E.C.; Frost, R.T.; Rutecki, D.J.: Electromagnetic
levitation facility incorporating electron beams. Rev. Sci. Instrum.
46 (1975) 1122.

28. Wouch, G.; Gray, E.L.; Frost, R.T.; Lord, A.E., Jr.: Estimation of
thermodynamic properties from solidification and cooling curves of
containerless melts in the terrestrial environment and in space. High
Temp. Science 10 (1978) 241.

29. Hendricks, C.D.: Levitation, coating, and transport of particulate

materials. Materials Processing in the Reduced Gravity Environment of
Space 9 (1982) 59 (G.E. Rindone, ed.), Amsterdam: Elsevier Science
Publishing Co.

30. Rhim, W.-K.; Collender, M.; Hyson, M.T.; Sims, W.T.; Elleman, D.O.:
Development of electrostatic positioner for space materials proces-
sing. Rev. Sci. Instrum. 56(2) (1985) 307.

31. Robinson, M.; Lacy, L.L.: Approaches and furnace for containerless
processing of high temperature materials in space. Invention Dis-
closure, MSFC/NASF MFS 28087 (1985).
Part IV:
Case Studies and Results
13 Metals and Composites

J.J. FAVIER
Commissariat a L'Energie Atomique, Centre d'Etudes Nucleaires, Grenoble,
France

Metallurgy was from the very beginning one of the most promising domains of
potential applications for space experimentation. In fact one of the first
problems considered in the context of the microgravity environment was its
capabil ity to modify the procedure for brazi ng or we 1di ng in space when re-
pairing spacecraft or assembling metallic structures in orbit. Later on,the
opportunity was envi saged to use the specifi c mi crogravity conditi ons a-
board satellites in orbit for improving metallurgical processes. This was
the situation when the first experiment opportunities emerged aboard SKYLAB
in the early seventies. A few years later, in 1975, the call for proposals
for the first Spacelab Mission found the European Scientific Community in
the same feeling. Some scientists, however, considered this as an opportu-
nity to test more fundamental material science concepts and to improve our
basic knowledge in metallurgy. This position was reinforced with the low
cost - low technological investment-rocket flight opportunities offered by
the SPAR programme in the United States as well as the TEXUS programmes in
Germany and later with the European Space Agency.

A considerable number of space experiments was flown during the past fif-
teen years, some from the eastern countries with the Salyut stations. The
metallurgy experiments can be divided out into three classes
- metallurgical technologies
- test of theory
- production of new or better materials

In the following a selection of significant experiments performed sofar

will be described and analysed following this scheme. In addition, special
attention will be paid to new experiments having well defined objectives
and considered as "second generation" experiments.
318

13.1 Metallurgical Technologies

Welding and brazing have already been mentioned as first importance metal-
1urgical processes for the development of future space programmes. These
techniques are, however, dependent on several basic mechanisms strongly in-
fluenced by the presence or absence of gravity such as:
stability of the molten puddle between the two solid parts to be joined
homogeneity and regularity of the microstructures formed by solidifica-
tion
- presence of voids.

Moreover, several engineering questions were open. Are the usual brazing
materials still useful in space, specially when working under space vacuum?
Or what is the optimum si ze for the molten puddl e or the gap between the
solid parts?
E.C. McKannan and R.M. Poorman [13.1] developed a first experiment aboard
SKYLAB with particular emphasis on the behaviour of molten metal, including
its stabil ity, and on the microstructures, grain size, and pattern forma-
tion of the resolidified melt. Shaped specimens of varying thickness were
partially melted using an electron beam gun as heat source. Chromium al-
loyed stainless steel, nickel aluminium alloy, and pure tantalum were tes-
ted as materials. The feasibility of electron beam welding was demonstrated
duri ng the experiment since surface tens i on was found suffi ci ent to hol d
the weld liquid zone in place. However, as far as microstructures of the
remelted pool is concerned, unpredicted results were observed: The space
structures are generally fi ner and more i sotropi c than the correspondi ng
earth ones. It was expected that, due to the absence of gravity, transport
through dendrite remelting woul d be less effective in space, reducing nu-
cleation of new grains. No expanation has yet been proposed for this fin-
ding.

More complex and more sensitive to the gravity level is the brazing pro-
cess. It consists of joining two metallic. pieces, called the base metals,
by filling the gap in between with a braze alloy of different nature which
is melted and resolidified. The interest in the method arises from in the
low heating level of the samples. The bond is established by diffusion at
the interface between liquid braze and base metal, giving rise to interme-
tallic compounds. Different mechanisms are involved in the process such as
capillarity for filling the gap, influenced by surface tension, and wetta-
 319

bility of the base metal, but also by the hydrostatic pressure in the braze
liquid. The cooling of the braze should be controlled in order to obtain
the desired microstructure and to avoid porosities due to the shrinkage
during the phase transformation. Gravity affects the process mostly through
the hydrostatic pressure in the filling liquid and through convection
during dendritic solidification of the braze. The first brazing attempt was
performed on SKY LAB by J.R. Williams [13.2]. Two nickel samples and two
different stainless steel samples were prepared for brazing with an
A90.7CuO.28 LiD. 02 alloy. Each sample consisted of a tube surrounded by a
sl eeve and fill ed with the braze. Gap wi dths up to 0.5 mm were carefull y
maintained by spacers.

The SKYLAB experiment verified the feasibility of the brazing operation in

space. Due to the low residual hydrostatic pressure existing in the liquid
braze, 10 times 1arger gaps than on earth were successfully brazed. Thi s
result leads to the conclusion that gap tolerances for brazing in space can
be considerably relaxed, simplifying machining and mounting of the metal
parts. Microstructure and void formation were not completly understood.

These latter points have been studied in more detail by K. Frieler, R.

Stickler et al. [13.3J during TEXUS missions and the SPACELAB I fl ight.
Rocket fl ightsare a convenient tool for gaining understanding of a short
duration process compatible with the 5 minutes microgravity phase. Special
emphasis was given to the gap-filling mechanism, flow patterns, and the
mixing of the braze and microstructures as a function of gap width in vacu-
um brazing experiments of nickel cylinders of various sizes inserted into
each other. The braze alloy was a commercially available A90.72CUO.28LiQOI4
alloy. Ag 110 or Au were added as a radioactive tracer allowing a conve-
nient evaluation of the homogeneity by autoradiography. Samples were heated
in evacuated cartri dges pl aced in isothermal furnaces so that the thermal
history was exactly the same at Ig and under ~g. Particular care was given
to cleaning and setting up of samples in order to remove superficial conta-
minations and oxide films. Contrary to the Skylab experiments, the gap was
fed from braze contained in a ring-shaped groove.

Considerable mixing of the molten braze was found in the space experiments,
as revealed by autoradiography (Fig. 13.1a), whereas ground reference expe-
riments exhibited "roll-type" convective patterns (Fig. 13.1b). Simulations
performed indicate that Marangoni flows were sufficiently efficient in
320

Fig. 13.1: Autoradiographies of braze:

a} ~g sample

b) Ig sample
showing more vivid mixing for the micro-
gravity case 13.3

space to mix the braze. Filling of large gaps was not conclusive because of
thermal limitations due to the fact that heat exchange in space takes place
only by radiation, whereas on earth the hydrostatic pressure imposes good
mechanical and thermal contact between the liquid braze and the base me-
tals. This can be avoided in further experiments by overheating the braze
before filling.

The microstructure analysis is very complex in the Ni-Ag-Cu system since Ag

and Ni are mutually immiscible in the temperature range considered (1033 -
1133 K) and the Cu-Ni system consists of a continuous series of solid solu-
tions. The microstructure of the joints is determined by the extent to
which the phase reactions may proceed.

The compari son between earth and space processed structures cl eary demon-
strated the absence of dendritic sedimentation (density difference between
melt and CuNi dendrites is typically Ig/qm 3 ), a more homogeneous structure
being therefore obtained in space . However , in the microgravity experiments
an increase in porosity was observed. This is due to the fact that bubbles
created by outgassing or shrinkage are not removed by buoyancy forces.

In conclusion, it has been demonstrated that the usual beam welding and
brazing techniques remain useful in the space environment. Larger 1iquid
 321

puddles in welding as well as larger gaps in brazing can be achieved in

space without any damage to the process. The formati on of the soli difi ed
structures is well understood and can be optimized, for instance by choo-
sing brazes avoiding outgassing. Full scale operations must now be att~mp­
ted.

13.2 Test of Theories

Metallurgy, although it is one of the oldest and most widely used processes
for producing materials is not very well understood, specially when sophis-
ti cated mi cro- and macrostructures must be achi eved. There is therefore a
need for testi ng and improvi ng sol i difi cati on theori es. The mi crogravity
environment constitutes one of the most original tool s in this respect,
particularly for processes involving second order phenomena such as eutec-
tic growth, segregation and morphological stability phenomena, or casting.

13.2.1 Eutectic Growth

The eutectic alloys are choice cases for investigating the solidification
theory si nce thei r growth temperature remai ns constant during the whole
process. Moreover, due to their particular two-phase structure affected by
the growth fluctuations, the local growth conditions can be deduced from an
analysis of the structures obtained.

The eutectic systems can be divided into three classes according to the
type of microstructures they produce: lamellar (Fig. 13.2a), fiber1ike
(Fig. 13.2b) or irregular. The potential of application is great as regula-
rity, fineness and anisotropy of a two phase structure ( A 'V 1-10 llm) are
decisive parameters for mechanical, electrical, optical, and other proper-
ties. The general aim of the eutectic studies undertaken under microgravity
concerns the comparison between structures obtained under Ig and microgra-
vity conditions in terms of phase distribution; regularity and crystallo-
graphy with systems of the three classes. In addition, the val idity of the
usual eutectic growth theories is tested and some differences in the micro-
structures can be analysed, taking into account the potential role of gra-
vity in the growth process.
322

Fig. 13.2: Sketch of regular

eutectic structures:
a) Lamellar eutectic

SOLID

b) Fiber1ike eutectic

The spacing is in the range of

1-10Ilm.

Lamellar Eutectics

Several experiments were performed from the very beginning with the A12CU-
A1 system. Due to the nearly equal amounts of the two phases appearing du-
ring the directional solidification, alternating plates or lamellae of two
different compositions form, oriented along the direction of sol idifica-
tion. For an alloy of exactly nominal eutectic composition in the phase
diagram, present theories [13.4 ]c1aim that the spacing between lamellae
varies as the inverse square root of the growth rate.

;\2 . R = const. (13.1)

This law is assuming that mass transfer i~ front of the solid structure is
driven only by diffusion, and it is generally observed for most systems on
earth.

A first experiment on the A1-Cu system was attempted by Hasenmeyer [13.5J

during the Sky1ab mission (experiment M566). The samples, sheathed in gra-
 323

phite, were melted back in space ina gradi ent furnace and di recti onally
resolidified. The experiment was not conclusive due to the bad wetting of
liquid melt on graphite, introducing free volumes in the sample. Moreover,
no systematic evaluation of the structure perfection has been undertaken.
More recent experiments were performed during TEXUS flights. Carlberg [13.6J
used mirror and gradient furnaces available in the TEXUS payload to solidi-
fy A1-Cu, Zn-Sn and A1-Si eutectic alloys. The crucible material was boron
nitride, allowing better control of the sample shape. The solidification
rate as well as the thermal gradient in the sample were evaluated by plot-
ting the isotherms along the sample and differentiating the curves obtai-
ned. The rate evolution during the growth has been characterized to be dif-
ferent during space and earth solidification, complicating therefore the
comparison. The microstructures, lamellar spacing and fault density, were
measured using phase distribution examination of metallographic pictures.
No structural differences between earth samples and space samples could be
detected, the magnitude of the statistical errors being of the order of the
deviations observed.

Favi er et a1. D.3.7 J performed simil ar experiments duri ng the TEXUS IV and
TEXUS VI flights. The TEM03 gradient furnace is better adapted to directio-
nal solidification. Again, boron nitrate crucibles were used. Special care
was devoted to the control of free vol umes appeari ng when the samp1 e
shrinks during solidification, employing a spring and piston system. The
microstructures are presently being studied using a specific diffraction
method D.3.8 J. A laser beam illuminates the surface of the samples at dif-
ferent area scales (100~m2 to several ~). The optical Fourier transform
is analysed giving directly the size of the lamellar spacing as well as the
fault density (Fig. 13.3). The evolution of the growth rate during these

Fig. 13.3: Different parameters to be measu-

red on the Fouri er spectrum gi ven by laser
beam diffraction on the eutectic structure
[13.8J
324

short duration experiments allows a study of its relationship to the lamel-

lar spacing. No significant difference between microgravity and earth
growth can be pointed out, demonstrating that microgravity does not modify
lamellar eutectic growth. This was confirmed during recent Spacelab experi-
ment under carefully controlled thermal conditions in the Gradient Heating
Facility by Fa\fier~et al. [13.9J.

Fiberlike Eutectics

Several organic, metall i c or semi conducti ng fiber systems have been studied
in space in view of potential specific applications. During Skylab and ASTP
missions Vue [13.10, 13.11J experimented with alkali halide eutectics for-
med with NaF or LiF fibers in a NaCl matrix. The purpose was mainly to eva-
luate the infrared transmission capability of these crystals. NaF or LiF
indeed are excellent IR transmitters and their crystals could well serve as
IR waveguides. This property is al so a good tool for judging the rod per-
fection. Fibers have been found aligned and continuous over larger distan-
ces in space than on earth, but the reason for this behaviour is not yet
known.

Larson [13.12J conducted several experiments aboard rockets (SPAR Pro-

grammes) with the Mn-Bi system formed by MnBi fibers in a Bi matrix. This
system was chosen because its microstructure may be sensi ti ve to thermo-
solutal convection and because the MnBi, which is ferromagnetic, is an ef-
ficient tool for characterizing any structure morphology change. In order
to reveal the interface shape and to measure the local growth morphology,
the interface demarcation technique by Peltier pul sing was used, with a
current density of the order of 80 Amps/cm2.

A very fascinating result has been obtained, which has been confirmed du-
ri ng 1ater experiments performed under the same conditions: morphol ogi cal
analyses on samples that were directionally solidified during a 240 sec low
g interval show statistically smaller interrod spacing and rod diameter
(30% lower) with respect to samples grown'under identical conditions in the
same furnace in a 19 environment. The amount of MnBi phase deduced from
magnetic measurements appears to be 7% lower in space (Fig. 13.4a).

The same result was obtained by MUller and Kyr on the InSb-NiSb system
grown under microgravity conditions during TEXUS rocket flights and on the
 325

SPACE EARTH
Mn.Bi

AI-Ni

Fig. 13.4: Transverse section of fiberlike eutectic samples grown in space

and on earth
a) Mn-Bi eutectic [13.12 J
b) Al-A13Ni eutectic [13.9J

Spacelab 1 mission ~3.13, 13.14 l The Peltier demarcation technique gave a

good knowledge of the actual growth velocity, which is not stationary even
during the low rate Spacelab experiment. The relative deviation in the rod
density per unit area again was found 20 to 30% lower in space.

Finally, Favier et al. grew an A13Ni-Al eutectic during TEXUS nights and
the Spacelab 1 mission [13.8, 13.9J. A precise relationship between inter-
rod spacing and growth velocity was difficult to establish in the rocket
experiments because backmelting of samples took place during the liftoff.
However, the experiments i ndi cated that was larger in space than on
earth, which is contrary to the MnBi or InSb-NiSb cases. This result was
confirmed during the Spacelab 1 mission where steady state growth was ob-
served with a 15 to 20% coarser structure than on earth (Fig. 13.4b).
326

Irregular Eutectics

The irregular eutectics have al so been studied under microgravity condi-

tions. Carlberg experimented with the Al-Si system during the TEXUS II mis-
sion [13.6]. Cast iron containing 250 ppm Sulfur [13.15J as well as Ag-Ge
alloys [13~9J wer~ solidified during the First Spacelab mission. This class
of eutectics is very sensitive to the growth mode of the non-metall ic
phase. The aim was therefore oriented to the potential changes in crystal-
lographic twinning and coupling behaviour of Si. C. Ge.respectively. No im-
portant change in the microstructures was observed. The absence of some
non-metall i c primary crystal sin space. appearing onl y near the peri phery
of the 19 samples. was reported. This may correspond to heterogeneous nu-
cleation on the crucible walls. which can be more active when hydrostatic
pressure imposes a direct contact between liquid and crucible.

Discussion of Results

From the numerous space experiments on eutectics. it results that the most
gravity sensitive systems appear to be the fiberlike ones. Some systems ba-
sed on non-metallic phases (MnBi and InSb-NiSb) show an increase of the
i nterrod spaci ng in space. whereas A13Ni -A 1 system decreases its i nterrod
spacing in space. Lamellar eutectics. however. seem to be not affected.
Finally fiberlike eutectics based on salts (LiF or NaF) give rise to more
continuous fibers in space. The effect of absence of gravity on eutectic
growth is not easy to understand. because. as already mentioned [13.16J.
bulk convective flow cannot directly affect the solute redistribution in
front of the growth interface. except under high convective levels (centri-
fuge [13.17. 13.18J)

Some suggestions explaining the variations of the fiberspacing by convec-

tion. and therefore with gravity level. have already been proposed. These
ideas have to be verified with future earth and space experiments.

Off-eutecti c growth may induce vari ati ons of the rodspaci ng as a functi on
of the convective level. The classical Hunt - Jackson constant in the A-R
relationship is a function of the volume fraction. which can vary with ma-
crosegregati.on duri ng growth. It has been demonstrated [13.9 ] that fi ber-
1 ike systems are more sensitive to that parameter than lamellar ones. In-
 327

deed, considering a simple boundary layer assumption, the relative varia-

tion of Ac including convection with respect to AD under pure diffusion can
be expressed by

-:-:-~.c;:.~'-E- -l:1-CE-)- - _l:1_:_E_

. [-:-. - 1

is the boundary layer parameter [13.19J

1 characteri zes the asymmetry of the phase di agram at

the eutectic composition CE
is the off eutectic composition (positive or negative)

Fiberlike systems have, in general, very asymmetric phase diagrams (large A

values), and are therefore more sensitive than lamellar ones. Moreover, hy-
po- or hypereutectic compositions could give rise to positive or negative
deviations in agreement with the observed space results.

Other qualitative explanations have been proposed such as microconvections

induced by shrinkage at the solidification front, which can also be nega-
tive or positive in different systems. All these assumptions must be quan-
tified and tested in future specific experiments.

A qual itative expl anation of the better regul arity of the salt eutectics
can be gi ven consi deri ng the hi gher Prandtl numbers of such systems wi th
respect of metallic alloys. On the ground, the solidification of salt sys-
tems should be more sensitive to thermal fluctuations of convective origin,
therefore inducing more structure defects than in space.

13.2.2 Directional Solidification

Macrosegregation and Morphological Stabil ity

Macrosegregat i on and morpho 1ogi ca 1 stabil ity are known to be strongly de-
pendent on the solutal field at the solid-liquid interface, therefore deep-
ly coupled to the convective flow in the bulk liquid. Preliminary experi-
ments have been performed aboard Salyut on Al-Cu and Sn-Pb alloys [13.20J.
328

Here the weightlessness offers the possibility of distinguishing between

the influence of different sources of convective motions, from thermal, so-
lutal or Marangoni origin. Alloys of low concentration have been used (0.4%
in mass) in such a way that solutal convection is negligible. In order to
quantify the effect of gravity on the morphological behaviour, the effect
of residual convec1;ion has been characterized on 200 ppm doped samples, lo-
cated in parallel within the same cartridges, submitted to the same thermal
conditions. With such small quantities of impurities the solid-liquid in-
terface remains planar and macrosegregation in the crystal s can serve as
tool for approaching residual convective flows.

Fig. 13.5 gives the profiles of longitudinal concentration in copper for

horizontal growth on earth and space growth outside the initial transient,
where nucleation took place. An homogeneous crystal was obtained under mi-
crogravity, indicating that a purely diffusive regime was achieved instead
of the usual crystal segregated due to mixing by convection on the ground.
Radial segregation was also found lower in space than on earth. This result
confirms the val idity of the order-of-magnitude analysis of the coupling
between fluid flow and growth [13.19], plotted on the Grashof and Schmidt
numbers versus Peclet number diagram, where the point representative of the
space experiment is located in the purely diffusive regime domain, while
the ground reference experiment falls in the convecto-diffusive domain
(Fig. 13.6). Therefore the destabilized experiments at higher concentration
(0.4% Cu or Pb) can also be interpreted has being driven by diffusion only.

Fig. 13.5: Macrosegregation

800
profiles in Al-200 ppm Cu di-
ppm t203S rectionally solidified in
eu space and on earth. No .segre-
I gation appears in the space
600 grown sample [13.20J.

400

200

Z em
0
0 5 6 8 10
 329

Fig. 13.6: Gr.Sc - Pe dia-

10
DIAGRAMME PE GRSC granme - exhibiting the con-
vectio-diffusive regime (upper
9 part) and the pure diffusive
regime. The ELMA 01 Al-Cu ex-
8
periment under 10- 4 g is loca-
7 0* ~ ted in the diffusive regime,
far from the transition con-
trary to most of the experi-
0 6 • ments.
,,5
U')

0
m
/
Hy R/.
~4 0
0-0_
3

2
o *
-----... •
'"
0 ... '" '" '"
-2 -1 0 2
10gPe

Fig. 13.7 shows transverse and longitudinal sections of samples in the re-
ference experiments (horizontal and vertical), together with the space sam-
pl e. The results cl earl y show the hi gher degree of destabi 1 i zation when
passing from 19 to Og. Cellular structure was observed in the horizontal
experiment, dendritic structure in the vertical case and more pronounced
dendritic structure in the space sample. The primary dendritic spacing was
found 1.5 times larger in space. An unexpected change in growth direction
«110> instead of typical <100)for fcc metal s on earth) is al so observed.

These preliminary experiments illustrate the capability of microgravity for

studying complex solidification phenomena still not well understood, such
as cooperative growth of arrays of dendrites, which are of prime importance
for controlling metallurgical processes on the ground.

Casting

Of prime importance in the casting process is the understanding of the

transition from columnar to equiaxed structures (Fig. 13.11). Mechanical
properties of alloys strongly depends on grain size, which in turn depends
330

AI .. c. 4 (u
Fig. 13.7: Characteristic
~Jmm transverse and longitudinal
sections of destabil ized
Al-0.4% Cu samples grown in
space and on earth. Notice
...c the unusual 110 growth
2 direction in space [13.20 J.
u
"
of>

j>

'c"
2
U
"
oil

structure
growth
cellular dendritic Tdendr'~
I late like)1
direction < 100 > <100 > < 110>
(a)

on the way the undercooled me l t solidifies during casting. Casting of sam-

ples of moderate size is a rapid process, compatible with microgravity
rocket or airplane flights. M.K. Johnston [ 13.21] and J. Papazian used
these means for investigating the nucleation of small grains in the equi-
axed zone. In a SPAR experiment, Johnston worked with NH40H + H20 as a
transparent model material. In the first experiment, the material was
cooled from two parallel sides, whereas during the second it was directio-
nally solidified. During the' KC135 airplane flights, however, the experi-
ments were cycled from low gravity ( 1072 g) to high gravity, so the net
changes in flow could be visualized, and t he despin and re-entry effects of
the rocket could be simulated. Fluid flow was observed to stop within eight
to ten seconds of low-g time, which is contrary to predictions [13.22J.

The first rocket experiment revealed that only few large grains nucleated
and grew into the center of the sample. No extraneous nucleation or dendri-
 331

te remelting was observed (Fig. 13.8). In the second experiment, however,

crystallites appeared ahead of the growth front. The airplane experiments
allowed to determine their origin as being formed and redistributed into
the melt by a premature cooling of the sample during launch and despin op-
eration of the rocket.

Fig. 13.8: Photographs of low

gravity and one gravity sol i-
dification of NH4Cl-H2 solu-
tion [13.21 J.

Metallic systems (Sn-15% wt Pb and Sn 3% wt Bi) were also tested during

rocket experiments. Large-grained and isotropic structures were obtained in
low gravity, becoming multigrained and anisotropic as the gravity level in-
creased duri ng re-entry. Subsequent experiments performed wi th a centri-
fuge' reaching 5 times the natural gravity level, confirmed this interpre-
tation.

13.3 Elaboration of New or Improved Materials

It is well established from a theoretical point of view that materials may

be devised that possess very particular mechanical ,electrical or physical
properties. This impl ies generally multi component systems, each component
giving the desired contribution to the combined material properties. In
many cases polyphases are required. Particle si;ze and regularity of distri-
bution are dominant parameters. The control of artificial composite forma-
tion is therfore an important domain in Materials Science. Microgravity
conditions are very helpful in achieving this goal, because sedimentation
in polyphase systems can be reduced. However, second order phenomena such
'as capillary action may become dominant, potentially counteracting the
desired goal.
332

The space programmes undertaken in this field follow two separate ways,
some contributing to a better understanding of composite formation, others
trying to improve directly the properties of materials of interest.

13.3.1 Particle Redistribution

H.U. Walter performed two TEXUS experiments [13.23J to determine the stabi-
lity of mu1ticomponent mixtures during melting, thermal soak, and solidifi-
cation under microgravity conditions. Samples containing large A1203
spheres or small Tungsten particles in a silver matrix were prepared from
powders (TEXUS I) or by hot isostatic pressing of carefully degassed powder
mixtures (TEXUS II). Different volume fractions of the two phases ranging
from 20 to 80% were chosen. These experiments also had the aim to contri-
bute to our understanding of immiscible alloy solidification.

Different behaviour has been observed between the first and the second ex-
periment, pointing out the role of voids, liquid vapour interfaces and Ma-
rangoni convection. By changing the nature of the particles (A1203 or W),
the respective role of wetting and disjoining pressure has been tested. The
residual sedimentation effect under 1O- 4 g has been identified by varying
the size of the particles. Complete separation was observed in certain sam-
ples (20 to 25% of A1203 in Ag) as a result of poor wetting between the two
components (wetting angle ~ 150 0 ). W-Ag were only partially segregated, in
spite of the density difference, because of the better wettabi1ity in this
case (wetting angle 'V 8 0 ) (Fig. 13.9).

Fig. 13.9: Geometry of a liquid

bridge connecting two spherical
particles. e is the wetting angle
[13.23J.
 333

The stabil ity of the mixture was demonstrated to be a function of the vo-
lume fraction of the two phases. If the shape of one of the components is
such that particles are in contact, chains of particles are formed and coa-
lescence results during melting, the chains having the tendency to be pin-
ned by the free surface and the crucible. Through optimization of all these
parameters fairly homogeneous distributions are achieved (Fig. 13.10) (100
- 200 ~m, Wparticles in a Ag (CuNi) matrix; 20% volume percentage of W).

Fig. 13.10: Cross section of a Ag

(Cu, N;) matrix reinforced with 5%
vol Wparticles: [ ~ (w) ~ 250-315~m
- 8 ~ 80 J. Space solidified sample
[13.23J .

Another crucial problem in the solidification of composite materials is the

behaviour of bubbles and dispersed particles at the solidification front.
In order to take advantage of the lack of sedimentation to prepare unique
composite materials, the trapping of the particles must be controlled du-
ring sol idification. Uhlmann [13.24 J performed a SPAR experiment with
microscopic size spheres in a liquid to be solidified. Two forces act on
the spheres, the drag force of viscous origin resisting its motion toward
the bul k, and the "disjoining pressure" due to long range molecular inter-
actions between the solidification front and the particle. This experiment
demonstrated the existence of a critical velocity above which a particle of
a given size is incorporated in solid.
334

13.3.2 Systems of Interest

Superconducting Properties

Type II superconductors are materi al s of interest for stori ng el ectri cal

energy. However, such materials must be ductile in order to be wired. Heye
and Klemm [13.25J proposed a SPAR experiment to solidify a mixture of Pb
with 10% Ag in a fine dispersion to get type II superconductor in which the
dispersion will act as flux pinning sites. BaO particles have also been ad-
ded to harden Pb so that Pb and Ag will deform at the same rate. The micro-
dispersion of Ag in Pb obtained with the flight sample was sufficiently
uniform to exhibit type II superconducting properties.

Mechanical Hardening

Most metall i c all oys for engi neeri ng purposes must be both ductil e and
hard. It is well known that such behaviour can be reached by reinforcing a
matrix with a very fine, regularly dispersed phase « 1 ~m in diameter).
With this aim in view, several experiments have been performed in space to
reach more uniform dispersions by avoiding sedimentation of the particles
in the liquid matrix.

Kawada et al. performed an experiment aboard Skylab [13.26J directed toward

preparing a high density, uniform dispersion of silicon carbide whiskers in
a silver matrix from the melt. Two to ten volume percent whiskers, 0.1 ~m
in diameter and 10 ~m in length, were mixed with silver powder grains,
0.5 ~m in diameter, compacted and sintered at gOOoe in a hydrogen atmos-
phere. A spring-loaded plunger was placed in the flight cartridges to avoid
formation of pores.

After soaking in the melt state and resolidification in space, the samples
exhibited a fairly uniform density of whiskers, whereas in the ground sam-
ples they agglomerated at the top due to d~nsity differences. Microhardness
was found hi gher and more uniform in the space samples than in the ground
reference samples. No brittle fracture was observed in microgravity samples
and showed larger ductility.
 335

Several SPAR experiments have been performed to produce dispersion hardened

magnesium by adding thoria particles. Raymond et al. [13.27J compacted 5 ",m
Th02 particles with Mg particles, or alternatively used Th and MgO to form
thoria directly by a chemical reaction during the process. After melting
and resolidification in space, the composite material obtained showed con-
siderably greater uniformity in the structure and greater average hardness.
indicating that buoyancy and sedimentation were minimized during space pro-
cessing. Voids arising from uncontrolled gas trapping were, however, obser-
ved leading to coarse particle dispersions in some parts of samples. In
Europe, Froyen -and al. [13.28J developed TEXUS and SPACELAB experiments
ori ented more to the understandi ng of the compl ex mechani sms i nvol ved in
the fabri cati on of composite materi al s. Speci al emphasis was devoted to
interfacial phenomena such as wetting, compound formation, as well as dif-
fusion between the metall ic matrix and the dispered phase. At the same
time, Barbieri et al. prepared a Spacelab experiment [13.29J focused on the
control of bubbles in such materials. Al, Cu, and Ag were used as matrix,
with SiC or A1203 as reinforcing dispersion.

The results indicate that exudation of large particles (diameter larger

than 100 ",m) occurs already during melting of compacted samples as a conse-
quence of the interfacial reaction between liquid matrix and particles.
This is independent of gravity conditions; exudation of finer particles is,
however, limited. Agglomeration of small particles may occur for different
reasons, as result of collision of particles by Brownian motion or residual
convection flow, leading to the formation of a skeleton of particles held
together by interfacial tension or by diffusion reactions (sintering mecha-
nism). Depending on the wetting angle e (see Fig. 13.9), three different
type of particle arrangements may be formed (Fig. 13.11):

A - normal sedimentation of individually settling particles ( e <90 0 )

B - formation of a three dimensional chains causing immobilization of par-
ticles (e = 90 0 )
C - formation of agglomerates of three or more particles, which move as
a group (e > 90 0 ).

The volume fraction remains a determining parameter. For most of the A1203
and SiC reinforced aluminium samples processed in space, improved uniformi-
ty was found for both the macro-hardn.ess and the adhesi on between SiC and
Al matrix, as compared to the reference samples.
336

A B c Fig. 13.11: Schematic over-

view of particles arrange-

~
o o
o ~ 'i9 ments at di fferent contact
o
o ~ angles [13.28J.
o
o 0 ~ A e < 90 0
o
o
o B e = 90 0
C e > 90 0

fo6\
~

13.3.3 Skin Technology

Skin technology is directed towards space processing of high value products

by a shape conserving remelting process in microgravity. In the absence of
convection and hydrostatic pressure in the melt, a thin ceramic layer could
be sufficient to preserve the contour of a complex remelted piece of al-
loy. Such a thin skin allows directional sol idification under high thermal
gradients that would be diffused by conventional mold techniques. Therefore
a significant improvement of the solid structure can be expected. Turbine
blades are examples of products that hold promise of substantial perfor-
mance advancements from this new technology. Sprenger [13.30J performed se-
vera 1 TEXUS experiments as well as a Space 1ab experiment to test thi s
idea. The fi rst experi ments permitted to quantify some parameters 1 ike
layer thickness, its nature, and its wetting behaviour. Second order pheno-
mena were found to pl ay a major role in space. Predominant amongst those
are the vol ume change during melting and the interfacial tension forces
between melt and skin. Although the first experimental results were not
fully successful, they are encouraging and lead to a design for a new ar-
rangement for future space experiments. A non-wetted pool must be main-
tained for improved compensation of the voJume change. The solid skin could
be replaced by a liquid non-miscible layer having a stronger wetting to the
container than to the sample alloy. Moreover heterogenous nucleation could
be eliminated.
 337

13.4 Characteristic Future Experiments

Most of the space experiments in metall urgy performed todate demonstrate

the feasabi1ity of the process involved in the space environment. However,
few experiments go beyond the verification of an idea towards a complete
quantification of the result. There is now a need for second generation ex-
periments, to be performed with better defined boundary conditions, desig-
ned to determine in full scale the second order phenomena identified up to
now. In situ diagnostics are required to answer more precisely the funda-
mental questions posed and to test the potential of space for specific ap-
plications. Two of these new sort of experiments are described in the fo1-
1owi ng.

13.4.1 The "GETS" Experiment (Interfaces in transparent melts under solidi-

fication)

The GETS experiment visualizes temperature and concentration profiles ahead

of a growing solid-liquid interface in a transparent model material. This
kind of material, even though it does not possess all the characteristic
properties of metall ic alloys (e.g. it has a higher Prandt1 number), can
help to improve our understanding of crystal growth. Ecker and Sahm ~3.3tl
propose to reconstruct the complete fields of mass and heat flow using the
technique of holographic interferometry together with classical temperature
measurements. In this way the two contributions to the variation of the re-
fraction index of the liquid phase can be separated and the morphology of
the solidification can be identified.

An experiment chamber has been developed for the 01 mission including two
plates for heating and cooling, which fits in a holographic interferometry
systems (HOLOP). Early tests performed on ground show the formation of lo-
cal cells due to thermoso1uta1 convection when a dendritic front develops
in a succinonitrile-ethano1 melt. This tool is! very useful specially for
characterizing non-steady states (Fig. 13.12).

13.4.2 The Mephisto Project

Favier et a1. [13.32J proposed to study directional solidification of

338

Fig. 13.12: Fluid flow instabi-

lity in front of the solidifica-
tion interface revealed by in-
terferometry on the ground
"GETS" experiment [13.31] (Suc-
cinonitrile-Ethanol)

metallic alloys and doped semiconductors in a collaborative programme with

NASA. Some theoretical problems difficult to examine on the ground, such
as morphological stability of the solidification front or segregation phe-
nomena will be studied under well controlled conditions. Convective effects
will be minimized or at least simpl ifed so the coupl ing between crystal
growth and fluid flow can be characterized. Some questions relating to more
applied problems will also be answered, in particular the influence of the
microgravity environment with all its imperfections (variations with time
in direction and intensity) on segregation phenomena during crystal growth
at macro- and micro-scales.

In such experiments, two kinds of requirements are imposed:

well defined and optimized solidification conditions in a large range of
parameters,
- "in situ" diagnostics during the experiment

The Mephisto apparatus will offer a continuous measurement of the solid-li-

quid interface temperature using the Seebeck effect at the junction between
the two phases, interface shape marking by the Peltier method and interface
quenching at the end of the experiment. The principle of the Seebeck mea-
surement is sketched in Fig. 13.13. If two solid-liquid interfaces are pre-
sent in the same sample, a thermocouple circuit is formed by the two solid
and liquid phases. No E.M.F. appears when the two interfaces are in thermo-
dynamic equilibrium. A voltage 6E is created when one moves one interface
in the sense of melting due to the preserlce of undercooling or supercooling
6T during the process and 6E = nsl 6T where nsl is the S/L thermoelectric
power.
 339

T
s s

An artists view of Mephisto is given on Fig. 13.14 where three samples are
visible subjected to the two opposite thermal gradients. One of the samples
will be used for the Seebeck measurement, the second for Peltier marking,
and the third for quenching. Many solidification-remelting cycles are pos-
sible, each of them giving a Seebeck signal characteristic of the particu-
lar growth conditions before the final quenching. This experiment is there-
fore specially well adapted to long duration missions.
340

13.5 Conclusions

Contrary to the early expectations at the beginning of metallurgy studies

under weightlessness, the most important return of experiments already per-
formed does not concern new or improved materials but fundamental studies.
This is partially due to the fact that space processing emphasizes second
order phenomena such as capillarity, which was underestimated before. The
first generation of experiments proved the feasability of metallurgy expe-
riments in space and validated some ground based technology such as welding
and brazing under microgravity conditions. Now there is clearly a need for
a second generation of experiments with well defined boundary conditions
and with "in situ" measurements of various parameters, clarifying the fun-
damental questions arising from experimentating in microgravity with all
its advantages and imperfecti ons. "Space processi ng" and appl i cations to
new or improved materi al s will only emerge when the different mechani sms
involved will be clearly understood.

References
[ 1] E.C. Mac Kannan, R.M. Poorman: Skylab experiment MS51 "Metal sMelting
Experiment". 3-Space Processing Symposium Skylab results Vol. I, p. 85
NASA Report M 74-5
[ 2J J.R. Williams: "Exothermic brazing". Ibidem, Vol. I, p. 33

[ 3J K. Frieler, R. Stickler, E. Siegfried: "Vacuum brazing under micro-

gravity". Results of Spacelab I, p. 95. 5th European Symposium on
Materials Sciences under Microgravity, SchloG Elmau (FRG) 1984, ESA
Report SP-222.
[ 4J K.A. Jackson, J.D. Hunt, Trans. AIME 236 (1966) 1129

[ 5J E.A. Hasenmeyer: Spacel ab experiment MS66 "Copper-aal umi ni urn Eutecti c"
Vol. I, p. 457, NASA Report M 74-5
[ 6J T. Carlberg: "Solidification of some eutectic alloys under microgra-
vity conditions and at 19" 3rd European Symposium, Grenoble (F) 1979,
ESA Report SP-142
[7] J.J. Favier, J. de Goer, R. Le M~guet: "Solidification dirigee des
systemes eutectiques A12CU-Al, et A13Ni-Al en fusee-sonde" Vol s TEXUS
IV and VI. Internal Report 1983, Centre d'Etudes Nucleaires de Gre-
noble/D.M.G.
[ 8J J.J. FAvier, J.P. Morlevat, J. Duvernoy: "Method of analysis of the
regularity of lamellar eutectic structures by diffraction of a laser
beam". Met. Trans. B, Vol. 14 B, (1983), 105-108
 341

[9 J J.J. Favier, J. de Goer: "Directional solidification of eutectic

alloys". Results of Spacelab 1, p. 127, 5th European Symposium on
Materials Sciences under Microgravity, SchloB E1mau 1984, (FRG), ESA
Report SP-222

110 J A.S. Vue: Sky1ab experiment MS64 "Metal and Halide eutectics".
3rd Space Processing Symposium Sky1ab Results, Vol. 1, p. 469, NASA
Report M 74-5

[11 J A.S. Vue: Appoll o-Soyuz test project experiment MA131. Final report
"Zero gravity growth of NaC1-Lif eutectic" (1977), NASA TMX-73360

D.2 J D.J. Larson: "Low gravity processing of magnetic materials". AIM 15th
Aerospace Sciences Meeting La (1977), AIAA Paper 77 (1977) 123

[13J P. Kyr, G. MUller: "Gerichtete Erstarrung des InSb-NiSb Eutektikums

unter verminderter Schwerkraft" (TEXUS 10), Z. F1 ugwi ssensch. u. We1 t-
raumforschung.

[14J G. MUller, P. Kyr: "Directional sol idification of InSb-NiSb eutectic"

Resul ts of Space1 ab 1, p. 141, 5th European Symposium on Materi a1 s
Sciences under Microgravity, SchloB E1mau 1984, (FRG), ESA Report
Sp-222

[15J H. Nieswag, T. Luyendijk, W.H.M. A1sem: "Unidirectional solidification

of cast iron", Experiment ES325, Results of Space1ab 1, p. 79, 5th
European Symposium on Material s Sciences under Microgravity, SchloB
E1mau 1984, (FRG), ESA Report SP-222

[16J J.D. Verhoeven, R.H. Homer, Met. Trans. Vol. 1 (1979), 3437

[17J J.M. Quenisset, R. Nas1ain, J. Cryst. Growth 54 (1981) 465

[18J J. Junze, K.F. Kobayashi, P.H. Shingu, Met. Trans. A, Vol. 15A (1984)
307

[19J D. Camel, J.J. Favier, J. of Cryst. Growth 67 (1984) 42 and 57

[20J J.J. Favier et a1., Acta Astronautica, Vol. 9, no. 4 (1982) 235

[21] M.H. Johnston, R.A. Parr: "Low gravity sol idification structures in
the Sn-15% Pb and Sn 3% Bi alloys", MRS Symposia, Proceedings Vol. 9,
G.E. Rindone editor, North Holland (1982)

[22] S.V. Bourgeois, P.G. Grodzka, J.E. Pond, loW. Spradley, LKHD Report
LMSC-HREC TR D 4977400, Contract No. NASS-32401

[23] H.U. Walter: "Stabil ity of multi component mixtures under microgravity
conditions", 3rd European Symposium, Grehob1e (F) 1979, p. 245, ESA
Report SP-142 I

[24] D. Uhlman, NASA Report TMX-3458, p. 111.1-111.40

[25] W. Heye, M. Klemm, NASA Report TMX-3458

[26] T. Kawada, S. Takahaski: Sky1ab experiment M 561 "Preparation of sili-

con carbide whisker reinforced silver composite material in a weight-
less environment", Sky1ab results, Vol. 1, p. 203, NASA Report M 74-5
342

[27J L. Raymond, NASA Report TMX-3458

[28J L. Froyen, A. Deruyttere: "Melting and solidification of metal matrix
composites under microgravity", Results of Space1ab 1, p. 69, 5th Eu-
ropean Symposium on Materials Sciences under Microgravity, Sch10B
E1mau 1984 (FRG), ESA Report SP-222
[29J F. Barbieri, C. Patue11i, P. Gonndi, R. Montanari: "Melting and soli-
dification in O-g of sintered alloys. Experiments ES 311A and B.Bubb1e
reinforced materials", Space1ab results ibidem.
[30J H. Sprenger: "Skin casting of alloys and composites. Results of SLl
and TEXUS experiments", Space1ab Results, p. 87 ibidem
[31] A. Ecker, P.R. Sahm, 4th European Symposium on Material s Sciences
under Microgravity, Madrid 1983, p. 331, ESA Report Sp-191
[32J J.J. Favier: "The MEPHISTO Project", Centre d'Etudes Nuc1eaires de
Grenoble (F), DMG Report (1985)
14 Binary Systems with Miscibility Gap in the
'Liquid State

European Space Agency, Paris

Summary
Systems with miscibility gap in the liquid state, "immiscibles", are of
fundamental interest and have potential for the preparation of dispersions.
The study of these systems and their application has, thus far, been very
limited. Under terrestrial conditions the liquid components separate
quickly due to sedimentati on and buoyancy. Component separat i on due to
nucleation and growth of nuclei and spinodal decomposition can, therefore,
not be studied under defined conditions and fine dispersions cannot be
prepared. Research under microgravity conditions in orbiting laboratories
or under free fall conditions opens new avenues for the study of these
systems. This paper summarizes the underlying thermodynamic and physical
principles and mechanismes and reviews results of recent experimental
investigations.

Introduction

Dispersions are of interest for a variety of appl ications. The

strengthening of metals, for example, especially at elevated temperatures,
by the dispersion of fine particles in the matrix is widely applied with
materials for mechanical appl ications. Optimum strenghtening is achieved
with particles of 0.1 ~m diameter and interparticle spacing around 1 ~m,
which amounts to 1-10vol% of the dispersed~omponent. Strengthening is due
to the fact that the inclusions, usually oxides, serve as pinning centers
for dislocations, thus prohibiting or reducing dislocation climb and
plastic deformation.

Alloys for self-lubricating bearings consist of a dispersion of a

i
lubricating component such as graphite, tin: or lead in a matrix for
mechanical support such as aluminium. Materials for electrical contacts
having high wear resistance are composites of hard particles (e.g.
tungsten or oxides) dispersed in a metallic matrix having good electrical
344

,-
.
..
':'-,' .\ . .
';.'~ .."..
,.,,' ~~.~~ . ......:\.
:
~ .

-. '
, 0, \~ ~o~>O' 0"
.

.
•
-t·· ·~~si4~,..·
I :

.....
.: .
..

....•
#~; :: :\:~~,
"
.
: .'
,' .
,' -
.:... ..
'
.

".
•
.
'• •
.,.
;~

Fig. 1. Configuration of AI-In sample

processed in space. AI: white [5J.

WEIGHT PER CENT INDIUM

tOJO JO to!ll 10 JO n 10 I! 10 II ,. " II

0

,,
r -- --- --- --- .... ----
'-

I
100 c-
TWO MELTS
~
U 700
o 66 <tr-..,j 6 3 7± 3 ° ~

1\
uI 4 .7 Ne9
a: '0 0
::> l17.3) (_972)
I-
<
a:
WSOo

\
D..

"
W
I-
40 0
no I I

~.
"0

zoo
640 "'..~ 4.7
634 - -
,
;..155' ...... 1 S5~
I I( 17.3) !

'00
610 0
I 4 \
•
0
o to 10 40 10 10 tIO
AL In
ATOMIC PER CENT INDIUM

Fig. 2. Equilibrium phase diagram

Aluminium-Indium [6J.
 345

conductivity, low hardness and yield pOint. The conductivity is not

preserved when alloy additions are used to to increase the hardness of the
contact material. More exotic potential applications of composite
materials include dispersions with superconducting properties. Using a
two-phase mixture with a ductile, metallic major phase (e.g. copper) and a
di spersed superconducting component (e.g. Niob ium) superconducting
properties of the composite can be achieved either by having an
electrically interconnected network of the superconducting minority phase
or by having a fine distribution with interparticle spacing less than the
coherence length, thereby rendering the matrix superconducting by
tunneling (proximity effect) [1,2].

Systems having a miscibility gap in the liquid state have potential for
preparing dispersions. More than 300 binary immiscible systems are known
[3] and the number of multicomponent systems having a miscibility gap in
the liquid state should be extremely large. Most of them have, however,
not been investigated in sufficient detail.

So far immiscibles have not been applicable for the preparation of

compos i tes because of rap id separat ion of the components duri ng c,ool ing
under the influence of gravity. Usually layered structures or only coarse
dispersions are obtained and only when space fl ight experiments became
possible with the Skylab and Apollo-Soyus Test Project (ASTP) and more
recently with the Spacelab/Shuttle programme and also Sounding Rocket
fl ights could the sa I ient infl uence of grav i ty be elimi nated. However,
even though residual accelerations during these flights are of the order
of 10- 3 to 1O- 59 (g = 9.81 m/s2) , the fine dispersions expected were
initially not obtained. Instead, coarse dlspersions and samples with large
inclusions of one component surrounded by the second component were
obtained. (Fig. 1), [4,5].

These unexpected results have spurred both ~heoretical and experimental

activities in order to identify the mechanis~s that cause coarsening and
component separation even when sedimentation and buoyancy is largely
el iminated.
346

1 2
e0
.....
CI
t
ao
"-
.......
1
~

Vl 'SO"K
<1 0
~ 700 0 K
...!.. 750"1(
E eooOK
::t:
<1 -1
e- to OK
~
<1
-2 10000 K

6G m

-3

-4

-s

-6

° 0,1 0,2 0,3 0,4 0,5 0,,6 0,7 0,8 0,9 1,0
(OMPOSIT lOiN XB ..
Fig. 3.~Hm, -T~S and resulting~3m as a function
of atomic fractions for a binary system having a
miscibility gap. ~Ho = 15 KJ/g-atom, R = 8,314 J/mol.K
(eqns. 1, 2, 3).

d2 ~ dA~
X :(~) =0; 0 :(-::~::l!L) = 0
dx2 T,p dx T,p
 347

14.1 Binary Systems with Miscibility Gap in the Liquid State

Fig. 2 shows the equilibrium phase diagram of the system Aluminium/Indium

[6]. Aluminium/Indium has been used as a model system in various micro-
gravity investigations [4, 5] because of the low melting temperature of
its constituents. The underlying thermodynamic principles of binary phase
diagrams with miscibility gap in the liquid state are depicted in Figs.3,
4. The case discussed is idealized, normally the miscibility gap is
asymmetrical.

At a given temperature T the free enthalpy t.Gm for a mixture (index m) is

defined by the Helmholtz-Gibbs equation:
(1)

t.Ym is the enthalpy andt.Sm the entropy of mixing.t.Hm is usually positive

for binary mixtures in the liquid state. At lower temperatures, therefore,
t.Hm dominates and t.Gm is positive, whereas at high temperatures the second
term is is larger and t.3m becomes negative.

t.Hm and t.Sm as a function of the atomic fractions XA, B of the components
(X A + XB = 1) at constant pressure and temperature are described by the
following equations:

(2)

(3)

t.Ho = const is a measure for the atomic interactions, R is the gas

constant.

With a value for t.Ho = 15 KJ/g-atom and R = 9,314J/mol.K plots of t.~m'

-T.t.Sm and the resulting t.Gm can be calculated, for different temperatures
for an idealized case (Fig. 3). Above a critical temperature (approx. 900K
for this case) the t.G m curves are concave, the free enthalpy of the
solution is lower than for the components and the mixture is, therefore,
stable for all compositions. At lower temperatures the t.Gm curves start
having two minima corresponding to stable compositions. The locus of these
348

1000 STABLE REGION

900
1 COHNOOAl
DR
IINOOAl
:.:: 800
•
....
700 UNSTABLE
REGION
0<0
600 / \
I I \

Y
\
500
\I1ETASTABLE REGION
0>0

o 0,1 0,2 0,3 0,4 0,5 0,6 0,7 O,B 0,9 1,0
COMPOSITION XB -

Fig. 4. Binary system with miscibility gap

as derived from Fig. 3 (x,o see Fig. 3).

early Interlledlate. final

a) Nucleatlon
and Growtb

~ --------------3l----
~-ff\\-
,J \..1
----- -----------
b) Spinodal
decompos it l on

Distance

Fig. 5. Concentration profiles during

a) growth of nuclei and
b) spinodal decomposition.
 349

mInima corresponds to the separation line between the one-phase

(homogeneous solution) and the two-phase region with two melts in the
isobaric temperature composition diagram (Fig. 4). It is denoted the
connodal or binodal curve, along which the chemical potentials of the
components of the two coexisting phases are equal. The locus of

d 2t.G
( --2m) =0 defines the spinodal curve (Fig. 4)
\ dx T ,p

d 2t.S
Within the spinodal region, for whictl~)
"\dX TP
< 0,
the melt is unstable. The smallest deviation from Xo lowers the free
energy and, therefore, separation poceeds spontaneously without
nucleation. In the region between spinodal and binodal curves, the melt is
metastable, separation of the components is due to nucleation and growth
of nuclei.

The situation can be viewed from a different perspective: Since the

diffusion coefficient is proportional to the second derivative of the free
enthalpy with respect to composition, D is positive in the metastable
region, negative in the unstable region and zero on the spinodal curve
[7]. This results in the two different types of separation mechanisms
mentioned above: nucleation and growth of nuclei in the metastable region
and "spinodal" decomposition in the unstable region. Fig. 5 illustrates
both cases.

Growth of nuclei starts from a critical embryo above a critical super-

saturation. The nucleus grows by depleting-its surroundings, a diffusion
layer is formed and material transport is due to diffusion directed
towards the nucleus. The number of nuclei per unit volume depends on the
cooling rate and the nucleation mechanism: homogeneous or heterogeneous.

Spinodal decomposition requires no supersaturation or undercooling. Any

statistical compositional variation of the melt is amplified, there is no
energy barrier to overcome. Materials transport is due to "uphill
diffusion" because of the negative diffusion coefficient. The wavelength
of the decomposition structure depends on the mobility of the atomic
350

species, their relative chemical potential, the spacing of binodal and

spinodal curves and the supercooling, which is the driving force.

The diffuse boundary of early spinodal decomposition (Fig. 5) sharpens as

the separation process proceeds unti 1 the morphology resembles that of
nucleation and growth. The distinction between the morphologies associated
with nucleation and growth and spinodal decomposition is, therefore,
limited to early stages. The morphology of early spinodal decomposition is
characterized by a superimposition of sinuso·idal variations of composit-
ions clustered about a wavelength /t max that is ampl ified strongest. The
characteristics and criteria for distinguishing between nucleation and
growth and spinodal decomposition are summarised in Table I [8J.

Investigation of spinodal decomposition was hitherto rather limited to

annealing of supersaturated solids. Most of the experimental work has been
on metal alloys and oxide glasses with little study having been directed
to nonmetallic crystalline systems such as oxides and alkali halides.

Under terrestrial conditions buoyancy and sedimentation cause rapid

component separation due to density differences and investigation of
decomposition in the liquid state is rendered extremely difficult. Under
microgravity conditions these mechanisms are virtually eliminated and the
study of these systems becomes feasible.

In the following are summarised the mechanisms causing component

separation when the influence of gravity is eliminated, as well as
experimental results that demonstrate the potential of research under
microgravity conditions.
 351

Table 1
Some Factors which Differentiate between Nucleation
and Growth and Spinodal Mechanisms [8J

Nucleation and Growth Spinodal Decomposition

Invariance of second phase composition Continuous variation of bOih

to time at constant temperature
Interface between phases is always
same degree of sharpness during growth
Tendency for random distributions of
particle sizes and positions in matrix
Tendency fOr separation of s~cond phase
spherical particles with low
connectivity
extremes in composition It.!ith
time until.equilibrium composit-
ions are reached
Interface between phases initially
is very diffuse, eventually
sharpens
~egularity of second phase
distribution in size and posit-
ion characterized by a geometric
spacing
Tendency for separation of
second phase, non-spherical
particles with high connectivity

14.2 Minimum Free Energy Configurations

Minimum free energy considerations give good insight into which geometric-
al configurat.ion is to be expected in the final stage of component
separation. Let us consider first the most general case of a heterogeneous
mixture consisting of liquid (l), solid (s) and gas (g). The free energy
of the system F is given by the sum of volume energy (F m), gravitational
energy (F g ) and surface energy (F o):

(4)

In equi 1ibrium the free energy F assumes a minimum. Since the volume
.
energy Fm is constant, it needs not to be considered in this context •
Under terrestrial conditions the equilibrium configuration is usually
dictated by the second term, FG, meaning that whenever the internal
352

IIQu !d I'

sol i d s

I iQuid 1"'

tr/.,'
liQu i d I '

Fig. 6. Equilibrium configurations of

a) two liquids in contact with a solid
according to Young's equation,
b) three immiscible liquids according
to Neumann's equation.

Fig. 7. Computer simulation of spinodal

decomposition [9J

oe

0.'

0 .4

0'
0 .1

0.1

Fig. Sa: Cross section of a 3-dimensional

matrix of equal spheres of random distribution
[ 10].
 353

friction of the system allows for it, minimization of the

potential energy is a good approximation for the equilibrium configuration.
In systems where .the majority component is a fluid this simply leads to
separat i on of the components accord i ng to thei r dens i ty • Layered
structures are formed due to sedimentation and buoyancy.

Under conditions of near weightlessness, the second term, FG, can be

neglected and surface free energy and interfacial energy are of primary
importance. The equilibrium condition is then reduced to

(5)

For two immiscible liquids in contact with a crucible the minimum free
energy configuration can be derived using Young's equation (Fig. 6a):

cos Q =isl' - dsl" (6)

'01'1"

The equi 1ibrium of three 1iquids in contact is described by Neumann's

equation (Fig. 6b):

(7)

The morphology of the space processed sample shown in Fig. 1 conforms with
the above conditions.

The kin e tic s 0f the pro c e s s by wh ich the components

separate, however, are much more difficult to analyze. In this respect,
microgravity environment offers the unique opportunity to investigate more
subtle basic underlying mechanisms causing component separation in
multiphase systems witi10ut the overruling int~rference of sediQ1~ntation,
buoyancy phenomena and grav i ty-dr i ven conNect i on. The absence of
hydrostatic pressure and the feasibility of containerless positioning,
handling and shaping of molten materials offers additional perspectives.
354

14.3.1 Simulation of Spinodal Decomposition and Growth of Nuclei

Spinodal decomposition as well as nucleation and growth of nuclei can be

simulated using a computer. In the case of spinodal decomposition any
random concentration fluctuation is amplified by uphill diffusion causing
rather spontaneous separation into two melts. A computer simulation on the
basis of the superposition of random sinusoidal compositional variations
with constant wavelength and a Gaussian distribution of amplitudes results
in a three-dimensionally entwined network of the two melts when one simply
separates positive and negative amplitudes [10J. For equal volumes the
result is shown in Fig. 7. If one volume fraction is smaller than the
other, interconnectivity is still maintained. The transition from a
connected minority phase to isolated regions occurs at approx. 15vol%
[10J. It is evident that depending on the viscosity and the wetting
properties of the two melts and the crucible, coalescence will quickly
lead to complete separation with the contact angle determining the final
configuration in equilibrium.

Simulation of nucleation and growth of nuclei also aids in determining the

I imits of prepari ng fi ne, homogeneous di spers ions by th i s approach [11].
Starting with a random distribution of point nuclei followed by
simultaneous growth until a certain volume fraction is reached (Fig. 8a)
it could be shown that the inclusions contact and intersect in surprising
numbers: At 50% volume fraction each sphere intersects, on an average, 5,5
others, only 0,4% of the spheres are unattached! At 33,3% volume the
corresponding numbers are 3,2 and 4%, and at 15% volume fraction sti1.l
only 25% of the spheres are isolated (Fig. 8b). This simple model, which
does, for example, not take into account the influence of overlapping
diffusion fields on the growth of nuclei has important implications. At
volume fractions of dispersed particles or droplets above 10%
agglomeration or coalescence of a large percentage of the inclusions is to
be expected in reality.

14.3.2 Nucleation

The number of nuclei generated per unit volume during cool ing from the
stable into the metastable region depends on a number of factors. When a
cluster of atoms, an embryo, forms, the free energy is altered for two
 355

-. -,-1 IIQ.1I1UCCUU
-l\lOLlM: OCCI.PIEO

I
Pi 3D

I
Lo",,!
L.,
..... -.

~20

i
01 02 03 04 05 0&
OCCUPIED VOLUME

Fig. 8b: Actual volume occupation versus

frequency for randomly dispersed, partly
overlapping spheres with intersecting
neighbours [11J.

'1 . ."
"
w
!C
III:

Z
2
!C
~
~
I

- UNDERCOOLlNG-

Fig. 9. Dependence of nucleation rate on the

potency of the nucleation catalyst present
(schematic) .
356

causes: It is changed by an amount V. t:..G v ' where Vis the vol ume of the
embryo and t:..G v is the free energy change per unit volume. Also, since an
interface is created between embryo and melt, the free energy is changed
by A.t:..G i , where A is the area of interface andt:..G i the interfacial energy
per unit area. The resultant free energy changeAG, will be given by:

(8)

t:..G. is always positive, whilet:..G is negative. The resultant t:..G as a

1 v
function of the radius of the embryo has a maximum that corresponds to the
critical radius r K, above which the nucleus is stable and may grow.
Homogeneous nucleation in immiscible systems is reviewed in detail in
[11] .

The rate of nucleation I depends primari lyon the undercool ing t:..T, the
principal dependence for homogeneous nucleation is given approximately by:

(9)

where C is a constant. The nature of this dependence is indicated in Fig.

9 by the curve marked GH" The nucleation rate remains neglibly small with
increasing undercooling and then rises very sharply over a small
temperature interval so that, for most purposes, homogeneous nucleation
can be considered to take place at a certain fixed value of t:..T.

It has been demonstrated that the undercoo ling requ i red for homogeneous
nucleation is much larger than that usually observed in bulk specimens.
For example, by dividing the sample int,o small droplets in order to
eliminate centers which can catalyze nucleation it has been shown that an
undercooling of approximately 300°C is required for homogeneous nucleation
of iron [13J. Also by means of vacuum distillation and flash heating large
undercooling has been achieved and metallic glasses of bulk samples could
be obtained [14J.

The fact that most metal I ic melts nucleate at an undercool ing much less
than that required for homogeneous nucleation has been explained in terms
of solid foreign substances in contact with the melt. The foreign
substance may consist of small particles suspended in the melt, oxide
 357

particles, the surface of the container or impurity clusters. An embryo in

contact with a solid will become stable at lower undercoolings. If the
contact angle Q is small, the embryo will have a larger effective
curvative radius and may act as if it were an'embryo containing many more
atoms. Therefore, its probability of formation is greater, as indicated
in Fig. 9 for decreasing contact angles Q1> Q2~ Q3. The nucleation rate is
approximately described by:

Ihet~ exp - [Cf(Q}/ (llT}2] (10)

The density of heterogeneous nucleation centers in metallic melts may be

extremely large (of the order of 10 6/CC) and it may be possible to tailor
dispersions of immiscibles by intentionally adding the desired density of
nucleation sites.

14.3.3 Terrestrial Observation of the Early Stages of Spinodal Decomposi-

tion and Nucleation

To investigate the evolution of the population of nuclei, their size.

distribution, growth, coalescence and the structures as they develop
during spinodal decomposition one can resort to a variety of experimental
techniques. Under terrestrial conditions, however, only the early stages
of decomposition of liquids can be captured, the later stages are
dominated by sedimentation and buoyancy. Experimental techniques, there-
fore, aim towards minimizing the salient influence of gravity.

Rap i d 0 b s e r vat ion of the kinetics of phase separation and rapid

changes of the experimental conditions (T.,p) to. quickly transgress from
the stable to the unstable or metastable region has recently been used
[15J. A transparent organic system (2-butoxyethanol/water) was investigatec
Demixing was initiated by a relaxation technique (change of pressure or
temperature to get into the unstable region within 0.1 ms) and the
decomposition was observed by light scattering:. The intensity of scattered
light passes through a maximum as a function of time (Fig. 10). This
maximum is attributed to a definite radius of the growing droplets. The
time from pass i ng the coex i stence curve and the occurence of the max imum
corresponds to the time tm wh ich is needed for the embryo to grow to a
sphere of about 0.2 urn at A = 600 nm. This time tm is observed to be
358

P R l~ SU A E

" P -138 bar,

(In c:a 100 fl' I

1m

I
/'NTENSITY OF SCATTERED UGHT

o 10
t/ms

Fig. 10. Scattered light intensity and

pressure VS. time t for a typical
pressure-jump experiment on 2-butoxythanol-
H2~ (flP o: ~38 bar, X(H,O) = 0.843;
T - 66.9 C, TE : 61.5 C). [15)

..
... . " .
, ,
•
.. '. • .
..
. '. '.. ..• 0'· • . .. .. .
' .
~

.
.. ..,. -, ... ff-".. . '. ..-=-
'.
~ ~ .~-~
'

.~
". ., • !
•

'.;.r •.- '. • •

. . ,
.• •

••
,
.

~.. .. ... ~ ... I~ · ~ '. • -... ~.~ ••'

l· · ~ ~~. ,_ eo •• 1".- ' • . -. Z..... : ~~~~n;~I1!11~
7C. . ~. ": .... . ' . -• .\-'
. .
c-....
:~~~:
":.,••-~ IL.......
,. ·. "qr - "
.:~~~:-;.:'"
. ., ,.. ~

Fig. 11, AI-1,5 at % Cd monotectic alloy

rapidly solidified bY18uwez gun technique
Cooling rate up to 10 °K/s [15],
 359

••
.,

0,5 ~m

Fig. 12. 40.000 x magnification of Pb in AI-matrix,

dispersion obtained by melt spinning with cooling
rates of 106K/s to 10 7K/s [17] .

Fig. 13. Na20-B203-Si02 decomposition structure.

Arrow indicates Si02 rich glass [18].
360

strongly dependent on how far the system is quenched into the miscibility
gap. At a given composition tm has been found to vary up to five orders of
magnitude by changing the quench temperature only. It is not quite clear
whether the structures observed are due to nucleation or spinodal decompo-
sition.

Rap i d s 01 i d i f i cat ion using piston and anvil techniques [16]

and more recently melt spinning [17J allowing for cooling rates from 10 5
up to 10 10 K/s have been used to freeze the early stages of separation and
to prepare dispersions. Figs. 11, 12 give an indication of the dispersions
obtained. The size of the inclusions is of the order of 0,05 to 3 fm. With
these techniques large surface to volume ratios are required and only thin
flakes or ribbons can be prepared.

Ann e ali n g 0 f Que n c h ed, Sup e r sat u rat e Sol ids has
been the basis to establish that spinodal decomposition is an operative,
observable phenomenon in binary systems having a miscibi 1ity gap in the
solid state. In principle, spinodal decomposition should be expected to
occur by quenching from above the critical temperature and ageing at a
temperature within the spinodal region, presumably the kinetics of the
decomposition process can be followed. The wavelength of the structures to
be expected is of the order of 100 A. Only in glasses or in solids, for
which the coherent spinodal is well below the melting pOint is there any
hope of obtaining a time scale long enough to suppress the reaction during
quenching, and then, studying i.t isothermally. For quench rates which are
rapid enough to preclude significant decomposition, the composition-
amplitude spectrum of spinodal decomposition should be independent of the
quench rate [10J. The experimental results obtained are somewhat ambiguous
since it is difficult to discriminate between nucleation and spinodal
decomposition (see Table I).

S Ys t ems h a v i n g h i g h vis cos it Y such as glasses enable one

to investigate the morphologies that devQlop in more detail over a longer
period of time. The separation process proceeds sufficiently slowly for
observation and can be arrested in various stages by further undercooling,
without the texture being destroyed by a crystallisation process. Liquid-
liquid phase separation in the immiscible system Na 20-B 203-Si0 2 was
induced by cooling the melt below the critical temperature followed by
 361

Fig. 14. Isopycnic system Cyclohexane +

deuterated Cyclohexane/Methanol:
90s after quench to Tc -10 mK [19].

- ---- -----
---- ---- .....
Nucleation Growth

s I.

Fig. 15. Principle of preparing dispersions

by directionally solidifying systems having
a miscibility gap in the liquid state.
362

annealing [17J. Three dimensional network structures rather than a

dispersion of isolated spheres of the minority component were obtained
(Fig. 13). This result agrees very well with the patterns obtained by
computer simulation (Fig. 7). The structures formed are due to diffusion,
viscous flow and coalescence and the result is explained not as a spinodal
structure but rather as a result of growth of randomly placed spherical
nuclei, which come into contact during the process and then coalesce.

Quasiisopycnic systems have recently been employed [19J. By

deuterating a fraction of Cyclohexane the densities of the immiscible
system Cyclohexane-Methanol could be matched. By this means the phase
transition could be investigated under conditions that are close to
microgravity. However, matching of the densities is not perfect and
because of the different temperature coefficients of the densities for the
components there is still residual flow which prohibits observing the
structures formed under stationary conditions. The results were, however,
very promising: macroscopic spinodal decomposition structures appear just
after the thermal quench (Fig. 14) and wetting configurations are observed
at the final equilibrium stage. These investigations are now being pursued
under microgravity conditions using sounding rockets. By this means Stokes
flow is reduced by four orders of magnitude.

Other experimental techniques have been devised to alleviate the influence

of gravity and prepare dispersions from immiscibles. Some experimenters
have appl ied these techniques under microgravity, thereby optimizing the
conditions for preparation of fine dispersions. Examples are as follows:

o ire c t ion a 1 Sol i d i f i cat ion [20, 21, 22]. The pr i nc i pie is
shown in Fig. 15. Ahead of the solidification front there is a layer of
liquid which is below the critical temperature in which nucleation and
growth of nuc lei takes place. Depend i ng on the grad i ent, the
sol idi fication rate and the rate of Marilngoni transport of droplets away
from the advancing solidification front, droplets are eventually engulfed.
An example of a dispersion obtained by this approach is shown in Fig. 16.
 363

Fig. 16. Cu-Pb alloy directionally solidified.

R~0,5 mmTs [20J.

dia llJml

70U

&00

500

1.00

300

200

100

--1--- ---------- ~
o 2 I. 6 8 10 12 11. 16 16 20 vol %
Fig. 17. Stability of Ag-glass disperslons
subject to remelting under microgravity
conditions [30J.
364

Acoustic or mechanical mixing during directional

solidifation has recently been employed. Experiments were performed during
the coasting phase of a sounding rocket where residual accelerations of
b <10- 49 are achieved. Larger droplets formed by coalescence are
redispersed by transients of the acoustic pressure waves in a continuous
manner. Good dispersions were thus obtained. [23J.

14.4 Results of Microgravity Investigations

A number of theoretical [24 - 27] and experimental investigations [4, 5,

19, 22, 23, 28 to 40J have been spurred since low-gravity environment has
become available for experimentation. First experiments were conducted on
board of Skylab in 1973 and ASTP in 1975 and during the following years
during the parabolic flight of sounding rockets (TEXUS and SPAR programme).
Most recently, the results of experiments conducted during the Spacelab 1
mission [34 - 37J have been reported.

In manned, orbiting laboratories residual accelerations of 10- 2 to 1O- 4g

(g= 9.81 m/s2) are obtained. During the free fall period of sounding
rockets above an a lti tude of 110 km, where the atmospheri c drag becomes
sufficiently small, residual accelerations amount to < 10- 49. Presently, a
European, unmanned, freeflying platform (EURECA) is being developed.
Residual accelerations should be below 10- 5 for frequencies below 1 Hz.
Above 100 Hz v i brat i on amp I i tudes of the order of 10- 3g appea r to be
acceptable.

Although the number of microgravity investigations is still relatively

sma 11 because of 1im i ted fl i ght opportun i ti es and a1though some of the
experiments did not perform nomi nally because of equ i pment rna 1functi ons,
some important results have been obtained which demonstrate the potential
of research under microgravity conditions. Some of the results will be
highlighted in the following:

Results of experiments employing a c 0 u s tic mixing and

d ire c t ion a I s o 1 i d i f i cat ion to prepa re fine dispersions
under microgravity conditions have already been mentioned above [22, 23J.

As outlined in section 4.1 theoretical analysis indicates that the

 365

Fig. 18. Depletion layer near crucible wall.

Left: 7 vol.%, right: 5 vol% glass in silver.
20 x [30J.

ttt
Fig. 19. Marangoni convection in a suspended
droplet surrounded by a fluid matrix subject
to a temperature gradient [42J.
366

statistics and the geometrical rei a t ion s hip s

involved in the process of nucleation and growth of nuclei (see Figs. 8a,
8b) limits the volume fraction of the minority component to < 12%. At
larger volume fractions the inclusions contact and the dispersion coarsens
as a result of the coalescence. This prediction was experimentally
verified by remelting and solidifying dispersions under free~fall
conditions during sounding rocket flights[30]. Silver was chosen as the
matrix and a sodium silicate glass as the minority component.

Remelting of a dispersion of known composition and known particle size

distribution has the advantage that all mechanisms pertaining to
nucleation and growth of inclusions are eliminated. The dispersion
obtained can be directly compared with the initial sample. Since the
matrix, Ag, has very good thermal conductivity, thermal gradients are
minimised. Since the glass has a relatively high viscosity even at the
process temperature of 1150°C, coalescence is slow and Marangoni-flow and
resulting transport of droplets to higher temperature regions is,
therefore, impeded. Coarsening and separation should be mainly due to the
influence of the volume fraction. Coalescence and wetting with resulting
secondary convection as a result of shape change should be the major
mechanisms contributing to coarsening of the initial dispersion.

The results are depicted in Fig. 17. The original dispersions are
pertained at volume fractions below 5% only, as compared to approx. 12%
derived analytically. Identical samples processed under quasi isothermal
and under gradient conditions yielded the same result, which indicates
that Marangoni transport (see later section) was of no importance. Since
glass wets the crucible wall better than silver (9 < 90°), droplets
contacting the crucible spread on the crucible walls and secondary
convection is induced because of the shape change. This flow is initially
directed towards the crucible and additional inclusions are transported to
the crucible wall. There is, therefore, a depletion layer near the
crucible wall which reflects the 10callly induced flow (Fig. 18). These
findings are corroborated by results obtained by Fredriksson [28] and
Ahlborn and L5hberg [34].
 367

Fig. 20. Cyclohexane droplets propelled by

Marangoni flow in a methanol matrix.
Temperature gradient from bottom to top of
the cuvette shown [43].

a.) terrestrial
Fog front!

~
EF;
:'
o
,'"",
2

69s
'53~' _____ ~m
5 5

I
i

i
'--' "1'" "---------
~ J 37 5 --,
210}Jm ~", Ii
b.) microgravity
~ 2 "- I
'0:;
~ ~i
I

e 1 2 " l
200 }JiTI --,

5 6
- I
I
7
drop migration rat2 [mm/sJ

Fig. 21. Migration rate of Cyclohexane

droplets in Methanol: a) Terrestrial
b) Microgravity [38].
368

To calculate the time required for two droplets in a liquid matrix to

coalesce and to estimate the induced flow fields is a rather involved
problem and only approximate solutions are available. Defined experiments
are difficult to conduct on the ground and microgravity should provide
better defined conditions.

Con v e c t ion at large leads to separation by transport of the

minority phase to energetically more favourable locations such as crucible
walls, but also by bringing inclusions into contact with each other
because of gradients in the flow velocity fields.

The importance of convective flow induced by grad ients of surface or

interfacial tension due to temperature or concentration gradients,
Mar a n g 0 n i flo w, could only be established in the course of
microgravity investigations. Floate zone geometries have been used by
Schwabe, Chun and Monti to experimentally demonstrate and investigate this
mechanism on board of sounding rockets (TEXUS). Marangoni flow generated
at the interface between a liquid inclusion and the surrounding liquid
matrix under the influence of a temperature gradient results in transport
of the droplet towards higher temperature, i.e. lower interfacial energy.
The flow field that propels the inclusions is schematically shown in Fig.
19 [42J. The terminal velocity vt as a function of the radius R and the
kinetmatic viscosities TJ is described by [41, 42]:

v = ~ • - "loR ( 11)
t 3 2TJ-O(+ + 3TJ i"+
where the gradient of interfacial tension

"10 = ~vr+ ~ vC ( 12)

BT Be
may be due to gradients of temperature or concentration.

Langbein et al [43] have investigated this type of transport by conducting

sounding rocket experiments (TEXUS) using the transparent immiscible
system cyclohexane!methanol. The fluid contained in a cuvette was cooled
into the miscibility gap while subject to a temperature gradient. The
cool ing front was observed by means of a movie camera. The principle of
 369

-1"(IclII
2,0
r 111

.....
11\

E
~

>
-10- 3,
1,0

10 20
R [}1m 1
Fig. 22. Velocity of droplet migration
(Si in Zn matrix) due to residual
gravity and Marangoni flow as a
function of radius [28].

Fig. 23. Al-Bi; 7vol% solidified radially

towards the center [30].
370

the experiment is similar to directional solidification of immiscibles

as shown in Fig. 15. According to the temperature field as it evolves
during gradient cooling, nucleation and growth of nuclei takes place ahead
of the frorlt that corresponds to the critical temperature (binodal
temperature) for the composition used. The minority component,
cyclohexane, initially forms a fog front. As the droplets increase in
size, Marangoni migration towards higher temperature is observed. When the
droplets reach regions of sufficiently high temperature, they start
dissolving and finally disappear (Fig. 20).

Growth and dissolution of droplets is due to diffusion. Without

considering overlapping diffusion fields, the radius of a growing droplet
R is proportional to the square root of the product of time t and
diffusion coefficient 0:

( 13)

P is a constant that describes the concentration field under steady state

conditions. Using 0 = 3-10- 5 cm 2/s droplet radii of 0.05 mm are reached
after ls, 0.2 mm after 16s, 0.5 mm after 100s, and 1 mm after 400s [38].

On the basis of eqn. 11, drift velocities of cyclohexane inclusions can be

estimated. With VCJ= 0.2N/m 2 , ,,= 3.1O- 3Ns/m 2 a migration rate of 5 mm/s can
be expected for droplets having a radius of 0.2 mm. The migration rates
observed for inclusions having approximately this radius are shown in
Fig.21 for terrestrial reference experiments and the microgravity
experiments. The results of the flight experiment agree well with
migration rates predicted as a result of Marangoni flow [38]. The
terrestrial results have to be explained on the basis of the dominating
Stokes sedimentation. Terminal velocity vs of spherical
inclusions with radius R due to gravity g, is:
2g ~p R2 "int +"ext
vs= - - -
3"ext ( 14)

~pbeing the difference in density between inclusion and surrounding

medium. Estimates [38] indicate that the migration rates observed
terrestrially are larger than to be expected due to Stokes transport
 371

(buoyancy). This means that Marangoni flow contributes

significantly on the ground as well to the migration of inclusions in the
system investigated.

Fredriksson [28J has also compared transport rates due to Marangoni flow
with Stokes sedimentation for bismuth droplets in a liquid zinc matrix
(Fig. 22). At a temperature gradient of 0.01°C/cm Marangoni transport is
comparable to sedimentation at 1O- 49. At larger gradients it may become
comparable to sedimentation under terrestrial conditions.

The importance of component separation due to Marangoni transport under

near weightlessness has been indirectly observed in a number of
experiments [30, 34, 38]. Just one example is shown in Fig. 23. The
sample, consisting of Aluminium with 7 wt% Bismuth was homogenized above
the critical temperature and then cooled and solidified under microgravity
conditions. The temperature gradients were directed radially towards the
center and the solidification front proceeded, therefore, from the
crucible walls towards the center. Under the influence of the temperature
gradient the bismuth droplets migrated towards the center, where a large
inclusion was formed. Due to their smaller Marangoni migration rate only
small inclusions were captured by the advancing solidification front. At
present this mechanism appears to be of greatest importance when
processing immiscibles under microgravity conditions. On earth it may be
of importance as well.

Coarsening processes in the system gallium-mercury were observed by Otto

[36J using X-ray transmission photography, which had a resolution of
0,2mm. Mercury concentrations ranged from 13 to 36 vol%. It was found that
a homogeneous dispersion is not achieved, the dispersed Hg-rich phase
tends to coalesce. In these experiments Marangoni transport was not
observed, although cooling rates up to 30 o K/min were applied.

Ahlborn and L6hberg [34] investigated the b~haviour of the monotectic

systems zinc-bismuth, zinc-lead and zinc-bismuth-Iead in a carefully
devised experiment focusing on the influence of volume fractions,
Marangoni transport and interfacial energies. The dispersions obtained
were rather inhomogeneous. The minority phase was transported to regions
of higher temperature due to Marangoni flow. Zinc-rich alloys yield finer
372

and more homogeneous dispersions, which is also tentatively explained as a

result of smaller Marangoni migration.

Os twa 1 d rip e n i n g, which is the isothermal coarsening due to

diffusion because of the dependence of vapour pressure or solubility on
the particle siz,e (curvative radius) is described by the theorY of
Lifshitz, Slyozow and Wagner. The study of Ostwald ripening of liquid-
liquid dispersions or dispersions of solid particles in a liquid matrix is
hardly possible on the ground since diffusion controlled conditions cannot
be realized because of sedimentation. Kneissl and Fischmeister [35] have
conducted experiments during the FSLP mission on Ostwald ripening of Zn-Pb
dispersions. Quench cast samples containing 2vol% to 5vol% Pb were
characterized in terms of particle size distribution (Fig. 24). They were
isothermally heat treated for 60 min under microgravity conditions at
temperatures within the miscibility gap and then solidified. The
dispersions remained homogeneous, which indicates that Marangoni transport
was negligible. Considerable coarsening of the Pb phase was observed in
all specimens (Fig. 24).

. ,··,.f
bfmrp
fllglht

50

40
I
;t
>- 30 --'~.
u
z
w
:::> I
0 20 ---I
w
...
cr

10 ----'

0,1 0,3 1 3 10 30
Pb DROPLET SIZE I pm I

Fig. 24. Frequency distribution of lead

particles in a zinc matrix before and
after isothermal treatment under
microgravity conditions [35J.
 373

The model on Ostwald ripening by Wagner, Lifshitz and Slyozow describes

the coarsening process as follows:

r(t)3 - r(0)3 = k.t.y (,) ( 15)

8a c on 2
k = 0
(16 )
9 RT

where
r(t) = mean particle radius after time t; •
a
phases, 90 - 100 mJ/m
2
= interfacial energy be ween the two liquid

= solubility of lead in molten Zn at 475°C, 2 w%.

n = molar volume of lead, 18 cm 3/mole
o = diffusion coefficient
R = gas constant (8.3 J/mole.K)
y (,) a function describing the increase of
coarsening rate with volume fraction of the minority phase.

By graphical evaluation of the data on the basis of eqn. 15 values for k

could be determined that correspond to a diffusion coefficient of Pb in
the Zn-rich melt of the order of 0 = 5.10- 5 cm 2/s. This agrees well with
known values and proves the feasibility of this approach. Further
experiments with longer and different heat treatment periods are in
preparation for the 0-1 and Eureca-1 missions. Oue to convective inter-
ference diffusion properties of fluids, i.e. heat and mass diffusivitY,are
extremely difficult to determine, errors are of the order of one
magnitude. Space environment may be the vehicle, by which these data can
be obtained much more precisely.

The i n t era c t ion 0 f i n c Ius ion s wit han a d van c i n g

solidification front in another mechanism to be considered
when analyzing coarsening processes and optimizing the experimental
conditions for the preparation of homogeneous, fine dispersions. These
interactions are also difficult to study on the ground. Isodensity systems
are practically not available and investigating thin, horizontally
oriented specimens still includes friction and sticking of inclusions to
the substrate. Theory describing these phenomena is not much advanced and
experimenta 1 data are needed for feedback. Understand i ng of these
interactions is also important for the preparation of hOOlogeneous fine
374

dispersions in alloys for technical applications and various groups have

started to investigate these phenomena.

14.5 Conclusions

Table II gives a summary of the more important mechanisms causing

coarsening and component separation with liquid-liquid dispersions. The
list of transport mechanisms by which an energetically stable equilibrium
configuration of a mixture could be achieved could be extended, however,
the ones mentioned have been shown to playa dominant role.

To summarize, it is clear that spinodal decomposition is not a feasible

approach to produce homogeneous compos i tes. 0 i spers ions fonned by
nucleation and growth of nuclei will only be homogeneous at low volume
fractions. Capi llarity phenomena playa dominant role in detennining the
equilibrium configuration under microgravity conditions. Transport of
inclusions due to Marangoni flow has been observed in various systems.
Therefore, temperature gradients have to be kept minimal during cooling
and solidification. One should consider investigating the influence of
added impurities that lower interfacial tension and eventually reduce
Marangoni flow. Ostwald ripening can be investigated under diffusion
controlled conditions and the interaction of the solidification front with
inclusions can be studied without the interference of sedimentation and
buoyancy.
 375

Table 11.

Mechanisms causing Coarsening and Component Separation during Formation

and Solidification of Dispersions

o Nucleation and growth

o Spinodal decompoSition
o Coalescence/agglomeration
o Capillarity phenomena
o Flow induced by shape changes or volume changes
o Marangoni convection
o Ostwald ripening
o Interaction with solidification front

Mechanisms virtually eliminated under Microgravity:

o Gravity-driven convection
o Sedimentation/buoyancy

14.6 References
1. Livingston, J.D., Journal of Applied Physics 39, 8,3836-3843 (1968)
2. Mordike, B.L., Z. Metallkunde, 65, 395-396 (1974).
3. Mott, B.W.: "Irrrniscibility in Liquid Metal Systems", J. Mat. Sci.,3,
424-435 (1968).
4. Gelles, S.H., Markworth, J.: "Microgravity Studies in the Liquid
Phase Irrrniscible System AI-In". 15th AIAA Conference, Los Angeles,
1977, Paper n° 77-122.
5. Ahlborn, H., Lohberg, K.: "Aluminium-Indium Experiment SOLUOG - A
Sounding Rocket Experiment on Immiscible Alloys"; 17th AIAA
Conferene, New Orleans, 1979. AIAA-paper n° 79-0172.
6. Predel B.: Z. Metallkunde 56,791 (1965)
7. Hilliard, J.E.: "Phase Transformations"; Am. Soc. Metals, Metals
Park Ohio, Chapter 12, (1970).
376

8. Jantzen, C.M., Hermann, H.: "Spinodal Decomposition - Phase Diagram

Representation and Occurence". Academic Press Inc., (1980).

9. Cahn, J.W., Charles, R.J.: Phys. and Chern. of Glasses, 6; 181-191

(1965) .

10. Cahn, J.W.: "Phase Separation by Spinodal Decomposition in Isotropic

Systems", J. Chern. Phys., 42, 93-95 (1964).

11. Seward III, T.P., Uhlmann, D.R., Turnbull, D: "Development of

Two-phase Structures in Glass, with special Reference to the System
BqO-Si0 2 ." American Ceramic Soc., 51 (11),634-643 (1968),

12. Predel, B., Arpshofen 1.: "lur Entmischung metallischer Schmelzen

unter besonderer BerOcksichtigung des Gravitationseinflusses "
Metallwissenschaft und Technik, 34, 5, 412-420 (1980).

13. Turnbull, D., Cech, R.E.: J. Applied Physics 21, 804 (1950).

14. Spaepen, F.: "Crystal Nucleation and Glass Formation in Metallic

Alloy Melts". Proceedings 5th European Symposium: Materials Sciences
under Microgravity, Schloss Elmau FRG, 215 ff, Nov. 1984.

15. Wenzel, J., Limbach, U., Beresonik G., Schneider G.M.: "Kinetics of
Phase Separation in Binary Liquid Mixtures", J. Phys. Chern. 84,
1991-1995, (1980).

16. Chattopadhyay, K., Ramachandrarao, P.: "Rapi d So Ii dfi cation and

Decomposition of a Hypomonotectic AI-Cd Alloy", J. Mat. Sci. 15,
685-692 (1980).

17. Sahm, P.R., Huk, W.: "Wissenschaft und Technologie der unterkOhlten
Schme lze", DGM-Hauptversamml ung, Aachen (1984).

,18. Haller, W.: "Rearrangement Kinetics of the Liquid-Liquid Immiscible

19. Beysens, D.: Stability of Critical Fluid Mixtures: Experimental

.
Phases in Alkali-Borosilikate Melts". Acta Met. 9, 686-690 (1961) •

Simulation of Microgravity Conditions. IAF Conference, Lausanne

1984, IAF paper n° 84-146.

20. Livingstone, J.D., Cline, H.E.: "Monotectic Solidification of Cu-Pb

Alloys" Trans. Met. Soc. AIME, 245, 351-357 (1969).

21. Pfefferkorn, R.: "Erstarrung monotektischer Schmelzen". Diss.,

Montanuniversitat Leoben, Feb. 1981.

22. Morgand, P., Potard C.: "Immiscible Alloys Experiment aboard Salyut
7: Results and Interpretation of AI-In Emulsions solidified in
Microgravity" , 25th COSPAR Conference, Graz, Austria, July 1984.

23. Langbein, D.: "Sounding Rocket Flight Test of an Acoustic Mixer by

Manufacture of a Pb-ln Emulsion Alloy in Microgravity", ESA-SP-191,
99-104. (1983).
 377

24. Bewersdorff, A., GorIer, G.P., Klein, H.: "Teilchentransport in

fluiden Medien unter reduzierter Schwere", Z. Flugwiss. Weltraum-
forschung, 5, 174-188 (1981).
25. Langbein, D.: "Theoret ische Untersuchungen zur Entmischung nicht
mischbarer Legierungen". Battelle-Institut Frankfurt, Report
BF-R-64.152-1, June 1980.
26. Langbein, D.: "On the Separation of Alloys exhibiting a Miscibility
Gap". Proceed i ngs of an RIT /ESA/SSC-Workshop , J1irva Krog, Sweden,
Jan. 1984. ESA SP-219, 3-13.
27. LOck, B. , Predel, B.: "Thennodynamics of the Decomposition of
Liquid Alloys".; ibid., 13-25.
28. Fredriksson, H., Space Results on the Solidification of Immiscible
Alloys; ibid, 25-36.
29. Fischmeister, H.F., Kneissl, A., Pfefferkorn, R., Trimmel, W.:
Solidification and Ostwald Ripening of Near Monotectic Zn-Pb Alloys
- Spacelab Experiment 1 ES 313; ibid, 41-42.
30. Walter ~ H.U.: Preparation of Di~persion Alloys Component
Separation during Cooling and Solidification of Dispersions of
Immiscible Alloys, ibid, 47-64.
31. Fischmeister, H.F., Exner, H.E.: Ostwald Ripening, Interfacial
Energies and Diffusion Coefficients in Monotectic Systems;ibid.~.
69-70.
32. Clancy, P.F., Heide W.: Acoustic Mixing of an Immiscible Alloy
(Pb-Zn) in Microgravity; ibid, 73-78.
33. Potard, C.: Filtration-Theory Approach to Immiscible-Alloys
Solidification; ibid, 79-82.
34. Ahlborn, H., LOhberg, K.: "Influences affecting Separation in
Monotectic Alloys under Microgravity". Proceedings of the 5th
European Symposium: Materials Sciences under Microgravity. Schloss
Elmau, FRG, Nov. 1984, 55-62.

35. Kneissl, A., F ischmei ster, H.: "Partic Ie Coarsening in Immi sc ible
Zinc-Lead Alloys under Microgravity"; ibid, 63-68.
36. Otto, G.H.: "Stability of Metallic Dispersions"; ibid, 379-388.
37. Gelles, S.H.: "Space Shuttle Experiments on AI-In Liquid Phase
Miscibility Gap Alloys"; ibid, 417-424.

38. Langbein, D., Heide, W.: "Entmischung von FHissigkeiten aufgrund von
Grenzfl 1ichenkonvekti on". Z. Fl ugw i ssenschaft und We I traumforschung ,
8,192-199 (1984).

39. Bergman, A., Fredriksson, H.: "A Study of the Coalescence Process
inside the Miscibility Gap of Zn-Bi Alloys". Material proceSSing in
the Reduced Gravity Environment of Space. Elsevier Publ. Inc.
(1982) •
378

40. Kneissl, A., Fischmeister, H.: "Solidification and Ostwald Ripening

of Near-Monotectic Zinc-Lead Alloys". Science, 225, 198-200 (1984).

41. Young, N.O., Goldstein, J.S., Block, M.J.: "The Motion of Bubbles in
a Vertical Temperature Gradient", J. Fluid Mechanics, 6, 350-356
(1959).

42. Langbein, D.: "Theoretische Untersuchungen zur Entwicklung nicht

mischbarer Legierungen". Battelle Inst. Frankfurt, Final Report,
01QV-558-AK-SN/A-SLN 7902-9, June 1980.

43. Langbein, D., Heide, ·W.: "The Separation of Liquids due to Marangoni
Convecti on". COSPAR Conference, Graz, July 1984. Advances in Space
Research, Vol. 4, 5, p. 27-36 (1984).
15 Crystal Growth
D T J Hurle

Gt. Mal vern,

Worcs, UK

Improved chemical homogeneity and structural perfection are the main goals
for crystal growth in space and the results of experiments in melt,
solution and vapour growth are reviewed. Future prospects and requirements
are indicated.

15.1 Introduction

The impetus behind experiments to grow crystals in space arises from the
expectation that such crystals will be structurally less defective and
chemically more homogeneous. This belief arose in the early days of the
NASA missions from the knowledge that turbulent convection was the cause of
dopant striations in crystals grown from the melt and from solution on
earth and that such convection would be absent in space. The production of
striation-free crystals was therefore anticipated but, at that time, the
importance of Marangoni convection was not appreciated and it is now known
that, in the presence of a free melt surface, time-dependent Marangoni flow
can arise and can generate striations in space-grown crystals also. The
high value of some of the more esoteric crystals being used by the
electronics industry led NASA to propose the manufacture of such crystals
in space [1) as an economically viable activity. However, this aspect has
received some criticism [2)

The principal effects of the micro-gravity environment on melt and solution

growth are:

1. The avoidance of all but very weak (laminar) buoyancy driven flow;

2. The absence of sedimentation of particulate matter

380

3. The absence of melt degassing

In addition there is an increased static stability of molten zones

(permitting use of the floating zone technique with materials of high
density and/or low surface tension) and the absence of stress in the
cooling crystal due to support of its own weight (which is of course
negligibly small in earth orbit). The absence of fluctuations permits more
careful control of supersaturation which may be of considerable importance
to the growth of low solubility materials. Further, weak laminar flow may
aid in the alignment of asymmetric molecules which may facilitate defect-
free crystallisation of complex molecular solids.

15.2 Space Relevant Growth Techniques

The technique most used for the production of a wide range of high
perfection single crystals on earth - the Czochralski technique - is not
deployable in a space environment depending, as it does, on the containment
of a melt by a crucible. (However, Wenzl [3] has suggested modifications
to the process which would make its use practicable.) The two most
exploited melt growth techniques are floating zone melting and the Bridgman
technique. The travelling heater method (THM) has been exploited for
semiconductor growth from metal solutions, Several configurations have
been deployed for aqueous solution growth. Vapour growth experiments have
been confined to closed tube transport methods. These several techniques
are now briefly reviewed.

15.2.1 Floating zone melting

The use of this technique has been pioneered by Professor Nitsche'.s group
at the University of Freiburg. They have used the mirror heating facility
(MHF) developed as part of the Materials Science Double-rack on Spacelab 1.

The furnace consists of a pair of ellipsoidal mirrors mounted in opposition

on a common axis with a common focus at which the sample to be crystallised
is located. At the other focus of each mirror are located 400W halogen
lamps. The rod sample (approximately 1cm in diameter) is mounted with its
axis orthogonal to the common mirror axis and it can be rotated about its
 381

axis. Zone motion is achieved by translating the mirror assembly relative

to the sample rod. The principal virtue of this equipment is its very high
thermal efficiency enabling temperatures up to 2000 0 C to be generated. Its
chief disadvantage from a crystal growth point of view is its lack of
radial symmetry in the thermal field.

During the Spacelab 1 mission two lcm diameter silicon rods doped with
phosphorus to 6xl0 18 cm- 3 were zoned.[4] The samples are shown in Fig.l. A
necking procedure was adopted to avoid dislocation propagation; this proved
very difficult to control and one of the experiments failed due to rupturing
of the zone in the neck region. The effective use of the video down-link
and good collaboration between the mission specialist and the scientist at
mission control ensured greater success of the second experiment.
Unfortunately partial freeze-up of the zone in the necking stage induced
polycrystallinity. This was due in part to the highly convex crystal-melt
interface shape which had been revealed on a preliminary experiment
performed in the TEXUS rocket programme. It did not, however, detract from
the significant result achieved by the experiment - namely, that the
pattern of solute striations (due to phosphorus concentration variations)
were very similar in earth and micro-gravity processed samples (Fig. 2).
This clearly suggests that the striations, both on earth and in space, were
the result of time-dependent Marangoni convection as has been demonstrated
in model experiments by Chun [5] and by Schwabe [6] and their co-workers.
This has been further proved in subsequent experiments on earth where
striations were eliminated by coating the melt surface with an inert
substance [4]. An unexplained difference between the earth and space-grown
samples was the absence of striations due to sample rotation in the space
environment.

The TEXUS single mirror lamp furnace was used by Carlberg [7] to grow
germanium crystals by the floating zone method. The rod samples were
contained in a quartz ampoule and platinum wir'es attached to it to permit
use of the current pulsing technique for interface demarcation [8] (The
(100) oriented samples were gallium doped to lxl0 18 cm- 3 .) Analysis of the
macro-segregation along the regrown crystal gave clear indication of
convective mixing which was in all probability surface tension driven, but
no evidence of solute striations of convective origin. (Striations in
certain parts of the crystal could be correlated with fluctuations in the
382

1. Float zoned silicon crystals

produced on Spacelab 1 [4]

A,B - earth-grown reference

samples

C,D - space-grown samples

2. Etched striation pattern on float zoned silicon crystals

a) space-grown; b) earth-grown [4]
 383

power control.) The relatively small zone size and low temperature
gradients associated with the high growth rate (SO-100um s-l) necessary to
complete the growth run within the short period of microgravity (approx. 6
minutes) are likely to have led to a significantly smaller value of the
Marangoni Number (Ma) as compared to that in the silicon experiments
described above and we may postulate that in the germanium experiments,
this value of Ma was below the critical value for the onset of time-
dependent flow.

Further corroboration of the above results was obtained on the Spacelab 1

mission by Kolker [9] who used the MHF to melt a droplet on the end of an
n-type doped (100) silicon rod. Rod translation was used to achieve
directional resolidification of the droplet. The recrystallised droplet
exhibited both rotational and "Marangoni" striations. However, the surface
of the melt suffered carbon contamination and more definitive results are
hoped for from the forthcoming Dl mission.

15.2.2 Bridgman Growth

Experiments to date have involved directional solidification of a number of

semiconductor materials in a variety of multi-purpose gradient furnaces.

Amongst the earliest are experiments on germanium, indium-antimonide and

indium-antimonide/gallium-antimonide alloys performed on Skylab [10]. In
experiment MSS9, a (Ill) oriented germanium sample doped with gallium was
partially melted and resolidified at a rate of Sums-I. Spreading
resistance measurements revealed that resistivity fluctuations were reduced
6-fold in the space-grown samples. Axial segregation indicated the
presence of residual convection which could have been surface tension
driven.

The same furnace was utilised by Walter to regrow a crystal of indium

antimonide (MS60) with a melt contained only by its own solid (Fig.3). The
shape of the regrown material is explained by the finite contacting angle
between the semiconductor and its melt [11,12]. Not explained were the
384

existence of quite marked solute striations.

Regrowth of indium antimonide was also performed on M562 but in this case
in a sealed quartz ampoule [13]. Tin and tellurium-doped samples had no
striations apparent on etched sections and the macro-segregation was
compatible with an effective distribution coefficient near unity. Marked
de-wetting of the molten indium antimonide from the ampoule wall was
evident, a consequence of the dramatic increase in the ratio of surface
tension to gravitational forces in space. The MIT group utilised the same
regrowth procedure on the ASTP mission [14] to obtain gallium doped
germanium crystals but with current pulsing to map the microscopic growth
rate. Again striations were absent except in the initial transient region
and the growth rate sequence closely followed that on earth grown samples
which had been oriented to minimise thermal convection.

Directional solidification of an indium antimonide-gallium antimonide alloy

melt was performed on M563 with a view to comparing defect structure in
alloys grown under conditions of constitutional supercooling [10].
Compositions of 50, 70 and 90% gallium antimonide were employed. Only
relatively minor differences were discerned between earth and space grown
ingots, though the twin density was somewhat lower in the space grown rods.
Compositional analysis indicated that some (weak) convective flow had been
present in the melt. Clearly, however, the micro-segregation effects
generated by constitutional super-cooling are not alleviated in space.

The favoured "model" materials - germanium and indium antimonide - have

also been studied by Soviet researchers on the Salyut-6 mission. Tellurium
doped and undoped Czochralski grown iI.dium antimonide samples contained in
graphitised quartz ampoules were partially melted and then directionally
resolidified at 3ums- l in the "Crysta~" multi-purpose furnace [15].
Resolidification was achieved by translating the sample rather than by a
power-down sequence, as in the Skylab experiment. Partial separation of
the melt from the ampoule wall occurred as in the Skylab experiments.
Single crystallinity was not obtained and the tellurium distribution along
the ingot was indicative of weak convective motion. Structural perfection
as indicated by dislocations and lamellar twin density was said to be
 385

3. Indium antimonide crystal

grown on Skylab 1
(H U Walter)

I,.,
POIYC'ytl

4. Principle of the
travelling heater
method [22]

groAn

's
crystal
sud ,~
386

superior in the space-grown samples.

Similar experiments were performed on germanium by Markov et al on the same

mission [16]. They also saw "relief mounds" indicative of crystal surface
out of contact with ampoule wall. They ascribed the observed enhancement
in crystalline perfection to the existence of the ridges and mounds on the
growing crystal surface which avoids tight contact between melt and
ampoule. Doping profiles were consistent with solely diffusive transport
when account was taken of the concave interface shape, which resulted in a
radial dopant concentration variation.

The "Crystal" furnace has also been used to grow tellurium-selenium alloys
[17] (with selenium concentrations varying from 0.1 to 50 atomic %) again
on the Salyut-6 mission. The conditions of resolidification were similar
to those deployed for indium antimonide and germanium. In this material
the crystal surface was characterised by a myriad of bubble holes due, it
was believed, to the rejection of dissolved gaseous impurities which, on
earth, escape from the melt due to their buoyancy. As might have been
anticipated, the more concentrated alloys exhibited cellular or dendritic
growth forms consequent upon a large degree of constitutional supercooling.

The solidification of self-levitated spheres of bismuth, tellurium, indium

antimonide and bismuth te lluride was undertaken by a joint French/Soviet
team [12] on Salyut-6. The molten spheres were positioned by support discs
which they wetted. Crystallisation of the four different materials was
achieved by a combination of sample translation and furnace cooling. Only
a limited structural examination of the samples was carried out but the
shape of the recrystallised spheres were studied and explained in terms of
the finite contact angle.

The directional resolidification of lead telluride in the gradient furnace

on Space lab 1 was successfully carried out in an experiment designed by Mme
Rodot [18]. Three samples, all slightly tellurium rich and doped with
silver to 10 19 cm- 3 were used; one unseeded, one seeded with a single
crystal seed and a third with a bi-crystal seed. The ampoule of the
 387

unseeded sample was found to be broken. As with the Soviet tellurium-

selenium samples, the surface of the ingots were covered in bubble holes
which were believed to be due to vapour generation. Whilst the seeding
attempts were not wholly successful due to ingress of melt past the seed
crystal, the degree of single crystallinity was higher in the space grown
samples than in the equivalent terrestrial ones. Additionally the cleavage
surfaces in the space samples were more perfect and flat, indicative of
higher structural perfection. Electro-chemical etching revealed a striated
distribution of the silver dopant in terrestrial samples which could not be
discerned in the space samples.

Cadmium mercury telluride was directionally solidified in joint

Polish/Soviet experiments on Salyut-6 utilising the SPLAV 01 furnace [19].
A polycrystalline charge of composition CdO.22HgO.78Te was used. The
properties of the regrown material depended sensitively on the rate of
growth and for a rate below 3mm per hour a homogeneous material was
obtained and the composition profile indicated that growth was diffusion
controlled.

Crystallisation of mercurious bromide dissolved in the eutectic melt with

mercuric bromide was performed in the MORAVA experiment jointly by czech
and Soviet workers [20] on Salyut-6. Also performed were experiments on
crystallising lead chloride from molten solution in silver chloride and in
copper chloride. As the indium antimonide and germanium experiments
described above had also shown, peculiar wetting conditions were obtained.
The habit of the mercurious bromide crystals differed in space as against
on earth. In microgravity, a rod-like shaped crystal was obtained whereas
the earth-grown ones had a plate morphology. Some porosity was evident in
crystals grown in both environments due to the high vapour pressure of the
components.

15.2.3 Growth from Metal Solution by the Travelling Heater Method (THM)

The travelling heater method has been identified as the most useful
technique for metal solution growth of semiconductors in space as it has
the potential to yield large crystals which are grown under clearly
388

definable and steady state conditions [23]. Two such experiments were
performed on Spacelab 1 and involved cadmium telluride and gallium
antimonide. Both experiments utilised the double ellipsoidal mirror
furnace as heat source.

In the gallium antimonide experiment [22] a 1cm diameter sample comprising

a (111) seed crystal, a 6mm long solution zone of gallium-3% antimony doped
with 6x10 18 cm- 3 tellurium and a feed rod was sealed in a quartz ampoule
(Fig.4). A low growth temperature of 530 0 C was chosen to simulate the
conditions which are used in industrial liquid phase epitaxy of this
material. Gallium antimonide was chosen as a representative III-V material
having the virtues of minimal volativity and toxicity. Unfortunately
instead of the planned 3.5mm of regrowth only some 200um were obtained due
to premature inadvertent shutdown of the experiment (the experiment is to
be repeated on the D1 mission). An additional problem that was encountered
was the wetting of the quartz ampoule by the molten gallium. It was
noticed that the crystal-solution interfaces were much more nearly planar
in the space processed sample in contrast to the case of the silicon
floating zone where very convex interfaces were obtained in space. There
was a marked reduction in the number and intensity of the tellurium dopant
striations (as revealed by etching) in the space sample and in the last
100um of growth none were visible. Moreover, sample rotation in the
azimuthally varying thermal field of the mirror furnace produced marked
"rotational" striations in the terrestrial samples which were barely
evident in the space processed ingot. This result can be explained by
hypothesising that the varying thermal field produces periodic
accelerations of the fluid through the effect of buoyancy on earth which
effect is, of course, largely absent in space. Hence, on earth the
thickness of the solute diffusion boundary layer is periodically modulated
resulting in striations in the growing crystal.

In the cadmium telluride experiment [23] (chosen as a representative II-VI

crystal) a similar configuration was employed with seed and charge
separated by a tablet of tellurium saturated with cadmium telluride. It
was important to avoid any free volume as this would fill with tellurium
vapour on melting the solution zone. Tellurium vapour spaces induce
unwanted vapour transport. The problem was overcome elegantly by melting
 389

the solution zone on earth and utilising a quartz piston to eliminate any
free volume. Unfortunately this experiment was also terminated prematurely
- in this case as a resul t of overheating of a mirror furnace lamp - and
only some 1.5mm of regrowth was obtained. Worse still, the safety shut-
down procedure caused the ingot to be quenched, resulting in multiple
cracking in the region of the solution zone. The dislocation etch-pit
density was found to be similar in the earth and space grown samples. The
technique for the avoidance of tellurium vapour bubbles proved most
successful. There was evidence of faceting at the dissolving crystal
interface. Striation studies are not possible with this material since
solid state diffusion coefficients are, in general, so large that any
grown-in micro-compositional variations would be smoothed out by diffusion
during the growth cycle.

The MHF proved to be less than ideal for both the THM experiments.
Problems of variation in the optical power reflected back into the lamp
filaments and in particular of positioning of the zone correctly in the
focus made adequate control of the starting conditions very difficult. (In
the terrestrial experiment, sagging of the lamp filament under gravity
presented a further problem.)

Gallium arsenide has been grown from gallium solution using thermal
gradient transport across an arsenic saturated molten gallium zone from a
polycrystalline feed rod to a (100) oriented single crystal seed [24].
Both undoped and heavily tellurium doped molten zones were used. Sample
diameter was 8mm and the temperature gradient in the liquid was 50 0 Ccm- 1
with a crystallising interface temperature of 800 0 C. A 48-hour growth run
on earth produced 0.8mm of regrowth, the material being polycrystalline.
The equivalent space grown crystal was some 3mm thick. Over those parts of
the interface where good wetting had been obtained, single crystalline
regrowth was obtained but with a few small disoriented crystals and some
gallium inclusions. Interestingly, clearly defined and very fine (less
than 10um) striations (which were curved and did not therefore delineate
faceting planes) were visible in the space grown tellurium doped sample;
these appeared to originate from the boundary of two disoriented crystals.
Dislocation density reflected the density in the seed crystal and was not
significantly lower in the space grown samples.
390

15.2.4 Growth from Aqueous Solution

The first experiments on crystal growth by precipitation from solution were

performed by Lind during the Skylab Science Demonstrations [25] where
crystals of Rochelle salt were grown.

Perhaps the most promising area of microgravity research into crystal

growth is the protein growth studies of Littke and John [26] aboard
Space lab 1. Single crystals of good quality and size are a prerequisite to
the X-ray structure determination of bio-crystals and hence are a subject
of considerable potential importance. Such crystals can be grown by
simultaneous counter diffusion of a protein solution and a salt solution
into a buffer solutio~ However, the markedly different densities of the
solutions resulting from the high molecular weight of the protein generates
turbulent convection in the mixing zone on earth, leading to multiple
nucleation and a large number of small, and rather imperfect, crystals. To
overcome this gels have been employed to contain the buffer solution in
order to suppress the turbulence. However, the fragile protein crystals
are damaged and hindered in the extent of their growth by the presence. of
the gel. Space therefore offers the promise of avoiding turbulent mixing
without use of a gel. The ingenious cam operated device employed in
Space lab 1 is shown in Fig.5. The apparatus is fabricated from plexiglass
and consists of 4 pairs of protein solutions and salt solutions juxtaposed
but separated by a cam driven sliding strip. Operation of this cam
interposes a volume of buffer solution between the sal t and the protein
solutions. In preliminary experiments on a TEXUS flight the diffusion
process was studied using schlieren optics and it was demonstrated that a
strictly laminar diffusive process occurred. The width of the diffusion
fronts could be varied by varying the width of the slot containing the
buffer solution (see Fig.5). A surprising resul t of the TEXUS experiment
was that, although the microgravity condition obtained for only about 6
minutes, nucleation and growth of several crystals (of beta-galactosidase)
occurred to a degree which would have taken several days on earth. Littke
and John state [27] that it is plausible that under conditions free of
turbulence, pre-ordered clusters of protein molecules can aggregate more
readily than under the turbulent conditions that pertain on earth, thus
 391

5. Schematic
representation
of the protein
crystal growth
facility on
Spacelab 1 [26]

6. Single crystal of Beta

galactosidase grown on
Spacelab 1 [26]

7. X-ray topograph of single

crystal of brushite grown on
Spacelab 1 [28]

The high dislocation density

skin formed during re-entry.
Growth bands and only a very
few dislocations are evident
in t he crystal interior

0.\50...
392

leading to more rapid growth.

Two proteins of very different molecular weights were chosen for the
Spacelab experiment; the first was lysozyme - a well-characterised low
molecular weight (14307) protein whose structure has been known for a long
time and which is available in high purity. The second chosen was
beta-galactosidase (molecular weight 465000) which had been carefully
purified by ion exchange and chromatographic techniques. It is a very
important enzyme in genetic studies whose structure has yet to be fully
determined. Preliminary results are as follows: because the diffusion of
the protein is very much slower than that of the salt, crystallisation took
place actually in the protein solution chamber. The quality of the
crystals as judged visually and in polarised light is very good and their
volume is some 27 times greater (beta-galactosidase) and some 1000 times
greater (lysozyme) than those obtained in the terrestrial experiments. The
beta-galactosidase crystals were rod-shaped and typically 0.6xO.06xO.06mm3
(Fig.6). The conditions favouring growth of large crystals were a wide
diffusion front and an applied temperature gradient. Crystals which were
free-floating and had not contacted the chamber walls exhibited perfect
habit. Further experiments are planned on the D1 mission with mercury
substitution.

A similar experimental configuration (but with a different method for

providing a connection between the 3 solutions) has been used to grow
several insoluble materials by precipitation from two interdiffusing
solutions. Robert, Lefaucheux and Authier [28] chose brushite (CaHP0 4 2H 20)
and lead monetite (PbHP0 4 ) for their experiments on Spacelab 1 because of
the relatively high growth rate (necessitated by the relatively short
experiment time) and the platelet habit which made the crystals suitable
for X-ray topographic characterisation. Turbulent convection on earth
produces local fluctuations in supen-saturation which can introduce
parasitic nucleation, precipitates, liquid inclusions and growth bands.

Brushite was obtained by counter-diffusing Ca(N0 3 )2 and NH 4 H 2 P0 4 into a

central volume of water and lead monetite similarly using solutions of
Pb(N0 3 )2 and H3 P0 4 • By this means a steady increase in super-saturation
 393

was obtained until after several days, nucleation occurred and a relatively
few crystals then grew with linear dimensions up to 5mm. These nucleated
crystals were found to be substantially free of dislocations except in the
surface layer which grew during re-entry (Fig.7). However, the crystals
did contain some growth bands and these are being studied in the hope that
their origin can be established and means for avoiding them devised.

The counter-diffusion technique has also been employed with other insoluble
materials by Lind and Nielsen and their co-workers, initially on ASTP [29]
and latterly on Space lab 1 [30]. The growth of crystals of calcium
tartrate and calcium carbonate has been demonstrated. On Space lab 1 it was
originally planned to study the growth of the important low dimensional
organic material TTF-TCNQ (a prototype material for studies of the
possibilities for relatively high temperature super-conductivity) but at a
late stage in planning, the experiment was rejected on the grounds of the
toxici ty of the chosen sol vent - acetonitrile. The growth of platinum-
complex crystals of the type (NH4)1.6Pt(C204)2 was substituted but
unfortunately the prolonged waiting period before launch resulted in
chemical disintegration of the complexes and useful results were not
obtained. Fortunately, however, the TTF-TCNQ experiment has gone ahead in
the collaborative experiment between Lind and Nielsen in the NASA LDEF
mis s ion [31].

15.2.5 Vapour growth

Experiments by Wiedemeier on Skylab (experiment M556) received early

prominence [32]. In this experiment, germanium selenide and germanium
telluride crystals were grown by closed tube vapour transport in germanium
iodide carrier gas. In terrestrial experiments, where convective transport
was believed to be dominant, the growth ~as dendritic with distinct
curvature of the dendrites. In microgravity, however, well-developed
single crystal (100) oriented platelets of up to 4x8mm2 were obtained.
Etchpit studies suggested a markedly lower dislocation density in the space
grown crystals. Observed growth rates in space were between 4 and 10 times
greater than predicted by diffusive transport alone and adequate
explanation for this has yet to be obtained. The experiments were
continued [33] aboard ASTP and STS7 with germanium selenide and solid
394

solutions of germanium telluride and selenide and germanium sulphide and

selenide transported using germanium iodide or chloride with or without the
addition of argon. The prime objecti ve was to study the homogeneity and
perfection of the solid solution crystals. The ground based samples
exhibited significant plastic deformation and residual strain which was not
apparent in the space grown crystals. The anomalously high growth rates
were again confirmed.

Despite this early interest in vapour growth in space, few other

experiments have been performed. Cadoret [34] grew crystals of mercuric
iodide by physical vapour transport in a sealed ampoule using a low
temperature heat-pipe furnace aboard Spacelab 1. He found a much lower
density of nucleii in the space grown samples and a large single crystal
(4.Sx4.Sx3.Smm 3 ) was obtained. The growth rate in the space sample was
lower than that in the terrestrial sample by a factor of 1.5. The
experimenter inferred that convection remained in the earth's sample, even
down to pressures of 10- 2 torr of argon. Increasing the pressure to 10-
1torr led to an increase in the density of nucleii in both space and
earth grown samples.

Closed tube vapour transport of cadmium mercury selenide and lead selenide
telluride alloys was performed [15] on Salyut 6. X-ray studies of the
structural perfection and EDAX measurements of the compositional
inhomogeneity in these two materials indicated that the sublimation
conditions were approximately the same in space as on earth.

15.3. Discussion

It is clear from the consideration of the floating zone and Bridgman

results that time-dependent thermo-capillary convection is a potent source
of solute striations in space grown crystals but that, if a free melt
surface is avoided, striations are eliminated and the observed macro-
segregation is indicative of near-diffusive transport. This does not,
however, mean that there is no macro-segregation as this can arise a) from
an initial transient where the final (steady state) boundary layer is
building up and b) radial and axial segregation, due to the non-planarity
 395

of the crystallising interface. The situation in metal solution growth is

less clear. Some residual striations were evident in both the Franco-
Soviet experiment on gallium arsenide and in the gallium antimonide
experiment of Benz and Nagel [22]. What is clear, however, is that space
processing does not remove or alleviate the problem of interface breakdown
caused by constitutional super-cooling as both the indium-
antimonide/gallium antimonide and the tellurium/selenium experiments show.
Overall, therefore, the apparent benefits from melt and metal solution
growth processing in a spacecraft are somewhat limited. However as a
laboratory environment for studying the subtle effects produced by the
interactions of diffusive flows with morphological instabilities and
surface tension effects the spacecraft is unique.

The utility of the space environment for aqueous solution growth of

insoluble or high molecular weight materials is more exciting with
increased perfection and increased crystal size already demonstrated in the
experiments of Robert et al [28] and of Littke and John [26]. These are
classes of materials which prove difficult to grow adequately under
terrestrial conditions. The protein crystal growth looks particularly
promising. Vapour growth in space has been little explored to date. The
anomalously high growth rates observed by Weidemeier [32] demand
explanation.

15.4. Future Potential

It is pertinent to ask what should be the main thrusts of future crystal

growth activity in space. One can identify three branches, namely:

1. Basic research

2. The production of samples for earth based research

3. The manufacture in space of crystals for sale and use on earth

The only significant feature of the space environment is micro-gravity and

the most important effect of micro-gravity is the dramatic reduction in the
degree of buoyancy driven convection. Secondary effects, such as the
396

absence of sedimentation and melt de-gassing, are irritating difficulties.

Whilst the absence of sample weight makes container less processing more
readily possible, the lack of confinement of a fluid by a container limits
the number of techniques which can be deployed.

The subtle ways in which buoyancy driven convection interact with the
growth process - with other forms of flow (eg thermo-capillary convection
or forced rotational flows) and with the dynamics of the crystallising
interface and with capillary forces - can be studied in space under
conditions which cannot be reproduced on earth. In the present writer's
view the work done to date on the various orbital and sounding rocket
missions amply justifies a programme of basic research i.n this field.
Moreover other work, and particularly the protein growth, shows
significant promise for the provision of samples for earth-based research
which could not be obtained in the necessary quality using terrestrial
processes. However, the viability of space manufacturing still appears
extremely doubtful and We should note the advice given by Fritis and
Byroade [35] that "if there is one over-riding message that we have, it is
that we must exercise patience and resist high, short-term expectations.
Overall we are still in a very embryonic stage of space manufacturing and,
if it is ever to come, as we believe it will, reaching full maturity is
still many years away".

If the emphasis is still to be on basic research we must enquire what are

the facilities required for that research. Such research is rather long
term and is not made any easier by being performed in the space environment
but it has the potential to benefit earth manufacturing processes
significantly. Its long-term nature makes it particularly appropriate to
University departments and for it to be nurtured it requires funding which
is separate from that used to support earth-based research for it is
improbable that space research can be made 'cost-effective in monetary terms
when judged against the likely returns from the investment of an equivalent
sum of money on earth-based research. However, for it to attract
researchers of ability and experience it is vital that it be cost-effective
in terms of the investment in time of the researcher. This requires a
streamlining of procedures and reduction in bureaurcracy. Up to the
present researchers have had to be content with the results of usually
 397

single experiments performed only after many years of planning and waiting.
The establishment of a micro-gravity laboratory as part of a space-station
complex in the mid-1990s will, however, change the situation radically. A
significant increase in the number of scientists working in the field will
be needed if a continuous programme of effective research is to be
sustained.

Further development in hardware will be necessary and in particular

improvement in hardware reliability, which has not always been adequate.
New tools, such as holographic techniques and sophisticated new growth
equipment like the French MEPHISTO project, will need to be developed. A
high level of preparatory ground-based research will remain vitally
important. Several basic technical requirements need to be continually
addressed. The first of these is the provision of heating power - and its
dissipation. To be really useful programmes need to encompass real
practically useful high melting point materials and not just low mel ting
point "model" systems. The scale of any future manufacturing activity in
the crystal growth field is likely to be limited by the availability of
adequate power sources.

The second basic requirement is the control of the micro-gravity

environment. Theoretical studies suggest that it is at low temporal
frequencies that the effects of micro-gravity on crystal growth are most
severe and this makes demands on the control of the orbit. Random and
uncontrolled accelerations ("g- jitter") can also inval idate the resul ts of
carefully designed experiments and this brings into question the role of
manned versus unmanned missions. The vital role of mission specialists, in
coping with unexpected situations - in particular equipment failures - has
already been demonstrated on a number of missions. However, there are some
cases where fully automated experiments can an'd should be designed where
the additional freedom from "g-jitter" provided by an unmanned mission is
requi red. It is the uncontrolled nature of the g vector - both in
magnitude and direction - which can vitiate the results of an experiment
and it would be highly desirable if a controlled micro-gravity environment
could be provided with, say, a well specified vector of magnitudes 10-3,
10- 2 and 1O- 1 g.
398

Finally, mission time can be an important parameter, particularly in

solution growth experiments where growth rates are very low. The typical
duration of the Shuttle mission (approx. 7 days) is inadequate for some
such experiments and for such experiments the longer mission time provided
by unmanned missions (such as EURECA) and the manned space-station will
become important.

15.5. Conclusions

Gravity is but one of many parameters which controls the process of crystal
growth. It is nonetheless an important but perhaps not the most important
one and the need to evaluate its effects justifies for crystal growth
research a place in any micro-gravity research programme. The fruits of
such research are likely to have a significant impact on earth-based
technology. Further, the space environment offers the possibility of
producing materials (needed for earth based research) which cannot be
obtained by terrestrial processing in the size or quality which is
required.
 399

REFERENCES

1. Bredt, J.H.; Processing and Manufacturing in Space. Proc. Frasc'ati

Symposium 205 (1974); ESRO SP-101 July 1974.

2. Material Processing in Space, NRC Committee Report. National Academy

of Sciences, Washington DC. 1978.

3. Wenzl, H.; Material Sciences in Space with Application to Space

Processing. Ed. Leo Stag. Prog. in Astronautics and Aeronautics. 52
(1977) 437-445.

4. Eyer, E., Leiste, H. and Nitsche, R.; Proc. 5th European Symposium on
Materials Science in Microgravity. Schloss Elmau, Nov. 1984. ESA SP-
222 1984.

5. Chun, Ch.-H.; J. Crystal Growth 48 (1980) 600-610.

6. Preisser, F., Schwabe, D. and Scharmann, A.; J. Fluid Mechanics 126

(1983) 545-567.

7. Carl berg, T.; Proc. 5th European Symposium on Material Sciences in

Microgravity, Schloss Elmau. Nov. 1984, 367-373. ESA SP-222.

8. Witt, A.F., Lichtensteiger, M. and Gatos, H.C.; J. Electrochem. Soc.

121 (1974) 787-790.

9. Kolker, H.; Proc. 5th European Symposium on Material Sciences in

Microgravity, Schloss Elmau, Nov. (1984) 169-172. ESA SP-222 1984.

10. Lundquist, C.A.; Processing and Manufacturing in Space. Proc. Frascati

Symposium, March 1974, 19-26. ESRO SP-101 1974.

11. Hurle, D.T.J.; Adv. in Colloid Interface Sci. 15 (1981) 101-130.

12. Rodot, H., Hamidi, M., Bourneix, J., Okhotin, A.S., Zoubridski, I.A.,
Kriapov, V.T. and Markov, E.V.; J.Crystal Growth 52 (1981) 478-484.

13. Witt, A.F., Gatos, H.C., Lichtensteiger, M., Lavine, M.C. and Herman,
C. J.; J. Electrochem. Soc. 122 (1975) 276-283.

14. Witt, A.F., Gatos, H.C., Lichtensteiger, M. and Herman, C.J.; J.

Electrochem. Soc. 125 (1978) 1832-1840.

15. Khashimov, F. R.; Proc. 3rd European Symposium on Material Sciences in

Space, Grenoble, April 1979, 9-15. ESA SP-142, 1979.

16. Markov, E.V. et al. ibid 17-23.

17. Ignatev, G.E., Okhotin, A.S. and Avraamov, Yu. S. ibid 33-39.

18. Rodot, H. and Tottereau, 0.; Proc. 5th European Symposium on Material
Sciences under Microgravity, Schloss Elmau, Nov. 1984. 135-139. ESA
SP-222.

19 •. Galazka, R.R. et al; Proc. 3rd European Symposium on Material Science

in Space, Grenoble; April 1979. 47-51. ESA SP-142 1979.
400

20. Barta, C., Trnka, J., Triska, A., Khrjapov, V.I., Ochotin, A.S. and
Zubrickij, I.A.; ibid 215-219.

21. Benz, K.W.; Processing and Manufacturing in Space. Proc. Symposium

Frascati, March 1974. 163-169. ESRO SP-I0l 1974.

22. Benz, K.W. and Nagel, G.; Proc. 5th European Symposium on Material
Sciences under Microgravity, Schloss Elmau. Nov 1984. 157-161. ESA
SP-222 1984.

23. Schonholz, R., Dian, R. and Nitsche, R.; ibid 163-167.

24. Rodot, H., Guillaume, J.C., Chevallier, J., Boulou, M., Kriapov, V.T.,
Kashimov, F.R., Markova, T.I. and Zoubridski, I.A.; Physica 116B
(1983) 168-176.

25. Ostrach, S.; Processing and Manufacturing in Space. Proc. Symposium

Frascati, March 1974. 11-18. ESRO SP-I0l 1974.

26. Littke, W. and John, C.; Proc. 5th Symposium on Material Sciences
under Microgravity, Schloss Elmau. Nov 1984. 185-188. ESA SP-222
1984.

27. Littke, W. and John, C.Z.; Flugwiss. Weltraumforsch 6 (1982) 325.

28. Robert, M.C., Lefaucheux, F. and Authier, A.; Proc. 5th Symposium on
Material Sciences under Microgravity, Schloss Elmau, Nov 1984. 193-
199. ESA SP-222 1984.

29. Lind, M.D.; Crystal Growth Expt. MA-028, Apollo-Soyuz Test Project
Summary, Science Report NASA SP-412 (1977) 555.

30. Galster, G. and Nielsen, K.F.; Proc. 5th European Symposium on

Material Sciences under Microgravity, Schloss Elmau, Nov. 1984. 189-
191. ESA SP-222.

31. Lind, M.D. and Nielsen, K.F.; Proc. 4th European Symposium on
Material Sciences under Microgravity, (1983) 167. ESA SP-191.

32. Weidemeier, H., Klaessig, F.C., Irene, E.A. and Wey, S.J.; J. Crystal
Growth 31 (1975) 36.

33. Wiedemeier, H., Sadeek, H., Klaessig, F.C. and Norek, M.; ASTP
Preliminary Science Report 27, NASA TMX-58173 Feb. 1976.

34. Kaldis, E.; Proc. 5th European Symposium on Material Sciences under
Microgravity, Schloss Elmau. Nov. 1984. 439-451. ESA SP-222 1984.

35. Fritts, E. and Byroade, A.; Proc. 3rd, European Symposium on Material
Sciences in Space, Grenoble. April 1979. 427-432. ESA SP-142 1979.
16 Fluid Dynamics
Dieter Langbein

Battelle-Institut e.V., Frankfurt am Main,

Federal Republic of Germany

The essential differences between material sciences experiments

in a laboratory on ground and in a microgravityenvironment re-
sult from fluidstatic and fluiddynamic or convective effects.
With the numerous implications of fluid physics on topics like
casting, separation of immiscible alloys, and crystal growth
being discussed in the preceding chapters, this chapter is de-
voted to the more basic phenomena capillarity, flow mechanics,
wetting and spreading, and interface convection.

16.1 Capillarity

There is, firstly, the field of capillarity. It is concerned

with the shape of liquid interfaces. It may be the shape ~f a
liquid drop, which may be sessile on or hanging at a solid sur-
face (Fig. 16.1), or else is freely falling or levitated. In
addition, it may rotate or be polarized by an e~ternal electric
field. A well-known example for a rotating drop, which later
has partly solidified, is the earth. As a result of rotation it
is slightly oblate at the poles. Other configurations of much
interest are liquid bridges between parallel plates, between
circular disks or between spheres. Liquid bridges between cir-
cular disks occur during crystal growth by the zone melting
method. Liquid bridges between spheres are used as model sys-
tems for the wetting of porous systems.

The shape of liquid surfaces and of the interfaces between two

liquids is generally given by the balance between surface ten-
sion, curvature, and pressure. The surface tension tries to
contract areas with convex curvature, the pressure works
against that. This balance is represented by the GauB-Laplace
equation [16.1 J
402

p (16.1)

where a is the surface tension, r1 and r2 are the main radii of

curvature, and p is the pressure. An equilibrium of forces cor-
responds to a minimum or, more generally, to an extremum of the
energy. A solution of the GauB-Lap1ace equation represents an
extremum of the liquid energy, which is made up by its poten-
tial energy and its surface energy.

Under earth's gravity, together with the f1uidstatic pressure

within a drop its curvature decreases with increasing height.
This causes the typical shape of the sessile and hanging drops
shown in Fig. 16.1. If the drops are immersed in a second,
heavier liquid, the exterior pressure gradient is stronger than
the interior, and the opposite variations in shape apply. Under
microgravity, there is no up and down, the drops are neither
sessile nor hanging. They are spherical and just supported by
the solid. Whereas on ground sessile and hanging drops are
always limited in volume, there is no such limitation under
microgravity. Drops of practically any size may be established.

The sessile and, hanging drops shown in Fig. 16.2 contact the
solid under angles of a = 150° and a =30°, respectively. Such
a change in contact angle is possible by either using different
liquids, different solids, or surface coatings. The contact
angle a between a solid 1 and the interface between two liquids
2 and 3 (one of which may be a gas) is generally given by the
equilibrium between the tangential components of the interface
tensions,

(16.2)

This equation is known as Young's formula (see also Chapter 6,

Fig. 6.14). If medium 1, rather than being a solid, is liquid
also, the sectors a 1 , a 2 , a 3 at the contact line, which are
 403

f-l9
V'p=O

Fig. 16.1: Fig. 16.2:

Hanging and sessile drops Hanging and sessile drops with
under earth's gravity (lg) increasing liquid vo1ume~
and microgravity (pg) --'--'-'maximum stable volume
- - - - unstable hanging drops

19

Vp=O

Fig. 16.3: Fig. 16.4:

Liquid bridges between co- The asymptotic shapes of liquid
axial circular disks bridges between coaxial circular
under earth's gravity (lg) disks in the limits of low and
and microgravity (pg) high Bond numbers
404

occupied by liquids 1, 2, and 3 arrange such that the directed

interface tensions add up to zero

o (16.3)

This condition is known as Neumann's equation.

If more liquid is added to the sessile drop shown in Fig. 16.1,

it widens. If more liquid is added to the hanging drop, it
lenghtens, see Fig. 16.2. Later a neck arises, which rapidly
slenders and eventually breaks. There exists a maximum to the
liquid volume of a hanging drop. A well-known method of deter-
mining the surface tension of a liquid consists in measuring
the volume of the resulting falling drops. This breaking of
drops, however, is not actually covered by the GauJ3-Laplace
equation. The latter results from equating to zero the first
variation of the liquid energy with respect to all surface de-
formations, which maintain the liquid volume. It does not take
into account whether this deformation describes a minimum, a
saddle point or a maximum of the liquid energy. Only inter-
faces, which represent a minimum with respect to all allowed
deformations, are stable. The second variation of the liquid
energy must be positive definite.

16.2 Stability

This stability criterium applies to all kinds of liquid sur-

faces. Fig. 16.3 shows liquid bridges with equal liquid volume
between coaxial circular disks. Under microgravity the fluid-
static pressure within the liquid is constant, Fig. 16.3b. By a
proper choice of liquid volume and disk separation a cylindri-
cal bridge results. Fig. l6.3a shows the same liquid bridge on
ground. Due to the fluidstatic pressure the curvature of the
liquid increases from the top to the bottom.

The stability of liquid bridges on ground is governed by the

gain in gravitational energy, when the liquid volume in the
lower half increases. In Fig. l6.3a this decrease in potential
 405

energy is still balanced by the increase in surface energy,

which results from the enlarged and reduced bridge diameters in
the lower and in the upper half, respectively. Again, with in-
creasing liquid volume or density or with decreasing surface
tension the latter can not balance the fluidstatic pressure any
more. The liquid bridge becomes unstable. This is convenient-ly
expressed by the Bond number

B (16.4)

where g is the gravity constant, p the density of the liquid, H

the height of the bridge and rr the surface tension. The criti-
cal Bond number Bcrit for liquid bridges between coaxial circu-
lar disks with radius R has been shown to be [16.2, 3J

Bcrit 3.6693 2 for R »Vrr/gp (16.5)

and

Bcrit = 24 R/H for R < < v7iT<iP (16.6)

Fig. 16.4 shows the shape of the liquid bridges resulting in

these limiting cases.

The axisymmetric solutions of the GauB-Laplace equation under

microgravity can be represented by complete elliptic integrals.
Solutions are periodic unduloids with a wavy surface (Fig.
l6.5a) and periodic nodoids, which intersect their own surface
(Fig. 16. 5b, c). For both types of surfaces it can be proved
that they are stable only if their height does not exceed a
single period. Otherwise, they break antimetrically in the
middle, i.e. one half widens and the other half narrows corres-
pondingly. This instability is called Rayleigh instability.
Lord Rayleigh proved as early as 1879 that a cylindrical liquid
jet becomes unstable if its length exceeds its circumference
[16.4]. The cylindrical liquid bridge is distinguished among
the class of unduloids by equal minimum and maximum radii.
406

/
/ .
/ /
//
Ii;
I

Fig. 16.5: Undu10ids (a) and nodoids (b, c) with varying

minimum radius and constant maximum radius

0.2
3

c) jumping rope

0)
8

\
M
b) two nfdes

.
I
i
RI/R 2 0 RI/R I 0 RIIR 2

Fig. 16.6: The stability limits of rotating liquid bridges.

The parameter shown is the Weber number W =pw 2 R3ja.
(a) The first antimetric instability
(b) The symmetric instability exhibiting two nodes
(c) The jumping rope instability
 407

The intermediate surface between the sets of unduloids and of

nodoids with constant maximum radius is a periodic series of
coaxial spheres. The intermediate surface between the sets of
unduloids and of nodoids with constant minimum radius is a
catenoid (a rotated catenary), which is distinguished by zero
fluidstatic pressure. Its convex, positive curvature around the
symmetry axis is balanced by the concave, negative curvature in
the meridian plane.

The catenoid becomes unstable, if its height H exceeds 2.2392

times its minimum diameter 2Rl' However, in contrast to the un-
stable deformations discussed so far, the unstable deformation
of the catenoid is symmetric with respect to the centre cross-
section and exhibits two nodes [16.5]. The symmetric instab-
ility with two nodes also dominates in the case of unduloids
and nodoids with small neck radii. Fig. 16.6 shows the stab-
ility diagrams for liquid bridges with height H, disk radius R
and minimum radius Rl' Fig .16. 6a represents the instability
with respect to the antimetric deformation with one node in the
centre cross section, Fig. l6.6b the instability caused by the
symmetric deformation with two nodes. Parameter of the differ-
ent curves is the rotational Bond number, the Weber number

W (16.7)

where w is the circular frequency of rotation.

The antimetric instability with one node intersects the set of

cylindrical bridges, which are distinguished by the minimum
radius Rl = R, at H/2R = 7r. This is the Rayleigh instability.
The symmetric instability with two nodes requires cylindrical
bridges with height H/2R = 4.4934. For, cylindrical bridges it
is always suppressed by the faster anti~etric instability. How-
ever, for bridges exhibiting a small neck radius Rl' the sym-
metric instability dominates. The cross-over point of both in-
stabilities for zero rotation is at H/2R = 2.1323, Rl/R =
0.4184. The respective unduloid may alternatively break accord-
ing to either of both instabilities.
408

With increasing frequency of rotation both instabilities arise

at liquid bridges of lower height H. The stability limit of
cylindrical bridges gets reduced according to [16.6]

H =2 7r R /-vr+W (16.8)

There are, on the other hand, liquid bridges not becoming un-
stable at all. This are bridges of a light liquid imrriersed in a
heavy liquid. In that case the density P in all preceding equa-
tions, which is actually the density difference between the
inner and the outer liquid, becomes negative. According to Eq.
(16.8), such a cylindrical bridge is stable for arbitrary
height, i f W :::;; -1.

16.3 Microgravity Experiments on Liquid Bridges and Drops

Investigations of rotating cylindrical bridges during the Sky-

lab mission in 1973 have shown the existence of a further in-
stability [16.7, 8]. This are the C-modes or jumping rope .in-
stabilities, see Figs. 16.6c and 16.7. The jumping rope modes
are particularly important with liquid bridges exhibiting a
belly rather than a neck. A rotating cylindrical bridge becomes
unstable with respect to the jumping rope deformation before it
breaks, if

W > 1/3. (16.9)

The stability limits discussed here are fluidstatic in nature.

They can be calculated by transforming to main axes the second
variation of the liquid energy. If one eigenvalue becomes zero
or negative, the corresponding deformation increases rather
than to decrease exponentially in time: it is unstable.

Under microgravity, it is possible to establish really large

liquid drops and bridges and to study their shape, vibrations
and stability. In view of this, the Drop Dynamics Module (DDM),
the Fluid Physics Module (FPM), and several sounding rocket
facilities have been developed, see Section 11.3
 409

Fig. 16.7 exhibits jumping rope modes, Fig. 16.8 shows the
shape of a bubble in a liquid container, which has been spinned
up in the FPM during the Spacelab-l mission.

Large liquid bridges are a promising tool for studying the

variation in surface tension due to a nearby solid, see Fig.
16.9. They amplify such a variation particularly, if they are
chosen close to a stability limit. The surface tension of a
liquid is due to the energy, which the surface molecules loose
by leaving the interior of the liquid. They loose the van-der-
Waals attraction by about one half of the molecules. Since this
attraction usually has a range just below a micron, only liquid
layers of at least that thickness may exhibit the normal inter-
face tension. The measurement of long-range van-der-Waals for-
ces on thi~ basis is the idea underlying the Spacelab-l and
Spacelab-Dl experiments by Padday [16.9).

What the Fluid Physics Module is for liquid bridges, is the

Drop Dynamics Module for liquid drops. It has been successfully
operated by Wang, the Principal Investigator, during Space-
lab-3. Apart from the scientific interest in liquid drops them-
selves, they are expected to provide highly interesting models
for nuclear, geo- and astrophysics as well.

Fig. 16.10 shows the shapes of freely rotating liquid drops.

Wi th increasing frequency W of rotation they become more and
more oblate. For W/8 > 1, they develop a dimple at the poles.
For W/8 = 2.3291 the poles touch each other in the centre. It
has been shown by Chandrasekar [16.10], that the stability
limit is given by W/8 0.4587. In addition, there exist
several unstable toroidal shapes of rotating drops (see also
Fig. 11.3).

16.4 Dynamic Models

Small amplitude vibrations of droplets have first been de-

scribed by Lord Rayleigh. For the circular frequencywn of the
vibration exhibiting n modes he derived [16.11)
410

Fig. 16.7: Jumping rope modes observed during the Spacelab-l

mission (courtesy of I. Martinez)

Fig. 16.8: The shape of a bubble in a liquid container,

(a) during rest (b) during spin-up (courtesy of J.P.B. Vreeburg)

rear
end plate

ideal catenoid shape

zone of thIckenIng
used to measure

front end plate

Fig. 16.9: The perturbation of a catenoid due to van-der-Waals

attraction by a nearby solid [16.9]
 411

(16.10)

This equation has later been extented to the vibrations of

drops immersed in a second liquid. In that case one has [16.12]

(16.11)

However, very little is known about large drop and bridge

vibrations [16.13, 14]. In this case the usual pertubation
theory is no longer applicable and a consistent theoretical
model of flow mechanics and surface deformation is required.
The Navier-Stokes equation and the GauB-Laplace equation must
be solved simultaneously. Lee [16.15] and later Mesequer et al.
[16.16, 17] developed a slice model for liquid bridges, which
assumes a uniform distribution of the kinetic energy onto a
radial cross-section.

An even simpler
, model just calculates the local differences in
pressure and assumes shrinking of the surface, wherevelr the
pressure is higher than average, and expansion of the surface,
wherever it is lower. This model ignores the actual profile of
the flow lines. A high viscosity leads to a slow fluid flow and
a long time scale, and vice versa. Fig. 16.11 shows the break-
ing of a cylindrical bridge with H > 2n R calculated according
to the slice model, which is valid in the case of low vis-
cosity, and according to the pressure equilization model, which
applies in the case of high viscosity. Both pictures on the
breaking look very similar, such that one may conclude that the
errors made can not be too serious.

Fig. 16.12 shows the fusion and vib:rration of two s~upported

liquid drops during the STS-5 mission: From the shape of the
separated drops one may conclude that there has been electro-
static charging. Fig. 16.13 shows trigonal shapes of water
droplets observed in an acoustic positioner.
412

Fig. 16.10: J •..-.-._._ . ........ -o.5 !

The shape of freely rotating I "/,,.... ". I
liquid drops. The parameter j /' ' .
shown is the Weber number
I /
/ "-.\ -0.25 I
w/8.
I / \ I
I. / .
. / 0 \ !
. I
I . \ .
i! \!
i .~_-_-~_-.::- 1.5 _ - _ " U

Fig. 16.11:
The breaking of a cylindrical
liquid column, whose height
exceeds its circumference in
the limits of low (a) and high
(b) viscosity

H ; 2.1 n R

/
 413

16.5 Wetting and Spreading

Much attention has to be paid to the practical formation of

liquid bridges. If they are built up too fast, inertia may
overcome surface tension. In this case sudden necks arise and
satellite drops are formed. Another critical problem is the
spreading of the liquid around the edges of the supporting
disks. The most appropriate method appears to inject the fluid
from a reservoir, which during disk separation releases the
appropriate liquid volume. In this case no net momentum of the
liquid arises. A further improvement may be achieved by using
antiwetting barriers. Another suggestion is to avoid spreading
by using sharp edges.

In general, the wetting conditions must be controlled carefully

in a microgravity environment. On ground, one is aware of the
fact that a wetting liquid moves up a thin capillary, but usu-
ally no attention must be paid to wetting in containers of more
than 10 mm in diameter. Under microgravity, a liquid may well
creep along all faces and edges of such containers.

The lower picture series in Fig. 16.14 shows the wetting of a

sinusoidal glass capillary by water during the TEXUS 3 mission
[16.18]. In the upper picture series microgravity has been
simulated on ground using two liquids with equal density, water
and a mixture of cyclohexane and carbontetrachloride. Wetting
under microgravity turns out to be slower in spite of the fact
that no viscosity of a second liquid must be overcome and the
static wetting angle of water has not changed. The dynamic wet-
ting angle under microgravity however has increased.

On ground we are used that hot water spreads on the top of

cold water. Hot water is lower in density and thus moves to the
top due to buoyancy. Under microgravity, hot water spreads
along the surface of cold water, whatever the shape of the sur-
face is. The surface tension of water, like that of most
liquids, decreases wi th increasing temperature, i. e • the
spreading of the hot water on the surface lowers the surface
414

Fig. 16.12: The fusion and vibration of two supported liquid

drops during the mission STS 5

Fig. 16.13: Trigonal shapes of water droplets levitated in an

acoustic positioner (Courtesy of W. Heide)

74
E
E

74
E
E

+-'
.c.
Cl
,-<
Q)
.c.
0
0 1 2 4
time (s)

Fig. 16.14: The wetting of a glass capillary by water.

(a) Simulation by removal of an equally dense liquid
(b) During the TEXUS-3 mission (Courtesy of P.J, Sell)
 415

energy. On the other hand, it increases the interface area

between the hot and the cold water, which also requires a
small, but finite interface energy.

Spreading of liquids generally happens if no Neumann triangle

according to Eq. (16.3) is possible between the relevant inter-
face tensions. Liquid 2 spreads on the surface of liquid 1, if

(16.12)

i.e. if u13 is so strong that it tugs liquid 2 between liquid 1

and medium 3. The latter may be a gas, a liquid, or a solid. In
the case of the hot water spreading on the surface of cold
water, the cold water is liquid 1, the hot water is liquid 2
and air is medium 3.

A similar situation may occur in a closed container. Once more,

there is a decrease in interface tension between water and the
container with increasing temperature. Are there container
materials where this decrease is sufficient to cause spreading
of the hot water along the container?

The spreading of a liquid on a container wall or on a growth

front becomes very important during production of fine-disperse
materials. For a particle 1 to move in a melt 2 before the
growth front of solid 3 it is necessary that the melt continu-
ously spreads into the interspace between particle and solid,
i. e. inequality (16.12) must be satisfied. Spreading of the
melt 2 becomes only active, if the interspace particle/solid
falls below the range of van-der-Waals attraction, such that
the macroscopic interface tensions do no longer apply. On the
other hand, spreading is limited by thefdynamic viscosity ~ of
the melt. The maximum velocity v, at w~iCh a particle may move
before a growth front, thus is given by
416

Similar arguments apply during cooling of alloys exhibiting a

miscibility gap in the melt. Since the interface tension a 12
between such liquid pairs vanishes at the critical point,
spreading of one liquid along the container wall is most
likely. Even more important, however, are the spreading con-
ditions at the monotectic point, when the higher meitin~
liquid starts to solidify. There is generally spreading of the
higher melting liquid on the growth front.

Immiscible metallic systems like Al/In have been processed re-

peatedly under microgravity. When A1203 containers are used, In
is found at the container wall. Potard has shown that the wet-
ting conditions change by using a TiC-container instead
[16.19]. Al now spreads at the container wall. Even on ground,
it separates the heavier In from the bottom by a layer of about
0.1 mm. That is about 10 3 times the range of van-der-Waals
attraction. Microgravity provides an excellent tool for further
investigating such long range forces.

The question raised is strongly related to that on the dynamic

contact angle. At which distance does a liquid actually recog-
nize a nearby solid? If this distance is short, the increase in
contact angle with the speed of wetting is strong, since the
wetting liquid moves to a sharp contact line rather than to a
broad contact region.

16.6 Interface Convection

Another important contribution to convection is interface con-

vection, which is known already since the last century. It has
been first observed by Lord Rayleigh and later described in
more detail by Marangoni, after whom it has been named
Marangoni convection. It has ofteh been considered negligible
as compared to gravity driven convection. The difficulties en-
countered in simultaneously solving the equations describing
convection (the Navier-Stokes equation) and the energy and mass
transport equations did not allow quantitative investigations
into Marangoni convection on ground. Marangoni convection
 417

therefore has become one of the primary objectives of fluid

physics under microgravity and is now much better' understood
than a few years ago, before the advent of microgravity
research.

If the interface tension varies along the surface of a liquid

or along the interface of two liquids, there arises a shear
force from regions with low to regions with high interface ten-
sion (Fig. 16.15), Le.

(16.14)

where ryl and ry2 are the dynamic viscosities of liquids 1 and 2,
uland u2 the respec.ti ve flow velocities, and the subscripts n
and t indicate the components normal and tangential to the
interface. It does not matter, whether the gradient of the
interface tension in Eq. (16.14) is caused by differences in
temperature, concentration or electric fields.

A well-known example of interface convection are the regular

Benard cells, which arise if a liquid in an open container is
heated from below. Interface convection dominating gravity
driven convection is evident from the fact that the liquid sur-
face is highest where the liqud flows downwards, and lowest
where the liquid flows upwards [16.20].

During various TEXUS missions Marangoni convection has been

studied at interfaces with two characteristic shapes: at free
cylindrical bridges and immersed droplets. The cylindrical
bridges are aimed at modelling convection during crystal growth
(see Chapter 15). Droplet migration due to interface convection
may be used to balance droplet sedimentation on ground, repre-
sents an important transport mechanism in space, and has to be
suppressed wherever liquid transport is annoying, as for ex-
ample during production of fine-disperse samples of immiscible
alloys.
418

liquid 2
10w interface high interface
tension (hot) tension (cold)

liquid 1

Fig. 16.15: The shear force and fluid flow due to a gradient in
interface tension

Fig. 16.16: (a) Dominating Marangoni convection in a liquid

bridge due to an upward temperature gradient
(b) Dominating gravity driven convection after
surface contamination (Courtesy of D. Schwabe)

Fig. 16.17: Convective rolls in the oscillatory regime of

Marangoni convection in a solicon oil column at
times t and t+T/4 (Courtesy of R. Monti)
 419

An impressive terrestrial demonstration of interface convection

at liquid bridges is shown in Fig. 16.16. A nearly cylindrical
bridge of sodium nitrate has been differently heated at the top
and at the bottom [16.21]. Due to the gradient of interface
tension being directed downwards, strong convection rolls
directed downwards close to the surface and upwards close to
the axis arise (Fig. l6.16a). When the surface is contaminated
by a highly viscous oil, the flow velocity decreases by at
least a factor three and the vortex centres move towards' the
axis (Fig. 16.16b). Interface convection dominates in the for-
mer, gravity driven convection dominates in the latter case.

16.7 Microgravity Experiments on Interface Convection

Several TEXUS and MAUS experiments on interface convection at

cylindrical liquid columns have been conducted [16.22-25]. The
temperature difference between the supporting disks has been
varied systematically in order to determine the onset and
fading out of oscillatory convective modes. It is usually de-
scribed by the Marangoni number,

M 6,a H/l1 K (16.15)

where H is the height of the liquid column, a is the differ-

6,

ence in interface tension at the bottom and the top and ry and
K are the dynamic viscosity and the temperature diffusivity of
the liquid used. The Marangoni number is the ratio of the driv-
ing over the damping forces. The critical Marangoni number, at
which convection becomes oscillatory, approximately equals 10 4 •
It depends on the aspect ratio H/R of the column under investi-
gation.

The oscillatory modes observed at cylindrical liquid bridges on

ground and in space are azimuthal, i.e. they exhibit am-fold
symmetry m 1, 2, 3 around the axis, around which they
rotate. Fig. 16.17 shows convective rolls in the oscillatory
regime in a silicon oil column of 18 mm in height and diameter
observed during the TEXUS 9 mission [16.24].
420

A liquid droplet gains interface energy by moving from a region

of high interface tension (a cold region) to a region of low
interface tension (a hot region). The driving force equals

(16.16 )

The fluid flow resulting inside and outside the droplet is

shown in Fig. 11. 8. By solving Eq. (16.14) together with the
equation for the fluid flow, the Navier-Stokes equation, one
obtains for the speed v of droplet migration [16.26]

2 R(-'\7a)
v (16.17)
'3 3'1int+2'1ext

Marangoni migration of droplets has been observed during mis-

sions TEXUS-7 and TEXUS-9 [16.27, 28]. Both experiments were
aimed at modelling droplet migration during cooling of immis-
cible metallic melts. Up to now no method is known to avoid
this unwelcome migration. Lowering the temperature gradient by
cooling down the sample isothermally has been suggested. This
certainly lowers the ve10ci ty of, but offers more time to
Marangoni migration.

During the TEXUS 9 mission a mixture of 5 weight percent meth-

anol in 95 weight percent cyclohexane has been cooled unidirec-
tional1y. The cooling temperature has been to _5° C in order to
study the effect of the solidification of cyc10hexane at +6° C.
During the first 10 s there is just the penetration of a fog
front indicating the cooling front. After that a second, darker
fog front arises. It moves faster than the first one and passes
it after about 18 s. It consists of methanol droplets under-
going collective Marangoni migr1tion. Then larger methanol
droplets migrate from the bottoI/l to the cooling front, see
Fig. 16.18. After 36 s, when solidification of cyclohexane
starts, the distribution of the methanol droplets becomes more
uniform, the average droplet size decreases. The growth front
hinders preferred nucleation at roughnesses of the cell bottom.
 421

The flight films reveals a faster coagulation of methanol drop-

lets in a cyclohexane matrix than of cyclohexane droplets in a
methanol matrix in spite of the fact that in both cases the
same interface energy is gained. A similar effect has been
observed in the Spacelab-l mission with the immiscible systems
Zn/Pb and Zn/Bi. Ph and Bi droplets in a Zn matrix coagulate
better than Zn droplets do in a Pb or Bi matrix [16.29]. - An
additional result from the TEXUS 9 mission is the formation of
regular convection rolls. They evolve more and more clearly
after about 3 min and can be ascribed to a correlation between
the growth front of cyclohexane and the nucleation and
Marangoni migraton of methanol droplets.

Solutal interface convection has been studied by BrUckner at

the ternary system water/toluol/acetone. During the TEXUS-3
mission the diffusion of acetone from water to toluol, during
the TEXUS-8 and TEXUS-ll missions the diffusion of aceton from
toluol to water has been investigated. In the earlier missions
the host liquids water and toluol have not been premixed ac-
cording to their miscibility gap (see Fig. 16.19), such that
large convection rolls result [16.30]. They stay for an average
of 30 s and then vanish by dissolution. In the TEXUS-ll mis-
sion, when using toluol premixed with water, only a slow liquid
motion has been observed.

A similar system, namely water/air/acetone, will be investi-

gated by Drinkenburg et al. during Spacelab-Dl [16.31].· Con-
tinuous diffusion of acetone from water into air is made sure
by putting a layer of active carbon on top of the air volume.
Fig. 16.20 shows four regular convection rolls obtained with
this system in a preparatory ground experiment.

Solutal Marangoni migration, in additiop, may actively contrib-

ute to coagulation, if the solubility of drops dispersed in a
liquid matrix rises with temperature. If there are two droplets
which, due to an increase in temperature, both enrich the
respective component in their vicinity, each droplet will see
the concentration gradient caused by the other droplet and
422

395 405 415 425 435 445 465 485 50s

Fig. 16.18 : Marangoni migration of methanol drople t s in cyclo-

hexane, A: cell bottom, B: first fog front, C: second fog front

Fig. 16.19:
Phase diagram of water/toluol/
acetone with mixtures used in
TEXUS-3, - 8, -11
(Courtesy of R. BrUckner)

toluol100~~=~=====:::::::=:::==::::;;~~~~1000
0 20 40 60 eo Mate

Fig. 16.20: Convection rolls due to the diffusion of acetone

from water to air. Continuous diffusion is achieved by acetone
absorption in active carbon (courtesy of J.H . Lichtenbelt)
 423

undergo solutal interface migration towards it. The opposite

applies, if both droplets are growing due to a decrease in tem-
perature.

References:

16.1 Langbein, D.: Gleichgewichtsbedingungen und Meniskusfor-

men. In: Proc. Workshop: FIUssigkeitsgrenzflachen uhd Be-
netzung, Battelle-Institut Frankfurt/Main (1981) 8-32
16.2 Heywang, W.: Zur Stabilitat senkrechter Schmelzzonen. Z.
Naturforschung lla (1956) 238
16.3 Langbein, D.: Form, Schwingungen und Stabilitat von FIUs-
sigkeitsgrenzflachen. SchluBbericht fUr das BMFT. Battel-
le-Institut Frankfurt/Main, Juni 1984
16.4 Rayleigh, Lord J.W.S.: On the Capillary Phenomena of
Jets. Proc. Roy. Soc. 29 (1879) 71
16.5 ErIe, M.A.; Gillete, R.D.; Dyson, D.C.: Stability of
interfaces of revolution with constant surface tension.
The case of the catenoid. Chern. Eng. J. ! (1970) 97
16.6 Gillis, J.: Stability of a column of rotating viscous
liquid. Proc. Camb. Phil. Soc. 57 (1961) 152
16.7 Carruthers, J. R.: Studies of Liquid Floating Zones on
SL-IV, The Third Sky lab Mission. Skylab Results,
M.P.L.Siebel (Ed.), NASA (1974) 837-856
16.8 Carruthers, J .R.; Gibson, E.G.; Klett, M.G.; Facemire,
B.R.: Studies of Rotating Liquid Floating Zones on Skylab
IV, AlAA-Paper 75-692 (1975)
16.9 Padday, J.F.: Fluid Physics in Space. Kodak Ltd. (1983)
16.10 Chandrasekar, S.: The stability of a rotating liquid
drop. Proc.Roy.Soc. (London) 286 (1965) 1-26
16.11 Rayleigh, Lord J.W.S.: The Theory of Sound. Republication
of 2nd edition of 1894. Dover, New York, Vol. 2, Chpt.364
16.12 Lamb, H.: Hydrodynamics. Cambridge University Press, p.
473-639
16.13 Trinh, E.; Zwern, A.; Wang, T.G.: An experimental study
of small-amplitude drops oscillations in immiscible
liquid systems. J. Fluid Mech. 115 (1982) 953-474
16.14 Trinh, E.; Wang, T.G.: Large-amplitude free and driven
drop-shape oscillations: experilllental observations. J.
Fluid Mech. 122 (1982) 315-338
16.15 Lee, H.C.: Drop formation in a Liquid Jet. IBM J. Res.
Dev. 18 (1974) 364-369
16.16 Meseguer, J.: The breaking of axisymmetric slender liquid
bridges. J. Fluid Mech. 130 (1983) 123-151
424

16.17 Rivas, D.7 Meseguer, J.: One-dimensional self-similar

solution of the dynamics of axisymmetric slender liquid
bridges. J. Fluid Mech. 138 (1984) 417-429
16.18 Sell, P.Jd Maisch, Ed Renzow, D.: Benetzungskinetik.
Status seminar Spacelab-Nutzung 1981, DGLR-Bericht 81-01,
75-78
16.19 Potard, C.: Etudes de base preparatoires de l' experience
de solidification dirigee d' alliages immiscibles Al-In
en fusee sonde. ESA-SP 142 (1979) 255-262
16.20 Velarde, M.G.7 Normand, Ch.: Convection. Sci. American
243 (1980) 82-108
16.21 Preisser, F.7 Schwabe, D.7 Scharmann, A.: Steady and
oscillatory thermocapillary convection in liquid columns
with free cylindrical surface. J. Fluid Mech. 126 (1983)
545-567 -
16.22 Schwabe, D.7 Scharmann, A.: Kritische Marangonizahl bei
thermokapillarer Konvektionsstromung. Z. Flugwiss. Welt-
raumforsch. ~ (1985) 21-28
16.23 Chun, Ch.-H.: Verification of turbulence developing from
the oscillatory Marangoni convection in a liquid column.
ESA-SP 222 (1984) 271-280
16.24 Monti R.7 Napilitano, L.G.7 Mannara, G.: TEXUS flight
resul ts on convective flows and heat transfer in simu-
lated floating zones. ESP-SP 222 (1984) 229-236
16.25 Schwabe, D.7 Scharmann, A.: Thermocapillary Convection in
Floating Zones. ESA-SP 222 (1984) 281-289
16.26 Young, N.O.7 Goldstein, J.S.7 Block, M.J.: The motion of
bubbles in a vertical temperature gradient. J. Fluid
Mech. ~ (1959) 350-356
16.27 Langbein, D.7 Heide, W.: Entmischung von F1Ussigkeiten
aufgrund von Grenzflachenkonvektion. ZFW ~ (1984) 192-199
16.28 Langbein, D.7 Heide, W.: The Separation of Liquids due to
Marangoni Convection. Adv. Space Res. ! (1984) 27-36
16.29 Ahlborn, H.7 Lohberg, K.: Influences affecting separation
in monotectic alloys under microgravity. ESA-SP 222
(1984) 55-61
16.30 BrUckner, R.7 Christ, H.: TEXUS-8 Experiment: Diffusions-
bedingte Grenzflachenkonvektion. Ergebnisbericht fUr das
BMFT, TU Berlin, Januar 1984
16.31 Drinkenburg, A.A.H.7 Lichtenbelt, J.H.7 Hoetink, F.:
Marangoni convection and mass transfer from the liquid to
the gas phase. Statusseminar'Spacelab-Nutzung 1982, DGLR-
Bericht 82-02, p. 61-68
17 Thermophysical Properties
G. Frohberg
Technische Universitat Berlin

From our present knowledge a significant influence of gravity on

thermophysical properties is only expected for liquids and
gases, because the origin is mainly related to gravity driven
convections. Hence all physical properties, mainly in liquids,
should be regarded which are sensitive to convections. All
corresponding properties of the convective flow may be relevant.
The motion itself may contribute to all transport properties as
e.g. to the transport of matter (diffusion>, the transport of
momentum (viscosity>, the transport of heat (heat conductivity>.
There should be no significant influence on the electrical
conductivity, since positive and negative charges are moved
together, but diffusion controlled electrical potentials in
electrolytes may be changed and magneto-hydrodynamic effects may
appear from convections. The kinetic energy associated wi,th the
convective flow contributes only little to the specific heat.
Convections may of course also originate from other sources than
gravity, e.g. from Marangoni-forces. Some details of the
mechanisms by which gravity driven convections may contribute to
the viscosity, the thermal conductivity and the specific heat
are discussed in Sect. 17.1. But the principal aim of this
chapter is to discuss the importance of space experiments on
diffusion and atomic transport (17.2-17.4> which are free from
gravity contributions.

17.1 Overview on Properties with 9ravity Influence

Prior to the possibility to do experiments in space under redu-

ced gravity it was known from experiments on the ground that
gravity induced convections play an important role in diffusion
and in atomic transport processes, as discussed in chapter 5.
While turbulent macroconvections normally can be detected by
typical deformations of the concentration profiles, this is
426

impossible for microconvections and weak laminar convections,

which may contribute in a similar manner to the mixing process
of diffusion. Some of such contributions seem to be present in
all ground experiments (see 5.3.4>. Hence it was quite natural
to do diffusion and atomic transport experiments in space.

From the well known theoretical relation between diffusion

coefficient D and viscosity ~ (see 5.3.1),

(17.1>

it could be suspected that there is a similar influence of

gravity on the viscosity (kbis the Boltzmann constant, T the
absolute temperature, s a correction factor (17.1],(17.2], r~an

atomic radius and D the self-diffusion coefficient). Apparently

this has not yet been checked or discussed and the influence is
perhaps smaller than in the case of diffusion. But from a
theoretical point of view, there should be an influence of
graVity-driven convection in addition to the measurement-induced
flow. This is e>:pected even if the gravity induced flow is
transverse to the measurement flow, because of the nonlinearity
of the Navier-Stokes-equations. The contribution ~conv from
convections will depend on vc/v, where Vc is the mean convective
velocity and v the mean velOCity of measurement. The measured
viscosity f"} then is

(17.2>

O>:ide fi lms on the surface of a melt in an osci llation or

rotation viscosimeter are known to enlarge the measured
viscosity. On the other hand, free surfaces are likely to induce
Marangoni-flows and to support gravitational convection (of
normally the same direction) r~sulting from small temperature
gradients in the oven. It should be emphasized that (17.1)
obviously is only valid for the quantities ry and D related to
the atomic processes, and not for the effective quantities ryeff
and Deff in an experiment, because otherwise the relation DQff>D
would give ne«<~' which is not at all plausible, since additio-
nal convections in a liquid will intensify the exchange of
 427

momentum in the liquid.

Similar to diffusion, experimental data of the viscosity are

usually described by an Arrhenius equation

'leff = '10 exp ( H'l / kl> T ) <17.3)

The coe>:istence of this equation with (17.1) and the Arrhenius-

description of the diffusion coefficient may be explained by the
inaccuracy of values !"Je.ff and Deff' together with the limited
temperature ranges of the measurements (see chapter 5). Theore-
tical calculations of the atomic part q usually yield three
contributions: ~k from the kinetic transfer of momentum, 'lh from
"hard sphere collisions" and ~s from the "soft part" of the ato-
mic interaction forces [17.3J

~I<. + '1 ... + r'}s <17.4)

Still the theoretical values are calculated too low (as low as
30% of the e>:peri mental val ues) wi th onl y a small temperature
dependence.

The thermal conductivity is another parameter in liquids which

is influenced by convections. If the measurement of the thermal
conductivity ~ is done in a cell with diameter d and height L.
the order of magnitude of convective contributions ~eO"V to the
measured value 7\~ can be estimated from

(17.5)

is the mean horizontal temperature difference in the

cell and ATt is the vertical temperature difference for the
measurement. For example with L=d and ATr =1K ,ATL=100K we get
Aconv /.\=1%. Hence the measured values are represented by

Aeff = A + i-.COV'lV <17.6)

Similar to viscosity, theoretical analysis yields at least three

contributions and in the case of metals an additional one from
428

the conduction electrons A

"'" + ~h +?-.s + 7\e <17.7)

The calculations reveal that almost 100% of the heat flow in

metals is due to the contribution Ae of electrons and the values
fit well to the experimental data [17.3]. Hence the Wiedemann~
Franz-law is found to be valid for almost all metals with some
exceptions (e.g. Hg, Ga)

A ~e = KL. T <17. B)

K~ is the Lorenz number of free electrons and ~ethe specific re-

sistivity of the metal (alloy). Probably the discrepancies are
due to inaccurate measurements of A. More accurate measurements
of the thermal conductivity ~ should be possible in space
experiments. In such experiments one may use another advantage
of space by performing the measurements "almost containerless"
i.e. only with a thin oxide layer at the surface. Thus heat flux
losses through the container walls would be avoided.

Among other thermophysical properties like thermal expansion,

temperature dependence of specific resistivity, emissivity,
surface tension and interface tension, only the "specific heat
capacity" shall be mentioned. Assume a convective velocity Vc in
a ground e>:periment depending I inearl y on the temperature
difference ATs relative to the surrounding. Then there will be a
contribution from the kinetic energy of the convective movement

cp(conv) (17.9)

But unless Vc >10m/s and ATS <2001<, the contributions are below
1% of the specific heat capacity.

Since present interest is mainly concentrated on diffusion and

some atomic transport properties, the relevant experiments and
the corresponding hardware aspects will be discussed in the
following.
 429

17.2 Design of Experiments for Reduced Gravity

(Diffusion and atomic transport)

17.2.1 Container Design

All capillaries or containers should be closed, at least in the

sense that undesired movements of the sample cannot occur. It is
not necessary to, close the container hermetically, provided the
sample can be kept inside by normal action of capillary forces
and no other undesired mass exchange arises as e.g. evaporation
of the sample material (especially if it is toxic or highly
teactive), reaction of the sample with residual gas atmospheres
or undesired gas pressure which raises the heat e>:change between
sample and container.

Due to the lack of gravity the contact between the container and
the sample may not be well defined. Hence attention should be
paid to the geometry of the container (capillary) and the
contact angle 8 between the liquid and the container material.
Because of the effects described in Chapter 5.2.4, one should
use the experience of ground experiments in choosing capillary
diameters de of about .5 to 3mm. Larger dc-values seem to be
suitable (see 17.3.1>, but Marangoni-convection may interfere
and its influence can be lowered by smaller diameters. The
length Le of the capillary (or approximately that of the sample)
might be about lO ••• 200mm, depending on the concentration
structures to be analysed and the lateral accuracy of analysiS.
If the sample is a solid and melted in the capillary (usually in
space), a spare volume for thermal e>:pansion and the volume
change on melting must be provided and the geometry of the
capillary must be designed for the sample volume in its liquid
state. Even for operation at normal temperatures, spare volumes
or flexible container walls should be prdvided.

The geometric form of the capillary (or container) should

guarantee that the liquid sample stays in a well defined contact
area with the capillary wall thus having a well defined geome-
tric shape. If 8)rr/2, or the supplement 8>~~TI'/2, a cylindrical
capillary with plane ends may be choosen (Fig.17.1). In the
430

solid state the sample should be fixed to the capillary wall to

prevent uncontrolled motions during melting. To prevent the
sample from moving in the liquid state it should touch one of
the ends of the capillary (Fig.17.1), normally that where the
last part of the sample was melted. But in the case of small
angles 8' the sample might easily be detached and move freely

[:::.... ...:- .. . '" "

: " "WA'- -][«
. ... ""'--4':.
.'
_-:.....
'.' ' , , ' , \

\~

Fig. 17.1 Fig. 17.2

Simple capillary (8)TTI2) Capillary with cone (8)n-/2)

upon small accelerations (see also 5.2.4). Hence it is advisable

to shape the capillary as a cone (with angle 0(. Fig.17.2) at
one end, with the spare volume designed such that the sample
also touches the cone. Then the contact angle 8' determines th.e
radius r of curvature of the sample in the cone region and hence
the internal pressure p in the sample :

rs = s sin (00 1 sin (TT/2 - ex. - 8') (17.10)

p = 2 eft 1 rS <17.11)

where c:fL is the surface tension of the liquid and s is the dis-
tance of the contact point to the e>:trapolated tip of the cone
(Fig.17.2), determined by the residual spare volume. If the
latter is designed small, s is small and hence from (17.10) and
(17,11), p is large, i.e. the sample is pressed to the left in
Fig.17.2. Alternatively and for symmetry reasons one might
choose cones at both ends. Since ? sin(oO(d~/2,

rs ( de. 1 2 si n ( TT/2 8' 0(.) <17.12)

P > (c:f~/dc) sin( ~/2 8' a",) with 01,. (n/2-8' <17.13)

If 8'>~ there would be an additional free surface between cone

and cylinder. Since the left side of the sample in Fig.17.2 can
be treated with ~= TT"/4, we get instead of (17.10)
 431

r,'
S
s' 1 Y2' sin ( rr/4 8' <17.14)
wi th 9' < ,,-/4

there the dash refers to the corresponding parameters at the

left side (except B'). If 8'>"/4 then the liquid will wet at the
left side. At the right side a proper function of the cone is
expected for 8·<rr/2-~.

to minimize axial movements from thermal expansion it may be

useful to adjust the spare volume for radial expansion, e.g. by
using a quadratic cross section for the capillary. Then the
sample will touch the plane ends of the capillary in the solid
state (Fig. 17.3a) and upon melting the liquid will be pressed
into the corners of the cross section (Fig.17.3b; see also 17.3.
s). From (17.14) we see that this method with rectangular cross
section is only possible for 8'(rr/4. For metallic melts this can
be realized in many cases by choice of suitable capillary
naterials.

[.",:.':'.' .
• ...:'~'~
1..:>.',;..._•..:.._
.... ..'~
:. . .
'

• ..:.'_.!.-._•
."
..
": ..:..:.:':.
.: .' ~ ]- --OJ
• ..:.•..;.'--.",,'~'_':..'_.",~...,. _ _ _ _
....:..-._.-=---'-....:.._._.'-.~
::,,:: :".
: '. : :.:. "~e
".. .•.• -
./

.11-
I

Fig. 17. 3a Fig. 17.3b

Capillary with quadratic cross section (9~/2).

[n cases with 8<n/2 a corresponding design for the capillary

ends may be used. An example is given in Fig.17.4. The cross
section for radial expansion is shown in Fig.17.5.

~ ........
.:
.. . .' :
. . .
- . .....
, " ..... ......... .-
.
' ....
' ..

Fig. 17.4 Fig. 17.5

Capillary cone for 8<rr/2. Cross section for 8<rr/2.
432

The discussion above reveals, that there will be almost always

free surfaces at the sample. Because Marangoni-convection may
have an adverse effect on diffusion samples (see 5.2.4; an ap-
pearance during seconds may invalidate the experiment totally),
precautions are always necessary to avoid convections.Marangoni-
forces cannot completely be ruled out, since temperature gra-
dients or concentration gradients (in the case of interdiffusion
samples) are always present, at least during melting or solidi-
fication. It has been shown (see 17.3.3) in a Spacelab-1-
experiment (HTT> that thin oxide films or films of other
suitable material) may be sufficient to prevent Marangoni-
convection [17.4]. Depending upon the strength of such films,
even air-grown oxide layers might be sufficient. The method of
using the oxides of the sample itself is quite suitable, as
cracks in the surface layer from thermal expansion are self
healing if the atmosphere contains a small amount of oxygen. Of
course, sufficient o>:idation must take place already at the
melting point and the oxides must be stable up to the highest
temperatures in the e>:periment. Furthermore, the oxides should
be stable against reactions with the capillary material. Oxygen-
containing capillary material often assists the growth of oxide
layers. The contact angles between the capillary material and
the liquid are of course different for the cases with and
wi thout 0:-:1 de layer. It is al so important that the contact angl e
does not significantly change as a result of reactions between
sample and capillary. It seems that in some diffusion
experiments performed in space fortunately the samples were
protected by oxide layers (see 17.3.1>. In other cases (see 17.
3.2), the results were "unexpected". The same is supposed to be
true also for many of the ground e>:periments.

The roughness of the prepared ca~illary wall is another aspect

in the selection of capillary mat~rial. If no stabilising oxide
layer is available and B>rr/2, the wall should be as smooth as
possible to ensure complete contact between melt and capillary
and thus to avoid Marangoni-microconvection (see 5.2.4),[17.4].
Of course the possibility of solution of sample material in the
capillary material and vice versa should be checked as well as
the diffusion of sample material through the capillary wall.
 433

efore using any capi llary in an e>:periment it should be

horoughly cleaned and carried through an offgassing procedure.

round the capillary other materials may be used, if there are

a undesired reactions between them. The thermal contact between
he heat source or sink and the sample should be as tight as
ossible to enable a fast and precise temperature control, which
s essential in diffusion experiments (see 17.2.2>. Hence all
aterials should have a good thermal conductivity. A good
lectrical conductivity is also advantageous, if electro-
agnetic fields have to be shielded to avoid the corresponding
tirring effects.

he experimental methods in using the capillary in space may be

he same as on the ground with a preference for the "long
apillary technique" or the "shear cell technique". The "capil-
ary reservoir technique" has some disadvantages related to the
.emperature profile and to reservoir handling (see 5.2.4>.

17.2.2 Temperature Control

Capillaries with integrated heaters have the advantage of good

chermal contact, low heat capacities and low energy losses
necause of the small heater size and should be preferred above
nulti-purpose heating devices. An integrated heater may be
optimized for each purpose (temperature interval, temperature
orofile along the sample, different profiles with two or more
separate heaters). in almost all applications resistance heating
will be the best solution for temperatures up to 1500 C. At
least two separately controlled heaters are advisable for
diffusion experiments, one of them for a homogeneous temp.erature
during diffusion and the other for a small and well defined
temperature gradient during melting and solidification. For the
case of thermotransport the heaters will be concentrated at one
end of the cartridge. Such heaters are cheap, uncomplicated,
easy to mount and to control. A suitable resistance material for
the use in vacuum is molybdenum isolated by ceramic tubes. The
heater wires should be arranged bifilar on the cartridge to
434

minimize electromagnetic fields at the sample. Additionally it

is advisable to place a metallic shielding between heaters and
sample. A complete cartridge is shown schematically in Fig.17.6
[17.5],

Fig. 17.6 Integrated cartridge for diffusion e}:periments.

An effective thermal isolation is necessary if only small

temperature gradients are allowed along the sample, as in the
case of diffusion measurements, but this is easily achieved with
a package of thin separated tantalum leaves or simply wool from
alumina or zirconia. The cartridge, i.e. the capillary with
integrated heaters and thermocouples, together with the thermal
isolation, should be placed in a vacuum chamber with sufficient
mechanical stability. Heat fluxes from the cartridge to the
vacuum chamber along heater wires, thermocouples etc. disturb
the temperature profile in the capillary and hence should be
minimized except for thermotransport e}:periments, where such
heat bridges may be combined with the necessary heat sink.

As alternative heating techniques electron beam heating or

radiation heating might be used. Both offer the possibility of
small thermal contact between the capillary and the chamber, but
then problems might arise from the lack of mechanical stability.

If a multi-purpose oven is used instead of an integrated heater,

the capillary usually must be sealed in a metallic cartridge to
avoid contamination of the oven. Normally there is little choice
of suitable temperature profiles. If the oven has an additional
gradient facility (see 17.4.1>, this may be well suited for
thermotransport experiments. A multi-purpose oven usually is not
well sui ted to serve for an el ectrotransport e>:peri ment, because
 435

of problems with the necessary high-current supply of the sample

und with the temperature control.

Regardless of the heating device. for temperature control in a

diffusion or transport e>:periment the temperature should be
neasured directly at the sample. Todatemainly thermocouples
have been used, but radiation sensors are an interesting
alternative for experiments performed at sufficiently high
cemperatures. Control circuits usually employ P-I-algorithms,
either by analog or digital electronics. The temperature program
Includes heat-up to the melting point, melting in a well
defined small temperature gradient, heating to the diffusion
temperature, diffusion anneal, cooling (usually with helium),
solidification in a defirted temperature gradient (the solidifi-
cation front should be plane and perpendicular to the capillary
axis). Similar rules apply to thermo- and electrotransport. For
an electrotransport e>:periment it may be necessary to use an
auxiliary heater at low temperatures and for a defined
temperatur-e gradient on melting or solidi-fication. In both
transport experiments the spare volume with the free surface
should be well separated from the transport region.

17.2.3 Analysis of Diffusion Components

The analysis methods kno,,"m from ground e>:periments may be used

for space e>:periments as well. e.g. radioactive tracers (there
may be restrictions in manned flights) [17.6], activation
analysis [17.7.17.8] or natural isotopes combined with SIMS
(Secondary Ion Mass Spectrometry) [17.5,17.9]. These methods are
suited for all types of diffusion and transport e>:periments
while another group of analysis techniques is only applicable to
experiment.s with chemically different components : electron
microprobe analysis [17.9], X-ray flourescence analysis,
chemical analysis. Some other methods belong to the same group,
but use techniques only applicable to special materials and
temperature ranges, as e.g. concentration measurements by e.m.f.
(mol ten sal ts, electrolytes) [17.10] or by interference of
light-beams (transparent media) [17.11]. It should be
436

emphasized that only two of the methods cited are favoured for
local analysis on the microscopic scale, which is necessary to
detect radial deformations of the concentration profile
analysis by SIMS and by electron microprobe. With a lower
resolution the autoradiographic method may be mentioned as a
similar technique [17.7].

17.3 Diffusion Experiments in Space

17.3.1 Selfdiffusion in Zn (Skylab)

Presumably the first diffusion experiment in space was done by

A.D. Ukanwa in a Skylab flight 1973 to measure the selfdiffusion
coefficient of zinc [17.6]. He processed 3 cartridges with Zn
samples in a gradient furnace, each sample 4.7cm in length and
.7cm in diameter. The average temperature was 550°C (cold end
463 ° C, hot end 656 D C) and the gradient about 45"C/cm. A Zn65
pallet (.bcm thickness) was placed as tracer in three different
positions at the cold end, at the centre and at the hot end.
Hence the effective diffusion temperatures and the effective
diffusion times were somewhat different. The accuracy of the
concentration profiles was surprisingly good and the average
diffusion coefficient at 550~C was found to be D=4.28.10Scm2./ s ,
which is 10% lower than the best ground based value. The radial
concentration profiles show (see Fig.17.7) still a remarkable

I-u
tJ

( ~
U
0

-- -- - , -- ----- -- t...v

-- -
\ I
./
..... ~
/' ..::::

Ir~
I
I
I

Fig.17.7 Radial concentration distribution from [17.6].

convective component. The origin probably is Marangoni

convection, but the direction of flow is not unique and the
 437

calculated velocities are too small to be explained by thermal

larangoni convection. The displacements of the profiles (Fig.17.
7) are about Imm, which is the expected size for thermal second
order Marangoni convection. Hence the presence of an oxide film
is suspected at t~e surface. Because of typical deformations of
the profiles just in the neighbourhood of the pallet, it seems
that the pallet contained small amounts of other material~,

perhaps products of radioactive decay, which may have produced

chemical second order Marangoni convection. In principle also a
self-thermotransport effect should appear, but the expected
displacement values are too small to be detected in this case.
Ukanwa's early results give a clear indication of the importance
of space experiments for liquid diffusion measurements.

17.3.2 Solute Diffusion of Au in Pb (Apollo-Soyuz>

Less than two years after Ukanwa's experiment Reed, Uehlhoff and
Adair performed a solute diffusion experiment of Au in Pb, which
was flown in the Apollo-Soyuz Test Project [17.7l. Six Pb-
samples were used with a cold-welded 3mm disc of Pb-.057.Au-alloy
at one end, an overall length of 32mm and 10mm diameter. The
experiments were done in a gradient furnace (.4 to 2·C/cm) with
two samples simultaneously at average temperatures of 450·C and
650°C. Run "A" was done in a graphite ampoule, the alloy discs
at the hot ends, run "AR" with discs at the cold ends and run
"B" in a mild steel ampoule, discs at the hot ends. Au was ana-
lysed by the activation technique and autoradiography. The mild
steel ampoule was expected to be wetted by the sample, but this
did not happen. In all experiments strongly deformed diffusion
profiles of Au-concentration were observed (Fig.17.8>, indi-
cating considerable convective veloci~ies in the liquid. The
experimenters explained this by the actibn of chemical Marangoni
forces (see 5.2.4>. Indeed, the surface energy of the PbAu-alloy
-$
was estimated to be by 37-10 N/m larger than that of Pb (.4N/m).
Thus Pb from the zone with low Au-concentration was flowing
along the surface to regions with higher Au-contents. The
maximum Marangoni velocity may be estimated from Chapter 5.2.4,
yielding about 15mm/s for a free surface. Since such velocities
438

would result in a total mixing, presumably the surface was almo~t

totally covered "lith an o}:ide layer, which in tiny parts of the

surface was broken, so Marangoni convection could develop. The
portion KS of free surface can be estimated to about Ks =.OOI,
possibly somewhat larger near the ends. Additionally there
should have been a thermal Marangoni velocity of about 3~lOmm/s.

This explains the observed differences between A- and AR-

samples. The investigators discussed a violation of the "zero-
slip boundary condition", but according to Chapter 5.2.4 even
the second order Marangoni convection in this case only yields a
drift of 2mm.

C(r) : Au

b)
r
0.)
Fig.17.8: Au-conc.: a)axial, b) a:-:ial section (A/650"C)[17.7]

17.3.3 Selfdiffusion in Sn (SPACELAB-l)

The self-diffusion e>:periment ES335(HTT) by Frohberg, Kraatz and

Wever [17.5] on the first SPACELAB flight was encouraged by
Ukanwa's results on zinc. The first aim was to do diffusion
experiments in space with a higher precision than possible
before on the ground, including the influence of wall effects.
This should then be used to analyse the temperature dependence
!
of diffusion mechanisms in I iquid1s and hence decide between the
existing theories on diffusion. The second aim was to measure
the isotope effect in liquid diffusion. The third aim, finally,
was to check in later experiments on interdiffusion (see 17.3.4)
whether a local environment reference system can be defined, i.
e. whether in an interdiffusion experiment there are also two
independent diffusion coefficients as is the case in solids. Tin
 439

was choosen for selfdiffusion experiments since diffusion

experiments with this material can be done in a wide temperature
range, and the material is thoroughly investigated in ground ex-
periments. In-Sn-alloys were choosen for interdiffusion experi-
ments, since a considerable dependence of the diffusion coeffi-
cient oh In-concen.tration had been found in ground experimen.ts:.,

The first 16 Sn-selfdiffusion samples were flown in SPACELAB-1

in November 1983. Eight diffusion runs were performed a~ dif-
ferent temperatures on two samples each, with diameters of the
graphite capillaries of 1mm and 3mm (to detect wall effects).
The experiments were done in the "High Temperature Thermostat"
(HTT>, a special furnace designed for diffusion experiments
using the "integrated heater technique" (see 17.2.2). The
operation of the furnace was fully automatic, controlled by the
computer of the "material science double rack". Unfortunately, 3
temperature profiles could not be evaluated because of system
problems during the flight. These experiments will be repeated
in the D1-flight at the end of 1985 together with a reduced
program for the first interdiffusion experiments.

Each sample, 55mm long, had a disc <4mm thick) of "pure" stable
Sn-isotopes joined at one end. The stable isotope in the 3mm-
samples was Sn124 (for selfdiffusion), while in the 1mm-samples
a mixture of Sn124+Sn112 was used <selfdiffusion and isotope
effect). The concentration profiles from the diffusion runs in
space were analysed by SIMS (see 17.2.3>. The measurements on
3mm-samples and on the radial isotope distribution have not yet
been completed, but the results obtained so far are encouraging.
The accuracy of diffusion coefficients was typically .4 to 1.07.,
comparable to accuracies achievable so far only in solids. Hence
it was possible to measure the isotope effect E of diffusion
(see 5.3.7> with acceptable tolerance. Farst preliminary results
are given in table 17.1. E-values are averaged from different e-
valuation methods,D-values represent a single set of evaluation.
The increase of E-values with temperature seems to indicate that
the elementary diffusion mechanism at lower temperatures is
bound stronger to collective motions than at higher temperatures
(see 5.3.7). A typical plot of In(C) versus square of diffusion
440

Table 17.1 Selfdiffusion in Sn

chamber 8 3 6 1 2
T (cC) 270 328 388 491 775
t (s) 38060 15516 21079 16120 9459
~S' :I
D (10 cmi's) 2.248 2.742 3.263 4.349 8.29.1
D ( l u Scm2./ s ) 2.228 2.680 3.164 4.255 8.088
E .5;t.3 . 4±. 1 .. 4j: .. 2 .5±.1 .7;t.3

depth >: is shown in Fig.17.9 for both isotopes, demonstrating

the accuracy of the results and the isotope effect.
x:z. (rrun2 )

250 500 750

o
~
o
o
H Snl12
(j)
U
<1l
H
o
.j.J

Sn124
O'l
o -1
H 1 0
1000K/T
Fig.17.9: Sn112 and Sn124 Fig.17.10: Arrhenius plot for
diffusion at 328°C. space results of Sn.

D-values from space are about 40'l. lower than the best ground
based values, indicating a substantial contribution from convec-
tions in ground experiments [17.5].

Another striking first result is the quantitative determination

of the temperature dependence of the diffusion coefficients. For
D(Sn), averaged over all Sn isotope masses,the result is

D(Sn) K,i. T 2. with K~ .745"10

-w cm 2.. IK 2 s (17.15)

i.e. a pure square dependence on temperature with an accuracy of

±2%, which clearly favours Swalin's "fluctuation theory" (see 5.
3.4). Fig.17.10 demonstrates that an Arrhenius dependence on
temperature can be e>:cluded. From (17.15) and the isotope effect
 441

E the diffusion coefficient for any Sn-isotope mass m and any

temperature T can be calculated :

D(Sn,m) D(Sn) [ 1 + E (m -m)/2 m] iii 118.7 • <17.16)

Further analysis and the 3 additional e>:periments in the Dl-

mission will be integrated in the future.

17.3.4 Self- and Interdiffusion in Sn/In (Dl Flight)

In the Dl flight the HTT furnace was originally designed for

interdiffusion experiments in the system In/Sn only.As described
in 17.3.3, three additional e>:periment runs on selfdiffusion in
Sn will be performed and hence the interdiffusion program has
been shortened accordingly. Ten interdiffusion samples have been
prepared, each 55mm long and 2mm in diameter, fitting in a cy-
lindrical capillary with a cone (Fig.17.2). Each sample consists
of two 20mm portions of different In/Sn-alloys, seperated by a.
joined disc of average composition and made from "pure" Sn124-
and In113-isotopes. In type "A" samples, 157. and 257.Sn-alloys
are combined, and in type "S" 357. and 457.Sn-alloys. Each of 4
cartridges contains samples A and B and they will be run at
temperarures of 260, 400, 660 and 900°C. The alloy compositions
in a fifth cartridge (660 (I C) are equal for all parts in the
sample, being 207.Sn and 407.Sn for the two samples, suited for a
pure selfdiffusion experiment in these alloys. With the other 8
samples, the interdiffusion coefficient of Sn and In will be
measured simultaneously with the selfdiffusion coefficient of In
and Sn in the developing alloy ranges. An additional aim of
these experiments is to check whether there is a drift between
the centres , and whether the common
of the two isotope profiles
center of both profiles may be used ~s a reference system for
partial diffusion coefficients (see 5.2.1,17.3.3).

17.3.5 Interdiffusion in Pb/Zn (Dl Flight)

In the GPRF2 (one of the "General Purpose Rocket Furnaces") Pond

442

and Winter [17.15) will perform interdiffusion experiments in

the PblZn system during the D1 flight. This system is one of the
most interesting ones with respect to the separation of immis-
cible metallic melts. In contrast to the interdiffusion
e>:periment on InlSn (see 17.3.4), in this system interdiffusion
is possible with a boundary between the Zn- and the Pb-melt. It
was concluded from ground based studies that reasonable results
can only be obtained from diffusion e>:periments in space. Two
e>:periments wi 11 be performed : one at 440 0 C (just above the
monotectic temperature) and the other at 820°C (just above the
consolute temperature). Both e>:periments start with a Pb-Zn
diffusion couple. After a soak time of 40 minutes the samples
will be cooled down rapidly which will be the main problem in
this experiment. It is known from other experiments that
segregation may also take place in space experiments because of
Marangoni forces. Sometimes this can be avoided by rapid
quenching which is also necessary for a sufficient small
particle size in the concentration analysis.

17.3.6 Interdiffusion in Salt Melts (D1 Flight)

Diffusion e>:periments on mol ten salts allow for observation

techniques not possible with metals. In this case an optical
interference method is used to analyse directly on line the
diffusion process (Savart-interferometer with 16mm-camera in the
D1-mission>,[17.11J. The interdiffusing partners will be joined
just before the diffusion starts in a "flowing-junction cell".
The procedure has already been tested in the TEXUS-program. It
will be very interesting to compare the results of salts with
those of metals in order to check whether there are differences
in the diffusion mechanisms.

17.4 Transport Experiments in Space

17.4.1 Thermotransport of Co in Sn (SPACELAB-1 and D1)

The first thermotransport experiment in space was performed by

 443

Malmejac and Praizey in a SPACELAB-1 experiment on solute trans-

port of Co in Sn [17.81. This is an e>:ample for an experiment
which cannot be done on the ground. The capillary must be in a
vertical position in a ground e>:periment, hot end upwards.
Because of a negative heat of transport Qa;v the originally
homogeneous melt wiil be enriched with Co in the upper part,
which means a higher density at the top, so convection will
occur. Indeed, in thermotransport experiments on the ground
always total mixing was observed (Qe~=O, see Fig.17.11). In the
space experiment, 4 samples, 2mm diameter and 18mm in length,
were placed in a zirconia shear cell (see 5.2.4> and heated in
the "Gradient Heating Facility" of SPACELAB for 6 hours at a
temperature gradient of 200K/cm (320 to 660~C), sufficient to
attain the steady state (see 5.2.2). At the end of the
experimen.t the samples were divided into 6 parts by shearing. On
the ground the parts were treated by activation analysis. The
concentrations at the ends were found to be .035r.Co (bottom) and
.07r.Co (top). Hence the heat of transport is negative, which
could not be detected in ground experiments. The results are
shown in Fig.17.11.
1 .4

0 1.3
u
lI-f 1 .2
0
~ 1.1
0
OM
.j.l
nl 1.0 19
H
.j.l
I=: 0.9
Q)
0
0 0.8
~

.-1
0
. 0.7
Q)
H
0.6 Temperature
500 600 (OC)
400
Fig. 17.11 Thermotransport of Co in Sn (ground and space)

Since the electronic part of Qeffis small in this case, the

flight data have been evaluated for the intrinsic part, yielding

with K, = (1.62~.04~10
-4
eV/K <17.17)
444

Thus at 320°C we get Qeff = -.096eV and Qeff = -.151eV at 660°C,

which is quite reasonable (for comparison : ~=(.004±.007)eV

for Ag in Sn, Qaff=.2eV for Cu in Li, [17.14]).

17.4.2 Thermotransport in AgI/KI (D1 Flight)

The first thermotransport e>:periment on molten salts in space is

prepared by Bert and Dupuy [17.10] and will be performed in the
"Gradient Heating Facility" of SPACELAB in the Dl-mission. A
mixture of AgI.r5 KI,'2.5, corresponding to the eutectic composition,
is placed between two isolated silver electrodes. Similar to the
thermotransport experiment on Co in Sn, it should be e>:pected
that the heavy Ag-ions will migrate to the hot end, while the K-
ions will migrate to the cold end. Hence in the D1-flight, the
concentration changes at the ends of the sample can directly be
measured by the e.m.f. between the silver electrodes, which will
be monitored continuously during the e>:periment. Since the
mobilities of Ag and K are ma>:imum at the eutectic composition
the raise of the e.m.f. can be measured with sufficient accuracy
in 6 hours.

The problems of ground e>:periments are the same as for Co/Sn.

Hence, reliable data can only be produced in space e>:periments.

17.5 Summary and Outlook

As the discussion in the sections above has clearly demonstrated

there is a number of processes in liquids, predominantly diffu-
sion, thermo- and electrotransport, thermal conductivity and
probably viscosity, the mechanisms of which can hardly or never
be investigated in ground e:·:peri$llents. Gravi ty-dri ven convec-
tion, often inevitable on the ground, will produce bad or even
wrong results. Hence it is desirable to do the corresponding
experiments in space, which is an ideal environment for such
investigations. First experiments in this field of research have
been successfully performed and have demonstrated the ability of
crew and hardware in space as well as of supporting and
 445

oreparing staff and equipment on the ground to optimize

conditions for success. Since the knowledge about the different
nechanims in the discussed physical processes in liquids and the
corresponding basic data is essential for many techical and
oiological processes, e.g. in the development of new materials,
the interest will be increasing in future. The development of
technology in space has just begun and the first e}lperiments
will be continued, but several effects,as indicated, still await
their investigation in space.

Ref ere n c e s

17.1. Walls, H.A.; Upthegrove, W.R.; Acta Met. 12, 461 (1964)

17.2. Edwards, J.B.; Hucke, E.E.; Martin, J.J.; Met.Rev.13, 1

(1968) and Met.Rev. 13, 13 (1968).

17.3. Shimoji, M.; "Liquid Metals". Academic Press,Loridon 1977

17.4. Kraatz, K-H.; Frohberg, G.; Wever, H.; investigations in

relation to [17.5], unpublished.

17.5. Frohberg, G.; Kraatz, K-H.; Wever, H.; "Selfdiffusion

of Sn112 and Sn124 in Liquid Tin" in "Results of
SPACELAB-l" (see [17.12]).

17.6. Ukanwa, A.O.; M558, Proc. III. Space Processing Sympos.

Skylab Results (1979), MFSC, Alabama, USA 35812,p.427.

17.7. Reed, R.E.; Uehlhoff, W.; Adair, H.L.; "Surface-Tension-

Induced Convection", NASA SP-412, Apollo-Soyuz Test
Project Vol.l, 367 (1977).

17.8. Malmejac, Y.; Praizey, J.P.; "Thermomigration of Cobalt

in liquid tin - Experiment 1 ES320 -" in "Results of
SPACELAB-1" (see [17.12]) and in [17.13].

17.9. Kraatz, K-H.; Frohberg, G.; Wever, H.; "Interdiffusion

446

in schmelzflussigen Metallen" in "Wissenschaftliche

Ziele der deutschen SPACELAB-Mission 01" (see [17.13]).

17.10. Bert, J.; Dupuy, J.; "Space Thermal Diffusion Experi-

ment in a Molten AgI-KI Mixture" in "Wissenschaftliche
Ziele der deutschen SPACELAB-Mission 01" (see [17.13J)'

17.11. Merkens, W.; Richter, J.; "Interdiffusion

in Salzschmelzen" in "Wissenschaftliche Ziele der
deutschen SPACELAB-Mission 01" (see [17.13J).

17.12. ESA; "Results of SPACELAB-l". 5th European Symposion

on Material Science under Microgravity, Elmau 1984.
ESA, Paris 1984

17.13. Sahm, P.R.; Jansen, R.; "Wissenschaftliche Ziele der

deutschen SPACELAB-Mission 01", DFVLR-PT-SN, Koln 1984.

17.14. Wever, H.; Frohberg, G.; Adam, P.; "Elektro- und Thel"mo-
transport in Metallen". Joh. Ambrosius Barth, Leipzig,
1973.

17.15. Pond, R.B.; Winter, J.M.; "The Diffusion of Liquid Zinc

and Lead" in "Wissenschaftlic:he Ziele der deutsc:hen
SPACELAB-Mission D1" (see [17.13]).
18 Glasses

R. H. DOREMUS
Materials Engineering Department
Rensselaer Polytechnic Institute
Troy, New York 12181

Containerless processing of glass in low gravity has the prospect of devel-

oping new and purer glassy materials and providing measurements of proper-
ties that are difficult or impossible to determine in a container. The
usual processing of glasses in a container often leads to contamination and
nucleation of crystals at the container walls.

In this chapter containerless processing of glass in microgravity is sum-

marized. Uses, processing, formation and crystallization, diffusion and
bubbles in glasses are described as background for discussions of space ex-
periments. Then space experiments already carried out and planned are dis-
cussed. The emphasis is on oxide glasses, mainly silicates, and fluordde
glasses, because these are the glass types being studied in space. A bib-
liography of books and articles on glass is given at the end of this chapter.

18.1 Uses and Types of Glass

The original use of glass was for decorative and artistic objects, and this
use continues to this day. One need only visit the Stueben exhibit in New
York City, the Corning museum in Corning, New York, or glass exhibits in
Czechoslovakia to sense the originality and excitement of present day artis-
tic work in glass.

The next use of glass was for containers, for food, perfume, oils, and many
other substances; this application still uses t~e most glass today: The
production of flat glass, mainly for windows in buildings and vehicles, is
now the second largest item of glass manufacture. Lamp envelopes and seals
are another major area of use. There are many special applications of glass,
some in small quantity but of high value, most of which have been developed
in the last few decades. Some of these special applications are glass
448

ceramics and surface strengthened glass for higher strength and chemical du-
rability; light weight composites of fiber glass in polymer matrixes; glasses
for laser hosts and optic wave guides for long-distance communication; fused
silica for melting semiconductors, telescope mirrors, and arc lamps; amor-
phous silica layers on silicon in electronic devices; encapsulation of these
devices; and as a medium for solidifying radioactive wastes.

These uses of glass are based on a variety of desirable properties, such as

ease of forming into many different shapes; cheap, widely available raw ma-
terials; chemical durability; transparency; high temperature durability;
wide "solubility" of constituent oxides; and low electrical conductivity.

The possibility of incorporating a large number of different oxides in a

silicate glass has led to a wide variety of commercial glasses. Neverthe-
less there are a relatively small number of glasses that make up the large
majority of glass production.

By far the most common glass is based on the soda-lime-silicate (sodium cal-
cium silicate) system. All ancient glasses contained oxides of sodium, cal-
cium and silicon. These glasses are cheap, chemically durable, and relative-
ly easily melted and formed. Many minor additions to the basic composition
(not far from 70% silica, 15% soda, Na20, 10% CaO + MgO, and 5% other oxides)
are made to improve properties of melting and forming: alumina for improved
chemical durability and reduced devitrification (crystallization), borates
for easier working and lower thermal expansion, zinc oxide for lower melting
temperatues, and arsenic and antimony oxides for fining (removal of bubbles).
Soda-lime glass is often termed "soft" glass because of its relatively low
softening temperatures.

Pyrex borosilicate glass was developed by Corning Glass Works to be more re-
sistant to thermal shock and more chemically durable than soda-lime glass,
yet still to melt at a similar temperature. The borate in this glass re-
duces its viscosity and the coefficient of ~hermal expansion, and allows low
sodium content, which increases chemical durability. Pyrex borosilicate
glass is often called "hard" glass because of its higher softening tempera-
ture compared to soda-lime glass, and is somewhat more expensive than soda-
lime glass because of its higher melting temperature and more expensive bo-
rate raw material. The mirror for the Mount Palomar telescope was made of
Pyrex borosilicate glass because of its low thermal expansion; nevertheless
 449

it is necessary to correct minute distortions of the mirror surface caused

by temperature differences.

Vitreous silica is made of pure silica, Si02, giving it excellent high tem-
perature stability, optical properties, and thermal shock resistance.

A variety of lead glasses are important as low-melting sealing and solder

glasses with a wide working temperature range. Lead glass for fine "crys-
tal" contains much more lead than these glasses.

New compositions of both oxide and non-oxide glasses are being rapidly de-
veloped for a variety of new applications. Often compositions of interest
cannot be formed into glass because of rapid crystallization; containerless
processing offers the possibility of enlarging the composition range that
form glasses by eliminating nucleation at container walls and catalysis by
impurities from the container.

Zirconium fluoride glasses are an exciting class of new glasses because they
have a wide range of transparency in the infrared to about 8 or 9 ~m, whereas
in usual thicknesses silicate glasses have an absorption edge at about 4 ~m.
These fluoride glasses have the potential of greater transparency for opti-
cal wave guides made of glass fibers that are replacing telephone cables.
The silica fibers presently used for optical wave guides have a transmission
minimum determined by the intersection of scattering and infrared absorption.
Because of lower absorption in the infrared the zirconium fluoride glasses
have the potential of a substantially lower absorption minimum, which could
provide longer cable lengths between amplifiers.

18.2 Melting of Glass

The main raw materials for silicate glasses are silica sand (Si02), sodium
carbonate and nitrate, calcium and magnesium carbonate, feldspar [Na,
K(A1Si3)08, and sodium borate. These materials are mixed as powders and
melted in crucibles or a continuous furnace called a glass tank. Crucible
materials are clay, porcelain, mullite, alumina, or platinum; glass tanks
are lined with special refractories, usually aluminosilicates or high in
zirconia. Heat sources are combustion of natural gas for larger furances
and electricity for smaller and laboratory furnaces. Air is the usual at-
mosphere.
450

Melting of the sodium carbonate above about 850 0 e provides a flux that dis-
solves the sand and higher melting minerals. In a crucible, melting tem-
peratures of soda-lime glasses of 13oo o-14oo oe are usual; in a continuous
tank the maximum temperature can be somewhat lower. "Harder" compositions
such as Pyrex borosilicate and aluminosilicates require higher temperatures,
whereas high lead or high borate glasses can be melted at lower temperatures.
The viscosity of the glass is the most important parameter determining the
melting temperature. A viscosity of less than 1000 poise is desirable to
provide homogenization and fining (bubble removal) during melting of the
glass.

The above procedures are appropriate for silicate glasses, but other glass
compositions require different methods. The melting of zirconium fluoride
glass is described here because it is being used in experiments in the space
shuttle.

A typical fluoride glass composition is 62 mole % ZrF4' 33% BaF2and 5% LaF3.

The fluorides are melted in a vitreous carbon crucible for a few hours in
an atmosphere of nitrogen plus 3% e12 or some carbon tetrachloride. If the
starting materials are oxides, an excess of ammonium bif1uoride is added to
the melt to convert the oxides to fluorides. The chlorine in the atmosphere
helps to provide a clear glass; without it, black specs often occur in the
glass. They are possibly chemically reduced centers. A maximum temperature
of about goooe is required for complete melting, and a clear glass can be
cast in brass molds.

Homogenization of glass is aided by flow of the glass, which can result from
thermal and density gradients, and can also be induced by stirring. In a
glass tank flow through the furnace promotes homogenization; sometimes ob-
structions are built into the furnace to break up the flow and increase con-
vection. Molecular diffusion is usually too slow to give homogenization on
a scale of greater than about a millimeter. so bulk homogenization in the
melt depends mainly on convection.

The most important determinant of good homogeneity is proper mixing of raw

materials. In the laboratory fine powders (10 ~m or less in size) can be
mixed in an organic fluid (e.g. alcohol) in a b1endor, and the fluid care-
fully evaporated. Uniform mixing is much more effective than remelting in
ensuring a homogeneous glass.
 451

Small glass melts in low gravity do not have much convective flow, so homo-
genization by flow is difficult. Again thorough mixing of raw materials is
the best way to guarantee homogeneity.
Removal of bubbles (fining) occurs either by rising to the glass surface by
buoyancy or dissolution of their gases into the glass. The former mechanism
is of course not available in low gravity, so bubble removal may be a problem .
•
A special section is devoted to bubbles in glass because of their importance
and interest.

To make pure, homogeneous starting materials for glass processing the glass
components can be mixed as liquid organic compounds and precipitated as a
gel [lJ. This "sol-gel" method is too expensive for most commercial uses
but is valuable for specialized applications, such as preparing granules
for making tiny thin-walled glass shells as laser fusion targets. New glass
compositions can be made by this method because of the lower temperatures
of consolidation.

In one sol~gel method alcoholic solutions of metal alkoxides, such as sili-

con ethoxide [Si(OC2H5)4J, are mixed to form a solution with proportions of
the glass composition desired, and then hydrolyzed to form a gel. The hy-
drolysis conditions depend upon the form of the final glass product (slab,
granules, or fiber). For solutions containing many components, gelling con-
ditions must not result in preferential precipitation or segregation. To
form a precipitate water or acid can be. added to the alkoxide solution:

(1)

For more uniform gelation leading to large pieces or fibers, water or acid
dissolved in alcohol can be added for hydrolysis.

The gel is converted to glass is by heating, during which the water and or-
ganic substances evaporate. Control of the heating rate is critical to pre-
vent crystallization or cracking.

18.3 Glass Formation and Crystallization

In principle any substance can be made into a glass by cooling it from the
liquid state fast enough to prevent crystallization. The final temperature
must be so low that the molecules move too slowly to rearrange to the more
stable crystalline form. Alternatively one can imagine building up the mate-
452

rial onto a substrate. either by deposition or chemical reaction from the

vapor. the substrate being .so cold that rearrangement cannot take place. In
actual practice glass formation has been achieved with a relatively limited
number of substances.

If a glass is formed from a liquid. it must be cooled below its melting point
so fast that the supercooled liquid does not crystallize. Thus the rate of
crystallization of a material controls whether it can form a glass. As an
example. the velocity of crystallization of cristobalite from fused silica
is shown as a function of temperature in Fig. 1 from the work of Wagstaff
[2]. As the silica is cooled below the melting point of cristobalite. the
rate of crystallization rises to a maximum value and then decreases. At
much lower temperatures (below about 900°C for pure vitreous silica) the
rate of crystallization is so slow that even for long holding times no ap-
preciable amount of crystalline material is formed. Thus. if the silica
is cooled rapidly enough from above the melting point to below 900°C. no
appreciable amount of crystalline cristobalite is formed. and the silica
becomes a stable glass.

12

Z
~ 4
"-
Q
0
E
::l.
-4
W
~
c::(
0:: -8

-12

1450 ISOO 1550 1600 1650 1700 1800

TEMPERATURE (oe)

Fig. 1 The rate of crystallization of cristobalite from vitreous silica.

Data of Wagstaff [2].

The relationship between the rates of crystallization and other properties

of the liquid is now considered. A simple theoretical equation for the velo-
city v of crystallization of a liquid at a temperature T is (Doremus. 1973.
p. 93ff):
 453

L(Tm-T)
v =-...;,;-- (2)
3na 2nTm

where L is the heat of fusion at the melting temperature Tm,n is the viscos-
ity of the liquid, and a is a distance of the order of a lattice spacing.
Of the factors in the equation the viscosity varies much more than L/Tm or a
from one material to anlYther. Thus a liquid with a high viscosity near its.
melting point has a low crystallization velocity and can be more easily,
formed into a glass. Furthermore the high viscosity of a glass-forming ma-
terial helps to prevent the rearrangement of its molecules to the crystall ine
state at temperatures below that of maximum crystallization rate. For some
glasses the ratio vn/~T is a constant as demanded by eq. 2; for others it is
not constant, and in these glasses a contribution from heat flow is likely.

The cooling rates necessary to prevent crystallization in many materials

are impractically large, yet they are easily cooled to the glassy state.
Therefore another barrier to bulk crystallization must exist in many glass-
forming materials. This barrier can be the rate of nucleation of crys-
tals [3].

The rate of homogeneous nucleation of a crystal from a liquid is

I = K exp (RT)
w* (3)

where W* is the work involved in forming the critical nucleus, and K is a

coefficient whose dependence on temperature is neglected here. The work
done in forming a spherical, isotropic, crystalline critical nucleus with
isotropic surface energy y from a liquid of the same composition is

16ny3V2T2m
W* (4)
3L2(1IT)2

where V is the molar volume of the liquid, L is its heat of fusion, and ~T
is the difference between the actual temperature and the melting temperature
Tm·

Equations 3 and 4 are valid for homogeneous nucleation. In actual practice

nucleation is rarely homogeneous, but takes place on impurity particles,
vessel walls, defects, or some other heterogeneity. These heterogeneities
effectively lower the interfacial tension y.
454

In condensed systems the nucleation rate can be limited by the rate of mole-
cular rearrangement of the liquid, and this transport limitation is particu-
larly important in viscous systems such as the glasses being considered here.
One way to take account of this transport limitation is to multiply Eq. 3
for the nucleation rate by a factor that is inversely proportional to the
viscosity of the liquid. Then the nucleation rate also shows a maximum with
undercooling. Usually this maximum is at a lower temperature than for crys-
tallization.

In looking for new glass-forming systems one can search for phase regions
with "deep" (low temperature) eutectics. The viscosity in the low tempera-
ture eutectic is high, reducing the rate of crystallization and favoring
glass formation.

18.4 Diffusion
Many properties of silicate glasses, such as fatigue, chemical durability,
electrical conduction, gas permeation, and fining (bubble shrinkage) depend
upon the rates of diffusion in the glass. Diffusion in glass can be distin-
guished as molecular (gases), ionic (monovalent cations) and lattice.

Gases dissolve and diffuse molecularly in glasses because of their open

structure. The permeation flux J of a gas through a membrane of glass of
thickness L at steady-state is:

J = CDIL (5)

where C is the dissolved concentration of gas at one surface of the membrane,

D is the diffusion coefficient of gas in the glass, and the gas concentration
at the other surface is assumed to be negligably small.

The solubility C of different gases is not much different for different

gases, is almost constant over a wide range of temperature, and is directly
proportional to the partial pressure of the dissolving gas.

The diffusion coefficient D increases with increasing temperature and de-

creasing molecular size. The activation energy Q for molecular diffusion of
gases in vitreous silica is directly related to their molecular size R by
the relation
(6)
 455

where Kl and K2 are constants. Inert gases (He.Ne.Ar.Kr,Xe) fit this rela-
tion as well as reactive multiatomic molecules (H2.02.N2.H20).

These latter gases dissolve molecularly in the glass and can also react with
the glass network. for example:

H20 + Si02 = 2SiOH (7)

H2 + Si02 = SiOH + HSi (8)

These reactions affect properties of the glass such as optical absorption,

viscosity. and electrical conductivity. and are important in fining.

Gaseous diffusion is rapid in vitreous silica and decreases as modifiers

are introduced into the glass. The lower densities of modified glasses
demonstrate the blocking of interstices in vitreous silica and the resultant
lower diffusion rate.

The ionic conductivity of almost all oxide glasses results from the trans-
port of monovalent cations. In most commercial glasses the conducting ion
is sodium. Reaction of silicate glasses with water involves interdiffusion
of monovalent cations and hydronium ions.

Below the glass transition temperature Tg of about 450 0 the electrical re-
sistivity fits the Arrhenius equation with constant activation energy.
whereas above Tg there is a break and a changing activation energy with tem-
perature.

The addition of most oxides of higher valent ions to a binary alkali sili-
cate glass reduces the diffusion coefficient of alkali in them; however.
addition of aluminum oxide in small amounts increases the mobility of the
alkali ion. When a second alkali ion is added to an alkali silicate glass
the conductivity decreases sharply in the "mixed-alkali" effect.

Cations of higher valence and anions diffuse much more slowly than mono-
valent cations in silicate glasses. Lattice elements (silicon and oxygen)
diffuse very slowly. but still more rapidly than predicted from the Stokes-
Einstein equation for a sphere of radius r:

D = kT/61Tnr (9)
456

where D is the diffusion coefficient, k Boltzmann's constant T the absolute

temperature, and n the viscosity. Thus it is uncertain if there is any
direct relation between viscosity and lattice diffusion.

18.5 Bubbles
Removal of bubbles from a glass melt is one of the most difficult steps in
the manufacture of glass. The rate of rise of gas bubbles dh/dt by buoyancy
is

dh =~ (10)
dt 9n

where p is the density of the glass, g the gravitational constant, R the

bubble radius, and n the viscosity of the glass. For a viscosity of 100
Poises, the rate of rise of bubbles 0.1 mm in diameter is about 10 cm/day,
which is too small to eliminate them from a normal glass tank. Thus small
bubbles can be removed from glass melts only by dissolution of their gas
into the glass melt.

If a glass is melted in low gravity, bubbles in it can be removed by dis-

solution or by moving the bubbles with forces other than buoyancy. Low
gravity provides a medium in which bubble motion can be studied without the
interference of buoyancy or buoyant convection in the glass.

A gradient of surface tension on the bubble surface can generate a force on

the bubble and cause it to move. Subramanian [5J has discussed this force
and its relation to melt properties. The gradient in surface tension can be
developed by gradients in temperature, composition, or electrical charge
density, because the surface tension varies with these factors. The gradient
in surface tension induces a tangential stress on the bubble surface, and
the bubble moves in the direction of decreasing surface tension. In a
temperature gradient the bubble moves to the hot end, because surface ten-
sion decreases with increasing temperature.

Subramanian [5J found the velocity of bubple migration v to be given by the

equation

.l = 1 .0209 M2 (11 )
Vo "2-

where Vo is the velocity

 457

~ldYIR
Vo = Of (12)
Tl

in which dT/dx 1S the temperature gradient and Idy/dTI is the absolute value
of the change of surface tension with temperature, assumed to be a constant.
The Marangoni number M. is
M= voR/a (13)

in which a is the thermal diffusivity. When the velocity Vo is small, the

bubble velocity is vo/2, which is the result for negligible convective trans-
port in the liquid.

The rate of shrinkage of a small bubble in glass is usually controlled by

the rate diffusion of gas in the bubble into the glass. The first approxi-
mation to the bubble radius R as a function of time t is [6]

2 2 2Ro
Ro - R = BDt(l + IiiD£ ) (14)

in which Ro is the initial bubble radius, D the diffusion coefficient of gas

in the glass, and B = (Ce-Ci)/(CB-Ce), where ci is the initial concentration
of gas in the glass, ce is the equilibrium concentration of gas in the glass,
assumed to hold at the bubble surface, and cB is the concentration of gas in
the bubble, assumed constant. Equation 14 is valid for dilute solution
(B « 1), and has been verified for nitrogen bubbles in molten boron tri-
oxide [7].

If the solution is not dilute, a variety of complications can arise, es-

pecially radial flow of the glass into the bubble [8,9,10]. Other complica-
tions include finite sample size [6], more than one gas in the bubble [6,11],
a rising bubble [12], surface reactions [13], surface tension effects [14],
and several bubbles with overlapping diffusion fields [15].

Certain compounds are added to glass melts to ai? in removal of bubbles.

The mechanism of these fining agents is being depated. Typical agents for
soda lime silicate glass are sulfates and arsenic and antimony oxides. For
many years it was thought that the arsenic released oxygen at glass melting
temperatures, which "swept out" the bubbles in the glass. However, the
calculation above shows that such a mechanism would not eliminate small
bubbles, and the elegant experiments of Greene and co-workers [16] showed
458

that arsenic enhances dissolution of oxygen bubbles in glass. Thus the

importance of arsenic and antimony oxide additions to the glass is to aid
in removal of fine bubbles, rather than to generate more gas.

In actual glass-melting carbonates are the usual source of sodium and cal-
cium oxides. Thus there is carbon dioxide in bubbles in glass as well as
oxygen and nitrogen from air. Arsenic can also increase the rate of carbon
dioxide diffusion into the glass [17,18].

18.6 Processing of Glass in Low Gravity

Low gravity for materials processing can be achieved in several different
ways [21]. A drop tower provides a few seconds of low gravity as a solid
or liquid drops from ·heights up to 100 meters. An airplane flying in a
parabolic course provides 10 to 20 seconds of low gravity. In a rocket
a few minutes of low gravity occur. Long periods of time for low gravity
experiments are available in vehicles orbiting the earth, such as the space
shuttle (see Chapter 3).

Tiny glass shells are needed to contain fuel fQr inertially confined fusion
experiments. In one method particles of a gel containing glass constituents
are dropped through a furnace tower to make shells. An example of shell
dimensions is 100 ~ in diameter with 5 ~ wall thickness. The experiments
require very smooth surfaces and a nearly perfect sphere.

The furnace tower is heated above glass melting temperatures, for example,
to 1500°C, and can be a few meters high. When the gel particles are fed
into the furnace, they reach the furnace temperature rapidly; during this
time the organic compounds decompose to silicates that melt and form a glass.
The gaseous decomposition products act as "blowing" gases and blow the glass
into shell. As the shells drop through the furnace surface tension forces
smooth the glass surface and round the glass to a perfect sphere. The fur-
nace contains gas. so the shells are not in free fall. Nevertheless a high
degree of surface smoothness and concentricity can be achieved. The mech-
anisms of smoothing and centering are not entirely understood.

Glass spheres were formed by melting the end of a ceramic rod spinning at a
high rate [22,23]. The ceramic was melted with a C02 laser and the drops
collected after they spun off the end of the rod and fell into a hopper.
 459

Many new glass compositions were made in this way, for example, in wt%,
15 CaO 85 Nb203' 10 CaO 90 Ta205, 20 CaO 80 Ga203' La203, Y203' Sm203,
Gd203, 25 La203 75 Ta205, and 50 La203 50 Nb205.

Some Ge-Sb-S glasses were melted in low gravity, apparently in a crucible,

in the Soyus-Salyut complex [24]. Comparable glasses melted on the ground
crystallized more easily than those melted in low gravity. The authors
suggested that this difference resulted because the sample melted in low
gravity had less heterogeneous nucleation because of the absence of convec-
tion. More experiments are needed to test this possibility.

Two experiments on glasses have been flown on the space shuttle, and repeats
of these experiments are planned on future shuttle flights.

Day used the single-axis levitator built by Intersonics Corp. for his samples.
In addition to three inert samples, there were five different glass samples
as listed in Table 1. These experiments were designed to test the possi-
bility of melting glass in space. They include studies of melting and
crystallization during cooling of different glass compositions (samples 1,
2, 3 and 5), of bubble behavior (samples 1 and 4), and homogenization (sam-
ples 1 and 4).

TABLE 1
Glass Compositions and Treatments in Flight Experiments
of Delbert Day. Univ. of Missouri. Rolla
40% Ga203 . 35 CaO . 25 Si02
1. Hot-pressed plus Si02 particles. Melt at 1500°C.
2. Divitrified glass, colored drop on surface. Hold at 1500°C.

56% Ga203 - 44 CaO

3. Divitrified glass. Hold at 1500°C.

33% Na20 - 67% B203

4. Glass + Bubbles. Hold at 900°C.

45% Na20 - 55% Si02

5. Divitrified glass. Hold at 1350°C.
400

In the first flight the cooling shroud stuck open before any of the glass
samples could be processed. Sample 1 was partially melted and showed bub-
ble formation in post-flight analysis. The moving picture camera did not
operate properly, so no in-flight pictures were recorded. Other samples
were not processed as planned.

The heating sequence for flight experiments by Doremus and Elleman in a

three-axis acoustic levitator built at JPL is given in Table 2.

TABLE 2
Sample Compositions and Heat Sequence in Flight Experiments
of Robert Doremus, Rensselaer Polytechnic Institute
and Dan Elleman. Jet Propulsion Laboratory
Samples: Glass spheres 1 cm in diameter with a small boss and a bubble
about 2 mm in diameter.
Glass Composition: 62 mol% ZrF4' 33% BaF2, 5% LaF3

Heating Schedule
1. Heat to 600°C. Glass should soften above 300°C, then crystallize, and
finally the crystals melt above 540°C.
2. At 600°C. Measure surface tension and viscosity of melt by oscillation
and rotation of sample. Observe bubbles.
3. Crystallize glass on cooling.

In the first flight the sample was observed during the first portion of the
heating cycle (up to about 500°C) but was then lost from view because of
acoustic instabilities. The surface of the sample showed changes, probably
softening, but the viewing capability was not adequate to resolve details.
The sample was recovered as coarse granules; a dark indent on one chunk
indicated that the sample stuck to the wire restraining cage in the furnace.
The sample showed a fine crystalline microstructure (< 1 ~m) compared to the
much larger columnar crystals that grow on slow cooling in a container.
X-ray diffraction showed the same crystalline phases in the flight and
ground samples, but in different proportfons.
i

18.7 Measurement of Properties of Glass in low Gravity

Interdiffusion experiments in glass melts were carried out in the low gravi-
ty provided during a rocket flight [25,26]. In one experiment a Na20·3 Si02
 461

glass and a Rb20·3 Si02 glass were held together at a mean temperature of
about 1160°C for an effective time of about 135 sec. The profile of Fig. 2
was measured by the electron microprobe. An identical sample on the ground
showed interference caused by convection. The authors interpreted their pro-
file with a concentration dependent interdiffusion coefficient; however, the
curve in Fig. 2 is drawn from the equation for a concentration independent
diffusion coefficient for a couple, and fits the data well except for a few
points at high sodium concentration.

1.0 ..-<>-£]0-0---,.;-------------------,
o
c: o
.Q .8
~
~
§ .6
u
E
.='
~ .4
.~
<;
~ .2

°O~----.LI---~.2~---~~~~~.4
Distance, em

Fi g. 2 Profile of sodium and rubidium in a couple of Rb 0·3SiO and

Na?0·3Si0 2 glasses after 135 sec. at 1160°C in 16w grav~ty during a
rocket flight. From ref. 25. Points, experimental, line for a
constant diffusion coefficient.

The rate of dissolution of vitreous silica in Na20'2 Si02 and Na20'3 Si02
melts were also measured under low gravity in a rocket flight [26J. It was
found that dissolution occurred slightly more rapidly in low gravity than
in identical ground experiments. The authors suggested this result was
caused by the action of convection vortices.

18.8 SUlIIIIary
Low gravity provides exciting opportunities for original experiments on glass
formation, melting, and property measurements. Future experiments will test
further the role of convection, nucleation in containerless melting, and new
measurement methods. For example the surface tension and viscosity of corro-
sive melts can be measured without a container by vibrating and rotating
462

levitated drops.
BIBLIOGRAPHY
Books on Glass
Babcock C.L. 1977 Silicate Glass Technology t4ethods, Wiley, New York.
Doremus R.H. 1973 Glass Science, Wiley, New York.
Douglas R.W.; Frank S; A History of Glass Making, Hen1ey-on-Thames: G.T. Fou1is
1972.
Holloway D.G. 1973 The Physical Properties of Glass, Wykeham Publications,
London. 200 pages. An introduction to the structure and properties
of glass.
McMillan P/W. 1979 Glass Ceramics, 2nd ed., Academic Press, New York.
Morey G.W. 1954 The Properties of Glass, Reinhold, New York.
Collections of Review Articles
Mackenzie J.D. (ed.) 1960, 1962, 1964 Modern Aspects of the Vitreous State
Vo1s. 1-3. Butterworths, London.
Pye L.D.; Stevens H.J.; LaCourse W.C. (eds.) 1972 Introduction to Glass
Science, Plenum Press, New York.
Tomozawa M.; Doremus R.H. (eds.) 1977, 1979, 1982, 1985 Treatse on Materials
Science and Technology Vo1s. 12,17, & 23, Glass I, II, III, IV,
Academic Press, New York.
Uhlmann D.R.; Kreid1 N.J. (eds.) 1980 - Glass: Science and Technology,
Academic Press, New York.

References
1. Sakka, S.: Gel method for making glass in Treatise on Materials Science
and Technology, Vol. 22, Tomozawa, M., and Doremus, R. H., eds.,
Orlando, FL: Academic Press 1982.
2. Wagstaff, F. E.: Crystallization and melting kinetics of cristoba1ite.
J. Amer. Ceramic Soc. 52 (1969) 650.
3. Doremus, R.H.: Glass Science, New York, Wiley and Sons 1973, p. 16ff.
4. Zachariasen, W. H.: J. Amer. Chern. Soc. 54 (1932) 3841.
5. Subramanian, R. S.: Slow migration o~ a gas bubble in a thermal gradient.
A. J. Ch. E. Jounra1 27 (1981) 646-654.
6. Doremus, R. H.: Diffusion of oxygen from contracting bubbles in molten
glass. J. Amer. Ceramic Soc. 43 (1960) 655-661.
7. Brown, R. B.: Doremus, R. H.: Growth and dissolution of gas bubbles in
molten boric oxide. J. Amer. Ceramic Soc. 59 (1976) 510-519.
 463

8. Ready, D. W.; Cooper, A. R.: Molecular diffusion with a moving boundary

and spherical symmetry. Chem. Eng. Sci. 21 (1966) 917-922.
9. Duda, J. L.: Vrentas, J. S.: Mathematical analysis of bubble dissolution.
A. J. Ch. E. Journal 15 (1969) 351-356.
O. M. C. Weinberg, P. J. K. Onorato, and D. R. Uhlmann, Behavior of bubbles
in glass melts I, dissolution of a stationary bubble containing a single
gas. J. Amer. Ceramic Soc. &l, 175 (1980).
1. M. C. Weinberg and R. S. Subramanian, J. Amer. Ceramic Soc. 63, 527
(1980) .
2. Onorato, P. J. K.; Weinberg, M. C.; Uhlmann, D. R.: Behavior of bubbles
in glass melts III, dissolution and growth of a rising bubble containing
a single gas. J. Amer. Ceramic Soc. 64 (1981) 676-682.
3. M. C. Weinberg and R. S. Subramanian, The dissolution of a stationary
bubble enhanced by chemical reaction. Chem. Eng. Sci. 36,1955 (1981).
4. M. C. Weinberg, Surface tension effects in gas bubble dissolution and
growth. Chem. Eng. Sci.~, 137 (1981).
5. M. Zak and M. C. Weinberg, Multibubble dissolution in glass melts, J.
Non-cryst. Solids 38 &~, 533 (1980).
6. Greene, C. H.; Gaffney, R. F.: Apparatus for measuring the rate of ab-
sorption of a bubble in glass. J. Amer. Ceramic Soc. 42 (1959) 271-275.
7. Cable, M.: Clarke, A.R.; Haroon, M. A.: The effect of arsenic on the
composition of the gas in seed during refining of glass. Glass Tech-
nology lQ (1969) 15.
8. Doremus, R. H.: Glass Science. New York, Wiley and Sons 1973, p. 237ff.
9. Greene, C. H.; Platts, D. R.: Behavior of bubbles of oxygen and sulfur
dioxide in soda-lime glass. J. Amer. Ceramic Soc. ~ (1969) 106-109.
~O. Harding, F. L.; Ryder, R. J.: Effects of silicon nitride additions to
container glass batch. Glass Technology 11 (1970) 54.
~l. Naumann, R. J.; Herring, H. W.: "Materials Processing in Space: Early
Experiments", Washington, NASA, 1980.
~2. Topol, L. E.; Hengstenberg, D. H.; Blander, M.; Happe, R. A.;
Richardson, N. L.; Nelson, L. S.: Formation of new oxide glasses by
laser spin melting and free fall cooling. J. Noncryst. Solids 12 (1973)
377-390. -
~3. Topol, L. E.; Happe, R. A.: Formation of newclanthanide oxide glasses by
laser spin melting and free-fall cooling. J. Noncryst. Solids li (1974)
116-124.
~4. Barta, C.; Trnka, J.; Triska, A.; Frumar, 14.: Recrystallization of
glasses of the Ge-Sb-S system prepared under conditions of zero gravity.
464

25. Herr, K.; Barklage-Hilgefort, H. J.; Frishat, G. H.; Reactions between

glass melts. Proc. 3rd European Symp. on Material science in Space.
ESA SP-142, 1979.
26. Blier, W.; Braedt, M.; Frischat, G. H.: Reactions between vitreous silica
and sodium silicate glass melt under weightless conditions. Phys. Chern.
Glasses 11 (1983) 1-4.
19 Separation Techniques
ROBERT S. SNYDER
Space Science Laboratory
NASA Marshall Space Flight Center
Huntsville, AL 35812

Summary
The use of the microgravity environment to separate and purify biological
cell s and proteins has been a major activity since the beginning of the
NASA Microgravity Material Sciences and Appl ications program. Purified
populations of cells are needed for research, transplantation and analysis
of specific cell constituents. Protein purification is a necessary step
in research areas such as genetic engineering where the new protein has to
be separated from the variety of other proteins synthesized from the
microorganism. Currently available separation methodology is not suffi-
cient for the established goals of the biomedical community for purifica-
tion and production.
At this time, three separation techniques have been identified that are
limited by gravity and these are being evaluated by intensive ground-based
research and flight experiments. Electrophoresis of particles, such as
cells, to improve the resolution of separation and of proteins to increase
the concentration that can be separated have been investigated by the
Marshall Space Flight Center and the McDonnell Douglas Astronautics Com-
pany, respectively. Free flow isoelectric focusing, done in a recycling
mode, requires flow stabilization in the laboratory. Most recently, phase
partitioning of cell s has been shown to be degraded by fl ows induced by
gravity. This paper describes the results of research exploring the
benefits of weightlessness for each of these separation techniques.

Biological purification [1] requirements have generated a variety of

instruments in the past decades that separate on the basis of biochemical
properties of the cells and proteins, such as affinity methods, fluores-
cent markers, etc., and those that separate on the basis of physical
properties, such as size and electrical charge differences. NASA has
concentrated on physical methods of separation in particular, electrophor-
esis, as part of an investigation into fluid transport and chemical pro-
cesses with the principal objective to determine the influence of gravity.
Over the past several years, this has involved a variety of tasks includ-
ing: 1) evaluation of available electrophoresis apparatus and the capa-
466

bility of this instrumentation to satisfy the needs of the biomedical

community; 2) understanding the limits that flow disturbances and particle
interactions impose on the separation and 3) development of new designs or
operating protocol to evaluate improvements in resolution or throughput
for laboratory or space use. Working with NASA in these investigations
have been univers,ity and industry scientists.

19.1 Electrophoresis
Analytical electrophoresis takes place in either thin slabs or narrow
columns as illustrated in Fig. 7.1. The electrodes at either end provides
the electric field to the central electrophoresis chamber. Electrolysis
products and evolved gas must be removed, as shown, and membranes limit
these reactions to the electrode compartments. Sample is inserted as a
thin section and electrophoresis then separates this sample into a series
of bands, or zones.

1-1

Fig. 19.1 Diagram of column electrophoresis

 467

Electrophoresis of proteins and macromolecules is usually carried out in

the presence of a gel or other stabilizing medium. Although the gel
offers an advantage of physical sieving, its primary purpose is to prevent
convective mixing of the separating molecules due to temperature gradients
in the buffer. The gel structure restricts the quantities that can be
separated, complicates the extraction of the fractions, and also precludes
use of the technique for biological cells and particles.

One technique for minimizing some of these restrictions for cell electro-
phoresis is the use of density gradients in columns. Vertical columns
contain layers of solution of increasing density to stabilize the fluid
against buoyancy-induced convection. Sedimentation of cells concentrated
in fluid droplets remains a problem but columns can be oriented horizont-
ally and rotated slowly to minimize these effects. Thermal convection
can be reduced by operating at low appl ied electric fields. Thin wall
capillaries are oriented horizontally during the microscopic measurement
of cell mobilities as the analytical analog for cells of gel electrophore-
sis. Thermal convection is small because the capillaries are immersed in
a temperture-control led water bath and the applied field is low. Sedimen-
tation is perpendicular to the electrophoretic migration and mainly limits
the duration of the mobility measurement. Although column electrophoresis
has enjoyed only limited success in the laboratory, it was a first choice
for space, where the fluid could be uniform and stationary with no distur-
bance due to buoyancy-induced convection or sedimentation.

The first experiments done on Apollo flights, [2-3J exhibited both elec-
trophoresis and electroosmosis and although the process was easily re-
solved analytically, a good separation of the sample composed of two sizes
of polystyrene latex microspheres was not achieved. However, no addi-
tional disturbances were noted. A low zeta potential coating (methyl
cellulose) was applied to the next set of columns flown during the Apollo-
Soyuz Test Project (ASTP) in 1975. [4J Although this experiment developed
some new problems, most of the electrophoresi~ experiments were not affec-
ted and electroosmotic flow was negligible duting the separation of fixed
red blood cells. Human kidney cells were also fractionated and analysis
of enzymes produced by the separated cells showed some separation of the
ki dney ce 11 s occurred accordi ng to functi on. Co 1 umn e 1ectrophores is in
space has been shown to extend analytical electrophoresis on Earth by
468

providing high resolution of small quantities of sample. [5] However, even

in space, column electrophoresis is still a batch process.

19.2 Continuous Flow Electrophoresis on Earth

Continuous or free-flow electrophoresis was developed to allow continuous
insertion of sample and collection of fractions, permitting fractionation
of preparative quantities of materials during multi-hour operations. Fig.
7.2 shows the major features of the process which determine the quality of
the separation. The two electrodes extend down the entire length of the
thin chamber. Sample enters the buffer curtain with circular cross-
section but this structure changes under the influence of two effects.
Electroosmosis and Poiseuil le flow are factors that form the crescents du-
ring the laminar flow of sample and buffer through the chamber.

MEMBRANE
ELECTROOSMOTIC
FLOW

SAMPLE

MEMBRANE
POISEUILLE
FLOW

ELECTRODE
eLECTRODE
+

THERMAL
(BUOYANCY)
EFFECT

RESULTANT
BUFFER FLOW

Fig. 19.2 Diagram of the major fluid dyna~ic perturbations to continuous

flow electrophoresis

Continuous flow electrophoresis has generated most interest as a separa-

tion technique for biological cells but it has problems of operation and
 469

apparatus design, many of which are gravity related. The selection of the
electrophoresis fluid medium is a compromise between the requirements for
viable cell s and optimum fractionation. Biological cells prefer immersion
in buffered electrolytes of physiological ionic strength. The cells enter
the el ectrophoresis channel at a predetermined concentration in a fl uid
whose properties are comparable to the flowing curtain buffer medium. The
electric field applied to this buffer curtain and sample insertion stream
induces an e 1ectri c current proportiona 1 to its e 1ectri ca 1 conducti v ity.
Cells are typically not very mobile in any electrolyte and high electric
fields are required to achieve any significant migration. The combination
of high applied voltage and high electrical conductivity results in the
generation of intense heat in the fluid medium which can destroy the
delicate cells. Fortunately, the mobility of cells increases as the
electrophoresis buffer ionic strength is decreased and advantage of this
phenomenon can be taken provided cell viability is not affected by the low
ion content. A longer residence time in the electrophoresis chamber can
also give better separations but cell survival is reduced in low ionic
strength buffers even though they are i sotoni c. Thi s gi ves a range of
options for operation with cells and buffer medium.

The apparatus design must consider means to remove the heat from the
buffer that do not inhibit the separation efficiency. Cooling of the
chamber wall s is commonly done but this aggravates thermal convection
which is proportional to the temperature gradient in the buffer. The
thermal convection disrupts the rectilinear flow through the chamber and
distorts any separation. Additionally, the temperature gradient causes a
gradient in other fluid properties, such as viscosity and electrical
conductivity, which further influences flow and particle migration. By
making the chambers very thick, gradients in fluid properties and unwanted
flows can be minimized, but with a concomitant loss in its efficiency as a
preparative electrophoresis device. The chamber cannot be too thin or the
sample stream through the chamber will not contain enough cells to permit
adequate throughput in a reasonable length of time. The cross-section of
the sample stream should be small both in the direction of the electric
field to increase the resolution of separation and perpendicular to the
field to reduce the impact of the fluid cross flow (electroosmosis} near
the walls of the chamber. If the sample stream cross-section is a signif-
icant fraction of the chamber thi ckness, then e 1ectroosmot i c cross fl ow is
470

necessary to compensate for the parabolic (Poiseui11e) downf10w through

the chamber and yield at least one relatively narrow fraction. The var-
ious interacting phenomena described so far lead to operating procedures
and apparatus design that must be a compromise. Since gravity has a role
in most of these interactions. weightlessness can be anticipated to offer
some advantages.

Analysis of these advantages for continuous flow electrophoresis began

soon after the ASTP experiment. Ostrach [6-7] eva 1 uated the sources of
convection in liquids flowing through rectangular chambers and provided
numerical estimates for the importance of convective effects in different
geometries. He defined flow reversal as the limit of stable operation on
the ground and claimed that upf10w of buffer and sample was preferable to
the normal downf10w of existing devices. Subsequent analysis has shown
that the process is significantly more complicated. Experiments by Rhodes
[8-9] and ana 1yti ca 1 models by Sa vi 11 e [10] eva 1uated the flow and temper-
ature fields in continuous flow electrophoresis. Chambers were construc-
ted with patterns of thermocouples to measure temperature gradients along
all major axes and a flow visual ization method was used to observe and
measure flow velocities associated with these gradients. It was fO\.i·hd
that very small lateral gradients (on the order of 0.1 CO cm- 1) deform the
uniform base flow and mask additional flow distortions caused by an ad-
verse axial temperature gradient. [11] These experiment results supported
the prediction of hydrodynamic instabilities due to temperature gradients
developed by Saville that occurred at Rayleigh numbers as low as 6. These
results confirmed the operation of ground-based instruments, where the
devices designed by Hannig [12] with thickness 0.5 mm were minimally
disturbed by thermal gradients and thicker chambers of Strickler [13]
showed more sensitivity to temperature gradients. Naumann [14] also
developed a two-dimensional model of the thermal field to predict stable
operation and confirmed many of the predictions of Saville and experiments
of Rhodes. This model is developed in terms of dimensionless parameters
so the solution can be applied to a variety of operating conditions.

19.3 Continuous Flow Electrophoresis in Space

A major design objective of electrophoresis devices has always been to
increase the amount of sample separated in a given time interval. The
particle concentration that can be separated by electrophoresis in a
 471

weightlesf environment should be significantly higher than on Earth be-

cause droplet formati on and sedimentation compounded by buoyancy-induced
convection will not occur. The first experiments were done by Hannig and
his co-workers on ASTP. Red blood cells and viable cell mixtures from
rats were used to evaluate the increase in sample flow rate and sample
resolution achievable in space. [15] In 1978 the McDonnell Douglas Astro-
nautics Company (MDAC) designed a Continuous Flow Electrophoresis System
(CFES) for operation in space that would increase the quantity of material
that could be separated without diminishing the resolution. Doubling the
chamber thickness to 3 mm and increasing the sample concentration. MDAC
anticipated a significant improvement of throughput in space.

MDAC proposed a Joint Endeavor Agreement (JEA) to NASA to share the costs
of developing the space apparatus and conducting the necessary experiments
in space. Electrophoresis chambers built for the laboratory testing and
space operati on were all 120 cm long and 16 cm wi de wi th the 1 aboratory
chamber only 1.5 mm thick. The first experiments on Shuttle Mission STS-4
in June 1982 successfully separated rat and egg albumin at a rate nearly
500x greater than achieved with their ground-based instrument.

On STS-6 in April 1983. MDAC began separating a proprietary protein mix-

ture supplied by the Johnson and Johnson Company. As part of the JEA.
NASA was given the opportunity to conduct their own experiments on certain
MDAC missions and. supported by an ad hoc advisory group. hemoglobin and
polysaccharide were processed on STS-6. [16] One sample consisting of
only human hemoglobin A at a 9.6% concentration migrated electrophoretic-
ally as a band that broadened extensively because electroosmosis modified
the sample cross-section into an elongated crescent. The separation of a
lower concentration of hemoglobin A (1.8%) and a 2% concentration of a
pneumococcal capsular polysaccharide was distinct but again the bands were
broad. The band spread was not anticipated because the sample should not
have been transported toward the wall where electroosmosis dominated the
flow. by the sample insertion or simple diffusion. The cause of these
observations was found in the conditions fbr el ectrophoresis in space
which were partially dictated by the power available for the chamber from
the Shuttle. Power constraints 1 imited the app 1i ed fi e 1dto 1ess than 25
V cm- 1 and required a low ionic strength buffer for the relatively large
internal volume of the electrophoresis chamber. The concentrated hemoglo-
472

bin sample had an electrical conductivity that was three times the buffer
conducti vity and the second sampl e matched the first. It was proposed
that the mismatch in electrical conductivity caused the electric field to
be modified at the sample-buffer interface and the sample moved to the
chamber walls following the field lines.

A second opportunity for flight on STS-7 in June 1983 permitted confirma-

tion of this model for band spreading. A change in the electrophoresis
buffer by MDAC required a change in the sample material and three sizes of
polystyrene latex microspheres, dyed different colors to distinguish the
populations photographically, were used. One mixture was prepared with
electrical conductivity matching the buffer while sodium chloride was
added to the second sample to give an increase in conductivity to 3X. The
experiments done in space confirmed the model of band spreading. [17J

The CFES sample handling and collection was then slightly modified to
fractionate mammalian cells for the flight of STS-8 in August 1983. Rat
anterior pituitary cel ls,·cultured human embrionic kidney cells and canine
pancreatic islet cells were separated into subpopulations having different
functions in the laboratory version of the CFES and the space experiment
confirmed that the effectiveness of separation was similar. [18J This
space experiment investigated several new procedures, such as keeping the
cells in culture media before and after separation and modifying the col-
lection system to specifically collect the desired cell population. It
will be necessary to repeat this experiment series to provide some confi-
dence in the observed separation.

The development of CFES has been continued and expanded by MDAC and their
associates at Johnson and Johnson. After a problem of chamber sterility
compromised the separation of a protein preparation during a 100-hour
operation on Shuttle Mission 41-D in August 1984, the results from 51-D in
April 1985 are good. Development is also proceeding on the twelve foot
long, sixteen inch wide electrophoresis chambers to be mounted in the
Shuttl e payload bay which is part of EOS (El ectrophoresis Operations in
Space). MDAC's long-range commercial program then leads steadily to large
automated systems on the Space Station.

A different concept of electrophoresis for space has been under develop-

 473

ment at MSFC for several years. A "moving wall" electrophoresis device

[19] takes advantage of the negligible electroosmosis due to methyl cellu-
lose and chamber walls that move with the velocity of the buffer curtain.
Elimination of electroosmosis and Poiseuille flow removes two major sour-
ces of fluid disturbances in continuous flow electrophoresis and analysis
shows that the highest. resolution for electrophoresis should be achieved.
[20] A series of experiments on the ground have confirmed specific as-
pects of the ana 1ysi s. Methyl cell ul ose has been app 1 i ed to belt loops of
Mylar that carry the buffer through the chamber and sample particles have
been transported through the chambers without di storti on.[21] Effort is
now underway to separate and collect sample in this device to evaluate its
performance in the laboratory. The remaining source of fluid disturbance,
buoyancy-induced convection, could be eliminated by operating this system
in space. Several laboratory prototypes have been built but these devices
are extremely sensitive to temperature and concentration gradients. Con-
firmation of its projected resolution will thus require operation in
space.

The NASA program is continuing to investigate the basic processes that

control electrophoresis. Saville and Zukoski have recently evaluated trr~
electrokinetic properties of suspended particles in dilute and concen-
trated suspensions and the role of the electrical conductivity of the
suspending fluid. [22] Using polystyrene latex particles, the elec-
trophoretic mobility has been shown to be independent of particle concen-
tration for a large range of concentrations. However, the models show the
sensitivity of the system to conductivity mismatch as observed in the
early CFES experiments. Experiments of Rhodes with analysis by Roberts
have confirmed the band spreading of hemoglobin due to electrical conduc-
tivity gradients in gels. [23] This work has led to a small continuous
flow electrophoresis chamber which will be observed along all three rec-
tangular axes to monitor sample stream distortions under conditions such
as high power levels and different values of electroosmosis.

19.4 Isoelectric Focusing

Isoelectric focusing, an electrokinetic method for proteins, separates by
electrophoresis in a pH gradient. For isoelectric focusing, the central
chamber of Fig. 7 filled with a buffer would now have a mixture of carrier
ampholytes added to it. The sample would be uniformly mixed throughout
474

the chamber rather than localized as a starting zone. Applying the elec-
tric field causes the ampholytes to form a pH gradient in the chamber.
The proteins also migrate in the electric field to the pH region corre-
sponding to their isoelectric point, where they acquire zero net charge.
The isoelectric point of a protein is a charac., ,tic parameter and is a
sensitive basis for separation.

Isoelectric focusing achieves high resolution fractionation of proteins

but has encountered the same problems of convective disturbances during
scale-up to process higher quantities. Bier [24J has investigated the
technology of large-scale isoelectric focusing systems with particular
emphasis on new apparatus development, buffer pH gradients, and mathemati-
cal models for experiment design. A recycling isoelectric focusing system
(RIEF) [25J has been built to investigate preparative isoelectric focusing
in the laboratory and identify problems in a comparable instrument for the
microgravity environment. Its essential features are shown in Figure 7.3.
Fluid stabilization in
the rectangular separa-
tion chamber is accom-
plished by an separation
chamber is accomp 1 i shed
by an array of thin
fi lters para 11 e 1 to the
flow. A computer con-
trolled data acquisition
system optimizes the
operation and provides
data for the computer
modeling of the isoelec-
tric focusing process.
Recyc 1 i ng extends the
residence time in the
separation chamber and
provides the routing
through the sensors and
heat exchange reservoir.
Bier and his colleagues Fig. 19.3 The recycling isoelectric focusing
have fractionated up to (RIEF) apparatus
 475

ten liters of protein solution into ten channels in a few hours of

Dperation, which has been sufficient for many of their materials.
The scale-up has confirmed the problems of commercial carrier ampholyte
preparations, such as cost and variabi 1 ity. Extending past work in devel-
oping pH gradients using mixtures of simple buffers, stable gradients have
been developed using monovalent buffers and two human hemoglobins were
separated. This work was aided by a general mathematical model which was
able to predict the progress of isoelectric focusing (in addition to other
electrokinetic processes) based upon chemical equilibria and physical
transport phenomena. [26]

An early goal of the RIEF development was the removal of the parallel
filters that stabilize the flow. These polymeric filters can adsorb
proteins as they pass through the pores. In addition, proteins can come
out of solution at their isoelectric point and the precipitate of concen-
trated proteins can plug the filters. The filter elements also cause
electroosmosis and differential pressures between the various subchannels.

It was proposed that these filters could be removed in space but it became
clear from the modeling that just removing the filters would not eliminate
all electroosmosis. Wall electroosmosis presently masked by the plug
electroosmosis due to the filters, would be disruptive as the protein
mobilities reduced to zero at the isoelectric pOint and electroosmosis is
difficult to predict in the continuously variable buffer used for isoelec-
tri c focusing.

An apparatus was developed for the middeck of the Space Shuttle, (Fig.
7.4) to photograph isoelectric focusing in small cyl indrical chambers
[27]. Either computer-optimized buffer or commercial ampholyte buffer
were used in a group of eight chambers. Two chambers were coated with the
methyl cellulose used for the ASTP column electrophoresis and two were
uncoated for comparison. One chamber was partitioned with the same fil-
ters used for RIEF and the remaining three contained baffles that restric-
ted wall flow. A non-gassing electrode system was developed by Bier for
the 90 minute space experiment.
476

Fig. 19.4 Middeck isoelectric focusing experiment apparatus

The experiment was conducted on STS-ll in February 1984. The photographs

taken at three and two minute intervals showed focusing of a mixture of
hemoglobin and bromphenyl-dyed albumin in space was not as good as in
comparable apparatus in the laboratory. For example, rotation of the
space columns on Earth provided some stabilization not seen in space.
Electroosmosis was not eliminated in space but the results were not clear.
The electrical current should decrease monotonically as focusing proceeds
and the proteins approach their isoelectric point. In five of the eight
columns, the current ceased its expected rapid decrease of current within
thirty minutes and the current instead increased for the remaining hour of
the experiment. This current increase was accompanied by fl uid mixing
that disrupted any forming protein bands.

Electroosmosis remains a problem in space rbut its importance or elimina-

tion is apparently complicated by fluid flows that may be due to residual
gravity levels below 10- 3 g. As pointed out by Ostrach [7] and Saville
[28], microgravity does not mean the elimination of all fluid velocities.
The middeck unit is manifested to fly on a future STS mission with columns
 477

which will separately evaluate electroosmosis and residual fluid flow.

19.5 Phase Partitioning

Phase partitioning was proposed as an alternative method for separation of
biological cells by Brooks in 1975. [29] Aqueous solutions of two differ-
ent polymers that are mixed above specific polymer concentrations form
immiscible two-phase solutions. Addition of a cell population to such a
two-phase solution, which is shaken and then allowed to settle, will
frequently result in a partition, or separation, of the cells between one
of the phases and the interface. [30] The effectiveness of the process is
increased by sequential partitions in a countercurrent distribution ap-
paratus in the laboratory. Phase systems composed of dextran and poly-
ethylene glycol (PEG) mixtures have yielded separations of cell popula-
tions comparable to electrophoresis whereas theory predicts a signifi-
cantly higher sensitivity of partitioning to interfacial free energies and
ce 11 surface properties.

Although gravity is necessary to separate the phases on Earth, the separa-

tion of the ce 11 sis strongl y dependent on the ce 11 surface charge, the
interfacial free energy at the interface between the cell and the solution
in addition to the interfacial tension between the liquid phases. A
thermodynamic theory for the equilibrium distribution of particles between
the phase interface and bulk has been developed which confirms many quali-
tative features of cell partitioning. [31] However, the equations are
based on a Boltzmann distribution which is more applicable to molecules
than larger particles, such as cell s. Cell s have very small diffusion
coefficients and dynamic processes such as sedimentation are essentially
unaffected by diffusion. Thus quantitati ve agreement with the present
theory requires thermal energies due to temperatures of the order of 10 5 K
to cause the observed cell partitions. The partition process is sti 11
statistical in nature and if not due to thermal energies, an additional
"randomi zi ng" energy must be sought. Brooks proposes that dynami c factors
associated with phase partitioning, e.g., ,settl ing of the phases and
sedimentation of the cell s are the randomizing factors because of the
fluid shear and intercellular collisions observed in the laboratory.

The proposal that the randomization associated with phase separation and
cell sedimentation is caused by gravity has led to a careful observation
478

of the several stages of phase partitioning. Shaking the two liquid

phases with cells results in a micro-emulsion which coalesces to larger
droplets. Sedimentation and flotation of the drops of increasing size
involves shearing at the drop interface where many cells are attached and
collisions of the smaller drops.

Electric field-driven phase separation was investigated as a means to

separate the phases in the absence of gravity and experiments showed that
drops of each phase migrated in opposite directions. Recently, experi-
ments in wei ght 1essness ha ve shown that phase separati on occurs without
the imposition of an externally applied force. Experiments in the KC-135
airplane providing up to 25 seconds of microgravity have shown that coa-
l escence of the phases occurs even in the absence of gra vity. [32] The
rapidity of the formation of droplets was observed in Earth's gravity but
streaming of the droplets past each other made predictions of the ultimate
microgravity result in question.

A small plexiglas apparatus (5x3.5xl inch) was developed at MSFC with

fifteen 3 ml cavities to provide multiple experiments. This apparatus was
filled with PEG/dextran mixtures of different volume fraction, viscosity
and interface potential. The PEG was dyed with Trypan blue dye for visi-
bility. The experiment on STS 510 in April 1985 consisted of rapid sha-
king in space with observation (photography) taking place a quickly as
possible and extending past one hour. Fig. 7.5 shows the separation of
the two phases in the lower ten cavities. The upper five cavities con-
tained small glass cuvettes which were coated with PEG or dextran in order
to preferentially adsorb the selected phase. The coating was not suffi-
cient to provide a reliable method of controlling the different phases and
will be developed further. Two additional observations, that (1) the
presence of cells does not apparently alter the microgravity phase separa-
tion, and (2) the rate of phase separation was significantly greater than
predicted by current theories of phase separation, will be evaluated
during subsequent flights.
 479

Fig. 19.5 Separation of blue-dyed polyethylene glycol

and dextran in space

Conclusions
Space experiments to date have clarified the role of many of the fluid
phenomena that have limited several phenomena that have limited several
separation techniques on Earth. This research has led to redesign of
laboratory devices and to better understanding of the basis operating
parameters necessary to achieve improved separations. Over the past
fifteen years, there have been insufficient flight opportunities to
completr lny of the programs planned to resolve unequivocably the advan-
tages of weightl essness on a specific separation technique. More fre-
quent flights are now becoming available on the Space Shuttle and the
next several years should see significant progress as the sophistication
of the flight experiments and supporting laboratory research increases.

References
1. Commercial Biotechnology: An International Analysis (Washington,
D.C.: U.S. Congress, Office of Technology Assessment, OTA-BA-218,
January 1984).
2. McKannan, E.C; Krupnick. A.C.; Griffin. R.N.; McCreight. L.R.:
Electrophoresis separation in space - Apollo 14. NASA TM-64611,
1971.
480

3. Snyder, R.S.; Bier, M.; Griffin, R.N.; Johnson, A.J.; Leidheiser,

H.; ~licale, F.J., Ross, S.; Vanderhoff, J.W.; van Oss, C.J.:
Free Fluid Particle Electrophoresis on Apollo 16, Sep. Purif. Meth.
2 (1973) 259-282.
4. Micale, F.J.; Vanderhoff, J.W; Snyder, R.S.: Analysis of elec-
trophoresis on Apollo 16, Sep. Purif. Meth. 6 1976, 361-372.
5. All en, R.E.; Rhodes, P.H.; Snyder, R.S.; Barlow, G.H.; Bier, M.;
Bigazzi, P.E.; van Oss, C.J.; Know, R.J.; Seaman, G.V.F.; Micale,
F.J.; Vanderhoff, J.W.: Column electrophoresis on the Apollo-Soyuz
test project; Sep. Purif. Meth. 6(1) (1977) 1-59.
6. Ostrach, S.: The influence of convection in continuous flow elec-
trophoresis, ESA Special Publication No. 114 (1976) 141-148.
7. Ostrach, S.: Convection in continuous flow electrophoresis, J.
Chromo 140 (1977) 187-197.
8. Rhodes, P.H.: High resolution, continuous flow electrophoresis in
microgravity, NASA Technical Memorandum, TMS 78158 1978.
9. Rhodes, P.H.: Sample stream distortion modeled in continuous
flow electrophoresis, NASA Technical Memorandum TMX-78178 1979.
10. Saville, D.A.: The fluid mechanics of continuous flow electrophor-
esis, Physiocochemical Hydrodynamics 2 (1978) 832-912.
11. Rhodes, P.H.; Snyder, R.S.: The effect of small temperature gra-
dients and flow in a continuous flow electrophoresis chamber in
materials processing in the Reduced gravity environment of space,
New York: El serier Publ ishing Co. 1982.
12. Hannig, K.: Separation of cells and particle by continuous
free flow electrophoresis, Tech. Biochem. Biophys. Morphology,
1 (1972) 191-232.
13. Strickler, A.: Continuous particle electrophoresis: a new
analytical and preparative capability, Sep. Sct. 2(3) (1967)
335-355.
14. Naumann, R.J.; Rhodes, P.H.: Thermal considerations in con-
tinuous flow electrophoresis, Sep. Sci. Tech. 19(1)(1984) 51-75.
15. Hannig, K.; Wirth, H.; Schoen, E.: Electrophoresis (MA-014)
NASA Summary Science Report SP-412 (1977) 335-352.
16. Snyder, R.S.;, Miller, T.Y.;, Rhodes, P.H.;, Herren, B.J.;,
Sloyer, J.L.; Karr, L.H.; Seaman, G.V.F.: Continuous flow
electrophoresis of model proteins in space, in preparation.
17. Snyder, R.S.;, Rhodes, P.H.; Miller, T.Y.; Micale, F.J.; Mann,
R. V.; Seaman, G.V.F.: Polystyrene latex separations by
continuous flow electrophoresis on the space shuttle, accepted
by Sep. Sci. Tech. 1985.
18. Barlow, G.H.; et. al.: Continuous flow electrophoretic sepa-
ration of proteins and cells from mammalian tissues, submitted
 481

to Science.
19. Rhodes, P.H.:, High resolution continuous flow electrophoresis
in the reduced gravity environment, in Electrophoresis '81, Berlin,
New York, Walter de Gruyter 1981 919-932.
20. Rhodes, P.H.: U. S. Patent 4,358,358 (1982).
21. Rhodes, P.H.: private communication.
22. Zukoski, C.F.; Saville, D.A.: The interpretation of el~ctro­
kinetic measurements using a dynamic model of the Stern layer,
submitted to J. Coll. Interface Sci.
23. Rhodes, P.H.; Snyder, R.S.; Herren, B.J.; Roberts, G.O.:
Advances in Electrophoretic Separations, Electrophoresis '84,
Tucson, AZ.
24. Bier, M.; Egan, N.B.: Large scale recycl ing isoelectric
focusing, Electrofocus 78, Elsevier Publishing Co. 1979.
25. Bier, M.: Recycling Isoelectric Focusing Experiment, NASA
Contract NAS8-32950, 1981.
26. Bier, M.; Palersinski, O.A.; Mosher, R.A.; Saville, D.A.:
Electrophoresis: Mathematical modeling and computer simu-
lation, Science 219, 1983 1281-1287.
27. Bier, M.; Twitty, G.E.; Egan, N.B.: Electroosmosis in iso-
electric focusing - ground-based and space experiments,
Electrophoresis '84.
28. Saville, D.A.: Flow processes in a micro-gravity environment,
Biorheology, 16, 1, 1979 23-28.
29. Brooks, D.E.; Strickler, A.: Design study for countercurrent
distribution studies, Final Report, NAS8-32086 1979.
30. Walter, H.; Brooks, D.E.; Fisher, D.: Partitioning in aqueous
two-phase systems, Academic Press, to be published January 1986.
31. Brooks, D.E.; Bamberger, S.B.; Harris, J.M.; Van Alstine, J.M.:
Rationale for two phase polymer system microgravity separation
experiments, 5th Symposium Material Sciences Under Microgravity,
ESA SP-222 (1984) 315-318.
32. Van Alstine, J.A.; Harris, J.M.; Snyder, R.S.; Curreri, P.A.;
Bamberger, S.B.; Brooks, D.E.: Separation of Aqueous two-
phase polymer systems in microgravity~ 5th Symposium Material Sciences
Under Microgravity, ESA SP-222 (1984).
Subject Index
-A-
acceleration compensation , 257
Acoustic Container less Experiment System (ACES) , 245 , 301 , 302
acoustic levitator , 300 , 301 , 305 , 460
mixing device , 258
activation analysis , 434
energy, 173
enthalpy of diffusion, 116
adsorption, 129 , 208 , 210
aerodynamic levitator , 306
aircrafts (for weightlessness simulation), 13, 14, 15, 28, 34
48 , 330 , 458 , 478
albumin , 471
alloys , 343
amorphous containment , 184
solid phases , 168
antimetric instability , 407
Antonov rule , 209
Apo 110, 3, 13, 13 13, 16, 20, 467
Apollo-Soyuz Test Project (ASTP), 16 19, 23, 24, 25, 324
345 , 364 , 384 , 393 , 467 , 470 , 471
aqueous solution , 390
Arrhenius-function, 116 , 117
atmospheric drag, 36, 37
atomic transport, 93, 97, 100 , 424
autocorrelation functions, 118
autonomous closed packages , 241
payloads , 243

-B-
Benard cells, 417
beta-galactosidase , 390 , 392
bifurcation point, 8
binary fluids , 218
mixture , 193
systems , 343 , 347
biological cells , 465
purification , 465
biotechnology, 28
bismuth , 386
telluride , 386
blood cells , 467
Boltzmann-Matano method , 104 , 106 , 108
bond number , 129
brazing, 11 , 16, 317 , 318
breaking of drops , 404
bridge formation, 413
Bridgman growth , 383
Bridgman-Stockbarger furnace, 70
484

method, 25
Brownian motion , 335
brushite , 392
bubble migration , 456
motion , 282
Bubble, Drop and Particles Unit (BDPU) , 283 284 , 2e5 , 286
bubbles, 57, 451 , 456
buoyancy, 8, 11, 55, 320 , 345 , 353 456
driven flow , .379
buoyant convection , 456

-c-
caqmium mercury selenide , 394
mercury telluride , 387
telluride , 388
calcium carbonate , 393
tartrate , 393
canine pancreatic islet cells , 472
canthotaxis , 141
ca~illarity , 129 , 142 , 401
capillary , 428
forces, 11
materials , 430
reservoir technique , 107 , 432
stability, 145
technique, 108
waves, 58
with cone , 429
casting , 321 , 329
catenoid , 143 , 407
cavitation, 182
cavity acoustic levitator , 300
cell electrophoresis , 467
cellular growth, 151
structure , 329
center of mass system, 101
of particles system, 102
of volume system, 98 102
chemical diffusion, 97
diffusion coefficients, 98
reaction heating, 241 241
vapor transport, 21
cloud microphysics, 28
cluster formation, 172
clusters and nuclei, 169
coagulation , 421
coalescence , 354 , 366
coarsening , 366 , 371
coexistence curve , 193 , 204 , 209
collective atomic motions, 94, 121 , 438
~Iarangoni migration , 420
 485

combustion, 11 , 28
commercial utilization, 4
composites, 9 , 317 , 333
composition, 176
compositional partitioning, 176
constitutiQI,al supercooling , 123
undercooling , 151
contact angle, 139 , 140 , 141 , 402 , 428 , 431
circle, 173
container less levitation , 234
processing, 25, 28, 169 294 306, 310 , 447
undercooling, 8, 185
continuous flow electrophoresis , 468 , 470
controlled micro-gravity , 397
convection, 55, 125 , 187 , 212 , 368 , 461
coordinate system of diffusion, 96
Goriolis acceleration, 40
forces, 42, 287
corrections-to-scaling , 200
correlation factor, 121
function, 197 , 199
length , 197 , 199 , 214
crew motion, 44
critical adsorption , 210 , 214
behavior , 192
exponents , 198
fluid dynamics , 201
Marangoni number, 419
mixture , 220 , 221
nucleus radius, 172
opalescence , 196
phenomena, 28
point, 8, 12, 222 , 282
point wetting, 23 26
region , 201
system, 8
crystal growth, 9, 11, 21
crystallization, 125 , 171
dynamics, 179
Gzochralsky configurations , 234

-D-
D-l mission (see Space lab D-1 mission)
dendritic growth , 151
solidification, 123
structure , 329
density fluctuations, 94
gradients, 211
deuterated cyclohexane , 219
dextran , 479
diffusion, 22, 93, 94, 96, 107 , 117 , 121 , 125 , 150 , 174
486

327 , 328 , 424 , 454

coefficient, 98, 104 , 111 , 116 ,117 454
dilute solute diffusion, 104
directional solidification 68 70 , 327 362 , 364 , 370
disk floating zone , 242
dispersion, 23, 343
techniques, 184
distribution coefficient , 155
drag free satellite, 39
drendritic arm spacing, 180
drop, 57
-charged, 82
-uncharged, 81
dynamics, 57, 80
Drop Dynamics ~Iodule (DDH) , 276 , 278 , 294 , 301
drop facilities, 13, 14 16, 23, 28, 34 49 , 185 , 295
296 , 311 , 458
oscillations, 81 , 409
droplet formation , 471
migration, 417
dynamic nucleation, 187
surface tension, 138
wetting angle, 413

-E-
effective charge, 99
exponent , 200
effects of micro-gravity , 379
electrical discharge heating , 234
potentials in electrolytes , 424
electro-osmosis, 110 , 467 ,469 476
electro-osmotic flows, 12, 24
electrodiffusion, 99
electrolysis , 271
electromagnetic levitation, 186 , 295 , 307 , 308 , 432
electromigration, 99
electron beam heating , 233 , 296 , 433
microprobe analysis , 434
microscopy , 259
electrophoresis , 6 13 23, 24, 271 , 465 , 466 , 467
electrostatic effects 147
levitation, 309 , 310
electrostriction , 207
electrotransport, 99, 109 , 110 , 119 , 433
ellipsoidal mirrors , 254
ellipsoids , 237
embryo, 172
end face system, 104
enzymes , 467
ethyrocytes, 24
EURECA, 38, 244 , 373 , 398
 487

eutectic alloys , 121

growth , 321
solidification , 162
system, 23
eutectics , 454
exopack , 241

-F-
fetal kidney cells, 24
fiber glass , 448
fiberlike eutectics , 324
Fick's second law, 104
finite elements computer model , 229
size effects , 208
First Spacelab Payload (see Spacelab-1 mission)
floating melting , 380
zone, 19, 68, 78
flow transitions, 66
flows, surface-tension driven thermocapillary, 57
fluctuation theory, 116 , 117 , 439
fluctuations of density, 119
of the order parameter , 196 , 197 , 204
Fluid Experiment Apparatus (FEA) , 245
Experiment System (FES) , 242 , 245 , 259 , 279 , 280
Physics ~Iodule (FPN) , 273 , 274 • 275
fluxing material , 184
foams 12
free energy barrier. 172
energy difference, 171
fall, 31
fall trajectories, 33
surfaces, 114
free-fall methods , 47
freely floating particle, 42
furnaces , 227 , 237 , 243 • 244 , 245 • 246 , 250 • 253 , 257 • 260
384 , 387

-G-
g-jitter, 35. 44, 397
gallium antimonide , 383 , 384 , 384
arsenide, 5, 389
solution , 389
gas/liquid critical point, 213
transition, 195 , 196
Gauss-Laplace equation , 145 , 401
Geophysical Fluid Flow Cell (GFFC) • 287 , 288
germanium , 381 • 383 , 386
antimonide , 384
gallium-doped, 72
selenide 393 393
sulphide , 394
488

telluride , 393
Gibbs dividing surface, 130
equation, 131
model , 130
glass 9 , 447
formations , 294
in low gravity , 458
shells , 458
speres , 458.
temperature , 179 , 455
glassy metals , 9 , 168
gradient freezing , 249
furnace , 249
heating , 227
Gradient Heating Facility (GHF) , 243 , 250
gradient of interface tension, 417
graphite, 214
Grashof number , 328
gravitation, 31
gravitational parameter of the earth, 35
transport , 100
Gravity Gradient Node, 37
gravity-driven convection, 109 , 111 , 353 , 425
growth of nuclei , 171 , 354

-H-
Haeffner effect, 99
heat capacity , 214
of fusion , 172
pipe heating , 234 , 241
heating principles , 227
rates, 181
techniques , 231
Helium He' , 216
He" , 216
hemoglobin , 471
heterogeneous nucleation, 13, 168 , 326 , 459
High Temperature Thermostate (HTT) , 243
holographic interferometers , 269
observation systems , 259
optics laboratory (HOLOP) , 281
techniques , 268
holography , 279 , 285
homoclastic surface , 143
homogeneous nucleation, 168 , 294
hydrodynamic behavior , 207
instability , 206 , 470
hydrostatic pressure , 8, 12, 294 , 326 , 336 , 353
hypercooling , 176
 489

-1-
immiscihle liquids , 124
melts , 441
indium antimonide , 383 , 384 • 386
inductive electron beam , 241
heating , 233
Intercosmos , 246
interdiffusion , 105 , 106 , 440 , 441 , 460
coefficient , 103
interface convection 416 , 419
demarcation , 252
energy, 171
interfacial tension, 196 , 199 , 209 , 212
interference levitator , 302 , 305
interferometer , 215 , 268
intermolecular forces, 8
ionic conductivity , 207
solutions , 222
ionized liquids , 207
irregular eutectictics , 326
isolectric focusing , 473
Isothermal Furnace , 244 , 258
isothermal heating facilities , 242
Isothermal Heating Facility (IHF) , 243
isotope effect, 94, 120 , 437 , 438

-J-
Jackson and Hunt theory, 26
jumping rope instabilities , 408

-K-
KC-135 (see aircraft)
Kelvin equation , 144
kidney cells , 467
kinetics of cooling, 176
of solidification, 176
Kirkendall effect , 104

-L-
lamellar eutectics 322
Landau free energy 194
theory , 204
Laplace equation , 142
laser fusion targets, 451
heating , 240
laser-doppler anemometry , 259
latex microspheres , 467
LDEF (Long Duration Exposure Facility) , 393
lead monetite , 392
selenide tellu~ide , 394
telluride , 386
490

levitation, 28, 69 , 303 , 304

acoustic 25 82
, electromagnetic, 25
, electrostatic, 82
lifetime of fluctuations , 203
light scattering, 197 , 214 , 215
liquid bridge, 12, 332
shell, 57
skin technology, 188
liquid-gas transition, 193
liquid-liquid transition, 193 , 195 , 196
liquid-vapor transition, 210
local environment reference system , 437
long capillary technique , 432
Lorentz (J x B) forces , 307
Lorentz-Lorenz formula 215
lutidine water , 221
lymphocytes , 24
lysozyme , 392

-M-
macroconvection , 111
macroscopic interface tensions , 415
macrosegregation , 327 , 328
magneto-hydrodynamic effects, 424
mammalian cells , 472
Narangoni convection , 21 , 109 , 113 , 115 , 138 , 150 , 283 , 332
362 , 366 , 368 , 371 , 379 , 416 , 428 , 431
forces, 124 , 319 , 424 , 436
migration of droplets , 420
number , 419 , 457
mass conductivity , 203
Naterials Experiment Nodule (NEN) , 38
Science Double Rack (~ISDR), 44 46
Science Lab , 309
Science Laboratory , 251
mechanical hardening , 334
loads , 228
stability , 433
~IEDEA 243
melt degassing , 380
fluxing method , 184
melting , 432 , 434
of glass , 449
Nephisto , 243 , 250 , 251 , 337 , 397
mercuric bromide , 387
iodide , 394
metastability , 205
metastable phases, 13, 168
structures, 9
Hethanol , 219
 491

microconvections , 425
microgravity, 35, 187
microstructure refinement , 180
microstructures , 321
microwave heating , 241
mirror , 241
heating , 236
heating facility , 380
miscibility curve, 193 " 204
.gap, 12, 343 , 345 , 347
model of critical volume, 117
mole fluxes , 102
monodisperse latex spheres, 6
monotectic alloy, 13
systems, 23
morphological stability , 321 , 327

-N-
natural convection , 150
Neumann's triangle, 137
new materials , 331
nodoids , 405
non-equilibrium phenomena. 129 , 203
process , 168
nonequilibrium solidification, 176
nucleation. 168 • 173 • 173 • 204 • 205 • 221 , 357 , 447
catalyst • 178
dynamics , 168
in container less melting • 461
rate. 174
theory. 168 • 169

-D-
off-eutectic growth , 326
optical fibers • 294
Optiklabor , 259
orbital flight, 34
order parameter • 192 • 195 , 199 • 214
parameter decay rate • 202
parameter fluctuations • 214
organic crystal growth facilities • 242
oscillation. chaotic. 56
time-periodic. 56
oscillatory convective modes • 419
Ostwald ripening, 23. 124 • 139 , 372
oxidation proceses , 186
oxide film , 425 , 436
layers • 431

-p-
parasitic accelerations , 230
492

partial diffusion coefficients , 103 , 104

particle engulfment , 152
mobility, 98
subdivision, 185
Peclet number, 58, 328
phase changes, 57, 168
diagram, 168 , 205
separation, 203 , 204 , 212 , 217 , 218 , 219 , 220 , 221 , 477

planetary circulations , 287

Plateau tank , 299
Plateau's method, 80, 130
platinum-complex crystals , 393
pneumococcal capsular polysaccharide , 471
polyethylene glycol , 477 , 479
polysaccharide , 471
polystyrene latex particles , 473
positioning forces, 187
pressure equilization model, 411
gradient, 99, 120
prewetting , 208 , 210
line, 210
transition, 210
principle of equivalence, 32
propellant management , 11 , 146
protein crystal, 6, 7 , 465 , 473 , 474
growth , 390

-Q-
quasi-isopycnic systems , 362
quasicrystalline model, 103 , 104 , 117

-R-
radial segregation, 12
radiation , 236
heating , 433
pressure, 12
rapid cooling, 183
solidification , 360
rat anterior pituitary cells , 472
rate of homogeneous nucleation , 453
of shrinkage , 457
Rayleigh instabilities, 68, 145 , 298 , 405
number, 211 , 470
reactors for protein crystallization , 242
recalescence , 176 , 297
reference system for diffusion, 101
regular interface convection , 421
removal of bubbles , 456
renormalization group, 196 , 198 • 202 , 203
research aircrafts (see aircrafts)
 493

resistance 241
furnace , 295
heating , 231 , 432
robotics , 230 , 260
Rochelle salt , 390
rotating drops , 277

-8-
Salyut , 34 317 327 387
.6 , 394
scaling laws , 59 , 192 196 , 198
Schlieren , 279
method , 269
Schmidt number , 328
second order Narangoni convection, 115 , 437
order transition, 193
sedimentation, 8 , 12, 150 , 187 , 212 , 217 , 320 , 332 , 335
345 , 353 , 379 , 467
Seebeck effect , 252
segregation , 321 , 451
segregations solidification, 176
self-levitated spheres , 386
selfdiffusion , 104 , 107 , 108 , 435 , 437 , 440
coefficient , 425
semiconductor, 5
materials, 70
separation , 218
techniques, 9, 465
shape of liquid surfaces , 401
shear cell , 442
cell technique , 108 , 432
flow, 204
silicon , 381 , 383
simulation of growth , 354
of nucleation , 354
skin technology , 336
Skylab, 16, 17, 18 19,21,22,24,25,27,34
44 267, 272 , 294 , 317 , 318 , 319 , 324 , 334 , 345 , 383
393
slice model, 411
solar heated furnace , 239
radiation pressure, 39
solid-liquid interfaces , 159
solidification, 56 121, 149 , 168 , 434
front , 149 , 362 , 373
kinetics, 178
solubility , 177
solutal convection , 328
interface convection , 421
~larangoni migration, 421
solute diffusion , 107
494

striations , 394
Solution Crystal Growth Facility (SGF) , 243 , 244
Soret diffusion, 12
effect, 8, 98
sounding rockets , 34 , 47 , 249 , 345
Soyus-Salyut , 459
space manufacturing , 6 , 396
Space Processing Applications Rocket (SPAR) , 2 5 26 27 48
301 , 304 , 317 , 324 , 330 , 333 , 334 , 335 , 364
Shuttle Orbiter 37
Station, 41 , 259
space utilization, 4 5
vacuum , 254
Space lab , 3, 34 41, 272 273 290, 335 , 345 , 386 , 388
392 , 393 , 394
Space lab D-l mission, 46, 250 , 373 , 392
Spacelab 1 mission, 7, 26 44 317 319 325 , 383
Spacelab 3 mission , 245 , 266 , 277 , 280 , 294 301
spacing of lamellae , 322
spare volume , 428 , 434
specific heat , 196 , 199 , 213 , 427
spinodal curve , 205
decomposition , 204 , 205 , 220 , 349 , 357
region , 349
splat-cooling, 183
Splav 246, 255
spreading conditions , 416
of liquids , 415
stability , 404
criteria, 151
diagrams , 407
of liquid bridges , 404
static wetting angle, 413
steady state diffusion , 105 , 442
Stefan flows, 12
Stokes sedimentation , 370
Stokes-Einstein equation , 455
stratification, 217
striation, 56, 381
superconducting properties , 334
superconduction , 345
supercooled liquid , 452
supercooling , 205
superfluid , 213
transition of Helium, 193
surface activity, 134 , 137
energy, 132
induced nucleation, 185
tension, 12 23, 129 , 133 , 134 , 137 , 138 , 172 , 294 , 429
456
susceptibility, 195 , 199 , 214
 495

-T-
telescience , 260
tellurium , 386
tellurium-selenium , 386
temperature dependence of the diffusion coefficients , 439
TEXUS 48, 244 , 301 , 317 , 319 , 323 , 324 , 325 , 335 , 336 , 364

isothermal furnace 258

theories of diffusion, 94, 116
·of transport , 119
thermal conditioning , 228
conductivity, 203 , 211 , 216 , 426
convection , 467
expansion , 428
second order Marangoni convection , 436
thermocapillary, 23
flows, 12
thermodiffusion, 98
thermodynamics of irreversible processes, 95
thermomigration, 98
thermosolutal convection, 77, 155
thermotransport, 98, 109 , 110 , 115 , 120 , 432 , 433 , 441 , 443

thin layer diffusion, 104

tidal acceleration, 44
force, 36
time-temperature-transformation , 179
transformation of diffusion coefficients , 103 , 168
transparent model system , 157
transport by gravity, 120
coefficient , 201 , 202 , 203
correlation factor 98
forces , 105
phenomena, 55, 70
travelling heater method , 387
TRIAD I , 39
two-phase region , 209 , 220
two-scale factor universality, 199 , 200

-u-
ultrasonic m1x1ng system , 258
undercooled melts , 294
undercooling , 168 , 176 , 176 , 297 , 356
unduloids , 405
upper critical dimensionality, 197 , 204
urokinase 24

-v-
Van der Waals forces , 209 , 409 , 416
Vapor Crystal Growth System , 252
496

vapour growth , 393

viscosity, 116 , 203 , 216 , 424 , 425
volume change on melting , 428
fluxes , 102
increment , 150

-w-
wall effect, 110 , 113 , 119
water near the gas-liquid critical point , 207
weightlessness, 31
simulation methods 33
welding, 11, 16 242 317 318
wetting, 129 , 208 , 209 , 212 , 332 , 413 , 413
layers, 212
transition , 209
Wiedemann-franz-law 427
Wulff equation, 139

-x-
x-ray 197
X-ray 259
x-ray 434

-y-
y-point of He , 212
Y-point of He , 214
Young's equation, 137 , 139 , 353

-z-
zirconium fluoride glass , 450
Zisman plot , 142
zone furnace , 255
heating , 227