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Diffusion in the C15-type intermetallic Laves phase

NbCo2

Martin Denkinger & Helmut Mehrer

To cite this article: Martin Denkinger & Helmut Mehrer (2000) Diffusion in the C15-type
intermetallic Laves phase NbCo2 , Philosophical Magazine A, 80:5, 1245-1263, DOI:
10.1080/01418610008212113

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PHILOSOPHICAL A, 2000, VOL. 80, No. 5, 1245-1263
MAGAZINE

Diffusion in the Cl5-type intermetallic Laves phase

NbCoz

MARTIN
DENKINGER?
and HELMUT
MEHRER*
Institut fur Metallforschung, Universitat Miinster, Wilhelm-Klemm-StraOe 10,
D-48149 Munster, Germany

[Received 25 May 1999 and accepted in revised form 12 July 19991

ABSTRACT
Self-diffusion of both constituents in the Laves phase NbCo2 has been
explored using the tracer method and the radioisotopes "Co and 95Nb in
combination with sputter and grinder sectioning. The temperature dependences
of the Co diffusivity in Nb31C069and Nb29C071(two compositions inside the
phase field of NbCo2) and of the Nb diffusivity in Nb3,Co69 are reported. All
activation enthalpies are of similar magnitude. Nb diffusion in NbCoz is
significantly slower than Co diffusion. Co diffusion itself is considerably faster
in the alloy with higher Co content. The diffusion results are discussed in
connection with the structure of and the scarce information available about
atomic defects in NbCo2. We propose that diffusion is mediated by thermal
vacancies. Furthermore, the results are compared with self-diffusion data for
the C14-type Laves compounds MgZnz and TiFe2, with interdiffusion data
obtained from multiphase diffusion experiments in our laboratory, and with
self-diffusion in the also close-packed L1 intermetallics.

5 1. INTRODUCTION
Intermetallics (intermetallic compounds and ordered intermetallic phases) are
compounds of two o r more metals or semimetals whose crystal structures differ
from those of the constituents (Sauthoff 1995, Westbrook and Fleischer 1995).
Intermetallics have given rise to developments of functional materials and some
are promising for applications as structural materials at high temperatures
(Sauthoff 1995).
The most numerous group of intermetallics is formed by the Laves phases which
belong to the family of Frank-Kasper phases showing topologically close-packed
structures (Sinha 1970, Sauthoff 1995). Considering individual polytypes, more than
900 binary and ternary Laves phases are known including more than 360 binary
Laves phases (Thoma and Perepezko 1995). Binary Laves phases can be formed
if the effective atomic radii of the two constituents exhibit a ratio of approximately
(3/2)'12 = 1.225 (Dwight 1960) which allows a high packing density of 72% (Thoma
and Perepezko 1995) and an average coordination number of 134 (Schulze 1974).
Laves phases have an approximate composition AB2 and crystallize in the three
intimately related structures C 15 (cubic, MgCu2 type), C14 (hexagonal, MgZn2

t Present address: Gotz-Udo Hartmann GmbH, D61279 Grarenwiesbach, Germany.

* Author for correspondence: e-mail: mehrer@nwz.uni-muenster.de
Philosophical Magazine A ISSN 0141-8610 print/lSSN 1460-6992 online 0 2000 Taylor & Francis Ltd
http://www.tandf.co.uk/journals
1246 M. Denkinger and H. Mehrer

type) and C36 (hexagonal, MgNi2 type). Since these structures differ only in the
stacking sequence of the same two-layered structural units, transformations between
them can easily occur by gliding of partial dislocations and formation of stacking
faults (Allen et a/. 1972, Allen and Liao 1982). Their bonding is controlled by both
the atomic size factor and the electronic factor (Wernick 1967). Which of the three
crystal structures is stable is determined by the valence electron concentration. All
structures have a high atom coordination and a high packing density, and indeed
Laves phases primarily reveal metallic properties (Sauthoff 1995).
Various Laves phases are of interest for functional applications as superconduct-
ing materials, magnetic materials and H storage materials. Furthermore, Laves
phases are promising for structural applications at high temperatures. However,
the high brittleness at room temperature hampers technological application. Laves
phases have a brittle-to-ductile transition at about two thirds of the melting tem-
perature (Sauthoff 1995).
NbCo2 shows interesting magnetic properties due to its particular electronic
structure (Sauthoff 1995). Together with the Laves phases NbCr2, HfCrz and
NbFe2 the material NbCo2 has the best balance of high melting temperature, high
strength, low density and high oxidation resistance compared with other topologi-
cally close-packed intermetallics, which makes them promising for use in advanced
aero-propulsion systems (Anton and Shah 1992). To overcome room-temperature
brittleness, materials development utilizes ternary alloying (e.g. Nb(Cr, C O ) ~and/or
)
production of two-phase alloys (e.g. Cr-NbCr2 or Nb-NbCr2) (Kumar 1996).
Knowledge of diffusion is fundamental for an understanding of processes that
occur in solids a t high temperatures. Diffusion is, as a rule, the slowest step in
reactions in the solid state and hence is of great importance for the production
and the practical use of intermetallics as well as of all solid materials at elevated
temperatures. In particular, for structural applications of ordered intermetallic
phases, knowledge of the diffusion behaviour is important, since their high-tempera-
ture strength is limited by diffusion-controlled creep processes (Sauthoff 1993).
Diffusion in intermetallics has been reviewed several times (Bakker 1984, Wever
et a/. 1989, Wever 1992, Larikov 1995, Mehrer 1996, 1997, Nakajima et al. 1996)
showing that information on diffusion in Laves phases is very scarce. Until recently,
only two investigations of tracer self-diffusion in Laves phases were known, namely
self-diffusion of 65Zn in MgZnz (Gunzel et af. 1970) and of "Fe in TiFea (Shinjaev
1975).
In this paper we present results of self-diffusion of 57C0 and 95Nbin the cubic
Laves phase NbCo2. 57C0 diffusion has been studied for two different compositions
Nb3,Coh9and Nb2&07,, and "Nb diffusion for Nb31C069only. Some results of the
present study have been published in a short form elsewhere (Denkinger and Mehrer
1997, 1999). In this paper we present the complete and comprehensive study with
experimental details. According to our knowledge the present experiments represent
the first study where self-diffusion of both constituents in a Laves phase is reported
as well as the first investigation of self-diffusion in a C15 type Laves phase.

$2. PHASEDIAGRAM OF N b C o A N D STRUCTURE OF NbCo2

There are two recent versions of the phase diagram of N b C o (Brandes 1983,
Massalski 1986). The more reliable version (underlying investigations (Batalyova et
al. 1970, Brandes 1983)) is shown in figure 1. The solid-solid equilibria in this
diagram have recently been confirmed in interdiffusion studies from our laboratory
 Diffusion in the Laves phase NbCoz 1247
wt.-Y. co

At.-% CO
Figure 1. Nb-Co phase diagram according to Batalyova et al. (1970).

(Sprengel et af. 1994a).According to figure 1, five intermetallic phases crystallize in the

binary system Nb-Co (see figure 1): two hgh-temperature phases, namely XI (C14
type), NbCo3 (C36 type), and three intermetallic phases existing over a larger tempera-
ture range, namely NbCo (W6Fe7structured), Nb2C07 (C36 type (Nemoshkalenko et
af. 1977)), and NbCo2 (C15/C14 type), the phase which is of interest here.
NbCoz is a congruently melting compound (T, = 1793 K) and mainly exists on
the Co-rich side of the stoichiometric composition Nb33.3C066.7.Multiphase diffusion
experiments performed in our laboratory gave homogeneity ranges from 67.3 to 73.5
at.% Co at 1176 K and from 66.4 to 76.2 at.% Co at 1453 K (Sprengel et al. 1994a).
For temperatures below 1573 K, NbCo2 exhibits the C15 structure which
changes at higher temperatures to the C14 structure (Sauthoff 1995, von Keitz et
af. 1998). Since the C14 structure is stable above 1573 K, which in the present work
was chosen as the highest annealing temperature, we shall focus only on the C15
structure. The compositions and temperature ranges investigated in the present study
are indicated in figure 1 as bars.
The C15 crystal structure has cubic symmetry and in the completely ordered state
(composition AB2 (NbCo2)) contains 24 atoms per unit cell: eight A atoms (Nb) and
16 B atoms (Co) (Sinha 1970) (figure 2). It consists of two interpenetrating sublat-
tices where the larger Nb atoms (open circles) form a diamond-type sublattice. The
smaller Co atoms (full circles) form a tetrahedral network with adjacent tetrahedra
being joined to each other at their vertices. The Nb atoms have polyhedra? of CN 16

t The Kasper polyhedra are specified by the coordination number (CN) of an atom which
is situated at their centre.
1248 M. Denkinger and H. Mehrer

ONb oco
Figure 2. MgCuz-type (C15) structure of the Laves compound NbCo,.

around them occupied by four other Nb atoms at a distance of 3”2a/4 and 12 Co

atoms at a distance of 11 ‘/,a /8 .Each Co atom is surrounded by six other Co atoms
at a distance 2’/2a/4 and by six Nb atoms at a distance of 1 1’/2a/8 (CN 12).
As mentioned above, NbCo2 mainly exists on the Co-rich side of the stoichio-
metric composition. Deviations from stoichiometry can be compensated either by
structural vacancies or by antistructure atoms. The fact that NbCo2 mainly exists on
the Co-rich side together with the knowledge that Co atoms are considerably smaller
than Nb atoms suggest that Co antisite atoms are formed to compensate the devia-
tion from stoichiometry. This is strongly supported by a comparison of gravimetric
densities with X-ray densities for NbCo, performed by Saito and Beck (1960).

0 3. EXPERIMENTAL
PROCEDURE

3.1. Sample material

Two alloys within the phase field of NbCo2, having the nominal compositions
Nb3,C O and ~ Nb29C071,
~ were prepared by repeated electron-beam melting from the
pure elements Co and N b (99.9% purity each). Fabrication of cylindrical rods was
performed using the spark erosion technique. Standard metallographic procedures
were used to polish a reference sample of each alloy. The resulting compositions were
checked by electron microprobe analysis, showing that the alloys were enriched in
Nb compared with the starting composition obtained from the weighed amounts of
Co and Nb (table 1).
Reference samples were examined by optical metallography. Chemical etching
was done with a solution of H 2 0 , H N 0 3 and HF (for Nb31C069r 50 ml H 2 0 , 25 ml

Table 1. Compositions,grain sizes, mass densities, and microhardnesses of the NbCo2alloys

investigated in this work.
~ ~

Starting Resulting Grain

Co content Co content Nominal size Density Microhardness
(at.YO) (at.%) composition (P) (gem- 1 (HV)
69.3 68.7 f 0.5 Nb3l c069 150 8.97 f 0.01 1174f9
~ 7 2 71.1 f 0.5 NbioCOw >200 8.90 f0.02 1132f7
 Difluusion in the Laves phase NbCo2 1249

HN03 and 10 ml HF for 5 min; for Nb29C071,40 ml H20, 10 ml HN03 and 10 ml

H F for 2 min). Nb-rich precipitates at the grain boundaries could be removed by
annealing the samples for at least 12 days at 1376 K under vacuum. Optical metallo-
graphy after the annealing treatment revealed no second phase.
The alloys were also checked by X-ray powder analysis in a diffractometer.
Powders were prepared by crushing solid specimens. The X-ray diffraction patterns
were taken with a 8-8 diffractometer (D 5000, Siemens, Munchen) using Cu K a
radiation. All Bragg peaks could be adequately indexed on the basis of a MgCuz type
(C15) structure (figure 3). No Bragg peaks of a second phase were detected.
Reference samples of the homogenized alloys were examined with the help of
optical metallography (see above), gravimetric measurements (weighing the samples
in air, in water and in methanol) and Vickers hardness testing. The information
about the grain size, the density and the microhardness is listed in table 1.

3.2. Preparation of difusion samples

Specimens of about 3 mm height were cut from the cylinders by spark erosion.
They were polished with the help of a precision grinding machine employing grind-
ing films (Imperial Lapping Film, 3M, Neuss) down to 5 pm grade. Because of their

. [311

10400 -

21
7 800 -
v)
CI
C
a
3
5200-

J
!22]

I
40 50 60 70 80 90 100 110

2 0 I Degree
Figure 3. X-ray powder pattern of a reference sample of the alloy Nb29C071performed with
Cu Ku radiation (A = 0.1541 nm), 10s counting time per step and a step width of
0.040".
1250 M. Denkinger and H. Mehrer

high degrees of brittleness and hardness, grinding of the NbCo2 samples had to be
performed slowly to avoid surface damage.
The radioisotopes 57C0and 95Nb were used to study self-diffusion in NbCo2.
57
Co with a half-life of 271 days was purchased from Du Pont de Nemours (Bad
Homburg) as chloride solution. Normally, 5-20 p1 of the diluted solution were
trickled on to the polished sample surface and dried. For specimens to be sectioned
with ion-beam sputtering upon diffusion, s7C0 was evaporated under vacuum by
resistance heating from a tungsten boat.
95Nb (half-life of 35 days) is the daughter isotope of 95Zr (half-life of 64 days).
95
Zr was produced by neutron activation of enriched stable 94Zr (natural isotope
abundance in Zr, 17.3%; enriched, greater than 95%) in the reactor of the
Forschungszentrum Jiilich making use of the reaction 94Zr(n,Y ) ~ ’ Z ~ The
. neutron-
activated powder (about 5.8 mg) containing both isotopes 95Zr and 95Nb was dis-
solved in a solution consisting of 185 p1 HzO, 175 pI H N 0 3 and 11 pl HF. 95Nbhad
to be separated from 95Zr in order to obtain reliable penetration profiles.?
Separation was done with the help of a special evaporation procedure. The solution
of the tracers 95Zr and 95Nb was dripped on to a clean pre-annealed W boat and
dried. The boat was installed in a evaporation apparatus which was evacuated to
lop3Pa. In a first step the tungsten boat was heated and held for 3 min at 1320 K
(heating current, 50 A), for 5 min at 1420 K (heating current, 55 A), for 3 min at
1520 K (heating current, 60 A) and for 2 min at 1770 K (heating current, 70 A).
During this heat treatment the Zr reacts with the W of the boat. In a second step the
W boat was heated for 9G100 s to 1970 K (heating current, 80 A). Then, almost only
95Nbwas evaporated onto the samples. To ensure that all Zr reacts with the W boat,
the amount of tracer used had to be limited. The procedure was applied twice
employing each time a 95Zr-9SNb mixture with an absolute activity of 45 kBq. As
a result the diffusion samples had an absolute activity of 210-410 Bq of 95Nb
depending on the efficiency of evaporation. By using this procedure we were able
to bypass the very laborious and sophisticated radiochemical separation of the iso-
topes.

3.3. Difusion anneals, sectioning and counting

The samples were wrapped in Ta foil. Those with 95Nbtracer were additionally
covered with a dummy sample to reduce evaporation losses of the very small amount
of tracer. After evacuation to roughly lop4 Pa the diffusion samples were enclosed in
quartz glass ampoules under an Ar atmosphere. The amount of Ar was chosen in
such a way that at the annealing temperature the Ar pressure was equal to the
ambient pressure.
Diffusion anneals were carried out in resistance furnaces which controlled the
temperature to within f l K. The temperature was measured either with (Pt-RhbPt
or (Ni-Cr)-Ni thermocouples carrying an overall error of about 5 K due to addi-
tional uncertainties during their calibration. Self-diffusion of 5 7 Cin~ Nb31C069was
studied between 1143 and 1523 K, self-diffusion of 95Nbin Nb31C069between 1143
and 1569 K and self-diffusion of s7C0 in Nbz9C07, between 1141 and 1423 K.
Annealing cycles ranged from 45 rnin to about 41 days. To end a diffusion run the
ampoule was cooled in a less hot region of the furnace and in air to avoid cracking of

t95Zrreacts with NbCo2 at the sample surface during annealing when both isotopes were
evaporated on to the sample. The resulting penetration profiles were not Gaussian.
 Diflusion in the Laves phase NbCo2 1251

the very brittle samples because of thermal stresses. Experience showed that
samples were destroyed if the ampoules were quenched in water. For diffusion
times less than 5 h a heating-up correction was performed according to Itayama
and Stuwe (1974).
Serial sectioning of some samples was carried out using a precision grinding
machine in combination with microgrinding films. The same device had been used
for polishing. Otherwise (especially for small diffusion penetration) an ion-beam
sputtering device was employed for serial sectioning. Both devices have been
designed and constructed in our laboratory. For a detailed description of the sput-
tering device see Wenwer et al. (1996). Before rinder sectioning the sample cylinders
B
were reduced in diameter by at least lO(Dt)' to eliminate lateral diffusion effects.
This was done by slowly grinding off material from the cylinder surface of the
samples with a device constructed in our workshop. Employing ion-beam sputtering
as a sectioning technique, lateral diffusion effects could be eliminated by using a
mask.
The section thickness after grinding was determined from the section mass (i.e.
the difference between the sample masses before and after grinding off one section),
the diameter and the density of the specimen. After each sectioning step the sample
was cleaned with cotton sticks. Weighing was done on a microbalance (4503 Micro,
Sartorius, Gottingen).
In the case of ion-beam sputtering the sputtering rate was determined from the
amount of material sputtered off and the total sputtering time. From the fraction of
time pertaining to each section, one obtains the individual section thickness. The
sputtered-off material was collected on a Mylar foil which was moved stepwise in a
camera-like collector device (Wenwer et al. 1996). Each section corresponds to one
step.
Each grinding film (together with the cotton sticks) or each piece of the collecting
foil was folded and inserted into counting vials. The counting rate per section was
determined by y counting either in a well-type NaI(T1) scintillation counter or in a y
spectrometer with an intrinsic Ge(Li) detector. After counter background subtrac-
tion and decay corrections the counting rate was normalized to the section mass.
This yields the specific counting rate which is proportional to the tracer concentra-
tion. By plotting the logarithm of the specific counting rate versus the square of the
penetration distance (i.e. the distance from the surface to the centre of the section),
one obtains the penetration profiles.

54. RESULTS
4.1. Penetration profile
In figures 4 and 5, examples of penetration profiles for self-diffusion of "Co and
95Nbin Nb31C069are shown. All penetration profiles could be fitted by the thin-film
solution of Fick's second law:
M
c(x, t ) = -
(nDt)
Here c denotes the tracer concentration, D the diffusivity, t the diffusion time, x the
penetration depth, and M the amount of tracer deposited per unit area.
The solid lines in figures 4 and 5 represent fits of the thin-film solution of Fick's
second law to the data. The diffusivity is deduced from the slope rn = - 1 / ( 4 D t ) of
1252 M. Denkinger and H. Mehrer

Penetration Distance / pm

0 10 15 20
E

j -\
0 10
1143 K ; 40 d
20 30 40

Penetration Distance Squared / lo-" m2

Figure 4. Penetration profiles of 57C0in Nb31C069(grinder technique).

the straight line and the diffusion time t. Profiles for 57C0 diffusion in Nb2&07,
showed near the surface a marked decrease in specific counting rate followed by
Gaussian penetration. In these cases the Gaussian parts were used to determine the
diffusivities.
As already mentioned the samples were polycrystalline with grain sizes listed in
table 1. The annealing conditions were chosen to be appropriate for a measurement
of volume diffusion. In principle they belong to type B diffusion kinetics (Kaur et al.
1995). However, usually no or only little influence of grain-boundary diffusion could
be detected. This may be due to long diffusion times and high annealing tempera-
tures yielding a small @ value. @ is the so-called Le Claire parameter given by

s = 2D(Dt)lf2'
where S denotes the grain-boundary width and Db the grain-boundary diffusivity.
Only two profiles (not shown in figures 4 and 5) exhibited so-called 'grain-boundary
 Diffusion in the Laves phase NbCol 1253
PenetrationDistance I pn

0 0.6 0.8 1.0 1.2 1.4

8 , 1

0 5 10 15 20 25

13 2
Penetration Distance Squared I 10- m
Figure 5. Penetration profiles of 95Nbin Nb3,Cob9(sputter technique).

tails’ for larger penetration depths. The 0values deduced from these profiles were in
the range 7-9. A correction of the effect of grain-boundary diffusion on the bulk-
diffusion-dominated parts of the penetration profiles resulted in slightly smaller
diffusion coefficients. However, the difference was less than 3% and hence
could be neglected. The diffusion coefficients are listed together with the annealing
temperatures, the annealing times and the methods used for sectioning in tables 2
and 3.

4.2. Temperature dependences

The diffusivitiesare plotted as an Arrhenius diagram in figure 6. Least-squares
fits of an Arrhenius equation ( T is the temperature, Do the pre-exponential factor, Q
the activation enthalpy and R the gas constant)
 1254 M. Denkinger and H. Mehrer

Table 2. Diffusivities of 57C0in NbCoz alloys.

T f D
ComDosition (K) (S) (m2 s - ' ) Method Figure
~~

Nb31 co69 1523 5 225 2.29 10-l~ Sputtering

1473 7390 8.78 x Sputtering -

1423 25 200 4.18 x Grinding 4

1373 36 OOO 1.92 x Grinding 4
1323 144000 8.18 10-l~ Grinding 4
1273 144000 2.43 10-l~ Grinding 4
1223 604 800 6.29 x lo-'* Grinding 4
1183 1 382400 2.38 x lo-'' Grinding 4
1143 3 528 000 1.10 x lo-'* Grinding 4
Nb29C071 1423 8 760 3.1 1 x Grinding -
1373 36 000 7.1 1 x lo-" Grinding -
1323 86 700 2.59 x lo-'' Grinding -
1273 259 200 5.96 x Grinding -
1223 255 600 3.14 x Grinding -
1183 518400 2.10 x Grinding -
1141 1 382400 6.72 10-l~ Grinding -

Table 3. Diffusivities of "Nb in Nb31C069.

D
(m' s-I) Method Figure
1569 9 027 2.24 x Sputtering
1519 21 600 9.45 x 10-l~ Sputtering
1469 28 800 3.51 x Sputtering
1469 1188800 4.01 10-l~ Grinding
1419 36 000 1.46 x 10-l~ Sputtering
1369 262 800 5.51 x lo-'* Sputtering
1369 518400 9.42 x lo-'' Grinding
1320 241 200 2.10 x lo-'* Sputtering -

1270 144000 9.19 10-l~ Sputtering 5

1220 183600 2.97 x 10-l~ Sputtering 5
1180 435 600 1.28 x 10-l~ Sputtering 5
1143 1 260000 4.56 x Sputtering 5

yield for 57C0diffusion in Nb31C069

D c 0 ( T )= (2.84Tf::;) x m2 s-I exp (- 294.7 f 5.6 kJ mol-'

RT ) (4)

and for 57C0diffusion in Nb29C071

279.5 f 23.2 kJ mol-I
D c o ( T ) = (3.32';$) x m2 s-' exp
RT
The temperature dependence of 95Nb diffusion is described by

DNb(T ) = (9.24';::) x m2 s-I exp (- 292.0 f 5.0 kJ mol-'

RT
 Diflision in the Laves phase NbCoz 1255

Temperature I K

1600 1500 1400 1300 1200

60 65 70 75 80 85 90

Reciprocal Temperature / 10” K-’

Figure 6. Survey of the results for self-diffusion in the cubic Laves phase NbCo2 in an
Arrhenius diagram.

Table 4. Arrhenius parameters for Co and Nb diffusion in NbCo2.

~~ ~ ~ ~~~

Q DO Temperature range
Isotope Alloy ( k ~mol-’) (m2 s-’) (K)
57c0 Nb3l co69 294.7 f 5.6 2.84 1 0 - ~ 1143-1 523
95Nb Nb31co69 292.0 f 5.0 9.24 1 0 - ~ 1143-1 569
57c0 Nb29C071 279.5 r)r 23.2 3.32 1 0 - ~ 1141-1423

The relatively large scatter of D values for 57C0diffusion in Nb29C0~~

may be due to
errors in the sample area. Breaking of corners of the very brittle material during
reduction in the sample diameter destroyed the circular form of the surface. This
effect was approximately corrected by estimating the surface area. The Arrhenius
parameters and the investigated temperature ranges are summarized in table 4.

5 5 . DISCUSSION
5.1. Diflision in NbCor
The most conspicious characteristics of figure 6 and table 4 are the following.
1256 M. Denkinger and H. Mehrer

(1) Co diffusion in NbCo2 is significantly faster than Nb diffusion.

(2) Co diffusivity in NbCo2 increases with increasing Co content.
(3) The activation enthalpies of Co and Nb diffusion are similar.
As already mentioned in the introduction the Co atoms are significantly smaller
than the Nb atoms. The faster diffusion of Co in NbCo2 is not very surprising in view
of this difference in atomic size. Moreover, it is consistent with the so-called ‘Cu3Au
rule’ (d’Heurle et af 1995). This rule states that, in compounds of the type A,B,
where the ratio n/m 2 2, the majority element B diffuses faster than the minority
element A.t
Co diffusion in Nb&07, is considerably faster than in Nb31C069.This raises the
question whether structural vacancies act as diffusion vehicles. As already mentioned
in $2, deviations from stoichiometry can be caused either by antisite atoms or by
structural vacancies. Both alloys have compositions on the Co-rich side of the
ideal Laves phase stoichiometry. In principle, Co antistructure atoms or structural
vacancies on the Nb sublattice could compensate Co-rich off-stoichiometry. Saito
and Beck (1960) compared gravimetrically measured densities with X-ray densities
for NbCoz alloys on the Co-rich side of the stoichiometric composition. Their mea-
surements showed that the existence of NbCo2 on the Co-rich side is the result of the
formation of Co antistructure atoms and not the formation of structural vacancies.
In figure 7, both tracer diffusivities in Nb31C069are shown together with some
interdiffusion coefficients D in NbCoz. The latter were determined for several com-
positions from multiphase diffusion studies in the Co-Nb system using electron
microprobe analysis and the Boltzmann-Matano method (Sprengel et af. 1994b).
It is interesting to note that interdiffusion coefficients as well as tracer diffusivities
increase with increasing Co content. The interdiffusion coefficient reaches a max-
imum at compositions between 73 and 74.5 at.% Co, which have not been studied in
the present tracer experiments. According to the Darken-Manning equation (for
example Philibert (1991), Heumann (1992) and Mehrer (1996)) the interdiffusion
coefficient D is related to the tracer self-diffusion coefficients D c o and D k b of the
components in a homogeneous alloy or compound via

D = XCoDkb + X N b D * , o ) @ v (7)
where Xco and XNbdenote the mole fractions of the components, @ is the thermo-
dynamic factor and V is the vacancy wind factor. Equation (7) was derived originally
(Manning 1968, 1970, 1971) for a random alloy. It has been rederived for a B2
intermetallic phase showing antistructural disorder (Belova and Murch 1997).
Several Monte Carlo studies have shown that equation (7) is a good approximation
for LIZ, DO3 and ,415 structures (Belova and Murch 1998). This suggests that it is
permissible to use equation (7), tentatively, for the C15 Laves phases as well.
The thermodynamic factor @ is unity for ideal solutions. In intermetallic com-
pounds, @ is often larger, (sometimes even considerably larger) than unity owing to
the attractive interaction between the constituents. Since the vacancy wind factor V
is close to unity, interdiffusion coefficients for ordered compounds are often larger
than the term in parentheses in equation (7). Activation enthalpies for interdiffusion
are often smaller than those for tracer diffusion owing to the temperature variation
?There are examples in which the ‘Cu3Au rule’ is violated. The LIZ phase N&AI very
probably violates this rule (for example Mehrer and Wenwer (1997)).
 Difusion in the Laves phase NbCoz 1257

Temperature / K

1600 1500 1400 1300 1200

1o-”g ’ I 1 I

Nb27c073
; Interdiffusion in X Nb29cO71

1o-20
1

60 65 70 75 80 85 90
-5 -I
ReciprocalTemperature / 10 K
Figure 7. Comparison between tracer and interdiffusion in the Laves phase NbCoz.

in the thermodynamic factor. The activation enthalpies of interdiffusion in NbCo2

vary from 182 to 163 kJ mol-I for 68 to 73 at.% Co (Denkinger and Mehrer 1997).
From equation (7) we estimate thermodynamic factors for Nb31C069to be between
74 at 1473 K and about 800 at 1173 K. Unfortunately, according to our knowledge
no values of the thermodynamic factor for NbCo2 are available in the literature. On
the other hand, one should also be aware of the fact that interdiffusion coefficients
deduced from multiphase diffusion couples often differ from those stemming from
single phase diffusion couples. Interdiffusion in multiphase couples can be enhanced
by the existence of phase boundaries and/or by grain boundary contributions (van
Loo 1990). It can also be lowered by a smaller D in one of the other phases present in
the diffusion zone (Hirano and Iiijima 1985).

5.2. Diffusion in Laves phases

Information about diffusion in Laves compounds is very scarce (Mehrer 1990,
1996). According to our knowledge the present results represent the first study where
self-diffusionof both components in a Laves phase has been investigated. In figure 8
these results are compared with the literature data for self-diffusion in other Laves
1258 M. Denkinger and H. Mehrer

T I T,

1 0.8 0.6 0.5

3
a

1.00 1.25 1S O 1.75 2.00

T, I T
Figure 8. Self-diffusion in Laves phases. For references see text.

compounds. The diffusing element has been underlined. Only data for self-diffusion of
majority elements Zn in MgZn2 (Giinzel et af.1970)and Fe in TiFe2 (Shinjaev 1975)are
available. Because of the very different melting temperatures (NbCo2, 1793K; MgZn2,
863 K; TiFe2, 1700 K) the comparison is performed on a homologous temperature
scale normalized to the melting temperature T,. We emphasize that MgZn2 and TiFe2
are Laves phases with the hexagonal C14 structure whereas NbCo2 is cubic. Diffusion
of the majority component Fe in TiFe2 is very close to self-diffusion of the majority
component Co in Nb31C069. Self-diffusion of the minority components in the
hexagonal Laves compounds MgZn2 and TiFe2 has not been studied.
A little more information is available for interdiffusion in Laves phases.
Interdiffusion has been measured in the C 15-structured Laves compounds ZrMo2
(Hartley et af. 1965) and CuBe2 (Reinbach and Krietsch 1963), in the C14 phase
TiFe2 (Tsuji 1976), and in the hexagonal C36 phase TiCoz (van der Straten et al.
1976). The results are shown together with interdiffusion data for NbCo2 from our
laboratory (Sprengel et af. 1994b) in figure 9. Again, the temperature scale has been
normalized with the melting temperatures (ZrMo2, 2153 K; CuBe2, 1492 K; TiCo2,
1483 K; others, see above).
The interdiffusion coefficients for different compositions of NbCo2 lie between
the values for ZrMo2 and CuBe2, both stemming from reaction diffusion experi-
 Digusion in the Laves phase NbCoz 1259

T I T,

1 0.8 0.6 0.5

I
1.oo 1.25 1.50 1.75 2.00

T, I T
Figure 9. Interdiffusion in Laves phases. For references see text.

ments, too. Interdiffusion in the hexagonal Laves compound TiFe2 (C14) is slower
than in NbCo2 and similar to interdiffusion in ZrMoz. Interdiffusion in TiCo2 (C36)
has been studied for relatively h g h homologous temperatures. The pertaining D
values are in the same range as those for NbCo2 alloys extrapolated to higher
temperatures. NbCo2 and TiFe2 have a further common feature; the interdiffusion
coefficients are significantly higher than the tracer diffusivities of the majority com-
ponents Co and Fe.

5.3. Comparison with self-difusion in LIZphases

Laves phases and L12 compounds both have close-packed structures. Self-diffu-
sion in intermetallic compounds with L12 structure has been studied in more detail
than self-diffusion in Laves phases. A comparison of self-diffusion in NbCo, with
self-diffusion in some L12 compounds (again in homologous temperatures) is shown
in figure 10. The diffusivities of the majority component Ni in Ni3Ge (Nonaka et al.
1997), Ni3Ga (Nakajima et al. 1997) and Ni3Al (Frank et al. 1995) are very similar to
the diffusivity of the majority component Co in Nb31C069.Diffusion of the minority
components in L12 compounds and in NbCo2 is slower in all cases where data are
1260 M. Denkinger and H. Mehrer

T I TM

L "

1.o 1.25 1.5 1.75

T~ r T
Figure 10. Comparison of self-diffusion in NbCoz with self-diffusion in some Llz
compounds. The diffusion component has been underlined. For references see text.

available. This asymmetry for diffusion in Ll2 phases is largest for Ni3Ge and
smallest for Ni3Ga.
Self-diffusion in intermetallic compounds with L12 structure is mediated by
thermal vacancies. The majority component of the L12 compounds diffuses on its
own sublattice by a vacancy mechanism (Mehrer 1996, Koiwa et al. 1997). For the
diffusion of the minority component, several mechanisms are under consideration.
The most probable mechanism is the migration of the minority component as anti-
structure atom via vacancies on the majority sublattice (Koiwa et a/. 1997, Nakajima
et al. 1997, Belova and Murch 1998).
The similarities to the diffusion in LI compounds together with the knowledge
that Co antistructure atoms are formed in the investigated alloys of the NbCo2 phase
support a vacancy mechanism mediated by thermal vacancies for self-diffusion in
NbCo2 as well. In principle, Co atoms can migrate via vacancies on their own
sublattice (see figure 2). In addition, on the Co-rich side of the stoichiometric com-
position, Co antistructure atoms are present. The increase in the Co diffusivity with
increasing Co content can be attributed firstly to an increase in the thermal vacancy
concentration and, to a smaller degree, secondly to the occurrence of additional
 Difusion in the Laves phase NbCoz 1261

diffusion paths via antistructure atoms. On the contrary, it is rather unlikely that the
large Nb atoms invade the Co sublattice. As already mentioned, NbCo2 mainly
exists on the Co-rich side of the stoichiometric composition. This also indicates
that occupation of Co sites by Nb atoms is energetically unfavourable. We suppose
that the relatively slow Nb diffusion is restricted to the Nb sublattice.

5 6. SUMMARY AND CONCLUSIONS

Self-diffusionof '7C0 and 95Nbin the cubic Laves phase NbCo2 has been studied
using the radiotracer method in combination with serial sectioning by grinding or
sputtering. The temperature dependences of the Co diffusivity in Nb31C069and
Nb2&07, and of the Nb diffusivity in Nb31C069are reported for temperatures
where NbCo2 is C15 structured. According to our knowledge the present experi-
ments represent the first study where self-diffusion of both constituents in a Laves
phase is reported. The most salient features of the present study are the following.
(a) Co diffusion in NbCo2 is significantly faster than Nb diffusion. In Nb31C069
the ratio Dco/DNb is approximately 25.
(b) All activation enthalpies are of similar magnitudes.
(c) Co diffusivity in NbCo2 increases with increasing Co content.
(d) Interdiffusion increases with increasing Co content too and interdiffusion in
NbCo2 is faster than tracer self-diffusion.
(e) Self-diffusion of the majority component Co in Nb3,Co69 occurs at similar
rates to the self-diffusion of the majority component Fe in TiFe2 (C14) and
to the self-diffusion of the majority component Ni in the LI2 phases Ni3Ge,
Ni3Ga and Ni3Al.

A discussion of the present self-diffusion results in connection with information

about stability and structure of NbC02 and about point defects in NbCo2 and a
comparison with interdiffusion in NbCo2 and to self-diffusion in the L12 phases that
are also close-packed led to the following conclusions.
(I) Diffusion in NbCo2 is mediated by thermal vacancies.
(2) The increase of the Co diffusivity with increasing Co content is mainly
attributed to an increase in the thermal vacancy concentration and, to a
smaller extent to additional diffusion paths via antistructure atoms.
(3) The relatively slow self-diffusion of the large Nb atoms is very probably
restricted to the Nb sublattice.
(4) The similarity of self-diffusion in NbCo2 to self-diffusion in L12 phases also
supports a vacancy mechanism for self-diffusion in NbCo2.
( 5 ) The difference between tracer and interdiffusion coefficients is attributed to
the temperature-dependent thermodynamic factor.

ACKNOWLEDGEMENTS
Financial support by the Deutsche Forschungsgemeinschaft(project Me 480/24)
is gratefully acknowledged. We are grateful to Dr V. Semenov (Cernogolovka,
Russia) for preparing the alloy Nb29C07,, to Dr H. Liebertz (University of
Dortmund) for Vickers hardness testing and to B. Hiirttlen (Forschungszentrum
Julich) for the neutron activation of 94Zr. We also appreciate critical reading of
the manuscript by several members of the Munster diffusion group (R. Galler,
Chr. Khoukaz, M. Salamon, Dr. N. A. Stolwijk, E. Tanguep).
1262 M. Denkinger and H. Mehrer

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