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R. H. Mitchell, M. I. Novgorodova, E. I. Semenov (Auth.), Prof. Dr. a. S. Marfunin (Eds.) - Advanced Mineralogy_ Volume 1 Composition, Structure, And Properties of Mineral Matter_ Concepts, Results, A
R. H. Mitchell, M. I. Novgorodova, E. I. Semenov (Auth.), Prof. Dr. a. S. Marfunin (Eds.) - Advanced Mineralogy_ Volume 1 Composition, Structure, And Properties of Mineral Matter_ Concepts, Results, A
Advanced
Mineralogy
Volume 1
Composition, Structure, and Properties
of Mineral Matter:
Concepts, Results, and Problems
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
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Budapest
Prof. Dr. A.S. MARFUNIN
Geological Faculty
University of Moscow
119899 Moscow
Russia
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Preface
Introduction . . . . . . . . . . . . . . . . . . . . XXIII
Important progress has been made in numerous fields of mineralogy over the
last decades and even in the most recent years. The time has now come to
summarize these new results on structural crystallography.
After more than half a century of determination and precision refinement of
crystal structures (which still continues for new mineral species) scientists are
now facing new problems and purposes.
Based on the enormous amount of data on the atomic arrangement in
minerals various new insights in the structure of minerals have been achieved,
including
Two important systems are derived from these results: the crystallographic
classfication of minerals and the systematics of structural geometry existing in
minerals and crystalline matter. Sophisticated data bases for crystal structures
and powder diffraction patterns are now available.
This amount of data on crystal structures and solid-state spectroscopy
parameters has led to a breakthrough in studies of chemical bonds in minerals
and crystalline materials.
The quantum mechanical formalisms, computations and concepts intro-
duced to mineralogy by the outstanding works of several groups of chemists and
mineralogists in the 1980s have transformed the mostly qualitative patterns of
chemical bonding in minerals into calculations of their characteristics. Numer-
ous methods of calculation have been brought together and presented in a
systematic way, composing a system of contemporary approaches to chemical
bonding, including first-principle approximations ("molecules as models of
XXIV Introduction
Vast and new developments in surface science over the last decade stimu-
lated studies of mineral surfaces: e.g. STM, ESCA, LEED, among other meth-
ods, theoretical calculations of surface electronic structure and properties,
electron spectroscopy for surface analysis, consequences of the role of surfaces in
catalysis, chemisorption, solubility, sorption reactions at the aqueous solution-
mineral interfaces.
Two different fields revolutionized the concept of mineral properties:
1. Mineral Physics. The necessity of using the most elaborate theoretical
approaches and experimental studies under extreme pressure and temperature
conditions, corresponding to the Earth's mantle and the Earth's core, attaches a
new quality to the understanding of mineral properties in general and to studies
of elastic and anelastic properties, inelastic deformation and solid mantle flows,
transport processes and point defects, thermal and electrical conductivity,
diffusivity, creep deformation, mineral magnetism, phase transformation, the
nature and movement of melts, high-pressure crystal chemistry and computer
simulations of crystal structures.
These theoretical and experimental data of mineral physics present an
objective basis and constraints for all geophysical interpretations and for
understanding the solid Earth and planets.
Introduction xxv
available sources for metals, energy and solid matter are fairly well known. As a
consequence, technological mineralogy (so called process mineralogy) has to
seek new ways to improve their effectiveness. These include: a concentration on
low-grade, difficult to process ores from giant mineral deposits; mineralogical-
technological mapping; purposive induced changes in mineral properties for ore
separation and processing; complex and less waste producing ore and metal
production; enormous accumulations of billions of tons of anthropogenic waste
still containing unextracted metals, suitable for conversion into industrial and
other materials.
The biggest industrial enterprises are involved with the extraction, pro-
cessing and consumption of mineral resources. However, they are also, at all
stages of their activity, the main cause of ecological disasters. Mineralogical and
geochemical aspects compose an essential part of environmental studies.
The most striking changes in several branches of the mineral industry over
the last decades are related to studies of mineral matter, including the mineral-
ogy of gold, mineralogy of platinum group metals, mineralogy of uranium, rare
metals and rare earth minerals, mineralogy of diamond, mineralogy of phos-
phates, borates, nonmetallic resources etc. These results represent extremely
important aspects of mineralogical studies.
There are now more than 100 known varieties of natural minerals occurring
in gem-quality crystals. Jewelry can be regarded as an aesthetic aspect of
mineralogy. On the other hand, physico-mineralogical methods and theories
present scientific bases for the identification, synthesis, improvement, and the
technology of grading and faceting of precious stones.
The aesthetic properties of gems in combination with their physical proper-
ties can find impartial expression through measured spectroscopic parameters
and details of their chemical composition. The development of synthetic ana-
logues resembling natural minerals in detail and the increasing number of
shrewd methods of identification of natural, synthetic, treated stones and
imitations give rise to the speculation whether precious stones will remain
precious.
The breakthroughs regarding the mineral composition of the mantle, moon,
and ocean floor, and the earliest stages of the earth's evolution as well as the
advancements in the measurement and analysis of mineral matter have contrib-
uted to the creation of modern geology. The two final aims of geology are: the
understanding of the global evolution of the Earth and its units, and the global
mineral and energetic potential of the planet.
CHAPTER 1
Minerals are defined as any naturally occurring crystalline substance. While over
1 million compounds have been synthesized in the laboratory, only about 3500
minerals have been recognized. Geochemical factors, e.g. element abundance,
solid solution limits, mineral stability, place a limit on the composition and
stability of naturally occurring compounds, hence, the relatively small. number of
minerals. Minerals and synthetic compounds may have identical structures.
However, they differ in that minerals are rarely pure substances and typically
show wide compositional variations. Minerals range in terms of their composi-
tion from pure elements (Fe,Au,Ag) through relatively simple compounds (PbS-
galena, KCI - sylvite) to very complex compounds, e.g. steenstrupine -
Na14Ce6Mn2+Mn3+Fe~+(Zr,Th)(S018h(P04h· 3H zO. Chemically simple
minerals (Si0 2 ) do not necessarily have simple structures, e.g., alpha quartz.
Minerals are usually named after scientists (kullerudite, gagarinite, ringwoodite)
or the place of first recognition (isokaite, bytownite, atacamite). This practice
leads to the introduction of names that provide no information concerning the
composition or structure of the mineral.
Chemical classifications of minerals are based on the predominant anion
or anionic group. The following classes are recognized: (1) native elements;
(2) sulphide, telluride, arsenide and selenide minerals including sulphosalts of
antimony and bismuth; (3) halides; (4) oxides; (5) hydroxides; (6) carbonates; (7)
nitrates; (8) borates; (9) chromates; (10) tungstates; (11) molybdates; (12) phos-
phates; (13) arsenates; (14) vanadates; (15) silicates and aluminosilicates. Because
of the dominance of oxygen, silicon and aluminum in the earth, silicates and
aluminosilicates are quantitatively the most important class of minerals. Miner-
als of mixed anion composition, e.g. F in topaz or apatite, S in helvite-danalite,
OH in phyllosilicates, CI in rasvumite, are usually classified according to the
nature of the dominant anion. Hybrid minerals, such as valleriite and tochilinite,
which are sulphides containing layers of hydroxides, are not common.
Each major compositional class of minerals is subdivided into groups of
minerals having similar crystal structures. Thus, the silicate and alumino silicate
class comprises orthosilicates, sorosilicates, inosilicates, phyllosilicates and
tectosilicates. Each of these divisions is further subdivided into mineral groups of
different structure, e.g. the cyclosilicates into, among others, the beryl, tourma-
line and axinite groups.
The divisions arise because atoms of similar size and bonding character
adopt similar structures with a particular anion or anionic group. Hence,
minerals of very different composition possess the same crystal structure.
Structurally identical, but compositionally dissimilar, compounds are referred to
as isomorphs. Isomorphic compounds typically exhibit extensive solid solution
1.1 Chemical Composition of Minerals 3
M1+
Lithiophosphate Li Na
Zirsinali te H Lovoserite
Albite
Analcite
Teepleite
[N'
Na
Na
Na
K
Cs
Cu
Microc1ine
Pollucite
Bandylite
Jarosite Na Ag
Lepidolite Rb
Avogadrite
Murunskite
Alum [i Cs
Tl
NH4
Cs
Tha1cusite
Tschermigite
Pollucite
[Rb -
Astrophyllite Rb Tl
Galkhaite Cs Tl
Marshite [cu Ag Myersite
Copper Cu Au Gold
Silver Au Gold
[Ag -
Rayite Ag Tl
4 Chapter 1. The Chemical Nature of Minerals
Table 1. (Continued)
M 2 -'
Phenakit.e
Musgravite
~Be
Be
Zn
Mg
Willemite
Taalfeite
Magnesite Mg Ca Calcite
Chondrodite Mg Mn Alleghanyite
Forsterite Mg Fe Fayalite
-
Bobierrit.e Mg Co Erythrite
Bobierrite Mg Ni Annabergite
Hoernesite Mg Zn Koettigite
Aragonite Ca Sr Strontianite
Calcite Ca Ba Benstonite
Pectolite Ca Mn Serandite
Wollastonite Ca Fe Bustamite
Calcite Ca Cd Otavite
Apatite Ca Pb Pyromorphite
Strontianite Ba Witherite
[sr
Strontianite Sr Eu
Barite Ba Ra Ilmenite
Pyrophanite Fe Ilmenite
Ilesite
Fauserite
[M"
Mn
Mn
Co
Ni
Aplowite
Morenosite
Helvite Mn Zn Genthelvite
Siderite Fe Co
Siderite Fe Ni Gaspeite
Iron [Fe Pt Platinum
Siderotil Fe Cu Chalcantite
Erythrite Co Ni Annabergite
Devillite Cu Zn Ktenasite
Smithsonite Cd Otavite
Sphalerite
Smithsonite
lZ"
Zn
Zn
Hg
Fe
Metacinnabar
Siderite
Hawleyit.e Cd Hg Saukovite
Herzenbergite Sn Pb Teallite
M3 -
Variscite Al Sc Eggonite
Hibonite Al Ti
Corundum Al V Karelianite
Spinel Al Cr Chromite
Andalusite Al Mn Kanonaite
Zoisite Al Fe Epidote
Tugtupite Al Ga
[
Thortveitite Y
Thortveitite Sc Ln(Yb) Keivyite
Abukumalite Y (Ce) Britholite
Gadolinite Y Bi Minasgeraisite
Monazite Ce La
1.1 Chemical Composition of Minerals 5
Table l. (Continued)
Gadolinite [La Lu
Monazite Ln Ac
Sohngeite Ga In
[~
Karelianite Cr Escolaite
Karelianite Fe Hematite
Brownite Fe
Mn TI
GMn Avicennite
Boweite Rh Ir Kashinite
Sohngeite Ga In lalindite
Arsenolite As Sb Senarmontite
-
Stibnite Sb Bi Bismuthinite
M4 +
Stishovite [Si Ti Rutile
Stishovite Si Ge Argutite
Rutile Ti Ge Argutite
Astrophyllite Ti Zr Zircophyllite
Titanite Ti Sn
~~~
Malayaite
Rutile Ti V Paramontroseite
Rutile Ti Mn Pyrolusite
Senaite Ti Re
Ulvite Ti Pt
Rutile Ti Pb Plattnerite
Rutile Ti Te Paratellurite
Argutite Sn Cassiterite
Argutite [:Ge
Ge Pb Plattnerite
Schaurteite Ge Mn Oespujolsite
['
Zircon Hf Hafnon
Zr Th Thorite
Zr U Coffinite
Terskite Zr Sn
Cassiterite Sn Pb Plattnerite
Hafnon [Hf Th Thorite
Hafnon Hf U Coffinite
Cerianite [ce Th Thorianite
Ce U Uraninite
Thorianite Th
-
U Uraninite
Scotlandite S Se Molybdomenite
Chalcomenite Se Te Teineite
Tugarinovite Mo W
M5 +
~
Pyromorphite V Vanadinite
Pyromorphite As Mimetite
Rhabdophanite Nb
Vanadinite V As Mimetite
Stibiconite Sb As
Pyrochlore
Pyrochlore ~b
Nb
Sb
Ta
Romeite
Microlite
6 Chapter 1. The Chemical Nature of Minerals
Table 1. (Continued)
M6 +
[~
Arcanite Cr Tarapakaite
Anglesite Se Olsacherite
Olascherite Se Te
Fornacite Cr Mo
Powellite [MO W Scheelite
Powellite Mo U
X1-
Apatite
Apatite [f CI
OH
Chlorargyrite
Nantokite
[9
CI
Br
-
I
Bromargyrite
Marshite
Bromargyrite Br Iodargyrite
X2 -
Cancrinite 0 S Bystrite
Galena
Galena [~ Se
Te
Clausthalite
Altaite
Clausthalite Se Te Altaite
Augite
NaTi SrFe Lamprophyllite
Weloganite NaZr CaY Donneyite
Orthoclase KSi BaAl Hyalophane
4. Li1+Nb s + Mg2+Ti 4 + Taeniolite
Lueshite ~NaNb CaTi Perovskite
NaNb CaZr Eudialyte
Steenstrupite NaP CaSi
Berzeliite NaAs CaSi
KNb BaTi Labuntsovite
5. Li1+Nb s + AI3+ AI3+ Polylithionite
6. Cesanite ~Nal +S6+ Ca 2+ps+ Apatite
NaS CaAs Tirolite
Alunite KS SrP Svanbergite
7. Nat +W 6 + Ce 3 +Ti 4 + Marignacite
8. Gadolinite Be2+y3+ B3 +Ca 2+ Datolite
MnY AICa Grossular
Chevkinite FeY FeCa
Allanite FeCe AICa Epidote
FeSb AICa Vesuvianite
9. Vaterite Ca 2+C 4 + Ce 3 +B 3 +
Tugtupite BeSi AlAI Sodalite
Melilite
~MgS; AlAI
Enstatite MgSi ScAI
MgSi CrAI
Grossular
~caSi
CaSi
CeB
YAI
Stilwellite
Table 2. (Continued)
[YbP ZrSi
--
Zircon
CeP ThSi Thorite
r
FeP ThSi Thorite
ZrTi
--
Zirkelite
CeNb ThTh Thorite
Aeschynite CeNb ThTi
YNb UTi Brannerite
Behierite BTa SiZr Zircon
Samarskite FeTa TiSn
Melanostibite FeSb TiTi
16. Fe3+W 6 + Ti 4 +Ta5+ Samarskite
17. Ti 4 +W 6 + Nb5+Nb 5 + Pyrochlore
Cluster isomorphism
18. Ilmenorutile Fe2+Nb~+ 3Ti4 +
19. Florencite Ce3+p~+ Kl+S~+ Jarosite
elements are present only in trace quantities. The mineralogy of the crust is
therefore dominated by minerals based upon these major and minor elements.
The composition of individual minerals reflects the local geochemical environ-
ment in which the mineral formed. Compositional ranges are restricted by the
possible simple and coupled substitutions permissible for a given crystal
structure. Elements which have low natural abundances will typically substitute
for major elements at lattice sites as trace components, e.g. Sr for Ca in diopside,
Pb for K in potassium feldspar, Re for Mo in molybdenite. This dispersion of
1.1 Chemical Composition of Minerals 9
trace elements within other minerals is the principal reason for the limited
number of naturally occurring minerals.
Trace elements in the earth's crust may be concentrated by geochemical
processes which cause them to reach, locally, major element status, e.g. the
minerals of ore deposits, evaporites, sublimates etc. The rare earth elements
(REE) exemplify these processes. In many common minerals REE may be found
dispersed throughout the crystal lattice where they typically replace Ca, Sr, Ba,
Zr or Th. Only in low-temperature hydrothermal/carbothermal environments
do they become sufficiently concentrated to form REE-based minerals. Although
the REE typically behave as a chemically coherent group, selective concentra-
tion of individual elements is possible, e.g. La in davidite, Ce in fluocerite, Gd in
samarskite.
Many elements are found in minerals which do not occur in structural lattice
sites yet are an integral part of the mineral. In these cases the mineral has a
relatively open structure and contains channels which accommodate large
cations. Two examples of this phenomenon are the presence oflarge cations (Cs)
located within the silicate rings of the cyclosilicates beryl and kupletskiite; and
the presence ofBa and K within the tunnels formed by chains of Ti0 6 octahedra
in the hollandite group of oxides. Further examples are found in the zeolite
group of tectosilicates. The open framework structure of these minerals permits
the entry of cations into the large spaces within the structure. Because the size of
the pore spaces is determined by the composition of the zeolite, individual
minerals exhibit selectivity as to the nature of interlattice cations. Thus,
mordenite, clinoptylolite and erionite may contain Cs, Rb, and Ba, whereas
zeolites with smaller pore spaces, such as analcime and natrolite, cannot
accommodate these elements.
10 Chapter 1. The Chemical Nature of Minerals
In some minerals not all lattice sites are occupied by cations (or anions). Such
lattices are known as defect lattices and the vacant sites are represented by holes
which may act as electronic color centers. Minerals possessing defect lattices are
non-stoichiometric compounds. Common examples include wustite (Fe1-xO)
and pyrrhotite (Fe1-xS). In the structural formula, x represents the atomic
fraction of vacant lattice sites and typically ranges up to 0.2. Lattice vacancies are
also commonly developed in many minerals as a consequence of complex,
coupled substitutions, e.g. the substitution of one Ba atom for two K atoms in
phyllosilicates results in the creation of a lattice vacancy (Table 4).
Many of the elements reported in bulk analyses of minerals reflect the
presence of microinclusions of other phases. These elements are impurities and
not integral parts of the minerals. Microinclusions may be easily recognized by
electron microbeam and X-ray investigations of minerals. The inclusions may be
solid or fluid and originate during growth of a mineral from a liquid or in the
solid state. Such inclusions were never structurally or chemically part of the host
mineral. Important in this category are fluid inclusions representing samples of
the fluids from which the host mineral grew. The inclusion may consist of COz,
CH 4 , and H 2 0 in various combinations with dissolved salts (Na,K,CI,SO~-).
Physically, the inclusion may consist of supercritical fluid, fluid + liquid (brine)
or fluid + liquid + solid. In the latter, minerals differing in composition from the
host crystal are precipitated from the trapped fluids upon cooling, e.g. halite in
calcite host crystal.
Other microinclusions result from ex solution; in this case, solid solutions,
which are complete at high-temperature, breakdown upon the cooling of a
previously crystallized mineral. Physically, the exsolution process is manifested
by the formation of microinclusions of the ex solved phase in the host mineral.
Commonly, ex solution is confined to particular crystallographic planes of the
host. Examples include the ex solution of rutile (Ti0 2 ) from quartz (Si0 2 ); the
breakdown of continuous alkali feldspar solid solutions into albite and ortho-
clase; the ex solution of dolomite from calcite.
Some minerals contain occluded gases which may be trapped in structural
voids, or adsorbed onto crystal surfaces during growth of the host. For example,
the cyclosilicates beryl and cordierite commonly contain trapped argon. Natural
diamonds may contain substantial amounts of N (up to 0.5 wt%) together with
occluded He, Ar, Kr and Xe. The N commonly occurs in discrete aggregates
termed platelets. These may have formed by aggregation of substitutional
nitrogen atoms subsequent to the growth of the diamond. Occluded gases
(N 2 ,C0 2 ,CH 4 ) in graphite may form clathrate impurities in the interlayer spaces.
Other impurities in minerals arise from the adsorption or precipitation of
finely dispersed, commonly colloidal compounds, on crystal faces during growth.
This material may recrystallize into aggregates of microinclusions. Common
examples are the hydroxides of Fe and Mn included in the citrine and rose
varieties of hydrothermal quartz. Included material may be expelled from a
crystal during prolonged recrystallization, e.g. the expulsion of graphite from the
chiastolite variety of andalusite.
1.1 Chemical Composition of Minerals 11
~e
Fe
KFe
NaFe
Astrophyllite
Hastingsite
~Bi
Bi
CuPb
AgPb
Aikinite
Benjaminite
r
[~e HBa
HCa
loakinite
Churchite
3. H 1 +B 3 + Datolite
Si LiAI Virgilite
Si NaAI Heulandite
Si KAI Heulandite
Ti NaFe Titanite
Zr NaFe Zektzerite
concerning its crystal structure. Many systems of notation have been devised,
giving greater or lesser structural detail, including those by Hey (1950), Povaren-
nykh (1972), Strunz (1982), and more recently Lima-de-Faria et al. (1990), the
latter being recommended by a subcommittee of the International Union of
Crystallography. The notation recommended would give for example, for pyrite:
Fe[601{g} [SP;llt], indicating Fe in sixfold octahedral coordination by sulfur
and S tetrahedrally coordinated by 3 Fe and 1S, and for Mg, Al spinel:
°
[Mg[4tlAI2[60104[1,3;12C01], indicating Mg in fourfold tetrahedral and Al in
sixfold octahedral coordination, with one Mg and 3AI neighbors and self-
coordinated by a cubo-octahedron of oxygens. Lima-de-Faria et al. also give
the so-called Bauverband description indicating structure types by a lattice-
complex notation.
The full notation gives information about structural units (chains, ~ layers, ~
etc.) and the packing of structural units, as well as the coordination of atoms and
the presence of interstitial atoms. Use ofthe full notation is suitable for relatively
simple inorganic compounds, but is impractical for many minerals which have
complex chemistry and structure, and for these a system like that of Strunz
(1982), giving less complete structural information, is more appropriate. Thus
alternatives for the formula for muscovite would be:
Minals. It is often useful in the case of solid solutions to express the composition
as percentages of end-member "molecules" sometimes called minals since the
structures do not really contain molecules. Thus, as examples, an olivine
Mgo.64Fe1.36Si04 may be expressed as Mg 2Si0 4 (forsterite) 32%, Fe 2Si0 4
(fayalite) 68% or F0 32 Fa 6S ' a sphalerite (Zno.slFeo.10Mno.09)S may be plotted
on a triangular diagram as 81 % ZnS, 10% FeS and 9% MnS, and a garnet
Ca3(Alo.s6Feo.lOCro.o4}z(Si04h as grossular 86%, andradite 10%, uvarovite
4%.
The direct method can be used for partial as well as full analyses, and the
errors and assumptions involved have been discussed, e.g., by Hey (1939, 1954),
Nicholls and Zussman (1954), Bulakh (1969, 1970, 1984), and Dollase and
Newman (1984).
When the cell volume and density are not known, the chemical analysis still
provides the relative proportions of the various atoms, and these can be
converted to absolute numbers of atoms in a formula in relation to an assumed
number for anyone of them, usually an anion (most commonly oxygen) or an
anion group, most commonly E"(O,OH,F,Cl), or a cation group, e.g., E"R
octahedral; the number assumed has to be based on sound crystal-chemical
principles.
Thus, it would be unwise to use cation groups that include sites that may
have vacancies, e.g., the A sites of amphiboles, or the octahedral sites in micas,
which may be intermediate between di- and tri-octahedral in character. In
practice, scaling of atom proportions should be to as large a number of ions as
can be assumed with confidence, e.g., E" (oxygen, etc.), or E" (all cations), since
scaling to small groups will propagate greater errors.
When normalizing to a number of cations N c , the number of R atoms NR is
given by NR/Nc = PR/Pc . P R and Pc are the atomic proportions of Rand C
respectively.
When normalizing to total oxygen (N EO ) the required expression is
NR/N"o = PR/P"o'
The methods of calculation are best illustrated by examples as in Table 5, a
sphalerite, Table 6, an ilmenite, and Table 7, a clinohumite.
The third example (Table 7) is instructive as to the method of dealing with a
mineral that contains structural (OH), wholly or partially replaced by (F, CI). In
Table 7 it is seen that the wt. % of the oxygen equivalent of F present must be
subtracted in column 1 (2.74 x 16/38 = 1.15) and the atomic equivalent of F
present subtracted in column 3.
In many published analyses values for H 2 0 + and for F are lacking or may
be suspect. In Table 7, for example, H 2 0 and F can be ignored and anion
100.12 2:0
= 2.0199 3.000
101.41 2.8871
-O=F 1.15 - 0.0721 ( =! xO.1442)
Total 100.26 2.8150
18
--= 6.3943
2.8150
proportions can be scaled, making the total 0 atom proportions equal 17, i.e.,
18-1- (OH,F,CI). [This procedure makes the assumption of 2(OH,F,CI) and is
also equivalent to re-calculating cations to balance 34 negative charges.] The
result in Table 7 is: l: 0 props. = 2.6577, giving 17/2.6577 = 6.3965 as the
scaling factor, which in this case is very close to the 6.3961 previously used, and
almost identical cation numbers will result.
1.2.1 Structural Formulae 17
References
Bulakh AG (1969) Calculation of mineral formulas 2nd edn. Nedra, Leningrad (In Russian).
Bulakh AG (1970) Berechnung von Mineralformeln. VEB Deutscher Verlag fUr Grundstoffin-
dustrie, Leipzig
Bulakh AG (1984) On errors in formulas of minerals recalculated from inaccurate chemical
data. Mineral J (Kiev) 4: 87-92 (In Russian)
Deer WA, Howie RA, Zussman J (1962,1963) Rock-forming minerals, vols 1-5. Longman
Deer WA, Howie RA, Zussman J (1992) An introduction to rock-forming minerals, 2nd edn.
Longman
Dollase WA, Newman WI (1984) Statistically most probable stoichiometric formulae. Am
Mineral 69: 553-556
Droop GTR (1987) A general equation for estimating Fe3+ concentrations in ferromagnesian
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431-435
Hey MH (1939) On the presentation of chemical analyses of minerals. Mineral Mag 25:
402-412
Hey MH (1950) An index of mineral species and varieties arranged chemically. London, British
Museum
Hey MH (1954) A further note on the presentation of chemical analyses of minerals. Mineral
Mag 30: 481-497
Lima-de-Faria J, Hellner E, Liebau F, Makovicky E, Part he E (1990) Nomenclature of
inorganic structure types. Report of the International Union of Crystallography Com-
mission on Crystallographic Nomenclature Subcommittee on the Nomenclature of In-
organic Structure Type, Acta Crystallogr A46: 1-11
Nicholls GD, Zussman J (1954) The structural formula of a hydrous amphibole. Mineral Mag
30: 717-722
Povarennykh AS (1972) Crystal chemical classification of minerals, vols 1 and 2. Plenum Press,
New York
Robinson P, Spear FS, Schumacker JC, Laird J, Klein C, Evans BW, Doolan BL (1982) Phase
18 Chapter 1. The Chemical Nature of Minerals
relations of metamorphic amphiboles; natural occurrence and theory. In: Veblen DR, Ribbe
PH (eds) Reviews in Mineralogy, 9B, pp 1-227, Min. Soc. America
Rock NMS, Carroll GW (1990) MINTAB: A general-purpose mineral recalculation and
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Strunz H (1982) Mineralogische Tabellen, 8 Auff. Akad Verlag, Leipzig
reinvented numerous times in different sciences and many names thus are
associated with mathematical methods of classification. Some of these are
cluster analysis, discriminant analysis, multidimensional graphical procedures,
pattern recognition, decision theory, image analysis, assignment analysis, homo-
geneity analysis, and various other multivariate statistical methods.
Three major aspects commonly are revealed by these multivariate statistical
techniques. They provide a classification of objects in a population, they provide
a determination of informative combinations of characteristics associated with
each object, and they provide an estimation of relations between random
variables.
Classification methods can be considered easily to be primarily of two types.
"Assignment" classification is interested mainly in classifying new observations
as belonging to one of a finite number of known, already established sub-
populations, or groups. "Identification" classification, on the contrary, is divid-
ing a population into an unknown number of subpopulations or groups, so that
similarity within each group is greater than similarity across groups. The
resulting groups were not known a priori but are determined by data of the
population being classified. Discriminant analysis (Eisenbeis and Avery 1972;
Hand 1981) is an example of a multivariate method originating primarily for
assignment classification, whereas cluster analysis (Romesburg 1984) is designed
for identification classification.
Many of these employ procedures that are based commonly on Euclidian
distances in multidimensional space, in which dimension is determined by the
number of attributes (m) recognized or utilized for each object being classified.
Normally those classifications having the smallest intra-group distances and the
largest intergroup distances are considered optimum.
Although these methods provide an objective classification based on data
available or utilized, empirical data do not necessarily provide clearly defined, or
"natural" groups. Often boundaries will be gradational and some arbitrary and
subjective judgements must be imposed upon the methodology; the result is an
arbitrary classification.
Alternately, the formalized procedures of an expert system (James 1985;
Negoita 1985; Haux 1986; Lausen and Vach 1986) may be substituted for
statistical methods. Here, an expert system is a computer program designed to
act like a human, mineralogical expert who will place objects in an ideal
classification. The system is based on present mineralogical concepts, knowl-
edge, and experience of the designer. The resulting classification will not be
dependent solely upon the empirical data, as in mathematical classifications,
although an expert system can be designed to change in some specified ways as a
result of new empirical data; that is, the expert system can learn as new data are
acquired and the computer program will change automatically to reflect this
new knowledge.
The objects may be individual rock samples collected in some specified
space, perhaps a geographical area or a lithostratigraphic unit. Each object is
described in some fashion mineralogically, commonly by chemical analyses.
20 Chapter 1. The Chemical Nature of Minerals
Cluster Analysis
The manner in which cluster analysis is applied will not necessarily be the
same in different situations. For example, different types of distance measures or
relatedness may be used other than a Euclidian measure, and in fact many of
these are more widely used because they are superior in various ways. Certainly,
identical rules can be established for clustering in different situations but this
will not always guarantee optimum clusters. An objective criterion for com-
paring clusters based on different sets of data is difficult to construct. Estimation
indices which have been deduced from criteria for internal (intracluster) and
external (intercluster) values and from measures of regeneration (Kleijnen 1987)
can be used. Alternately, correspondence analysis (Bezdek 1981; Greenacre
1984) can be substituted.
The most widely used cluster analysis methods used in mineralogical
research are based on agglomerative hierarchical procedures (Romesburg 1984).
Distance between all pairs of objects in m-dimensional space, where m equals
number of attributes given for each object, is calculated and tabulated. Sequen-
tially, clusters are aggregated by combining those two clusters that are nearest.
Merging may continue until some specified criterion is met; this might be a
specified number of clusters, a minimum distance between clusters, a maximum
distance between any points in a cluster, or many other possible criteria.
Similarly, mean distances and/or maximum distances can be computed for
all objects in each cluster and compared to mean and/or minimum distance
between all clusters to establish some stopping point in the classification.
Optimum clustering normally is considered to occur when a minimum number
of clusters are found which neither overlap nor are so close together to make
addition of new objects to clusters difficult. Another way to think about a good
classification is that it minimizes the probability of misclassification when new
objects are assigned.
The process can be carried to extreme so that all objects fall into a single
cluster, g = 1, but then no classification of the population is made. Just where
the process terminates is a matter of individual judgement, experience, and
knowledge; in some cases, the purpose of the classification may playa part in
this decision.
This approach is based on the heirarchical principles;
1. Agglomeration into clusters is governed by
where Lpk is mean distance of points P k to the center of mass in cluster K for
step Z of agglomeration, Lkr is mean distance of points P k + 1 to the
center of mass in cluster K for step Z + 1 of agglomeration.
The manhattan norm may be taken as a measure of distance between two points
of M -dimensional space (P l' P 2):
Lpl -p2 = (XPl - Xp2 ),
where X is location specified by m coordinates on m orthogonal axes.
Image Analysis
Sensitivity Analysis
Here, zones of the ore body are considered fixed; they are not arbitrary.
However, results of the chemical analyses show all the properties of a random
variable.
Next, a large number of ore bodies are now included in the study. If the
domains are tested in such a way that chemical compositions of arsenopyrite are
determined only within individual zones, results of these tests can be regarded as
a random sampling of all possible alternatives. Dividing this random sampling
into three groups, each corresponding to a specific zone in the ore body, the
influence of zonation on chemical composition can be estimated.
The parameters involved in sensitivity analysis above are different in each
case but the same goal is achieved. In the first case, expected values of average
sample values for concentration of chemical elements in arsenopyrite are treated
as an unknown constant; whereas, in the second case, expected values of the same
geochemical variables are treated as a realization of random variables.
This example illustrates that care must be exercised when choosing criteria
for statistical testing and verification of hypotheses and when using multivariate
analyses.
Cautions
distribution required by clustering theory, the classification will not be valid and
any corrections will further distort the reality of the data.
Mineralogists must also be concerned about using data that represent a
closed data set (Aitchison 1986, 1990). Because mineralogical data and analyses
normally sum to one, or 100%, or can be represented in a ternary, or tetrahedral
diagram, they are constrained in some manner. Care thus must be exercised in a
statistical analysis because constraints will yield false correlations and covarian-
ces for the variables in the analysis. Adverse effects due to closed number systems
will diminish as the number of variables increases (m becomes larger).
Users of multivariate statistical methods must be familiar with all mathemat-
ical assumptions and limitations inherent in each method and determine if their
data meet these criteria. If they do not satisfy the assumptions, an analysis must
be made as to what the effect has been for their data. Many times the resulting
consequence is small and not significant; but nevertheless, failure to note the
violations is dangerous and can be extremely misleading.
Mineralogical Aspects
Summary
References
Aitchison 1 (1986) The statistical analysis of compositional data. Methuen, New York, 405 pp
Aitchison 1 (1990) Relative variation diagrams for describing patterns of compositional
variability. Math geol 22(4): 487-511
Anderson TW (1984) An introduction to multivariate statistical analysis, 2nd edn. Wiley and
Sons, New York, 665 pp
Bezdek lC (1981) Pattern recognition with fuzzy objective functions. Plenum Press, New York,
256 pp
Bezdek lC, Co ray C, Gunderson R, Watson 1 (1981a) Detection and characterization of
cluster substructure. I. Linear structure: fuzzy c-lines. SIAM 1. Appl Math 40: 339--357
Bezdek lC, Co ray C, Gunderson R, Watson 1 (1981b) Detection and characterization of
cluster substructure. II. Fuzzy c-varieties and convex combinations thereof. SIAM 1 Appl
Math 40: 358-372
Conover Wl (1980) Practical nonparametric statistics. 2d edn. Wiley and Sons, New York,
485 pp
Eisenbeis RA, Avery RB (1972) Discriminant analysis and classification procedures: theory
and applications. Lexington Books, Lexington, Massachusetts, 250 pp
2d Ed., Marcel Dekker, Inc., 398 p.
Good IJ (1977) The botryology of botryology. In: van Ryzin 1 (ed) Classification and
clustering. Academic Press, London, pp 73-94
Granath, G (1984) Application of fuzzy clustering and fuzzy classification to evaluate the
provenance of glacial till. Math Geol 16(3): 283-301
Granath G (1988) Pattern recognition in geochemical hydrocarbon exploration: a fuzzy
approach. Math Geol 20(6): 673-691
Greenacre Ml (1984) Theory and applications of correspondence analysis. Academic Press,
London, 357 pp
Hand Dl (1981) Discrimination and classification. Wiley and Sons, Chichester, Great Britain,
209 pp
1.3 The Mineral Composition of the Earth's Crust 27
Haux R (ed) (1986) Expert systems in statistics. Gustav Fischer, Stuttgart, 190 pp
Hendrickson RG (1984) A survey of sensitivity analysis methodology. National Bureau of
Standards, NBSIR 84-28114, Washington DC, 83 pp
James M (1985) Classification algorithms. Wiley-Interscience, New York, 220 pp
Jolliffe IT (1986) Principal component analysis. Springer Series in Statistics. Springer, Berlin
Heidelberg New York, 271 pp
Kacewicz M (1989) On the problem of fuzzy searching for hard workability rocks in open-pit
mine exploration. Math Geol 21(3): 309-318
Kleijnen JPC (1987) Statistical tools for simulation practitioners. Marcel Dekker, New York,
407 pp
Lausen B, Vach W (1986) Estimation, graphical representation and judgement of evolutionary
trees in expert systems. In: Haux R (ed) Expert systems in statistics. Gustav Fischer,
Stuttgart, Germany, pp 61-74
Negoita CV (1985) Expert systems and fuzzy systems. Benjamin/Cummings, Menlo Park,
California, 183 pp
Romesburg HC (1984) Cluster analysis for researchers. Lifetime learning Publ, Belmont,
California, 329 pp
Serra J (1982) Image analysis and mathematical morphology. Academic Press, London, 601 pp
Serra J (ed) (1988) Image analysis and mathematical morphology, vol 2: Theoretical advances.
Academic Press, London, 405 pp
Urmantsev Yu A (1986) Symmetry of system and system of symmetry. Comput Math Appl
12B: 379-405
van Rijckevorsel (1987) The application of fuzzy coding and horseshoes in multiple corres-
pondence analysis. DSWO Press, Leiden, 271 pp
van Ryzin J (ed) (1977) Classification and clustering. Academic Press, London, 458 pp
Yager RR, Ovchinnikov S, Tong RM, Nguyen HT (1987) Fuzzy sets and applications: selected
papers by Zadeh LA. Wiley and Sons, New York, 684 pp
Zadeh LA (1977) Fuzzy sets and their applications to pattern classification and clustering
analysis. pp 251-299 In: van Ryzin J (ed) (1977) Classification and clustering. Academic
Press, London, pp 251-299
Up to 1990 about 3500 mineral species have been found. The latest Glossary of
Mineral Species by Fleischer (1987, 1989) contains 3430 mineral species and
varieties. At present, about 60-70 new minerals are described every year (one or
two new minerals every week).
Nearly all the minerals were discovered in the Earth's rocks and ores, while
only 17 were first found in meteorites (some specific sulfides, phosphates,
2 This is a preliminary overview. Mineralogy of the mantle, meteorites, and Moon is considered
in special Chapters of Vol. 3.
28 Chapter 1. The Chemical Nature of Minerals
silicates, carbides, and nitrides) and only two (armalcolite and tranquilitite) on
the Moon.
The increase in the total number of minerals has depended on several factors:
introduction in mineralogy of the new methods (after optics and wet chemistry,
X-ray diffraction, instrumental analytical methods, and especially microprobes),
the industrial use of new types of mineral resources (uranium, thorium, rare
metals, rate earths, borates) and new geological types of ore deposits, the
enormous development of prospecting and mapping, detailed mineralogical
studies of large ore deposits and the largest intrusive massifs, especially such
unique massifs as the Khibin massif in the Kola peninsula (where more than 500
minerals were described), Green River, Tsumeb, Franklin, and other mineral
deposits.
By the mid-1960s about 1700 mineral species had been established (in 1966
A.S. Povarennykh listed 1692 minerals). Now, about 25 years later, this number
has increased twofold.
The causes of the limited total number of minerals in comparison with the
number of chemical compounds included the following aspects. (1) The composi-
tion of the Earth's crust (and mantle) is dominated by eight major elements
(O,Si,AI,Fe,Mg,Ca,Na,K) and four minor elements (Ti,Mn,P,H), while all other
elements are present only in trace quantities. This element distribution depends,
in turn, on the chemical composition of the protoplanetary nebula. (2) Extensive
solid solutions are formed in most groups of minerals and especially minor and
trace elements occur as disperse impurities in the crystal structure of minerals
(see Chap. 1.1). (3) There are some crystallochemical constraints. (4) Thermodyn-
amic factors, as well as the narrow ranges of acid-alkaline and redox conditions
4
o
o
H •
Ca Fe Si
3
As Pb~U
S
•
Fl Mn M9.NIfAI
•
Ag
Sb
0 Bi
°u0 CI' C •
Boo Ni~n • • F , . K
0
Te o S S Nb •• • .Ba TI
III 2 o e Hg
0
n Be.N V Tr
Cii Pd 00 Ta.. ..U ••• Sr
.c Pto AJj 0 TI~oWTh. Ca CrZr
E
:l
Cd l .Ge
Z
In·
• **
*
C>
.2
Re
o
O~TnMTnnTnnTrnTnMTnnTnMTnnTnnTrnTnnTnnTnnTrnTn
* *
-6 -4 -2 o 2 4 6
Fig. 1. Number of mineral species for the chemical elements vs. element abundances in the
Earth's crust
1.3 The Mineral Composition of the Earth's Crust 29
Compiled from M. Fleischer's Glossary (1987, 1989) with additions by V.A. Frank-Kamenet-
sky to the Russian edition (1990).
Table 9. The numbers of the minerals of different chemical classes in the Earth's crust, Moon,
and meteorites
and water and carbon dioxide activities are typical for the geological conditions
of mineral formation.
A correlation exists between the number of minerals containing an element
and the abundance ofthe 52 elements in the Earth's crust (Fig. 1). However, there
are several exceptions which include (1) the elements which are primarily
dispersed in natural matter (Rb,Ga,Hf,Sc,Cs,Br), and (2) the elements which have
some crystallochemical constraints for their scattered insertion in crystal
structures of the rock-forming minerals and which form their own mineral
phases (H,S,P,B,Se,Te,As,Sb,Bi,Cu,Ag,Au,Pb,Hg,Pt, and Pt-group metals).
The number of minerals containing an element, and the distribution of
minerals and classes of minerals in the Earth's crust, meteorites, and Moon are
shown in Tables 8 and 9.
The mineral composition of the Earth's crust is presented in Table 10 for the
sedimentary, granite-metamorphic, and ocean basaltic shells.
These data are based (1) on the estimations of the relative volumes of the
principal rock types in these shells (Table 11) and (2) the modal compositions of
the rocks, taken from their average mineral compositions (Bogatikov 1983, for
magmatic rocks; F. Clarke, F. Pettijohn, M.S. Shvetsov for sedimentary and
metamorphic rocks).
Other minerals and the less common rocks as well as ores compose in total
no more than 0.1 % of the Earth's crust.
W uile the estimates should not be taken as absolutely accurate, they show a
strong predominance offeldspars, quartz, and groups offemic minerals (olivines,
Table 11. Abundances of the main rock types in the Earth's crust.
(Ronov et al. 1990)
Sedimentary shell
Sands and sandstones 21.8
Clays and shales 44.6
Carbonates (limestones, dolomites) 17.8
Evaporites (gypses, halite etc.) 2.0
Volcanics
- Basalts 7.5
- Andesites 4.0
- Dacites 0.6
- Rhiolites 0.6
Granite-metamorphic shell
Granites, granodiorites, granito-gneisses 46.5
Gabbros and related rocks 1.9
Syenites and nepheline syenites < 0.1
Ultramafic rocks < 0.1
Meta-arkoses and metagraywackes 4.0
Paragneisses and schists 39.1
Metacarbonates 1.6
Silica-iron formations 0.4
Amphibolites and related basic rocks 4.1
Metamorphosed silicic volcanics 2.3
Basaltic shell of the ocean
Olivine tho lei tic basalts and related
metamorphosed rocks 99.4
S ubalkalic basalts 0.6
pyroxenes, amphiboles, and mica), as well as clays and carbonates (calcite and
dolomite). The mineral composition of these upper shells ofthe continental crust
is much more diverse than that of deeper geospheres, meteorites, or the Moon.
The mineral composition of the deeper zones of the continental crust (its
granulite-basi tic shell) is considered to be similar to the mafic magmatic rocks
(plagioclase, pyroxenes, olivine, ore minerals, garnets).
The mineral composition of the Earth's mantle (from the Mohorovicic
discontinuity down to 2900 km) has to be considered separately for the upper
mantle (down to 350 km), the middle or transition zone (350-900 km), and the
lower mantle (deeper 900 km).
Estimations of the composition of the upper mantle are based mostly on
geophysical data (velocity of longitudinal seismic waves 8.2 ± 0.2 km/s; density
3.3-3.1 g/cm 3 ) and the mineral composition of xenoliths:
- spinel peridotites (up to 80% of xenoliths), pyroxenites, and other ultramafic
rocks, and small quantities (2-5%) of eclogites, brought by alkali basaltoids
from depths of about 80 km,
32 Chapter 1. The Chemical Nature of Minerals
- spinel and garnet peridotites and eclogites brought by kimberlites from about
130 km depth.
The mineral composition of these rocks includes olivine, orthopyroxene
(enstatite-hypersthene), clinopyroxene (chromdiopside, omphacite, augite),
pyrope, spinel, chromite, amphiboles, phlogopite, plagioclase, apatite, and
diamond.
These petrological, geophysical, and geochemical studies suggest that the
essentially peridotite composition of the upper mantle (Ringwood 1975) with
some heterogeneous lateral and vertical changes is due to mantle metasomatism.
The rapid increases in the velocity of longitudinal seismic waves and in the
density of the rocks in the middle zone are related to the phase transitions which
lead to changes in the mineral composition. According to experimental data,
olivine (Mg 2 Si0 4 ) transforms at these pressures into the phase with a spinel
structure (SiMg 2 0 4 ) and pyroxene transforms into the granate structure phase:
2Mg 2 Si 2 0 6 -+Mg 3 (MgSi)Si 3 0 12 . At a depth ofabout 650 km, spinel transforms
into the assemblages MgO (periclase structure) and MgSi0 3 (perovskite struc-
ture).
The main minerals of the lower mantle are magnesto-wiistite (Mg,Fe)O and
silicate-perovskite MgSi0 3 .
The Earth's core is composed, according to recent models, of Fe-Na alloy
similar to the iron meteorites.
Lunar Mineralogy
About 90 minerals were discovered on the lunar surface, and most are of
magmatic origin; however, under the influence of meteorite impacts, processes of
impact metamorphism (crushing, thermal action, caking) occurred. There are
three groups of minerals formations (rocks) on the Moon:
1. Basalts of lunar mares (about 3.9-3.1 billion years old). They are formed due
to the near-surface crystallization of basaltic lavas. The main minerals are
pyroxenes, plagioclase, olivine, and ilmenite.
2. ANT rocks (anorthosite-norite-troctolite) comprising the predominant part
of the lunar highland material and consisting of plagioclase, pyroxene, and
olivine. Their ages are 4.6-4.1 billion years. They are breccias of various rocks
which were reworked by meteoritic impacts.
3. KREEP rocks. These are impact, metamorphosed breccias often containing a
glass. Their name is an acronym formed from the chemical elements which
enrich these rocks: K, rare earth elements, P. They correspond to the basalts
and are composed of plagioclase, pyroxene, and glass.
Thus, the main minerals of the lunar surface are plagioclases, clinopyroxenes
(augite and pigeonite), orthopyroxenes, olivine; in several types of rocks ilmenite
and armalcolite are found. The minor minerals are represented by chrome-
containing spinel and silica minerals. Together there are only nine minerals.
1.3 The Mineral Composition of the Earth's Crust 33
There are another 80 minerals (zircon, some sulfides, and some phosphates)
which play the role of accessory minerals or rarities.
In the form of films on the surfaces of grains in lunar regolite, as micro-
inclusions, and in small voids there are rare occurrences of the Moon minerals in
the form of native metals (Fe,Ti,AI) and water-containing minerals (amphiboles),
halite.
The mineral composition of the interior zones of the Moon is hypothetical. A
survey of this problem is given by Ringwood (1979), who suggests that the
average composition of the interior layer down to hundreds of kilometers [the
lunar mantle and core (?)] is similar to the pyrolite of the Earth's upper mantle.
The normative mineralogy of the Moon was calculated by Wanke and Dreibus
(1988); Dreibus and Wanke (1990); plagioclase (12.7%), pyroxenes 34.6%, olivine
51.7%, chromite 0.6%, other minerals 0.4%.
About 100 minerals were discovered in meteorites, more than 20 of them are
minerals specific to meteorites and have not as yet been found on Earth.
Meteorites vary considerably in their composition, texture, and structure. They
can be divided into three classes; stony (95.5%), iron-stony (1.3%), and iron
(3.2%); these classes can be divided into 20 chemical groups. The most
widespread and typical minerals of meteorites are olivines, pyroxenes, plagioc-
lases, taenite, kamacite, troilite, and schreibersite.
The average mineral composition of the most widespread meteorite types -
ordinary chondrites which may be generally considered as a good representative
of known meteorite matter - can be calculated from data on the average
chemical composition of H- and L-chondrites (Table 12). For the character-
ization of meteoritic matter, carbonaceous chondrites are of particular signifi-
cance. The chemical composition of carbonaceous chondrites is considered to be
representative for the composition of the nonvolatile fraction of matter from the
Solar System. Their most important peculiarity is the presence of hydrated
phases (montmorillonite, serpentine, chlorites, hydrocarbonates, hydrophospha-
tes), magnetite, and carbonaceous material containing various organic com-
pounds (including amino acids). Hydrosilicates, magnetite, and carbonaceous
particles have also been found in the composition of cosmic dust distributed
along the Solar System.
Another peculiarity of some carbonaceous chondrites is the presence of
inclusions consisting of high-temperature minerals assemblages (spinel, anor-
thite, melilite, perovskite, hybonite, as well as rate and extremely rare minerals
such as hedenbergite, andradite, sodalite, unusual metallic alloys, and some
others, which are unusual for meteorites).
From specific minerals, known only for meteorites, it is necessary to mention
nitrides (carlsbergite CrN, os bornite TiN, sinoite Si 2 N 2 0), sulfides of lithophile
elements [niningerite MgS, oldhamite CaS, brezinaite Cr 3 S4, caswellsilverite
NaCrS 2 , heideite (Fe,Cr)l +x(Ti,FehS4]' and minerals such as lawrensite FeCI 2 ,
kosmochlor NaCrSi 2 0 6 . Most of these minerals were formed in a unique
environment of very low oxygen fugacity (in enstatite chondrites).
Table 13. Probable rocks and minerals of Mercury, Venus, and Mars
Table 14. Probable rocks and minerals of outer planets and some satellites
Satellites of
Jupiter
10 S Surface Voyager and
S03-ice Pioneer spectral data
Europa H 2 O-ice Surface Voyager and
Pioneer spectral data
Ganymeda H 2 O-ice Surface Voyager and
Pioneer spectral data
Callisto H 2 O-ice Surface Voyager and
Pioneer spectral data
Satellites and
rings of Saturn
Rings H 2 O-ice Grain surfaces Voyager spectral data
Some satellites H 2 O-ice Surfaces Voyager spectral data
Satellites of
Uran
Ariel H 2 O-ice Surface Voyager spectral data
Titania H 2 O-ice Surface Voyager spectral data
Pluto CH 4 -ice Surface Voyager spectral data
Asteroids Olivine, pyroxene, Surfaces Spectral data
hydrosilicates,
metal (Fe-Ni)
the planets and suggested models of their mineral composition. The normative
mineral composition of the inner planets was calculated by Morgan and Anders
(1978). Other methods still give limited results, but they are based on studies of
planets with data obtained by devices installed on space vehicles. These types of
data are summarized in Tables 13 and 14 using different sources.
This information indicates the common mineral nature of the matter of inner
planets (terrestrial planets) and the predominance of ices (carbon dioxide,
methane) in the composition of solid satellites of giant planets. Ices and silicates
with a significant admixture of carbonaceous material compose also the main
mass of comets.
References
Bogatikov OA (1983) Magmatic rocks, parts 1 and 2. Nauka, Moscow 766 p (in Russian)
Dodd RT (1981) Meteorites. A petrologic-chemical synthesis. Univ Press, Cambridge
Dreibus G, Wanke H (1990) Comparison of chemistry of Moon and Mars. Adv Space Res
10(3-4): 7-16
Fleischer M (1987) Glossary of mineral species. Mineral Record Inc Tucson, 227 pp
Fleischer M (1989) Additions and corrections to the glossary of mineral species. Mineral
Record Inc. Tucson, 30 pp
36 Chapter 1. The Chemical Nature of Minerals
Florensky CP, Bazilevsky AT, Burba GA et al. (1981) Essays of comparative planetology.
Nauka, Moscow, 326 p (in Russian)
Frondel JV (1975) Lunar mineralogy. Wiley and Sons, New York
Phillips RI, Hartman WK, Taylor GI (eds) Origin of the Moon (1986) Lunar Planet Inst,
Houston
Mason B (1979) Meteorites. US Geol Surv Prof Pap 440-B-l
Morgan JM, Anders E (1978) Moon and Planets 18: 465-478
Petaev MI (1988) List of meteoritic minerals. Meteoritika Nauka, Moscow 47: 156-166
(in Russian)
Povarennyk AS (1972) Crystal chemical classification of minerals. Plenum Press, New York
(translated from Russian edition, 1966, Naukova Dumka, Kiev)
Ringwood AE (1975) Composition and pet~ology of the Earth's mantle. McGraw-Hili,
New York
Ringwood AE (1979) Origin of the Earth and Moon. Springer, Berlin Heidelberg New York
Ronov AB, Yaroshevsky AA, Migdisov AA (1990) Chemical structure of the Earth's crust and
major element geochemical balance. Nauka, Moscow, 180 pp
Sidorov YuI, Zolotov MYu (1989) Rocks and soils of the Martian surface. Nauka, Moscow,
224 pp (in Russian)
Smith JV (1979) Mineralogy of planets: a voyage in space and time. Mineral Mag 43 (325): 1-89
Taylor SR, McLennan SM (1985) The continental crust: its composition and evolution.
Blackwell, Oxford, 349 pp
Wanke H, Dreibus G (1988) Chemical composition and accretion history of terrestrial planets.
Philos Trans R Soc Lond Ser A 325: 545-557
CHAPTER 2
The discovery of X-ray diffraction (XRD) in 1912 (Friedrich et al. 1912) marked
the beginning of a new era in the study of the atomic structure of crystals, as it
became possible to "visualize" the arrangement of atoms in the unit cell repeated
periodically over all the crystal volume. From then on, numerous structure
studies have ensured deep insight into the complex and versatile world of
minerals. These studies are of tremendous scientific and practical significance, as
the knowledge of crystal structure is indispensable for reliable interpretation of
data on chemical composition and physicochemical properties of minerals, for
predicting and synthesizing crystals having specific properties, and for analyzing
the formation and transformation conditions of minerals in various environ-
ments.
In the first two decades of X-ray diffraction, beginning with the first crystal
structure determinations by Bragg (1913), hundreds of mineral structures were
deciphered including numerous halides, oxides, sulfides, carbonates, and the
main rock-forming silicates with different types of tetrahedral radicals. Struc-
tures were determined using the trial-and-error method where the correspond-
ence of a model to the actual structure was tested by comparing calculated with
experimental X-ray ciffraction intensities. This method required rich imagi-
nation, intuition, and the ability to guess a model near enough to the actual
structure. In addition, it stimulated the analysis of general rules governing crystal
structures. This promoted elucidation of relationships between structure, com-
position, and properties of minerals and, eventually, effective interpretation of
new and more complicated structures. A new scientific domain, crystal chemistry
of minerals, as part of a more general crystal chemistry, was thus created, and its
progress was accompanied by the revelation of still finer details of the mineral
structure. It was during the early period of the development of crystal chemistry
that the ionic model was elaborated, a system of ionic radii was proposed, and
the additivity rule of such radii as well as the rules governing essentially ionic
crystals was formulated. The concepts of the valence state of atoms, hybridiza-
tion of orbitals with overlap of electron density, electronegativity, and polariz-
ability of atoms formed the basis for the modern theory of chemical bonding.
Analysis of a great deal of experimental data provided new insights into the
2.1.1 Stages of Scientific and Technical Development 39
Impurity atoms, radiation centers, vacancies, and other point defects affec-
ting numerous physical properties (e.g., coloration, conduction etc.) are effect-
ively detected by a number of modern spectroscopic methods.
the lower limit for octahedral coordination, many germanates contain both
[Ge0 6 ] octahedra and [Ge0 4 ] tetrahedra under ambient P and T conditions.
For comparison, silicates with their lower radius ratio rsi: ro transform into
similar phases containing [Si0 4 ] and [Si0 6 ] polyhedra simultaneously under
the higher PIT conditions of the Earth's upper mantle. Germanates are,
therefore, suitable high-pressure models for silicates (Ringwood 1975).
The purpose of future studies should be, in addition to accumulating new
data and searching for empirical rules, to correlate structural transformations of
minerals under high P and T with their thermodynamical, physical, and chemical
properties. Very promising results in this field have, for example, been obtained
by developing the Landau theory further to a time-dependent order parameter
theory (Carpenter and Salje 1989) and measuring the order parameters through
various physical properties such as lattice parameters, intensities and broaden-
ing of superlattice reflections, birefringence, frequencies and line widths of
selected modes in IR and Raman spectra, NMR spectral peak intensities, etc. (e.g.
Palmer and Salje 1990; Palmer et al. 1990; Winkler and Buehrer 1990).
Melts and Glasses. Melts and glasses of diverse compositions are studied both to
determine their structural state and to analyze structural mechanisms of mineral
melting, differentiation, and crystallization of melts under various physicochemi-
cal conditions (e.g., Taylor and Brown 1979; Mysen et al. 1982). A model for the
melt structure should explain and predict various thermodynamic and rheo-
logical properties, such as viscosity, liquation, etc. Glasses that may be treated as
undercooled melts having similar structures are widely used. In particular,
special glasses are suitable to store or dispose radioactive waste.
The absence oflong-range order has for a long time been a serious hindrance
to unambiguous reconstruction of the three-dimensional structure of a poly-
component glass, even when a combination of diffraction, spectroscopic, and
electron microscopic methods were applied. Therefore, despite certain progress
in determining the main factors governing the glass structure and inter-
48 Chapter 2. Crystal Structures of Minerals
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Clifton IJ, Elder M, Machin PA, Papiz MZ, Zurek S (1989) 1 Appl Cryst 22: 483-497
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21: 905-910
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Co., Amsterdam, 157-202
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Murdoch lB, Stebbins lF, Carmichael ISE (1985) Amer Miner 70: 332--343
Mysen BO, Virgo D (1989) Amer Miner 74: 58-76
Mysen BO, Virgo D, Seifert FA (1982) Reviews Geophys 20: 353-383
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Palmer DC, Bismayer U, Salje E (1990) Phys Chern Minerals 17: 259-265
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Shannon RD (1976) Acta Cryst A32: 751-767
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50 Chapter 2. Crystal Structures of Minerals
v.A. KOPTSIK
In the second part of the 20th century, the classical theory of symmetry has been
enriched by many new fields, e.g., antisymmetry, colored symmetry, the sym-
metry of multidimensional spaces, etc. The use of symmetry theory in the natural
sciences - physics, chemistry, and biology - in their many ramifications has
become broader and deeper. The methods of symmetry have acquired a
philosophical significance: they have become some of the most general and
effective methods of theoretical investigation in contemporary natural philos-
ophy as a whole. The fundamental significance of this method arises from its
capacity to reveal the invariants of transformations and to describe the inner
structure of material and ideal systems - the objects of scientific and artistic
research.
The concept of symmetry has two opposing aspects: transformation (change)
and conservation (in variance}. That which is conserved during a change is an
invariant; the set of transformations which keeps something invariant is its
symmetry group or semigroup.
Different ways of distinguishing the structural sublevels associated with one
particular object lead to different definitions of its symmetry groups. We
therefore define symmetry as the law governing the constitution of structural
objects or, more precisely, as the highest group of automorphisms conserving the
qualitative completeness of the systems under consideration. In a single real
object we could see a whole hierarchy of symmetries, which are active at different
structure levels.
Growing in the soil of structural biology (and its precursor, structural
crystallography), structure-system methods of investigation have gradually
spread to other fields of modern natural science and art. The great generality of
these methods follows from the fact that structure is a common form of the
existence and development of matter.
The theory of symmetry took its modern scientific form, however, only after
the development of the concept of groups (Calois 1830) and then its gen-
eralization. At the beginning of the twentieth century the theory of crystal
symmetry was the most highly developed, taking the form of the classical space
group of rigid transformation (Fedorov and Schonflies 1891). After the develop-
ment of crystallography and crystal physics, group-theoretical methods were
applied in physics and other natural sciences, the method of symmetry has
become a powerful and effective instrument of theoretical research in modern
science. The problem of classification is a primary one for every science, so that
symmetry, which establishes structural invariants, constitutes an essential
technique for all of them.
2.1.2 Symmetry Bases. The Contemporary Symmetry Theory in Solids 51
It may be shown that classical three-dimensional space groups 1> are the
invariant extensions of the translation groups T by means of the crystallographic
points groups G or the groups by modulus G T isomorph with the group G,
1> = TIXG or 1> = TIXG T , for the groups ofsymmorphic and non-symmorphic
types correspondingly, IX being the symbol of the semi direct products of both
group.
In the same way one may consider all the generalized symmetry groups as
extensions of the corresponding classical groups by the use of certain groups of a
new kind. The latter include the antisymmetry (two-color) and poly-colored
point and space group in three- and n-dimensional spaces (n > 3).
The idea of anti symmetry was put forward independently by Heesch (1929)
and Shubnikov (1945). There exist 58 two-colored point groups G' isomorphic
with G. The classical operators g E G' constitute the subgroups He G' of index
two, the other operators g' E G' are combined with the antisymmetry operator I',
g' = gl' = l'g, g = 1,2, 3,4,6, I, 2 = m, 3, 4, 6.
In the same way, among 1651 anti symmetry space groups there are 230 1>-groups
of classical type, 230 (1) x 1')-neutral groups (direct product 1> with 1') and 11911>'
two-colored groups of the types TIXG' and T'IXG being in number 674 and 517
correspondingly.
We note that the antisymmetry groups describe the symmetry properties of
material two-colored figures (or the three-dimensional two-colored spaces
enveloping them). The nongeometric quality ascribed to the points of these
spaces is abstractly modeled by color or by any function that can take on two
values, for instance the function of atom magnetic moments ill (f) describing the
distribution of the moments ill(f) in ferromagnetic and antiferromagnetic
colinear crystalline structures. In another interpretation the anti symmetry
groups may be treated as the symmetry groups G(4) or 1>(4) of four-dimensional
spaces in which the nongeometric coordinate takes only two fixed values ± x4 .
For homogeneous four-dimensional spaces the number of point symmetry
groups increases from 58G'(3) to 227G(4) and of space symmetry groups from
11911>'(3) to 47831>(4).
If instead of antisymmetry operator I' = 1(2) the operators 1(p) which map
onto themselve p orientational states of magnetic moments ill(f) are introduced,
one receives the 256 (G x I(P») neutral and 81G (p) p-colored point groups with
the crystallographic number of colors or 134G(P)+-+32G(3), p = 3,4, 6, 8, 12, 16,
24, 48. Point groups with cyclic color permutations were first obtained by Niggli
(1959) and Indenbom et al. (1960). The theory of derivation of color groups was
developed by Van der Waerden and Burckhardt (1961).
The derivation of the true colored-symmetry groups, i.e., those not contain-
ing 1(p) subgroups, was started in 1969 by Zamorzaev, who calculated the
number of three-, four-, and six-colored space groups and obtained the corres-
ponding colored lattices.
In 1945 Shubnikov suggested the idea of many-fold anti symmetry and in
1960 the idea of similarity symmetry. Both ideas received ample development
52 Chapter 2. Crystal Structures of Minerals
and were further extended by Zamorsaev and collaborators. The idea of colored
symmetry received further development in the works of Niggli, Wondratschek,
Wittke, Van der Waerden, Burckhard, Pawley, Mascay, and Zamorzaev
(1959-1971). A number of works have indicated ways of obtained colored
symmetry groups containing classical subgroups which are not normal divisor.
Among them, Van der Waerden and Burkhardt groups are defined by a three-
termed symbol G jH' jH in which the classical group G is isomorphic to G(p), the
subgroup H' c G of index p corresponds by isomorphism to the subgroup
H!P)cG(Pi), which preserves the quality (color) i, and the normal divisor
H = G n G' is defined by the intersection of all the conjugate subgroups
H= ngH'g-l,gEG.
gEG
which means that symmetry groups ofi-th system consequence must include the
symmetry group of systems of reason, the latter being defined through the
intersection (the common part) of symmetry group of particular reason multi-
plied by some symmetrizer. For example, the symmetry group of system of two
equal cubes with common face is 4/mmm = 4mm x 4m.L' where 4mm = m3m(1)
nm3m(2) is the intersection and symmetry plane m.L is the symmetrizer. If the
system consists of an object (crystal) and some external action, then according to
the Curie principle, it may manifest only such physical properties whose
symmetry is
GphYSical propertYi;;;2 or .;::!, Gsystem = GObject (crystal)nGexternal action·
During the last two decades the symmetry theory of imperfect, magnetic,
nonrigid crystals with internal degrees of freedom, and also the incommensur-
able space-modulated crystal phases p(f) was developed. The theory is based on
the abstract symmetry conversation (or extension) law and on the construction
of wreath products of two groups, one of them being symmetry group of some
average basic structure Po(f) and the other being symmetry group of perturba-
tion function pp(f) which describes the distortion of the ideal average structure.
According to the Curie-Shubnicov principle, the symmetry group of composite
system is.
p(f) = Po(f) + bp(f) will be G p = (G pO nG bp ). Gsymmetrizer .
References
Hargittai I, Hargittai M (1986) Symmetry through the eyes of a chemist. VCH Verlagsgesells-
chaft, Weinheim
Hargittai I, Vainshtein BK, Udalova VV (eds) (1988) Crystal symmetries. Shubnikov centennial
papers. Comput Math App116: 351-669
Janssen T (1988) Aperiodic crystals: a contradicto in terminis. Phys Rep Rev Sect Phys Lett
168: 55-113
Koptsik VA (1966) Shubnikov groups. The reference book on symmetry and physical
properties of crystal structures. Moscow Univ Publ House (in Russian)
Koptsik VA (1975) Advances in the theoretical crystallography. Colour symmetry of defect
crystals. Kristall Technik 10: 231-245
Koptsik VA (1980) The symmetry of imperfect crystals. On the theory of structure phase
transition in crystals with internal degress of freedom: MATCH, Informal Commun Math
Chern 8: 3-20; 21-35
Koptsik VA (1983) New group theoretical methods in physics of imperfect crystals and the
theory of structure phase transitions. Symmetry principles in physics: J Phys C Sol State
Phys 16: 1-22; 23-35
Koptsik VA (1988) Generalized symmetry in crystal physics. Comput Math App116: 407-424
KoptsikVA (1991) Crystallography of quasicrystals: The problem of restoration of broken
symmetry. In: Manko V and Dodonov (eds) Lecture notes in physics. Springer, Berlin
Heidelberg New York, No 382: 588-600
Kotzev JN, Alexandrova DA (1988) Full tables of colour space groups with colour-preserving
translations. Acta Cryst A 44: 1082-1096
Kovalev OV (1987) Irreducible representations of the space groups. Gordon and Breach, New
York (1964); Irreducible representations, co-representations and induced representations of
the space groups. Nauka, Moscow (in Russian)
Shubnikov AV, Koptsik VA (1974) Symmetry in science and art. Plenum Press, New York
(translated from Russian edn. Nauka, Moscow 1972)
Smirnov VP, Evarestov RA (1988) Quantum chemistry of solids. The applications of symmetry
methods. Vysshaiya Schkola, Moscow (in Russian)
Talis AL, Koptsik VA (1990) Wreath algorithms for constructing of modular crystal structures.
SOy Cryst 35: 1347-1353
Vainstein BK (1979) Contemporary crystallography, vol 1. Symmetry and structures of
crystals. Nauka, Moscow (in Russian)
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Zamorzaev AM, Galarsky EI, Palistrant APh (1978) Colour symmetry: its generalizations and
applications. Shtiinza, Kishinev
W.H. BAUR
a crystal. This obscures two separate effects, namely the thermal motion of the
atoms and the random occupancy of sites where atoms are replacing each other.
Thus we see only a static picture of a crystal structure in which all atoms are
actually thermally vibrating, and we see only a superposition of statistical
occupancies of crystallographically equivalent sites by chemically different
atoms. The details of local, nonperiodic atomic environments get lost in the
process of a crystal structure determination. Nevertheless, the results of
thousands of precise crystal structure determinations have allowed us to
correlate observed interatomic distances and angles and structural geometries
with a number of empirical factors, thus giving us the possibility to make certain
predictions about details of crystal structures.
Polyhedral Distortions
we can say that Sn2+ engages in covalent bonds with the three oxygen atoms.
The fourth orbital (pointing away from the pyramid) is occupied by the lone
electron pair which acts as an additional ligand and prevent a close approach by
other oxygen atoms. Such asymmetric coordination environments are displayed
not only by Sn2+, but also by Ge 2 +, Pb 2 +, As3+, Sb3+, Bj3+, Se4 +, Te 4 +, Br 5 +,
15 +, and Xe 6 +.
Another example, where the geometry of the coordination polyhedra is
greatly distorted is provided by linear uranyl groups O-U-O and by vanadyl
groups Y-0. In both cases the bond lengths within these groups are much
shorter (1.6 to 1.8 A) than the remaining bond lengths (usually longer than 2.0 A)
within the coordination polyhedra around the y5 +- or U 6 +-ions. Obviously the
bonding (possibly multiple) within the UO~ + or Y03 + groups is stronger than to
further neighbors. One can assign to each of the different observed bond lengths
a corresponding bond strength, s, so that the sum of these s received by each
oxygen atom is 2.0 by constructing an empirical bond strength vs bond length
curve based on the available crystal structure data of the uranyl compounds.
These empirical bond strengths are not identical to the Pauling (formally
electrostatic) bond strengths obtained by dividing the formal charge of a cation
by its coordination number. However, they preserve, with a twist, Pauling's
postulate according to which the sum of the bond strengths received by the anion
should equal (with opposite sign) the formal charge of this anion. Alternately,
one can relate the observed bond lengths to bond orders using Pauling's
logarithmic formula
Dn - Dl = 2klogn. (1)
Assuming the single bond length Dl to be 1.81 A and a value of k of 0.39 one
obtains for vanadates bond orders which within reasonable limits add up to the
formal charges of 5 + for vanadium and of2 - for oxygen. By defining the bond
orders in this way Pauling's postulate is satisfied.
However, there are other distortions in crystalline solids which are not related to
electronic asymmetries or to preferential strong bonding between selected atoms.
This can be observed in a large number of individual crystal structures and their
interpretation shows that in cases in which Pauling's postulate is not obeyed an
effective charge balance is achieved by adjustments in the cation-anion dis-
tances. For instance, for a series of precisely determined borate structures this
was described by empirically derived bond strength vs bond length curves for the
B-O and O-H---O distances (analogously to the treatment of the uranyl
compounds). The difference lies in the fact that the short U-O bonds are inherent
to the uranyl groups, while in the borates (and the other structures mentioned in
this section) the short and long cation-anion distances are externally imposed on
the atoms by their "underbonding" or "overbonding" (Zachariasen).
58 Chapter 2. Crystal Structures of Minerals
Pauling postulated that his second rule shall be satisfied within rather narrow
limits. Accordingly deviations by as much as 1/6 valence units (v.u.) should be
rare in silicate minerals. Meanwhile it is obvious that even in stable rock-forming
silicate structures variations in the sum of the Pauling bond strengths received by
the oxygen atoms can range from 1.67 to 2.33 v.u. In less stable structures the
deviations can be even larger. Therefore, Pauling's postulate has to be modified
somewhat.
The value of Px received by the anions in a crystal structure is on the average
equal, with changed sign, to the valences of the anions. For any individual anion,
however, Px can deviate from this value up to about 50%.
The bond lengths to an anion vary proportionally to the Pauling bond
strengths received by this anion as the average bond strength received by all
anions in a coordination polyhedron is close to the ideal value (the charge of the
anion with reversed sign). If all anions in a polyhedron are over- or under-
saturated, the mean value ofthe cation-anion distance is not affected. This can be
summarized (Baur) by:
The average value of the distance d(A-X) within a coordination polyhedron
is approximately constant and independent of the sum of the Px values received
by all the anions in the polyhedron. Therefore, the deviation of an individual
bond length d(A-X) from d(A-X)mean is proportional to Apx and the bond
lengths d(A-X) can be predicted to a second approximation from equations of
the form
d(A-X) = (d(A-X)mean + bApx) A, (2)
where d(A-X)mean and b are empirically derived constants for given pairs of A
and X in a given coordination, and where Apx is the difference between the
individual Px and the mean Px for the coordination polyhedron:
Apx = Px - Px(mean)' (3)
This relationship can be called the extended electrostatic valence rule because it
2.1.3 Empirical Relationships in Structural Geometry 59
extends Pauling's original valence rule by accounting for bond lengths as well as
for bond strengths.
The agreement between predicted and observed interatomic distances has
been compared for several thousand examples. On the average, the predicted
distances based on this relationship agree within 0.01 Awith the experimentally
determined values for tetrahedrally coordinated ions of high formal charge (Si 4+,
p 5 +, S4+). For distances involving ions of smaller charge and/or higher
coordination number the average difference between prediction and observation
can be several hundredths of an A, reaching up to 0.1 A.
The possibility of predicting individual interatomic distances based on such
an empirical approach becomes useful when we predict distances serving as input
to the computer simulation of crystal structures, or when we use predicted
distances as a criterion whether or not a particular structure has been correctly
determined, or when we compare observed and predicted distances to establish
the correct crystal chemistry of a mineral. Above a linear relationship between
bond strength and observed bond length is assumed. The scatter in the
experimental data and the limited range of bond lengths investigated do not
allow to ascertain the existence of a nonlinear relationship.
Valence Balancing
Pauling's logarithmic formula (1) is the basis of the reverse procedure in which
the bond strengths are redefined in such a way that their sum yields the proper
valence at all the ions. This way nonlinear relationships can be represented. One
can employ nonanalytical bond strength versus bond length curves, or use
logarithmic forms, simple inverse relations, fit curves by third degree poly-
nomials, or balance the valences by assuming that the bond strengths are
proportional to the inverse n-th powers of the bond length. The approach most
used is the one favored by Brown and Shannon. It has been recently extended to
allow the prediction of bond valences and thus of bond lengths as well.
Of particular importance for many common minerals are the bond lengths in
silicates. It was realized a long time ago that experimentally determined bond
lengths can be used for estimating the AI-content of (Si,AI)O 4 tetrahedra and this
concept was subsequently refined. Since the mean Si-O distance depends on the
Si-O-T angle (where T is a tetrahedrally coordinated cation), on the mean
coordination number of the oxygen atoms and on the connectivity of the silicate
tetrahedron with other coordination tetrahedra, the relationship between mean
(Si,AI)-O distance and AI-content is actually more complex than originally
thought. Recently a computer program was written, which calculates the Si/ Al
ratio deduced for an (Si,AI)04 tetrahedron of known dimensions. Such empirical
60 Chapter 2. Crystal Structures of Minerals
While we cannot predict crystal structures from first principles, we can, for a
known or assumed topology, simulate the details of a crystal structure by a
distance least squares procedure (DLS). Empirical relationships of the kind
presented above are necessary to provide observations in terms of input of bond
distances and bond angles, and of weights for these observations. In fact, a
properly weighted DLS calculation is analogous to a force model, where the
predicted bond lengths correspond to the unstressed lengths of the springs, while
the squares of the weights correspond to the force constants (strengths) of the
springs. The Pauling bond strengths proved in this context to be excellent, when
used as weights in the DLS simulations.
References
Bersuker IB (1984) The Jahn-Teller effect and vibronic interactions in modem chemistry.
Plenum, New York
Bish DL, Post JE (eds) (1989) Modem powder diffraction. Reviews in mineralogy, vol 20,
Mineralogical Society of America, Washington, DC
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Chern Mineral 15: 30-34
Brown ID, Shannon RD (1973) Empirical bond-strength-bond-Iength curves for oxides. Acta
Cryst A29: 266-282
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601-621
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second-row atoms. J Mol Struct 130: 177-191
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Atomkoordinaten idealisierter Geriiststrukturen. Z Krist 129: 411-423
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71: 161-190
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16: 801-811
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W.H. BAUR
given type of polyhedron are fairly constant when values from different
structures are compared. The following treatment deals only with a discussion of
mean distances within coordination polyhedra.
The distance A-X (usually measured in Angstroms, A), between two atoms can
be expressed as
(1)
where rA and rx are the radii of atoms A and X. The radii are additive in the sense
that the interatomic distance is obtained as a sum of the radii. One can deduce
from a series of experimentally determined interatomic distances in metallic,
covalent, and ionic compounds a set of atomic radii for all elements. The mean
deviation between observed interatomic distances and those calculated from the
sum of such atomic radii is about 0.12 A. This agreement between observed
interatomic distances and the sums of the atomic radii is remarkable if one
considers the wide range of bond types covered by them. The atomic radii
correspond to the radii of maximum charge density of the outermost shells of the
atoms as shown by a comparison of these empirical radii with the radii of
maximum radial charge density of the largest shells of atoms calculated using the
self-consistent-field method. An approach oftwo atoms to a distance equal to the
sum of their atomic radii means that their outermost electron shells overlap, i.e.,
a covalent bond is formed between them. Therefore, atomic radii are parti-
cularly useful when we wish to test whether or not an experimentally determined
interatomic distance corresponds to a bond. The additivity of atomic radii only
works well within given classes of compounds and when the numbers and
arrangements of atoms around each other are similar. Consequently sets of
radii, which apply only to certain classes of compounds (ionic, covalent, or
metallic) were developed. Such more specialized sets of radii allowed for
corrections for valence state and coordination number.
Most important for mineralogical applications are sets of effective ionic radii
(Shannon-radii). These traditional ionic radii are approximately 0.8 A larger
than atomic radii for the anions and by the same amount smaller for the cations.
As long as only cation-anion distances are considered, any set of radii will of
course remain self-consistent when a constant amount is subtracted from all
cation radii and the same amount is added to all anion radii (and vice versa). This
is evident from Eq (1). Only the interatomic distance d(A-X) can be determined
experimentally. The apportionment of d(A-X) between rA and rx has to be based
on additional assumptions. Therefore we do not have an unambiguous method
2.1.4 Systems of Empirical Radii of Atoms and Ions 63
Possibly the calculated orbital radii of the valence electrons (i.e., pseudopotential
or nodal radii) are physically more significant. When linear combinations of such
radii are used as sorting parameters, one can construct structural maps in which
64 Chapter 2. Crystal Structures of Minerals
chemical compounds of the same crystal structure type are classified correctly in
the same areas of such maps. This approach is useful even for molecules.
References
Physical models of inorganic crystal structures can be divided into three kinds:
those made of spheres in contact with each other, those made of coordination
polyhedra, and finally the ball and spoke models produced out of small wooden
balls and hard wire. The illustrations of these models projected into the plane of
the paper fill our scientific papers and monographs dealing with crystal struc-
tures of minerals and inorganic compounds. These three manners of depicting
inorganic crystal structures correspond to the various mental pictures we make
for ourselves of the arrangement of atoms and their groupings in these struc-
tures. Each of these modes of visualizing crystal structures is useful for under-
standing the topology and geometry of a given crystal structure, for classifica-
tion purposes, as a help in solving unknown crystal structures and finally for the
generation of as yet unobserved, but hypothetically possible structures. The
various kinds of structural representation should be seen as complementary to
each other, because each stresses a different aspect of what we perceive as a
crystal chemical reality. Physical models of crystal structures are laborius and
expensive. Projected images of these models, however, can today be relatively
easily prepared with the help of numerous computer programs which are now
available.
Sphere Models
useful one, see Bragg. Viewing crystal structures as sphere packings makes the
implicit assumption that the forces between the atoms are radially symmetric.
Nevertheless, it is the basis of various systems of effective atomic, covalent, van
der Waals, metallic, orbital and ionic radii (see Chap 2.1.4) which have proved
their worth as empirical guideposts in crystal chemistry again and again. When
viewing a crystal structure as a packing of spheres, we are considering its
smallest possible building unit~, the atoms, and do not immediately perceive the
complete architectural complexity of the arrangement. Sphere packings can be
powerful classification devices, however, when we describe the various closest
packings of spheres and consider the possible stuffings of their interstitial spaces
by smaller atoms. In practical terms, both physical models constructed of
touching spheres and drawings of such models tend to obscure the insides of the
structure to be viewed. This can be avoided by making the spheres relatively
smaller (see below).
Polyhedral Models
Nets of Bonds
skeletons, the atoms are the nodes, and the connections between them corres-
pond to the bonds between the atoms. This emphasizes both the topology of the
links between the atoms, and the directional nature of the bonding arrange-
ments. On the other hand, the restrictions on the geometry of certain bonds may
impose limits on the topology of periodic systems of such bonding arrange-
ments. Nets are a particularly powerful way of depicting structures when dealing
with three-dimensional frameworks. A consideration of the connectivities of
2.1.5 Representation of Crystal Structures as Packings of Spheres 67
Fig. 2. Conld.
Computer Programs
a b
o o
o o
oo oo
oo oo
CD Fig.3a- b. View of the fibrou chain of natrolite parallel to
o
the 0- 0 vector of the outer oxygen atom of oppositely
c
0 located AI-coordination tetrahedra. The c-axis i pointing
IOwords the LOp. Same conventions as in Fig. I
2.1.6 Computer Simulation of Crystal Structures 69
References
Baur WH (1977) Computer simulation of crystal structures. Phys Chern Mineral 2: 3-20
Baur WH, Kassner D, Kim CH, Sieber NHW (1990) Flexibility and distortion of the
framework of natrolite: crystal structures of ion-exchanged natrolites. Eur J Mineral 2:
761-769
Bragg WL (1920) The arrangement of atoms in crystals. Philos Mag [6] 40: 169-189
Dowty E (1990) ATOMS, atomic structure display software. Shape Software, Kingsport
Fischer RX (1985) STRUPL084, a FORTRAN program for crystal structure illustrations in
polyhedral representation. J Appl Cryst 18: 258-262
Fischer RX, Ie Lirzin A, Kassner D, Riidinger B (1991) STRUPLO'90, eine neue Version des
Fortran Plotprogramms zur Darstellung von Kristallstrukturen. Z Krist Suppl 3: 75
Hawthorne FC, Smith JV (1988) Enumeration of four-connected three-dimensional nets and
classification of framework silicates. Combination of zigzag chains with 63 , 3.12 2 , 4.8 2 ,
4.6.12, and (5 2 .8lz(5.8 2)! nets. Z Krist 183: 213-231
Johnson CK (1970) ORTEP: a FORTRAN thermal-ellipsoid plot program for crystal
structure illustrations. ORNL-3794, Oak Ridge National Laboratory, Oak Ridge
Liebau F (1985) Structural Chemistry of Silicates. Springer, Berlin Heidelberg New York
Meier WM, Olson DH (1987) Atlas of zeolite structure types, 2nd edn. Butterworths, London
Pauling L, Sturdivant JH (1928) The crystal structure of brookite. Z Krist 68: 239-256
Pauling L (1960) The nature of the chemical bond, 3rd edn. Cornell Univ Press, Ithaca
Smith DK (1989) Computer analysis of diffraction data. In: Bish DL, Post JE (eds) Modern
powder diffraction. Reviews in mineralogy, vol 20, Mineralogical Society of America,
Washington, DC, pp 183-216
Stewart JM, Hall SR (eds) (1990) XTAL System of crystallographic programs, release 3.0.
Universities of Maryland and Western Australia, Perth
Tillmanns E, Hofmeister W, Baur WH (1985) Variations on the theme of closest packing: the
structural chemistry of barium titanate compounds. J Sol State Chern 58: 14-28
Wells AF (1977) Three-dimensional nets and polyhedra. Wiley, New York
Wells AF (1984) Structural inorganic chemistry, 5th edn. ciarendon, Oxford
Significant progress has been made in the past 10-15 years in the application of
computer modeling to the prediction of crystal structures and their spectro-
scopic, thermodynamic, and defect properties. The approaches used range from
simple static energy minimization codes, through more sophisticated free-energy
minimization methods based on the calculation of lattice dynamical properties
within the quasi-harmonic approximation, to molecular dynamics, and most
70 Chapter 2. Crystal Structures of Minerals
References
Burnham CW (1985) Mineral structure energetics and modelling using the ionic approxima-
tion. Reviews in Mineralogy 14, Springer, Berlin Heidelberg New York, pp 347-388
Catlow CRA, Mackrodt WC (1982) Computer simulation of solids. Lecture Notes in Physics,
166, Springer, Berlin Heidelberg New York
Catlow CRA, Price GD (1990) Computer modelling of solid-state inorganic materials. Nature
347: 243-248
Catti M (1986) Theoretical computation of the physical properties of mantle minerals. In:
Saxena S (ed) Advances in physical geochemistry 6. Springer, Berlin Heidelberg New York
Matsui M (1986) Computer simulations of structures and elastic constants of minerals.
J Mineral Soc Jpn 17: 169-179
Parker SC, Price GD (1989) Computer modelling of phase transitions in minerals. In: Catlow
CRA (ed) Advances in solid state chemistry, London, AI Press 1, pp 295-327
Urusov VS, Dubrovinsky LS (1989) Computer modelling of crystal structures and properties
of minerals. Moscow Univ Press, Moscow (in Russian)
72 Chapter 2. Crystal Structures of Minerals
There are two ways to obtain the electron density of minerals. The first is to
calculate electron density by quantum chemistry methods, the second is by
X-ray diffraction measurement. In the latter case, a special experimental
procedure is needed and the accurate single-crystal X-ray diffraction analysis is
used for this purpose. The total X-ray intensities are measured with an accuracy
of about I % and secondary diffraction effects such as absorption, extinction,
thermal diffuse scattering, and anomalous dispersion are appropriately correc-
ted. As a result, moduli of structure amplitudes are obtained. For the extraction
of crystal chemical information from X-ray data, the values of structure
amplitudes are approximated by their theoretical analogs, calculated from the
model of a given mineral. The refined parameters of the model are atomic
coordinates, harmonic and anharmonic characteristics of atomic thermal vibra-
tions, and populations of valence electron shells of atoms. In this way the atomic
charges in many minerals have been determined.
The electron density in the unit cell can be mapped by Fourier series using
structure amplitudes as coefficients (Fig. 4). The phases of structure amplitudes
are calculated by means of a crystal model. The "experimental" electron density
maps have a resolution of 0.2 A and they are the basis for studying chemical
bonding in minerals. The deformation electron density (OED) is usually
calculated, in order to obtain characteristics of a chemical bond. OED is the
difference between crystal electron density restored from the X-ray diffraction
data and electron density of the ensemble of spherically symmetric atoms
calculated by quantum chemistry methods. DED describes the redistribution of
electrons during crystal formation from atoms.
There are general principles for the interpretation of DED maps. The excess
of DED appears as peaks on these maps in regions of bonding overlap of the
atomic orbitals and in the regions of the orbitals of electron lone pairs location.
Negative DED is connected with anti-bonding orbital overlap regions, and with
the regions where bonding overlap of atomic orbitals are subjected to weaker
changes than mutual penetration of atomic clouds. The DED peaks connected
with n-bonds are elongated in the internuclei space perpendicular to the line
linking the interaction atoms. In ionic bonds, DED peaks are displaced along the
bond line to more electronegative atoms and in strained bonds these peaks are
shifted from bond line.
An example of the significance of electron density studies for minerals is the
rutile-type high pressure porymorph of silica stishovite SiOz' In this mineral,
Si is coordinated by six oxygen atoms in an octahedral configuration. The
structure contains two nonequivalent Si- O bonds: the longer (equatorial) bonds
are 1.757 A. and are about 3% shorter than axial bonds; but the ionic model
predicts that ratio between Si- Oe and Si- O. bond length should be more than
unity. Furthermore, non bonding 0 - 0 edges of Si- octahedra (2.29 A.) are
a b
Fig. Sa, h. Experimental deformation electron density (the difference between measured elec-
tron density for crystal and sum of calculated atomic electron densities) for stishovite Si0 2 . a
Map of the octahedron axial/equatorial bond plane. b Map of the coordination plane of the
oxygen atom. The contour interval is 0.05 eA - 3. Excess of electron density (dark lines) on the
bond lines is responsible for chemical bond forming: electron density peaks are shifted to more
electronegative oxygen atoms and elongated perpendicular to the bond line (n-character of the
bond). Negative electron density (dashed lines) characterizes the region from which the electron
is removed when the crystal is formed from atoms
74 Chapter 2. Crystal Structures of Minerals
shorter than the double oxygen radii (2.54-2.80 A). Thus, the real structure
contradicts the Pauling rule of shortening the shared edges of the polyhedra in an
ionic model. The DED maps (Fig. 5) reveal the bonding peaks with a height of
0.47 eA -3 on the Si-O. bonds and of 0.29 eA -3 on the Si-O. bonds. These
peaks are shifted toward oxygen atoms (partly ionic covalent u-bond) and shifted
from the bond line (some strain in the four-membered ring). The maxima in the
equatorial plane are linked by "bridges" of electron density. These bridges have a
shielding effect on the cation interaction across the shared edge, and reduce the
repulsive forces between Si atoms. Thus, electron density study explains the
origin of the Pauling rule violation. Note that the average distance between the
Si atom and the nearest DED peak is 1.10 A, which is close to the Slater atomic Si
radii of 1.15 A..
The observation of splitting of 3d-element electron energy levels in a crystal
field via electron density maps can be demonstrated for high-pressure phase
y-M 2 Si0 4, where M = Fe, Co, and Ni. These minerals belong to normal spinels
in which transition-metal atoms are situated in the centers of oxygen octahedra
(B-position) with symmetry position D 3d • Eight positive peaks 0.9-1.0 eA -3 in
height located at the corners of a cube have been revealed on the DED map for y-
Ni 2Si0 4 near a B-position (Fig. 6). The octahedral crystal field symmetry in the
position of a Co atom is more trigonally distorted, and peaks ofDED lying along
the threefold axis of the octahedron are higher. A further trigonal distortion of
the Fe-octahedron leads to the presence of excess DED peaks only along the
threefold axis. These DED maps may be interpreted in terms of the crystal field
theory as follows. The trigonal distortion of octahedron in this spinels is its
compression along the threefold axis [111]. This compression leads to the
splitting the 3d-electron energy levels of B-cations into a singlet ag with
corresponding orbital lies along the threefold axis, and two doublets: eg and e~
(the latter are described by n-orbitals lying in the plane perpendicular of the
threefold axis). The level a g is the lower in energy than e~. In the near perfect
octahedral environment, six of the eight 3d-electrons of the NF + must be
occupied ag and e~ orbitals and the remaining two must be occupied eg-orbitals.
Thus, Ni 2 + electronic configuration (ag)2(e~)4(eg)2 may be expected. Excess and
deficit of the electrons on corresponding orbitals as compared to the spherical
atom average orbital populations, equal to 8/5 electrons, are reflected in the
formation of positive and negative regions around Ni atoms on the DED map.
The position ofDED minima and maxima correspond to the crystal field theory
picture. As the number of 3d-electrons of the B-cation in a series Ni-Co-Fe
decreases, geometrical distortions in the structure increase, and the electron
density around the B-cation is changed: the ag-orbital electron population grows,
and the electron density of the e~-level decreases. This picture agrees well with the
simple qualitative predictions of the crystal field theory.
The results of experimental electron density analysis can be summarized as
follows. In all minerals (from halite-type to silicates, spinels, garnets, etc.) atomic
charges are smaller than the formal atomic oxidation numbers. The difference is
greater when a real chemical bond is distinguished from an idealized ionic bond
2.1.7 Precision Electron Density Calculations 75
[100] [100]
- - -....-[110]
a
-b--"-- [110]
[100]
References
Gibbs (1982) Molecules as models for bonding in silicates. Am Mineral 67: 421-450
Kirfel A, Eichorn k (1990) Accurate structure analysis with synchrotron radiation. Acta Cryst
46: 271-284
Lewis J, Schwarzenbach D, Flack HD (1982) Electric field gradients and charge density in
corundum, IX-Al z0 3 • Acta Cryst A38: 733-739
Marumo F, Isobe M, Saito Y et al (1974) Electron-density distributions in crystals of Ni zSi0 4 •
Acta Cryst B30: 1904-1906
Marumo F, Isobe M, Akimoto S (1977) Electron-density distributions in crystals of y-Fe zSi0 4
and y-Co zSi0 4 . Acta Cryst B30: 713-716
Sasaki S, Takeuchi Y, Fujino K, Akimoto S (1982) Electron-density distribution of three
orthopyroxenes, Mg zSi z0 6 , Co zSi z0 6 and Fe zSi z0 6 . Z Krist 158: 279-297
Spackman MA, Hill RJ, Gibbs GV (1987) Exploration of structure and bonding in stishovite
with Fourier and pseudoatom refinement methods using single-crystal and powder X-ray
diffraction data. Phys Chern Mineral 142: 139-150
Tsirelson VG, Ozerov RP (1994) Electron density and bonding in crystals. Adam Hilger,
Bristol
Tsirelson VG, Evdokimova OA, Belokoneva EL, Urusov VS (1990) Electron density distribu-
tion and bonding in silicates. Phys Chern Mineral 17: 275-292
Three simple rules describe the basic features of thermal deformation of crystals.
Rule 1. The effect of temperature is scalar; therefore, thermal deformation of
a crystal is controlled by a structure and is described by a second rank tensor.
Rule 2. Anharmonicity of thermal oscillations of atoms results in an increase
in interatomic distances, i.e., in thermal expansion. More anharmonic oscilla-
tions with higher amplitudes, i.e., weaker bonds, result in more pronounced
thermal expansion.
Rule 3. An increase in crystal temperature is equivalent to an increase in the
intensity of thermal motion (vibrations, rotations, and jumps) of atoms and
molecules and gives rise to a chain of transformations whose tendency is toward
rising crystal symmetry: rising vibrational symmetry of atoms and mole-
cules -+ deformation-structural rearrangement in the direction of rising sym-
metry -+ transformation into more symmetrical high-temperature modification.
The following regularities were obtained from a generalization of experi-
mental data. They follow from the principles given above.
-
rt1000
1 ad
= ~ aT ~ 4.0(4)
(n) _
S2 ZcZa x 10
6 0 -
C,
1
(1)
t(S
x
points)
30
\\
(a)(S2ZxZa) = 4.0(4) X 10- 6 °e l
\~\ \
c:
0
II>
c: 2S a Oxides 8. Silicates
0 \ \
x Halides
~\1+
Co
)(
w 0 Carbides 8. Nitrides
0
E
4;-
20 \\ :
\ + Sulfides, Selenides, 8.
Tellurides
l!,,~
.J:.'
~ ~
- co
~ 0 IS
"0 -
'" X
'11
.J:.-
>- 0
0 0
Cl. 0
~
la- 10
0
'"
c:
.-I
+"
..," .......
c: ..... -....;
.......
.......
0
S
'"
:::;;
+ -- ---.:::~
--
0
0 f 1i
0 0.2 0.4 0.6 0.8 1.0 1.2
S2 ze Zo
n
Pauling Bond Strength
Fig. 7. The inverse relationship between polyhedral thermal expansion and Pauling bond
strength. (Hazen and Finger 1982)
can be used for predicting the effect of temperature on the polyhedron; fi. does
not depend on the structural bonds in the polyhedron. Furthermore, all coord-
ination polyhedra with similar values of Pauling bond strength have a similar
coefficient IX. For example, in octahedra with divalent Ni,Mg,Co,Fe,Cd,Mn,
Ca,Ba, and Sr fi. 1000 = 14 ± 1 x 1O- 6 °C- 1 .
In a structure with more than one type of cation polyhedron, the effect of
temperature is proportional to a polyhedral size. However, thermal expansion of
a crystal is usually not just the simple sum of changes in the cation-anion
separation; changes in angles between polyhedra must be also considered.
Shears. The cell angles of triclinic and monoclinic crystals are not fixed by
symmetry; with changing temperature crystal structures are subjected to shears,
which are by nature highly anisotropic. Many oblique-angle crystals reveal
anisotropic thermal deformations, including a negative thermal expansion in
some directions.
Crystals with negative linear thermal expansion are uncommon in hexagonal,
trigonal, tetragonal, and orthorhombic materials, but in monoclinic and triclinic
crystals such an expansion is common. Note, however, that negative volumetric
thermal expansion is observed in few materials, except at temperatures near
absolute zero.
Oblique-angle crystals such as feldspars, amphiboles, many pyroxenes, and
micas, due to highly anisotropic deformations, are responsible for the decom-
pression of the rocks which they make up, as well as for increases in rock
permeability by fluids and in some cases for the accumulation of ores under
metamorphic conditions. Higher thermal deformation anisotropy, for instance,
the anisotropy of calcic pyroxenes (Fig. 8a-b) relative to alkaline (Fig. 8c-f) is
suggestive of a higher capacity for thermal decompression of the rocks.
Similarly, highly anisotropic thermal expansion of calcite is responsible for
the thermal decompression of marbles; the anisotropy of feldspars, specially of
high albite, for the decompression of rocks bearing them; and a sudden change
in volume for 0.6% during rx-fJ transformation in quartz at the temperature of
573°C is responsible in part for the decompression of granites, etc.
Three rules describe continuous structural variations with changing pressure for
most oxide and silicate minerals.
Rule 1. Changes in lattice parameters and atomic coordinates may be
characterized by second rank tensors. Lattice volume change with pressure is
constrained to be negative, and crystal axes almost always compress. (In
80 Chapter 2. Crystal Structures of Minerals
Tm
= :x _ _
~, !~ /
/
[T0 3 ]4- [T0 3 ]3- [T0 3 ]2- [T0 3 r [T0 3 ]0 [T0 3 ]+ Isolated
/
/ triangles
/ [T0 3 ]
/
/
/
[T02.5r- [TO Z •5 ]2- [T02.5r [T02.5]O [T02.5] + [TO Z •5 ]2+ Double
/
/ triangles
/ [T Z 0 5 ]
/
/
/
[T0 2 ]2- [T0 2 r [TOz]O [TO z ]+ [TO z ]2+ [TO z ]3+ Rings
/
/ [TO z ],
/ chains
I [TO z ]",
I
I
I
[ TO 1.75 ]1.5- [TO 1.75 ]0.5-
I [TO 1.75 ]0.5+ [TO 1.75 ]1.5+ [TO 1.75 ]Z.5+ [TO 1.75 ]3.5+ Double
I chains
/ [T4 0 7 ]",
/
/
/
[T01.5]O
I
/
/
[TOx]Z is the formula of the radical on a one-central-atom basis; X is the extent of polymerization of
triangles or tetrahedra through common tops (X = O:T): Z is the radical charge available for bonds
out of the polyion; =0>, -+ are the basic tendencies of variations in strength of the compounds; ex is the
coefficient of thermal expansion; Tm is the melting point.
2.1.8 High-Temperature and High-Pressure Crystal Chemistry 81
Tetrahedral radicals
Isolated
tetrahedra
[T0 4 ]
/
/
/
[T0 3 . 5 ]0 Double
/ tetrahedra
/
/ [T 207]
/
/
[TO;]O Rings
/ [T0 2 ],
/
/ 'pyroxene'
I chains
I [T0 3 1o
I
I
[ TO 2.75 ]3.5- [TO 2.75 ]2.5- [TO 2.75 ]1.5- [TO 2.75 ]0.5-
I [TO 2.75 ]0.5+ [TO 2.75 ]1.5+ 'Amphibole'
I double
chains
/'
I [T 4 0 11 J"
/'
c d e J+ f
Nare ex,,, CY-" NaAL J +
LiALH 0<./1
a
n
po
p:
'1:l
<t
...,
t'"
otJ3
~ ;;;" C -k / c -Y . I c ,=-== C n
...,
~
E
~
...,
rl
'...,2"
(1)
en
o....,
Fig. 8a-f. The figures for the coefficients of thermal expansion of the ac plane in diopside (a), hedenbergite (b), spodumene (c),
ureyite (d), acmite (e), and jadeite (f). (After Filatov 1990). Each radius-vector represents the value of the coefficient of thermal a:::
~.
expansion in a given direction. Shaded areas correspond to negative thermal expansion ...,
~
2.1.8 High-Temperature and High-Pressure Crystal Chemistry 83
LaNb0 4 one axis becomes slightly longer with pressure, but this expansion is
coupled to greater compression of a pseudo-orthogonal cell axis).
Rule 2. Cation-oxygen bond distances, d, show an average compressibility,
if (Fig. 9):
P- = - d1ap
ad ~ 0.044 (d
S2ZcZa
3) -6 bar -1 ,
X 10 (2)
where Sand Z are defined as above. Thus a given type of cation coordination
polyhedra (e.g., Mg0 6 ) displays similar compression in different structures.
Rule 3. Total volume compression of Il}ost rock-forming minerals is the sum
of polyhedral compressibilities, plus interpolyhedral compression related to
changes in cation-oxygen-cation angles. Polyhedral distortion (as characterized
by changes in oxygen-cation-oxygen angles) plays a minor role in mineral
compression below 100 kbar.
The driving force behind structural changes with pressure is volume reduc-
tion. Discontinuous structural changes involving increase in cation coordina-
tion are of special importance in understanding the Earth's deep interior.
Transformations, such as those of MgSi0 3 from pyroxene to garnet to perov-
skite, result in large density increases because of increased atom packing effici-
ency. Surprisingly, however, cation-oxygen distance generally increases across
such transitions (cation-anion distance increases with coordination number), so
high-pressure phases are often more compressible than their low-pressure poly-
morphs.
.......'... 2 o
III
.c
~ o
o
ICC
The Analogy of the Variation of Volume with Temperature, Pressure, and Com-
position. Variation of coordination polyhedral volume can be predicted on the
basis of simple bond parameters: cation- anion separation (d), coordination
number of the cation (n), cation radius (r), cation and anion formal charges
(Zc and Za , respectively) and ionization (S2) :
IXv=-y
I (av)
aT (n)
~12.0 S2ZcZa xlO
-6 0
C
-1
, (3)
(4)
(5)
800
d e
Fig. lla-e. Examples of the similarity of crystal deformations of various nature. (Filatov
1990). Compound~ with the clinopyroxene structure. a Coordination polyhedron M2 control-
ling the deformation of the crystal lattice. b Thermal-induced deformations of diopside.
c Pressure-induced deformations of diopside. d Thermal-induced deformations of vanadate
Li2 V206' e Chemical deformations of Li2 V206 (substitution Li-Na in M2). Arrows indicate
an increase in bond lengths, LlI, in M2 multiplied by 10 for thermal-induced and pressure-
induced deformations and by 5 for chemical deformations. Figures of deformations are given
for the crystal lattice
86 Chapter 2. Crystal Structures of Minerals
IDEAL CASE
Structural Parameter
~creaSing
Pressure
a
Fig. 12a-c. To the problem of the "inverse" relationship between thermal- and pressure-
induced deformations of crystals. a Ideal case, after Hazen and Finger 1982. b Example of the
inverse relationship in low albite (Hazen and Prewitt 1977b). c Example of the absence of the
inverse relationship in rutile, after Hazen and Finger 1981
2.1.8 High-Temperature and High-Pressure Crystal Chemistry 87
~ c
111.0 ::J
Ul
Ql
Cl (')
"C ~
Ql
116.6 III
Qi ::J
-,
u co
CD
Ul
c 116.2
::J 0
7.18
7.16
7.14
b 7.12
\jlYo
D
1.02
/lncreaSing Temperature
1.01
t
Y...
cIa ,/
0.646
./"
0.647
Vo 1.00
/ . ~ 'ncreasing Pressure
, Cryogenic "'-
0.99
Temperatures '~
l(
0.98
c
50 '0
;(3 ~
:l
'>0 c:
c:0
Q)
0 0 a
40 .t:: 0 U
0 .!!!
~ "0
(J
.....
(/)
30
«;
.0
I~ 20
10
4km 40km 2900 km
10 100 1000 h. km
60 b c d
/(
40
20
2 3 4 6 8 10 12 1 12 24 36 48
p. g/cm 3 (f
Fig. 13a-d. Pressure equivalent of thermal deformation (rxIP), averaged on a mineral basis for
different zones of the Earth, as a function of depth to zone h (a), mean rock density under
atmospheric conditions p (b), P-wave velocities Vp within zone (c) and mean symmetry of
minerals in zone (J (d). (Filatov 1988). AI granite-metamorphic layer of continental crust;
A2 granulite-basite layer of crust; B upper mantle; C I transitional zone of mantle; C2 mantle at
depths of 600-800 km
In the deep-seated zones such a comparison can be made with the use of
approximate values a./p. With depth, expansion is slowed down as a conse-
quence of a decrease in the temperature gradient with depth, the proportion of
compression increases.
Beneath the stable continental regions, the top of the upper mantle separates
a near-surface shell of intense cooling of the planet (we may assume that the
mean value of the temperature gradient with depth is approximately 20 DCjkm
near the surface and 10 DC/km at a depth of 40 km) from the quite thermostable
upper mantle, in which the temperature gradient may be taken as constant and
equal to 1.3 DC/km. The pressure gradient is also constant to a first approxima-
tion and may be estimated at 1/3 kbar/km. As a result, during the subsidence of
rocks in the upper mantle, a temperature increase of 1 DC appears to correspond
2.1.8 High-Temperature and High-Pressure Crystal Chemistry 89
to a pressure increment of 1/4 kbar. This is 20 times greater than near the
surface, and an order of magnitude greater than at the Moho discontinuity.
Thus, the rates of pressure and temperature change with depth vary, and
their ratio may be estimated at 12 barre near the surface, 25 barre at a depth
of 40 km, and 250 barre in the upper mantle. The ratio of velocities equal to the
deformation equivalent for rocks of the upper mantle, a/f3 = 40-50 barre, is
reached between the Moho discontinuity and the stable portion of the upper
mantle, that is, in the top the upper mantle. This means that compensation for
thermal expansion by the lithostatic compression of the rocks is achieved at the
top of the upper mantle. During subsidence to greater depths, the rocks of the
upper mantle are subjected to a strongly rising pressure and are therefore
compressed. The effect of the slowly rising temperature may be neglected in
making approximate estimates.
Experimental data (e.g. f3 = 0.8 '10- 6 bar- i for diopside in the 0-53 kbar
range) have enabled us to estimate the average value of the coefficient of
lithostatic compression in the depth interval of 40 km (approximate pressure
10 kbar) to 320 km (110 kbar) for minerals of the upper mantle, at f3 = 0.5-0.7
(10- 6) bar-i. From this it follows that under conditions of relative constancy of
chemical and phase compositions, the density of the pyroxenes, olivines, and
garnets that make up the upper mantle increases monotonically during subsid-
ence from 40 to 320 km by 5-7%.
In the transitional zone (320-400 km), compressibility as a result of PT
deformations turns out to be a minor factor compared to the effect of phase
transitions (apparently, pyroxene-garnet and 0Iivine-spinel-f3-Mg 2 Si0 4 (Ring-
wood 1975)), each of which is accompanied by a density increase of approxim-
ately 10%, and creates an important seismic discontinuity.
In the lower mantle, the pressure gradient increases to 1/2 kbar/km, and the
temperature gradient apparently does not exceed 1 °e, and so the change in
parameters with depth exceeds 1/2 kbar per °e (Ringwood 1975). This means
that compressibility in the lower mantle predominates over thermal expansion;
but compression as a result of phase transformations predominates.
Thus, volume and density of rocks change during vertical displacements in
the Earth, primarily as a result of phase transformations and to a lesser degree
owing to PT-induced deformation. During subsidence from the Earth's surface,
rocks subjected to the contrary influences of pressure and temperature expand
as a result of PT-induced deformation. With depth, expansion is slowed down as
a consequence of a decrease in the temperature gradient with depth and the
proportion of compression increases until compensation is reached at the top of
upper mantle. At greater depths, compression predominates. These volume
effects of deformation cause a monotonic change in the rock density with depth,
and although minor in magnitude compared to the effects ofthe numerous deep-
seated phase transitions, they make a substantial contribution to the change in
rock density in the absence of significant volume effects of phase transitions, for
instance in the stable inner portion of the upper mantle.
90 Chapter 2. Crystal Structures of Minerals
References
tttJj tttjj~
~E
Spinodal Decomposition
A long period modulation arises at the first stages of atom clustering which is
followed by phase unmixing with a spinodal mechanism. Indeed, the sinusoidal
compositional changes during ex solution spread as a rule along one crystallo-
graphic direction perpendicular to a constant composition plane which can be
considered as a one-dimensional substitutional longitudinal modulation. Elec-
tron diffraction patterns from such a crystal volume have satellites.
Thermodynamics Aspects
a result of the introduction of the displacement wave with energies near the
Fermi level. A universal phenomenological second-order phase transformation
theory explains the appearance of incommensurate and modulated structures.
Its initiation has been caused by the reduction of the free energy of a crystal close
to the transition temperature using an order parameter and group theoretical
approach.
Time-dependent order parameter theory allows the description by one
equation of both spinodal decomposition and order-disorder transition with
modulation.
A modulation state is as a rule transitional and nonequilibrium, and is an
object of nonequilibrium thermodynamics.
Methods of Study
found at 90 K. Within the temperature range 123- 90 K there are two stripe
systems. These stripes can be interpreted as different phases.
Examples of great theoretical and applied interest have been the high-
temperature superconductor ceramics. All of them are layer structures with
interchanging layers of two types - perovscite- and rock-salt-like ones. For the
Bi- Sr- Ca- Cu- O system the crystal structure was investigated by both high-
resolution electron microscopy and diffraction (X-ray and synchrotron).
In Fig. 15 electron images of the structure of 2212 along two different
directions are shown. One can see modulation along axis Y - displacive and
substitution. Diffraction data have permitted the quantitative evaluation of
incommensurate modulation for every sort of atom. Four cations and one anion
have displacements with the different amplitudes and the same wavelength.
Hybrid mixed-layer structures are examples of incommensurate or com-
mensurately modulated ones (see Chap. 2.2.2).
Conclusion
References
Buseck PR, Cowley JM (1983) Modulated and intergrowth structures in minerals and electron
microscope methods for their study. Am Mineral 68: 18-41
Carpenter MA, Salje E (1983) Time-dependent Landau theory for order-disorder processes in
minerals. Mineral Mag 53: 483-504
Cowley JM, Cohen ID, Salomon MV (eds.) (1979) Modulated structures. Proc Int Conf Am
Inst of Physics, New York, p 430
Dolino J, Becheimer JP, Berge CM, Zeyen E (1984) Incommensurate phase of quartz: I Elastic
neutron scattering. J Phys 45: 361-371
Makovicky E, Hyde BG (1981) Non-commensurate (misfit) layer structures. Struct Bond 46:
101-170
Morimoto N (1978) Incommensurate superstructures in transformation of minerals. Recent
Prog Nat Sci Jpn 3: 183-203
Organova NI (1989) Crystallochemistry of incommensurate and modulated mixed layer
minerals. Nauka, Moscow, pp 144 (in Russian)
Seifert F, Zank MC, Simons B, Sahmahl W (1987) A commensurate-incommensurate phase
transition in iron-bearing akermanites. Phys Chern Mineral 14: 26-35
Yamamoto A (1986) Refinement of polytype, modulated and quasi-crystal structures - higher
dimensional approach. Int Conf Poly type Modul Str Abstr, Wroc1aw, pp 16-17
R. ALLMANN
Hybrid layer structures are composed of two kinds of differently charged layers,
which because of charge compensation exactly alternate in stacking direction.
The single layer ions may be silicates, hydroxides, sulfides, or chlorides with a
hexagonal or tetragonal (sub)structure. One of the two layers may even be
composed of isolated ions and water molecules only. Here we will confine
ourselves mainly to such compounds with hexagonal brucite-like layer cations
[Me(II)l-x Me(III)iOHhY+ (the main layers).
The most frequently occurring but negatively charged layers occur in
the well-known phyllosilicates and clay minerals, [A12 -xMgiSi4-yAlyOlo/
(OHh]<x+ y)- for instance, but these compounds are not called hybrid layer
structures, even though they obey the above definition.
In nature these two kinds of layer ions are counterparts in their ability to
absorb charged radicals at their surfaces and within the interlayers: the phyllo-
silicate layers bind cations (like K +), whereas the brucite-like layers bind anions
(e.g., CO~-). This capacity may even have triggered the polymerization of amino
96 Chapter 2. Crystal Structures of Minerals
and nucleic acids during the prebiotic evolution of life. As both layer types have
similar dimensions and opposite charges, they can even be combined to form
minerals of the chlorite group.
The most simple hybrid layer structures belong to the hydrotalcite (or
pyroaurite/sjogrenite) group. Hydrotalcite itself has the approximate formula
[Mg 6AI 2(OH)16]2+. [C0 3 ·4H 20]2-, but the amount x of the Al contents may
at least vary from 0.2-0.33. As Mg and Al are distributed statistically within the
octahedral sites of the main layer (avoiding direct AI-AI contact) and as the
interlayer is completely disordered (i.e., liquid-like), the lattice constants reflect
only the size of the octahedral site (ao '" 3.1 A) and the thickness of the double
layer package (c' '" 7.7 = 4.8 + 2.9 A) with c = 3c' because of the rhombohedral
stacking sequence ... BC. .. CA ... AB. .. BC ... of the OH-groups. In nature the
hexagonal sequence ... BC. .. CB. .. BC. .. is also found (mineral manasseite), but in
all laboratory syntheses until now only the rhombohedral. Another reason for
reflection broadening is turbostratic disorder, i.e. individual layer packets are
twisted against each other. Stacking was found with more or less disorder, i.e.,
the reflections 012, 015, and 018 are mostly broader than reflections independent
of the stacking mode (e.g., 003, 006, 110, and 113). In extreme cases, the stacking
sensitive reflections vanish completely.
The a o value varies with the AI-contents (for x = 0.25 ao = 3.07 A, for
x = 0.33 ao = 3.05 A). Mostly, x = 0.33 is the upper limit of the AI-contents, but
when using a pressure of 1 kbar during synthesis, x could be increased to at least
0.44. However because Al octahedra must then be directly connected, the
repulsion AI-AI will counteract the shrinking of the Me(OH)6 octahedra,
i.e., above x = 0.33 a o is about constant at 3.04 A.
As an OH-group connected to 1 Me(III) and 2 Me(II) has to balance a
charge of 1·3/6 + 2·2/6 = 7/6, the OH bond strength must be reduced from 1 to
5/6, i.e., these OH-groups must be involved as donors in hydrogen bonds
between main and interlayer with OH .... O '" 2.9 A. This is reflected in a
decrease ofthe wave number of v(OH) to about 3450 cm -1 and in a shrinking of
c' ( = 7.71 for x = 0.25, 7.60 for x = 0.33, and about 7.40 for x = 0.44). The
thickness c' can also be decreased by heating, as the interlayer water is zeolitic
and can be removed by heating up to 180°C without destroying the structure.
The [Mg 1- xAl x(OHhY+ layer cation is remarkably stable in chemical
reactions. The AI-contents prevent solution in acids for PH > 4.5 and even for
smaller PH - values in a first step the CO~ - of the interlayer will be replaced by
the acid anion (e.g., CI-) before the solution of the main layer starts. This is the
reason why hydrotalcite is a much better antacid than magnesia (or brucite)
alone. Nevertheless, the carbonate forms are the most stable (and less reactive)
compounds of the hydrotalcite family.
Even oxidation and reduction of, for instance, Fe(II,III) in the main layer
may occur without destroying the layer. Thus, an iron brucite (Mg,Fe)(OH)2
with x = 0.19 Fe(II) changed in open air within 1 year to coalingite, in which
two slightly charged brucite layers alternate with one interlayer [C0 3 • nH 20]
(c' = 12.6 A). The final product of this spontaneous oxidation and CO 2 uptake
will be pyroaurite, the iron analogon of hydrotalcite.
2.2.2 Hybrid Layer Structures, Commensurate and Incommensurate 97
,
.1
c' 0 0
o 5
• [o,l-fg
• AUe
. ' .
o--d ~ );). o I1g
o H
Fig. 16. Structure of wermlandite. The OH(I) groups are bound to 3 Mg and form no
hydrogen bonds, whereas OH(2) and OH(3) are bound to 2 Mg + I(AI,Fe) and form hydrogen
bonds of OH ... 0 = 2.92 and 2.91 A respectively
In the above compounds the interlayers consist of individual ions and water
molecules and may be disordered, more liquid like as in hydrotalcite, or ordered
as in wermlandite. The interlayers, however, may be two-dimensional layer
cations by themselves, as the mica layer in chlorite. Both layers must have
numerically the same, but opposite charges per unit area; but it is not necessary
that they fit together geometrically. If they do not, incommensurate hybrid layer
structures are formed, Their diffraction patterns look like a superposition oftwo
independent patterns with only the 001 reflections in common, to which both
substructures contribute coherently,
As a commensurate layer anion the mica layer of chlorites was already
mentioned. Another kind of silicate layer was found in vertumnite,
~ [Ca 2 AI(OH)6J +. [Si30sH3' 2H 2 0 r (c' = 12.56 A.), with Si 4 0 s double
layers as in HT-Celsian, in which about 25 to 33% of the tetrahedral sites
remain empty (Si + 4 -> 3H +). Similar interlayers were also found with Mg,AI-
main layers (c' ~ 11.94 A.).
More interesting are the incommensurate hybrid layer structures with
chloride or sulfide interlayers, such as koeneite, valleriite, and tochilinite.
Koenenite occurs in salt deposits and has the approximate formula
[Mg 7 AI 4 (OHbl [Ca 2 Na 4 Cl 12 J. The lattice constants are a OH = 3,05, aCt
= 4,07, c' = 10.88 A with C OH = 3c' and C CL = c', The angle between a OH and aCt
is 28.3° (Fig. 17). No superstructure reflections common to both lattices could be
2.2.2 Hybrid Layer Structures, Commensurate and Incommensurate 99
#
{13,5.0j {13,5,O}
.{too],.
Fig. 17. Possible but not proven supercell for koenenite. Left for chloride partial structure;
right for hydroxide partial structure
detected. The ratio OH:Ci is fixed by aEl:a~)H = 1.78 and may vary only slightly
with changing composition of the chloride layer: some Ca can be replaced by
Mg and 2Na + by Ca 2 + + D, yielding an end member [Ca 4D 2CI12]. Such Na-free
koenenites could be synthesized at 200-400°C. The chloride layer is very
sensitive to humidity and mechanical stress. Even short grinding yields separate
NaCI, and by humidity the chloride layer will be destroyed, leaving only 4 CI in
the interlayer, which are needed for charge compensation of the stable hydrox-
ide layer. Only storage in concentrated MgCl 2 or CaCl 2 solution will prevent
koenenite from decomposition.
Valleriite is a graphite-like bronze-colored sulfide-hydroxide mineral,
~ [Mg2AI(OH)6l(Fe,Cu)4S4J, with a OH = 3.07, as = 3.79, c' = 11.37 A. Here
aOH and as have the same direction. The ratio OH: S equals a~ : a~)H = 1.52 and
may vary from 1.47 to 1.71. Within the sulfide layers (Fe,Cu) occupies all
possible tetrahedral sites.
Even more exciting is the structure of tochilinite, ~ [Mg 3 . sFe1.5(OH)lOl
[FeS.4Do.6S6J, which was found as a main constituent of corbonaceous chondri-
tes. Here the pseudo-trigonal hydroxide layers are interleaved by pseudo-
tetragonal mackinawite-like sulfide layers with c' = 10.68, a'OH = 3.11 and a's
= 3.75 A. For tochilinite I a common supercell was reported with a = 5.37
= J3'a OH = J2'a s , b = 15.65 = 5'a OH = 3·J2·as , c = 10.72 A, a = y = 90°,
fJ = 95°, space group Cl. But for tochilinite II (with about 4.8 instead of 5.4 Fe at
the six tetrahedral sites of the sulfide layer), both layers are incommensurate
(OH: S in both cases about 1.67, but values from 1.61 to 1.75 were found also for
other tochilinites) (Fig. 18).
This alternation of hexagonal and tetragonal layers was also found for
several pure sulfide structures. Both layer types can be deduced from the PbS
structure (a = 5.94 A), cutting this parallel 111 to obtain a hexagonal layer H
with formula Me n- 1 Sn (thickness about n' 3.2 A) and parallel 100 to obtain a
tetragonal one (T, formula MeS, thickness per atom about 2.9 A). Both layers
have the direction [O-11J (d(110) = 4.20 A) in common, but the perpendicular
directions [ - 211J and [OllJ resp. have an incommensurate ratio of 1 J3:
100 Chapter 2. Crystal Structures of Minerals
o
10.8 A 6 (Fe, NI, Cu) 5
(A)
o ox+ I
8000 2
Fig. 19. Ideal scheme of H- and T-Iayers in cannizzarite. Only one T-Iayer is shown above.
I metal atoms; 2 sulfur atoms (different symbols correspond to different heights)
References
Among the many diverse structural arrangements that occur in minerals, there is
a large group of structures containing tunnels or channels. These tunnels are in
some cases vacant and in other cases occupied by molecular ionic species, large
cations, or water molecules. The tunnel-structure minerals include, for example,
silicates with broad channels that are rectangular in cross section (sepiolite and
palygorskite) and silicates with channels with more equidimensional cross
sections (zeolites). The oxides of AI, Fe, Mn, Ti and some other elements
encompass a wide variety of tunnel structures. Study of some of these oxides by
high-resolution transmission electron microscopy (HRTEM) has revealed a
variety of new structural types and has shown the occurrence of coherent
intergrowths between related structures.
Much attention has been given to the study of the tunnel-structure oxides,
not only as a result of their abundance in nature but also because of their present
and potential practical applications. Among the more significant applications
are their use as the cathodic material in dry-cell batteries, and their potential
uses as (1) ionic conductors, (2) as material for disposal ofradioactive waste, and
(3) as sources of transition metals in manganese nodules. For many of these
applications, detailed knowledge of the structures of the materials is important.
The basic structural unit of the tunnel oxides is an oxygen octahedron with a
cation in the center (the octahedral site). An octahedron can be linked to another
octahedron by sharing a common edge formed by two adjacent oxygens. Many
octahedra can be linked together in this manner to form a larger unit termed a
chain of octahedra. A chain has a width of one octahedron and a length that,
unless interrupted by defects, is limited only by the dimensions of the crystal in
which it occurs. These chains can, in turn, be linked to one another to form
larger units by sharing edges. These multichain units will here be termed
"ribbons".
lO2 Chapter 2. Crystal Structures of Minerals
a b
c d
Cl[JI
e f
9 h
Fig. 20a-h. Examples of octahedral-tunnel structures: a Rutile. b Ramsdellite. c Hollandite.
d Romanechite and e-h Various todorokite structures
(Fig. 20h) ribbon forms the second dimension of the tunnel. The tunnels can
contain Na, Ca, and K cations and H 20 molecules.
Coherent intergrowth between related structures is possible if a common
dimension or structural unit is present. Use of HRTEM has provided confirma-
tion of the suspected coherent intergrowth of pyrolusite and ramsdellite type
structures to form an intergrowth material termed nsutite (y-Mn02)' New
I ......1;;;.:0
•
3223232222322 2242222224 2322
533
1 1
.1
References
Burns RG, Burns VM, Stockman HW (1983) A review of the todorokite-buserite problem:
implications to the mineralogy of marine manganese nodules. Am Mineral 68: 972-980
Chukhrov FV, Gorshkov AI, Drits VA (1989) Hypergene manganese oxides. Moscow, Nayka
Liebau FL (1985) Structural chemistry of silicates. Berlin, Springer
Post JE, Von Dreele RB, Buseck PR (1982) Symmetry and cation displacements in hollandites:
structure refinements of hollandite, crystomelane and pride rite. Acta Crystallographica B38:
1056-1065
Tamada 0, Yamamoto N (1986) The crystal structure of a new manganese dioxide
(Rb o.27 Mn0 2 ) with a giant tunnel. Mineral J 13: no 3, 130-140
Turner S, Buseck PR (1979) Manganese oxide tunnel structures and their intergrowths.
Science 203: 456-458
Turner S, Buseck PR (1981) Todorokites: a new family of naturally occurring manganese
oxides. Science 212: 1024-1027
Turner S, Post JE (1988) Refinement of the substructure and superstructure of romanechite.
Am Mineral 73: 1155-1161
106 Chapter 2. Crystal Structures of Minerals
This condensation can also occur on two {11 O} planes related by a tetrad. This
gives rise to cyclic Li 4 0 12 tetramers in Li2 W0 4 -II. However, such an extension
is unjustified. The extended "polytypism" would cover a number of other terms
already introduced for different kinds of modular structures (MS), making them
redundant. The different kinds of MS are distinguished from one another by the
distribution of and stacking rules for the building modules (BM). "Topological
similarity" of BMs is defined by topological features of coordination polyhedra
and their recurring combinations, while size and shape variations may depend
on compositional differences. The composition may be fairly constant as in ZnS-
and kaolinite modifications, or variable as in mica- and serpentine modifications
o
00
Table 17
~----~----~I I I I
Layers Rods Blocks Modules Layers Rods Blocks
-----~
I
(j
Modules: fragments of one Different: One: ::r
I>'
or different structures Polysomes Monosomes "Sa
<>
...,
I
!'"'
Module proportions Variable: Constant: (j
...,
Mixed-layer structures ("Polytypes II") '<
en
("Polytypes III") a
I ...,~
I I (")
=
Module sequence order Periodic Aperiodic
2
I I --- ------ I I ~
en
o
-,
Succession of adjacent Ambiguous Unambiguous:
modules ~
I Hyt dS ~.
[
en
N
Ambiguous Unambiguous Stacking of adjacent Unambiguous: Ambiguous Unambiguous: Ambiguous tv
inhomogeneous :.,.
homogeneo~:nces
I -
mod"'" module sequences module sequ~ '"0
o
h -<
-<
"0
Equivalent: Nonequivalent Crystallochemical equivalence Equivalent: Nonequivalent ~.
Polytypes of module stacking variants Polytypes
5'
,- I -, I . - I I ~
Nonequivalent Equivalent: Symmetry equivalence of pairs Equivalent: Nonequivalent 5'
...,'"
I OD-structurr of adjacent modules OD-structures ~ ~
en
I ~---'I
I
I I
Periodic Aperiodic Periodic Aperiodic Stacking variants Periodic Aperiodic Periodic Aperiodic
succession
I I I I I I I ,----1 I I I I
Homogen.: Inhomogen.: Homogen.: Inhomogen. Sequence of Homogen.: Inhomogen. Homogen.: Inhomogen.:
simple complex MDO OD- stacking MDO OD- siinple complex
polytypes polytypes structures variants structures polytypes poly types
@
110 Chapter 2. Crystal Structures of Minerals
Fig. 21. Two molybdenite polytype structures (both 2H) composed of prismatic building
layers divided by octahedral interlayers
Polytype Nomenclature
in axial setting, or stacking variation or disorder in more than one direction can
be shown by using a more extended form of the symbol, as in xonotlite-Ma d 2bc.
The "ABC" notation for close packings is a simple example of descriptive
terminology. It is in fact somewhat redundant for close-packed structures and
their simple derivates (e.g., SiC, ZnS) since these structures have only two
distinguishable stacking vectors. Hiigg represented these as " + " and" - ", so
that the 2H structure is represented [+ - J and the 3C structure, [+ + + J
or [- - -]. Zhdanov (1945) condensed this notation by replacing strings of
one sign with the length of the string. 2H and 3C are then [1J2 and [00 J
respectively. A complementary notation developed independently by Ewald and
Hermann, Pauling and Belov uses hand k (or c) to denote layers which lie
between different and similar Hiigg signs (similar or different letters A, B, C)
respectively, indicating the local analogy to hexagonal and cubic close packings.
The micas, with six possible stacking vectors in each layer, require more
complex symbology. Zvyagin indicates absolute orientation of successive layers
enumerated from 1 to 6 (Fig. 22). Ross et al. use 0, ± 1, ± 2, 3 to indicate the
relative rotation between layers. The 2M! polytype of Smith and Yoder (1956) is
then (2 2), whereas 2M2 becomes (1 1). Thompson (1981) replaces these integers
by symbols emphasizing the local symmetry operators.
The 1: 1 phyllosilicates, the 2: 1 talc/pyrophyllite and the (2: 1 + 0: 1)-
chlorite minerals, are structurally more complex than the micas in that the
Fig. 22a, b. Scheme of two adjacent sheets (T- and 0-) in the normal projection on the plane,
ab, displaying six choices of axes a i which being parallel to a common axis, a, define possible
azimuthal orientations of phyllosilicate layers
2.2.4 Polytypism in Minerals 113
30
2T
1:[ 20,toH
2 M J+ (3M 2 +)
30H
0:1_
Fig. 23. Scheme of phyllosilicate layers 1: 1,2: 1 and of the combination 2: 1 + 0: 1
small admixtures of different polytypes present in one and the same or different
particles. This is indispensable in studying of such complicated mineral systems
as serpentines (polytypes with cylindrical lattices, superperiods ranging between
20 and 100 A).
Mardix (1986) stresses the utility of additional techniques such as birefrin-
gence measurement to identify specific stacking sequences. Many of the shorter-
period polytypes of Sb s0 7 I could be identified from their optical extinction
angle and ferroic transition temperatures.
Since intergrowth and stacking disorder are common in poly typic systems,
the combination of diffraction and direct imaging facilities provided by high-
resolution transmission electron microscopy (HRTEM) has proved invaluable
for precise identification of different stackings. Two-dimensional images may be
interpreted directly, or compared with calculated images. Even the contrast
variations in one-dimensional images may be correlated with ED and X-ray
intensities or simulations to characterize structures successfully.
HRTEM samples a very small specimen volume, and hence may not provide
representative data. However, it is a particularly good technique for the study of
intergrowths of different polytypes or polysomes, and isolated structure defects.
Many studies have discovered fine lamellae of new ordered structures which are
not known as macroscopic phases, e.g., Ca-Ce f1uocarbonates, biopyriboles, the
humite-olivine-leucophoenicite series. Veblen and Buseck devised a simple
statistical test to calculate the probability of such sequences occurring through
random stacking. In general, the new lamellar phases have low probabilities of
occurring through chance alone; hence their structures are probably determined
by local energetic considerations. It should be noted, however, that local
stacking variations could be considered as belonging to a definite poly type if
there were sufficient repeats in the corresponding stacking for distinctive
polytype reflections to appear. Combination of HREM with SAED thus permits
obtaining complete information on the distribution of polytypes and their
defects.
• 00 • 00 • 00 •
• • •
•• ••
0 0 0 0 0 0 0 0
0 0 • 0 BoO • • 0 0
00 00
O . 0 O· 0
0 · 0 0 0·0
00 • 00
• •
••
0 0 0
•
00
0 0 •
00
O· 0 0 0-0
0-0
• 00 •
•
•• •
•
0 0 0 0 0
,.
• 0 •
-
0 0 C 0 0
00 • 00 • 00
Fig. 27. The la yer cells and supercell in the superposition of astrophyllite T-Ia yers which differ
in azimuthal orientations
118 Chapter 2. Crystal Structures of Minerals
which all modules are crystallographically related, are very frequent. This is
understandable since less regular structures can be described as interlayerings of
different homogeneous structures, and will tend to be intermediate in energy
between the extreme stacking configurations represented by the homogeneous
phases.
The pressure, temperature, and compositional controls on the relative
stability of some silicate polytypes are fairly well known (zoisite, sapphirine, Mg-
rich pyroxenes). It is clear that the simple phases in these systems have stability
fields that are well-defined in P-T space, but are very sensitive to composition.
Although temperature plays some role in determining structure in the
classical polytypes, it has often been assumed that the known structures do not
in general correspond to equilibrium phases in one-component systems. The
only reversed equilibrium observed appears to be the 2H-12R transition in PbI 2 .
There are factors which appear to determine polytypic diversity in MX and
MX 2 compounds. Trace impurities, nonstoichiometry, and the concentration of
structure defects all have a significant effect on poly type stability, which is
presumably thermodynamic in nature. Thompson (1981) points out that the
incidence of stacking disorder in phyllosilicates should decrease as the crystal
size increases. For small grains, the configurational entropy associated with
stacking disorder provides a free energy which may compensate for the stacking
fault energy.
Kinetic factors such as crystal growth rate may also be important. Fast
crystallization of SiC favors metastable formation of the high-temperature 3C
structure, which has been observed to transform to other structures sub-
sequently. A specific growth mechanism is invoked to explain polytypic varia-
tion in the screw dislocation theory of Frank (1951). Most of the long-period
structures observed in polytypic systems can be derived by insertion of periodic
stacking faults into a simpler structure. According to Frank's theory, the
complex structure is, in fact, generated by propagation of a stacking fault by
growth around a giant screw dislocation. Subsequent developments of this
model hypothesise that stacking fault propagation relieves thermal stresses
during cooling (in vapor-grown ZnS whiskers), and that the faults initiate in
highly disordered nuclei before being propagated during a subsequent phase of
more orderely growth as in micas. Rai et al. (1986) show electron micrographs of
a spectacular long-period silicon carbide sample with a 1734R structure (c/3
= 1455 A). The repeat unit can be subdivided into four subunits of width 137,
131, 137, and 173 layers respectively. This correlates with the observation offour
interacting growth spirals on the surface of the crystal, but other studies on
various systems have failed to find quantitative correlation between growth
spiral step heights and the observed structure. In any case, the screw dislocation
model does not apply when layer-by-Iayer crystal growth occurs, and it cannot
account for the irregularly placed stacking defects so common in polytypic
systems.
Recently, models have been proposed which account for long-period struc-
tures as equilibrium phases. The axial Ising models map a suitable structural
120 Chapter 2. Crystal Structures of Minerals
parameter for each module onto a pseudo spin variable, and then generate phase
diagrams for a small number of different interactions between neighboring spins.
At low temperature, only a few simple phases are stable, but entropic contribu-
tions associated with spin flips stabilize longer-period phases as T increases. A
well-defined suite of polytypes emerges, in which the more complex structures
have progressively smaller stability fields. Distinctive poly type suites occur,
depending on which short-range interactions are most significant.
Pseudo potential calculations on systems such as SiC and ZnS have provided
quantitative estimates of the relevant interaction energies. The additional
entropy associated with long-period structures arises from a combination of
electronic and elastic interactions associated with small static relaxations in
interlayer spacing (0.0685% difference between the 2H and 12R polytypes
of PbI 2 ). Lattice vibrations also effect variation in the interlayer spacing
dynamically which is capable of stabilizing long-period structures provide
experimental evidence that Raman-active lattice modes are softer in the high-
temperature 12R phase of PbI 2 than in the 2H form.
Salje et al. (1987) give an alternative phenomenological treatment of PbI 2
polytypism in terms of Landau theory. The "ferro" (2H) and "antiferro" (12R)
phases are derived from a hypothetical "para" phase, which may be equated
with the disordered superposition structure of OD theory. Longer-period
phases can be stabilized by Umklapp terms in the Landau potential.
Applications of Polytypism
References
Smith JV, Yoder HS Jr (1956) Experimental and theoretical studies of the mica polymorphs.
Mineral Mag 31: 209-235
Tairov YuM, Tsvetkov VF (1984) Growth of polytypic crystals. In: Freyhardt HC (ed)
Crystals: growth, properties, and applications 10. Growth and defect structures. Springer,
Berlin Heidelberg New York pp 1-35
Thompson JB Jr (1978) Biopyriboles and polysomatic series. Am Mineral 63: 239-249
Thompson JB Jr (1981) Polytypism in complex crystals: some contrasts between mica and
classical polytypes. In: O'Keeffe M, Navrotsky A (eds) Structure and bonding in crystals II.
Academic Press, New York pp 167-196
Trigunayat GC (1989) Present status of polytypism in MX 2 compounds. Phase Transit 16/17:
509-527
van Landuyt J, Amelinckx S (1975) Multiple beam direct lattice imaging of mixed-layer
compounds of the bastnaesite-synchisite series. Am Mineral 60: 351-358
van Tendeloo G, Verwerft M, Amelinckx S (1989) Long period mixed layer polytypes in TJ-Ba-
Ca-Cu-O superconductors. Physica CI62/4: 947-948
Veblen DR, Buseck PR (1979) Chain-width order and disorder in the biopyriboles. Am
Mineral 64: 687-700
Verma AR, Krishna P (1966) Polymorphism and polytypism in crystals. Wiley and Sons,
New York
Yamanaka T, Mori H (1981) The structure and polytypism of IX-CaSi0 3 (pseudowollastonite).
Acta Cryst B37: 1010-1017
Yeomans JM, Price GO (1986) An equilibrium theory ofpolytypism. Bull Mineral 109: 1-13
Zhdanov GS (1945) The numerical symbol of close packing of spheres and its application to
the theory of close packing. Ookl Akad Nauk SSSR 48: 39-42
Zvyagin BB (1967) Electron diffraction analysis of clay minerals. Plenum Press, New York
Zvyagin BB (1988) Polytypism of crystal structures. Comput Math Appl 16: 569-591
9.78
G
Fig. 28. Comparison between experimental (circles) and calculated (full line) XRD curves for
an interstratified leucophyllite-montmorillonite (I-m) solvated by ethylene glycol. The para-
meters of the model used for the calculations were WI: Wm = 0.89: 0.11; P mm = P mlm = O. P mUm
= 0.15; R = 3 d 1 = 9.88 A, d m = 16.6 A,s,,; N ,,; 10
2.2.5 Mixed-Layer Minerals 127
003 reflection is broad and the 005 is sharp, then the cause can only be some sort
of irregular interstratification.
In some MLM structures, the thicknesses of alternating layers are related as
d 1 = nd 2 (n is an integer), and then the diffraction pattern is not irrational and
the line-broadening pattern will cycle with respect to diffraction angle in some
fashion such as broad-sharp-broad-sharp for the 001, 002, 003, and 004 reflec-
tions in, for example, diffraction patterns from mixed-layered chlorite that
contains some serpentine layers. But for all such structures, a detailed analysis of
basal reflection intensities and line breadths, or the application of high-resolu-
tion electron microscopy is required.
Interpretation ofXRD patterns of all types of MLM requires development of
special techniques. Identification of incommensurable MLM is most effectively
accomplished with selected-area electron diffraction.
Methods for the Study of MLM Structures and Their Crystal Chemistry
A wide range of methods are used for studying MLM structures and crystal
chemistry that include X-ray powder diffraction, selected-area electron diffrac-
tion, microanalytical techniques for chemical composition, NMR, and IR
spectroscopy.
2.2.5 Mixed-Layer Minerals 129
The XRD powder method is the main method for determining structural
characteristics of mixed-layer minerals. At present, there are two approaches to
the interpretation of experimental diffraction patterns. One is based on direct
methods of Fourier transformation which provide structural parameters for the
sample (values of Wi' W ik , Wikl' etc.) using the measured values of d-spacings and
basal-reflection intensities. These methods, however, have certain serious theor-
etical and practical limitations and are rarely used.
The most widely used approach is based on the simulation of diffraction
effects from mixed-layer structural models and their comparison with experi-
mental diffraction patterns. The basic advantage pf indirect methods is that they
may be used to predict diffraction effects from all theoretically possible struc-
tural models. This method makes it possible to analyze the effect of various
chemical and structural parameters for a MLM. The calculations can deal with
proportions of the different layer types, their chemical compositions, the
thicknesses of alternating layers, their alternation patterns, microcrystal thick-
ness, and the distribution of thicknesses. The effects of all of these on the
positions, intensities and profiles of basal reflections can be determined. A
systematic and purposeful analysis of the data obtained using the approach
described has led to a set of diffraction criteria widely used for the identification
and quantification of the most abundant MLM.
Effective application of indirect methods requires that the initial structural
models be as close to the actual structures as possible. This requirement may be
a rather difficult task to cope with in the general case, since even if the choice of
the model is correct (i.e., with very good values of S, Wi' P ik ), its refinement will
require a great number of various parameters (composition, z-coordinates of
atoms, layer thicknesses, microcrystallite dimensions, instrumental factors)
many of which can be determined only by the trial-and-error method.
The most widely and successfully used recently developed procedures for
MLM studies are high-resolution transmission electron microscopy (HRTEM)
combined with energy-dispersive X-ray analysis (EDX). Their combination
provides information on the structure and composition of the objects from tens
to hundreds of Angstrom units in diameter. The HRTEM and EDX reveal data
on the specific distribution of sheets and layers with a resolution of structural
components of the order of 3 A. In particular, this technique was used to
visualize particles with alternating 14 A chlorites layers and 7 A berthierine
layers. Such mixed-layer structures are difficult to identify using XRD, and can
be dealt with only by very careful studies of line-broadening of basal reflections.
HRTEM and EDX can potentially provide an altogether new level of
knowledge of MLM structures which can be vital in revealing the mechanisms
of formation and transformation of MLM.
Structural parameters for which the best possible agreement is achieved between
the X-ray diffraction intensity distributions of the simulated and experimental
130 Chapter 2. Crystal Structures of Minerals
XRD curves can be considered as those that adequately describe the MLM
structure (Fig. 28). Reliability of structural determinations substantially in-
creases if, with the same probability parameters, the same agreement between
observed and calculated patterns is obtained for two different states of a given
sample (e.g., saturated with ethylene glycol and glycerol) that produce different
positions and intensities of reflections (Fig. 29). This method is very time-
consuming, so researchers often confine themselves to semi-quantitative fitting
of experimental and simulated XRD curves (Fig. 30).
lB.~
a
3.56 3.56
a c
1.80
7.80
7.60 1.65
3.48 Fig. 30a, b. Comparison between ex-
b d
3.48 perimental (a) and calculated (b)
XRD patterns for an interstratified
kaolinite-montmorillonite (k-m) sol-
3.34 vated by ethylene glycol (a) and after
dehydration at 350°C (b). The para-
meters of the model used for calcu-
lations were W k : Wm = 0.75: 0.25; R
=0, d k =7.15A, dl"=17.78A
(curve c) and d m = 9.6 A (curve d),
10:::; N:::; 20
2.2.5 Mixed-Layer Minerals 131
The common interest from MLM stems from their wide abundance in diverse
geological environments - weathering crusts, contemporary sediments, hydro-
thermally altered rocks, and rocks having undergone postsedimentary trans-
formations. They are found in oceanic sedimentary rocks, nonmarine sediments,
and altered oceanic basalts. The important point is that various types of MLM,
especially mixed-layer clays, are associated with definite geological environ-
ments, and their identification and description is essential for determining the
genesis of the enclosing rocks.
Mixed-layer illite-smectite, for example, is one of the most common clay
components in sedimentary rocks that have been subjected to diagenesis and
low-grade metamorphism. Such MLM are also widespread among the hydro-
thermally altered rocks of subsurface mineral ore deposits. Illite-smectites with
R> 1 make up the bulk of the K-bentonites of Silurian and Mid-Ordovician
deposits of the Baltic region, Sweden and North America. Peculiar inter-
stratified leucophyllite-smectite minerals have been found in ash strata of a
number of salt-bearing deposits.
Ordered or almost ordered chlorite-saponites (corrensites) can be grouped
into five major genetic categories based on composition and paragenetic
associations.
(1) Mg-rich diagenetic corrensites of evaporitic terrigenous chemogenic and
carbonate formations, and of hydrothermally altered dolomite-gypsum rocks.
(2) Mg-Fe corrensites of thick clastic volcano-sedimentary and sedimentary
rocks transformed under regional epigenesis. (3) Fe-rich corrensites formed in
the course of postsedimentary transformation of terrigenous rocks. (4) Corren-
site with variable compositions resulting from post-magmatic alterations of
basic and intermediate rocks on land and under water. (5) Corrensites as
weathering products and soil components. Depending on the exact geologic
setting, corrensites may form distinct paragenetic associations with Fe-illite,
laumontite, and analcime.
MLM are widely studied because their structural and compositional pecu-
liarities sometimes reflect the dynamics of physicochemical changes in the
course of a geological process. Thus MLM are often an intermediate link in the
series of stage-by-stage transformations of layer silicates. Such transformations
132 Chapter 2. Crystal Structures of Minerals
are possible largely because it is the phyllosilicate interlayers that are most
sensitive to environmental changes, so that a change from one structural type to
another can proceed without radical restructuring of the silicate layers. Clay
mineral reactions take place at relatively low temperatures, so the possibility
must always be considered that the reaction progress is kinetically controlled
and does not necessarily represent equilibrium conditions with respect to any
specific chemical environment.
Despite the complexity of possible kinetic constraints, revealing relation-
ships between physicochemical conditions of the environment, and structural
and crystal-chemical peculiarities of the mixed-layer phases favor the use of
MLM as indicators of various stages of regional epigenesis and of the degree of
hydrothermal alteration of rocks.
A transition from one mineral to another via a series of mixed-layer phases is
not necessarily the result of a solid-phase transformation. MLM may form as a
result of synthesis from a solution, or through dissolution-reprecipitation or
metasomatic reactions. Therefore, in an analysis of the alteration of MLM at
any stage of their existence, much attention is paid to determining the structural
mechanism for MLM formation. These data, together with detailed tectonic,
lithological, and petrographical studies of enclosing rocks can provide a basis
for the solution of various geological problems. As an example, interstratified
illite-smectites are being used to unravel the thermal history of sedimentary
rocks, processes of sandstone cementation, dynamics of oil migration, and the
origin of hydrothermal solutions.
Despite intense and comprehensive research on MLM that involves con-
siderable intellectual efforts throughout the world, there still are a lot of spots in
our knowledge of these minerals. Development of new methods and improve-
ment of existing ones should help to determine unambiguously the status of
MLM, their fine structural and crystal-chemical features, the rules that govern
the patterns of alternation of different layer types, and analyses at the atomic
level. Synthesis of such information should lead to a good understanding of the
formation mechanisms as well as the transformation dynamics. The sophisti-
cation of emerging methods should add considerably to the range of examples in
which an irregular alternation of two-dimensional structural fragments takes
place. There is still much to be done to elucidate the effect of various factors
(e.g., temperature, presssure, porosity, rock type and age, composition of
solutions, kinetics of the processes) that are responsible for the detailed morpho-
logical, structural, crystal-chemical and, finally, indicator characteristics of
various mixed-layer minerals.
References
Drits VA, Tchoubar C (1990) X-ray diffractIOn by disordered lamellar structures. Springer,
Berlin Heidelberg, New York, 370 pp
Drits VA (1987) Electron diffraction and high resolution electron microscopy of mineral
structures. Springer, Berlin Heidelberg New York, 304 pp
2.2.6 Structural and Magnetic Phase Transitions 133
Nadeau PH, Tait JM, McHardy WJ, Wilson MJ (1984) Interstratified X-ray diffraction
characteristics of physical mixtures of elementary clay particles. Clay Mineral 19: 67-76
Reynolds RC (1988) Mixed-layer chlorite minerals. In: Bailey SW (ed) Hydrous phyllosilicates
(exclusive of mica). Reviews in Mineralogy. Mineral Soc Am, pp 601-629
Reynolds RC (1980) Interstratified clay minerals. In: Brindley GW, Brown G (eds) Crystal
structures of clay minerals and their X-ray identification. Mineral Soc, London, pp 249-303
Srodon J (1980) Precise identification of illite/smectite interstratification by X-ray powder
diffraction. Clays Clay Mineral 28: 401-413
S. GHOSE
Two types of phase transitions in minerals, structural and magnetic, which are
continuous or nearly continuous (second- or nearly second-order) have been
extensively investigated in the last few years. These transitions are characterized
by a change in symmetry (structural or magnetic) as a function of an external
variable (temperature T, pressure P, chemical composition, X, etc.) such that the
symmetries are related by a supergroup-subgroup relationship. Familiar ex-
amples are pI-II transition in anorthite, CaAl 2Si 20 g at 514 K; P2t/c-+C2/c
transition in clinohypersthene (Fe, Mg)2Si206' at '" 1000 K, the IX-P quartz
transition at 846 K, etc. For continuous structural transitions, an order para-
meter, '1, is defined which describes the pattern of atomic displacements, which is
responsible for the lowering of symmetry; '1 decreases continuously as T
approaches the critical transition temperature, Te. The order parameter is
usually described by a particular wavevector within the Brillouin zone and may
be written as '1j (q), where q is the wave vector of j'th phonon branch. During the
paraelectric (cubic) to ferroelectric (tetragonal) transition of BaTi0 3 with the
perovskite structure, the Ti-ions are displaced away from the center of the
oxygen octahedra, causing thereby an electric polarization. This distortion
corresponds to a transverse optic mode (TO), whose phonon frequency depend-
ence on temperature is given by w 2 TO = C(T - T c), which has been experi-
mentally observed by inelastic neutron scattering. Such a phonon mode, whose
frequency approaches zero as T -+ Tc is known as a soft mode. In BaTi0 3 , the
wavevector q of this mode is zero which lies at the zone-center, and two unit cells
have nearly the same volume. In SrTi0 3 on the other hand, the cubic to
tetragonal transition requires alternate clockwise and anticlockwise rotation of
the [Ti0 6] octahedra, resulting in a cell doubling below Te ( '" 105 K); here the
q is at the zone boundary point, R [111]. The index (1 ~ j ~ n) describes the
number of components of the order parameter. In cubic ferroelectrics such as
BaTi0 3 n = 3, corresponding to polarization along x, y, or z crystal axes.
Following Landau theory, for the simplest possible case of the single
component order parameter (n = 1), the free energy of the crystal through the
134 Chapter 2. Crystal Structures of Minerals
microscopy (e.g., a-[3 quartz transition: Van Tendeloo et al. 1976; pI-II-
anorthite transition: Van Tendeloo et al. 1989). Further above T e, both the
increasing fluctuation frequency and decreasing correlation length (cluster size)
with increasing temperature can be measured by inelastic neutron- and Raman
scattering. In most cases, the phase transition is initiated by a soft mode
(displacive) mechanisms in the low temperature phase, but finally driven by
critical fluctuations near T e, where an order-disorder mechanism predominates.
In such a case, the average order parameter may have a small nonzero value
above T e because of the persistence of small clusters of the low temperature
phase within the stability field of the high temperature phase. Immediately
above T e, the high temperature phase is a statistical dynamical average of
domains of the low temperature phase. Again, a-[3 quartz and pI-II anorthite
transitions serve as good examples.
in acmite (TN = 8 K) nearly parallel to c (Ghose et al. 1988; Ballet et al. 1989).
Fayalite, Fe~+Si04 where Fe 2 + ions occur on two types of octahedral sites M1
and M2, shows a more complex behaviour. Below TN (65 K), the spins on two
M2 sites (with M1 in the middle) are parallel and anti parallel to b, whereas the
spin on M 1 is canted away from b and still fluctuating. With decreasing
temperature, the M 1 spins rotate and finally order below about 23 K (Fuess et
al. 1988). The complex spin ordering processes result in a sharp lambda peak in
the specific heat at 65 K followed by a broad shoulder around 30 K (Robie et al.
1982). Quite a different magnetic ordering behavior is shown by the mixed-
valence iron silicate, ilvaite, (CaFe 2 +Fe H )Fe 2 +Si 2 0 40(OH), where Fe 2 + and
Fe 3 + ions occur in double octahedral chains (A sites), above the below which
occur larger Fe 2 + octahedra (B sites). Below TN (120 K), within one octahedral
chain, the alternating Fe 2 + and Fe 3 + ions are ferromagenetically coupled,
which are antiferromagnetically coupled to the edge-sharing adjacent
Fe2+ -Fe H chain; the Fe2+ spins (B site) are still fluctuating and order at a
much slower rate from below TN to about 50 K, at which point they order
rapidly. This behaviour stems from spin frustration; the B site spin, which occurs
at the apex of a slightly distorted square pyramid, senses parallel A site spins on
one side and anti parallel spins on the other. It finally adopts a parallel
configuration to the nearer set of A site spins. This effect is shown also by the
magnetic susceptibility measurements and specific heat. The evolution of the
magnetic moments and the internal magnetic fields as a function of temperature
has been measured by neutron diffraction and M6ssbauer spectroscopy, respect-
ively (Ghose et al. 1990).
References
Ballet 0, Coey JMD, Fillion G, Ghose S, Hewat A, Regnard JR (1989) Magnetic order in
acmite, NaFeSi 2 0 6 • Phys Chern Mineral 16: 672-677
Boysen H (1990) Neutron scattering and phase transitions in leucite. In: Yalje E (ed) Phase
transitions in ferroelastic and coelastic crystals. Cambridge Univ Press, Cambridge, U.K.,
pp 334-349
Cochran W (1960) Crystal stability and theory of ferro electricity. Adv Phys 9: 387-423
Coey JMD, Ghose S (1988) Magnetic phase transitions in silicate minerals. In: Ghose S, Coey
JMS, Salje E (eds) Structural and magnetic phase transitions in minerals. Springer, Berlin
Heidelberg New York, pp 162-184
Dolino G (1988) Incommensurate phase transitions in quartz and berlinite. In: Ghose S, Coey
JMD, Salje E (eds) Structural and magnetic phase transitions in minerals. Springer, Berlin
Heidelberg New York, pp 17-38
138 Chapter 2. Crystal Structures of Minerals
enables the analysis of the local structure around atoms of interest, oxidation
state, and the pattern in the cation distribution.
Methodologically, it is most important that the results obtained by spectro-
scopic methods be always treated in the light of diffraction data on the structural
peculiarities of the sample involved. For example, EXAFS and XANES spectra
of todorockite and vernadite are practically identical; they indicate similar
short-range order in these Mn-oxides. Diffraction data, however, show that their
three-dimensional structures differ substantially.
At present, comprehensive studies of PCM real structure are being in-
tensively developed. The appropriate approach to such studies is to apply a
representative panel of modern solid-state physical and chemical methods to the
same sample (not just to the same mineral!) and to obtain compatible results.
References
Buscek P, Cowley J, Ewing L (eds) (1989) High resolution electron microscopy. Univ Press,
Oxford 645 p
Drits VA (1987) Electron diffraction and high resolution electron microscopy of mineral
structures. Springer, Berlin Heidelberg New York
Drits VA, Tchoubar C (1990) X-ray diffraction from disordered microdivided lammelar
structLires. Theory and application to silicates and carbons. Collaboration with Besson G,
Bookin A and et al. Springer, Berlin Heidelberg New York
Hawthorne FC (ed) (1988) Spectroscopic methods in mineralogy and geology (1988) In:
Hawthorne FC (ed) Reviews in mineralogy, vol 18. Mineral Soc, Washington, DC
Zvyagin BB (1967) Electron diffraction analysis of clay mineral structures. Plenum, New York
..
Fig. 31a-c. High-resolution transmission electron micrographs and electron diffraction pat-
terns of zircon. a The least-damaged area displays mottled diffraction contrast in the (101)
plane. Two-dimensional lattice fringes are evident and a unit cell (a = 0.66 nm and c
= 0.60 nm) is outlined. Some lattice fringes are bent and discontinuous. Examples of aperiodic
domains (I to 5 nm) in which lattice fringes are almost absent, possibly because of alpha-recoil
tracks, are indicated by arrows. In spite of these bright-field features, the electron diffraction
spots are sharp and clear. b The intermediately damaged area. The bright-field image is
paralled to (Ill). The spots in the diffraction pattern are broad and diffuse, which corresponds
to increased structural distortion. Although the aperiodic domains are as abundant as the
domains of distinct lattice fringes, the distorted crystalline domains have the same orientation.
Lattice dimensions are given for the [110] (1.01 nm) and [OIl] (0.97 nm) directions. c The most
damaged area. The bright-field image shows no evidence for long-range periodicity. In
addition to diffuse rings, the electron diffraction pattern has powder rings that result from
misoriented microcrystallites. The arrow points to a micro crystallite displaying [100]
(0.66 nm) lattice fringes. (Chakoumakos et a!. 1987)
144 Chapter 2. Crystal Structures of Minerals
X-ray absorption spectroscopy has been the most commonly applied tech-
nique for the determination of the structure of the metamict state, as it can
provide information on coordination number and bond-lengths in the first and
second coordination spheres. However, because the compositions of most
metamict minerals are so complex, it has not been possible to construct a unique
model for the aperiodic arrangement that is consistent with bulk properties such
as density. Still, principal conclusions from XAS studies include: (1) For most
phases, nearest-neighbor coordination geometries (eN and M-O distances)
remain nearly constant with the possibility of limited distortion of the coordina-
tion polyhedron. Major changes in the coordination geometry are a result of the
stereochemistry of the cations involved. (2) The loss of long-range periodicity is
2.2.8 The Metamict State 145
References
Akimoto J, Imafuku M, Sugitani Y, Nakai I (\988) Fe K-Edge Xanes and Mossbauer study of
the amorphous state in metamict gadolinite and samarskite. In: Synchrotron radiation
applications to mineralogy and petrology. Theophrastus, Athens, Greece, pp 141-171
Chakoumakos BC, Murakami T, Lumpkin GR, Ewing RC (1987) Alpha-decay induced
fracturing in zircon: the transition from the crystalline to the metamict state. Science 236:
1556--1559
Clinard FW, Jr (1986) Review of self-irradiation effects in Pu-substituted zirconolite. Ceram
Bull 65: 1181-1187
Ewing RC (1975) The crystal chemistry of complex niobium and tantalum oxides. IV. The
metamict state: discussion. Am Mineral 60: 633-728
Ewing RC, Chakoumakos BC, Lumpkin GR, Murakami T (1987) The metamict state. Mater
Res Soc Bull 3: 58-66
Ewing RC, Chakoumakos BC, Lumpkin GR, Murakami T, Greegor RB, Lytle FW (1988)
Metamict minerals: Natural analogues for radiation damage effects in ceramic nuclear waste
forms. Nucl Instr Meth Phys Res B32: 487-497
Farges F, Calas G (1991) Structural analysis of radiation damage in zircon and thorite: an
X-ray absorption spectroscopic study. Am Mineral 76: 60-73
Farges F, Ewing RC, Brown GE (1993) The structure of aperiodic, metamict,
(Ca,Th)2Zr2Ti4014: an EXAFS study of the Zr, Th, and U sites. J Mater Res 8: 1983-1995
Greegor RB, Lytle FW, Chakoumakos BC, Lumpkin GR, Ewing RC, Spiro CL, Wong J
(1987) An investigation of the Ta site in radiation damaged natural pyrochlores by X-ray
absorption spectroscopy. In: Bates JK, Seefeldt (eds) Scientific basis for nuclear waste
management. Mater Res Soc Proc 84: 645-658
Hawthorne FC, Groat LA, Raudsepp M, Ball NA, et al. (1991) Alpha-decay damage in titanite
Am Mineral 76: 370-396
Holland HD, Gottfried D (1955) The effect of nuclear radiation on the structure of zircon. Acta
Cryst 8: 291-300
Lumpkin GR, Ewing RC (\988) Alpha-decay damage in minerals of the pyrochlore group.
Phys Chern Mineral 16: 2-20
Lumpkin GR, Chakoumakos BC, Ewing RC (1986) Mineralogy and radiation effects of
microlite from the Harding Pegmatite, Taos County, New Mexico. Am Mineral 71: 569-588
Lumpkin GR, Eby RK, Ewing RC (1991) Alpha-recoil damage in titanite (CaTiSi05): Direct
observation and annealing study using high resolution transmission electron microscopy.
J Mater Res 6: 560-564
Murakami T, Chakoumakos BC, Ewing RC, Lumpkin GR, Weber WJ (1991) Alpha-decay
event damage in zircon. Am Mineral 76: 1510-1532
Nakai J, Akimoto J, Imafuku M, Miyawaki R, Sugitani Y, Koto K (1987) Characterization of
the amorphous state in metamict silicates and niobates by EXAFS and XANES analyses.
Phys Chern Minera115: 113-124
2.3 Systematics of Crystal Structures and Crystallochemical Classifications 147
Wang LM, Eby RK, Janeczek J, Ewing RC (1991) In situ study of ion-beam-induced
amorphization of complex silicate structures. Nuc1 Instr Meth Phys Res Beam interactions
with materials and atoms. B59/60: 395-400
Weber WJ (1983) Radiation-induced swelling and amorphization in Ca2Nd8(Si04)602.
Radiat Elf 77: 295-308
Weber WJ (1990) Radiation-induced defects and amorphization in zircon. J Mater Res 5:
2687-2697
Weber WJ, Eby RK, Ewing RC (1991) Accumulation of structural defects in ion-irradiated
Ca2Nd8(Si04)602. J Mater Res 6: 1334-1345
2.3.1 Prolegomenon
P.B. MOORE
What is the goal of crystal structure analysis? What purpose does contemporary
crystal structure analysis and refinement serve? The goal is to provide a correct
structure solution and a high level of precision for the refined data. Modern
technology can allow very precise data, indeed. Much of the quality of the data
hinges on the quality of the crystal. A small, ground sphere has many advant-
ages, as correction for absorption anisotropy is usually the most critical aspect
in preparing good observed structure factors. Film data should always be
collected in advance, and careful check for twinning, spot shape, and possible
weak superstructure reflections can be more easily facilitated. The range in the
final discrepancy index (R) should be below R = 0.06, and superior cases will
provide R = 0.01 -0.03.
Many structure refinements are hampered by lack of elemental analysis of
the sample. For minerals, where solid solution and mixed valences abound, lack
of assayed cation and anion content could be disastrous. A good electron probe
analysis should accompany the structure study. Unfortunately, many mineral
crystals are not simple parsimonious things but can be very complex, and a few
contain over 20 different ionic components in amounts greater than 0.5 wt. %
each. Clearly, not much of their crystal chemistry can be known with any degree
of precision, let alone confidence, in the absence of some preliminary analytical
study. In crystals with more than one structure domain or with an extensively
disordered region such as a sheet component, even R < 0.10 may be hard to
achieve. Such structure solutions and refinements are called "averaged struc-
tures".
The purpose of crystal structure analysis is quite another matter. In the past,
structure work often accompanied more general studies by a mineralogist or a
petrologist. (Naturally, a firm background in inorganic chemistry is implied in
148 Chapter 2. Crystal Structures of Minerals
these disciplines). It is a sad but ineluctable modern fact that many crystallogra-
phers who study mineral structures are neither mineralogists nor petrologists at
all, but treat the structure investigation as an end in itself. Alas, all the time and
effort is put into the problem which often becomes an "abandoned orphan of
science". But the superior refinement can provide a check on the indexed powder
data files; an explanation of hardness and cleavage; a check on specific gravity
by density calculation; a suggestion toward explaining color, pleochroism, and
reflectance; a possible calculation of the optical characters including indices of
refraction; bond distances, bond angles, coordination polyhedra, solid solutions,
bond strength, and bond valence sums - all these characters which make up so
much of mineralogy from one crucial study! For this reason, crystal structure
analysis should be in the armamentarium of every good mineralogist.
Beyond the physical characters, resides the classification of the mineral. And
here, the most essential experimental tool is crystal structure analysis. At the
most rudimentary level, classification serves as a "pigeonholing" of the structure
in the large class of known mineral structures. In principle, there are infinitely
many classifications but we are only interested in those which possess a
hierarchy. Mineral classification today is largely chemical-crystallographic,
where the connectedness of the hierarchical tree is based on some rules which
define structure similarity. A paragenetic classification of minerals is com-
mendable and is based on associations in the field (the "sociology" of crystal
phases), P-T -X conditions and Eh-pH diagrams in the laboratory. The
wedding of mineral paragenesis to structure type would be a fruitful albeit
difficult task, say toward unravelling the geochemistry of some complex ore
deposit such as at Franklin, New Jersey, USA.
Recently, evidence has been accumulating concerning the uncanny fre-
quency of close eutactic arrangement of cations in an oxysalt mineral to the
elements in some intermetallic phase. The path-breaking paper by O'Keeffe and
Hyde (1985) is one such example. This relationship, the observations of which
can no longer be denied, languishes for want of some underlying theoretical
basis. It seems, however, that many such cases involve oxysalts/intermetallics
which are based on the close-packing of cations/elements rather than the
classical model of anion close-packing which, by the way, does not have a strong
theoretical basis either. At best, we can declare that a troubling array of
structure/anti structure pairs exists, e.g., CaF 2/0Li2'
Unfortunately, a disturbing number of reported crystal structures of minerals
are wanting an appropriate representation (the "abandoned orphan" idea looms
forth again!). Appropriate representation is how we relate structures to each
other. About the highest structural character in any good structural hierarchy is
the fundamental idea of close-packed spheres of anions or of cations (or in
mixed-layer structures as in perovskite, Ti[03Ca]"). Once the stacking sequence
of close-packed layers is known, the refined structure can be directly compared
with the ideal calculable geometrical model. Yet ironically, but few investigators
go through the trouble to demonstrate this comparison. Close-packed struc-
tures open up a whole new world in combinatory theory, order-disorder,
2.3.1 Prolegomenon 149
the number of elements (called "animals") in the set is usually so large that the
framework eventually collapses.
Another famous problem involves the populations of valence electrons
remaining for a cation. An element can be considered in a mineral crystal as (1) a
metal (as in native elements and intermetallics), (2) an anion (closed Lewis octet),
(3) a Jahn-Teller cation (polyhedral distortion for certain d; -y2, d; popula-
tions), (4) a lone pair cation (ns 2 valence electrons remaining, n = row of
Periodic System), and (5) a naked cation (an element stripped of all valence
electrons to form a closed core). Categories (2) and (5) are the classic examples
which Pauling used to obtain his electrostatic valence rules. These rules are not
very helpful for categories (1), (3), and (4). However, the eutactic relation of
atoms in metal phases in category (1) to cations in oxysalts in (2), (3), (4), and
(5) is intriguing. Some examples are presented where the relation is calculated as
(d), the atom coordinate difference between oxysalt and metal, scaled to the
larger oxysalt cell:
4Pb2Mn~ + 0z(Si 20 7) SURe 2(' ch .), d = 0.00-0.34 A
kentrolite (5 unique cations) a Laves phase, e.g., MgZn2
3Mni+ Mn~+Sb5+Si2024 4SLa (. ch .), d = 0.00-0.32 A
hlngbanite (13 unique cations)
4Mg 3 Ti0 2(B 20 6 D) 4Na 2CaZrF 2(Si 20 7 ) SC0 2Si, d = 0.00-0.62 A
warwickite wohlerite synthetic
(3 unique cations) (14 unique cations)
These are but few of many such relationships. Note the diversity covered in
the third line. For some structures, it seems our notions of mineral atomic
arrangements are turned on their heads, as if the cation packaging provides the
interstices for the anions!
Jahn-Teller ion and lone pair ions invariably induce a distortion in the
coordination polyhedron. Distortions can be severe. For example, [9] Pb 2+_0 2-
= 2.2-3.2 A range is a consequence of lone pair-bond pair interactions. In
naked [6] Pb4 +-0 2- = 2.16-2.20 A, the range for the highly charged cation
is small and its oxide coordination octahedron is fairly regular. In fact, the
Pb 4 +_0 2- = 2.IS A average is roughly the lower limit found for Pb2+ _0 2-.
The lone pair distortion is fairly well understood only recently with the advent of
precise structure refinements. It appears to be an electrostatic phenomenon.
Thus, the short Pb 2+_0 2- = 2.2 A values are not indicative of covalent
bonding, but are bonded on that side of Pb 2+ (the "naked side") opposite the
centroid of the lone pair. Jahn-Teller ions such as 4d 4Mn3+ and 4d 9 Cu2+ can
be similarly treated: the distortion is a more symmetrical version of the lone pair
distortion. For example, four long equatorial (dx 2_y2 electron population) and
two short apical octahedral bonds for Mn3+ _0 2- create an oblate ellipsoid and
the more frequent four short equatorial and two long apical (dz 2 electron
population) octahedral bonds create a prolate ellipsoid. In turn, these ellipsoids
provide directed bond strengths whose Pauling sums to anions are more nearly
152 Chapter 2. Crystal Structures of Minerals
neutral. Similar reasoning has been applied to the distorted polyhedra envelop-
ing a lone pair cation, but here the displacement of the central cation toward the
lone pair centroid can be predicted by use of the Pauling electrostatic valence
rules.
These are but a few of the examples which face the chemical crystallographer
of minerals. Electronic distortions result from a wide variety of origins, but all
seem to manifest themselves in well-refined crystal structures. For this reason,
the crystal and chemical aspects of structure are inseparable and both require
equal attention. Let us remark finally that nearly every topic in this book
ultimately touches upon some aspect of chemical crystallography.
G.B. BOKIY
the functional systems. The predictive models are intended for enumerating the
taxa, i.e., they fulfil the same functions which lead to the descriptors in the
classification of biological objects.
In the descriptor automatic information systems where there is a set of the
physical objects and documents of the information, the automation of the clas-
sification methods is necessary for the creation of the data banks of the "expert"
system for general use.
The mathematical methods: cluster analysis and the methods of grouping
are used simultaneously with the intuitive methods for the construction of the
classifications. Counting theory plays a role here. The purpose of the cluster
analysis is a choice of the groups of the synonymous objects, the various groups
differing greatly between each other. In general, it is clear that when using
the whole system of attributes, a full correspondence can be made between "the
space of the attributes" and the "space of the objects".
It is absolutely clear that the task of the recognition of the images and the
tasks of the classification have the same purposes, and it is impossible to solve
these without use of the modern developments of applied mathematics and the
computer technology.
All classifications according to their internal structure are divided into
hierarchical and combinatorial ones. On the other hand, it is possible to
subdivide all classifications into two groups: the Natural classifications and the
Artificial classifications, the former reflecting the laws of Nature.
The artificial classifications are created for a variety of purposes. For
example, the purpose of the artificial classification can be simply the creation of
the searching system. The Natural classifications are equal to the laws of Nature,
i.e., it is unreasonable to put the question: "What are they for?"
There are a plethora of artificial classifications, much more than natural
ones, as they are used in all spheres of human activity. For natural classifica-
tions, which relate mainly to the exact and usually fundamental sciences, their
number is much less.
These types of classification are discriminated also by the character of the
attributes they use. The use of many attributes is typical for the Artificial
classifications. The special divisions of mathematics (statistical methods, cluster
analysis, and so on) are often used for investigations with these attributes. The
attributes become synonymous for this purpose. They are often contrived, i.e.,
the subjective aspect is brought into the classification. In the Natural classifica-
tions very few attributes are used, ideally only one. This attribute must be the
essential one. The change of one essential attribute by another one is always "an
event". Recalling that in evolving the Periodic System of the chemical elements,
more than 50 years were needed to effect the change of "an atomic weight" into
"an atomic number". One (essential) attribute among the set of the properties
existing for every chemical element was given, which was the basis of the
classification.
In another instance, the classification attribute "crystal form" was replaced
by "symmetry". The choice of the essential attribute and its replacement by
another more essential one bears an objective character.
154 Chapter 2. Crystal Structures of Minerals
G.B. BOKIY
These two approaches depend on what is taken for the first basis of a
classification: (1) chemical composition of minerals or (2) crystal structure.
In the first case it is division of minerals (chemical compounds) into chemical
types, subtypes, classes, and the structural classifications are applied to these
classes of minerals. This is a classification of minerals which are fundamentally
chemical compounds, each possessing a crystal structure.
In this manner, structural classifications have been elaborated for several
classes of minerals: silicates, sulfates, arsenates, vanadates, sulfosalts. Povaren-
nykh (1972) applied this principle to the whole domain of minerals, sys-
tematically presenting chemical-structural distributions of all minerals known at
that time.
This approach permits more detail and versatile consideration of each class
of mineral structures which differ radically from crystal structures of other
classes of minerals. An attempt to summarize the principles for this chemical-
plus-structural, i.e., crystallochemical, systematics is portrayed in Chapter 2.3.4.
In the second case, a rather new and quite special approach was developed
for classification, which takes structural criteria as a basis. It is a systematics of
structure types independent in principle of their chemical composition. Thus
NaCI-MgO-PbS present one structure type which finds its place in the classi-
fication. .
This is a logically natural stage in the evolution of crystal structure analysis.
It could be useful from the point of view of contemporary materials science
which considers, for example, garnets as composed of rare-earth oxides, Y-AI,
Y-Fe, and silicate garnets all having the same crystal structure; but this is just a
geometrical systematics of crystal structures, not only of minerals. Attempts to
find general principles which can include all different classes of compounds of
extreme diversity can lead to artificial and complicated schemes.
2.3.4 Crystallochemical Classifications of Minerals 155
G.B. BOKIY
Table 19. Division of the type of the oxides (61) into classes
Me [H-O] Me [He-O]
6171 6181
Me [B-O] Me [C-O] Me[N-O] Me [0-0] Me [F-O] Me [Ne-O]
6132 6142 6152 6162 6172 6182
borates carbonates nitrates peroxides fiuorates
Me [Si-O] Me [P-O] Me [S-O] Me [Cl-O] Me [Ar-O]
6143 6153 6163 6173 6183
silicates phosphates sulfates chlorates
Me [Ge-O] Me [As-O] Me [Se-O] Me [Br-O] Me [Kr-O]
6144 6154 6164 6174 6184
germanates arsenates selenates bromates
Me[Sn-O] Me [Sb--O] Me [Te-O] Me [J-O] Me [Xe-O]
6145 6155 6165 6175 6185
stannates stibates tellurates iodates
Me [Bi-O] Me [Po-O] Me [At-O] Me [Rn-O]
6156 6166 6176 6186
bismuthates pollonates astatates
Table 20. Subclasses in the class of the silicates and the corresponding silicon-oxygen radicals. (Si: 0 = a numerator, 0: Si = a denominator) N
W
~
N Name Si:O and O:Si ratios (')
and
symbol
.:!
1:4 2:7 3:10 4:13 5:166:19 1:3 7:206:175:144:11 7:19 10:27 3:8 8:21 5:13 12:31 2:5 5:128:19 3:7 10:23 4:9 5:11 6:13 20.41 1:2 ~
of the a
subclass 4.00 3.50 3.33 3.25 3.20 3.17 3.00 2.86 2.83 2.80 2.75 2.71 2.70 2.66 2.63 2.60 2.51 2.50 2.40 2.37 2.33 2.30 2.25 2.20 2.17 2.05 2.00
Island
n
noming In
f.
a
2 Island I, 9
ring Q
'"
f!l.
3 Chain C 10 2 g>
e?
4 Band B 3 3 2 In In In o·
el
'"o
5 Tube T 4 -.
T 3::
~.
6 One· L, 3n 5 In
store a
layer '"
7 Two- Lz 2
store
layer
8 Three- L3 2
store
layer
9 Frame- F In 5
work
10 Zeolite Fz 7
---------
Numbers in the table show the number of the varieties in the subclass.
n = nonmineral
.....
VI
-.I
Table 21. Family of pyroxenes M 2 M, T 206 .....
Vl
00
Cations M2 Mg Fe 2 Fe 2 Mg Fe 2 Mg Li Na Na Na Na Na Na Na
in the Ml
m n
Mg Mg Fe 2 Mg Mg Mg
11
Al Mg Sc 3 V3 Cr Fe 2 Fe' Al
positions
000 o 00
MS and ...0
their names '"c .~ c
'" '"c
-5'" ~ :2
u
.~ '" ~ S .;;; 0 c
6 .=~ .;:J '";;l .;:::
'" ~
'"6 oI~
... c "0 'E .iii
~
>.
'"t: e~ '08- 0 0
~0 ·SO "0
... >.
~c 0. .
w :I: "-'" ~ iJ ~..r:: as Vl S'" ~ -<:
'" ..,
N 2 3 4 5 6 7 8 9 10 11 12 13 14
with each other (these substances do not contain the metallic elements in their
composition).
3. * Metals with the nonmetallic elements of subgroup IIIB (borides).
4. Metals with the nonmetallic elements of subgroup IVB.
5. Metals with the nonmetallic elements of subgroup VB.
6. Metals with the nonmetallic elements of subgroup VIB.
7. Metals with the nonmetallic elements of subgroup VIIB.
8. * Metals with the nonmetallic elements of subgroup VIIIB.
The empty sections for mineralogy are marked by an asterisk. The second set
of subdivision gives 31 types (for minerals, 20) (see Table 18). Two figures in the
decimal system correspond to this action.
Under a type of the oxides (61) including the chemical compounds and the
minerals, oxygen predominates in the anionic composition. The number of such
minerals (in percent) exceeds the number in other types. As oxides, in the narrow
sense of this term, so the silicates and other salts of the oxygen acids relate to this
type. This type is divided into six subtypes (Table 19).
These chemical divisions are followed by structural classifications for classes
and orders of minerals.
Principles of the classification of silicate minerals are presented in Table 20.
As an example, the structural classification of the pyroxene family is given in
Table 21. See also classifications of silicates by Zoltai (1960) and by Liebau
(1985).
The crystal structure classifications have been presented for several classes of
minerals:
- borates (based on the polymerizations of the B0 3 and B0 4 anionic groups) by
Christ and Clark (1977).
- phosphates, sulfates, arsenates, vanadates (based on the polymerization of
M2+ and M3+ cation octahedra) by Moore (1980).
- aluminum hexafluorides by Pabst (1950).
- sulfosalts by Makovicky.
J. LIMA-de-F ARIA
use of a chemical classification of minerals for more than 100 years, and of
chemical formulae to characterize the mineral species. Substantial structural
data have been accumulated since the discovery of X-ray diffraction by crystals,
in 1912, and it is convenient to take advantage ofthese data by clarifying certain
structural mineralogical concepts, and by developing a new crystal-chemical
classification, a structural classification of minerals, where structures are
brought together not by their chemical similarity but the resemblance of their
atomic structural arrangements, and consequently bringing together minerals
that belong to the same structure type.
tiomorphism of the space group, similarity of axial ratios and interaxial angles,
values of the adjustable positional parameters, coordinations of atoms, same site
occupancy allowing given sites to be occupied by different atomic species.
Some of the important homeotypic structures are the so-called distortion
and substitution derivatives. In the case of distortion derivatives, the atomic
arrangement suffers a slight distortion. Examples are NaCI (halite) and FeSi
(fersilicite) or TiCa03 (ideal perovskite) and CuKF 3, with subgroup symmetry.
Other relative structures may be considered such as; polytypic structures (SiC
polytypes), "interstitial" or "stuffed" derivatives (AuCu3 and TiCa03), and
recombination structures (olivine-norbergite homologous series).
The classification of minerals has changed throughout the ages, the criterion of
classification following the development of the mineralogical sciences.
A sketch of the evolution of the basic criteria of the mineralogical
classification has been already presented by Lima-de-Faria (1983). It is apparent
from this sketch that the classification of minerals went through different stages:
from practical, to physical, to physical-plus-chemical, to chemical, to chem-
ical-pIus-structural. Although the chemical classification of minerals seems to be
well established, some dissatisfaction has become apparent particularly during
the last decades, and other criteria have been proposed for the classification of
minerals. Some criteria are related to particular domains of application, such as
geological (Lapparent 1884) or geochemical (Uklonskii 1940; Kostov 1954);
others, to more theoretical purposes, such as the one proposed by Machatschki
(1953), which was based on crystallochemical grounds and on the hierarchy of
the complexity of their formulae. It seems that it is now time to attribute the
primary role to the structural criterion and to propose a structural classification
of minerals. Such classification has been proposed (Lima-de-Faria 1983, 1988),
and is in a certain wayan extension of the structural classification of silicates to
the whole domain of minerals, and also the result of the application of the
general structural classification of inorganic structures to mineral structures.
Minerals belonging to the same structure type are placed together, and
within each category, they are ordered chemically. As an example, the halite
structure type includes the halogenides, followed by the oxides, sulfides,
tellurides, and nitrides, belonging to the halite structure type. This clearly shows
that the classification is not purely structural, but a structural-chemical
classification of minerals. Part of this synthesis is shown in Table 22 to give an
idea of its construction.
2.3.5 The Structural Classification of Minerals 163
Table 22. First part of the outline of a structural classification of minerals. (Lima-de-Faria 1983)
ATOMIC
Bokii (1982) and Hawthorne (1984,1985) have also suggested new classifications
of minerals based on their general classifications. A structural classification of
minerals, restricted to those that contain octahedral cations, has been suggested
by Moore (1974).
Hawthorne (1984, 1985) has suggested a general structural classification of
mineral structures based on the polymerization of coordination polyhedra (not
necessarily of the same type) with the higher bond valence, as a consequence of
the application of bond-valence theory to inorganic structures. The structures
are organized by families based on different arrangements of fundamental
building blocks or modules. The possible modules are the tightly bound units
within the structure, and correspond to clusters of polyhedra that are most
strongly bonded. One of the differences of this classification concept from that
proposed by Lima-de-Faria is based on the fact that for Hawthorne the
"modules" (or structural units) are only polyhedra, and never individual atoms,
as admitted by Lima-de-Faria. For instance, olivine, Mg 2 Si0 4, would be
classified according to the Hawthorne model in the category of unconnected
polyhedra, the Si0 4 tetrahedra being the structural units; for Lima-de-Faria,
Olivine is an atomic (or close-packed) structure, where the oxygens (individual
atoms) are the structural units forming an hexagonal close-packing, with
magnesium and silicon located in the interstices (octahedral and tetrahedral,
respectively); the corresponding structural formula is therefore Mg~SjI[04]h.
P.B. MOORE
the oceans have water in them. Tetrahedral chain periodicity, loops (rings), open
wings, closed cages, etc. all bear upon the classificatory scheme of Liebau (1985),
which results in a magnificent edifice. One is struck, as with any structure
classification, that the number of arrangements increases exponentially as the
number of participating fundamental units. The problem in classification is not
one of pigeonholing but one of taxonomic gigantism. As more and more useful
distinguishing characters appear, so do the labels until the edifice collapses by
sheer weight. This will always remain a problem for classifications based on
structure, perhaps less so for classification based on paragenesis or even anion
packing efficiency.
It is reasonable to assume that the known mineral structures which are based
on some bonding principle number far fewer than all the structures which could
possibly exist according to the same bonding principle, for example the silicates.
Counting theory helps guide the investigator in ascertaining how many struc-
tures could theoretically exist under an appropriate principle, and may even
contribute to an understanding why certain arrangements frequently appear in
crystals while others are singular in their very absence of any known crystalline
representative.
McLarnan and Moore (1981) is a brief introduction to counting problems
applied to mineral structures; it has references to some of the key literature in
this rapidly growing field. Solutions from counting (or graphical enumeration)
problems tend to exponentially increase as the elements in a domain increase.
For example, four kaolinite polytypes occur among one-layer structures but
ca. 10 17 arrangements occur among 12-layer structures! Investigators in
counting theory get used to these large numbers. The underlying principle
is the famous Polya's Theorem, PET. More recently, more powerful generaliza-
tions of PET have appeared. All consist of several sets of objects, briefly written
M, H, G and Z{G}. The number of elements in a set S will be designated lSI.
The set to be colored is M. For an octahedron, it could represent the domain
of vertices (IMI = 6), edges, (IMI = 12), or faces (IMI = 8). Such domains are
appropriate for convex polyhedra, in particular the tetrahedron, octahedron,
cube, icosahedron, and pentagonal dodecahedron. In these cases of the regular
polyhedra, a domain of elements (such as the labeled edges) are equivalent to
each other, which one quickly notices by some reorientation either of the labels
or of the polyhedron itself.
H are the colors to be applied to the domain. The order, lSI or number of
elements in the set, is usually written in magnitude notation I I. For example in
the octahedron, IMI = 12 for the edges. Typical colorings of octahedral edges
may involve IHI = 1 (one color) to 12 (12 colors) where 1 and 12 are obviously
trivial. Most commonly IHI = 2 (occupied/empty, on/off, yes/no, black/white,
shared/unshared, etc.). This approach is especially convenient in retrieving
clusters, such as occupied/empty for octahedral edges: (12/0, 11/1, 10/2,9/3,8/4,
7/5,6/6 ...). Note distributions are symmetrical about (6/6) merely by switching
the two colors. Colorings may also be distributed over lattices. Here, clever
algorithms may be devised based on a generalization of PET, such as for the
166 Chapter 2. Crystal Structures of Minerals
References
All crystals have point defects that are formed as the consequence of both
thermal activation and aliovalent impurities. Properties such as diffusion, creep,
and electrical conductivity have been shown to depend on point defects in all
types of crystals. This has been demonstrated well for olivine, for example [Jaoul
et al. 1980; Ryerson et al. 1987; Kohlstedt and Hornack 1981; Hermeling and
Schmalzried 1984; Schock et al. 1989; Bai et al. 1991 J. The minerals pyroxene
[Duba et al. 1973; Huebner et al. 1979J and spinel, as well as polymorphs of
these minerals and olivine [Hirsch & Shankland 1991J, which are stable at
higher temperatures and pressures, are also likely to have their, physical
properties determined by point defects [Paterson and Kekulawala 1979; Linker
et al. 1984]. The mechanical properties of quartz, the dominant constituent of
the crust, are also related to point defect concentrations.
An impetus for ascertaining the role of point defects in determining physical
properties of earth materials is to obtain a means of predicting physical
properties of these materials at conditions not attainable in the laboratory but
which can prevail in the Earth's interior. A good case in point is the recent
theoretical prediction of point defects in the high-pressure perovskite phase of
pyroxene [Hirsch and Shankland 1991J based on earlier work done on magnes-
iowiistite, olivine, and pyroxene. Critical to development of these predictions are
experimental data under known thermodynamic conditions of pres-
sure, temperature, and component activities. The experimental data usually
comprise determination of the effect of variation of the oxygen fugacity on a
transport property while pressure, temperature, and the activity of other
components is held constant. These data together with other relevant data are
then used in conjunction with models of defect behavior to determine the
particular defect mechanism that prevails.
Olivine is the most studied mineral in these terms because it is a major
constituent of Earth's upper mantle and provides a good example of the
development of our understanding. Schock et al. (1989) conclude that the low
activation energies for electrical conduction in olivine compared to those
relative to the band gap make it unlikely that intrinsic electronic conduction is
occurring in olivine during laboratory measurements. Since some of these
measurements have been made at pressures and temperatures equivalent to
about 150 km in the Earth's interior, Schock et al. conclude that point defects
playa key role in determining the electrical properties of olivine to at least this
depth in the Earth.
Defect models for conduction in olivine have been generated by Stocker
(1978) from theory and by Schock et al. using data available from the
measurement of electrical conductivity as a function of oxygen fugacity, the
directional dependence of conductivity in olivine's orthorhombic structure, and
the sign of the dominant change carriers as determined from measurement of the
3.1 Point Defects in Minerals 171
References
Bai Q, Mackwell SJ, Kohlstedt DL (1991) High-temperature creep of olivine single crystals:
I. mechanical results for buffered samples. J Geophys Res 96: 2441-2464
Duba AG, Boland IN, Ringwood AE (1973) Electrical conductivity of pyroxene. J Geol 81:
727-735 .
Hermeling J, Schmalzried H (1984) Tracer diffusion of the Fe-cation in olivine
(Fe xMg ' - xhSi04 (III). Phys Chern Mineral ll: 161-166
Hirsch LM, Shankland TJ (1992) Olivine point defect chemical model and the role of Fe-
impurities: insights on electrical conduction, diffusion, and creep. J Geophys Int 144: 21-35
Hirsch LM, Shankland TJ (1991) Point defects in (Mg,Fe)Si0 3 perovskite. LA-UR 90-3736
Geophys Res Lett 18: 1305-1308
Huebner JS, Duba A, Wiggins LB (1979) Electrical conductivity of pyroxene which contains
trivalent cations: laboratory measurements and the lunar temperature profile. J Geophys
Res 84: 4652-4656
Jaoul 0, Froidevaux C, Durham WB, Michaut M (1980) Oxygen self-diffusion in forsterite:
implications for the high temperature creep mechanism. Earth Planet Sci Lett 47: 391-397
172 Chapter 3. Real Structures of Minerals
Kohlstedt DL, Hornack P (1981) Effect of oxygen partial pressure on the creep of olivine. In:
Stacey FD, Paterson MS, Nicholas A (eds) Anelasticity in the Earth. Geodyn Ser, vol 4.
AGlJ, Washington, DC, pp 101-107
Kroger FA, Vink Hl (1956) In: Seitz F, Turnball D (eds) Solid state physics, Advances in
Research and Application, Academic Press New York, pp 307-435
Linker MF, Kirby SH, Ord A, Christie 1M (1984) Effects of compression direction on the
plasticity and rheology of hydrolytically weakened synthetic quartz crystals at atmospheric
pressure. 1 Geophys Res 89: 4241-4255
Paterson MS, Kekulawala KRSS (1979) The role of water in quartz deformation. Bull Mineral
102: 92-98
Ryerson Fl, Durham WB, Cherniak D, Lanford WA (1987) Oxygen diffusion in olivine. EOS
Trans AGU 68: 417
Sato H (1986) High temperature a.c. electrical properties of olivine single crystal with varying
oxygen partial pressure: implications for the point defect chemistry. Phys Earth Planet Int
41: 269-282
Schock RN, Duba A, Shankland TJ (1989) Electrical conduction in olivine. 1 Geophys Res 94:
5829 -5839
Smyth DM, Stocker RL (1978) Point defects and non-stoichiometry in forsterite. Phys Earth
Planet Int 17: 118-129
Stocker RL (1978) Influence of oxygen pressure on defect concentrations in olivine with a fixed
cationic ratio. Phys Earth Planet Int 17: 118-129
In some mineral structures, point defects can cluster into linear or planar arrays,
producing systematic variations in the projected atomic density. These vari-
ations can be imaged using normal bright-field, multiple-beam HRTEM ex-
periments, in which the image is formed from the central electron beam plus
some of the surrounding diffracted beams. In addition, the superperiodicities
produced by the ordering are manifested by additional, superstructure spots in
electron diffraction patterns.
Examples of ordered defect distributions include the various pyrrhotite
structures, Fe1-XS, which contain substantial numbers of metal vacancies. At
high temperatures, the vacancies are disordered, but at lower temperatures they
order into various patterns, producing a variety of commensurate and incom-
mensurate superstructures that are a function of composition and annealing
temperature. Columns of Fe atoms containing appreciable numbers of the
vacancies are readily imaged with HRTEM (Pierce and Buseck 1974; Nakazawa
et al. 1975). The Cu-Fe sulfides of the bornite-digenite series also show ordering
of defects into vacancy clusters, which have been imaged using both bright-field
and dark-field HRTEM methods (Pierce and Buseck 1978).
The ordering of vacancies and metal atoms in silicates and oxides also can
produce superstructures that are observable with electron diffraction and direct
HRTEM imaging. For example, oxidation of Fe 2 + to Fe 3+ in olivine minerals
can proceed by reactions of the type
Fe 2 Si0 4 + 0.44 O 2 --+ DO.67Fe1.33Si04 + 0.22Fe 30 4,
in which the iron component of the olivine reacts with oxygen to form a
vacancy-rich olivine component plus an oxide such as magnetite. This vacancy-
rich olivine-type structure is called laihunite and is produced during the
oxidation of fayalite. It occurs as several structural variants in which the
vacancies are ordered onto specific planes of Fe atoms, and the resulting
superstructures can be observed with electron diffraction or imaged with TEM
(Kitamura et al. 1984). In the oxidation of more magnesian olivine, ordered
intergrowths of Mg-rich and Fe/vacancy-rich structure form, and the vacancy-
rich regions can be imaged directly with HRTEM (Banfield et al. 1990).
Furthermore, the ordering of vacancies and metal ions in some silicates can
result in the formation of an antiphase or twin domain structure that can be
imaged with either amplitude-contrast or phase-contrast TEM experiments, as
in the case of vesuvianite (Veblen and Wiechmann 1991).
contrast. Iijima et al. (1973) interpreted this effect in tourmaline as resulting from
variations in the cations occupying these sites. However, the quantitative
interpretation of such subtle variations in image contrast in terms of the precise
occupancy of individual sites has not been explored.
The theoretical feasibility of imaging individual vacancies and interstitial
defects in minerals has been explored by Bursill (1985). Using computer image
simulation methods, it can be shown that individual point defects should be
observable in bright-field images formed from the central beam and the diffuse
scattering that lies inside the first set of Bragg diffracted beams (i.e., no diffracted
beams contribute to the image). Furthermore, different types of defects should
produce different types of contrast in such images, and hence it should be
possible to differentiate different defect types. Point defects also may produce
interpretable contrast in lattice images, although the strong contrast arising
from the basic crystal structure may overwhelm the defect contrast, unless the
defects are clustered.
Although it is theoretically possible to image the original distribution of
point defects in a mineral, it is essential for such studies to eliminate a variety of
artifacts that can result from specimen preparation and interaction with the
electron beam, as well as to differentiate between surface and bulk defects.
Nonetheless, Bursill (1985) and his coworkers have produced high-resolution
images showing defect clusters in slightly reduced synthetic rutile and chrom-
ium-doped rutile, as well as in several nonmineral structures, including
(Sr,Ba)Nb4 0 12 and (W,Nb)02.93. Bursill and Glaisher (1985) used computer
simulations to interpret images of defects in natural gem-quality diamonds
corresponding to clusters of four missing carbon atoms.
Intermediate between the cases of disordered point defects and ordered
arrays of such defects is the situation known as short-range order, or SRO. In
this case, the defects are ordered, but the size of the ordered domains is too small
(e.g., 10 nm or smaller) to give rise to the diffraction effects generally associated
with ordered structures, such as superstructure spots. Instead, organized diffuse
intensity appears between the Bragg beams in diffraction patterns (Cowley
1950; Clapp and Moss 1968), and dark-field TEM images formed from the
diffuse scattering show a characteristic speckling related to the SRO domain
structure (Howie 1988). However, as shown by Cowley (1973), this speckling
generally cannot be interpreted directly as the SRO domains themselves, due to
electron optical effects such as dynamical diffraction and overlapping of do-
mains in the specimen. An evaluation of the effects of dynamical diffraction on
HRTEM images of thin alloy films with SRO (Tanaka and Cowley 1987)
suggests that at least semi-quantitative interpretations of image intensities are
feasible for this imaging mode. Although most studies of SRO have been
confined to alloys, another example of these diffraction and imaging effects
occurs in the high-pressure hydrous magnesium silicate known as Phase E
(Kudoh et al. 1990). This material contains partially occupied octahedral and
tetrahedral sites, the occupancy of which is correlated over short distances.
Whereas there have been numerous TEM studies of minerals exhibiting
ordered point defects, relatively few systematic studies have explored randomly
3.3 Point Defects and Diffusion in Minerals 175
References
Banfield JF, Veblen DR, Jones BF (1990) Transmission electron microscopy of subsolidus
oxidation and weathering of olivine. Contrib Mineral Petrol 106: 110-123
Bursill LA (1985) The interpretation of HRTEM images of crystals. Ultramicroscopy 18: 1-10
Bursill LA, Glaisher RW (1985) Aggregation and dissolution of small and extended defect
structues in Type Ia diamond. Am Mineral 70: 608-618
Clapp PC, Moss SC (1968) Correlation functions of disordered binary alloys, II. Phys Rev 171:
754-763
Cowley JM (1950) X-ray measurement of order in single crystals of Cu 3 Au. J Appl Phys
21: 24-30
Cowley JM (1973) High resolution dark-field electron microscopy. II. Short-range order in
crystals. Acta Cryst A29: 537-540
Howie A (1988) Highly disordered materials. In: Buseck PR, Cowley JM, Eyring L (eds) High-
resolution transmission electron microscopy and associated techniques. Oxford University
Press, Oxford, pp 607-632
Iijima S, Cowley JM, Donnay G (1973) High resolution electron microscopy of tourmaline
crystals. Tschermaks Mineral Petrogr Mitt 20: 216-224
Isaacson M, Ohtsuki M, Utlaut M (1979) Electron microscopy of individual atoms. In: Hren
JJ, Goldstein JI, Joy DC (eds) Introduction to analytical electron microscopy. Plenum Press,
New York, pp 343-368
Kitamura M, Shen B, Banno S, Morimoto N (1984) Fine textures of laihunite, a non-
stoichiometric olivine-type mineral. Am Mineral 69: 154-160
Kudoh Y, Finger LA, Hazen RM, Prewitt CT, Kanzaki M, Veblen DR (1990) Phase E: a high-
pressure silicate with unique crystal chemistry. Trans Am Geophys Union 71: 528
Nakazawa H, Morimoto N, Watanabe E (1975) Direct observation of metal vacancies by
high-resolution electron microscopy: 4C type pyrrhotite. Am Mineral 60: 359-366
Pierce LP, Buseck PR (1974) Electron imaging of pyrrhotite superstructures. Science 186:
1209-1212
Pierce LP, Buseck PR (1978) Superstructuring in the bornite-digenite series: a high-resolution
electron microscopy study. Am Mineral 63: 1-16
Tanaka N, Cowley JM (1987) Electron-microscope imaging of short-image order in dis-
ordered alloys. Acta Cryst A43: 337-346
Veblen DR, Wiechmann MJ (1991) Domain structure of low-symmetry vesuvianite from
Crestmore, California. Am Mineral 76: 397-404
Point defects may be vacancies, created when a regular lattice site is left
unoccupied, or interstitials, if the normally unoccupied interstices between
regular lattice sites are occupied. These intrinsic defects are present in all crystals
in equilibrium at temperatures above 0 K. Point defects are also required to
accommodate deviations from ideal atomic ratios in nonstoichiometric crystals.
Substitutional disorder is produced by the insertion of an impurity atom/ion
into a normal lattice site. Substitutional disorder can be coupled to the
production of vacancies or interstitials by the insertion of aliovalent cations or
anions. In order to maintain electrical neutrality, this excess charge localized
at the aliovalent ion site must be compensated by an opposing charge at a
neighboring site. Such extrinsic defects are primarily a function of crystal
composition.
A type of substitutional disorder that is particularly important in rock-
forming minerals is the substitution of iron for magnesium in phases such as
olivine and pyroxene. If the oxidation state of the iron is trivalent, a net + 1
charged is localized on that site is produced requiring charge compensation on a
neighboring site; the concentration of point defects is, therefore, dependent upon
the fugacity of oxygen.
The relationship between diffusion and point defects is immediately appar-
ent when one considers the steric complications associated with the alternative,
diffusive transport in a perfect crystal. Diffusion of ions in densely packed
lattices by mechanisms such as direct exchange or cyclical exchange of two or
more ions is highly unlikely, due to the large lattice distortions required
(cf. Schmalzried 1981). As such, the elementary steps in the transport of ions
(and, hence, charge) within a lattice are coupled to the complementary flux of
point defects. The description of diffusion and point defect chemistry are, thus,
inseparable.
Variations in point defect concentrations are a function of the independent
thermodynamic variables and can be formulated using the law of mass action
for the various defect-forming reactions coupled with assumptions of conserva-
3.3 Point Defects and Diffusion in Minerals 177
D = d2 vX e _ [AhmJ (1)
v 3 v RT'
Xv = e-[~J
2RT '
(2)
where A he is the enthalpy of formation for the vacancy (see Lasaga and
Kirkpatrick 1981, for a more detailed derivation of this relationship). Equation
(2) illustrates the concentration of intrinsic vacancy drops exponentially with
temperature; this is in contrast to the relatively constant concentration of
extrinsic defects due to impurity atoms. Hence, at high temperatures, intrinsic
defects dominate the point defect concentrations, but at lower temperatures
extrinsic defects predominate. Comparison of Eqs. (2) and (3) with the Arrhenius
relationship,
D = Do e-[~J
RT'
(3)
indicates that the activation energy, Q, in the intrinsic region is equal to:
Ahe
Q =T+Ahm. (4)
Equation (4) predicts that the activation energy should undergo an abrupt
decrease at the transition temperature between intrinsic and extrinsic behavior
as the concentration of defects is no longer related to temperature in the
178 Chapter 3. Real Structures of Minerals
The relationship between the point defect chemistry of olivine and diffusion of
Fe/Mg, 0 and Si in both Fe-bearing olivine and forsterite has been the subject of
a number of investigations. Such investigations are intimately related to studies
of electrical conductivity, plastic deformation, and thermogravimetry. In many
of these investigations, attempts have been made to constrain the thermodyn-
amic state of the sample during the measurement through the imposition of solid
buffers and f0 2 -controlling gas environments. To date, the thermodynamic
variable of prime interest has been f0 2 , since it can be easily varied over a wide
range of values, and the results can be directly related to the defect models.
Both Fe/Mg interdiffusion (Buening and Buseck 1973; Nakamura and
Schmalzried 1984) and Fe tracer diffusion (Hermeling and Schamlzried, 1984)
have been measured in Fe-bearing olivine (F0 9o). The f0 2 exponent for these
experiments lies between + 1/5 and + 1/6. Based upon thermogravimetric data
from unbuffered olivine, Nakamura and Schmalzried (1983) concluded that the
majority defects are a magnesium vacancy, V~g, a trivalent iron ion on a Mg-
site, FeMg , and the associate [Fe~i Fe Mg ] and that the f0 2 dependence is for V~g is
+ 1/5. For a similar charge neutrality condition, 2[V~g] = [FeMg ], Stocker and
Smyth (1978) found an f0 2 -dependence of + 1/6 for [V~g]. Hence, measured
diffusion of these cations (via a vacancy mechanism) is in good agreement with
predictions based solely upon defect thermodynamics, as well as those based
upon related experimental data.
Silicon has been shown to be the slowest diffusing major species in both Fe-
bearing olivine (Houlier et al. 1988, 1990) and forsterite (Jaoul et al. 1981). Jaoul
et al. (1981) demonstrated f0 2 -independent Si diffusion over nine orders of
magnitude variation in f0 2 for MgO-buffered forsterite. This observation is in
agreement with Smyth and Stocker (1975), who concluded that the concentra-
tion of silicon interstitials, was independent of f0 2 • Houlier et al. (1990) obtained
a - 1/3 fOrdependence for silicon diffusion in Fe-bearing olivine buffered with
orthopyroxene. This is in agreement with the calculations of Stocker and Smyth
(1978), which predicted such a dependence for the concentration of silicon
in tersti tials.
Oxygen diffusion has been measured in both Fe-bearing olivine (Ryerson
et al. 1989; Gerard and Jaou11989) and in forsterite (Jaoul et al. 1980,1983). The
studies agree to the extent that both experiments determined a positive fOr
dependence for oxygen diffusion. However, quantitatively, they are in disagree-
ment. Ryerson et al. (1989) observe a f0 2 -dependence of approximately + 1/5
(Ryerson et al. 1989) while Gerard and Jaoul (1989) observe a f0 2 -dependence of
+ 1/3. In both cases the positive fOrdependence rules out the participation of
3.3 Point Defects and Diffusion in Minerals 179
oxygen vacancies since Stocker and Smyth (1978) have shown that doubly
o, o,
ionized, V and singly ionized, V oxygen vacancies have f0 2-dependencies of
- 1/6 and - 1/3, respectively. Based on comparison with the Stocker and
Smyth (1978) calculations, Ryerson et al. (1989) suggested that oxygen diffusion
takes place by transport of a doubly ionized oxygen interstitial, 0;'. Gerard and
Jaoul (1989) reformulated the calculations of Stocker and Smyth (1978) to
account for the role of singly charged oxygen interstitials, 0;, and found a + 1/3
dependence comparable to that observed in their experiments. Both studies
alluded to the steric difficulties produced by the presence of oxygen interstitials
in a closely packed oxygen lattice.
There is no straightforward or unequivocal manner with which to reconcile
the differences in the two sets of oxygen diffusion data. Gerard and Jaoul (1989)
used a hydrous carrier gas (Ar/H2 + H 2 18 0) while Ryerson et al. (1989)
employed a nominally anhydrous mixture OfCI80/CI802' It is possible that the
presence and transport of 18 0 as hydrous species coupled with differences in
buffer assemblages could be responsible for the differences observed. Zhang
et al. (1990) have suggested that diffusion of 18 0 as hydrous species may be
important in silicates and help in reconciling the differences in diffusion
coefficients measured under dry and wet conditions. Little quantitative informa-
tion ofthe concentration of water in olivine as a function offO 2 and temperature
exists. It is conceivable that such a dependence could influence the diffusivity of
oxygen and its f02-depend~nce. In this regard, Mackwell and Kohlstedt (1990)
have demonstrated relatively rapid hydrogen diffusion in San Carlos olivine.
A number of investigations should be undertaken in order to improve the
data for oxygen diffusion in Fe-bearing olivine. Specific investigations should be
undertaken to determine the effects of hydrous multi-species diffusion on oxygen
diffusion as well as the solubility and homogeneous equilibria of hydrous
species. As part of such an effort, methods for using C180/C180Z without
restriction to solid buffers should be developed to improve the data coverage for
the anhydrous case. Finally, experiments should be conducted imposing vari-
able activities of orthopyroxene. Stocker and Smyth (1978) demonstrate that the
concentrations of defects should vary with silica activity, as well as fO z , and
such measurements would provide an additional means of validating defect
models.
References
Buening DK, Buseck PR (1973) Fe-Mg lattice diffusion in olivine. Geophys Res 78: 6852-6862
Condit RH (1981) An approach to analyzing diffusion in olivine. In: (Schock RN, ed) Point
Defects in Minerals. Geophys Monogr Ser vol 31, pp 106-115, AGU, Washington, DC
Gerard 0, Jaoul 0 (1989) Oxygen diffusion in San Carlos olivine. J Geophys Res 94:
4119--4128
Hermeling J, Schmalzried H (1984) Tracer diffusion of Fe-cations in olivine, (Fe x Mg 1 - x)zSi0 4
(III). Phys Chern Minerals 11: 161-166
Hirsch LM, Shankland TJ (1991) Determination of defect equilibria in minerals. Geophys Res
(in press)
180 Chapter 3. Real Structures of Minerals
Houlier B, Jaoul 0, Abel F, Liebermann RC (1988) Oxygen and silicon self-diffusion in natural
Many of the local (point) defects in solids are paramagnetic or can be made so,
and hence are amenable to study by electronic paramagnetic resonance (EPR) as
well as by optical spectroscopy. In many cases, it is convenient to classify these
into two general types: missing-electron species and excess-electron species, as
compared to some diamagnetic precursor. The concept of holes is useful when
the number of electrons is insufficient to fill a given atomic or molecular orbital.
Typically, when one more electron is required for this completion, i.e., one
negative charge is missing (this is theoretically equivalent to the presence of a
hypothetical positive charge), then one can speak of the existence of a hole in the
orbital, and treat this as a physically meaningful entity. It is fruitful to speak of
the paramagnetism and EPR spectrum of such a hole. However, the concept is
3.4 Point Defects as Precursors of Electron-Hole Centers 181
not universally valuable, e.g., for species HO and Fe 3 + which have half-filled
shells.
Electron and hole centers occur ubiquitously, in solids found in nature as
well as in those prepared by man. They can be important in various areas of the
Earth Sciences: dating rocks by determination of the concentration of such
centers accumulated over geological time; describing the thermal history of
rocks by the use of the thermal stability of such centers; discerning genetic types
of ore deposits, their zonality, and the stages of mineralization. Moreover, the
knowledge of the structural and chemical nature of such centers in minerals and
also in glasses (Griscom 1990), is fundamental in the comprehension of the
physical properties such as electric conductivity and color. The presence of such
defect centers often results in a loss of quality and reliability for using the
crystals, for instance in high-technology applications that depend on their
piezoelectric and nonlinear optical properties (e.g., frequency doubling oflight).
Various different types of electron/hole centers have been observed in
silicates, carbonates, and other minerals. They display a wide variety of struc-
tures and properties, as compared to the traditional atom-vacancy defects
(e.g., the so-called f centers in alkali halides). The former centers appear mostly
in connection with impurities and other nonthermal defects, in crystal structures
greatly different from that of the simple binary halides. Moreover, the centers in
noncubic minerals were observed to be similar to those found in chemistry and
biology representing fragments of molecular radicals, especially ions formed by
trapping or losing an electron. A listing of relevant species and their magnetic
properties has been prepared. (Morton and Preston 1977, 1987; von Zelewsky
et al. ibid). The interpretation of such free radicals in irradiated inorganic
crystals (Atkins and Symons 1967) has given the foundation to the mineralogists
for identifying these centers in natural minerals.
Studies of the electron/hole centers in minerals often are based on the
observation of EPR spectra. The subsequent interpretation of the measured
parameters is based on the molecular orbital pattern of the center, on the crystal
structure, relative covalency, and ionicity of the structure, as well as on the
impurity composition of the mineral. To access a substantial relevant biblio-
graphy focused on the field of mineralogy, the reader may refer to two reviews
(Marfunin 1979; Vassilikou-Dova and Lehmann 1987).
symbolizes the missing atom. Every defect is a potential precursor for various
centers.
In ionic crystals, the presence of an anion vacancy implies the lack of negative
charge. The charge-compensation requirement often results in formation of an
electron center (f center). By contrast, a cation vacancy, or the presence of a
structural cation impurity with a too-small positive charge, implies a local
deficit of positive charge. Such a negatively charged structure can act as an
effective trap for a hole. For instance, in the case of a Na + vacancy in NaCl,
electroneutrality can be achieved via loss of an electron from the outer shell of a
neighboring chloride ion. This (p-orbital) hole is in fact found to be delocalized
over two chloride atoms, forming the "molecular" center el;.
Another kind of electron center is due to substitutional cations with
inappropriate charge states:
X+ IM 2 + IM 2 + +e- IM+.
substitution irradiation electron trapping
Here X is a structural atom and for example could be Na, while its replacement
M could be Mg. The electron source is not specified.
In more covalent materials, similar electron transfers can occur (say, via
irradiation), leading to ions with unusual oxidation states. For example, in
oxides with tetrahedrally coordinated cations, one has:
[X0 4 ]O--+ [X0 4 ] + + e-
[Y0 4 ]O + e- --+ [Y04 r.
The total charge of the local cluster is indicated as a superscript. For instance,
X could be AI, Ga ... , and Y could be Ge, Fe, P, Ti .... The bracket notation
denotes that the cluster is embedded in the crystal structure.
In crystalline quartz, when AI3+ replaces Si 4 +, an electron is easily remov-
able from a neighboring oxygen ion to form what is effectively a hole center, 0-
In such cases, the unpaired electron density is not located at the primary defect
(AI) but is on a structural neighboring site (O). In this sense the trapping process
is not generally symmetric for a hole center as compared to an electron center. In
all cases, the surplus electron or hole is distributed to some extent throughout
a group of atoms and its behavior must be interpreted in terms of molecular
orbitals.
Radicals in Crystals
species. Consider the relatively simple ions denoted by AWn), AB~n), AB~n), and
AB~) (Atkins and Symons 1967). Atoms A and B often encountered include: B,
Al (n = 3); C, Ge (4); N, P, As (5); 0, S, Se (6). Some corresponding diamagnetic
complex ions are BO~ - (n = (1 x 3) + (3 x 6) + 3 = 24), CO~ - (24), POl- (32),
SO~ - (32). Here the charge number q indicated (as an unparenthesized super-
index) is a formal one, that of the sum of all electrons and nuclei in the cluster of
interest, no account being taken of covalency when the ion is imbedded in a
crystal. If the latter situation is to be emphasized, then the notation [AWn)]q may
be used.
By trapping an electron, each of the complex ions listed above can become
an electron center (e.g., PO!- (33), with formal valency p 4 +). The unpaired
electron is found in a molecular orbital derived mainly from the sand p orbitals
of the central cation.
By losing an electron, the diamagnetic complex ions become hole centers
[e.g., PO~ - (31)J; the remaining unpaired electron occurs in a molecular orbital
consisting predominantly of oxygen nonbonding orbitals.
These processes can be written as reactions:
CO~- + M2+ -CO~- + M3+ electron center (e.c.)
CO~- + M2+ -CO;- + M+ hole center (h.c.)
For more information regarding the EPR technique and relevant notation,
the reader is asked to refer to Chapter 10.8, this volume. The identification of
electron/hole centers from EPR spectra generally occurs in two stages:
1. Observation ofthe EPR spectrum. Relevant information includes the number
of absorption lines, their intensities, the line splittings, and the behavior of the
spectrum on rotation ofthe crystal relative to the applied static magnetic field
(flux density) B. The field magnitude, B, is measured in units of Teslas or
Gauss (1 mT = 10 Gauss).
2. Interpretation of the measured parameters based on the molecular orbital
pattern of the centers, as well as on the crystal structure and impurity
composition of the mineral.
These two stages of the study generally allow identification and site assignment
of the paramagnetic center in the crystal. Let us turn to details of these stages:
184 Chapter 3. Real Structures of Minerals
1. The Number of Lines. In most cases, a single fine-structure line occurs and is
due to an electron or hole center with an electronic spin S = 1/2. In the presence
of nuclear spins I on the central and neighboring atoms, the electronic-nuclear
spin coupling(s) leads to splitting, i.e., hyperfine structure (HFS) in the spectrum.
In the presence of a Zeeman interaction, the relevant energy operator (spin
Hamiltonian) is
N
JI'=PB·g·S+S·A
e 0 ·1+ "S·A.-f.
~ 1 P
i-I
intensities, whereas the AI3+ -0- -AI3+ center in alkali feldspars shows 11 lines
with unequal intensities (Fig. 33). Here the notation -0- - denotes the absence
of the non bonding electron from the oxygen ion, i.e., presence of a hole.
If there are several isotopes with applicable abundance (some with nonzero
nuclear spin), then the spectrum is more complex, and the intensity of the lines
arising from the hyperfine couplings is a function of the natural abundances of
the isotopes (e.g., boron: lOB 18.83% I = 3, and liB 81.17%, I = 3/2; evenSi
95.33%, I = 0; and 29Si 4.67%, I = 1/2). The hyperfine splitting patterns provide
valuable clues for the interpretation of EPR spectra. Furthermore, the hyperfine
splitting values L1A often allow identification of the different paramagnetic
centers. Thus, for phosphorus: 31 P 100% I = 1/2, the L1A values occur in the
ranges: PO!- (110-120mT), POI- (2-5), PO~- (45-70), and PO~- (4-9).
AI-O--Si
AI-O--AI
I
314 324 334 344
MAGNETIC FIELD B(mT)
to the principal values of gx gy gz and in the same way the three values (for each
nucleus) of the principal hyperfine parameters Ax Ay Az, which often but not
always occur at nearly the same crystal positions as those for g. The values and
the corresponding orientations of the g principal axes and HFS axes (of A)
relative to the crystal-axis system generally allows one to locate the center and
to suggest a possible model for it. Moreover, the form of the g and A matrices is
connected with the symmetry (e.g., group C 3v for CO~ -) of the paramagnetic
species.
3. The HFS Components. The principal values Ax, Ay, and Az give details of the
hyperfine coupling, and thus an idea of the highest occupied molecular orbital
involved in the paramagnetic center. The isotropic component Aiso = (Ax + Ay
+ Az}/3 of A is related to the magnetic interaction of the unpaired electron (in
186 Chapter 3. Real Structures of Minerals
the s-electron orbital portion of its wavefunction) with the nucleus; the aniso-
tropic part Aaniso is related to interaction of the unpaired p (also d and f, if any)
electron(s) with the nucleus. Thus the relation between those two parts yields the
degree of sp hybridation of the unpaired-electron wavefunction.
If the unpaired electron resides in a molecular orbital formed chiefly from the
central-atom orbitals, then the magnitude of the hyperfine interaction with the
nucleus of the central cation is strong and consequently a substantial splitting
---- 5 01 ,*
----20~*
2pC
2pO
V--' /, 25C
H
h'--ft 10 2
Ie"
A
3e
##
#=fF 2e'
I
I
I 2e
#=4f
H I02II I
ENERGY 50 1
H
HH Ie' Ie
##
tf 40 1
I
40 1
H
. 5 , 52 5 3 5 15 2 5 3
~
As,(2"? (0,,) AS,(2'¥C,,)
Fig. 34. Qualitative molecular-orbital schemes for radicals ABj23) (planar: CO.l. PO~) and
AB~25) (pyramidal: CO~ -, PO~ -, S0.l). The energy levels are labeled with group-theoretical
symbols. The 23rd electron (ABj23/) is in the non bonding molecular orbital la~ formed
primarily from atomic 2p orbitals of the three oxygens; thus the interaction of the 23rd electron
with the central nucleus is weak, and the hyperfine structure very small. The 25th electron
(AB~25») lies in the molecular orbital 6aj formed mainly from sand p orbitals of the central
atom; thus large hyperfine structure occurs in the EPR spectrum. (Marfunin 1979, p. 250)
3.4 Point Defects as Precursors of Electron-Hole Centers 187
is visible in the EPR spectra (when I > 0). If the molecular orbital is based
primarily on nearest-neighbor atoms, say it is formed from oxygen orbitals, then
there is a weaker interaction of the electron with the cation nucleus, as evidenced
by a much smaller (superhyperfine) splitting in the EPR spectra. The molecular-
orbital situation for two such situations is depicted in Fig. 34.
The sign of the shift Ag = g - ge (where ge = 2.00232 is the free-electron
value) of the g-factor measured is determined by the relative ordering and
energies of various outer-electron molecular orbitals. The analysis is complic-
ated. The Ag value tends to be negative for electron centers and positive for hole
centers, but depends also on covalency effects.
Let us turn to some examples. In irradiated calcite, the 13C (1.11 % abun-
dance, I = 1/2) hyperfine structure visible in the EPR spectra of C0 3 center
AB~23) is relatively small (ca. 10 G, nearly isotropic) due to very weak interaction
between the 23rd electron and the central nucleus (Serway and Marshall 1967).
In the case of the CO~- radical AB~25), interaction with the central atom
is strong and hence the hyperfine structure in large (Ax = Ay = 111 G and
Az = 171 G). These species are, respectively, isoelectronic with (for instance)
N0 3 and NO~ -, and thus are similar in their EPR characteristics.
Electron paramagnetic resonance of a natural barite crystal (Ryabov et al.
1983) has revealed the presence of several distinct electron centers (Fig. 35). Ions
S03 and PO~ - both belong to the radical type AB~25), with the 25th (unpaired)
even 80 3- ~
even 802-
\1\
10- 2
r
X
j
r
~ ~+ +---i
Fig. 35. EPR spectra of oxygenic phosphorus and sulfur radicals in barite (290 K; X band;
Bllb), exhibiting site splittings and showing central-nucleus hyperfine multiplets. (Ryabov et al.
1983)
188 Chapter 3. Real Structures of Minerals
electron in the molecular orbital 6at. The two centers evenS03" and evenso; do
not show hyperfine structure (S33 = 1/2 and 1 = 0 for all nuclei), i.e., show only
one line. The 33S03" center (S = 1/2,1 = 3/2) shows 21 + 1 = 4 lines with a large
hyperfine splitting. The two different 31PO~- centers (S = 1/2, 1 = 1/2) show
two lines with a very large hyperfine splitting. The ions SO; belong to the
ABi19 ) radical type with the 19th electron in the antibonding molecular orbital
2bt formed mainly from a p orbital of the central atom.
Table 23. Systematic survey of the electron/hole centers in inorganic compounds and minerals
ne
1 F center F+ = F- Sl HO Lio Mg+ Ca+ Be2+ Ge3+ p 4+
()(-center Pb 3 +
2 F(2) = F(~) F(l) pI Tl o Pb+
M-center
3 F(3) = F(;) F(3) dl Ti3+ V4+(*) Cr 5+ Mn 6 yZ+ Zn3+ ...
R-center * often occurring as VOZ +
4 F(4) = dn Fe+ ~ Fe z + ~ Fe3+ ~ Fe 4 + Ni+
N-center ~ Ni2+ ~ Ni3+ ...
d10S l Cu o AgO Zn +
fn RE+ ~ RE2+ ~ RE3+ ~ RE 4+
Because of the selected bibliography, all the results presented in this chapter are
not referenced. For more information the reader may write to the authors. Most
electron/hole centers are formed by natural or artificial irradiation (IX-, X-, y-rays,
electrons, neutrons). Numerous studies on electron-hole centers in major rock-
forming minerals (such as quartz, feldspars, calcite, anhydrite, and accessory
minerals such as zircon and apatite) have been carried out (e.g., see the two
reviews cited in the introduction). The technique provides an excellent means for
characterizing these minerals and the rocks enclosing them. We turn now to
some specific systems:
Quartz. Crystalline silicon dioxide is the most studied mineral, not only on
natural specimens because of its geological importance, but also on synthetic
crystals on account of the fundamental interest in it and its technological
applications (e.g., electronic oscillators and laser modulators). Quartz can be
called the "hydrogen atom" of minerals. The EPR characteristics of the different
center types have been reviewed (WeilI984) with 230 references. In IX-quartz, the
space group is P3 1 21 or P3 2 21 (left or right quartz), each with two sets of crystal
twofold rotational axes (the first set bears silicon atoms; the second, at 30° to set
1, carry no atoms) which are electrically polar. The local symmetry at each Si0 4
tetrahedron is only the twofold axis, consistent with the presence of two Si-O
bond types with lengths: "short" 1.610 and "long" 1.645 A at 94 K (Fig. 36a, b).
Perfect (ground-state) quartz would not contain unpaired electrons and hence
would yield no EPR spectrum. In practice, numerous paramagnetic centers arise
from impurity ions (Ag, AI, Cu, Fe, Ge, H, P, Ti) as well as from centers (E')
associated with oxygen vacancies in the quartz structure. The kind of charge-
compensator ions M+ (H+, Li+, Na+, Ag+) present in the structural channels,
as well as the exact positions of the compensators, cause occurrence of many
varieties of the centers.
/\
Y
o SILICON
o OXYGEN
/\
~~~~--~~~------~~---+ X
""
If"
I, 1\
" Z
""
"
Lx
/I
,
""'6il- .
~--"':'~~if.{}-=':'::'-~. ::.:---.
>r
/1/
H
I"
,I "
/I
,I ""
Fig. 36a, b. a-Quartz structure (a) projection onto the plane perpendicular to the c axis
(b) Si0 4 tetrahedron showing two non-equivalent Si-O bonds and two possible sites for
interstitial ions in the middle of the large c-axis channels. (Weil 1984)
B
1.0 mT '1
C t
ENERGY
causing broadening of the EPR spectrum. The hole transfer also can be induced
by absorption of light (smoky quartz color), and this has been studied (Meyer
et al. 1984) by optically detected magnetic resonance (ODMR). In addition, by
irradiation below 77 K without subsequent warmup, an unstable center
[AI0 4]+ forms and can be observed by EPR. This species contains two holes,
on nearest-neighbor (short-bond) oxygen ions related by the structural twofold
symmetry axis, in a triplet state. Similarly, a center in which four protons appear
to have replaced a Si 4+ ion leads on irradiation to an oxygen hole center
[(OH)4] + which transforms to [O(OHh]O by proton loss, both observable
by EPR.
r
The [Ge0 4 center (formally Ge3+) is obtained in the same way, by
electron trapping at the diamagnetic precursor [Ge0 4]o. EPR spectra from the
ground-state species as well as from a thermally accessible excited-state species,
[Ge04]~' are observed. However, above 100 K, charge compensation occurs,
via migration to the anions of Li + ions along the c-axis channels. Thus the two
best-known centers are [Ge04/Li]O with Li+ in either of two different sites.
With Na + as compensator ion, only one such center is stable at 300 K, and none
occurs with H + or K + ions. Other Ge 3 + centers have been observed, including
[Ge04/H-Li+Li+]O and [Ge04/H-H+H+]o.
With phosphorus as an impurity, X-irradiation creates p 4 + centers. Here as
with germanium, two EPR spectra, from [P0 4]O and [P04]~S' are observed. In
192 Chapter 3. Real Structures of Minerals
another a-quartz species, the EPR hyperfine structure has been attributed to the
cluster [03AI-0- -P0 3]+ (Maschmeyer and Lehmann 1983).
In natural rose quartz, the diamagnetic species [Ti0 4]0, as a result of
X-irradiation below tOO K, accepts an electron to yield the 3d 1 center [Ti0 4 r,
which is unstable at room temperature. On warming, diffusion of an M + cation
leads to formation of centers [Ti0 4 /Li]O, [Ti0 4 /Na]O and/or [Ti0 4 /H]o. The
latter is formed from [Ti0 4 ]O by accepting a hydrogen atom. Various iron (III)
centers have been characterized, corresponding to substitutional sites, including
[Fe0 4r, [Fe0 4 /H]o. [Fe0 4 /Li]O, [Fe04 /Na]O and [Fe0 4 ]o. The EPR spectra
of [FeO 4] - have been used to investigate the a-fJ phase transition of crystalline
quartz (847 K) and of berlinite (Lang et al. 1977).
Centers Due to Oxygen Vacancies. The best-known such center, E'l' (Fig. 38a, b)
results from a missing bridging oxygen ion between two silicon ions and can be
depicted as [03Si· Si0 3] +. The unpaired electron is predominantly located on
one silicon ion, Si(1). The presence of E'l centers is applicable in mine prospect-
ing (Chatagnon 1986). A similar center, E~, is found in irradiated quartz and
exhibits EPR hyperfine structure attributed to a remote hydrogen ion, with the
unpaired electron density appearing to be greatest on Si(2) (Fig. 39). The E~
center simultaneously present contains a proton bonded as a hydride ion:
[03Si' H: Si0 3]O; this increasingly hops between the Si ions as the temperature
is increased.
Various discussions on the origins of quartz coloration have been published,
as well as investigations of defects in shock-loaded quartz, connected with
metamorphism.
Feldspars. The distribution of centers varies in the many feldspar types. Micro-
cline presents the greatest number of centers, followed by orthoclase, sanidine,
plagioclases, and their end members albite and anorthite. Irradiation develops
oxygenic hole centers 0 - in all feldspars.
The replacement Si --. Al here too is the principal cause for various para-
magnetic centers to be observable. In feldspars, each structural alumina tetra-
hedron normally is surrounded by four silica tetrahedra. The replacement of a
silicon by an aluminium ion produces a local structure Al (structural) -0 - -AI
(impurity) with loss of an electron from the bonding oxygen between the two
tetrahedra. The number of lines in the EPR spectrum of such a center is
2 (2 x 5/2) + 1 = 11. The number of nonequivalent centers observed in the feld-
spar depends on the symmetry (triclinic or monoclinic) and on the twinning
(cross-hatched in microcline) present. Other centers occur as clusters containing
at least three aluminium ions. They are not detectable by EPR except at low
temperatures, indicating that here too the hole is rapidly transferred between
nearly equivalent oxygens. The probability for having such a cluster increases
3.4 Point Defects as Precursors of Electron-Hole Centers 193
+ +
1\
Y
f------'.,. 1\
X
markedly as the Al/Si ratio approaches the value 2. It seems that the Si-O - -AI
center, only observed after low-temperature ( < 77 K) irradiation, is unstable,
relative to the AI-O- -AI center at higher temperatures.
In amazonite, a pale-green variant of microcline (KAISi 3 0 s), the Pb impu-
rity center is converted to Pb-O- -x by X-irradiation and the color thereby
194 Chapter 3. Real Structures of Minerals
...
~~
O.2SmT
I I I I
, f I I I
E4 'L __________ I ___________ IL __________ .JI
~
Fig. 39. EPR spectra of centers E~ and E~ in a-quartz (300 K; 9.8 GHz; Bile) normal hyperfine
I H doublet of E~ and unusual 1 H quartet of E~, with 29Si superhyperfine structure on both.
([soya et al. 1981)
attains a brownish tint. A [Ti04]O center is reported in some feldspar types - its
principal EPR values are similar to those observed in quartz. The formation of
NHj and N 2 - centers from NHt ions is connected with the presence of M +
vacancies. The NHj EPR spectrum disappears after heating the specimen to
temperatures higher than ca. 470 K, whereas the N 2 - center is stable up to
ca. 820 K. Also observed were the formation of atomic hydrogen from an
OH- group, and the E'l center (similar to the E~ center in quartz) stable up to
ca. 420 K.
The study of irradiation defects in 15 feldspars of various compositions
(utilizing EPR, optical absorption, and thermoluminescence emission bands)
shows that these are remarkably independent of the mineral specimen, composi-
tion, and AI/Si structural disorder.
Cubic Ionic Crystals. Many detailed studies of the defects in alkali halides,
alkaline oxides and chalconides have been published. Commonly, sites where
atoms (ions) are missing from the regular structure lead to paramagnetic species
amenable to EPR investigation.
The first color-center studies were performed on the F centers in alkali
halides. The understanding of their properties has been arrived at with the use of
polarized absorption, luminescence, and (above all) with EPR and electronic-
nuclear double-resonance (ENDOR) spectroscopy. These methods have con-
firmed that the F center is an electron trapped at an anion vacancy, and that the
electron interacts equally with the six nearest-neighbor cations.
EPR spectroscopy shows that the F-center electron interacts not only with
the six nearest cations but also with anions and cations in further coordination
spheres, up to the 16th. The EPR spectrum shows an unusually broad band,
from 58 Gauss in KCl to 800 G in CsC!. The broadending is due to the resol-
ved hyperfine structure arising from interaction of the F-center electron
with neighboring nuclei such as 6.7Li, 23Na, 39.41 K, 85. 87Rb, 133CS or
196 Chapter 3. Real Structures of Minerals
19F, 35, 37 Cl, 79,81 Br, all with nonzero nuclear spins and appreciable natural
abundances. The densities of the spin states determine the relative intensities of
the hyperfine-structure lines. In some alkali halides (LiF, NaF, RbCl, CsCI),
partially resolved hyperfine structure has been observed. The use of ENDOR
substantially improves the resolution, making it possible to measure transitions
between nuclear spin levels and enabling measurement of the isotropic and
anisotropic parts of the electron-nuclei hyperfine interactions.
The F centers give intense bands (e.g., at energy 2.6 eV) in optical absorption
spectra, corresponding to electronic transitions. The F-center concentration can
be determined by measuring the optical absorption coefficient, by chemical
analysis, magnetic susceptibility measurements and by EPR intensity measure-
ments. In addition, aggregate F centers called f(2) ... f(4) form in alkali halides,
corresponding to clusters of two, three, and four F centers.
The F center also occurs in other crystalline compounds in which halogen,
oxygen, sulfur vacancies trap electrons, e.g., in compounds with the fluorite
structure (CaF 2, SrF 2' BaF 2) or with the rutile structure (MgF 2)' In apatite and
fluorite, one finds F centers each consisting of a fluorine vacancy containing a
trapped electron, and 0 2- centers formed due to the substitution 0 2- ~ F - .
The centers in fluorite allow its use as a radiation dosimeter. In these, the g-
factor values exhibit a greater shift ~g than in the case of the alkali halides. The
features of the hyperfine structure of EPR spectra are dominated by the isotope
compositions of the nearest cations. Nonmagnetic nuclei prevail in the alkaline-
earth compounds. In alkaline-earth oxides, the F center contains two electrons
in an anion (X2 -) vacancy, and thus is neutral. Because of spin pairing, it is
diamagnetic and EPR-mute. Optical excitation can unpair the electrons, yield-
ing a triplet state accessible to EPR, as is the ionized center F (Henderson and
Wertz 1977). The F center is also thought to be present in silicates such as
sodalite and zeolite (but not in quartz).
References
Atkins PW, Symons MCR (1967) The structure of inorganic radicals. An application of
electron spin resonance to the study of molecular structure. Elsevier, Amsterdam
Bershov LV, Marfunin AS (1967) Paramagnetic resonance of electron-hole centers in minerals.
Dokl Akad Nauk 173: 410-412
Bershov LV, Martirosyan VO, Marfunin AS, Speranski AV (1975) EPR and structure models
for radical ions in anhydrite crystals. Fortschr Mineral 52: 591-604
Bill H, Calas G (1978) Color centers associated rare-earth ions and the origin of coloration in
natural fluorites. Phys Chern Mineral 8: 161-166
Chatagnon B (1986) La resonance paramagnetique electronique du center E'l dans Ie quartz.
Aspect fondamental et interet en geologie et en prospection miniere. These d'Etat INPL
Nancy
Edgar A, Vance ER (1977) Electron paramagnetic resonance, optical absorption and magnetic
circular dichroism of the CO; molecular ion in irradiated natural beryl. Phys Chern
Mineral 1: 165-177
Griscom DL (1990) Electron spin resonance. Glass Sci Technol 48: 151-251
Henderson H, Wertz JE (1977) Defects in alkaline earth oxides. Wiley, New York
3.5 Structural Types of NonStoichiometry in Minerals 197
D.R. VEBLEN
Some minerals possess virtually fixed stoichiometry, with the coefficients in the
structural formula all being integers. Naturally occurring quartz, for example,
does not deviate far from pure Si0 2 • Many other minerals, however, can exhibit
198 Chapter 3. Real Structures of Minerals
The simplest types of point defects that cause variations in mineral stoichio-
metry are vacancies (missing atoms in normally occupied crystallographic sites)
and interstitials ("extra" atoms that occur at normally vacant positions in the
structure). Vacancies and interstitials can involve either cations or anions.
Cation Vacancies
the defects on a given site may be vacancies for one structure but interstitials
relative to another, closely related structure (as in the case of the amphibole
A-site).
Spinel Structures and Hematite. Numerous materials that crystallize with the
spinel structure exhibit deviations from the ideal stoichiometry A2+ B ~ + 4,
yielding formulae of the type DX/3Ai~xB~~2x/304' where A and B refer to
°
tetrahedral and octahedral sites respectively. Here we consider two important
cases, spinel proper (Mg-Al) and defect Fe-rich spinels, which have been studied
extensively as ceramic and magnetic materials and are important for rock
magnetism. In the Mg-AI-O system, Viertel and Seifert (1979) synthesized and
characterized physical properties of a large number of spinels ranging from
stoichiometric MgAl204 to the defect spinel y-AI 20 3, or AI 2.67 0 4, which is an
important catalyst support material. This alumina material, which is commonly
synthesized by dehydroxylation of Al hydroxides, can occur with either dis-
ordered or ordered vacancies. The structural chemistry of intermediate com-
positions is very complex, with cation vacancies potentially occurring on both
types of sites, variations in Mg and Al occupancies, and, in some cases,
interstitial cations as well; the exact defect structure depends not only on
composition, but also on the precise synthesis route and conditions of equilibra-
tion (Moroz et al. 1987). The details of the non stoichiometry are important,
because they can influence the mechanical properties of Mg-AI-O ceramics
(Chiang and Kingery 1989).
Because of their importance as carriers of rock magnetism and in magnetic
recording media, the defect structures of magnetite, Fe 30 4, the defect spinel
maghemite, y-Fe203' their compositional intermediates, and titanium-substi-
tuted variants have been examined extensively by X-ray, electron, and neutron
diffraction (Fleet 1982; Greaves 1983; Boudeulle et al. 1983), as well as by
Mossbauer spectroscopy (Weber and Hafner 1971; Collyer et al. 1988) and by
measurement of electrical and magnetic properties (O'Reilly 1983; Wu and
Mason 1981). The defect structures and their relationship to physical properties
are reviewed by Gleitzer and Goodenough (1985), and Lindsley (1976) reviewed
the departures from stoichiometry that occur in the magnetite-ulvospinel series
(ideally Fe30cFe2 Ti0 4).
Fe-rich spinels, like their Mg-AI-O counterparts, possess a range of defect
structures involving both vacancies and interstitial atoms. Even nominally
stoichiometric magnetite at room temperature has interstitial Fe atoms that
form defect clusters with surrounding vacancies. The interstitials and vacancies
can occur in both octahedral and tetrahedral sites; octahedral vacancies as high
3.5 Structural Types of NonStoichiometry in Minerals 203
as 7% have been reported (Fleet 1982). The defect structure is annealed out at
high temperatures, where stoichiometric magnetite approaches the ideal inverse
spinel structure (Fleet 1984). In maghemite, the vacancies appear to be predom-
inantly on the octahedral sites and can order, leading to a reduction from cubic
to tetragonal symmetry (Smith 1979; Greaves 1983). Collyer et al. (1988) showed
that the vacancies in titanomaghemite also occur on the octahedral sites
and discussed the structural formula of this nonstoichiometric oxide. As in
Mg-AI-O spinels, the exact defect structure of Fe 3- x0 4 and titanomaghemites
that accommodates the non stoichiometry is strongly dependent on the condi-
tions and mechanisms by which the material formed (O'Reilly 1983). Most, ifnot
all, maghemites also contain hydrogen, but its precise structural role and
whether H is an essential component have not been resolved.
The iron hydroxide goethite, nominally IX-FeOOH, always contains excess
water, presumably in the form of interstitial H 20 molecules. During dehydrox-
ylation, the goethite framework collapses to a nonstoichiometric hematite-
like structure, Fe2-x/3(OH)x03-x, with x approximately equal to 1 (Wolska and
Schwertmann 1989). Upon further dehydroxylation, another transitional, hema-
tite-like phase appears at x ~ 0.5, before finally being replaced by a true
hematite structure that is still hydrogen-bearing and non stoichiometric.
Wustite and M agnesiowustite. Wiistite is important both for materials science (it
is a major component of the oxide scale that forms on iron alloys) and earth
science (magnesiowiistite is thought to be an important lower-mantle phase).
The defect chemistry of wiistite is very complex and has been covered by several
reviews (Hazen and leanloz 1984; Gleitzer and Goodenough 1985; Mrowec and
Podg6recka 1987). Although wiistite is here classified in the section on cation
vacancies, interstitial defects play an equally essential role in the defect chemis-
try and nonstoichiometry. The chemical formula is commonly written Fe1-xO,
but it should more properly be given as VI[Fei '::3xFe~:_t D x+t] IVFe~ +0, where
VI and IV indicate octahedral and tetrahedral coordination, to emphasize the
nature of the defect chemistry (Hazen and leanloz 1984). Ideal, stoichiometric
FeO possesses the NaCI structure, and since the early work of Roth (1960),
numerous diffraction and spectroscopic studies have confirmed that the primary
cause of nonstoichiometry in wiistites is a defect cluster in which a Fe 3+ ion
occupies a normally vacant tetrahedral site in the FCC oxygen framework. The
occupied tetrahedral site is surrounded by four vacant octahedral sites in a
tetrahedral arrangement. These 4/1 clusters can order to form larger clusters,
as shown in Fig. 41. The magnetite structure contains 4/1 clusters that share
corners, but the predominant defect types in wiistite involve 4/1 clusters that
share faces and edges.
In addition to diffraction studies, there have been numerous investigations of
the physical properties of wiistite and magnesiowiistite. The precise defect
structure and physical properties strongly depend on the method of synthesis
and history of the sample (Hazen and leanloz 1984). It is not yet clear whether
diffusion in wiistite occurs by the movement of nondissociated defect clusters or
204 Chapter 3. Real Structures of Minerals
14/11 =
Type 1
Type 2
Type 3
17/21
~17/21 @16/21
116/51 fHj.
• • 19141
@ """ ti1Y
~113/81
Fig.41. Defect clusters in wiistite. At the top right is shown an isolated cluster, which consists
of an interstitial Fe 3 + atom (triangle) surrounded by a tetrahedron of octahedral vacancies. In
the remaining diagrams, these clusters are represented by cubes in which the interstitial atom is
shown as afWed circle. The clusters may be linked by corners (Type 1), as in magnetite, but
face-sharing (Type 3) clusters apparently are the most common, followed by edge-sharing
clusters (Type 2). The symbols are derived from the ratios of vacancies to interstitials in the
cluster. (Hazen and leanloz 1984)
by the migration of free vacancies dissociated from the clusters (Mrowec and
Podg6recka 1987).
Sheet Silicates. Like the rock-forming amphiboles, many sheet silicates are
almost invariably nonstoichiometric, but with both partially filled interlayer
sites (analogous to the amphibole A-site) and nonintegrally filled octahedral
sites. In addition, many sheet silicates are prone to non stoichiometry resulting
from mixed-layering defects, as discussed below. Most 2: 1 sheet silicates
(e.g., micas, illite, smectites, talc) are apparently seldom, if ever, truly stoichio-
metric, although it is extremely difficult to determine accurately the degree of
nonstoichiometry, due to the problems of renormalizing analyses and in finding
suitable crystals for single-crystal diffraction studies. Due to chemical substitu-
tions that commonly involve all of the metal sites, the interlayer sites are almost
invariably only partially occupied (Foster 1960; Guidotti 1984). Based on
hundreds of analyses from the literature, Guidotti (1984) indicated that inter-
layer occupancies are generally 0.90 to 0.96 in muscovite and also deviate from 1
in biotite, although analytical ambiguities prohibit accurate determinations of
vacancy concentrations and H 30 + may occupy some of the apparent vacancies.
The nonstoichiometry varies with rock type and conditions of equilibration
(Wang and Banno 1987). Muscovite, which is nominally dioctahedral, typically
shows octahedral occupancies ranging from 2.01 to 2.05, rather than the
stoichiometric ideal of 2; there are thus 1 to 5% interstitial cations in the
nominally vacant octahedral sites. Similarly, octahedral occupancies in biotites
(nominally trioctahedral) generally range from 2.80 to 2.95, indicating approx-
imately 2 to 7% vacancies. The sodium trioctahedral mica wonesite is highly
nonstoichiometric, with interlayer occupancy close to 0.5 (Spear et al. 1981;
Veblen 1983a). Pyrophyllite octahedral occupancies vary between 1.95 and 2.05,
and those of talc can show minor deviations from the ideal occupancy of 3.0.
Na, K, and Ca in talc and pyrophyllite may be accommodated as inter-
layer interstitials, or as planar defects (Evans and Guggenheim 1988, and see
below).
206 Chapter 3. Real Structures of Minerals
Illites and smectites, which are important 2: 1 clay minerals, are by definition
nonstoichiometric, with much larger proportions of vacancies in the interlayer
sites. Illites commonly show interlayer occupancies of about 0.75 (Srodon and
Eberl 1984), while smectites exhibit wide variations with interlayer occupancies
as low as about 0.25. The interlayer cations in smectites are exchangeable, and
smectite interlayers can swell, as described in the section on interstitial cations
and molecules.
Framework Silicates and Silica Minerals. Substitutions of the type (K, Na, Li,
1/2Ca, etc.) AI ...... D Si can produce substantial deviations from stoichiometry in
framework silicates and silica minerals (Veblen 1985a). Feldspars can show
substantial deficiencies in alkali cations or Ca, attributable to solid solution
involving a component such as D Si 4 0 8 (Smith and Brown 1988). Anorthite can
form solid solutions with Si0 2 attaining up to 11 % vacancies on the Ca sites
under some conditions (Ito 1976; Longhi and Hays 1979), as can the alkali
feldspars. Diffusion studies suggest that, when small in number, the defects
responsible for feldspar nonstoichiometry are largely dissociated at high temper-
atures (Behrens et ai. 1990).
The feldspathoid leucite and stuffed derivatives of tridymite and cristobalite,
such as nepheline, can show a marked deficiency ( > 10%) in alkali cations and
excess Si, due to a coupled incorporation of vacancies and Si replacing AI, as in
feldspars (Deer et ai. 1963; Edgar 1984; Rossi et ai. 1989). The reverse substi-
tution (i.e., interstitial alkali cations coupled with substitution of Al for Si) can
occur in the silica minerals with open frameworks, and analyses of naturally
occurring terrestrial tridymite and cristobalite invariably show substantial
alkali ions and AI.
In the previous section, it was noted that a number of mineral groups that show
major deviations from stoichiometry due to cation vacancies also exhibit
important deviations due to interstitial defects (e.g., magnetite, wiistite, some
sheet silicates, silica polymorphs). Here we explore additional examples, where
cation or molecular interstitials form the major contribution to the non-
stoichiometry.
<
of cations. The occupancy of the tunnel
sites depends on the Mn oxidation state.
(Post and Bish 1989)
Zeolites possess very open alumino silicate frameworks and can possess
cation-vacancy non stoichiometry analogous to that exhibited by feldspars. In
addition, zeolites with interconnected tunnel structures can absorb variable
amounts of interstitial water, commonly referred to as "zeolitic water," and are
hence generally nonstoichiometric with respect to H 20. Similarly, many zeolites
can absorb other molecular species that can fit through the apertures of their
tunnels. This interstitial nonstoichiometric behavior of swelling clays and
zeolites gives them a number of industrially useful chemical properties, such as
catalytic activity (Barrer 1978).
Anion Vacancies
ted from satellite intensities of a mullite with x = 0.40 to show that the
modulation results from two ordering patterns, one of occupied and vacant Oc
sites and the other of tetrahedral Al and Si. Their results are consistent with the
theoretical considerations of McConnell and Heine (1985). The modulated
structure and associated microstructures at different compositions have been
imaged with HRTEM, and computer simulations have been used to interpret
the images (Nakajima and Ribbe 1981; Schryvers et al. 1988; Rahman and
Weichert 1990). Wei berry and Withers (1990) used a novel approach in which
they obtained optical diffraction patterns from masks prepared by Monte Carlo
generation of defect structures. They compared these patterns with X-ray diffuse
scattering observed with a position-sensitive detector system. The diffuse
scattering favors a model in which each Oc atom is bonded to only three, rather
than four, tetrahedral cations. Mullite is thus a good example of how new
diffraction, imaging, and theoretical methods can work together in the develop-
ment of structural models for incommensurate nonstoichiometric materials.
Perovskite Structures and their Derivatives. Synthetic mixed oxides with the
perovskite structure are commonly nonstoichiometric as a result of planar
defects (discussed below), oxygen point defects, or both; the equilibria of defects
in oxygen-deficient perovskites have been reviewed by Smyth (1989). Depending
on their concentration, oxygen vacancies may be isolated, ordered into linear
arrays, arranged in microdomains of ordered rows, or ordered into defect planes
which can themselves occur in either ordered or disordered sequences (Grenier
et al. 1981; Gonzalez-Calbet et al. 1987). Vacancies in the oxygen sites can result
in unusual four- and five-fold coordination polyhedra for the cations, and there
are numerous structures based on different arrangements of these polyhedra and
the normal perovskite polyhedra (Reller et al. 1984).
The new high-temperature ceramic superconducting materials are non-
stoichiometric, perovskite-derivative layer structures, such as YBa Z Cu 3 0 7 - 0 • In
some of these structures, the superconducting properties depend critically on the
number of oxygen vacancies (15), which is coupled with the valence of Cu.
Nonstoichiometry in these oxide superconductors is reviewed by Raveau et al.
(1990).
Anion Interstitials
0 0 0 0 0 0
• •
0 0
• •
0 0
0 0
• • Fig. 44. The complex cuboctahedral
0 0 defect cluster in V0 2 +x' The sym-
bols are as follows: (0) normal oxy-
• • gens at z = ± 1/4; (e) uranium at z
= 0; (®) oxygen interstitials at z
0 0 0 0 0 0 = 0; (EEl) oxygen interstitials at z
_Go = ± 1/4. (Murray and Willis 1990)
3.5 Structural Types of NonStoichiometry in Minerals 211
I ,
I I
I I
I I
I I
I I
B~.B
I I
I I I
I I, ,I I
I I, I I
I I ,. I I
I I I
I I I
I I I
I I I
I I I
Pra : Mica Pya Mica Pya: Mica : Pya
Pya Mica Mica Pya MiCO Mica Pya Mico Mir.o Pya:
b
Fig. 45a, b. Clinoamphibole (a) and the triple-chain silicate clinojimthompsonite (b), showing
that these structures are comprised of (010) mica and pyroxene slabs in the sequences (MP)
and (MMP). (Thompson 1978; Veblen 1981)
Because they are constructed from exact ratios of two different components,
pyroxenes, amphiboles, jimthompsonite, and micas are all stoichiometric miner-
als (assuming the ideal case of no nonstoichiometry resulting from point defects).
It is possible, however, to combine the polysomatic slabs in a disordered fashion,
which produces a nonstoichiometric crystal with a chemical composition that
lies between those of two ordered members of the series. Although poly somatic
disorder of this sort can be difficult to recognize with many experimental
methods, it is readily observed using HRTEM: Fig. 46 shows an example of a
crystal that is predominantly the amphibole anthophyllite (double silicate
chains), but with defects corresponding to triple chains (the isolated sequence
MMP), quadruple chains (a defect with structure MMMP), and sextuple chains
3.5 Structural Types of NonStoichiometry in Minerals 213
.:.=
:-=""=
-- - --_ . : . : . :. :. :-: -:
........ -
... :......
.: . :-:.:.:
~ - ...... ---- .
.':-:"':.:'.:":.:.,
....: ..... : . : . . :-: -:. :.: -:-:-:-:-:.:.: . . :.: ..: ..:.:.:.
:-=. . :. . :.:-: . :. :-:-:-;-:. :-:-:.:-:--:.:-: . :-:.:-:
.:, ~
.. :--:-=-: .. :.. :-: . . : . . : .. : .....":.: ... :-:-:.:.:.: ..: ..:-:..:-:.
--: ......
....=.:-: -: -:- :-:
-::-=~:~:.:
...=-. =.-.-. :-:-: -: . -. :-=
. :-: ......... .
.. ....: .. :-:-:-:-:-:.:~:-:-:.:-=-',
·:~:·:"':·:-:·:·:"':...:..:-X-.:.. ~
- ...... - - ..
~--.--.-
.....-,
- ........-.., ....-.. - - .... .. :... : ~~
. . :-:.: ........ :-:.. :.:-:.:.:-: .. .. ..--.
..- .....- .. - .....-.-......
: ...
....:.:-......
..........
.. X .
"
.. .... ..:-:..:-. .
--
_............. --. -··
.... ..............
:-: :-.:.:-:-:-:-:-: ...:;:.:-:-:-.:-:.:-:-:.
..
~-
_.......................-
-.-- ..:-:...
~
........
-_
..................
...... -- ....... -.. ~ .~ -...... ~--.~~
---.:.....:-::......
. . . . . . . . . . .
.. ..:........:-:-
:-::~:
. -.--,
.
:.:.:.:~ ,
. . . . . .••..
. .
......
....
. .
__
.
. . . . . . . . . . . . ...0-. . . . . . .
:.:.
..
--.
~ ..... 9 .... - •
:.:-...::::..:.:-:
... -~£'\'--" .. -
-~-
......':"""'-.~'--,
~
131 6 1
Fig. 46. A c-axis HRTEM image of a nonstoichiometric crystal that is predominantly the
amphibole anthophyllite. The defects that cause the nonstoichiometry consist of slabs with
triple chains (3). quadruple chains (4). and sextuple chains (6). (Veblen 1981)
Other Chain and Sheet Silicates. Several other polysomatic series occur in the
chain and sheet silicates, and disorder and resulting nonstoichiometry have been
observed in all of them (Veblen 1991). A partial list includes the following
groups. (1) Members of the pyroxenoid series, which can be represented as
intergrowths of pyroxene and wollastonite slabs parallel to {II I} of pyroxene,
commonly intergrow and show polysomatic defects (Czank and Liebau 1980;
Veblen 1985b). (2) The mixed-layer clays are polysomatic structures, and when
disordered they are nonstoichiometric (in addition to point-defect nonstoi-
chiometry discussed above). In more coarsely crystalline sheet silicates, unit-cell-
214 Chapter 3. Real Structures of Minerals
scale intergrowth among the 1: 1,2: 1, and chlorite structures is common and
likewise results in nonstoichiometry (Thompson 1978; Veblen 1983b; Veblen
and Ferry 1983). (3) The antigorite structure can be represented as a polysomatic
series with three types of slabs. Especially in low-temperature occurrences, it
shows major structural disorder and hence nonstoichiometry (Livi and Veblen
1987; Mellini et al. 1987). (4) Carlosturanite is nonstoichiometric due to polyso-
matic disorder based on intergrowth of lizardite slabs and slabs of a hypo-
thetical chain-silicate structure (Mellini et al. 1985).
Olivine and the Humite Group. Many olivine specimens do not show any planar
defects (White and Hyde 1982), but others can contain planar defects that cause
nonstoichiometry. Olivine and minerals of the humite group form a polysomatic
series, and intergrown slabs with humite structures can perturb the chemical
composition of olivines to less silica-rich compositions and also contain hydro-
gen (Kitamura et al. 1987). Similar polysomatic disorder leads to nonstoichio-
metry in the humite-group minerals (White and Hyde 1982). In laihunite, a
Fe H -rich derivative structure of fayalite, vacancies on Fe sites order to form
planar defects that accommodate the nonstoichiometry (Kitamura et al. 1984).
Similar defects also form during the natural oxidation of relatively magnesian
volcanic olivines (Banfield et al. 1990). Olivine also can possess significant
nonstoichiometry based on point defects (Jaoul et al. 1987), but the extent of the
compositional deviations is not well known.
Oxides
and any composition can be accommodated; the term infinitely adaptive com-
pounds has been used to describe such structures (Anderson 1973). For some
cooling rates, unit-cell scale features called platelet defects develop to accom-
modate the nonstoichiometry (Bursill et al. 1984). Most metamorphic rutiles
contain some Fe 3 + in solid solution, and upon cooling the nonstoichiometry
results in the formation of analogous Fe-rich platelets (Banfield and Veblen
1991). These platelet defects can be described as having a structure similar to
hematite and are typically only one or two unit cells thick.
Perovskite Structures and Other Derivatives of the Re03 Structure Type. The
concept of homologous series in solids was first developed by MagneIi (1953),
based on observations on W0 3 - x and Mo0 3 - x , which are crystallographic
shear structures derived from the Re0 3 structure type. The shear planes
can occur with different orientations, spacings, and in ordered and disordered
arrays (Tilley 1980). The perovskite structure, which is of critical importance in
geophysics and materials science, is a simple stuffed derivative of the Re0 3
structure. As noted above, perovskites can accommodate deviations from the
ideal AB0 3 stoichiometry with point defects, but many families of perovskite
derivative structures are based on planar defects and can also be described as
polysomatic series. Many of these structures are reviewed by Tilley (1980) and in
Navrotsky and Weidner (1989), and nonstoichiometry based on planar defects
in perovskite-derivative high-Tc superconductors was reviewed by Raveau et al.
(1990).
Sulfosalts
Summary
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Minerals in rocks are usually rather imperfect, but individual minerals which
have been allowed to grow without hindrance and with free surfaces, such as in
pegmatites or druses, may be highly perfect. X-ray topography is an imaging
technique which is very sensitive to local strains and which is therefore applied
to perfect or nearly perfect crystals. It enables one to visualize and to charac-
terize defects such as dislocations, growth bands, growth sector boundaries, low
angle grain boundaries, stacking faults, twin boundaries, etc. It has been used
successfully to assess the crystalline perfection of many types of minerals,
carbonates (calcite, dolomite, magnesite, cerussite), quartz, silicates (beryl, topaz,
spodumene, orthose), diamond, fluorite, phosphates (apatite), etc. The main
motivation for such studies is the determination of the growth history of the
minerals and the understanding of their genesis. But they are also very useful to
determine the characteristics of the defects responsible for the deformation of
minerals.
After pioneer works in 1931 and 1944-1945, the first topographic techniques
enabling the imaging of individual defects such as dislocations were developed in
1957-1959, the method most often used in mineralogy being that due to A.R.
Lang. It enables one to observe the three-dimensional distribution of defects
in large samples up to a few square centimeters and 100 J1.m to 1 mm thick,
depending on how absorbing it is. The radiation used is MoKoc or CuKoc from
conventional tubes, occasionally AgKoc. The width of dislocation images is of the
order of a few microns and the magnification of the image of the crystal on
the photographic plate is of the order of one. The operation conditions of the
technique are therefore widely different from those of electron microscopy and
one understands that, if it is possible to observe large samples, these must be
highly perfect; the density of dislocations which can be separated is of the order
222 Chapter 3. Real Structures of Minerals
There are several possible origins for the formation of images on a topograph:
misorientation or variation of lattice spacing between one region and another
one (the so-called orientation contrast), or variation of the diffraction and
propagation properties of X-rays in regions of different degrees of perfection (the
so-called extinction, or diffraction contrast). The latter is the more important
effect to be considered for the interpretation of the contrast of the images of
isolated defects such as dislocations or planar defects.
It is precisely the origin of the contrast of the defect images which explains
why the crystallographic characteristics of the defects can be determined: in the
case of a dislocation, for example, the lattice planes which are parallel to
the Burgers vector are least deformed, in particular, the planes parallel to the
Burgers vector of an edge dislocation and normal to the line are not deformed at
all. The contrast of dislocation images on topographs taken using reflecting
planes parallel to the Burgers vector is therefore very weak; by taking a series of
topographs with various orientations of the reflecting planes, it is thus possible
to find the orientation of the Burgers vector of dislocations.
3.6 X-Ray Topographic Study of the Real Structure of Minerals 223
There are two families of setups. In the first one, due to IB. Newkirk (1959), a
divergent beam falls on the crystal at the Bragg angle at a grazing incidence, and
a photographic plate is placed at an angle as small as possible to the crystal
surface (Fig. 47). If there are large distortions or variations in the degree of
perfection along the surface, a small area A may diffract more, or less, than the
neighboring areas (orientation or extinction contrast, respectively). This will be
recorded on A' on the plate, giving rise to an image.
In the second type of setup, a nearly plane wave coming from a mono-
chromator falls on the crystal at an incidence angle corresponding to a reflected
intensity of about half the maximum value (double crystal topography). Any
small distortion at the surface of the crystal will give rise to a fluctuation of the
reflected intensity which will be recorded as an image on the plate. The observed
images are highly strain sensitive.
Again, the various topographic techniques can be sorted in two classes: those for
which the incident beam is either collimated characteristic radiatic-' or nearly
parallel synchrotron white radiation, and those for which the incident beam is a
nearly plane wave produced with a monochromator using radiation coming
either from a tube or from a synchrotron source.
The former situation is schematically described on Fig. 48 for the case of
collimated characteristic radiation (the method due to A.R. Lang). The angular
and spectral widths of the beam are in general so large that only a small part of
the incident beam is reflected through the crystal. The remaining part, or direct
beam, propagates undergoing only normal photoelectric absorption. The part
which is reflected generates a fan of wavefields which, inside the crystal,
propagate within a triangle, ABC, limited by the incident and reflected direc-
tions, called the Borrmann triangle. Its sides make an angle equal to twice the
Bragg angle.
The image of a defect is due in part to the kinematical diffraction of the direct
beam AB by the distorted areas, the so-called direct image, and in part to the
perturbation by even slightly deformed areas of the paths and phases of the
wavefields propagating within the Borrmann triangle ABC. The former is used
to obtain a general picture of the defect distribution in the crystal, while the fine
structure of the latter gives information on the strain field of the defect, usually
through comparisons between experimental images and computer simulations
performed using the dynamical theory of X-ray diffraction.
As an example, Fig. 48 illustrates the image formation in the case of a
dislocation line; the volume around the intersection of the line with the direct
beam AB behaves like a small imperfect crystal and diffracts this direct beam
giving rise to the direct image (D on Fig. 48). At the same time, the dislocation
line perturbs the propagation of wavefields inside the Borrmann triangle and
casts a shadow along its projection AP drawn from the apex, A, of the Borrmann
triangle (Fig. 48). This shadow is called the dynamical image.
There are many variants of the setups used in transmission topography.
Only the principle of the most important ones is given in the following:
Traverse
Fig. 48. Principle of transmission X-ray topography. F X-ray source; D direct image;
P dynamical image. The height of the slit in front of the crystal in the out-of-plane direction
can be up to a few centimeters
3.6 X-Ray Topographic Study of the Real Structure of Minerals 225
Section Topographs. By simply putting a photographic plate after the slit shown
on Fig. 48, one can record the various components of the image: D, the direct
image of the intersection of the defect with the direct beam, from the distance of
which to the edge of the topograph one can deduce the depth of the defect, and
P, the dynamical image, respectively.
There are many kinds of defects contained in minerals. They may have
originated at various stages in the history of the mineral: during the growth
itself, immediately after growth, during cooling, for instance, or during a
deformation completely independent from the growth period. The main types
are briefly reviewed in the following.
Growth Bands. The inevitable instabilities of the growth front result in vari-
ations in the level of impurities of minor elements incorporated in the growing
crystal. When these variations are large, they result in zoning which is visible
optically, but when they are small, they give rise to growth bands which are only
visible by X-ray topography. The correlation of the growth bands observed on
the X-ray topographs with the variation of the impurity content has been
established using many techniques for the detection of impurities, such as
thermoluminescence, cathodoluminescence, and electron microprobe analysis.
These growth bands usually fill up completely a growth sector. They indicate the
successive positions of the growth front and the direction of the growth. They
are very useful to reconstruct the evolution of the habit of the crystal during the
226 Chapter 3. Real Structures of Minerals
Growth Sector Boundaries. The average lattice parameters usually have slightly
different values in different growth sectors (for instance, lattice parameter a takes
different values in a (100) and a (010) growth sector of a tetragonal crystal. For
this reason, there is always a small strain and a small phase shift associated with
the boundary between two neighboring growth sectors which are revealed by a
characteristic contrast on X-ray topographs.
Example. One can observe contrast at the boundaries between growth sectors on Fig. 49. It
can either be due to a diffraction effect, as between the (120) and (ITO) growth sectors, or to a
decoration by inclusions as between the (023) and (III) growth sectors.
a b
Fig. 49a, b. a X-ray topograph of a (001) slab cut normal to the c-axis of a prismatic topaz
crystal from Nigeria. 120 reflection, MoKIX radiation. Height of the crystal: 13.9 mm. (Giacov-
azzo et a\. 1975). b Drawing of the successive habits of the crystal during its growth. 1{120} ;
m {IIO}; u {Ill} f {021}; x {023}
3.6 X-Ray Topographic Study of the Real Structure of Minerals 227
Precipitates. When the mineral is a solid solution of one phase in another one,
and the temperature is decreased below the saturation value, demixion occurs
and that phase precipitates.
minimizes the elastic energy. This direction of minimum energy depends on the
direction of their Burgers vector and on that of the growth, that is on the
orientation of the growth sector within which the dislocation lies. It may happen
that a dislocation crosses a growth sector boundary, going from one growth
sector to the other. As it does so, the direction of the dislocation changes because
the direction of minimum energy is different in both sectors. The dislocation
thus appears to have been refracted when crossing the boundary. As a disloc-
ation cannot terminate inside the crystal unless it is a loop, the dislocations
formed at inclusions constitute bundles which are quite characteristic of solu-
tion-growth. If they have a strong screw component, they may play an import-
ant role in the growth mechanism and growth kinetics. When such a dislocation
intersects a growth face, it gives rise to a growth spiral.
Example. Figure 51 is the X-ray topograph of a 1.5 mm thick slice cut normal to the c-axis of a
quartz crystal (Ser et al. 1980). The growth sectors are clearly visible, the orientations of which
are given on the figure. So are also dislocations lines. Some are isolated, D, others lie in dense
(1100)
Fig.51. X-ray topograph of a quartz plate, 1.5 mm thick, normal to the c-axis. (Ser et al. 1980).
toTO reflection, MoKa radiation. Height of the crystal: 18.6 mm. The major growth sectors are
indicated on the topograph. They correspond to the {lOTO} prism faces and to the {toTI}
rhombohedral faces. Dislocation bundles, B, originate at the growth sector boundaries
between the (toTO) and (toT I), and (OITO) and (OlIl) growth sectors, respectively. Isolated
dislocations can be seen in the other growth sectors. Brazil twins and stacking faults can also
be observed in the (OlIO) growth sector
3.6 X-Ray Topographic Study of the Real Structure of Minerals 229
bundles, B. The latter have originated at inclusions which decorate growth sector boundaries
between growth sectors.
Stacking Faults separate parts of the crystals which are shifted with respect to
one another by a translation which is a lattice vector. This shift results in a phase
shift between the structure factors of the two parts which gives rise to a contrast
observable on X-ray topographs. These stacking faults are bordered by partial
dislocations with Burgers vectors which are not translations of the lattice.
taken with the 3031 and 3031 reflections, respectively. The former presents growth bands and a
few individual dislocations, while the latter presents a few dislocation bundles originating at
inclusions. The twin boundary is clearly to be seen on Fig. 53a. The reason for the difference in
contrast of the two parts of the twin on the three topographs is the following: they are rotated
with respect to one another by 60° around the c-axis and, while they have the same structure
factor for the 1010 reflection, they have very different structure factors for the 3031 and 3031
reflections. Twins according to the Brazil law can also be seen on Fig. 51.
Twins can be formed during growth, but also through the application of a stress
(mechanical twinning), as in calcite. In the latter case, twinning dislocations are
usually observed in the twin boundary.
Conclusion
X-ray topography is an ideal tool to reveal growth defects in large size nearly
perfect minerals. These growth defects, growth bands, inclusions, dislocations,
can be correlated to variations of the chemical composition of the growth
medium or to accidents which occurred during the growth. They are therefore
very useful to reconstruct the growth history of the minerals. These successive
accidents are usually characteristic of the growth medium and can therefore be
found in different specimens coming from the same source. X-ray topography
is also a very good tool to study the early stages of plastic deformation, but
minerals are less ductile than metals, and these early stages are difficult to
observe by this technique, electron microscopy being much better adapted.
References
On the Method
Authier A (1967) Contrast of dislocation images in X-ray transmission topography. Adv X-ray
Anal 10: 9-31
Authier A (1972) X-ray topography as a tool in crystal growth studies. J Cryst Growth 13/14:
34-38
Authier A (1977) X-ray and neutron topography of solution-grown crystals. In: Kaldis E,
Scheel HJ (eds) Crystal Growth and Materials. North Holland, pp 516-548
Authier A (1980) Recent developments in the topographic assessment in crystals. J Cryst
Growth 48: 683-686
Lang AR (1958) Direct observation of individual dislocations by X-ray diffraction. J Appl
Phys 29: 597-598
Lang AR (1959a) The projection topograph. A new method in X-ray diffraction micrography.
Acta Cryst 12: 249-250
Lang AR (1959b) Studies of individual dislocations in crystals by X-ray diffraction micro-
radiography. J Appl Phys 30: 1748-1755
Newkirk JB (1959) The observation of dislocations and other imperfections by X-ray
extinction contrast. Trans TMS-AIME 215: 483-497
Tanner BK (1976) X-ray diffraction topography. Pergamon Press, Oxford
Zarka A (1972) Etude de defauts de croissance dans des carbonates rhomboedriques naturels.
Bull Soc Fr Miner Crist 95: 24-32
A.C. McLAREN
c-axis and are called Dauphine twins. These twins are not observed when
normal petrological thin sections are viewed between cross-polarizers because
the axes are parallel in the twins. For the same reason, Dauphine twins are not
readily detected in normal X-ray and electron diffraction patterns. However,
because the modulii of the structure factors F(hkil) and F(hkil) of the original
and twin orientation are significantly different for some reflections (e.g., 0111
and OlIl), Dauphine twins can be observed by X-ray topography and by
transmission electron microscopy.
In sanidine (monoclinic; space group C2/m) the Si and Al atoms are
disordered among the tetrahedral T sites. Over geological time, ordering takes
place and in maximum microcline (triclinic; space group CT) the ordering is
complete. In this structure there are four main orientational variants: two
orientations related by the albite twin law (rotation of 180 about b*) and two
0
orientations related by the pericline twin law (rotation of 180 about b). The
0
composition planes are (010) and the rhombic section which is parallel to band
approximately normal to (001), respectively. Thus, the cross-hatched pattern
observed in (001) sections between crossed-polarizers is generally interpreted as
intersecting sets of albite and pericline twin lamellae formed as a consequence
of the transformation from monoclinic to triclinic. However, recent studies of
micro cline using transmission electron microscopy, indicate that this is a
simplistic picture although the observed cross-hatched patterns are based on the
four orientational variants.
Tweed structures due to the intersection of two near-orthogonal sets of
modulations that are qualitatively related to albite and pericline twin lamellae
are often observed by TEM in partially ordered orthoclase and adularia.
Deformation (or mechanical) twinning is an important mode of plastic
deformation in some common rock-forming minerals, such as calcite, for
example. In most cases, the twinned orientation is produced from the host lattice
orientation by a simple shear parallel to the composition or twinning plane K j
and in the twinning direction M l ' as shown in Fig. 54. A large shear (S = tan!{!,
where !{! is the angle of external rotation) may be achieved by small local
rearrangements of the atoms.
s
--+
References
Barber OJ, Wenk H-R (1979) Deformation twinning in calcite, dolomite, and other rhombo-
hedral carbonates. Phys Chern Mineral 5: 141-165
Fitz Gerald JD, McLaren AC (1982) The microstructures of microcline from some granitic
rocks and pegmatites. Contrib Mineral Petrol 80: 219-229
Frondel C (1962) Dana's system of mineralogy, vol III. Wiley and Sons, New York, pp 76-87
McLaren AC, Fitz Gerald JD (1987) CBED and ALCHEMI investigation oflocal symmetry
and AI, Si ordering in K-feldspars. Phys Chern Mineral 14: 281-292
McLaren AC, Phakey PP (1969) Diffraction contrast from Dauphine twin boundaries in
quartz. Phys Stat Sol 31: 723-737
Nicolas A, Poirier JP (1976) Crystalline plasticity and solid state flow in metamorphic rocks.
Wiley and Sons, London, pp 45-46; 218-219
Putnis A, McConnell JDC (1980) Principles of mineral behaviour. Blackwell, Oxford,
pp 119-121
CHAPTER 4
Natural Glasses
238 Chapter 4. Natural Glasses
Silica
The three principal groups of structure models are the random network
structure, pseudocrystalline structure, and coexisting discrete structure. The
individual groups of structural models are not distinctive in the sense that
aspects of one cannot be incorporated into another.
The random network structure model rests on the premise that in a glass
such as that of Si0 2, all oxygen and all silicon structural positions are
energetically equivalent. In this model there is no ordering except for the
existence of individual SiO!- tetrahedra where the oxygen corners are shared
between neighboring tetrahedra. Experimental support for the random network
model has been found in spectroscopic analysis of Si0 2 glass. The neutron,
Raman, and infrared spectra of vitreous Si0 2 and related compounds can be
reproduced theoretically from the random network model, although there are
some important discrepancies between calculated and measured spectra.
Discrepancies between theoretical and observed spectra point to the fact that
some ordering must exist. In early attempts to deduce the structure of vitreous
Si0 2 from X-ray data, local structural similarity between vitreous silica and
cristobalite was suggested. More recent interpretations of the X-ray data
(Fig. 55) indicate that the greatest similarity is between the structure of tridymite
and that of vitreous Si0 2 and that this similarity persisted to distances of
15-20 A. X-ray data can displayed in terms of pair function distributions
(Fig. 55). The first three peaks, at 1.62, 2.65, and 3.12 A (Fig. 55A) are the
contributions from the nearest neighbor Si-O, 0-0, and Si-Si in the sample.
The Si-O distance to the second nearest oxygen neighbor appears near 4.15 A.
It can be seen from the difference curve (C) between the observed curve (A) and
the sum of the contributions from the Si-O, Si-Si, Si-2nd 0, and Si-2nd Si
(curve B), that the observed spectrum is quite well matched through the nearest
neighbor pairs (1.62, 2.65, and 3.12 A), but the difference between the observed
and calculated curves increases rapidly at greater distances.
Structural studies of vitreous and molten Si0 2 have also utilized vibrational
spectroscopy and to a lesser extent 29Si NMR. A principal aim of these studies
4.1 Structure and Properties of Silicate Glasses and Melts 239
4000 A
c 3000
.Q /--------./
t5
c
.2
'co 2000
~
0...
'C
1000
2 3 4 5 6
Radial distance, A
c
.Q 40
t5
c
.2 C
c 30
0
"-5 c
.0
.;:: ~20
ti W
0...
'6 10
Q)
c;,
c
<l: 0 180
120 140 160
Si-O-Si angle, degree Si-O-Si angle, degree
Fig. 55A-C. A Pair function distribution curve for vitreous Si0 2 . B Angle distribution
function (intertetrahedral angle, Si-O-Si) versus intertetrahedral angle for vitreous Si0 2 .
e Intertetrahedral angle (Si-O-Si) distribution in vitreous Si0 2 from molecular dynamics
calculations
has been to obtain better characterization of the Si-O-Si angles and their
distribution (120-180°; see also Fig. 55B, C). From the discrepancies in the
spectral interpretations on the basis of a single structure it has been suggested
that the vibrational spectra are better interpreted on the basis of two or more
three-dimensionally interconnected structures. The differences between the
structures might be different intertetrahedral angles and angle distributions
and, perhaps, different Si-O bond lengths. Raman spectra of vitreous SiOz are
consistent with the coexistence of at least two coexisting, three-dimensionally
interconnected structures with different average intertetrahedral angles (5-10°).
The exact nature of the rings (in particular the number of Si per ring) remains
under debate.
240 Chapter 4. Natural Glasses
Metal Oxide-Silica
A variety of structural models has been proposed. These are the polymer
model, the multicomponent mixing model, and the pseudocrystalline model.
The principal structural premise of the polymer model is that silicate melts
and glasses can be viewed as continuously evolving polymers containing
bridging (0°), nonbridging (0-) and free (0 2-) oxygen. An equilibrium of the
form:
0° + 0 2- ¢>20-, (1)
can be written. The equilibrium constant for reaction (1) is:
K1 = (ao _)2 .
(2)
a o Oa o 2-
In the simplest case, the mixing is considered ideal and activities can be
substituted with mol fractions. The abundance of oxygen species can then be
calculated from the bulk composition of the melt. Three examples with K1 = 0,
K 1 = oc, and K1 at an intermediate value are considered. With K = 0 only free
and bridging oxygens exist in the melt. With K = oc, either only free and
nonbridging oxygens coexist or bridging and non bridging oxygens coexist. At
exactly 33 1 / 3 mol %, only nonbridging oxygens exist. This composition corres-
ponds to that of orthosilicate stoichiometry. Thus orthosilicate melts would
consist only of SiO:- tetrahedra in association with metal cations. For any
intermediate value of K 1, all three oxygen species coexist in the melt.
In developing a thermodynamic basis for a multicomponent mixing model, it
is assumed that the structural units present in a multicomponent melt system are
those that are produced by melting of the known crystalline materials in the
system. This assumption is also made in the polycrystalline model. For example,
in the system MgO-Si0 2, liquidus phases are periclase (MgO), forsterite
(Mg 2Si04 ), clinoenstatite (MgSi0 3 ), and silica polymorphs (Si0 2). The species
assumed to exist in the liquid were MgsOs, Mg 4 Si 20 s, Mg2.67Si2.670s, and
Si 4 0 s. The model reproduces the liquidus phase diagram in the system
MgO-Si0 2. Thus, provided that sufficient thermodynamic data are available,
the model of multicomponent mixing can be used to calculate liquidus phase
equilibria.
In Raman spectroscopic studies involving a variety of metal oxide silicate
glasses and melts in the compositional range from near that of orthosilicate
(NBO/Si 3 = 4) to fully polymerized melts (NBO/Si = 0), it has been found that
the compositional ranges within which vibrations from Si-O - in the structural
units (SiO:-, Si20~-, SiO~- and Si20~-) could be identified, varied as a
function of the type of metal cation (Table 24). As the M/Si was varied within a
3 NBO/Si: Nonbridging oxygen per silicon. A more general form by which to describe degree
of polymerization is NBO/T; nonbridging oxygen per tetrahedrally coordinated cations.
4.1 Structure and Properties of Silicate Glasses and Melts 241
NazO-SiO z
> 0-0.05 SiOz, SizO~-
0.05-1.0 SiOz, SizO~ -, SiO~
1.0-1.4 SizO~-, SiO~-, SiO!-
1.4-2.0 SizO~-, SiO~-, SizO~-, SiO!-
BaO-SiO z
> 0-0.2 SiOz, SizO~-
0.2-1.0 SiOz, SizO~ -, SiO~-
1.0-1.1 SiO z, SizO~ -, SiO~ -, SiO!-
1.1-2.4 SizO; -, SiO~ -, SizO~ -, SiO!-
> 2.4 SiO~-, SizO~-, SiO!-
CaO-SiOz
> 0-0.3 SiOz, SizO;-
0.3-1.0 SiOz, SizO; -, SiO~-
1.0-2.2 SizO; -, SiO~ -, SiO!-
2.2-3.0 SiO~-, SizO~-, SiO!-
> 3.0 SiO~-, SizO~-, SiO!-, oz-
(Cao.sMgo.s)O-SiOz
> 0-1.2 SiOz, SizO; -, SiO~-
1.2-2.0 SiOz, SizO~ -, SiO~ -, SiO!-
2.0-2.4 SizO;-, SiO~-, SiO!-
2.4-3.0 SiO~-, SizO~-, SiO!-
> 3.0 SiO~-, SizO~-, SiO!-, 0 2-
given system, the degree of polymerization of the individual structural units does
not change as a function of bulk melt polymerization. Only their relative
abundance changes.
With this information in hand, a set of equations that describe the anionic
equilibria in the bulk melt compositional range between ortho- and tecto silicate
can be written;
2SiO!- <o:>Si20~-+ 0 2-, (3)
3Si20~- <o:>2SiO~- + 2SiO!-, (4)
6SiO~- <0:> 2Si 20;- + 2SiO!- , (5)
2SiO~- <o:>Si0 2 + SiO!-, (6)
and
(7)
1.0 1.0
0.8 0.8
0.6 0.6
0.4 0.4
.... 0.2
·c 0.2
_::J 0.0
0 2 0 .0
c: 0 1 0 1 2
0 NBO/Si NBO/Si
-
U
nl 0.6 0.6
'-
~~ao-sio21
T02 T03
"0 0.5 0.5
:2: ~
T20 S
0.4 \ •
,~ 0.4
.'
TO..
0.3 0.3
,,
0.2
~
0.2
0.1 0.1
0.0 /+ 0.0
0 2 3 2 3 4
NBO/Si NBO/Si
Fig. 56. Molar abundance of structural units in quenched melts on metal oxide-silica joins as
indicated as a function of bulk melt NBO/Si. Shaded symbols represent data obtained with
29Si NMR
decreasing shielding of the 29Si nucleus as AI3+ is substituted for Si4 + in the
tetrahedral network. The line width, however, does increase with increasing
polarizing power of the charge-balancing cation. Similar behavior has been
observed in the 29Si NMR spectra of metal oxide-silica melts. This line-
broadening may possibly be ascribed to a wider range of T -0-T angles in the
network as the polarizing power of the metal cation(s) increases.
Systematic studies of melt and glass structure on aluminate-silica joins as a
function of AI/(AI + Si) and electronic properties of the charge-balancing metal
cation have relied primarily on Raman spectroscopy as the structural probe.
The variations in spectral topology of Si0 2-NaAI0 2 glasses with AI/(AI + Si)
might be viewed as reflecting a gradual decrease in the Raman frequencies of
(Si,AI)-OO (0°; bridging oxygen) stretch bands as a function of bulk Alj(AI
+ Silo This decrease might result from increasing substitution of AI3+ for Si4 +
in the network. In contrast, in the spectra of alkaline earth aluminosilicate glass
the Raman frequencies of individual stretch bands did not shift with changes in
bulk melt AI/(AI + Silo Only the intensities of particular bands and, therefore,
the proportions of the structural units in the melts varied. The spectra are
consistent with two or three different coexisting three-dimensional intercon-
nected structural units in fully polymerized alkaline earth aluminosilicate
244 Chapter 4. Natural Glasses
glasses. One was the A12Si20~ - unit (this unit could be viewed as the equivalent
of the "anorthite" entity suggested for CaAl 2Si 20 s composition glass from x-
ray data). A second unit may be a six-membered, three-dimensionally intercon-
nected ring similar to that of molten Si0 2. Finally, there are indications of AIOi
units in very aluminous melts [Alj(AI + Si) > 0.5]. The abundance of these
units in CaAI 20 4-Si0 2 quenched melts follows a pattern as a function of the
Alj(AI + Si) of the melt such as that shown in Fig. 57, with a gradual increase in
abundance of A12Si20~ - units with increasing Alj(AI + Si) to a maximum at
Alj(AI + Si) slightly greater than 0.5, followed by an abundance decrease as the
aluminum content is increased further. In the same concentration range, the
coexisting Si0 2 units decreased in abundance. A similar abundance behavior
was suggested for MgAl 20 c Si0 2 composition melts (Fig. 57).
In depolymerized alumino silicate melts and glasses, the structural com-
plexity is increased because AI3+ may be partitioned between coexisting struc-
tural units of varying degree of polymerization. In melts with three or more
coexisting units of differing degree of polymerization, the preference is for the
most polymerized unit followed by the unit of intermediate degree of polymeriz-
ation [i.e, Alj(AI + SW0 2 > Alj(AI + SW205 > Alj(AI + SW03]' Raman and
29Si NMR spectra of quenched melts in the system Li 20-Na 20-K 20-
CaO-AI 20 3 -Si0 2 show that in depolymerized melts [where structural units
with different degree of polymerization coexist, i.e., Eqs. (3)-(7)] Al 3 + exhibits a
strong preference for the most polymerized of these coexisting structural units.
This conclusion is also consistent with observations of the crystal chemical
behavior of AI3+ in aluminosilicate crystals wherein AI3+ tends to associate
with a tetrahedral site nearest the smallest available intertetrahedral angle. In
de polymerized silicate melts with coexisting structural units, the structural unit
with the smallest intertetrahedral angle is the three-dimensional network unit.
The structural behavior of AP+ under these circumstances can be illustrated
by substitution of charge-balanced (MAI)4+ (M = 0.5 Ca, Mg, M = K, Na and
100
"::'
0 !.
(5
80
E
ai
0
60
c:::
C\l
"0
c::: 40
:::::I
Fig. 57. Molar abundance of three-dimen-
..
.0
c:t: sionally interconnected structural units in
20 CaAI 2 0 c Si0 2 and MgAI 2 0 4 -Si0 2 quen-
ched melts as a function of bulk melt All
(AI + Si)
0.2 0.4 0.6 0.8 1:0
AI/(AI+Si)
4.1 Structure and Properties of Silicate Glasses and Melts 245
-
'::l
c
0.6
0.5
B
e
::l
0.4
U
2
iii 0.3
PTPs+T03
U5 0.2 I
+ I
I
~ I
:ii: P
I
Fig. 58A, B. A Abundance of coexisting structural units in quenched melts along tetrasilicate-
tetra-aluminate joins (M2Si409-M6AI409 joins with results from the Na2Si409-Na6A1409
join as examples). B Aluminum content of individual structural units in quenched (from
1400 °C and 1 bar) melts
Li) for Si 4 + (Fig. 58A) where there is a systematic increase in the abundance of
T0 2 units (or Q4) and a concomitant decrease in the abundance of T 20S units
(Q3). This trend is accompanied by an increase in abundance ofT0 3 units (Q2).
An equilibrium of the form;
(8)
might explain the observations. The equilibrium shifts to the right thus forming
T0 2 and T0 3 units as Alj(AI + Si) of the system increases. The Alj(AI + Si) of
the T0 3 unit is significantly less than in T 20S units and that in T 20S units less
than in T0 2 units (Fig. 58B). The extent of this aluminum preference diminishes
in a systematic manner as a function of increasing Zjr2 of the metal cation.
Iron-Bearing Systems
Iron is the only major element that occurs in more than one oxidation state in
natural magmatic liquids under terrestrial rock-forming conditions. The local
structural environments in Fe-bearing silicate melts have been studied by
Mossbauer, luminescence, absorption, EPR spectroscopy, and by Raman,
NMR, and X-ray absorption K-edge spectroscopy.
On the basis of several hundred M6ssbauer spectra of iron-bearing glasses,
by using structural inferences from other spectroscopic techniques (lumin-
escence, optical absorption, EPR, EXAFS), and by comparison with M6ssbauer
spectra of ferri-silicate minerals with well characterized ferric iron-oxygen
polyhedra, it is generally concluded that with the isomer shift of ferric iron
(IS Fe 3 + ) less than about 0.3 mmjs (relative to metallic iron) for spectra recorded
at 298 K, this ferric iron is in tetrahedral coordination. From 298 K spectra of
crystalline material, IS Fe 3 + > 0.4 mmjs is diagnostic of octahedrally coordinated
ferric iron. From spectra of glassy materials, this latter value appears greater
246 Chapter 4. Natural Glasses
than about 0.5 mm/s. The isomer shifts of ferric iron vary with Fe3+ / EFe. With
up to about 10 wt. % iron oxide added as Fe 2 0 3 , the IS Fe 3 + remains nearly
constant (between 0.25 and 0.35 mm/s for 298 K spectra) in the Fe 3 + I EFe range
0.5- 1.0. In the Fe 3 + I EFe range 0.5- 0.3, the IS Fe 3' increases to above 0.50 mm/s
with decreasing Fe 3 + I EFe and remains constant for Fe3+ I EFe values lower
than about 0.3. These observations indicate that for oxidized, iron-bearing
silicate melts (Fe3+ I EFe > 0.5), ferric iron is principally in tetrahedral co-
ordination, whereas for reduced (Fe 3 + I EFe < 0.3) melts, ferric iron is in
octahedral coordination. In the intermediate Fe 3 + / EFe range (0.5- 0.3), these
Mossbauer data are consistent with coexisting tetrahedrally and octahedrally
coordinated ferric iron.
Ferric iron occurs in clusters in silicate melts and glasses. From the Raman
spectroscopic data either these clusters have invariant Fe/ Si or Si 4 + is absent. A
structural model with FeOi complexes (or units) and units stoichiometrically
resembling Fe 3 0 4 in highly oxidized melts, and Fe3+ as a network modifier
(octahedral coordination) in very reduced compositions has been suggested
from spectroscopic observations (Fig. 59). The proportions of these structural
units vary with Fe3+ / EFe.
Optical absorption spectra of quenched melts in Fe-bearing alkali silicate
melt systems may indicate the presence of two ferrous iron-oxygen polyhedra
(near 5000 and 10000 em - 1) with Fe 2 + in octahedral coordination. Whereas in
Fe3+ -free, iron-bearing samples, from Mossbauer spectroscopy the IS Fe 2+ val-
ues of both doublets accord with those found for octahedrally-coordinated
ferrous iron ( '" 1.1 mm/s), with increasing Fe 3+ / EFe, the average IS Fe 2+ values
tend to decrease below 1 mm/s (relative to Fe metal). The decrease in IS Fe 2 +
might be due to different number of oxygens in the Fe 2 + -polyhedra (e.g., four
rather than six). Four-coordinated Fe2+ has also recently been suggested for
melts on the basis of EXAFS and Raman spectroscopic data although this
conclusion differs from that based on optical and luminescence spectroscopy. It
is also difficult to rationalize why Fe 2 + should prefer tetrahedral coordination
0.12,....---- - - - - - - --------,
.;, 0.08
u. Fe(IV)o;~ Fe3+(VI) + 20 2-
X
0.04 ","",c---.",,-c,IV)02~ 4FEf++ 6d- + 02
!~""':"~~~~- 4Fe 3"'(VI) + 2cJ-~ 4Fe 2\ 0 2
0.00
0.7 0.6 0.5 0.4 0.3 0.20.1 0.0
Fe3+ILFe
Fig. 59. Proportions of four- and six-coordinated ferric iron in Na-silicate melts as a function
of Fe 3+ /1:Fe of the melt
4.1 Structure and Properties of Silicate Glasses and Melts 247
Other Cations
Among the major element oxides in igneous rocks, titanium, and phosphorus
generally are the least abundant. Nevertheless, these two oxides have attracted
considerable attention because even in their natural abundance ranges melt
properties are profoundly affected.
Titanium. The coordination number ofTi 4 + has been defined with XANES and
EXAFS data, which indicate that there are two different Ti-O polyhedra in
Si0 2- Ti0 2 glass. One has a Ti-O distance of 1.80 ± 0.02 A, and the other 1.92
± 0.02 A. The shorter distance is characteristic of Ti + in fourfold coordination,
whereas the latter is consistent with Ti 4+ in six-fold coordination. Four-fold
coordinated Ti 4 + occurs in all concentration ranges and nearly 100% of the
Ti 4 + is in tetrahedral coordination in the concentration range between about 1
and 7 wt. % Ti0 2. This concentration range is that most relevant to natural
magmatic liquids. Six-coordinated titanium becomes rapidly important as the
Ti0 2 content decreases below 1 wt. %. As the Ti0 2 content increases above
about 7 wt. %, the proportion of octahedral Ti 4 + increases concomitantly with a
reduction in abundance of tetrahedrally coordinated Ti4 +. The general conclu-
sions from X-ray absorption studies accord with the interpretations of the
vibrational spectra of Si0 2- Ti0 2. Less is known about the structural role of
Ti 4+ in depolymerized melts and glasses. The existing structural data are
derived principally from Raman spectroscopy. Most of this information is
consistent with Ti 4+ in tetrahedral coordination, but the data do not conclu-
sively rule out other interpretations.
Perhaps the most important conclusion to be drawn from the rather extensive
experimental and simulation studies of silicate melts and glasses is that these
materials cannot be viewed as continuous polymers that evolve continuously as
a function of changes in melt polymerization. Instead, it has been found that a
small number of comparatively simple tetrahedral complexes (units) coexist.
Their proportions (and activities) are bulk compositionally dependent. It is also
notable that cations other than Si 4 + in tetrahedral coordination do not always
substitute randomly for Si 4 +. Instead clusters or units with local order are
found. Further, tetrahedrally coordinated cations other than Si 4 + tend to favor
particular structural units in the melts and glasses.
These structural features appear reflected in a variety of melt and glass
properties. The activity coefficient of Si0 2 in metal oxide-silica melts with the
same overall degree of polymerization (NBO/Si) is a positive function of the
ionization potential of the metal cation. The relative abundance of Si0 2
structural units is also positively correlated with the ionization potential, thus
suggesting that at least some of this increase in activity coefficients is directly
related to the anionic structure of the melt as controlled by the properties of the
metal cation.
Rheological properties of silicate melts can be characterized in part via an
understanding of the properties of bonds that need to be broken and recreated
during flow, and activation energies of viscosity, diffusivity and conductivity
may respond to the bond energies. In simple metal oxide-silica melts, the
activation energy of viscous flow exhibit discontinues functional relations to the
degree of polymerization of the melts (Fig. 60). The melt compositions at which
these discontinuities are observed correspond to those where the anionic
equilibria [Eqs. (3)-(7), see also Table 24] change. Molar volume versus com-
position functions also display discontinuities at these compositions (Fig. 60).
Further, the compositions at which the discontinuities are observed are sys-
4.1 Structure and Properties of Silicate Glasses and Melts 249
I~
~ 40
CD
c:
.Q
iii
.<!: 20
~
Li~O
O'---'-___'---'-----I'--...L---1----.J
o 20 40 60
mol % metal oxide
29 r-----.---..-----~
o
E
C')- 27 25.0 36.3
5 I
t
I
I
25
B
~
g 23L-_ _...L~_~_ _~
o 20 40 60
mol % metal oxide
20 40
mol % N~AI4,\
250 Chapter 4. Natural Glasses
(11)
where n is the electric charge of the network -modifying metal cation, Mi'
Similar expressions have been derived empirically for the abundance of
AI-bearing structural units;
Xi = a + b [Alj(AI + Si)] + c [Alj(AI + Si)]2
+ d [Alj(AI + Si)]3 + e [Alj(AI + Si)]4, (12)
where Xi is the abundance of the particular unit, the Alj(AI + Si) is the bulk
melt Alj(AI + Si). From considerations such as this, it has been found that the
two most important structural units in natural magmatic liquids are the fully
polymerized units (T0 2), and units with two nonbridging oxygens per tetrahe-
drally coordinated cations (T0 3). Orthosilicate units (T0 4) are also important
in particular for systems where alkaline earth contents are high. In an analysis of
a wide variety of extrusive igneous rocks ranging from rhyolite to picrite, it has
been found that in 90~95% of the cases, at least 50% of the structure consists
of T0 2 units.
From results of structural calculations as illustrated with Eqs. (10)~(12), it
has been found that molar volumes of natural magmatic liquids are linearly and
positively correlated with the concentration of T0 2 units in the melts and
linearly and negatively correlated with the abundance of T0 3 and T0 4 struc-
tural units. Similar numerical experiments have been conducted for viscosity. A
bimodal distribution in isothermal viscosities and activation energies of viscous
flow of natural liquids has been observed. Rhyolite and dacite comprise the
high-viscosity maximum, and the remaining, less polymerized melts define the
other maximum. Exponential functions describe the relationships between
structural unit abundance, melt viscosity and their activation energies of viscous
flow. In light of the Eyring relation [Eq. (9)], similar relations are likely for
diffusivity (and conductivity) of natural magmatic liquids.
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The development of new and traditional methods for atomic structure deter-
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structure, as well as modeling the effects of glass structure on scattering and
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sized here.
4.2 X-Ray Studies of Glass Structure 255
Natural Glasses
Natural glasses are a variety of materials that include volcanic glasses, tektites,
impactites, fulgurite glasses, glasses from the lunar regolith, natural gels, micro-
crystalline precipitates, and metamict minerals. Problems of nomenclature are
compounded by the complexity of the phase composition and microstructure of
natural glasses. These materials consist of a glassy matrix and distinct crystalline
phases (phenocrysts). The glassy matrix usually contains microcrystals of these
minerals. This necessitates the combination of several diffraction and spectro-
scopic techniques for understanding the structure and composition of natural
glasses and the implications to earth sciences.
256 Chapter 4. Natural Glasses
Synthetic Glasses
Much greater attention has been drawn to the investigation of synthetic glasses
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been proposed that structural models of feldspar and feldspathoid composition
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model, that is made up of six-membered rings and is similar to the nepheline
(Na 2 AI 2 Si 2 0 s ) structure. The anorthite glass structure can be modeled as a
feldspar-like quasi-crystalline structure that is based on four-membered rings.
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a very different effect on glass structure compared with the divalent network-
modifier Ca2+.
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probably taking into account only part of the network-modifying coordination
environment. The structural role of Al as a network-former in sodium-alumino-
silicate glasses was clearly determined qualitatively by XANES (X-ray absorp-
tion near-edge structure) and quantitatively by EXAFS.
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Like minerals and rocks, natural glasses, can provide important information on
the history of the Earth, the Moon, and the planets. However, they are much
rarer on the surface of the Earth than crystalline rocks and minerals (mineralo-
gists have described about 3450 minerals). The reason for this difference can be
found in the contents of water and other volatiles in the parental melt. These
components reduce the viscosity of terrestrial magmas and increase the diffusion
rate of dissolved oxides, with consequent crystal growth. It is unusual to find
lava on the surface of the Earth that has solidified sufficiently fast to be
preserved as glass. Conditions on the Moon are different. The lunar surface has
4.3 Terrestrial and Lunar, Volcanic and Impact Glasses, Tektites, and Fulgurites 259
been found to contain a wide variety of different kinds of glass, but only about
90 minerals have been identified. A similar, though less pronounced, phe-
nomenon can be observed for the meteorites except for "wet" carbonaceous
chondrites.
Natural glasses are formed from a liquid state by supercooling, as conden-
sates from a rapidly cooled sublimate or by pressure destruction of the crystal
structures of substances.
Natural glasses can be classified as: (1) terrestrial, lunar and planetary
volcanic glass, (2) impact glass formed by thermal fusion ofthe original minerals
and rocks during impact on the Earth, Moon, planets, and meteorites, including
tektites, (3) diaplectic glass formed during impact by a pressure shock wave,
(4) fulgurite glass formed after lightning shock. There are also glasses formed
during the combustion of coal seams and oil, and also during tectonic processes
(frictionites). Glassy meteorites from the Moon have been described by Fudali
et al. (1984).
All natural glasses are thermodynamically unstable under conditions on the
Earth's surface and have a tendency to chemically weather or recrystallize
(devitrification). These processes lead to glass destruction. Volcanic glasses of the
Earth are rarely older than 65 Ma, but silicate glass may exist over geological
ages in other environments, e.g., the age of lunar glasses is hundreds of million
and billion years. Older impact glasses have undergone alteration and the oldest
North American tektites have been dated at 35 Ma.
Volcanic glasses are produced by rapid cooling oflava. Their chemical composi-
tion is as differentiated as that of any volcanic rock (basaltic, intermediate, and
acid volcanic glasses). Moreover, the glasses are more enriched in silica and
alkalies than the corresponding volcanic rocks. Basaltic opaque glass packed
with fine particles of ore minerals is sometimes called tachylite; transparent
basaltic glass is known as sideromelane. Fibrous basaltic glass in the Hawaiian
Islands is named Peleine's hair and the lapilli of this glass are called Peleine's
tears.
The chemical composition of basaltic volcanic glasses varies within the
following ranges (wt.%): Si0 2 (49-54), Ti0 2 (0.5-1.0), Al 2 0 3 (15-17), Fe 2 0 3
(3-5), FeO (4-6), MnO (0.1-0.2), MgO (9-10), CaO (8-10), Na 2 0 (2.5-3.5), K 2 0
(0.5-2), H 2 0 (0.1-1.0); F, CI, S, CO 2 -tenths of a percent (Nasedkin 1985). The
values n ~ 1.6, p ~ 2.8-2.9 gcm- 3 •
Acid volcanic glasses are usually designated according to their water content
and structural and textural properties. Their composition ranges (wt. %): Si0 2
(71-77), Al 2 0 3 (12-14), FeO + Fe 2 0 3 (1), CaO + MgO (0.5-2), Na 2 0 (3-5),
K 2 0 (3-5).The values n ~ 1.480-1.493, p = 2.27-2.40 gcm- 3 •
Obsidian is a compact black, grey, purple, or reddish glass with a water
content of up to 1%.
260 Chapter 4. Natural Glasses
Some glasses possess a high water content (perlite 1.5-6 wt. %; pitchstone
6-16 wt. %). Pumice is usually considered to be foamed obsidian, but often has a
water content similar to that of perlite. It is light and floats on water.
Experimental data (IR, PMR) and geological observations reveal that the
high water content (up to 16 wt. %) of some volcanic glasses is due to the reserve
of endogenic water under instant isobaric chilling. During this process the
greater part of it remains in molecular form. As the pressure decreased while
the glass was being formed, the water content in the melt also diminished
(Marakushev et aI., 1988). Consequently, a small quantity (less than 1%) of it can
be found in obsidians in a dissociated form. Study of the isotope ratios (15 18 0,
15 D) indicates that all water in pitchstone is meteoritic in origin. The water was
absorbed by the glass at low temperature.
Lunar volcanic glasses differ radically from terrestrial ones by the absence or
very low content of water and other volatiles (carbonaceous compounds, sulfur
etc.). Volcanic origin was first assigned to the green glass from the regolith
collected by Apollo 15 and the orange glass collected by Apollo 11, and
especially Apollo 17. Lunar volcanic glasses are of basaltic composition and
originated in the period 3.7 x 109 to 3.3 X 109 years ago. Lunar basaltic glasses
are rich in Fe and Ti (1.5 times more than terrestrial ones) and depleted in
alkalies (3-7 times less than terrestrial analogs). Concerning trace elements, a
lack of volatile chalcophiles (Ag, Zn, Cd, Au, Te, Bi) is characteristic (two orders
of magnitude less), but an abundance of refractory elements such as Zr, Hf. High
reduction conditions (partial pressure of oxygen is only 10- 13 in contrast to
10- 8 in terrestrial basalts) are also typical, which is why there is virtually only
Fe 2 + present, and no Fe 3+ . (Here also, Ti3+, Cr2+, Eu 2 + can be found).
Impact Glasses
Tektites
Tektites (Greek tektos = molten) are usually small (their size varying from
microscopic grains - microtektites to 12.8 kg - the Muong Nong type from
Thailand, usually only a few cm long) rounded, natural acidic silicate glasses,
black, brown or green in color, with a high melting point (1320-1640 K). They
are scattered in a number of regions on the surface of the Earth, which are called
strewn fields:
1. North American tektites and microtektites (bediasites, georgianites from
Texas, Georgia, Martha's Vineyard, Barbados, Cuba). Radiometric age
(K;'Ar, Ar/Ar, fission track methods): 35 Ma. Estimated amount: 1010 tons.
2. Urengoites from Novyi Urengoi, West Siberia, CIS. Radiometric age: 24 Ma.
Amount: (to date only three specimens).
3. Moldavites from Czech Republic (Radessen and Altenburg, Austria; around
Dresden in Germany). Radiometric age: 14.7 Ma. Estimated total amount:
3000 tons.
4. Tektites and microtektites from the Ivory Coast (ivorites). Radiometric age:
1.1 Ma. Estimated amount: 10 7 tons.
5. Irghizites and microirghizites from the Zhamanshin crater, Kazakhstan.
Radiometric age: 0.8 to 1.1 Ma. Estimated amount: dozens of tons.
6. Australasian tektites and microtektites (australites, indochinites, billitonites,
thailandites, javanites, phillippinites, malaysianites, Muong Nong type).
4.3 Terrestrial and Lunar, Volcanic and Impact Glasses, Tektites, and Fulgurites 263
Radiometric age 0.7 Ma. (Asian tektite field) and 0.83 Ma. (Australian tektite
field). Estimated total amount: 108 tons.
Tektites are not known in older geological formations. If older tektites
existed, they were probably destroyed by transport or completely dissolved.
Tektite glass can be divided into four major types: (1) layered Muong Nong type,
(2) frozen droplets from splashed melt, which include spherical and teardrop
shapes, so called shaped tektites, (3) ablation types, mainly in Australia, and
(4) microtektites.
Muong Nong tektites are very similar to normal tektites except for high
intrasample variation, corresponding to chemical layering. Shaped tektites
obtained their shape (sphere, ellipsoid, disc, lens, teardrop, etc.) through rotation
ofthe viscous melt - the splash form. These tektites are usually characteristically
sculptured. The sculpture is a result of chemical corrosion.
Tektites with ablation phenomena (button-shaped) are modified by atmo-
spheric ablation at their rims during remelting as they re-entered the Earth's
atmosphere. The button shape of tektites has also been formed artificially in
aerodynamic tunnels. Microtektites are shaped identically to other shaped
tektites, but are defined as bodies less than 1 mm in diameter. Microtektites are
found in deep ocean sediments (Australasian, North American, and Ivory Coast
microtektites).
The Australasian microtektite layer is associated with the Brunhes-
Matuyama reversal of the Earth's geomagnetic field, while the Ivory Coast
microtektites are associated with the Jaramillo event. The North American
microtektite layer is probably connected with the Eocene-Oligocene boundary.
Tektite glasses have a fluidal texture and commonly contain particles of pure
quartz glass (lechatelierite) which was formed by fusion of quartz grain. This
substance is absent in all volcanic glasses. The fluidal texture of tektites is
marked by schlieren. Commonly bubbles of different sizes are present. The gas
pressure in tektite bubbles is very low and corresponds to one thousandth to one
twentieth of the pressure of the Earth's atmosphere at sea level. Rare inclusions
(from tens to a few hundred microns in size) usually are formed by quartz,
coesite, baddeleyite (a decomposition product of zircon), zircon, corundum
(probably a decomposition product of AI 2 SiO s), rutile, chromite, and monazite;
occasionally, Ni-Fe spherules containing schreibersite and troilite have been
described as well as an magnetic spherules. These mineral inclusions lie in a
similar size fraction (silt to fine sand) and their original presence in graded very
fine well separated sediments would thus seem possible. Finally such associ-
ations as quartz, chromite, and zircon are not found together in any type of
igneous rock. Some of these relict minerals are cracked and show signs of shock
metamorphism. The average values of the density and refractive index of tektites
vary: n = 1.485-1.518, p = 2.335-2.502 g cm - 3.
The chemical composition of tektites manifests a close similarity with the
sedimentary rocks of the Earth's surface. The silica content in tektites is greater
than would be expected on the basis of the mafic oxide content, and thus
264 Chapter 4. Natural Glasses
Fulgurites
Fulgurites originate when lightning strikes soil, sand, or rocks, causing melting
of these materials and glass formation when all the material in the immediate
vicinity of the strike site vaporizes. Fulgurites (Latin fulgur = lightning) form
glassy tubes in soil and sands and glassy crusts (1-3 mm thick) in crystalline
rocks. They are exceptionally found up to 20 m long and 20-30 em wide in
sandy deserts. The glass of fulgurite is heterogeneous, with abundant inclusions
and fragments of target minerals bearing marks of shock metamorphism (planar
elements, lower values of birefringence and refractive indices of the shocked
4.3 Terrestrial and Lunar, Volcanic and Impact Glasses, Tektites, and Fulgurites 265
minerals, the appearance of coesite). Also identified were native iron, carbon
(chaoite), gold, silicon, aluminum, phosphides, sulfides and silicides of iron, and
other reduced phases (log f02 = - 20 to - 10) which had developed under high
temperature. The structure, temperature, and cooling rate of fulgurite glass are
similar to those of impact glass originated by thermal fusion. The changes in
chemical composition appear on a micrometer scale. Usually the fulgurite glass
is enriched in Si0 2, and K prevails over Na compared to the target rock,
resulting from selective volatilization of the elements, melting at high temper-
ature (up to 3000°C and shock pressure of 20-25 GPa) and the short duration
of the whole process. Fulgurites have been produced artificially in sand by an
electric discharge or have been found in nature where high tension electricity
wires have fallen to the ground, i.e., pseudofulgurites.
At the strike of an electric charge of lightning (temperature up to 30000 K
and shock pressure about 0.05 GPa) while traveling from the atmosphere (gas)
to the ground (solid phase) there occurs a decrease in temperature of one order
and an increase of pressure of two to three orders accompanied by melting and
selective vaporization of the target rocks.
References
High- and intermediate level, long-lived wastes (class I and II wastes: IAEA
1981) result from the irradiation of the nuclear fuel within a reactor and its
subsequent reprocessing. They include the fission products, actinides, and heavy
elements formed in the fuel by neutron capture and radioactive decay reactions.
The largest volumes are produced during spent fuel reprocessing and contain
only about 0.1 % of the uranium and 1% of the plutonium (Roxburgh 1987) and
are referred to as high-level wastes (HL W). HL W need to be contained in an
environment providing an efficient shielding and isolation from biosphere as
well as an efficient dissipation of the heat generated by the radioactive decay of
the waste. At present, most HLW are stored in liquid cooling tanks, though they
are not thought to provide a long-term solution to the disposal of high-level
nuclear waste. The long term disposal option remains deep geological burial,
isolating the waste from the biosphere for the requisite periods of time, mostly
by preventing from transportation by groundwater. Among the main technical
requirements of solidified HL Ware low leachability, high chemical, thermal,
and mechanical stability as well as industrial feasability. A large number of solid
waste forms meet these criteria, and they include glasses, cements, and synthetic
rocks. Nuclear waste glasses of borosilicate composition are now developed at
an industrial scale (Sombret 1985) and we will survey below some recent findings
concerning their structure. Attention has also focused on the use of an artificial
rock, known as SYNROC (Ringwood et al. 1979; Ringwood and Kelly 1986).
SYNROC contains various crystalline phases able to fix some radionuclides: for
example actinides, Cs/Ba and Sr are incorporated into zirconolite, hollandite,
and perovskite phases, respectively.
On account of the high activity and the chemical complexity of glasses
containing HL W products, most studies of the glasses including structure and
leaching rates have been conducted on analogs which are less active and
chemically simpler. Two typical compositions are reported in Table 25. These
has been shown to have a negligible influence on the leaching rate of this element
(Schreiber et al. 1985).
The local surrounding of the other actinides is only partly known owing to
the diflkulty of investigating highly radioactive glasses. Neptunium is probably
the transuranic element which has received the greatest attention. 237Np
Mossbauer spectroscopy provides an unambiguous way to determine the
oxidation state of neptunium, together with optical absorption spectroscopy
(Veal et al. 1987; Boge et al. 1986; Eller et al. 1985; Karraker 1982). Neptunium is
present under the tetravalent state in glasses equilibrated in air, but may exist in
the pentavalent state as neptunyl groups (NpOi) ou Np3+ions under oxidizing
or reducing conditions, respectively. A comparative EXAFS study (Petit-Maire
1988) of tetravalent actinides (Th, V, Np) has shown that a coordination 6 is
favored as Z increases, in accordance with the decrease of the ionic radius
("actinide contraction"). This systematics is obeyed for Pu 4 + -containing glasses
(Knapp et al. 1984). In the case of the Np3+ ions, EXAFS data are difficult to
analyze on account of an important radial disorder (distance distribution
between 2.4 and 2.8 A). Finally the geometry of the neptunyl group is similar to
that of uranyl groups, with Np-O distances slightly larger than the V-O
distances: the cation-oxygen distance relaxation, despite the similarity of the
ionic radii of V 6 + and Np 5 + is accounted for by the smaller oxidation number
of Np (Petit-Maire et al. 1989).
The spectroscopic investigation of actinides in multicomponent borosilicate
glasses of industrial interest show the importance of the chemical selectivity of
these methods to obtain quantitative information on elements which are
only minor components of these glasses. One of the major conclusion is that
these elements are located in fairly well-defined environments, whatever their
oxidation state. Spectroscopic methods have provided structural models to
explain actinide solubility in borosilicate matrices molten under various redox
conditions (Veal et al. 1987) as well as they have given a coherent model
concerning the processes monitoring glass leaching at low temperature (Greaves
1989). However, the coexistence of various oxidation states makes it difficult to
use model glasses to investigate the actual surrounding of actinides in industrial
glasses used for HLW storage.
References
Abrajano TA, Bates lK, Woodland AB, Bradley IP, Bourcier WL (1990) Secondary phase
formation during nuclear waste-glass dissolution. Clays Clay Mineral 38: 537-548
Boge M, Blaise A, Bonnisseau D, Fournier 1M, Therond PG, Poi rot I, Beauvy M (1986) 237Np
Mossbauer spectroscopy on neptunium doped borosilicate glasses. Hyperfine Interactions
28: 765-767
Brown GE, Calas G, Waychunas GA, Petiau J (1988) X-ray absorption spectroscopy:
applications in mineralogy and geochemistry. Rev Mineral 18: 431-512
Calas G (1979) Etude experimentale du comportement de l'uranium dans les magmas: etats
d'oxydation et coordinance. Geochim Cosmochim Acta 43: 1521-1531
4.4 Nuclear Waste Glasses: Recent Advances in the Spectroscopic Investigation 269
Calas G, Brown GE, Waychunas GA, Petiau J (1987) X-ray absorption spectroscopic studies
in minerals and glasses. Phys Chern Mineral 15: 19-29
Calas G, Manceau A, Petiau J (1988) Crystal chemistry of transition elements in minerals
through X-ray absorption spectroscopy. In: Synchrotron radiation applications in miner-
alogy and petrology. 77-95, Teophrastus Sub., Athens
Calas G, Manceau A, Combes JM, Farges F (1990) Applications of EXAFS in Mineralogy. In:
Mottana A, Burragato A (eds) Absorption spectroscopy in mineralogy. Elsevier, New York,
pp 171-204
Eller PG, Jarvinen GD, Purson JD, Penneman RA, Ryan RR, Lytle FW, Greegor RB (1985)
Actinide valences in borosilicate glasses. Radiochim Acta 39: 17-22
Godon N, Thomassin J, Touray J, Vernaz E (1988) Experimental alteration of R7T7 nuclear
model glass in solutions with different salinities (90°C, 1 bar): implications for the selection
of geological repositories. J Mater Sci 23: 126-132
Greaves GN (1989) EXAFS, glass structure and diffusion. Philos Mag B60: 793-800
IAEA (1981) Underground disposal of radioactive wastes, Basic Guidance. IAEA Safety
Series, No 54, Vienna
Karraker DG (1982) Actinide valences in borosilicate glass. J Am Ceram Soc 65: 53
Knapp GS, Veal BW, Paulikas AP, Mitchell AN, Lam DJ, Klippert TE (1984) EXAFS study
of sodium silicate glasses containing dissolved actinides. In: Hogdson KO, Hesnner Band
Penner-Hahn JE (eds) EXAFS and near edge structure. Springer Proc Physics 2: 305-308
Milnes AG (1985) Geology and radwaste. Academic Press, London
Petiau J, Calas G, Dumas T, Heron AM (1984) EXAFS and edge studies of transition elements
in silicate glasses. Springer Proc Phys 2: 291-296
Petiau J, Calas G, Petitmaire D, Bianconi A, Benfatto M, Marcelli A (1986) Delocalized versus
localized unoccupied 5f states and the uranium site structure in uranium oxides and glasses
probed by X-ray absorption near edge structure. Phys Rev B34: 7350-7361
Petit JC, Dran JC, Trotignon L, Casabonne JM, Paccagnella A, Della Mea G (1989)
Mechanism of heavy element retention in hydrated layers formed on leached silicate glasses.
In: Lytze W (ed) Scientific Basis for Nuclear waste management XII, Mater Res Soc Symp
Proc 127: 33-40
Petit-Maire D (1988) Structure locale autour d'actinides et d'eU:ments nucleants dans les verres
borosilicates d'internh nucleaire: resultats de spectroscopie d'absorption x. Thesis, Uni-
versite Pierre et Marie Curie, Paris 6
Petit-Maire D, Petiau J, Calas G, Jaquet-Francillon N (1986) Local structures around
actinides in borosilicate glasses. J Phys 47-C8: 849-852
Petit-Maire D, Petiau J, Calas G, Jaquet-Francillon N (1989) Insertion of neptunium in
borosilicate glasses. Physica B158: 56-57
Roxburgh IS (1987) High level nuclear waste disposal. An introduction. Chapman and Hall,
London
Ringwood AE, Kelly PM (1986) Immobilization of high-level waste in ceramic waste forms.
Philos Trans R Soc Lond Ser A 319: 63-82
Ringwood AE, Kesson SE, Ware NG, Hibberson W, Major A (1979) Immobilization of high-
level nuclear wastes in SYNROC. Nature 278: 219
Schreiber HD, Balazs GB (1982) The chemistry of uranium in borosilicate glasses. Part 1.
Simple base compositions relevant to nuclear waste immobilization. Phys Chern Glass 23:
139-146
Schreiber HD, Balazs GB, Solberg TN (1985) The chemistry of uranium in borosilicate glasses,
part 6. The leaching of uranium from glass. Phys Chern Glass 26: 35-45
Sombret CG (1985) The vitrification of high-level radioactive wastes in France. Nucl Energy
24: 85-98
Veal BW, Mundy IN, Lam DJ (1987) Actinides in silicate glasses. In: Freeman AJ, Lander GH
(eds) Handbook Phys Chern Actinides, Elsevier, Amsterdam, pp 271-309
CHAPTER 5
In recent years there has been a rapid growth in the applications of computa-
tional quantum chemistry to mineralogy. Band structure and molecular orbital
calculations are being used to understand mineral spectra, equations of state,
and crystal structures. In this survey various computational methods used to
study the electronic structures of molecules and solids are briefly reviewed.
The electronic structure of an atom, molecule, or solid is given by the
solutions to the time-independent (stationary) Schrodinger equation
Ap = EP, (1)
where A is the Hamiltonian operator, P is the wavefunction of the system and
E is the total energy. First, we will assume that it is sufficient to use the
nonrelativistic approximation, so that the total Hamiltonian A tot in Eq. (1)
comprises the kinetic energy T of nuclei (n) and electrons (e) as well as their
potential energy V, and only the Coulomb interaction between charged particles
is taken into account
(2)
Second, we will assume that the electron motion may be considered separately
from the nuclear motion (Born-Oppenheimer approximation). Our electronic
Hamiltonian will then be A(e) = A tot - Tn. An eigenfunction of this operator
[the total electronic wavefunction, p(e)] describes electron motion in the field of
the motionless nuclei, while the eigenvalue, E(e) is the total energy of the system
with a particular nuclear configuration or adiabatic potential. It is the electronic
Schrodinger equation f!<e)p(e) = E(e)p(e) in the simple adiabatic approximation
that is solved in the methods reviewed here.
Hartree-Fock Formalism
The Independent Electron Approximation. We are still faced with the dilemma
that our electronic SE is a many-body problem. When solving a differential
equation for a function of several variables, it is a common strategy to try and
express the solution in terms of the product of functions of only one variable.
For the multielectronic Schrodinger equation, this approach was used by
Hartree, who expressed the multielectronic wavefunction in terms of the product
of one-electron wavefunctio!ls:
(3)
where ri is the coordinate of electron i. Hartree's trial wavefunction, however,
5.1 Survey of Quantum Chemistry and Methods 273
violates the Pauli exclusion principle which requires that the wavefunction must
be anti symmetric under electron exchange (that is, the wavefunction must
change sign when any two electrons are interchanged). Algebraically, we can do
this if the wavefunction takes on the form of a linear combination of determi-
nents over the one-electron orbitals. In the case of an N-electron closed shell
system (Na = Np = N/2 where ()( and f3 refer to spin-up and spin-down), P (index
"e" omitted) is a single determinant of one-electron orbitals, each of which must
not be occupied by more than two electrons (the certain occupation of these
levels defines the electronic configuration)
(4)
The Variational Principle and the Fock Equations. If Ptrial is any antisymmetric
trial wavefunction, then one can evaluate an expectation value for the total
energy associated with that wavefunction
Etrial = < Ptriad B I Ptrial) == JP*B P dr,
where dr means we integrate over all space. If P is the correct wavefunction,
then Etrial = E. However, if P is any other normalized, anti symmetric wavefunc-
tion, the variational principle states that Etrial > E. Hence, we can improve our
trial wavefunction by minimizing the total energy. If we take the single deter-
minental wave function and substitute it for P(rl' r2, ... , rN) in the electronic
Schrodinger equation, we generate an expression for the total energy
E = <PIBI P) = L>d cPr(1)h1cPi(1)drl
+ Li<j nind cPr(1)cPj(2)r~2[cPi(1)cPj(2)
- cPj(1)cPi(2)] dr l dr2. (5)
Now, we use the variational principle to minimize the total energy with respect
to each one-electron orbital subject to the constraint that the orbitals are
orthonormal. Doing this yields a set of simultaneous equations for the one-
electron orbitals known as the Hartree-Fock equations:
(6)
In Eq. (6) F is the Fock operator defined through the MOs; Gi is the one-electron
energy level, h = Te + Vne ; the Coulomb Jj and exchange Kj operators are
related to the operator Vee = Li> jriJ 1 and define the contributions to the
effective SCF potential from the electron-electron interaction.
orbitals. These can then be fit to some analytic form (such as Slater or Gaussian
orbitals discussed below). For a molecule or crystal, a natural way to construct
the one-electron molecular or crystal orbitals is to express them as a finite linear
combination of atomic orbitals (LCAO):
Each of Xli is an atomic orbital centered on one of the nuclei of the molecule. The
one-electron orbital formalism has dominated the theoretical study of the
electronic structure of atoms, molecules, and solids. Not only is it used in
calculations of physical observables but it also provides the "language" to
describe electronic structures and chemical bonding.
We can use the variational principle again to solve for the coefficients C ili of
the atomic orbitals. This gives the set of SCF LCAO MO equations
L
L(F liv - EiSliv)Civ = 0, (8)
Ii
where the elements of the Fockian F and overlap S matrices are defined in terms
of the LCAO basis {Xli}
Fliv = Hliv + GliV ; (9)
SliV = <X~l) IX~l), (to)
where
(11 )
(12)
(13)
The large number of two-electron integrals [/lV IAt5] limits the size of practicable
calculations. The summation in Eq. (8), which is limited by occupied MOs only,
yields the density matrix: PA~ = 2L~ccCiACi~' Equation (8) is solved iteratively
since the matrix F itself depends upon unknown MOs (or upon unknown C ili in
the LCAO approximation). The MOs obtained from the solution of Eq. (6) are
called canonical. The restricted HF method (RHF) described above is usually
employed in such form for closed-shell systems, when the nuclear configuration
does not strongly differ from that at equilibrium.
arising from the configuration). For such configurations one can make use of
RHF algorithm for open-shell systems developed by Roothaan. Here eigenfunc-
tions and eigenvalues for closed- (<Pd, Bd) and open- (<p .. lOs) shells are found from
the system of coupled SCF equations:
Fd<Pd = Bd<Pd; (14)
Fdv = h + I~ (2Jd - K d) + ~
L ( JS - -1 KS ) (d + v) (16)
d= 1 s=N,+ 1 2
N, N.
F'v = h + L (2Jd - K d) + L (P - KS)(s + v) (17)
d=l s=N,+ 1
N, N.
Fdv = h + I(2Jd - K d) + I J'(d + s), (18)
d=l s=N,+l
which are obtained using the energy stationary criterion found with variation
mixing of the double (d) and single (s) occupied and virtual (v) MO subspaces.
These operators are not diagonal in the complete space dis/v, but each operator
is diagonal in own subspace. The effectiveness of the PHF appreciably increases
if instead of Eq. (12) one makes use of the single FPHF where
FP ¢~ = [ h + t + 1f - Kf) ] ¢~ £~ ¢~
(Jj = (23)
J
Ecorr
E~orr
- - - -
(30)
It is particularly important to take CI into account when considering open-shell
systems or excited states, because in such cases there are configurations with
nearly the same energies that mix together.
The CI procedure involves several stages, among which the stage of config-
uration selection (usually in basis of canonical, rarely of localized MOs) is
particularly important. Because of great computational difficulties, which oc-
curs even in the case of small molecules, different ways to the number of terms in
Eq. (28) are used instead of the CI with complete (valence) active space of
orbitals. The iterative procedure with the pseudo natural orbitals, as well as
using the multi-reference configurations resulting in correct disassociation
limits, are probably preferable in practical calculations. Different selection
5.1 Survey of Quantum Chemistry and Methods 279
Where the tPo is defined by Eq. (21) and the tPk are obtained from the tPo via
substitutions ¢i --+ ¢., ¢j --+ ¢b etc. The use of perturbation theory (to second
order) results in the MP2 expansion of the total energy:
b
E=(tPoIHltPo >+ L (tPo IHltPi >2 + ... ,
j
i<j;.<b ei + ej - e. - eb
(32)
where the terms beginning from the second relate to the correlation energy. The
results of calculations depend on the order of the perturbation theory, the kinds
of electron excitations and the chosen active orbital space. Usually for medium-
sized molecules the MP2 with single and double excitations and valence active
orbital space yields more than 50% of the correlation energy.
280 Chapter 5. Chemical Bonding in Minerals
The search for effective correlation methods is one of the most intense
activities in the development of quantum chemistry. Additional correlation
methods being used include:
Group orbital method, particularly, geminal models, based on dividing of
the N-electron system onto weakly interacting groups of electrons.
Coupled pair and coupled cluster approximations (CPA, L-CPMET, CEPA,
MR CC, etc.), based on dividing of the N-electron system onto subsystems of
less sizes, but without dividing onto weakly interacting subsystems.
Methods based on the valence bond theory taking into account many
"resonant" structures.
Many-body perturbation theory (MBPT) or diagrammatic perturbation
theory (DPT). This approach is the basis for effective analysis of various
correlation methods for atoms and molecules. Moreover, it is used to develop
working schemes of calculations.
The DPT gives the clear ordering parameter for expansions of wavefunction
and corresponding eigenvalues, providing with the least biased estimate of
relative importance of different components and unambiguous criteria of limited
expansions.
Basis Set Functions. The accuracy of the nonempirical (ab initio) calculations
mentioned above depends not only on the specific method applied but also on
the "completeness" of the AO basis set. Basis sets may be "minimal" (i.e.,
includes only AOs occupied in ground states of atoms) or extended (i.e., includes
additionally external AOs). Atomic orbitals can take two analytical forms in
routine calculations: the Slater-type orbitals (STO) with the radial parts
R~~P '" ro-Ie-~r (and angular parts in a form of spherical harmonics, Y1m(lj, ¢)
are used in studies of atoms, diatomic molecules, and linear polyatomic mole-
cules. In the general case of polyatomic molecules, however, Gaussian-type
functions are used: R~Y '" ro-Ie-ar2. The form of the Gaussian-type orbitals
simplifies the computation of molecular integrals; in particular, evaluating the
many-center integrals becomes much easier.
A major drawback of the GTFs is their wrong behavior at r -+ 0 and
r -+ 00. Instead of replacing the Slater-type orbitals with a single Gaussian,
therefore, one typically replaces the STO by a finite expansion of Gaussians
xSTO(r,O = L CkxrTF(r, (Xk), (33)
k
where the numerical parameters C k and (Xk are determined by, e.g., least-square
fitting the STO. It is desirable, or course, to use wide expansions, particularly,
when the double or polyexponential STO sets as well as the HF AO bases are
approximated. Expansions that are too elaborate, however, will make the
calculation impracticable. It is very common to see STO's expanded in terms of
three gaussians (the STO-3G scheme). However, this basis set is too simple to be
very reliable. We can greatly improve the flexiblity of the valence electron
orbitals by using a "split valence shell". This represents the outer valence shell by
5.1 Survey of Quantum Chemistry and Methods 281
HF limit
basis set. At present, the choice of basis set is largely up to the art and intuition
of the investigator and the amount of computer memory and time available.
Density functional theory underlies most currently used methods applied to the
electronic structures of solids. The formalism is based on a theorem by Hohen-
berg and Kohn (1964), which states that the total energy of a many particle
system can be expressed in terms of the ground state single-particle charge
density, p(r). Hohenberg and Kohn (1964) also showed that the total energy
assumes its minimum value (the ground state) for the correct charge density.
Consider the Hamiltonian for an n-electron system in some external poten-
tial V:
H =T+ U + V, (34)
where T is the kinetic energy, U is the interelectronic potential. For an atom, the
external potential V would be the potential due to the electron-nucleus inter-
action. In terms of the charge density, p(r), we can write the total energy as
E[p(r)] = T[p(r)] + U[p(r)] + fV(r)p(r)dr. (35)
T[p(r)] is the kinetic energy of a set of interacting electrons. Consider now a set
of noninteracting electrons with kinetic energy To[p(r)] in some external
potential V(r)
E[p(r)] = To [p(r)] + fV(r)p(r) dr. (36)
If we minimize the total energy with respect to the charge density p(r) subject to
the constraint that the total number of electrons is constant, we obtain a set of
one-electron Schrodinger equations:
[ - V 2 + V(r)]cl>i(r) = Bjcl>i(r). (37)
The charge density in this case is then given in terms of the one-electron orbitals
p(r) = L nd (/>;(rW, (38)
where nj is the occupancy of orbital i. What is significant is that this can be done
for a noninteracting set of electrons in any external potential V (r). This led Kohn
and Sham (1965) to express the total energy of the interacting system in terms of
the kinetic energy of a fictitious non interacting set of electrons and an "ex-
change-correlation" energy
E[p(r)] = To[p(r)] + (1/2) If 2p(r)p(r')/ Ir - r'l drdr'
+ Exc[p(r)] + fV(r)p(r)dr (39)
= To + fVext(r)p(r) dr.
The second term is the classical Hartree contribution to the interelectronic
5.1 Survey of Quantum Chemistry and Methods 283
potential. The third term is the "exchange-correlation" energy and includes the
difference between T and To together with the nonclassical (exchange) part ofU.
If we use the variational principle and minimize the total energy with respect to
the charge density, we obtain the Kohn-Sham equations
{ - V2 + S2p(r)/ Ir - r' Idr' + v(r) + vxc(r) }¢(r) = ei ¢;, (40)
where Vxc is the exchange-correlation potential defined as
d Exc [p(r) ]/dp. (41)
If we knew Exc[p(r)] or vxc(r), we could express the exact solution for any
system in terms of single-particle (one-electron) functions ¢i. Note that the
"one-electron" functions ¢i do not really correspond to the electrons in the
system, but instead to fictitious quasielectrons that do not interact with one
another. The orbital energies actually correspond to the chemical potentials of
these quasielectrons. In practice, the distinction between the real electrons and
the fictitious quasi electrons is ignored.
The Local Density Approximation. Thus far, everything we have done is "exact".
Unfortunately, Exc is unknown and it contains the whole complexity of the
many-body problem. On the other hand, Exc is much smaller than either the
kinetic energy or the Coulomb energies. A reasonable approximation to
Exc might allow one to do accurate electronic structure calculations. A common,
and practical, approach to evaluating the exchange-correlation potential is to
start with the local density approximation
(42)
where exc is the exchange-correlation energy density. In the local density approx-
imation, we assume that the inhomogenous charge density of the interacting
system can be broken up into infinitesimal regions of constant (homogenous)
charge density. This is exact in the regime of slowly varying charge densities. The
reason why this approximation is useful is that there are stochastic models for
the behavior of a homogenous gas of electrons and these can be used to derive
analytic expressions for the exchange-correlation energy density. Below, we will
derive the simplest form of the local density exchange-correlation potential.
However, a number of other analytic forms for the exchange-correlation poten-
tial have been proposed, the most commonly used being that of Hedin and
Lundquist (1971). In passing, note that we can extend the density functional
formalism to a spin unrestricted one by defining separate charge densities for
spin-up and spin-down electrons. In conjunction with the local density approx-
imation, the resulting theory is often referred to as the local spin density (LSD)
formalism.
the Hartree-Fock exchange term. We can show, however, how the XIX potential
and the local density approximation relate to the Hartree-Fock formalism in
a more general sense. We will do this in the spin-unrestricted formalism.
Let us start with spin-up and spin-down charge densities
p"(r) = L nf4>f(l)4>i(l)
i
(43)
pP(r) = L nf4>f(l)4>i(l).
i
We can write the Hartree-Fock total energy in terms of the charge density
(44)
where
(45)
(47)
The exchange charge density has several properties that help clarify its physical
meaning: First,
(48)
The exchange potential U XHF , therefore, serves to correct the coulomb potential
for an electron's interaction with itself. If we integrate the exchange charge
density over all of the coordinates of electron 2, we find
Jp~(l, 2)dr2 = - 1 (49)
This means that the exchange charge represents an electron hole of charge + 1
that follows the electron and defines a region of space where electrons of the
same spin are excluded. This electron hole is often called a Fermi hole.
The local density approximation is that we can express our exchange charge
density in terms of the charge density of a single electron and a function which
describes the shape of the Fermi hole:
(50)
5.1 Survey of Quantum Chemistry and Methods 285
For the case of a free-electron gas, we can calculate U~HF(l) exactly and hence
we can calculate p~(1, 2) and the shape function exactly. We then find that
(52)
The a parameter is chosen so that the total energy of the free atom is the same as
the Hartree-Fock value. This approximation of the exchange potential results in
the Hartree-Fock-Slater (HFS) equations [cf. Eq. (4)]:
(53)
where VXa = (2/3)U xa . We can solve the HFS equations for a molecule or solid
using the LCAO approach as before. However, now that we have expressed
everything in terms of the charge density, we are liberated from using an
analytical expansion of the one-electron orbitals. Moreover, we can simplify the
geometry of the crystal or molecular potential to a "muffin-tin" form.
where R!(K: r) is the solution to the the radial Schrodinger equation within the
atomic sphere
~~I'z dr
[ -- r2 dr ~ + 1(1 r2+ 1) + yj(r)
c
+ yj(r)
x
- KZJRj(K' r) = 0
I ,
(57)
and Y1m(r) is the spherical harmonic with angular quantum number I and
magnetic quantum number m (where m takes the values - 1, ... , + I).
In the region between the spheres, the superimposed atomic potentials are
averaged over the interatomic volume to give a constant potential. For a nega-
tive constant potential, we can express the solution in the interatomic region as
a linear combination of spherical Hankel functions:
(59)
This generates a set of simultaneous equations for the coefficients elm and A!m.
Finding the zeros of the corresponding determinent gives the molecular orbitals
and their energies. However, to set up the equations, we need to express the
partial waves h,Krj in terms of a single atomic center i. This is done using the
expansion theorems in Johnson (1973).
p(r) = L aj fj(r)
j
(60)
Vxa(r) = L bjgj(r),
j
where the coefficients aj and b i are found by least-squares fitting on each step of
the iterative procedure.
(62)
e:
where s is the energy of orbital i in the configuration halfway between that of
A and B. The transition state procedure allows us to account for orbital
relaxation during the electronic transition.
Semi-Empirical Methods
The spatial and energetical separation of core and valence electrons, taking
place for any molecule, leads to the valence approximation and makes it
possible to solve the SCF equations only for valence electrons, which determine
the major physical and chemical properties. This approximation does not
impair the results appreciable if the valance AOs are orthogonalized to the core
ones of all the atoms of system and if the potential set up by atomic cores are
correctly allowed for.
The valence approximation is used in all semiempirical methods, parti-
cularly in zero differential overlap (ZDO) techniques, based on the neglect of
terms of the type in molecular integrals [except for H, Eq. (7)] and results in
a large reducing of the number of them. The available ZDO methods in
accordance with their formal schemes can be conventionally divided into three
groups.
In the simplest scheme CNDO (complete neglect of differential overlap) all
integrals with above-mentioned distributions are neglected. Moreover, appreci-
able simplifications are accepted to retain the invariance of the SCF equations
with respect to orthogonal transformations.
There is intermediate scheme INDO (intermediate neglect of differential
overlap) that is more rigorous than previous, where all of one-center integrals
and averaged (interatomic) values of the two-center Coulomb integrals are
accounted for. In this scheme the SCF equations are solved with additional
limitation that they are invariant under any local orthogonal transformations.
In the most rigorous NDDO scheme (neglect of diatomic differential over-
lap) all the one-center and two-center Coulomb integrals are retained.
Along with above mentioned ZDO methods, developed by Pople and
coworkers, many other ZDO algorithms were introduced, which differ from
each other in concrete ways of estimation of the diagonal and off-diagonal
H matirix elements and electronic interaction integrals as well as in schemes
of parametrization, basis sets and invariance criteria used. Various CNDO
methods, such as CNDO/2, CNDO/K, CNDO/S, CNDO/R, CNDO/SW,
CNDO/BW, differ from each other mainly the parametrization schemes. The
projection technique of diatomic differential overlap in all of two-center elec-
tronic interaction integrals is used in the PDDO and LEDO (here and further
the author's abbreviations of methods are retained). In the PRDDO (as in the
AAMOM) the diatomic differential overlap is retained only partly and accord-
ingly all the two-center integrals are taken into account. In the latter much more
"physically justified" assumptions are made, that results in appreciable simplifi-
cation of calculation procedure. In the various ZDO schemes (e.g., SESMO,
MINDO/I) some integrals or whole matrix elements are considered as para-
meters and are estimated from experimental data for isolated atoms and ions
(usually spectroscopic) and for molecules (heats of formations and geometrical
parameters). In the SESMO, besides, the MOs are constructed from STOs
having own scale factors. The major peculiarity of MNDO and MINDOs is the
use of a number of fitting functions, that allow simply evaluate all required
integrals. In the "combined" IRDO method, the NDDO rules of matrix element
5.1 Survey of Quantum Chemistry and Methods 289
calculations is used for the "classical" chemically bonded atoms and CNDO/2
rules for unbonded atoms. Various multiple expansions of charge distribution
potential (as i/rij) in series of spherical harmonics are used in the DRINDO,
which is an intermediate scheme between the NDDO and INDO ones. Directed
character of chemical bonds is taken into account in MCZDO and CNDO/R. It
should be pointed out different schemes, formulated in the frame of the hybrid
orbital method, where "chemical MOs" in systems are constructed from approx-
imately orthogonalized hybrid AOs. There are several working schemes,
accounting for configuration interaction (CI) and thereby being suitable for
computing excited state properties (MNDOC/CI, MINDO/CI, PCILO, etc.).
There are some ZDO schemes, which are especially oriented to calculation of
spectral data (SPINDO, CNDO/S), magnetic properties (CNDO/SP, DEPAC),
thermochemical and other energy parameters (CNDO/SW, CNDO/BW,
MINDOs, MNDO, AMi).
It has been shown that with certain approximations ZDO calculations (as
correct to the terms of the S2 order in matrix elements ofSCF equations) may be
considered as imitation of SCF ones (without the ZDO) carried out in a sym-
metrically-orthogonalized basis set related to initial basis as. The analysis of this
problem in the framework of more general theory leads to still less conforming
conclusions. Therefore, one should attach with care to the results of this
semiempirical method. Nevertheless, it should not be forgotten, that the ZDO
methods (and Pariser-Parr-Pople as the first ZDO method) have played excep-
tionally important roles in quantum chemical studies in 60th-80th years and
many obtained results are valuable up to date. At present, when nonempirical
methods become much more accessible, the application of ZDO-based methods
sharply decreased even for medium size systems. The extended Huckel method
(EHT) that combines various versions of simple MO theory, provides the
roughest approximation since it does not account for electronic interaction
even for valence electrons. Today these methods even in the most sophisti-
cated iterative versions (SCEHT, IEHT, etc.) are practically not applied at all.
Table 26 shows the main available methods of quantum chemistry.
Everything we have described about molecules and clusters is also true for the
electronic structures of solids. The electronic states of a molecule must be
invariant under the rotations of the point group. The electronic states of
a crystalline solid, however, must also be invariant under the translational
periodicity of the space group. Hence,
¢(r + R) = ¢(r), (64)
where R is a translation vector of the lattice. To account for this periodicity,
Bloch showed that our crystalline orbitals must have the form
¢(k; r + R) = ¢(k; r)e ikR . (65)
Table 26. Different methods of quantum chemistry in molecules tv
'-D
o
Nonempirical methods
Correlation methods
M611er- Plessett Configuration Multi- Group Orbital Valence bond Coupled Cluster Many-body
perturbation interaction configuration method theory ("multi- coupled pair perturbation
theory SCF ("geminals") structure") approximations theory
'"
n
::r
'"('i'3
e:.
I;tl
o
5.
S·
OQ
S·
~
S·
'"
a
en
5.1 Survey of Quantum Chemistry and Methods 291
depend on energy as well. The linearity of functions does sufficiently simplify the
computational problems.
In the OPW method all electronic states in crystals are divided onto core
and valence ones. Core states are defined by the Bloch sums in the LCAO form
and OPW functions are found in a form of plane waves and the linear combina-
tions of core functions with the coefficients that are determined from the
orthogonality conditions of the OPW functions to the Bloch sums of core
electrons. Resulted OPW functions are used then as basic ones, over which the
unknown valence Bloch functions are expanded.
In the PP method the idea that the orthogonality of valence wave functions
to core ones is an equivalent of effective repulsion is realized. The latter partly
compensates the attractive potential, acting on valence electrons. Thus the
Schrodinger equation for these electrons can be substituted by equation
"pseudo-potentials", which is affected by the weak pseudopotential instead of
real one. This potential is often designed in model forms using simple analytical
functions with fitting parameters (model PP method). In another version of the
PP (so-called empirical PP method) crystalline pseudopotential is expanded in
Fourier series with coefficients that are regarded as fitting parameters (usually
it's needed a great number of such coefficients).
There are nonrelativistic as well as relativistic forms of the band theory
methods mentioned above. The latter is preferable in the case of heavy element
compounds. However, this approach may be used for other purposes, e.g., for
detail description of level splittings due to spin-orbital coupling.
Quantum chemical models and methods, which are used in cluster and solid-
state approaches to the crystal structure, are summarized in Table 27.
The Nature of Chemical Bonds. From the one-electron orbitals, we can investi-
gate the nature of bonding in a molecule or solid. This can be done according to
the Mulliken population analysis via AO populations P~ which is the total
number of electrons on X~ in all filled molecular (or crystal) orbitals. For
a closed-shell system:
occ
P~ = 2 L (CC)2 + k L P~VB, (66)
B
en
...,<=
H'l' = E'l' <:
."
'<
o
-.
I 10
<=
Pol
::l
Shell Electron Ionic model Band theory a-
model correlation I S
(j
::r
."
SCF
N
v:>
HF Limit w
294 Chapter 5. Chemical Bonding in Minerals
References
Anderson OK (1975) Linear methods in band theory. Phys Rev B12: 3060-3083
Binkley IS, Pople lA, Hehre WI (1980) Self-consistent molecular orbital methods 21. Small
split-valence basis sets for first row elements. I Am Chern Soc 102: 939-946
Dovesi R, Pisani C, Roetti C, Silvi B (1988) CRYSTAL88. An ab initio all-electron LCAO-
Hartree-Fock program for periodic systems. QCPE Program 577. Quantum Chemistry
Program Exchange, Indiana University, Bloomington, Indiana, USA
296 Chapter 5. Chemical Bonding in Minerals
Gordon MS, Binkley JS, Pople JA, Pietro WJ, Hehre WJ (1982) Self-consistent molecular
orbital methods, 22. Small split-valence basis set for second row elements. J Am Chern Soc
104: 2997-2803
Hedin L, Lundquist BI (1971) Explicit local exchange-correlation potentials. J Phys C (Solid
State) 4: 2064-2083
Hehre WJ, Radom L, Schleyer VvR, Pople JA (1986) Ab initio molecular orbital theory.
Wiley-Interscience, New York, pp 1-548
Herman F, Skillman S (1963) Atomic structure calculations. Prentice-Hall, New Jersey
Hohenberg P, Kohn W (1964) Inhomogenous electron gas. Physical Rev B 136: 864-871
Johnson KH (1973) Scattered wave theory of the chemical bond. Adv Quant Chern 7: 143-145
boundary: Geophys Res Lett 16: 515-518 (1989)
Kohn W, Rostoker J (1954) Solution of the Schrodinger equation in a periodic lattice with
applications to metallic lithium. Phys Rev 94: 1112
Kohn W, Sham LJ (1965) Self-consistent equations including exchange and correlation effects.
Physical Rev 140A: 1133-1140
Korringa J (1947) On the calculation of the energy of a Bloch wave in a metal. Physica 13: 392
Muhlhausen C, Gordon RG (1982) Density-functional theory for the energy of ionic crystals:
test of the ionic model. Phys Rev B 24: 2147-2160
Pisani C, Dovesi R, Roetti C (1988) Hartree-Fock ab initio treatment of crystalline systems.
Lecture Notes in Chemistry, 48. Springer, Berlin Heidelberg New York, 193 pp
Schwarz K (1972) Optimization of the statistical exchange parameter IX for the free atoms
H through Nb. Phys Rev B 5: 2466--2468
Skriver HL (1984) The LMTO method. Springer Ser in Solid State Sciences, 41. Springer,
Berlin Heidelberg New York
Slater .IC (1974) The self-consistent field for molecules and solids, vol 4. Quantum theory of
Molecules and solids. McGraw-Hill, New York, 583 pp
Wilson S (1984) Electron Correlation in molecules. Clarendon Press, Oxford
How the nature of chemical bonds in silicates governs their structural and
physical properties has long been of interest. Experimentally, the bonding in
silicates can be investigated using spectroscopy and by mapping electron density
distributions with X-ray and neutron diffraction. Since the 1970s, there has also
been much effort directed towards the study of bonding from first-principles
electronic structure calculations using molecular orbital and band theory. This
chapter will review the experimental and theoretical investigations on the nature
of the Si-O bond.
X-ray spectroscopy studies the interaction offree electrons or photons with fixed
electrons and measures the energies of core electron states of atoms in solids.
From the core-state energies, one may determine the site symmetry and
coordination of an atom and the atom's effective charge. X-ray spectra also are
used to study the nature of chemical bonds and the energy level schemes of
electronic states in the valence and conduction bands.
5.2 Chemical Bonding in Silicates 297
4a,3t 2
b
S;L".", ~
80 120 E, eV
1820
AOSi MO SiOa- AO 0
eV Si spectra 0 spectra
0 in Si0 2 in Si0 2
3t ~2
3d -+ t2 e
_t2:(~~I':(')=:
-
10
_~ 3p~~ -
~- -
3,~a,
-'2 1e
20 -
--
-ID 2a, - ID_
2S -+ t2 a,(u)
30 1t2 --~---
~"'- -« 1a ... «_ ....
~
"'- , ~
40 en ...J
-- L(C)
en '0
L(B) 0
5
" Q)
50 g.--=
>0 en
L( A) ~
x
SiL ~ ---- =
11.111 - - - - - -
1
lU
2s
Kx(C)
510 ~p, X(B)
520 Kx(A)
530 1S
1S - - - - - - OK
Kp
1820
1830
Fig. 64. Molecular orbital diagram for the SiO!- -
1840 SiK ~--- group with X-ray spectra (Marfunin 1979, p. 278)
In this fashion, the effect of the trans-influence upon the structure of the valence
band of atoms from various tetrahedra is displayed.
Investigations of X-ray photoelectron spectra reveal that the range of the
shifts of the main electronic levels of Si, AI, 0 does not exceed 1.5 eV. There is a
tendency for the Is level of 0 and the 2p level of Si to be displaced to greater
binding energies as the condensation of silicon oxygen radicals increases and
Si-O bond length decreases (i.e., upon going from neso silicates to framework
silicates).
X-ray spectra are usually interpreted in terms of the molecular orbitals of a finite
cluster of atoms. For example, the X-ray spectra of many silicates might be
5.2 Chemical Bonding in Silicates 299
interpreted (to first order) in terms of the molecular orbitals of a (SiO)! - cluster.
It is found that irrespective of the calculation method and basis set of atomic
orbitals (AOs), an identical sequence oflevels for a tetrahedral complex of SiO!-
has been obtained: inner ones (purely atomic)-Ia 1 , 2a 2, H 2, 3a 1 , 2t 2, and valent
levels-4a l , 3t 2, 5a l , 4t 2, Ie, 5t, HI (Fig. 65).
The qualitative interpretation of X-ray emission spectra, absorption spectra
and X-ray photoelectron spectra is essentially the estimation of the degree of
participation of different AOs in occupied and free molecular orbitals (MOs).
Low-lying valence levels 4a and 3t are loosely binding and consist essentially of
oxygen 2s AOs with admixture of silicon 3s (for 4a 1 MO) or 3p (for 3t 2 MO)
AOs. The 5a l and 4t2 orbitals are multicenter MOs responsible for the
formation of a-bonds and formed as a result of the interaction between 3s and
3p silicon AOs and 2p oxygen AOs. The composition of the next MO group Ie,
5t 2 and 1tl is governed to a considerable degree by 2p oxygen AOs. Also, under
the conditions of symmetry vacant 3d silicon AOs may take part in the
formation of MO e and t 2 . Early molecular orbital calculations suggested that
Si20~·
(r------------~A~ ___________ ,
18
16
the Si d-orbitals playa substantial role in forming the Si-O bond. However, as
the reliability of spectroscopic measurements and quantum mechanical calcu-
lations has increased, it has become apparent that the degree of the participation
of 3d-orbitals of Si is only a few percent for ordinary silicates.
Although the (Si0 4 )4- cluster provides a useful starting point, it still gives
an incomplete description of the band structures of even simple silicates. For
example, the electron density distribution in a (Si0 4)4- cluster cannot account
for the high-energy part of the intensity distribution in the L",III Si emission
spectrum ofSi0 2 . A more complex ditetrahedral cluster, (Si 2 0 7 )6- resolves this
problem since the intercluster interaction generates additional levels occupied
by 3s states of silicon at the top of the valence band (Fig. 66). The results of the
calculations of (Si 2 0 7 )6- cluster reveal that changes of the angles of Si-O-Si
from 180 to 147 induce slight alterations in MO, and only subsequent decrease
0 0
-2
:;-
.!!!. -4
>-
Ol
Gic: -6
w
-8
-10
Fig. 66. The energy bands for cristo-
balite (bond orbital approximation)
L Arb. XZW K 1: r
5.2 Chemical Bonding in Silicates 301
bridging oxygens. This is expected insofar as the M-O(ap) bond is much more
ionic than the Si-O bond. The larger charge density of the apical oxygens allows
the Si-·O(ap) bond to be more covalent than the Si-O(br) bond.
Electron density distribution studies in olivines and orthopyroxenes have
shown that the effective charges of ions in the M2 sites of forsterite and fayalite
are higher than those of ions in the Ml sites. In enstatite and hyperstene,
however, the situation is reverse. To explain this phenomenon calculations were
performed using CNDO/2 method for large clusters comprising, along with the
central polyhedron, all the edge-sharing polyhedra. Hydrogen atoms were
added to exterior atoms of oxygen in clusters to assure electro neutrality. As a
result, values of 0.68 and 0.80 e in forsterite and 0.73 and 0.69 e in enstatite were
obtained for cations in Ml and M2 positions respectively, which qualitatively
correlates with X-ray study data.
A final example worth mentioning are the electron density distributions in
beryllium silicates. Because Be is a strong Lewis acid and forms covalent bonds
with oxygen, its presence may affect the nature of the Si-O bond. The electron
distribution in beryl shows that Si-O bonds have predominantly covalent
character and peaks of deformation electron density are shifted to oxygen atoms
and directed to peaks of Si0 4 -tetrahedron according to sp3-hybridization. At
the same time there are no localized directed covalent bonds in silicon oxygen
tetrahedra in phenakite, and one can observe a shift of electron density in
direction of the edge of tetrahedron parallel to the channels in the structure. The
explanation of subtle characteristic properties of electron density distribution in
these phases requires detailed quantum-chemical analysis.
addition to the 2s-electrons ofthe oxygen bridge atom, has six valence electrons.
They are located upon bonding (J- TBO t/lb' as well as upon n-orbitals. Thus the
occupied valence band, for instance, in a-cristobalite (where the Si-O-Si angle
equals 180°) contains two bands, one being formed predominantly by TBO t/lb,
the other by Sp3 -orbitals of Si and n-orbitals of the bridging oxygen. Due to the
stronger interaction between Sp3 AO's of silicon and (J-bonding 0(2p) orbitals,
the t/lb band lies significantly lower than the n-band. These bands do not cross
and are separated by a moderately wide gap. Vacant TBO t/ln and t/la generate an
unoccupied conduction band. This conduction band is separated from the
valence band by a gap whose width determines optical and electro physical
properties of the crystal.
If the Si-O-Si angle is less than 180° (as, for instance, in a-quartz), then one
of 2p oxygen AOs can interact with sp3-hybrid orbitals of the silicon forming a
new band. With small deviations of the Si-O-Si angle from 180 0 this band may
be overlapped with band, and with big deviations with t/lb-zone. Hence, though
qualitatively the band structure of different modifications of Si0 2 is similar, the
width of band and densities of states are different. On the whole the TBO model
ensures good reproduction of the band structure and of the photoelectronic and
vibrational characteristics of polymorphic modifications of Si0 2 •
The band structure of amorphous Si0 2 and silicate systems shows that most
sensitive to local disordering are bands located near the forbidden band and that
the change of the angle of Si-O-Si from 90 to 180 is accompanied by the
0
r P6mm
13
(1b)
1
r P31m
11
(4a)
1
Fig. 67. Selected states ofp6mm and p31m2 [Si 2 05]2- tetrahedral sheets at the center of the
Brillouin zone (Bleam and Hoffmann 1988)
-14
-
-16 -
-18L---~~------~
- 31
4a,/r 7
-33~==========~
- 35
-37L---------____~
r K
Fig. 68. Brillouin zone for single-layer lizardite (Bleam and Hoffmann 1988)
and ( O(ap)- Si-O(br) may be both smaller and greater as compared to the
tetrahedral angle, the difference being insignificant in this case (the conclusions
are true for the coordination number equal to two).
These qualitative results are confirmed by the calculations of clusters H6 T zO
(T - C,Si,Ge,Sn) and Hn T Z07 (T - Si,P,S). Electron density concentration on C- O
bonding is observed in H 6 C ZO cluster having an acute angle, whereas a more
uniform distribution of electron density occurs on H 6 Si zO, H 6 Ge ZO, H 6 Sn ZO
clusters (T - 0 - T angle is obtuse). The analysis of theoretically plotted maps of
deformation electron density shows that a systematic decrease of T -0- Tangle
in the clusters H 6 Si z0 7, H 4 P Z0 7, H ZSZ0 7 also correlates with the decrease of
the charge density within the T -0- T triangle. All this enables us to consider the
increase of the T -0- T valence angle to be induced by electron repulsion at T - 0
bonding and in the inner region of TOT. On the whole, the calculations give a
reasonable explanation of the observed decrease of angles in the series
Si- O(br)-Si, P-O(br)- P, S- O(br)- S upon bridging atoms of oxygen in crystal~
of the respective compounds.
Quantum-chemical study of clusters of a mixed composition TSi0 7-
(T = B,Al,P) revealed that addition of a group with a more electronegative or
equal atom to silicon-oxygen tetrahedron leads to the loosening of Si- O(br)
bonding as compared to Si- O(ap) bonding with the respective redistribution of
silicon atomic orbitals from the levels of intra tetrahedral interaction. On the
contrary, when tetrahedron with a central atom, more electropositive than
silicon, becomes adjacent with silicon-oxygen tetrahedron, there occurs a sharp
strengthening of intratetrahedral interactions due to levelling of population of
5.2 Chemical Bonding in Silicates 307
°
model object chosen was Si50~~ - clu·ster neutralized by hydrogen atoms which
were located at a distance of 1 A from each non bridging atom of so that the
Si-O-H angle was rectangular. The initial angles of O-Si-O equalled 109.47°.
The symmetry of the initial cluster was T d - 43 m R(Si-O) distances and
Si-O-Si angles varied during modeling the structures of polymorphic modifica-
tions of Si0 2. In this case the cluster symmetry was fixed in the framework of
point groups D 2d and C v whereas the changing of R(Si-O) distances and
Si-O-Si angles was made in such a way as to escape the alternation of the
number of degrees of atom freedom in the cluster. In the first model (symmetry
D 2d ) interatomic distances Si-O were fixed at the value 1.611 A, whereas
Si-O-Si angles were changed in the range of 140-180° and the change of the
total energy Et of cluster depending on the Si-O-Si angle. Energy minimum
was found from the condition of equality of zero of Et derivative with respect to
the Si-O-Si angle; it corresponds to the value of 146°. This result is in good
agreement with the observed Si-O-Si angles in the studied polymorphic
modifications of Si0 2.
Calculations based on the second model having Cv symmetry, concerned
three clusters H12S15016. All the Si l -0 2-Si 2 angles in each cluster was fixed at
the value of 180°, and all the Si 2-0 2 distances were equal to 1.611 A. Study was
made of the change of the energy of the interatomic interaction E(Si-O),
E(Si-Si) and the energy of Et cluster as a function of the Sil-Ol-Si l angle. The
investigations reveal that there is a relationship between R(Si-O) and values of
the minimum of interatomic interaction energy in each cluster. The theoretical
dependence of R(Si-O) from sec «Si-O-Si) reproduces fairly well the experi-
mental data for polymorphic modifications of Si0 2.
5.1). The potential surface can be fit to a model potential such as the 1-3
covalent potential
Vij = KjiRjj - R?/ + (qjqiRjj) (1)
or the Morse potential
Vjj = Dij{exp[ - 2lXjj(R jj - R;j)] - 2exp[ - lXij(Rij - R;)]} + (zjzj/Rjj), (2)
where kjj , Rij, R;j, D jj , IXjj are the potential parameters and qj, Zj are the effective
changes.
Good agreement between the data calculated with the use of potentials
(1) and (2) and the experimental data on the structure and the elastic properties
of quartz and forsterite indicates that the described methods of extending the
results of quantum-chemical investigations of clusters of crystals have broad
opportunities. The success of this approach is determined by the dominant
contribution of short-range interactions of modeled properties of crystals.
Since 1972, the so-called electron gas approximation for the nonempirical
evaluation of the interionic repulsion in crystals has been developed. Various
contributions made to such a repulsion are calculated by methods of quantum
mechanics from the electron density of the interacting ionic pair which is formed
by the superposition of electron densities of individual ions. Later, to this
approach were added corrections for the compression of the electron shell of
anions in the electrostatic field of surrounding cations (enlargement of the
electron shell of cations is less significant). The crystal field is modeled by the
charged spheric shell around the anion; the radius r of this shell is determined
from the condition of equality of potential within sphere Vj = qJr j (qj-the anion
charge) to the electrostatic potential in the position of anion in the crystal
[approximation of the modified electron gas (MEG)]. Calculations of the
structure and properties of polymorphic modifications of Si0 2 , Mg 2 Si04 ,
diopside, and a number of silicates in MEG approximation are known.
The structure of the low-temperature IX-quartz, for example, was calculated
with the radius of the shell 0 2 - equal to 0.93 A. The calculated parameters of
the cell and the volume turned out to be more alike the structure of the high-
temperature IX-quartz, but the Si-O distance is considerably shorter (by
0.03-0.04 A) than the observed one. Generally speaking, the increase of the
radius of the shell 0 2 - improves the agreement of calculated distances with
experimental values, but the volume of the elementary cell in this case becomes
substantially larger (by 5-10%) than the observed one and the structure stability
increases.
Particularly unsuccessful is the modeling of the configuration of bonding
among tetrahedra: the calculated (Si-O-Si is significantly greater than the
observed one, though there is a considerable improvement as compared with the
earlier calculations which yielded (Si-O-Si 180°. The energy of the lattice is
nearly 6% less than the experimental value which may be attributed to the
neglect of considerable covalence of Si-O bonding. It should be particularly
noted that the improvement of MEG model for quartz is achieved by the
5.2 Chemical Bonding in Silicates 309
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Bleam WF, Hoffmann R (1988) Orbital interactions in phyllosilicates: pertrubations of an
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McMillan PF, Hess AC (1990) Ab initio valence force field calculations for quartz. Phys Chern
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Pantelides ST (1977) Recent advances in the theory of electronic structure of Si0 2 • Comm Sol
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Post J, Burnham CW (1986) Ionic models of mineral structures and energies in the electron gas
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310 Chapter 5. Chemical Bonding in Minerals
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Phys Chern Mineral 11: 81-84
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TossellJA, Lazzeretti P (1986) Ab initio calculations of 29Si NMR chemical shifts for some gas
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D.W. BULLETT
isolated atoms. This approach then bridges the gap between the mathematically
elegant localized-orbital transformations arising out of the linear muffin-tin-
orbital method (Andersen and Jepsen 1984), and the semi-empirical Huckel-type
parameterisations that have also seen remarkable success in solid-state appli-
cations to complex structures by Hoffmann and coworkers.
Transition-Metal Dichalcogenides
~-.,......
... . -.. :
..... z
I
: "'~
c/2
s I
. - - - - n(E)
Fig. 70. The octahedral and trigonal prismatic coordination of metal atoms in the layer
dichalcogenides TiS 2 and MoS 2 , and the calculated electron energy bands and densities of
states for these semiconductors. Symmetry points in the irreducible Brillouin zone have been
given their conventional labeling. (Bullett 1989)
---0,-
Fig. 71. The cubic pyrite and orthorhombic marcasite structures of FeS 2
314 Chapter 5. Chemical Bonding in Minerals
IE,
. F
Calculated density-of-states spectra for the pyrite series of sulfides are shown
in Fig. 72 (Bullett 1982). The main features are confirmed by experimental
photoelectron distributions (Li et al. 1974; Yamamoto et al. 1977; van der Heide
et al. 1980). Figure 73 displays a more schematic block representation of the
individual band limits as a function of energy below the highest occupied state in
each material, to emphasize the general trends associated with the stronger
binding of the metal d-state as we traverse the series.
At strong binding energies 10-19 eV below the Fermi level lie the two
discrete bands originating from bonding and antibonding s-states between S2
pairs. The next higher group of bands may be loosely labeled as the 5 S p-states
for each S2 pair in the unit cell (although of course they do also contain a
substantial proportion of metal d-orbitals). The sixth p-band, associated with
S2PU* anti bonding pair orbitals, lies several volts higher in energy. For FeS 2
~~U________LJ~J=kIJ
5
-5
-10
~~~
-15
~ f[][[§a-~
Fig. 73. Schematic block diagram of the valence and conduction bands in the pyrite series
FeS z to ZnS z. In this figure the zero of energy corresponds to the highest filled state
316 Chapter 5. Chemical Bonding in Minerals
these occupied S p-states extend from 1.6 to 8.5 eV below the valence band
maximum; in ZnS z the top of the S p-band forms the valence band maximum
and the calculated bandwidth is 6.6 eV.
Metal d-states descend towards and through the main S p-block as we cross
the series. In the calculated results for FeS z a clear gap of 0.7 eV separates the
occupied t 2g d-manifold from the unoccupied eg d-states; there is no complete
distinction between e g and SzPO"* bands, although the latter orbitals contribute
principally at the top of the first conduction band, 2.2-2.7 eV above the valence
band maximum. The size of the experimental band gap in pyrite, as determined
from optical and photoelectrochemical measurements, has been the subject of
much investigation, recently reviewed by Ferrer et al. (1990); estimates range
from 0.7 to 1.2 e V depending whether results are analyzed in terms of an indirect
or direct transition model. In CoS z the e g sub-band is 25% filled, and in this
calculation for assumed paramagnetic material the t Zg sub-band is about 0.9 eV
lower than in FeS z. At NiS z the Fermi level falls in the middle of the eg states
(and the occurrence of antiferromagnetism is not altogether surprising for a half-
filled band) while the t Zg sub-band just touches the top of the S p-band. For the
copper compound the d-states lie entirely within the S p-band and contribute
the sharp peak 3 eV below E F . Finally at ZnS z the d-states sink below the
p-band and a semiconducting gap ~ 2 eV separates the latter from the lowest
conduction band states.
While states within the "metal d-band" energy range, ~ 1.5 eV in CuS z
and ~ 3 eV in FeS z, are overwhelmingly metal d-states, the metal d-orbitals do
also make a substantial contribution throughout the sulfur p-bands. The
calculated ionicity increases steadily through the series, from FeO. 6 + (SO.3 -}z to
Zn1.4+ (SO.7-}z.
The essential modification in the electronic structure of the marcasite phase
is the extra splitting of the t Zg orbitals in the more distorted quasi-octahedral
environment. Increased metal-metal interactions can be seen in the reduction of
dynamical effective ionicities in the a and c directions, relative to pyrite (Lutz
and Wiischenbach 1985). Atomic-orbital-based calculations (Bullett 1982) pre-
dict some overlap of the lowest metal d-band with the S p valence bands and a
slight decrease to 0.4 eV in the FeS z (marcasite) semiconducting indirect gap
between filled t Zg and empty e g bands. Other density-of-states features are
broadly similar to those of FeS z (pyrite).
Tetrahedrite is a common mineral that occurs in most sulfide ore deposits. Early
studies proposed the chemical formula Cu 12 Sb 4 S 13 and a crystallographic unit
cell that can be derived by imposing ordered sulfur vacancies on a sphalerite-
type (ZnS) super-structure (Pauling and Neumann 1934), a structure sub-
sequently confirmed by Wuensch (1964, Wuensch et al. 1966). However, natural
5.3 Chemical Bonding in Sulfide Minerals 317
undisplaced Cu
displaced Cu
Fig. 74. Calculated densities of electron states and its projection on individual sites in the
tetrahedrite structures Cu 12 Sb 4S 13 and CU14Sb4S13' Results for the copper-rich phase
demonstrate the similarity of contributions from the displaced and undisplaced copper sites.
(Bullett 1987)
References
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7: 2208-20
5.4 Bonding in Oxides, Oxyanions, and Halides 319
Bullett DW (1982) Electronic structure of 3d pyrite and marcasite-type sulfides. J Phys C 15:
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Bullett DW (1987) Applications of atomic-orbital methods to the structure and properties of
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Bullett DW, Dawson WG (1986) Bonding relationships in some ternary and quaternary
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Li EK, Johnson KH, Eastman DE, Freeouf lL (1974) Localised and bandlike valence electron
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Makovicky E, Skinner BJ (1979) Studies of the sulfosalts of copper. ':::an Mineral 17: 619-34
Pauling L, Neumann EW (1934) The crystal structure of binnite, (Cu,Fe)12As4S13' and the
chemical composition and structure of minerals in the tetrahedrite group. Z Krist 88:
544-62
van der Heide H, Hemmel R, van Bruggen CF, Haas C (1980) X-ray photoelectron spectra of
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Wuensch Bl, Tajeuchi Y, Nowacki W (1966) Refinement of the crystal structure of binnite
CU12As4S13' Z Krist 123: 1-20
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D.S. URCH
The most direct way to investigate the electronic structure of minerals is by PAX
(photoelectron and X-ray emission) spectroscopy. X-rays which are generated
by electron transitions from the valence band to a core hole (valence X-rays,
VXR) exhibit fine structure which is determined by the energies of the molecular
orbitals (MOs) and by the atomic orbital (AO) composition of those orbitals.
320 Chapter 5. Chemical Bonding in Minerals
One of the first oxide minerals to be studied by PAX spectroscopy was periciase.
It was thought that its simple cubic structure would be reflected in simple VXR
spectra from both magnesium and oxygen. However, as can be seen from
Fig. 75, this is not so. The main peak in both the 0 and the Mg spectra is split,
indicating the presence of two bands of orbitals. Furthermore, the observation
5.4 Bonding in Oxides, Oxyanions, and Halides 321
-.-.-.-_..-1'
.l.J ,
'-
scale) and Mg L2 • 3 M (dashed
line lower energy scale); bottom
valence band X-ray PE spec-
trum. All spectra aligned to the
lower, molecular orbital energy
scale
,
" ,-v
"
1280 1290
30 20 10 o
The PAX spectra of brucite [Mg(OHh] have been reported. As with periclase,
the presence of a Mg Kf3 spectrum indicates that the bonding between magne-
sium and hydroxide must have some covalent character. A detailed investiga-
tion of the PE and VXR spectra shows, however, that the most important
covalent bond exists between the oxygen and hydrogen of the hydroxyl group.
The orbitals about oxygen can then be described as, two 0 2p lone pairs (A), an
o 2s orbital (B) and a O-H (J bond with considerable 0 2p character (C). The
disposition of 0 2p character can be determined directly from the 0 Ka VXR
spectrum which shows an intense peak at 526 eV (A) and a peak with about 25%
intensity at 521 eV (C). The Mg Kf3 spectrum, which follows the 0 Ka spectrum
closely, can be rationalized as due to weak covalent bonding between magne-
sium and oxygen. Magnesium interacts with both A and C orbitals but causes
only a minor perturbation. Relative peak intensities in the valence band PE
spectrum provide evidence for the presence of a little 0 2s character in the O-H
(J bond.
Similar PAX spectra are observed from gibbsite [AI(OHh] from which it
may be concluded that the nature of the bonding is similar to that in brucite. The
Al Kf3 VXR spectra have been reported for the oxy-hydroxides diaspore [a-AIO
(OH)] and boehmite [y-AIO(OH)]. In these minerals the changes in the peak
profile can be directly related to the structural changes in the chemical environ-
ment of the aluminum.
Bonding in Oxyanions
After silicates, carbonates form the largest group of minerals which contain oxy-
anions. Other oxy-anions of mineralogical importance include borates, sulfates
and phosphates. In this section the bonding in these latter, tetrahedral anions
will be considered first as their high symmetry makes the classification of
molecular orbitals easier.
Tetrahedral Anions. A qualitative molecular orbital energy level diagram for the
tetrahedral unit M0 4 is shown in Fig. 76. It has been assumed that M is a main-
group atom like sulfur, phosphorus, or boron. The same figure can therefore be
used to discuss the bonding in SO~ -, PO~ - and B01-. The diagram indicates
that the B Ka and S or P Kf3 spectra could have three peaks, reflecting valence
shell p character in 1t 2 , 2t 2 , and 3t 2 orbitals. This can be seen in the S Kf3 VXR
5.4 Bonding in Oxides, Oxyanions, and Halides 323
--
Left hand column atomic or-
xxx 35 - 2 p bitals for M (assuming M to be
~a1-1i0J]2t-T3t2 1t1 I 1e a 2nd row element - if M were
I 2 I from the 1st row then 3s be-
=25
n~a L_~1t2 I
I comes 2s, 3p becomes 2p and
3d is absent). The orbitals are
Ii II I I coded as follows: 3s (or 2s)
II i: I i cross; 3p (or 2p) open circle; 3d
solid dot. Next column, atomic
il II I ! orbitals for oxygen: 2s open; 2p
-2p It II i ! solid. To the right of the verticai
II line the molecular orbitals that
-25 II arise from the interaction of
II the M and oxygen valence or-
II bitals are grouped according
II to the irreducible representa-
II tions of the tetrahedral point
-15 Ii o Ka
group. Relative contributions
of different AOs to the MOs
II are indicated, in a qualitative
II way, by area. The VXR spectra
II are shown as follows: 0 Ka
II
II solid lines; M Kf3 dashed lines;
-15 --------ij~-------------Kf3 M L 2 •3 M dot-dashed (3s --> 2p),
dot-dot-dashed (3d --> 2p)
spectrum for sulfate in Fig. 77. The Kf3' satellite peak at 2453 eV shows the
presence of some S 3p character in the 1t2 orbitals which are mostly 0 2s. The
Kf3-Kf3' separation is determined by the difference between 2s and 2p ionization
energies on the ligand atom. The energy of this separation can therefore be used
to identify the ligand (see below "Halides").
The main peak at 2467 eV shows the presence of much more S 3p character
in the 2t2 orbitals. This peak aligns with the 0 Koc peak at 521 eV showing that
2t2 orbitals have both S 3p and 0 2p character and are therefore strongly
(J bonding. The very weak feature at 2471 eV aligns with the main 0 Koc peak
and locates the 3t 2 orbitals. From the intensity of the 0 Koc peak these orbitals
are almost exclusively 0 2p lone pair in character. The sulfur L2,3M spectrum is
especially interesting. The tetrahedral symmetry of the anion restricts 3s char-
acter to the la l and 2a l orbitals which can be ascribed to peaks at 140 eV and
155 eV. As there are no other occupied orbitals of a l symmetry, the only
reasonable explanation for the peak at 162 eV is that it is due to MOs with 3d
character. The peak aligns with a shoulder on the low energy side of the main
o Koc peak as would be expected if empty 3d orbitals were to interact with the
o 2p "lone pair" orbitals, Ie and 3t 2 . The observation of this peak in the PAX
spectra for phosphate and sulfate (also silicate) thus provides direct evidence for
the use, by second row elements, of their 3d orbitals in chemical bond formation.
324 Chapter 5. Chemical Bonding in Minerals
/
I
/
----------' "
500 510 520 530'
.r·'\ \
•
\
,..-.-- ,/ •
...-- '--.-.,/ '-
150
30 20 10 o
Fig. 77. PAX spectra for the sulfate anion. Top oxygen Ko: (dashed line is solid line x 10);
center sulfur VXR spectra, S Kf3 solid line (lower energy scale) and S LZ,3M dot-dashed line
(upper energy scale); bottom, valence band X-ray PE spectrum. All spectra are aligned to the
lower, molecular orbital, energy scale
Whilst the L2,3M spectra provide convincing proof of the role played by 3d
orbitals, the presence of a weak "high energy" satellite peak in the K{J spectrum
is also of significance in understanding the nature of the bonding in tetrahedral
anions. This peak shows that 3p character is present in the 3t 2 orbitals that are
mostly oxygen "lone pair". This in turn implies the existence of (J-rr; mixing,
i.e., an interaction between the 2t2 (J bonds and oxygen lone-pair orbitals.
PAX spectra from borates in which the boron enjoys tetrahedral coordina-
tion by oxygen are restricted to boron and oxygen VXR spectra and the PE
valence band spectrum. An examination of such spectra, from minerals such as
pinnolite and danburite reveals a very similar basic picture to that found in
sulfate and phosphate. 1t2 is mostly 0 2s in character, but there is evidence for
some participation by B 2p in the presence of the B KIX' peak at 167 eY. The
5.4 Bonding in Oxides, Oxyanions, and Halides 325
main boron KO( peak, at 182 eV, aligns with the shoulder in the 0 KO( indicating
the presence of both B 2p and 0 2p in the B-O (1 bonds. There is no X-ray
emission spectrum that involves B 2s orbitals and so no direct evidence of the
role played by these orbitals in bonding.
The bonding in halide minerals (e.g., halite, fluorspar) is mainly ionic and VXR
spectra (e.g., F KO( from CaF 2) show only small perturbations which can be
ascribed to partial covalency. A different situation exists for the one halide
mineral for which PAX spectra have been measured - cryolite (Na 3 [AIF6]). In
this mineral the aluminum atom is surrounded by six fluorine atoms ranged at
the apices of an octahedron. The molecular orbital energy level diagram (based
on Oh point group symmetry) has many similarities with that for the tetrahedral
326 Chapter 5. Chemical Bonding in Minerals
Conclusion
Whilst, in isolation, PAX or even VXR spectra can give valuable, qualitative
indications as to the nature of chemical bonds in minerals, their greatest value is
when used in combination with theoretical calculations. PAX spectra are unique
in giving data (energy levels, AO coefficients) that can be compared directly with
theoretical predictions. When good accord is achieved, it is then reasonable to
assume that the theoretical model provides an accurate picture of the electronic
structure of the mineral.
References
Haycock DE, Kasrai M, Nicholls CJ, Urch DS (1979), The electronic structure of magnesium
hydroxide (brucite) using X-ray emission, X-ray photoelectron and Auger spectroscopy.
J Chern Soc Dalton Trans: 1791·1796
Hessabi R, Urch DS (1990) J Chern Soc Faraday Trans 86: 247-252
Nefedov VI, Buslaev Yu A, Sergushin NP, Kokunov Yu V, Kovalev VV, Bayer I (1975)
J Electron Spec Rei Phenom 6: 221-229
Kosuch N, Wiech G, Faessler A (1980) J Electron Spec Rei Phenom 20: 11-23
Urch DS (1985) X-ray spectroscopy and chemical bonding in minerals. In: Berry FJ, Vaughan
DJ (eds) Chemical bonding and spectroscopy in mineral chemistry. Chapman and Hall,
London, pp 31-36
Urch DS (1988) PAX (Photoelectron and X-ray emission) spectroscopy: Basic principles and
chemical effects. In: Gomes Ferreira J, Teresa Ramos M (eds) X-ray spectroscopy in atomic
and solid state physics. NATO Sci Affairs Div, Plenum Press, New York, pp 155-200
5.5 Electronic Structures of Iron Oxides and Silicates 327
D.M. SHERMAN
Insofar as iron oxides and silicates are crystalline solids, one would expect that
their electronic structures should be given in terms of Bloch wavefunctions.
However, the orbitals of interest in silicates and oxides, namely those in the
328 Chapter 5. Chemical Bonding in Minerals
Fe(3d) orbitals, are quite localized. (This reflects the partial ionic character of
the bonding in these minerals.) Bloch wavefunctions are awkward to use when
attempting to describe electronic transitions between localized states. A different
approach would be to look at the electronic structure of a small cluster of atoms
representing some structural unit in the crystal by using molecular orbital
theory. With increasing cluster size, the molecular orbital description will
converge to the band structure of the crystal. The molecular orbital view can
account for both localized (ionic) electrons and (if the cluster is sufficiently large)
delocalized (metallic) electrons. We should, at least to a first approximation, be
able to describe the Fe(3d) electronic states in terms of the molecular orbitals of
simple Fe06, and Fe04 clusters. This approach has its precedent in ligand field
theory and should be useful to the extent that the Fe(3d) electrons are localized.
As will be discussed below, this approximation might completely break down in
the Earth's interior where FeO may undergo a Mott transition. Even in the
Earth's crust, there are some electronic states (in particular, those involved in
Fe 2+ --> Fe 3 + charge transfer) in which the Fe(3d) electrons are de localized over
more than one Fe06 coordination polyhedron. To understand such delocalized
states, we will have to use larger clusters or approach iron oxides and silicates in
terms of band theory. Calculations on (Fe2010)15- dimers have been done to
describe intervalence charge transfer and will be described here. As computers
become faster, sophisticated calculations on even larger clusters will become
practicable.
Accurate molecular orbital calculations on transition metal oxide clusters
cannot be easily done using current Hartree-Fock type ab initio methods based
on the linear combination of atomic orbital (LCAO) formalism. A very
successful approach, however, is the XIX-scattered wave method discussed earlier
in this volume.
-9
> -15
4e g
.!
>-
Cl } Fe(3d)
iiic:
W --- 2t 29
~
:0
0
-20
t
3eg
O(2pl
1t2g
-25
It is important to note that the orbital energy differences in the ground state
electronic structure do not correspond to electronic transition energies. The
latter are calculated using the transition state formalism (Slater 1974) which
accounts for the orbital relaxation about the excited state electronic
configuration. Two kinds of electronic transitions can be described using this
simple cluster: d-d or "ligand field" transitions and ligand-to-metal charge
transfer (LMCT) transitions. As discussed below, the one-electron orbitals give
only a partial description of the different ligand field states of the Fe 3 + cation.
The ligand to metal charge transfer transitions, however, seem to be well
described in terms of the one-electron orbitals of the (Fe06)9- cluster. The
lowest energy LMCT transition, from the O(2p) band to the 2t 2g (P) orbital, is
calculated to have an energy near 38000 cm -1. This energy agrees well with that
found in the spectra of iron(III)-bearing oxides, silicates and oxo complexes
(e.g., Tippins, 1970). The energies of the states arising from the different
330 Chapter 5. Chemical Bonding in Minerals
4E,4Al
20
10
It29)3Ie~)1Ittg)1
-L'T' 4Tl
extent to which the spin selection rule is relaxed depends on the strength of the
magnetic coupling between Fe 3 + cations. A pair of Fe 3 + cations are coupled
antiferromagnetically by superexchange. The superexchange interaction
depends on the nature of the bridging ligand L and on the Fe-L-Fe bond angle.
There is a great deal of theoretical work that can be done to understand
the quantum mechanical nature of superexchange and its dependence on the
mode of Fe-Fe bridging. Superexchange is a direct consequence of the
spin-dependency of the chemical bond (e.g., Goodenough 1972). We expect that
coupling due to superexchange will increase as the covalency of the Fe-L
bond increases. Superexchange coupling via Fe-O-Fe bridging is relatively
strong. However, if the bridging oxygen is also bonded to a strong
electron-withdrawing center (Lewis acid) such as H + or Si 4 +, then we would
expect the superexchange coupling to be weaker. This effect is seen in minerals:
strong superexchange due to Fe-O-Fe bridging in iron oxides results in strong
intensification of the Fe 3 + ligand field transitions and gives these minerals their
red to orange color. Weaker superexchange via Fe-OH-Fe and Fe-O(Si)-Fe
coupling in iron silicates (e.g., nontronite) results in a weaker intensification of
the Fe 3 + ligand field bands and gives nontronite a green to pale yellow color.
These effects in the spectra of iron sulphate minerals have been described by
Rossman (1974; 1975).
The strong magnetic coupling, and the consequent intensification of the
Fe 3 + ligand field bands, results in an absorption edge in the visible region
spectra of iron oxides. This edge is often mistaken for the optically induced band
gap transition. Since band gaps in semiconductors are often obtained from
optical measurements, one may see erroneously low values for the band gaps
energies of iron oxides in the literature. The band gap in iron (III) oxides and
silicates corresponds to the 0 2 - ---+ Fe 3 + charge transfer transition (i.e., the
0(2p) to Fe(3d) band gap). As discussed above, the lowest energy 0 2 - ---+ Fe3+
charge transfer transition in the (Fe06)9- cluster has an energy near
38000 cm -lor 4.7 eV; this is well into the near-ultraviolet.
Fe(4s)
-10
--_ 4eg
} Fe,"d)
:> -15
2t 2g
.!
>-
OJ
CD
c:
w
~
:e
0
-20
/ 3eg
,
} 0(2pJ
===---- 1t2g
q=A
/
>-
e>
OJ
c::
W
q= -A
-\. o
Configurational coordinate Iq)
Fig.81. Potential energy surfaces describing Fe 2 + [2 t 2 .(#)] ---> Fe 3 + [2 t 2 .(#)] charge transfer.
The solid curves correspond to the potential for the "ionic" states 1/1 1 and 1/1 2' The dashed curves
correspond to the potential energy surfaces for the states '1'+ and '1'_ that result from coupling
1/11 and 1/12' The curves a-a' correspond to the case of weak coupling and give an activation
barrier for thermally induced rVCT. The curves b-b' correspond to strong coupling which
completely delocalizes the Fe2 + [2td 2.(#)] electron over the two Fe sites
334 Chapter 5. Chemical Bonding in Minerals
edge. The dimer has C l v symmetry (Fe sites inequivalent). If we consider the two
sites A and B, we can consider two zeroth-order states corresponding to the two
possible charge configurations:
1/11 = Fe1+ Fd+
1/11 = Fel+ Fe~+.
We are interested in the energies of these states along a configurational
coordinate q which traps the electron to a given site. Here, q is a normal of Al
symmetry along which the Fe-O bond length of one site expands while that for
the other site contracts. Let us designate the equilibrium Fe2+ -0 and Fe 3 +-0
bond lengths by RI and R z , respectively. (In oxides and silicates, RI is about
216 pm and R z is about 200 pm.) We are interested in the electronic structure of
the dimer at several points along the configurational coordinate q: At q = - A,
we have R(FeA-O) = RI and R(FeB-O) = R z . At q = )~, we have FeA = Rl and
FeB = R I . At q = 0, R(FeA-O) = R(FeB-O) = (RI + R 2)/2. At q = - )~,
the lowest energy configuration is Fe1 + Fe~ +. At q = )~, the lowest energy
configuration is Fel+ Fe~+. If there is a weak coupling between the Fe atoms at
sites A and B (the nature of which will be described below), the states 1/1 I and 1/1 2
will mix to form the new states
P+ = (X 1/1 I + (1 - (Xl)+ 1/12
P _ = (1 - (Xl)1: 1/1 I - (X 1/1 2,
where (X is the delocalization coefficient and describes the degree to which the
Fe2+ [tlg(P)] electron is delocalized over the two sites. From simple pertur-
bation theory,
Here, LIE is the energy difference between 1/11 and 1/12; J is the "resonance
integral" which describes the degree of coupling between the states 1/1 I and 1/11.
At equilibrium, the Fe-Fe pair is at the point q = - Ie: The optical IVCT
transition is then P + ~ P _. The energy for this is indicated by Eop in Fig. 81.
Since (X is small, this effectively corresponds to an electron transfer from site A to
B. The thermally induced IVCT process is for the dimer to stay in the ground P+
state but to move along the q coordinate from q = -)~ to q = )~. If the coupling
between the ionic configurations 1/1 I and 1/1 z is weak (J = J I in Fig. 81), there will
be an activation barrier.
Molecular orbital calculations can give us some insight into the physical
nature of the coupling integral J. Coupling can occur either by direct Fe-Fe
bonding or through "superexchange" via the bridging oxygens. A simple
molecular orbital approach to the problem is to look at the electronic structure
of an (Fe20IO)15- cluster. The electronic structure of this cluster has been
calculated using the SCF-X(X-SW method. Fe2+ ~ Fe3+ charge transfer
is allowed through weak Fe 2+ - Fe 3 + d-orbital overlap across the shared
polyhedral edge. The J parameter is simply a description of the Fe l +- Fe 3 +
5.5 Electronic Structures of Iron Oxides and Silicates 335
O(2pl
-25
by Fyfe (1960). The idea has since been elaborated upon and refined by several
investigators (Strens 1969; Gaffney and Anderson 1973; Tossell 1976; Ohnishi
1976; Sherman 1988). The high-spin to low spin transition is geophysically
important, since it should give a significant volume decrease for FeO and greatly
affect the electronic properties of FeO.
The exchange splitting of the electronic orbitals serves to stabilize electronic
configurations which maximize the number of unpaired electrons. At zero
pressure, the high-spin configuration of octahedrally coordinated Fe 2+,
(2t2g)4(4eg)2 is stable relative to the low spin configuration (2t 2g )6 because the
crystal field splitting, 10 Dq, is smaller than the exchange splitting U ex (the
exchange splitting is that between the spin-up and spin-down Fe(3d) orbitals).
With increasing pressure, the crystal field splitting increases; eventually,
10 Dq > U ex and the low-spin configuration will be stable.
A number of attempts have been made to calculate the free energy of the
HS ~ LS transition of FeO as a function of pressure and temperature (e.g.,
Strens 1969; Gaffney and Anderson 1973; Tossell 1976; Ohnishi 1978; Jackson
and Ringwood 1981; Sherman 1988). Both the volume change, L1V, and the
entropy change, L1S can be estimated from first principles while the internal
energy change, L1U, can be approximated by the spin-pairing energy in
a (Fe06)10- or larger cluster. (This can be estimated from ligand field theory
or molecular orbital calculations.) However, estimating these quantities, in
particular, L1V, is subject to considerable uncertainty. Because the ionic radius
for low-spin Fe 2+ is 17 pm smaller than that for high-spin Fe 2+ (Shannon and
Prewitt 1969), the high-spin to low-spin transition of FeO is predicted to have
a volume decrease (at 0 GPa) near 2.50 cm 3 /mole. However, this is a crude
approximation; a first principles calculation of the equation of state of low-spin
FeO is needed. Nevertheless, it appears that a HS ~ LS transition of FeO
is a physically reasonable possibility within the range of pressures and
temperatures of the Earth's lower mantle.
planetary interiors. Several investigators (e.g., Strens 1976) have proposed that,
at high pressures, FeO might adopt an electronic structure corresponding to the
formal charge configuration Fe +0 -. The Fe +0 - -configuration requires an
O(2p) electron to be excited to the Fe(3d) band. It is clear, however, that the
internal energy of such a charge-transfer state is much too high to have any
geophysical significance.
One possible explanation (Sherman 1989) for the high-pressure metallization
of FeO is a breakdown of the Mott insulting condition (Mott 1961). This
illustrates an important case where the one-electron picture of electronic struc-
ture fails; hence, it is worthwhile to outline the essential idea. In FeO, the
minority spin t 2g Fe(3d) band is partially occupied. In the early Bloch-Wilson
view of electronic structure, this would imply that FeO should be metallic.
However, the t 2g Fe(3d) electrons are localized to their parent Fe atoms by the
interelectronic repulsion or correlation energy (Mott 1961). The correlation
energy might be thought of as that required for the charge transfer transition
Fe2+ + Fe 2 + --+ Fe 3 + + Fe+.
This energy is often referred to as the Hubbard gap and results, in part, from the
increased interelectronic repulsion that must be overcome to form an Fe +
cation. Phases which have localized electrons due to the correlation energy are
referred to as Mott insulators. The inclusion of this correlation energy is
a fundamental problem for electronic structure calculations and requires us to
go beyond the one-electron orbital formalism. The Hubbard gap for FeO is
presumably on the order of several electron volts so that the charge transfer
transition as given above is not possible under geophysically significant temper-
atures. Mott insulators can become metals if the 3d electrons have enough
kinetic energy to overcome the correlation energy. This is expected to occur at
high pressure and temperature: The kinetic energy increases with the width of
the Fe(3d) band which, in turn, increases with (nominally weak) metal-metal
bonding interactions between next-nearest neighbor Fe atoms. Fe- Fe bonding,
of course, increases with decreasing Fe- Fe separation. This mechanism for an
insulator (or semiconductor) to metal transition is known as a Mott transition.
Although FeO may become metallic at high pressures, we might expect it to
ultimately return to an insulating state if it undergoes a high-spin to low-spin
transition. Of course, if, with increasing pressure, FeO undergoes a high-spin to
low-spin transition before it undergoes a Mott transition, we would never see
metallic behavior in FeO. Since we do not know the equation of state for
low-spin FeO and the critical Fe-Fe separation needed to induce a Mott
transition, it is not clear which electronic phase transition FeO might undergo
first at high pressure.
The apparent metallization of FeO implies that FeO remains high-spin at
least to 70 GPa. Low-spin FeO could not be metallic because the t 2g band
would be full. This would imply that the volume change for the spin-pairing
transition is much smaller than that expected from ionic radii considerations.
An interesting possiblity is that FeO has adopted the CsCI structure at high
338 Chapter 5. Chemical Bonding in Minerals
References
Amthauer G, Rossman GR (1984) Mixed valence of minerals with cation clusters. Phys Chern
Mineral 11: 37-51
Banks RJ (1972) The overall electrical conductivity distribution of the Earth. J Geomagn
Geoelect 24: 337-351
Biazey KW (1977) Optical absorption of MgO:Fe. J Phys Chern Sol 38: 671-675
Burns RG (1981) Intervalence transitions in mixed valence minerals of iron and titanium.
Annu Rev Earth Planet Sci 9: 345-383
Burns RG, Nolet DA, Parkin KM, McCammon CA, Schwartz KB (1979) Mixed valence
mineral of iron and titanium: correlations of structural, Mossbauer, and electronic spectral
data. In: Brown DB (ed) Mixed-valence compounds. Riedel, Boston, pp 295-336
Cheng JC, Kemp JC (1971) Magneto-optical study of the spin-lattice relaxation of Fe3+ in
MgO. Phys Rev B Condens Matter 4: 2841-2846
Ducruix J, Courtillot V, Mouel JL (1980) The late 1960s secular variation impulse, the eleven
year magnetic variation and the electrical conductivity of the deep mantle. Geophys JR Astr
Soc 61: 73-94
Fujimori A, Kimizuka N, Taniguchi M, Suga S (1987) Electronic structure of Fe,O. Phys Rev
B 36: 6691-6694
Fukao Y (1969) On the radiative heat transfer and the thermal conductivity in the upper
mantle. Bull Earthquake Res Inst Tokyo Univ 47: 549-569
Fyfe WS (1960) The possibility of d-electron coupling in olivine at high pressures. Geochim
Cosmochim Acta 19: 141-143
Gaffney ES, Anderson DL (1973) Effect of low-spin Fe2+ on the composition of the lower
mantle. J Geophys Res 78: 7005-7014
Goodenough JB (1980) The Verwey transition revisited. In: Brown DB (ed) Mixed-valence
compounds. Reidel, Dordrecht, Netherlands, pp 413-415
Goodenough JB (1972) Metallic oxides. Prog Sol State Chern 5: 1-399
Jackson I, Ringwood AE (1981) High-pressure polymorphism of the iron oxides. Geophys JR
Astr Soc 64: 767-783
Jeanloz R (1989) High-pressure chemistry and physics of the Earth's mantle and core, chap 4,
In: Peltier WD (ed) Mantle convection, pp 203-259
Jeanloz R (1990) The nature of the Earth's core. Annu Rev Earth Planet Sci 18: 357-86
Jeanloz R, Ahrens TJ (1980) Equations of state of FeO and CaO. Geophys. J R Astr Soc 62:
505-528
Johnson KH (1973) Scattered wave theory of the chemical bond. Adv Quant Chern 7: 143-145
Knittle E, Jeanloz R (1986) High-pressure metallization of FeO and implications for the
Earth's core. Geophys Res Lett 13: 1541-1544
5.5 Electronic Structures of Iron Oxides and Silicates 339
Krebs JJ, Maisch WG (1971) Exchange effects in the optical absorption spectra of Fe3+ in
A1 20 3. Phys Rev B4: 757-769
Lad RJ, Henrich VE (1989) Photoemission study of the valence-band electronic structure in
Fe,O, Fe304 and IX-Fe203 single crystals. Phys Rev B 39: 13,478-13,485
Lohr LL (1972) Spin-forbidden electronic excitations in transition metal complexes.
Coordination Chern Rev 8: 241-259
Mao HK (1976) Charge-transfer processes at high pressure. In: Strens RGJ (ed) The physics
and chemistry of minerals and rocks. Wiley, New York, pp 573-582
Mott NF (1961) The transition to the metallic state. Philos Mag 6: 287-309
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Ohnishi SA (1976) A theory of the pressure-induced high-spin to low-spin transition of
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Ringwood AE (1977) The composition of the core and implications for origin of the Earth.
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Rossman GR (1975) Spectroscopic and magnetic studies of ferric iron hydroxy sulphates:
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Rossman GR (1976) Spectroscopic characteristics and magnetic studies of ferric iron hydroxyl
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340 Chapter 5. Chemical Bonding in Minerals
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Hydrogen Bonds
Hydrogen-Bearing Groups
°
(0 H rand (H 2 0) in the Structural Unit. The structural unit of a mineral is
that part of the structure that is strongly bonded together (e.g., a feldspar
framework, a mica sheet). For both (OH)- and (H 20)O, the bonding on the
anionic side of the group is fairly strong [ '" 1.2 v.u. for (OH) - and '" 0.4 v.u.
5.6 Hydrogen Bonding in Minerals 341
•I
0.2 ! .:0.33
. •.
I
~
0.33:
I
I
OH
(a) (b)
,
i
:0.33
(c)
(e)
(d)
If
,"0.25
•......
0.25
0.25
•...... 0.25, •... 0.25
}I' "
for (H 2 0)D] whereas the bonding on the cationic side of the group is much
weaker ( '" 0.2 v.u. for both groups). Thus on the anionic side of the group, the
strong bonding constitutes part of the bond network of the structural unit;
conversely, on the cationic side of the group, the hydrogen bond is too weak to
form part ofthe bond network ofthe structural unit. The role of both (OH)- and
(H 2 0)o is thus to "tie off" the polymerization of the structural unit in specific
directions. This is illustrated for artinite (Mg 2 (C0 3 )(OH}z(H 2 0h) in Fig. 84; the
occurrence of both (OH)- and (H 2 0)0 as anions bonded to octahedrally
coordinated Mg prevents further structural polymerization in any direction
except along the length of the ribbon. Thus the dimensionality of the structural
unit of a mineral is primarily controlled by the amount and role of hydrogen in the
structure. As the character of the structural unit is the primary factor affecting
the physical properties and stability of a mineral, it follows that hydrogen is
perhaps the most significant element in controlling the properties and behaviour
of minerals.
(H 2 0)0 Bonded Only to Interstitial Cations. Cations whose bonding is too weak
to be considered as part of the bonding network of the structural unit are called
interstitial cations; these are generally alkalis and alkaline earths. (H 2 0)0 can act
342 Chapter 5. Chemical Bonding in Minerals
• OH
Fig. 84. The structural unit in artinite, a ribbon of (Mg06) octahedra and (C0 3 ) triangles; all
anions not bonded to carbon are either (OH) - or (H 2 0)O
as a ligand for these cations, and often does for one or more of the following
reasons:
1. to satisfy bond-valence requirements around the interstitial cation in cases
where there are insufficient anions available from adjacent structural units;
2. to transfer bond-valence from the interstitial cation to a distant unsatisfied
anion of an adjacent structural unit;
3. to act as a bond-valence transformer between the interstitial cation and the
anions of the structural unit.
The structure ofstringhamite {Ca[Cu(Si0 4 )](H 2 0)} is a good example (Fig. 85).
The structural unit is a sheet of corner-sharing (Si0 4 ) tetrahedra and square-
planar (Cu0 4 ) groups arranged parallel to (010). These sheets are linked
together by interstitial Ca atoms, each Ca linking to 4 anions of one sheet and 1
anion of the adjacent sheet. The coordination number of [5], rarely observed for
Ca, is not adequate with regard to the satisfaction of local bond-valence
requirements at the Ca, and 2 (H 2 0)0 complete the Ca coordination; in addition,
these (H 2 0)0 groups carry the bond-valence (via hydrogen bonding) from Ca to
anions too far away to bond directly to Ca. Thus the structural role of such
(H 2 0)0 groups is very different from when (H 2 0)0 is part of the structural unit.
f
a
b ~I
Fig. 85. The crystal structure of stringhamite, showing the structural units linked by Ca that
also bonds to two interstitital (H 2 0)O groups
There are three principal methods by which presence and stereochemical details
of hydrogen-bearing groups can be detected: (1) neutron diffraction; (2) X-ray
diffraction; (3) infrared spectroscopy.
344 Chapter 5. Chemical Bonding in Minerals
.. , //
-1';:'' \
r" ~
,,
Tb
i . '
1 I~ a
------,I-~" "' - """"'"
I
+!,
-....,(
,
\ ~
~I
Fig. 86. The crystal structure of mandarinoite; note the two types of (H 2 0)O groups, one
bonded to cations of the structural unit, and the other held only by a network of hydrogen
bonds
X-Ray Diffraction. Hydrogen scatters X-rays very weakly, and the location of
hydrogen atoms directly by crystal structure refinement of X-ray data can be
difficult or unreliable. However, bond-valence and stereochemical arguments
involving the rest of the structure are generally sufficient to derive accurate
(although not very precise) hydrogen locations and/or details of hydrogen-
bearing groups present.
o+ vI o+ v2
(a) / ~ 3652cm- 1 (c) / ~ 1595cm-1
/'
H H
~
H
---.... -
....
H
(b)
Fig_ 87. The three normal modes of vibration for the H 2 0 group. a Symmetric stretch.
b Asymmetric stretch. c Symmetric bend
bonding; weak hydrogen bonds have absorption frequencies around 3600 em -1,
the frequency decreasing with increasing hydrogen-bond strength. The (HzO)O
group is a little more complicated. There are two fundamental stretching
motions and one bending motion (Fig. 87), and these give rise to a set of
characteristic absorptions in the infrared (Table 28), the exact energies of which
are affected by details of local stereochemistry. Thus polarized infrared spectro-
scopy is a powerful method for detecting the presence of hydrogen in a mineral,
and for determining its speciation. In turn, the method can also be used as a
probe of local structure (particularly order jdisorder) when details of the hydro-
gen speciation are known. This method has been particularly important in
detecting the presence of minor to trace amounts of hydrogen in minerals
previously thought to be anhydrous (e.g., olivine, feldspar, garnet).
There are approximately 3500 known minerals, and the maJonty of these
contain hydrogen as a major constituent. As noted above, both (OH)- and
(H 2 0)0 exert a dominant control on the dimensionality of the structural unit. It
is apparent that it is the availability of hydrogen, together with the weak and
anharmonic nature of the hydrogen bond, that accounts for the gradual increase
in number and complexity of minerals from the core through the mantle and
crust to the surficial environment.
References
Baur WH (1965) On hydrogen bonds in crystalline hydrates. Acta Cryst 19: 909-916
Baur WH (1972) Prediction of hydrogen bonds and hydrogen atom positions in crystalline
solids. Acta Cryst B 28: 1456-1465
Brown ID (1976) On the geometry of O-H ... O hydrogen bonds. Acta Cryst A 32: 24-31
Emsely J, Jones DJ, Lucas J (1981) Detecting and measuring strong hydrogen bonds: recent
developments. Rev Inorg Chern 3: 104-140
5.6 Hydrogen Bonding in Minerals 347
Properties of Minerals
350 Chapter 6. Properties of Minerals
Elasticity of solids is the property that restores their form after deformation. The
elastic properties of minerals and rocks are widely utilized in geophysics and
geochemistry to interpret information on the interior of the Earth and other
planets; these properties are indispensable in solid state physics for constructing
the acoustic branch of vibrational spectra and equation of state, and also in
geotectonics for characterizing the rheology of the Earth's crust and mantle.
To describe deformation of a single crystal, the continuous medium model
is generally used. In this model a material point represents a volume element
consisting of a great number of lattice cells. For a perfectly elastic ma-
terial Hooke's law establishes a linear relation between the stresses O"j and the
strains Gj:
6 6
O"j == L C j/ j
j = I
or Gj = L1 SjPj,
j=
where C jj are the elastic constants (the stiffness constants or elastic moduli), Sjj
are the elastic compliance coefficients, the indices 1,2,3 refer to the normal stress-
strain values, and 4,5,6 to similar shear characteristics.
The anisotropy of a crystal lattice leads to the anisotropy of elastic prop-
erties characterized by a set of elastic constants Cjj or Sjj. The number of
independent moduli corresponding to the crystal symmetry varies from 21 for
triclinic crystals to 3 for cubic crystals.
By using special combinations of the Cjj in an averaging procedure, we may
define two independent elastic moduli that completely describe the elasticity of
homogeneous, isotropic mineral aggregates. In practice, however, it is more
convenient to use a set of interrelated elastic characteristics such as Young's
modulus E, shear modulus 11, and bulk modulus K = - VL1P/L1V, where Pis
pressure and V is volume, Poisson's ratio 0", etc. All these values depend on the
thermodynamic P-T conditions of the deformation process. Therefore we
distinguish the isothermal and adiabatic constants KT and Ks as well as the
elastic constants Cr;
or C~j. In particular for isotropic material we have:
Ils = IlT' Ks = p(ap/ap)s = KT(l + ayT), Ks/KT = Cp/C v ,
where p is density, a = V-I (aV/aT)p is the volume coefficient of thermal
expansion, y = aKs/ pCp the thermal Griineisen parameter, and Cp and C v are
heat capacities at constant pressure and volume, respectively.
There are numerous possible schemes for averaging Cij over all of the lattice
orientations that give isotropic mineral properties. The most widely utilized
scheme for practical reasons is the method of Voigt-Reuss-Hill (VRH), which
averages Ks and 11. In the case of strongly anisotropic crystals with low
symmetry, the accuracy of VRH averaging is not sufficient, and the more
complicated Hashin-Strickman method is recommended as physically valid.
6.1 Elastic Properties of Minerals 351
The elastic moduli, K s , 11, and the density, p, determine one longitudinal
or compressional Vp and the two shear or transversal wave velocities Vs in
isotropic aggregate:
V~ = Ks + 4/3 11 , V~ = ~.
p p
The elasticity of heterogeneous polyphase mineral aggregates such as rock
can be characterized by a set of polycrystalline elastic moduli or constants Cij.
These values are related to the preferred orientation of constituent mineral
components. It should be mentioned that available seismic data for the Earth's
upper mantle suggests rather essential elastic anisotropy that could be inter-
preted in terms of the texture of anisotropic grains of olivine and the stress
fields in the mantle.
For a statistically isotropic, single-phase polycrystal which consists of a
compact mixture of chaotically oriented, small crystallites, the elastic constants
are naturally averaged values and consequently, measured velocities of Vp and
Vs in such a material should be close to the averaged properties of the
monocrystal. Experiments on natural and synthetic isotropic samples, however,
show different and not always understandable occurrences of their texture,
porosity, and other microstructural features which can plausibly account for the
observed discrepancies in elasticity of poly- and monocrystals. Thus in geophys-
ical applications, preference is given to monocrystal elastic data.
The macroscopic elastic properties of minerals are directly related to forces
acting between microscopic structural units of the mineral: atoms, ions, ion
clusters, and electrons. These forces are integral weighted characteristics of
interatomic interactions. For example, the elastic constants Cij can be expressed
in terms of the lattice-summarized force constants which represent the second
derivatives of the monocrystal potential energy on atomic displacements from
their equilibrium positions. The influence of temperature atomic vibrations on
elasticity is taken into account by the expansion of potential energy in a series of
atomic displacements. The truncation of the second order terms leads to a
quasi harmonic approximation but only the fourth order terms give complete
anharmonic approximation.
In a crystal lattice containing N atoms, the vibrational spectrum consists of
3N different types of oscillations or modes. The three elastic modes form the
acoustic branch and the remaining 3N - 3 oscillations form the optical branch of
the spectrum. In some circumstances, as proposed by Debye, the vibrational
spectrum can be entirely approximated by the acoustic branch. In this case, the
solid is considered as an isotropic elastic continuum, and the number of all the
elastic modes is assumed to be equal to 3N. In such a case, the vibrational
spectrum is limited by the highest cutoff frequency, Wm' which corresponds to a
Debye temperature eo : eo = wmfl/k, where fl is Planck's constant, and k is the
Boltzmann constant. In the Debye model, eo is expressed in terms of velocities of
the longitudinal Vp and the transversal Vs acoustic waves. In a low temperature
region when T ~ eo, almost all the optic lattice modes are "frozen" and the rest
of spectrum consists of only elastic vibrations which are correctly described
352 Chapter 6. Properties of Minerals
Elasticity of Minerals
Oxides
RPR data which had been obtained before 1983 for different simple oxides were
repeated for periclase and corundum over a temperature range up to 1300 K,
and showed that in general the values of Cij diminished linearly with temper-
ature. This fact leads to the approximately linear decrease of values Ks and j1. at
elevated temperatures. These results, combined with additional independent
data on volume thermal expansion, a:(T), and heat capacity, C p , have given other
elastic and thermodynamic characteristics for oxides. Thermal Griineisen
gamma Ylh is influenced insignificantly on T at P = const, but at V = const for
all considered minerals Ylh essentially decreases with T up to 30%, which
suggests some serious deviations from the Mie-Griineisen approximation
Y = y(V). At high temperatures, anharmonic parameters J T and J s tend
to constant values which satisfy a condition J T - J s ~ y. This corresponds to
(aKT/aT)v ~ 0, or with a good approximation J T ~ K~ and a:*K T ~ const.
These high-temperature elastic properties have been for the most part
confirmed by further RPR measurements on synthetic samples of periclase and
corundum over a temperature range of 1800 K (e/T = 1.8-2.2). Some weak
deviations from the usual linearity Cij(T) have been demonstrated at the highest
temperatures. It was especially pointed out that at extremely high T, distinctions
and scattering data of thermal expansion volume coefficient a:(T) strongly
influenced anharmonic properties, but calculated values of moduli Cij were
practically independent of a:(T) data.
Ultrasonic measurements (USV) of elasticity on MgO have been extended
to 78 kbar under quasi-hydrostatic conditions. The Birch-Murnaghan theory,
applied for extrapolation with experimental C jj , predicted elastic softening of
. Cll -C 12
modulus C 44 at - 1 Mbar, but a hardemng of shear constant C s = 2
that led to lattice instability and phase transition in the vicinity of 1 Mbar. The
next unusual result of extrapolation was a negative mean a:(T) at pressures
> 500 kbar, which could not be explained without the assumption on phase
transition.
Elastic moduli of spinel, MgAI 2 0 4 , up to 60 kbar showed agreement in
moduli with previous measurements, hence P derivatives received at high
pressure had marked difference from those at lower pressures. Extrapolation to
higher pressures according to the Birch-Murnaghan equation leads to softening
of the elastic moduli - all Cij < 0 and Ks < 0 at P > 200 kbar. This latter
confirms the supposed mechanical instability in spinels and testifies in favor of a
similar explanation of seismic anomalies in the transition zone of the mantle.
354 Chapter 6. Properties of Minerals
Silicates
The elastic properties of olivine have been studied in greater detail than any
other silicate material. High temperature RPR data on C ij of forsterite up to
1700 K (TIf) = 2.3) reveal the same regularities as in oxides: an almost linear
decrease of Vp and Vs with rising temperatures, a decrease of isothermal bulk
modulus with temperature being more essential than that of adiabatic value, K s ,
the difference reaching 10% at high T. From linear temperature dependence of
Vs and Vp, an important parameter v = (aln VslaIn Vp) ~ 1-1.4 has been found.
However, recent values for the lower mantle are v = 2 -:- 3.
Elastic moduli C ll-C 66 of forsterite, investigated up to 40 kbar in a
diamond anvil cell by BS, are almost the same as those measured by ultrasonic
methods. The pressure derivatives C'1l-C~3 are 7-22% higher than those
determined by USV, but C~4' C~5' and C~6 are lower. Negative values of second
P derivatives C~4' C~5' C~6 confirm Pourier's proposed mechanism for the
transformation from olivine to spinel structure by gliding of oxygen close-
packed layers.
A complete set of elastic moduli and their P-T derivatives have been
measured by USV for fayalite. These data are in excellent agreement with the
static X-ray measurements up to 70 kbar, but they differ significantly from high
temperature RPR results, which give values of Ks 8% higher.
The elastic properties of olivines - forsterite-fayalite solid solutions - have
an almost linear correlation with end members, as was established by ultrasonic
measurements of 12 intermediate compositions. The results of the investigation
are inconsistent with the systematic decrease in bulk modulus with increasing
molar volume found in olivine-structured silicates. For all silicate olivines the
longitudinal moduli decrease in the order C II > C 22 > C 33 , regardless of
composition.
Single crystal elastic moduli or y- and fJ-spinel phases of Mg 2 Si0 4 have been
determined by Brillouin scattering at ambient conditions. Values of the bulk
moduli of both of these phases are lower than previous measurements. Elastic
properties of y- and fJ-spinels Mg 2 Si0 4 are quite similar, with the greatest
differences related to the C axes of the beta, which is relatively softer under
compression. The polycrystalline acoustic velocities differ by only 1% for these
two phases. Thus there should be no seismic discontinuity associated with a beta
to gamma phase transitions. The derivatives of elastic moduli with respect to
iron content are very similar to those observed in olivine phases. The most
striking similarity of elastic moduli between IX-olivine and y-spinel is C II of
olivine and C~ I of spinel, which represent the stiffness along the close-packed
directions of each polymorph.
In silicate, as in other spinels, elastic anisotropy increases rapidly if the
crystallographic parameter, U, approaches a limiting value near 0.27, which may
be related to the mechanical stability of the spinel structure. Therefore, germa-
nium spinels which have U ~ 0.3-0.32 are inappropriate analogies of elastic
properties for silicate spinels. Polycrystalline y-Mg 2 Ge0 4 has pressure deriva-
6.1 Elastic Properties of Minerals 355
tives, especially /l', essentially lower than the values for spinel, MgA1204' and
y-Mg zSi0 4·
The bulk moduli of orthopyroxenes measured by different methods are
essentially constant for all compositions, but shear modulus, /l, decreases
linearly with increasing iron content. A striking feature in the ultrasonic data for
monocrystal bronzite, Enso and MgSi0 3 , is a high mean for the first (and/or
second) pressure derivative, K' = 10-11, that is much greater than the usual
range for many minerals K' = 4-6.
The same insignificant variations of moduli among Mg-Fe-Ca-bearing
monoclinic pyroxenes was demonstrated by BS measurements of hedenbergite
at P = 0. The dependence of the elastic properties on the composition of the
Ml site is affected by the composition of the M2 site. The substitution of AI3+
for Fe3+ on the Ml site has a great effect on those moduli when Na 1 + occupies
the M2 site instead of Ca Z +.
The high pressure phase of pyroxenes which constitutes the lower mantle of
the Earth is cubic or orthorhombic perovskite-like polymorph. Elastic proper-
ties of orthorhomobic MgSi0 3 were investigated by BS. Measured moduli are
10% lower than previously determined in diamond anvil cells, but the agree-
ment is reasonable when uncertainties of the compression studies are taken into
account. A MgSi0 3 is considered to be a ferroelastic phase. A great number of
single-crystal elastic moduli reflect the rigidity of the Si0 6 octahedron under
compression and shear. In particular the ratio of the shear modulus to bulk
modulus MgSi0 3 is larger than has been reported for any other compounds in
the structure of perovskite. This behavior is consistent with earlier observations
on the elastic properties of stishovite and MgSi0 3 ilmenite; but P and T
derivatives of bulk and shear moduli for the perovskite phase are not yet known
in detail.
The elastic moduli of garnet solid solutions have been measured by various
methods including RPR, USV, and BS, and they are safely described by the
linear relationship between the properties of end members. However, data on
the elasticity of majorite are inconsistent. According to ultrasonic measure-
ments, the elastic moduli of solid solution 70% of pyrope-30% of majorite are
almost the same as for pyrope, but X-ray data on the elasticity of solid solution
42% Py-58% Mj reveal a marked decrease in majorite bulk moduli in com-
parison with those for pyrope. There is the same tendency towards a decrease in
bulk modulus for almandine-ferrous majorite solid solution with increasing iron
content.
the lower mantle. According to seismic tomogrpahy, the mean c5 T ~ 2-3, but for
many substances, experimental data and equations of state showed that c5 T ~
4-6. It is supposed that the differences in c5 T are caused by variations in the
composition or the viscous peculiarities of the mantle.
The equation of state is directly connected with bulk moduli Ks or K T ·
Another principal parameter of isotropic minerals is the shear modulus, j1.,
which enters the equation of state in a nonevident way. Shear modulus is more
sensitive to the crystal structure of mineral than bulk modulus, but there are no
reliable methods to measure j1. at a pressure of more than 100 kbar. Hence the
study of this parameter influenced by T and P is of great interest, as it offers the
possibility of appreciating the rheological properties mantle of the Earth and
associating them with tectonic movements and continental drift.
References
S.V. TITKOV
The scratching and indentation methods are most widely used in miner-
alogy.
The Mohs' scratch hardness is defined as the ability of one mineral to be
scratched by another, harder mineral. Suggested in the early 19th century by
F. Mohs, the hardness scale of ten standard minerals has been applied up until
now. This scale is not linear, the difference in hardness between the first standard
minerals being much less than that between the last ones. Modern handbooks
give the optimal test planes of the standard minerals to eliminate the hardness
anisotropy effect.
The Vickers hardness, measured by indenting a diamond pyramid into
the mineral being tested, is determined as the ratio of the indentor load to
the indentation lateral area. After the removal of the load, the diagonal of the
pyramid indentation base is measured, and the indentation apex angle is taken
by convention to equal the indentor apex angle. Besides the Vickers square
pyramid, the Berkovitch triangular pyramid and Knoop rhombic pyramid are
used.
The indentation hardness is sometimes referred to as micro hardness, since
the measurements are performed in a limited region.
Many hardness data are express\!d as either Mohs or Vickers hardness, so
that conversion from one scale to the other is necessary. A comparison between
the Mohs and Vickers hardness reveals a nearly parabolic dependence. Nu-
merical correlations between Mohs and Vickers hardness for index minerals
were proposed by Reckmann: Hv = 86.3 - 90.9Hm + 34.6H~, and by West-
brook and Conrad: Hv = 5.25H!" 73.
Hardness of minerals is determined first and foremost by crystallochemical
factors. The hardness value varies in inverse proportion to the crystal inter-
atomic spacing (isodesmic compounds are characterized by an inverse quadratic
dependence). The hardness increases as the cation valence increases, which is
revealed even more strongly with the simultaneous increase in the anion valence.
The hardness increases discontinuously with the increase in the coordination
number. An increase in hardness is also observed at a higher density of atomic
packing. Other conditions being equal, mineral hardness increases at the
transition from the ionic to the covalent bond. The influence of the electron shell
structure is revealed particularly by the fact that the presence of the electron gas
shell reduces the hardness. The presence of hydroxyl or water molecules in the
mineral structure always reduces the hardness.
Proceeding from the main crystallochemical parameters, different formulae
for the calculation of mineral hardness have been suggested. However, the
theoretical results and the experimental data disagree appreciably. This is
related to the fact that being a strength characteristic, mineral hardness is also
determined by the peculiarities of the crystal internal structure and depends on
the presence of various types of dislocations, disoriented blocks, microinclu-
sions, and other defects. For example, the hardness of halite is 18-22 kg/mm2 for
ordinary cubic crystals and can be as high as 90 kg/mm2 for threadlike
dislocation-free crystals. Therefore, both the crystallochemical factors and the
360 Chapter 6. Properties of Minerals
crystal internal structure should be taken into account in the estimation of the
mineral hardness.
Compressibility of minerals is the isothermal change in volume of a crystal
with pressure, fJ = - (~) (:;)T. This property depends upon the same factors
that determine hardness. Compressibility can be measured directly from the
change in volume with confining pressure or can be computed from elastic
constants. The bulk modulus of minerals is the reciprocal of the compressibility,
and is more useful. Plendl et al. (1965) expressed the empirical correlation
H
between hardness and compressibility as: l/fJ = --/-, where Z is the maximum
Zm q
valence, m the number of components, and q the number of atoms per molecule.
It should be noted that in chemistry hardness is defined as the resistance of
the chemical potential to change with regard to the number of electrons
assumed for the classification of reactivity of molecular species. However, two
very distinct concepts of hardness, one for the microscopic chemical reactivity,
the other for microscopic mechanical resistance to destruction of minerals, have
a common ground in thermodynamics: they are both measures of N(Ofl/oN) or
its multicomponent generalization, where N is number of electrons, fl the
chemical potential. On the basis of this analogy, a theoretical relation between
mineral hardness (H) and compressibility (fJ) was proposed by Yang et al. (1987):
M
H = --, where M is the molecular weight, P the density, and q the number of
PqfJ
atoms in a formula unit.
The cohesive energy of solid state materials is defined as the work required
to dissociate 1 mol of the substance into its free constituents. It characterizes the
bond strength of the crystal and determines all its mechanical properties.
Cohesive energy U of an ionic crystal may be calculated using the equation:
U = - (ZaZce2NA/Z)(1 - l/n), where Za is the anionic valence, Zc the cationic
valence, e the electronic charge, n the repulsive force parameter, r the mean
atomic radius, Na Avogadro's number. Goble and Scott (1985) showed that the
Mohs hardness is proportional to the second derivative of the volumetric
cohesive (lattice) energy with a change in the interatomic distance (d 2U/dr2)ro.
References
Ivan'ko AA (1971) Handbook of hardness data. Israel Program for Scientific Translations,
Keter Press, Jerusalem
Plendl IN, Mitra SS, Gielisse PJ (1965) Compressibility, cohesive energy, and hardness of
nonmetallic solids. Phys Stat Sol 12: 367-374
Povarennykh AS (1964) A calculation of the hardness of minerals on the basis of crystallo-
chemical data. In: Battey MH, Tomkieft' SI (eds) Aspects of theoretical mineralogy in the
USSR. Macmillan, London
Simmons G, Wang H (1971) Single crystal elastic constants and calculated aggregate
properties: a handbook. The Mass Inst Technol Press, Cambridge, Mass
Urysovskaya AA (1981) Mechanical properties of crystals. In: Modern crystallography, vol 4.
Vainstein BK, Chernov AA, Shuvalov ZA (eds) Physical properties of crystals. Science,
Moscow (in Russian)
Wang HF (1978) Elastic constant systematics. Phys Chern Minerals 3: 251-261
Westbrook JH, Conrad H (1973) The science of hardness testing and its research applications.
Am Soc Metals, Columbus, Ohio
Yang W, Parr RG, Uytterhoeven L (1987) New relation between hardness and compressibility
of minerals. Phys Chern Minerals 15: 191-195
Yushkin NN (1971) Mechanical properties of minerals. Science, Leningrad (in Russian)
CA. BROOKES
The reader is referred elsewhere for a more general treatment of the hardness of
minerals (Bowie and Simpson 1977) but here we shall address the problems of
such measurements in very hard materials by summarizing work on diamond.
Not only is this the hardest material, but it is also the one where the phenomena
described below are most marked and therefore where control of the experi-
mental conditions will be critical in obtaining reproducible and accurate results.
The original Mohs hardness scale, which was based simply on the ability of
one mineral to make a visible scratch on the surface of another, represents a
remarkably diligent piece of research on many more materials than the ten listed
in the scale. However, a scratch can sometimes be produced on one material by
another whose Mohs number may be lower by up to two increments and the
introduction of indentation techniques enabled more quantitative measure-
ments to be made. The first method of measuring indentation hardness (Brinell)
was based on the use of a steel sphere to obtain a hardness number after dividing
the applied normal load by the curved surface area of the indentation. Such
indenters develop tensile stresses just outside the area of contact which encour-
age brittle fracture, rather than plastic flow, with a consequent lack of accuracy
in measurement of the permanent indentation. The pyramidal indenters -
Vickers, Berkovich, and Knoop - have all been used to indent the hardest solids
(Brookes and Moxley 1975) but there is little doubt that the shape of the Knoop
indenter is best suited for accuracy; minimizing cracking in the specimen; and
maintaining its own shape. This indenter has a rhombohedral base and pro-
duces an indentation in which, with the normal load still applied, the long
diagonal is seven times the length of the short diagonal. On removal of the load,
362 Chapter 6. Properties of Minerals
the long diagonal does not change, but elastic recovery of the short diagonal
occurs -- for diamond this recovery results in a ratio of about 14 rather than
seven. The projected area ofthe unrecovered indentation is determined using the
long diagonal length only, i.e., assuming the short diagonal to be about seven,
and dividing this area into the applied normal load yields the Knoop hardness
value in terms of a mean pressure. There is a direct linear relationship between
the relevant Mohs number and indentation hardness values for all minerals -
except for diamond (Tabor 1970). In this case, the extrapolation of the straight
line relationship for Mohs numbers 1 (talc) to 9 (corundum) would correspond
to a value of 15 and not 10. However, here we shall be concerned principally
with the Knoop indenter and we may note that 0.5-100 Gpa (50 to
10 000 kg/mm2) covers the range of hardness values for most materials. A more
detailed account of the important experimental variables which influence
hardness measurements has been published previously (Brookes 1984) but these
will be summarized.
The first consideration of the size of the indentation is with regard to the volume
of material which is being deformed by the indentation process. In the case of
metals, grain boundaries cause an increase in the measured hardness if that
volume extends beyond one grain. Hence, single crystals are significantly softer
than polycrystalline specimens of the same metal and the hardness value
increases with decreasing grain size. In minerals, grain boundaries are generally
much less important in hardness measurements - other than when associated
with impurities and/or environmental reactions. The hardest materials also have
a tendency to fracture and, since this is exacerbated with increasing normal
loads, most definitive measurements have been carried out at low loads within
individual crystals, i.e., micro-indentation hardness.
The law of geometrical similarity implies that, for pyramidal indenters, the
hardness of a crystal should be independent of the normal load. However, it is
now well established that, for measurements using normal loads of less than
20 N, the indentation hardness tends to increase with decreasing load (P) for all
crystalline solids, such that:
P = Ad n ,
where d is the diagonal length of the indentation, A is a constant and n < 2.
When the hardness is load independent n = 2, and therefore the magnitude of
the effect is increased as the value of the exponent decreases [i.e., H = f(d)-n].
This indentation size effect is such as to become more pronounced as the
intrinsic hardness ofthe specimen material increases. Thus, the lowest value of n
reported is that of about 1.5 for diamond whilst sapphire is 1.8 and most metals
are around 1.95. No entirely satisfactory explanation of the mechanism respons-
ible for this effect has yet been developed, but it does explain the apparent
6.2.2 Problems of Extra Hard Materials 363
discrepancy in hardness values quoted over the range of 80 Gpa to 180 Gpa for
diamond. This particular experimental variable has very important implications
for the measurement of the hardness of diamond and diamond-like coatings. In
those particular applications, the coating is generally a few micrometers thick
and light loads are necessary in order to keep the deformation within the
coating. Consequently, we should anticipate values of hardness towards the top
of this range.
The intrinsic rigidity and strength of diamond is due to the fact that every
carbon atom shares an electron with each offour nearest neighbors, i.e., covalent
bonds with tetrahedral coordination, representing the strongest possible type of
interatomic binding in crystals. Consequently, diamond has the highest theoret-
ical values of cleavage fracture stress and shear stress of any solid, i.e., 205 GPa
and 121 GPa respectively (Kelly 1966). In fact, these theoretical values are
6.2.2 Problems of Extra Hard Materials 365
reduced by stress concentrators on one hand and dislocations on the other but it
is unlikely that the hardness of diamond will be surpassed when measured with
due regard to the experimental variables identified earlier.
Nevertheless, the recent development of the so-called soft indenter technique
demonstrates vividly that hard materials can be plastically deformed, work
hardened, and worn by softer ones (Brookes et al. 1987). Thus, the clearest
demonstration of the difference in mechanical properties of various types of
diamond has been achieved through pressing a cone of cubic boron nitride onto
(001) surfaces at elevated temperatures. Whilst the cone blunts under the applied
normal load, the mean contact pressure is sufficient to initiate bulk plastic flow
and creep in the diamond. On the basis of this work, it has been shown that the
threshold temperature marking the onset of plastic flow is about 750 DC for
synthetic type Ib crystals, 950 DC for natural type la, 1000 DC for type lIb and
1100 DC for type IIa diamonds. In addition, whilst dislocation-induced cracking
on {1l0} planes is observed in both type I diamonds, fracture does not develop
around the impressions in type II. It is considered likely that the presence of
nitrogen in type la and Ib plays an important role in determining this mode of
behavior but, clearly, more research with this technique will provide valuable
information concerning the conditions which encourage plasticity in all hard
crystalline materials. Already we are able to confirm that the indentation
hardness of such materials is about 30 times the relevant critical resolved shear
stress - thus indicating that even the hardest of solids can be mechanically worn
by significantly softer ones.
References
Bowie SHU, Simpson PR (1977) Microscopy: refllight. In: Zussman J (ed) Physical methods in
determinative minerology, Chapter 3, Academic Press, London, 720, 2nd edn, pp 109-165
Brookes CA (1979) In: Field J (ed) The properties of diamond. Academic Press, London,
pp 383-402
Brookes CA (1986) Hardness measurements in the evalution of hard materials. Proc ICSHM2.
In: Almond EA, Brookes CA, Warren R (eds) Inst of Physics Publication CS 75, Adam
Hilger Press, pp 207-220
Brookes CA, Shaw MP, Tanner PE (1987) Non-metallic crystals undergoing cumulative work-
hardening and wear due to softer lubricated metal sliding surfaces. Proc R Soc Lond A409:
141-159
Brookes CA, Brookes EJ, Howes VR, Roberts SG, Waddington CP (1990) A comparison of
the plastic deformation and creep of type I, type II and synthetic diamonds at 1100 °C under
conditions of point loading. J Hard Mater 1(1): 3-24
Brookes CA, Moxley B (1975) A pentagonal indenter for hardness measurements. J Physics E
8: 456-460
Humble P, Hannink RHJ (1978) Plastic deformation of diamond at room temperature. Nature
273: 37-39
Kelly A (1966) Strong solids. Clarendon Press, Oxford, pp 12-28
Tabor D (1970) The hardness of solids. Rev Phys Sci Technol 1: 145-156
366 Chapter 6. Properties of Minerals
Slips Systems
(010), {Okl}. The stress necessary for breaking bonds is very similar for all these
planes. The preference for one or the other glide plane is therefore dependent on
small variations of the bond strength such as those induced by temperature
variation. Indeed, the dominant slip systems in olivine depend upon the
deformation temperature. At low temperature, the dominant slip system is
(100) [001] whereas at high temperature it is (010) [100] (Goetze 1978). In
pyroxenes, Si0 4 tetrahedra are linked along [001]. The glide planes are parallel
to this direction: (100), (010). The dominant slip system depends on the
deformation temperature as well. In orthopyroxenes, (100) [001] is dominant at
low temperature and (010) [001] becomes important at high temperature. In
tecto silicates (quartz, feldspars), any plane direction intersects strong Si~O~Si
bonds. Similarly, in the pyrite structure any plane intersects strong bonds
connecting S~S atoms or Fe~S atoms. Gliding of dislocations is therefore more
difficult; the easiest glide planes are assumed to be those cutting the smallest
number of strong bonds (McLaren et al. 1967). In pyrite, glide planes are {100}
that intersect only a few Fe~S and no S~S bonds (Levade et al. 1979). Besides
temperature, other parameters may modify this strength and therefore the
gliding of dislocations; e.g. a small amount of water within the quartz structure
weakens the Si~O bonds (see Chap. 6.3.5).
0.1 tJrn
I I
system (100) [001] involves dislocations which are dissociated into four partials
separated by a triplet of stacking fault ribbons, the wider lying between the other
two. These observations are explained by considering dislocations gliding and
dissociating between compact planes of the oxygen sublattice. Dissociation
occurs in two steps (Van Duysen et al. 1985): (1) [001] -> 1/6 [013] + 1/6 [013]
which creates a low-energy stacking-fault because it does not affect the oxygen
stacking; the corresponding stacking-fault ribbon is the wide one; (2) 1/6
[013] -> 1/6 [011] + 1/3 [001] and 1/6 [013] -> 1/6 [011] + 1/3 [001] which
modify the oxygen stacking and thereafter the shape of the interstitial cavities,
giving rise to cation displacement by a synchroshear mechanism; thus-created
stacking faults have a higher energy and correspond to the narrow ribbons. In
the uneasy slip system (l00) [010] of the pyroxene structure, dislocations are not
dissociated. Indeed, any dissociation would lead cations in forbidden octahedral
sites. In covalent bounded crystals, dislocation dissociation may be predicted
from the value of the energy as estimated from the deformation of atomic bonds
in modelized planar defects and dislocation cores. The efficiency of such
modeling is shown in feldspars (Fig. 89). In the feldspar structure, two glide
planes situated between the double-crankshaft chain involve the breaking of a
minimum of bonds: (001) and (010) (Tullis 1982; Gandais and Willaime 1984).
However the dislocation mobility along (010) is higher than along (001) due to a
dissociation giving rise to a stacking fault (010) 1/2 [001]. Examination of the
feldspar structure shows that such a fault is lying within the double crankshaft
chain. A dislocation gliding along this plane requires twice more broken bonds
than if it was gliding between the double chains, but the total energy involved is
lowered by the dissociation. Indeed, the core energy is reduced by the re-
construction of atomic bonds in the core; this is made possible by the high
6.3.1 Mechanisms of Plastic Deformation in Minerals 369
II
a b 6.5A
o
1 1
Fig. 893, b. (010) [001] dislocat ion in sanidine. 3 High resolution electron micrograph.
b Filtered image showing (001) planes. The dislocation is perpendicular to the foil plane. The
arrows indicate the partial dislocations bounding the (010) 1/2 [001] stacking fault
atomic density within the double chain, and the short Burgers vector of
dissociated dislocations (Zheng et al. 1988).
Dissociation of dislocations may hinder the gliding process and harden the
mineral. This occurs when the dislocation dissociates out of its glide plane, as it
has been shown in spinel: 1/2 [110] dislocations gliding in (nO) plane dissociate
into 1/4 [110] + 1/4 [110] in (110) plane (Doukhan et al. 1982). Other
deformation mechanisms involving the gliding of partial dislocations may occur
in peculiar mineral structure. Mechanical twinning is produced by the gliding of
a twin dislocation; in calcite partial dislocations with a Burgers vector parallel to
[010] (with respect to the cleavage cell) and only 0.13 nm long are responsible
for the mechanical twinning of the crystal (Sauvage and Authier 1965; Wenk
et al. 1990). M artensitic phase transformation is also the result of partial-
dislocation gliding under an applied stress. For instance, orthopyroxene crystals
may transform into clinopyroxene by gliding of dislocations (100) 0.83 [001]
(Kirby 1976). In both cases, the mineral is plastically deformed through a shear
of the structure, and the maximum strain has a finite value.
Conclusion
Valuable data on mechanical properties of the main mineral species have been
obtained by different means, including experimental deformation, transmission
370 Chapter 6. Properties of Minerals
References
Amelinckx S (1972) Dislocations in particular structures. In: Nabarro FRN (ed) Dislocations
in solids. North Holland Publishing Company, Amsterdam, pp 67-460
Christie JM, Ardell AJ (1976) Deformation structures in minerals. In: Wenk HR (ed) Electron
microscopy in mineralogy. Springer, Berlin Heidelberg New York, pp 374-403
Doukhan N, Duclos R, Escaig B (1982) Climb dissociation in {U3} planes in Al-Mg spinels.
J Physique 43: 1149-1157
Gandais M, Willaime C (1984) Mechanical properties of feldspars. In: Brown WL (ed)
Feldspars and feldspathoids. NATO ASI series C137, DReidel Publ Comp, Dortrecht,
pp 207-246
Goetze C (1978) The mechanisms of creep in olivine. Philos Trans R Soc Lond A 288: 99-119
Kirby SH (1976) The role of crystal defects in the shear-induced transformation of orthoensta-
tite to clinoenstatite. In: Wenk HR (ed) Electron microscopy in mineralogy. Springer, Berlin
Heidelberg New York, pp 465-472
Levade C, Couderc JJ, Bras J, Fagot M (1979) Etude par microscopie electronique en
transmission des dislocations dans la pyrite FeS 2 • Phil os Mag A 40: 111-120
McLaren AC, Retchford JA, Griggs DT, Christie JM (1967) Transmission electron microscopy
study of Brazil twins and dislocations experimentally produced in natural quartz. Phys Stat
Sol 19: 631-644
Sauvage M, Authier A (1965) Etude des bandes de croissance et des dislocations de macle. Bull
Soc Fr Mineral Cristallogr 88: 379-388
Tullis J (1982) Deformation offeldspars, In: Ribbe PH (ed) Feldspar mineralogy. Reviews in
mineralogy 2, 2nd edn. Chelsea, Michigan, Mineralogical Society of America, pp 297-323
Van Duysen JC, Doukhan N, Doukhan JC (1985) Transmission electron microscope study of
dislocations in orthopyroxene (Mg,FehSi 2 0 6 • Phys Chern Minerals 12: 39-44
Wenk HR, Barber DJ, Reeder RJ (1990) Microstructures in carbonates. In: Reeder RJ (ed)
Carbonates: mineralogy and chemistry. Reviews in Mineralogy 11, 2nd printing, Chelsea,
Michigan, Mineralogical Society of America, pp 301-394
Zheng Y, Gandais M, Heggie M (1988) Study of (010) [101] and (001) [110]/2 dislocations in
K-feldpsars by HRTEM and Modelling. Phys Chern Minerals 15: 349-354
Fracture Mechanics
Fracture mechanics is based on the pioneer work of Griffith (1920) and Irwin
(1957). It attempts to define material parameters which predict fracture re-
sponse; e.g., the critical stress intensity factor, K e , characterizes resistance to
fracture propagation at an existing crack-tip (i.e., fracture toughness). Experi-
mental determination of mineral fracture mechanics parameters is difficult
because most methods are unsuitable for individual minerals, or for studying
how variations in mineralogy and microstructure affect crack propagation.
Nevertheless, several fracture mechanics criteria can be defined depending on
scale, as follows.
372 Chapter 6. Properties of Minerals
Atomistic. Compression causes the average atomic spacing to be less than the
equilibrium spacing (a o), resulting in repulsive forces. Extension causes the
spacing to be greater than ao, resulting in attractive forces. Compression is
effectively stable, but tension eventually breaks atomic bonds resulting in
catastrophic failure at the theoretical strength (oth). However, this is rarely if
ever reached due to the presence of flaws in the crystal structure.
Macroscopic. Several different theories exist at this scale. (1) Energy balance
theories are based on identifying a dominant flaw which initiates fracture.
Parameters include flaw size distribution, applied stress and the energy required
to create new fracture surface (i.e., fracture energy). (2) Linear elastic fracture
mechanics (LEFM) relates all contributing parameters to a stress intensity
factor, K, which describes the total stress field around a crack or flaw and
therefore takes account of local inelastic deformations. Cracks propagate at a
value, K e, which is a function of crack opening mode (i.e., mode I, tensile
opening; mode II, shear opening; and mode III, tearing opening). Mode I is
commonest, possibly because all materials are weakest in extension; critical
stress intensity factor is defined by K'e = YaJ(2c) where Y is a function of crack
size, shape, and position. (3) Plastic instability occurs if crack-tip stresses exceed
the plastic yield stress over an area considerably greater than the crack size;
plastic yield occurs and fracture toughness increases due to crack-tip blunting.
Crack-tip plasticity is characterized by the stretch, d, in the plane ahead of a
propagating crack, fracture resistance being defined by the critical opening
displacement, de. The crack-tip plasticity consumes energy and results in
fracture arrest. Successive stages of crack development may be analogous to the
"crack-seal" process recognized in many vein array systems.
6.3.2 Fracture Mechanics and Fracture Mechanisms in Minerals 373
Fracture Mechanisms
Conclusions
Recent research shows that fracture processes in minerals are much more
complex than was hitherto assumed, and are often intimately linked to non-
fracture deformation mechanisms. There is an extensive body of fracture
mechanics theory but little of it is directly relevant to natural fracturing in the
Earth's crust. The experimental and theoretical foundations for understanding
fracture mechanisms in minerals and rocks are in their infancy.
References
S. AMELINCKX
High Resolution Images (foil thickness < 100 A, resolution < 2.6 A)
image. Unfortunately, the relative phases of the contributing beams are changed
in passing through the electron optical system due to lens aberrations and
defocusing. Computer simulation of images is therefore important for a correct
interpretation. However, in the very thin parts, close to the edge of the foil,
where the thickness is only a few unit cells ( < 100 A) the heavy atom columns
are imaged as dark dots whereas the light atoms and the inter-column channels
appear as bright spaces, and a directly interpretable image of the structure can
be obtained under suitable focussing conditions (Scherzer focus). In the thicker
parts heavy atom columns are imaged as bright dots. These phenomena are
explained by the strong forward scattering of electrons, the smallness of the
Bragg angles, and by noting that the electrostatic potential associated with an
atom column acts as an axially symmetric lens which periodically, along the
Fig. 9Oa-f. Diffraction contrast image of anti-phase boundaries in Anorthite. In-situ heating
cycle through the I -+ P -+ I phase transitions. The same area is imaged throughout from a to f.
In c the specimen is in the P-phase (high temperature phase). Note the pronounced "memory
effect", i.e., the same configuration of anti-phase boundaries as in a is re-established in f
6.3.3 High Resolution Electron Microscopic Techniques in the Study of Defects 379
~ -~\ ~ ~ ~
I,,,,,"' __ . . " ... .. • .. .... • ~_ _ "- ,.. • '" ... .., , ~- '-
A
.fI7I-."' "• . -:"
tI!l .. # til 4 I/If • ... ~ j. !' ;a J ,#' '"
•..... ......
·· .....
....' .. ..
II ... ,. - ........_ .... ., . . . . . . . . 10 .. t1 .......-..... - - ••
~_ ~ ~.~_.~~~K.'.~
·~·~~·&·~~·~·~.·.·.~
~-~~.~,.~4······~~~~~~~·~~4~
• • .fIt
w~~-~~ ••
10, ...·• ,,--.~ ... • "" .... -..",....... 4i "fIo," "'.--'" .............. ,..-'.,. •
•
...... .~ ...........'". + ,,~ -"IC.." ""
Fig. 93. High resolution image .........
ill •..,. . . . . . . . . . . *'';'''~
t ... i>c(ot,..... ·.....,"" ......... ,. ....
of "micro twin" in the sphalerite 3"0 .......... .\, .... ~. . . . It .. ~- • •;. .
~~+, ...... -* ••,If,..~,.... 4~~~~'ir!
structure (ZnS)
-
, 100 nm
Fig. 97. Intergrowth of different members of the synchisite-bastnaesite family of mixed layer
compounds. One-dimensional lattice fringes. (S synchisite layer; B bastnaesite layer)
Fig. 98. Anti-ferroelectric domain walls in titanite (diffraction contrast). The temperature (T)
of the specimen is indicated relative to the critical temperature (Te)
6.3.4 Hydrolytic Weakening of Quartz 383
Historical Overview
1 Quartz is so strong that Bridgmann considered at one time its use for fabricating pistons for
his high pressure apparatus but in fact this application was not pursued because of the
brittleness of the material (after Blacic and Christie 1984).
384 Chapter 6. Properties of Minerals
a(MPa)
4000
dry
2000
Griggs and Blacic showed in 1965 that synthetic wet 2 quartz is ductile under
moderate stress while natural (dry) quartz becomes ductile in the presence of
water. The strengths of such crystals are at least one order of magnitude lower
than those of natural crystals deformed in a dry assembly (Fig. 100). Water
contents as low as 0.005 wt. % (HjSi :::; 300 at. ppm) induce the weakening effect,
even without confining pressure (see for instance Baeta and Ashbee 1970;
Kekulawala et al. 1981; Linker and Kirby 1981; Doukhan and Trepied 1985).
Griggs and Blacic (1965) postulated that the weakening effect stems from the
hydrolysis of the strong Si-O bonds by the water molecules contained in the
crystal; an enhanced glide mobility of the dislocations would thus result. They
also suggested that other nominally anhydrous silicate minerals should similarly
be weakened by very small water contents. Although less marked than in quartz,
this effect has been detected in a number of minerals like olivine (Karato et al.
1986) and clinopyroxenes (Ross and Nielsen 1978); however, this effect seems
more marked in berlinite AIP0 4 , a structural analog of quartz (Boulogne et al.
1988). This probably means that the structure of the crystal is also a relevant
parameter of the weakening phenomenon.
Along the same lines McLaren and Retchford (1969) suggested that water
assists dislocation climb rather than glide. Both models are localized ones, i.e.,
only the water defects lying in the immediate vicinity of the dislocation core
enhance its mobility; hydrolytic weakening thus requires (is governed by?)
diffusion of the water defects towards the dislocation cores. In contrast, Hirsch
(1981) and Hobbs (1981, 1985) have proposed independently a delocalized
model. In strong analogy with the case of covalent semiconductors (Alexander
and Hasen 1968), they assume that dislocations in quartz are terminated by
unsaturated (dangling) bonds and that water (the dopant) induces shallow levels
in the band gap. Kinks and/or jogs, which form localized levels in the gap, can
thus trap the carriers of the shallow level and form new (charged) kinks and/or
jogs; the total density of kinks and/or jogs increases and an enhanced glide
and/or climb mobility of the dislocations results. Heggie and Nylen (1984,1985)
have performed computer simulations of dislocation cores in CL quartz and
shown that the cores should be reconstructed, i.e., the orbitals along the
dislocation core should rotate in such a way that they would overlap, forming
weak bonds. As a result no unsaturated (dangling) bonds are expected, i.e., no
extra kinks and/or jogs should form. It can thus be said that actually, the
mechanism(s) of hydrolytic weakening in quartz is not yet fully elucidated.
Clearly, a number of problems are still to be solved: what is the nature of the
water associated point defects? What is their solubility as a function of standard
thermodynamic parameters like T, P, P 02 ' etc.? What is their diffusivity? By
which mechanism do they enhance the glide and/or the climb mobility of the
dislocations? Is this mechanism identical for the various glide systems which can
be activated in quartz: glide directions (Burgers vectors) a, C and c + a in various
glide planes? What happens in other nominally anhydrous silicates?
A number of investigations by transmission electron microscopy (TEM)
have shown that in most wet synthetic quartzes, water is not truly dissolved; it
occurs under the form of tiny water bubbles 100 to 1000 A in diameter. During
high temperature deformation the state of dispersion of this water changes
continuously; the bigger bubbles grow at the expense of the smaller ones; this
requires some material to be removed from the bigger bubbles (to relax their
inner pressure) and diffused towards the cores of the mobile dislocations, thus
inducing their climb motion. Superimposed to the applied stress, the driving
386 Chapter 6. Properties of Minerals
Conclusion
References
Aines RD, Rossman GR (1984) Water in minerals? a peak in the infrared. J Geophys Res 89:
4059-4071
Aines RD, Kirby SH, Rossman GR (1984) Hydrogen speciation in synthetic quartz. Phys
Chern Minerals 11: 204-212
Alexander H, Hasen P (1968) Dislocations and plastic flow in the diamond structure. Sol State
Phys 22: 27-158
Baeta RD, Ashbee KHG (1970) Mechanical deformation of quartz. I Constant strain rate
compression experiments. Philos Mag 22: 601-624
Blacic JD, Christie JM (1984) Plasticity and hydrolytic weakening of quartz single crystals.
J Geophys Res 89: 4223-4239
Boulogne B, Francois P, Cordier P, Doukhan JC, Philippot E, Jumas JC (1988) Plastic
deformation of wet synthetic IX berlinite AIP0 4 • Philos Mag A 57: 411-430
Carter NL, Christie JM, Griggs DT (1964) Experimental deformation and recrystallization of
quartz. J Geol 72: 687-733
Christie JM, Griggs DT, Carter NL (1964) Experimental evidence of basal slip in quartz.
J Geol 72: 734-756
Cordier P, Doukhan JC (1989) Water in quartz, solubility and influence on ductility. Eur J
Mineral 1: 221-237
Cordier P, Doukhan JC (1991) Water speciation in quartz; a near infrared study. Am Mineral
76: 361-369
Cordier P, Boulogne B, Doukhan JC (1988) Water precipitation and diffusion in wet quartz
and wet berlinite AIP0 4 • Bull Mineral 111: 113-137
Doukhan JC, Trepied L (1985) Plastic deformation of quartz single crystals. Bull Mineral 108:
97-123
FitzGerald JD, Boland IN, McLaren AC, Ord A, Hobbs BE (1991) Microstructures in water-
weakened single crystals of quartz. J Geophys Res 96: 2139-2155
Gerretsen J, Paterson MS, McLaren AC (1989) The uptake and solubility of water in quartz at
elevated pressure and temperature. Phys Chern Minerals 16: 334-342
6.3.4 Hydrolytic Weakening of Quartz 389
Griggs DT (1967) Hydrolytic weakening of quartz and other silicates. Geophys J R Astr Soc
14: 19-31
Griggs DT (1974) A model of hydrolytic weakening in quartz. J Geophys Res 79: 1653-1661
Griggs DT, Blacic IN (1965) Quartz: anomalous weakness of synthetic crystals. Science 147:
292-295
Haggon JP, Stoneham AM, Jaros M (1987a) Transport processes in silicon oxidation. I Dry
oxidation. Phil os Mag 55(2): 211-224
Haggon JP, Stoneham AM, Jaros M (1987b) Transport processes in silicon oxidation. II wet
oxidation. Phil os Mag B 55(2): 225-235
Heggie M, Nylen M (1984) Dislocations core structures in ex quartz derived from a valence
force potential. Phil os Mag 51: L69-L72
Heggie M, Nylen M (1985) Dislocations without deep states in ex quartz. Philos Mag 51:
L69-L72
Hirsch PB (1981) Plastic deformation and electronic mechanisms in semiconductors and
insulators. J Phys C: 3149-160
Hobbs BE (1981) The influence of metamorphic environment upon the deformation of
minerals. Tectonophysics 78: 335-383
Hobbs BE (1985) The hydrolytic weakening effect in quartz. In. Schock RN (ed) Point defects
in minerals. Geophys Monogr 31. Am Geophys Union, Washington, pp 151-170
Karato S, Paterson MS, Fitzgerald JD (1986) Rheology of synthetic olivine aggregates:
influence of grain size and water. J Geophys Res 91: 8151-8176
Kekulawala KRSS, Paterson MS, Boland IN (1981) An experimental study of the role of water
in quartz deformation. In: Carter NL, Friedman M, Logan JM, Stearns DW (eds)
Mechanical behaviour of crustal rocks. Geophys Monograph 24 Am Geophys Union,
pp 49-60
Kronenberg AK, Kirby SH, Aines RD, Rossman GR (1986) Solubility and diffusional uptake
of hydrogen in quartz at high water pressures: implications for hydrolytic weakening.
J Geophys Res 91: 12723-12744
Linker MF, Kirby SH (1981) Anisotropy in the rheology of hydrolytically weakened synthetic
quartz crystals. In: Carter NL, Friedman M, Logan JM, Stearns DW (eds) Mechanical
behaviour of crustal rocks. Geophys Monograph 24 Am Geophys Union Washington,
pp 29-48
McLaren AC, Retchford JA (1969) TEM study of the dislocations in plastically deformed
synthetic quartz. Phys Stat Sol 33: 657-668
McLaren AC, Retchford JA, Griggs DT, Christie JM (1967) TEM study of Brazil twins and
dislocations experimentally produced in natural quartz. Phys Stat Sol 19: 631-644
McLaren AC, Cook RF, Hyde ST, Tobin RC (1983) The mechanisms of the formation and
growth of water bubbles and associated dislocation loops in synthetic quartz. Phys Chern
Minerals 9: 79-94
McLaren AC, FitzGerald JD, Gerretsen J (1989) Dislocation nucleation and multiplication in
synthetic quartz: relevance to water weakening. Phys Chern Minerals 16: 465-482
Ord A, Hobbs BE (1986) Experimental control of the water-weakening effect in quartz. In:
Hobbs BE, Heard HE (eds) Mineral and rock deformation: laboratory studies. Geophys
Monogr 36 Am Geophys Union Washington, pp 51-72
Paterson MS (1982) The determination of hydroxyl by infrared absorption in quartz, silicate
glasses and similar materials. Bull Mineral 105: 20-29
Paterson MS (1986) The thermodynamics of water in quartz. Phys Chern Minerals 13:
245-255
Ross JV, Nielsen KC (1978) High temperature flow of wet polycrystalline enstatite. Tectono-
physics 44: 233-261
Rovetta MR (1989) Experimental and spectroscopic constraints on the solubility of hydroxyl
in quartz. Phys Earth Plan Int 55: 326-334
Rovetta MR, Holloway JR, Blacic JD (1986) Solubility of hydroxyl in natural quartz annealed
in water at 900 °C and 1.5 GPa. Geophys Res Lett 13: 145-148
Weil JA (1984) A review of electron spin spectroscopy and its application to the study of
paramagnetic defects in crystalline quartz. Phys Chern Minerals 10: 149-165
390 Chapter 6. Properties of Minerals
M.R. DRURY
where t is the steady state strain-rate, a the stress, T the temperature, Tm the
melting temperature, P the confining pressure, E the activation energy, V the
activation volume and A, d the grain size, B, m, n, and g constants. When creep
occurs by dislocation processes the constants commonly have values in the
range of n = 3-5, m = 0-1, E = 1.5-0.6 ESD (where ESD is the activation energy
for self diffusion). For creep by diffusion processes or by grain boundary sliding
n = 1-2, m = 1-3, and E = 0.6-1.0 ESD '
The occurrence of steady state creep in crystalline materials enables the flow
of the material to be described in terms of a stress-dependent viscosity '1 = a/3t.
Most theoretical continuum models of flow in the Earth's mantle assume that
the creep in the mantle is a linear viscous process with the stress exponent n in
Eqs. (1) and (2) equal to one. In this simple case the solid state viscosity can then
be simply expressed as a function of temperature and pressure.
Recent experiments on olivine (Borch and Green 1987) suggest that the effect
of pressure is described best by a dependence of creep-rate on the homologous
6.3.5 High Temperature Flow in Minerals and Ceramics 391
temperature, e.g., Eq. (2). Borch and Green (1987), however, used the solidus of
the mineral assemblage to normalize their data. It is probably physically more
realistic to use the melting temperature of olivine.
The traditional interpretation of conventional creep curves has recently been
questioned. Evans and Wilshire (1985) suggest that a true steady state is never
attained. In their model the shape of the creep curve is related to the superposi-
tion of primary creep produced by work hardening processes and tertiary creep
produced by recovery processes. If this model is correct there are major
implications for the nature of large-strain creep processes in the mantle. In
particular it would no longer be possible to define a strain-independent solid
state viscosity. For a large-strain flow as encountered in the convecting mantle
the creep-rate could be cyclic with each cycle terminated by a creep instability.
The complex nature of minerals and ceramics is responsible for some com-
plications in creep behavior. Some of the more important effects are outlined
below.
1. Climb dissociation of dislocations is common in minerals and can result
in anomalous creep behavior where the viscosity increases with increasing
temperature (Doukhan and Paquet 1982). Climb dissociation is important
in spinels and perovskites (Poirier 1985; Poirier et al. 1989) and in olivine
segregation of hydrogen to dislocation cores can induce climb dissociation of
dislocations with Burgers vector b = [001] (Drury 1991).
2. Some ceramics and minerals exhibit inverse primary creep (Evans and
Langdon 1976; McLaren et al. 1989) with increasing strain-rate with time. This
behavior is observed in materials which have a low initial content of mobile
dislocations. The creep rate in this case is not controlled by hardening inter-
actions of dislocations but by the nucleation and multiplication kinetics of
mobile dislocations. Work on synthetic quartz (McLaren et al. 1989; Fitz Gerald
et al. 1991) suggests that the so-called hydrolytic weakening effect may be largely
related to the difficulty of dislocation nucleation and multiplication in dry
quartz crystals.
3. Grain boundary structures in rocks can have a range of structures from
narrow semicoherent structures with structural widths comparable to those in
metals (Hay and Evans 1988, Bons et al. 1990) and in simple oxides (Ruhle 1985)
to interfaces defined by thin films of a segregated second phase. The second
phase film can be crystalline (Bons et al. 1990) or a fluid or melt film. Differences
in grain boundary structure can lead to large differences in diffusion creep
kinetics. Semi-coherent grain boundary structures are likely to be more import-
ant in the transition zone and lower mantle owing to the predominance of cubic
and distorted cubic phases.
4. The polyphase nature of most rocks can lead to complicated rheological
behaviour. It is usually assumed that the predominant mineral in the assemblage
392 Chapter 6. Properties of Minerals
will provide a stress supporting framework and control the behavior of the rock.
During large-strain deformation, mechanical or chemically induced segregation
of a weak minor phase along the foliation can result in deformation being
concentrated in the weak phase. In many cases these weak bands can be
produced in rocks by the transformation of hard phases to fine-grained poly-
phase reaction products which deform by the Grain-Size Sensitive (GSS) creep
or dislocation creep of weak minerals. GSS creep in polyphase multi-component
materials can occur with faster kinetics than in single phase materials.
5. Minerals show a rich diversity of transformations which may have a
considerable influence on the high temperature flow behavior in some critical
regions of the Earth. The fundamental physical basis for transformation en-
hanced plasticity is poorly established at present. Traditional models derived
from studies on metals have considered the role of stresses induced by the
volume changes associated with transformation. Current research suggests that
other aspects of the transformation may also be important (McLaren and
Meike, in progess).
Experimental creep data on phases from the transition zone and lower
mantle are non-existent, although there is some information on the relative yield
strengths and hardness of the phases at room temperature and information
on the creep properties of structural analogs. Attempts have been made to use
generalized creep-systematics for crystalline materials to predict transition zone
and lower mantle rheology. These models predict viscosity structures which are
compatable with other geophysical contraints, which indicate that the lower
mantle has similar or higher viscosity than the upper mantle. The assumption of
whole mantle or layered convection has an important influence on the predicted
viscosity profiles (Ranalli 1987).
Using the approach of defining iso-mechanical groups of crystalline mater-
ials, it can be shown that garnets and spinels generally have very high normal-
ized (dislocation) creep resistance, higher than both upper and lower mantle
phases. If the rheology of the transition zone is controlled by these phases, then
the transition zone may conceivably be a zone of relatively high viscosity. The
occurrence of pyroxene in the uppermost part of the Transition Zone may lead
to the occurrence of weak zones developed by local segregation of the weak
phase. In addition, the possible effects of transformation-enhanced-creep may
possibly counter balance any intrinsically high viscosity of the predominant
phases. The high viscosity model for the Transition Zone assumes that disloca-
tion creep is the predominant creep mechanism. If GSS creep is predominant,
the Transition Zone will not necessarily be a zone of high viscosity. For
example, rheological data on MgGe0 4 (an analog for olivine) shows that fine-
grained y spinel has a viscosity about one or two orders of magnitude lower than
the coarse-grained olivine phase.
For the case of the lower mantle, the rheology will be sensitive to the bulk
composition which will control the amount of magnesiowiistite present. Micro-
structural observations (Poirier et al. 1986) suggest that perovskite has a higher
creep resistance than magnesiowiistite as is also suggested by normalized creep
data for structural analogs of these phases (Karato 1989). Normalized data
suggest that on average perovskites are weaker than olivine phases; however,
some perovskites have higher creep resistance than some olivine phases. Current
data on perovskite indicate that they do not form a well-defined iso-mechanical
group, so it may be difficult to infer the properties of MgSi0 3 perovskite from
studies of analogs. The results on yield strength experiments indicate that
MgSi0 3 perovskite has a higher creep resistance than olivine at room temper-
ature; however, extrapolation of these data to mantle conditions is extremely
hazardous until there are constraints on the temperature dependence of creep
in MgSi0 3 perovskite. Under most situations perovskite should control the
rheology of the lower mantle, but local segregation of magnesiowiistite in high-
strain zones could result in local rheology being controlled by magnesiowiistite.
In addition, a high magnesiowiistite content should inhibit grain growth of the
perovskite, thus favoring GSS creep processes over dislocation creep.
Owing to the difficulty of performing creep measurements on transition zone
and lower mantle phases, the rheology of these phases may not be understood
394 Chapter 6. Properties of Minerals
References
Mackwell SJ, Bai Q, Kohlstedt DL (1990) Rheology of olivine and the strength of the
lithosphere, Geophys Res Lett 17: 9-12
McLaren AC (1991) Transmission electron microscopy of minerals and rocks, Cambridge
University Press, New York
McLaren AC, FitzGerald JD, Gerretsen J (1989) Dislocation nucleation and multiplication in
synthetic quartz: relevance to water weakening. Phys Chem Mineral 16: 465-482
Meade C, Jeanloz R (1990) The strength of mantle silicates at high pressures and room
temperature: implications for the viscosity of the mantle. Nature 348: 533-535
Poirier JP (1985) Creep of crystals. Cambridge University Press, Cambridge
Poirier JP, Peyronneau J, Madon M, Guyot F, Revcoleshi A (1986) Eutectoid phase
transformation of olivine and spinel into perovskite and rock salt structures. Nature 321:
603-605
Poirier JP, Beauchesne S, Guyot F (1989) Deformation mechanisms of crystals with perovskite
structure, In: Navrotsyy A, Weidner DJ (eds) Perovskite: a structure of great interest to
geophysics and materials science. Geophys Monograph 45, Am Geophys Union, Washing-
ton DC, pp 119-124
Ranalli G (1987) Rheology of the Earth, Allen and Unwin, Boston
Ringwood AE (1975) Composition and petrology of the Earth's mantle, McGraw-Hill,
New York
Ruhle M (1985) Comparisons between observed and computed grain boundary structures and
energies in ceramics. J Phys Coli: C4- 281-292
Rutter EH, Brodie KH (1988a) Experimental "syntectonic" dehydration of serpentinite under
conditions of controlled pore water pressure. J Geophys Res 93: 4907-4932
Rutter EH, Brodie KH (1988b) The role of grainsize reduction in the rheological stratification
of the lithosphere. Geol Rundsch 77: 295-308
Vaughan PJ, Coe RS (1981) Creep mechanism in Mg 2 Ge0 4 : effects of a phase transition.
J Geophys Res 86: 389-404
T.O. MASON
where g is a geometric factor on the order of unity, N is the density of iron ions
involved in conduction (cm - 3), c is the fraction of these which are small
polarons, (I - c) is the fraction of iron ions which are of the opposing valence
and therefore available for hopping, e is the unit of electronic charge, a is the
jump distance (cm), v is the lattice vibrational frequency responsible for hopping,
k is Boltzmann's constant, and EH is the hopping energy. In Fez + jFe 3 + systems
the Fez + species are the small polarons, i.e., an electron plus the associated
lattice distortion. For such materials the Seebeck coefficient is given by:
where the parameters have been defined above. [A "transport term" often
appears in expressions for Seebeck coefficient; this is usually negligible in the
case of small polaron conduction, so has been omitted from Eq. (2)]. Given the
unique relationships between the electrical properties and the concentrations of
iron species involved in small polaron conduction, a powerful capability exists
to study defect phenomena in iron-based minerals and materials.
It is important to first establish whether or not small polaron conduction is
dominant in a given system. A number of techniques, based upon manipulations
of Eqs. (1) and (2) can be applied. The most basic, "isothermoelectric conduct-
ivity analysis" (Chen et al. 1982), involves demonstrating the existence of an
activated mobility by plotting the electrical conductivity at fixed Seebeck
coefficient vs. inverse temperature. This is tantamount to analyzing the conduct-
ivity at fixed carrier content; Arrhenius behavior is clear evidence of an activated
mobility. A second procedure involves isothermal plots of Seebeck coefficient vs.
the logarithm of electrical conductivity, so-called lonker plots, after Jonker
(1968). As opposed to conventional semiconductors, which exhibit a marked
discontinuity at the intersection of p-type and n-type legs at high carrier
contents, small polaron materials exhibit a smoothly varying "knee" at the
highest value of c(1 - c) = 0.25 for c = 0.5 in Eqs. (1) and (2). In addition, n-type
small polaron behavior is symmetric about a value of (X = - kje In 2 [see
Eq. (2)], whereas p-type small polaron behavior is symmetric about a value of
(X = kje In 2 [see Nell et al. 1989a for the p-type small polaron equation
analogous to Eq. (2)]. Thus, the sign of the small polaron can be determined.
Finally, in systems where there is a large and previously determined variation in
Fez + and Fe 3 + contents with composition, adherence to Eq. (2) can be taken as
confirmation that small polaron conduction is present (Wu et al. 1981).
Given the relationships between the electrical properties and the Fez + jFe 3 +
concentrations, Eqs. (I) and (2) have been used to study a variety of point defect
phenomena in iron-containing minerals and materials. A high temperature
6.4.1 Electrical Conductivity in Iron-Bearing Minerals and Materials 397
References
°.
Chen HC, Gartstein E, Mason TO (1982) Conduction mechanism analysis for Fel_~O and
CO l _6 J Phys Chern Sol 43: 991-995
Dieckmann R, Witt CA, Mason TO (1983) Defects and cation diffusion in magnetite (V):
Electrical conduction, cation distribution and point defects in Fe 3- 6 0 4 • Ber Bunsen-Ges
Phys Chern 7: 495-503
Dorris SE (1988) The electrical properties and cation distributions of the Fe30cMn304
solidsolution. PhD Thesis, Northwestern University, Evanston, IL
Dorris SE, Mason TO (1988) The electrical properties and cation valencies in Mn 30 4 • J Am
Ceram Soc 71: 379-385
Erickson DS, Mason TO (1985) Nonstoichiometry, cation distribution, and electrical proper-
ties in Fe30CCoFe204 at High Temperature. Sol State Chern 59: 42-53
Gartstein E, Mason TO (1982) Reanalysis ofwiistite electrical properties. J Am Ceram Soc 65:
C-24-C-26
Gartstein E, Cohen JB, Mason TO (1986) Defect agglomeration in wustite at high temper-
atures - II. An electrical conduction model. J Phys Chern Sol 47: 775-781
JonkerGH (1968) The application of combined conductivity and Seebeck-effect plots for the
analysis of semiconductor properties. Philos Res Rep 23: 131-138
6.4.2 Superionic Conductors 399
B.A. MAXIMOV
References
G.A. GORBATOV
All minerals, except native metals, are classified according to electrical proper-
ties as semiconductors (specific conductance u = 10- 7 _10 6 cm/m; the band gap
0< Eg < 4.5 eV for pyrite, galenite.) or dielectrics (u < 10- 8 cm/m, Eg > 4.5 eV
for quartz, feldspar).
In semiconductors directed mobility appears in two charge carriers; elec-
trons, in a normally unfilled conduction band, and holes in a normally filled
valence band, under the action of external electric and magnetic fields and
temperature gradients. The concept of a hole possessing a positive charge and
positive mass has been introduced to avoid the difficulties in describing this
mobility. The sources of charge carriers are the deviations from the stoichio-
metric compositions, the electroactive impurities of substitutional and inter-
stitial types (the impurities giving off the electrons into the conduction band are
known as donors, and the impurities taking up the electrons from the valence
band are referred to as acceptors) as well as the transfer of electrons through the
energy gap as a result of thermal excitation. If the latter is predominant, with
the densities of electrons and holes being equal, the conductance is called the
intrinsic conductance. Since the transfer of electrons and holes is proportional to
the acting force, the quantitative analysis of this transfer allows the experimental
determination of semiconducting characteristics of minerals, which are closely
connected with the band structure, chemical composition, and crystal structure.
The most widely used characteristics are the forbidden band width Eg , the
ionization energy of impurities E j , the chemical potential J.l*, the effective mass
m:,p, the concentration of n, p electrons and holes, the mobilities Un,p' the
scattering mechanisms of charge carriers, and the type of conductance. To
determine these characteristics the following values are measured: the specific
conductance u, the Hall effect RH , the thermoelectromotive force coefficient oc,
and the temperature dependences of the above values. Optical and other
methods to determine Eg , E j , and m:,p are also applied.
The semiconductor-specific conductance (J is usually measured by the DC
four-probe method. The value of specific conductance is expressed by the
relations (J = enU n, and (J = epU p for unipolar conductance; (J = en Un + epU p
for mixed conductance, where e is the electron charge, mobility U cm 2 /(V.s)
is the average velocity of charge carriers in a field of 1 B/cm. There is little
information to be obtained from measurements of (J at room temperature. Much
more information is provided by combined measurement of the Hall effect and
conduction, the analysis of the temperature dependence of conduction, the Hall
effect, the thermo-EMF coefficient; all of them give enough data to determine
the relevant characteristics of semiconductors.
The measurement of the Hall effect involves the passage of electric current Ix
through a sample in the form of a rectangular plate, the application of a normal
6.4.3 Electrical Properties of Ore Minerals 403
magnetic field Bz , and the measurement of the potential gradient Ey in the third
perpendicular direction. When the charge carriers are electrons, RH = - 1/2n;
in the case of holes, RH = l/ep. Simultaneous measurement of specific conduct-
ance allows the Hall mobility of charge carriers n = RH. (J' to be determined.
The peculiarities of natural minerals are responsible for difficulties in
measuring (J' (T), R H, RH+ (J', RH(T). Quite often the smallness of mineral grains
and their inhomogeneity, which may be accompanied by alternating charge
carriers, make it difficult (if not impossible) to prepare samples of the required
sizes and shape, i.e., plates and prisms with the minimal dimensions 1 x 2
x6mm.
The method of measuring the thermo-EMF coefficient is most widely used in
practice. The (X-probe method of measurement (two copper or tungsten thermo-
electrodes are attached to the surface of a mineral sample) makes it possible to
study minerals of various sizes and shapes, such as samples of ore, manufactured
pellets, agglomerations of grains and crystals as well as powdered mineral grains
of 0.1 mm. There are several modifications of this method: (1) measurements of
(X using manual probes or those unattached to a microscope; (2) scanning the
metallographic specimen surface using an automated system; (3) measurement
of the temperature dependence of the integral thermo-EMF using a com-
puterized, automated system; (4) "field" measurement of the sign and amplitude
of thermo-EMF without heating one of the probes (heating being substituted by
inelastic collision of the probe with the mineral surface). In the Zabaikal
Geological Institute (USSR), the specialized thermo-EMF meters (Znak-3,
ITRM-3, and others) are commercially manufactured as well as the KOD-1O
automated system supplied with PASCAL software for the evaluation of ore
deposits.
Pyrite FeS z, arsenopyrite FeAsS, chalcopyrite CuFeS z, galenite, PbS, mol-
ybdenite MoS z, and some other minerals belong to a well-conducting group of
semiconductors. Characteristically, within a certain temperature interval and
with certain "critical" concentrations of impurities, the electrical properties of
these semiconductors turn out to be similar to those of metals, although in a less
pronounced form. The transition from purely semiconducting properties to
degenerate ones can be observed quite often in the same mineral with changing
concentrations of donors and acceptors, temperature, and other parameters.
Pyrite is found in modifications ofn-, pn-, np-, and p-types, Eg '" 0.9 eY. The
mobility of the electrons is nearly by two orders greater than that of holes. Co,
Ni, Cu impurities, and S-vacancies represent donors, As, impurities and Fe-
vacancies are acceptors. The dependence of pyrite semi-conducting properties
upon the relative temperature of mineral formation has been established
(Fig. 102).
Arsenopyrite is found in modifications of n-, pn-, np-, and p-types.
Eg '" 0.34 eV. The mobility of electrons and holes is low, Un,p'" 0.1-1 cm z
V - 1 S - 1. Arsenopyrite with a nearly stoichiometric composition is an intrinsic
semiconductor at room temperature. S (substituting As), Co, and Ni are donors,
As (substituting S) is an acceptor. The dependence of arsenopyrite semi-
404 Chapter 6. Properties of Minerals
, )Ira
on the relative temperature of
d mineral formation. p Number
of charge carriers, cm- 3 ; IX
600 thermo-EMF coefficient in
MkVjdegree
400
200
- 200
- 400
- 600
References
Microwave (radar) remote sensing, for example with the satellite Seasat, the US
shuttle instruments SIR-A and SIR-B, and with the European ERS-l and the
future Radarsat, has the great advantage of being an all-weather technique, with
a certain power of ground penetration. Radar images are function not only
of the technical parameters of the sensor, for example the wavelength - centi-
metric - or the polarization state of the incident beam, but also of the terrain
topography and of the dielectric constants c; of the ground materials, particularly
the minerals and the rocks.
406 Chapter 6. Properties of Minerals
Some dielectric constants e (e' being the real part and elf the imaginary part)
measured for more than 100 pure minerals, using the resonant cavity perturba-
tion method, are given in Table 31a. It shows that at the wavelength A = 3.2 em,
e' and elf of the minerals vary by two to four orders of magnitude. Sulfides and
oxides have the largest range of variation, the sulfides having larger ranges than
oxides containing the same cation. Dielectric constants are generally low for
silicates and for complex oxides, except a few phyllosilicates, Pb-bearing and
mafic minerals.
Therefore, radar imagery of the ground is controlled by the dielectric
constants of the rocks, i.e., mixtures of minerals. Measurements have shown that
e' and elf of magmatic rocks decrease following the series ultra basic-
basic-intermediate-acidic. This correlation is consistent with the variation of
dielectric constants against the chemical compositions: e' and elf decrease with
increasing Si-, K- and Na-contents, and decreasing, Fe, Mg, Mn, Ti, and Ca
contents in the rocks. Dielectric constants of sedimentary and metamorphic
rocks vary similarly to those of igneous rocks, but in a more complex way,
following the chemical composition, metamorphic conditions and sedimentary
environment. The dielectric constants of some rocks are listed in Table 31 b.
Effect afthe Frequency afthe Radar Beam. For a perfect dielectric mineral, the
dielectric constants can be expressed as a function ofthe frequency (Xiao lin-Kai
1990), but departure from the perfect dielectric is usually observed because of
impurities and defects in natural minerals and rocks. Dielectric dispersion
200
100
90
80
70
'", 60
~ 50
U;
c
o
40
20 u
'",
cca
.\
\
-g
tl
Q)
Q)
30
.8
U;
\
~ o 20
c 10
0
u 9 .~~
+"-... ~ ___ 1
u 8
-;:
tl 7 ~P--:- ~----~. 2
~~~:
~ 6 10
... .
Q)
0 9
5 8
----- • 116
4 7 7
A 6 B
3 5L-~~--~~--~~--~~---
103 104 105 106 107 108 109 10 10 103 104 105 106 107 108 109 1010
Frequency (Hz) Frequency (Hz)
Fig. l03A, B. Dispersion of the dielectric constant (e) of some minerals against frequency.
f(Hz). e': real part. A 1 augite; 2 olivine; 3 witherite; 4 albite; 5 sodalite; 6 amethyst; 7 white
quartz. B 8 montmorillonite; 9 kaolinite; 10 opal; 11 hornblende; 12 glauconite; 13 orthoclase;
14 microcline
408 Chapter 6. Properties of Minerals
18 • BASALT 41
ANDESITE )( 2
against frequency f (Hz). E' real part
SLATE • 3
GRANITE + 4
16
SHALE 85
C 14
til
') ........
LIMESTONE
DOLOMITE. 7
Ii 6
iii \ "GD
c QUARTZITE 0 8
o \ 6.
() 12
<.>
.;:
\ .....
t5Q) ~.
" ......
\ \••.. 6
10 ~
",':>..:. "t,."···.e.......
Q)
Ci .~
...........
8 ~"-'" ........... e. . . . ....... . ~ ~
+,
.......... .. ~--- ...
-~-~--~...
~ ".
.... '::t:
+................. -......:::..... -~:::.." .
.............. .f="",_ + -............... __ -..;:
6 """""" --_ _.. -
----
(;'""-...o-_ ... ..£.._ - ---.. ,;5
... _ _~.-:-:..:.::::~
4L-~ __ ~ __L-__ ~~L-~ __~__- L _
103 104 105 106 107 108 109 10 10
Frequency (Hz)
curves are given for some minerals in Fig. 103, and for rocks in Fig. 104.
Generally, hydrothermal minerals are characterized by strong dispersion curves,
and minerals with relatively stable crystallographic structure and chemical
composition display lower dispersion.
Effect of the Soil Moisture. Water is a dipolar liquid with a high dielectric
constant. At 23°C and for ). = 3.2 cm, s' = 61.5 and s" = 31.4. Since s for
minerals and rocks is much lower, the dielectric properties of the ground can
vary to a great extent if water is present. Nevertheless, experiments have shown
that structural water has little effect compared with that of water adsorbed in the
porosity of the rock. Experiments indicate that for moistened minerals and
rocks, the relation between s' and volumic percentage of adsorbed water Sw can
be expressed as:
s' = s~ p s~ Sw,
where p is the porosity of the material, s~ the dielectric constant (real part) of
the material under water-free conditions, and s~ the real part of the complex
dielectric constant of water. Likewise, s" increases exponentially with the
adsorbed water content.
Effect of Chemical Substitutions. The types of cations and anions, the ionic radii
and the ionic polarizability determine directly the polarization intensity, then
6.4.4 Dielectric Properties of Minerals and Rocks 409
the dielectric constant of a mineral material. Experimental data show that 6' and
6" vary with the isomorphic substitution of cations. Table 32 gives the micro-
wave dielectric constants of some isomorphous mineral species.
Effect of Density. According to Olhoeft (1981), a linear relation between 6' and
the density d of Hawaii basalts has been established: In 6' = 0.839 + 0.524d.
e
1.0
0.5
0
Q) 1.0
Z'
.:;
·iii
·E'"
w 0.5
Q)
>
<IS
~
e
.~
4 5 6
~ 0
30 30 30 8°60
0
9
60 900 gO 60 900 90
1.0
Fig. 105. Microwave emissivity (e) curves of some geological samples H and V horizontal and
vertical polarization; 0° incident angle; J basalt; 2 limestone; 3 granite-gneiss; 4 iron ore; 5
desert sand; 6 violet organic soil; 7 lateritic soil; 8 water surface; 9 asphalt surface
belts, fractured and highly impregnated with water, can be mapped by micro-
wave remote sensing. Water prospecting is greatly facilitated by use of this
technology.
On the other hand, very dry grounds with a smooth surface (versus the
centimetric wavelength), for example a sandy desert, can be penetrated to a
certain extent by the microwave beam. This phenomenon allows the subsurface
mapping of arid regions up to a few meters, leading to many applications in
Earth Sciences. This ability to penetrate dry surface and vegetation layers makes
the radar imaging data particularly useful in structural geology. Linear features
such as faults, folds, and fractures can be detected remarkably well by micro-
wave remote sensing.
6.4.4 Dielectric Properties of Minerals and Rocks 411
Conclusion
Microwave remote sensing gives unique information for Earth Sciences. On the
one hand, visible and infrared imagery, using the reflected radiation of the sun,
provides information about the surface of the Earth. Geological imagery, in this
part of the electromagnetic range, is impossible when clouds, vegetation, snow,
or alteration cover mask the lithological features. On the other hand, radar
imagery, using a centimetric wavelength beam emitted from the satellite and
then completely independent of weather and illumination, allows probing a
few meters under the surface. It gives volumetric information, depending on the
dielectric constant and the 3D-heterogeneities of the near-surface layer.
Therefore, the registration of radar imagery with other types of remotely
sensed data, with different spectral and spatial resolution, is particularly profit-
able, for example with data acquired in the visible-infrared range (Spot 2 and 3,
Landsat 4 and 5, Cosmos 1870). The two technologies are not competing, but
complementary, especially for Earth Science purposes.
References
Blom R, Elachi C (1981) Spaceborne and airborne imaging radar observation of sand dunes.
J Geophys Res 86: 3061
Blom RG, Crippen RJ, Elachi C (1984) Detection of subsurface features in Seasat radar images
of Means Valley, Mojave Desert, California. Geology 12: 346-349
Carver KR, Elachi C, Ulaby FT (1985) Microwave remote sensing from space. Proc IEEE 73:
970-996
Cervelle B (1991) Application of mineralogical constraints to remote sensing. Eur J Mineral 3:
677-688
Cervelle B, Moelo Y (1990) Reflected light optics. In: Jambor JL, Vaughan DJ (eds) Advanced
microscopic studies of ore minerals. Mineralogical Assoc Canada, Ottawa, pp 87-108
Elachi C, Brown WE, Cimino JB et al. (1982) Shuttle imaging radar experiment. Science 218:
996-1003
Liu JY, Teng XY, Xiao J-K (1985) Application of the shuttle imaging radar image to land use
investigation. Kexue Tongbao 30: 1241-1246
McCauley J, S-.:haber GG, Breed CS et al. (1982) Subsurface valleys and geoarcheology of the
eastern Sahara revealed by Shuttle Radar. Science 218: 1004-1020
Olhoeft GR (1981) Electrical properties of rocks. In: Toiiloiikian YS (ed) Physical properties of
rocks and minerals. McGraw-Hili, New York, pp 257-330
Sabins FF (1983) Geologic interpretation of space shuttle radar images of Indonesia.
Am Assoc Petrol Geol Bull 67: 2076-2099
Teng XY, Shi CQ, Peng HX, Xiao J-K, Lai ZS, Yang BL (1984) Passive microwave radiometry
in the Gobi Desert region. Remote Sens Environ 15: 37-46
Wang JR (1980) The dielectric properties of soil-water mixtures at microwave frequencies.
Radiol Sci 15: 977-985
Xiao J-K (1985a) Microwave dielectric properties of minerals and rocks. In: ESA SP-247 (ed)
Proc 3rd Int Colloquium on Spectral Signatures of Objects in Remote Sensing, Les Arcs,
France, 16-20 Dec. 1985, pp 293-296
Xiao J-K (1985b) A study on microwave dielectric properties of solid bitumen. Geochem 4:
67-76
Xiao J-K (1990) Dielectric properties of minerals and their applications in microwave remote
sensing. Chin J Geochem 9: 169-177
412 Chapter 6. Properties of Minerals
ently. Instead, use is made of the translational symmetry of the crystal lattice.
Each primitive unit cell contains n atoms. The lattice vibrations take the form of
vibrational waves propagating through the crystal with the periodicity of the
underlying crystal lattice, and can be grouped into 3n branches. Within each
branch, the relative atomic displacements within each unit cell are similar, but
the phase of the displacements in adjacent unit cells varies to give a lattice
vibrational wave propagating through the crystal. This lattice wave is described
by the inverse of its wavelength, the wavevector q, in the direction of propaga-
tion. Within this model, each lattice vibrational mode Qi(W, q) is described by its
characteristic frequency wand wavevector q. Plots of the mode frequencies
against wavevector are known as the dispersion curves for the crystal lattice
vibrations. The minimum wavelength is fixed by the dimensions of the primitive
unit cell, and defines the boundaries of the first Brillouin zone in reciprocal
space. For very long wavelength modes, the magnitude of the wavevector q
tends to zero, which defines the center of the Brillouin zone.
The three solutions to the secular equation which correspond to translation
of the entire crystal involve all atoms in all unit cells being displaced in the t>ame
direction at the same time. This motion has no restoring force, so has zero
frequency. Shorter wavelength lattice modes of this type, with atoms in each unit
cell moving in the same direction, but adjacent unit cells moving out of phase, do
have finite frequencies. These displacements generate local density fluctuations
within the crystal, providing a mechanism for sound transport and the three
branches are known as acoustic branches. The remaining 3n-3 branches involve
relative atomic displacements of atoms within the unit cell which can generate
fluctuating electric dipole moment contributions. These modes can interact with
light, giving rise to infrared and Raman spectra, and these branches are referred
to as optical branches. The lattice modes are further classified as transverse or
longitudinal, depending on whether the atomic displacements within the unit
cell (and hence the direction of the dielectric polarization vector) are perpendic-
ular or parallel to the propagation direction of the lattice vibrational wave.
The normal vibrational modes or lattice vibrations of the crystal have been
described above via solution of the classical equations of motion for the atomic
or ionic displacements within the harmonic approximation. These can also be
obtained from a quantum mechanical treatment, solving the vibrational Schro-
dinger equation HA> = Ev<p, in which <p represents the vibrational wave func-
tion. If the vibrational Hamiltonian Hv is written in terms of the normal mode
coordinates Q(w,q), the vibrational energy levels Ev are given by (Vi + 1/2)hwi'
where Vi is a vibrational quantum number (Vi = 0,1,2, ... ), and Wi is the
classical vibrational frequency obtained above. Excitation of a vibrational mode
occurs via absorption of a quantum of energy hWi to change the vibrational
quantum number by one unit. This quantum mechanical model leads to a useful
descriptive terminology, in which each unit of vibrational excitation is termed a
phonon. These phonons can be treated as particles carrying the equivalent of
momentum (although no actual mass transport is involved) through their
wavevector q. Absorption or emission of one quantum of vibrational energy (in
414 Chapter 6. Properties of Minerals
contributions, the full lattice dynamics are easily calculated via diagonalization
of the dynamical matrix. Recent improvements on the original MEG model
include the potential-induced breathing (PIB) model, in which the anion charge
density is allowed to relax during vibrational displacements, and the variational-
ly stabilized MEG (VSMEG), in which the crystal free energy is minimized
during vibrational (or static) distortions. These methods have been applied with
considerable success not only to the vibrational properties, but also in calcu-
lating elastic and thermodynamic properties, of a range of important minerals,
especially MgO and related oxides and halides, rutile, corundum, and MgSi0 3
and CaSi0 3 perovskites. As might be expected, this approach works best for
more "ionic" structures with high symmetry. In general, calculated zone center
vibrational mode frequencies are in excellent agreement with available experi-
mental data, although LO mode frequencies are overestimated, due to the
assumption of spherical charge densities. Calculations on more "covalent"
minerals such as quartz have been less successful, and have required the
inclusion of additional, empirical, parameters to account for nonspherical
polarization of the electron density.
Very recently, more intrinsically ab initio approaches have been applied to
the static and dynamic lattice properties of minerals and related complex
crystals, in which an approximate electronic wave equation for the crystal is
solved directly, providing a potential energy function for obtaining the classical
vibrational modes of the crystal. Several approaches have been used. In tight-
binding methods, the total electronic wavefunction is modeled as a linear
combination of overlapping atomic orbital wavefunctions. These methods are
most applicable to insulators, but fail badly for metallic solids. In plane wave
methods, the wavefunction for the crystal is expanded in a series of plane waves,
which works well for metallic systems. Augmented plane wave techniques, which
combine a plane wave expansion with more rapidly varying basis functions in
the core region, were developed to account for the rapid oscillations in charge
density in the vicinity of the cores. Pseudopotential methods provide a conve-
nient way of modeling the local potential in the core region seen by valence
electrons, without including a large number of basis set terms to model the core.
Once the model wave function has been constructed, the electronic energy
(including exchange and correlation energies, depending on the method of
solution) can be obtained and combined with core-core repulsion terms to
provide an ab initio crystal potential V. At this point, the atoms can be moved
along coordinates corresponding to vibrational mode displacements Qj, and the
total energy re-evaluated at each step. Differentiation of the function V(Qj)
determines the stability of the crystal against that type of atomic displacement,
which can be extremely useful in studying displacive phase transitions associ-
ated with soft mode behavior, and allows calculation of the vibrational mode
frequency from the ab initio potential energy surface. This type of dynamical
calculation is known as a "frozen phonon" approach, and has been applied
successfully to graphite and diamond, and very recently to stishovite and
lanthanum copper oxide superconductors. In Hartree-Fock-Slater self-con-
418 Chapter 6. Properties of Minerals
sistent field theory applied to molecular systems, methods have been developed
to directly obtain the first, second, and higher derivatives of the total energy with
respect to atomic displacement coordinates. These calculations are particularly
useful, in that they provide information on all of the vibrational modes of the
molecule, in a single calculation step. Hartree-Fock calculations are now being
carried out for minerals, including forsterite, corundum, spinel, quartz, and clay
minerals, and derivative Hartree-Fock methods are being developed and coded
for these complex crystalline systems. These ab initio techniques will revolu-
tionize the study of the vibrational, thermodynamic, and elastic properties of
minerals, especially when used in a complementary fashion with experimental
data.
References
Bilz H, Kress W (1979) Phonon dispersion relations in insulators. Springer, Berlin Heidelberg
New York, 241 pp
Born M, Huang K (1954) Dynamical theory of crystal lattices. Oxford, University Press,
Oxford, 420 pp
Burnham CW (1990) The ionic model: perceptions and realities in mineralogy. Am Mineral 75:
443-463
Chelikowsky JR, Chou MY (1987) Pseudopotential approaches to the structural energies of
crystalline solids and solid surfaces. Phys Chern Mineral 14: 308-314
Cohen RE, Boyer LL, Mehl MJ (1987) Theoretical studies of charge relaxation effects on the
statics and dynamics of oxides. Phys Chern Mineral 14: 294-302
Cohen RE, Pickett WE, Krakauer H (1989) First-principles phonon calculations for
La 2 Cu0 4 . Phys Rev Lett 62: 831-834
Ghose S, Hastings JM, Corliss LM, Rao KR, Chaplot SL, Choudhury N (1987) Study of
phonon dispersion relations in forsterite, Mg 2 Si0 4 by inelastic neutron scattering. Sol State
Comm 63: 1045-1050
Guth JR, Hess AC, McMillan PF, Petuskey WT (1990) A valence force field for diamond from
ab initio molecular orbital calculations. J Phys C: Sol State Phys 2: 8007-8014
Hemley RJ, Jackson MD, Gordon RG (1987) Theoretical study of structure, lattice dynamics,
and equation of state of perovskite-type MgSi0 3 and CaTi0 3 . Phys Chern Mineral 14: 2-12
Hemley RJ, Chen RE, Yeganeh-Haeri A, Mao HK, Weidner DJ, Ito E (1989) Raman
spectroscopy and lattice dynamics of MgSi0 3 , perovskite at high pressure. In: Navrotsky A,
Weidner DJ (eds) Perovskite: a structure of great interest to geophysics and material science.
Am Geophys Union, Washington DC, pp 35-53
Jackson MD, Gordon RG (1988) MEG investigation of low pressure silica-shell model for
polarization. Phys Chern Mineral 16: 212-220
Lazarev AN (1988) Vibrational spectra, lattice dynamics and chemical constitution of oxides.
Phys Chern Mineral 16: 61-72
Lazarev AN, Shchegolev BF, Smirnov MB, Dolin SP (1988) Quantum chemistry of molecular
systems and the crystal chemistry of silicates (in Russian). Nauka, Leningrad
Louie SG (1985) Pseudopotential and total energy calculations: applications to crystal
stability, vibrational properties, phase transformations, and surface structures. In: De Vreese
JT, Camp P van (eds) Electronic structure, dynamics, and quantum structural properties of
condensed matter. New York, Plenum, pp 350-396
McMillan PF (1985) Vibrational spectroscopy in the mineral sciences. In: Kieffer SW,
Navrotsky A (eds) Microscopic to macroscopic: atomic environments to mineral theromo-
dynamics, reviews in mineralogy, vol 14. Mineral Soc Am, pp 9-63
McMillan PF, Hess AC (1990) Ab initio valence force field calculations for quartz. Phys Chern
Mineral 17: 97-107
6.5.2 Lattice Dynamics and Thermodynamic Properties of Minerals 419
Mehl MJ, Hemley RJ, Boyer LL (1986) Potential-induced breathing model for the elastic
moduli and high-pressure behavior of the cubic alkaline-earth oxides. Phys Rev B 33:
8685-8696
Pisani C, Dovesi R, Roetti C (1988) Hartree-Fock ab initio treatment of crystalline systems.
Lecture Notes in Chemistry 48. Springer, Berlin Heidelberg New York, 193 pp
Price DL (1988) Lattice dynamics and inelastic neutron scattering from forsterite: phonon
dispersion relation, density of states and specific heat. Phys Chern Mineral 16: 83-97
Price GD, Parker SC, Leslie M (1987) The lattice dynamics and thermodynamics of Mg 2 Si0 4
polymorphs. Phys Chern Mineral 15: 181-190
Reissland JA (1973) The physics of phonons. John Wiley, New York, 319 pp
Wolf GH, Bukowinski MST (1987) Theoretical study of the structural properties and
equations of state of MgSi0 3 and CaSi0 3 perovskites: implications for lower mantle
composition. In: Manghnani MH, Syono Y (eds) High pressure research in mineral physics.
Terra Scientific Pub/Am Geophys Union, pp 313-331
Wolf GH, Bukowinski MST (1988) Variational stabilization of the ionic charge densities in the
electron-gas theory of crystals: applications to MgO and CaO. Phys Chern Mineral 15:
209-220
More realistic model potentials for anharmonic crystals include higher order
terms in the power series expansion for V(r) and are used to model thermal
expansion and thermal conductivity. In the so-called quasiharmonic approx-
imation, the temperature dependence of the force constants and phonon vibra-
tional frequencies is assumed to be due only to the effects of thermal expansion.
That is, the normal vibrations are still assumed to be uncoupled, but the force
constants and, therefore, the vibrational frequencies of the crystal change with
pressure and temperature because the equilibrium positions and distances
change.
More complicated models attempt to account fully for anharmonic effects by
including many-body interactions as well as effects thermal of expansion and the
coupled effects of phonon-phonon interactions.
The thermodynamic properties are given by integrals of energy functions
over the vibrational spectrum. For example, the heat capacity, C v , is given by
Cy = Jg(w) E (hw/kT) dw.
In this equation, E represents the Einstein heat capacity function, h is the Planck
constant divided by 2n, k is the Boltzman constant, and T is absolute temper-
ature.
Data from elastic, infrared, Raman, and inelastic neutron scattering ex-
periments can now be used, in conjunction with theoretical models of lattice
vibrations, to construct approximations to the total vibrational spectra, g(w).
Information from individual experiments is typically limited, e.g., optical spec-
troscopic methods give information primarily about the behavior of the modes
at the center of the Brillouin zone, whereas elastic measurements give informa-
tion only about long wave-length behavior. However, enough information can
be extracted from lattice dynamics and crystal structure systematics to allow
useful thermodynamic calculations to be made.
The practical and applied significance of lattice dynamics investigations is in
the establishment of quantitative ties between the microscopic and macroscopic
properties of crystals. If these ties are well established, then properties can be
predicted from statistical thermodynamics. This is particularly valuable in the
case of metastable minerals that are only formed at high pressures and temper-
atures since the amounts of sample that would be required for calorimetry or
ultrasonic experiments may not be available. Calculation of the thermodynamic
properties by statistical mechanics methods is also of use when reaction kinetics
inhibit laboratory measurements, viz., isotopic fractionation at low temper-
atures.
Until a decade ago, it was common to use the Debye approximation based
on acoustic properties (elastic constants) to calculate mineral thermodynamic
6.5.2 Lattice Dynamics and Thermodynamic Properties of Minerals 421
. v.::
1.
/::
1
1
1
....~
....
three branches - two transverse
and one longitudinal. The
;
/: / f :
/1 .. : 1
.. dashed curve shows a truncated
Einstein
oscillators
optic
continua Fig. 107. Schematic diagram of
a spectrum that allows for sep-
arate representation of three
acoustic modes, three different
types of optic modes grouped
into optic continuua, and four
Einstein oscillators
co
vibrational modes (n), and the number (m) of high frequency Einstein modes that
have been represented separately:
BR = BD*(l - m/n)1/3.
Over the temperature range from 200 to 1500 K, this kind of model can give
values of C p and S¥ that agree with measured values within 2.5 to 3%.
For the more complex silicates, this simple modification of the Debye
spectrum may not be adequate to predict thermodynamic properties for which
a high degree of accuracy is required (e.g., phase equilibria for which the free
energy differences are small; low-temperature isotopic fractionation). A gen-
eralized spectrum that has been applied to a number of minerals over the past
decade is shown in Fig. 107. In this representation (referred to below as the
Kieffer model), acoustic and optic modes are properly enumerated according to
mineral structure (viz., considerations given in the previous chapter). Anisotropy
and dispersion in acoustic modes are modeled semi quantitatively by incorpora-
tion of a spectral form based on that appropriate to a diatomic solid. Optic
6.5.2 Lattice Dynamics and Thermodynamic Properties of Minerals 423
Applications
SiO z , GeO z , and TiO z Polymorphs. Knowledge of the phase boundaries in the
Si0 2 system is important because of the ubiquitous occurrence of the minerals
on the surface of the Earth (quartz, glass, cristobalite, tridymite), and in the
interior (coesite, stishovite). Determination of the phase boundaries, particularly
of the high-pressure polymorphs, has proved difficult because ofthe sluggishness
of the reactions under laboratory conditions. There has also been some question
about the meaning of the thermochemical data on coesite and stishovite because
the data were obtained on natural samples from Meteor Crater, and the purity
and grain size in the samples were not ideal for calorimetric samples. Theoretical
calculation of the heat capacities from spectra has addressed the problems in
the calorimetric data and calculation of the free energies has contributed to
narrowing the range of plausible the phase boundaries.
Considerable work has been devoted to obtaining and interpreting vibra-
tional spectra of different polymorphic modifications of silica (SiO z), parti-
cularly the high-pressure polymorphs coesite (monoclinic) and stishovite
(tetragonal). GeO z provides a good structural analog for Si0 2 because it has
isomorphous forms with quartz and stishovite, and the rutile-structured GeO z
and Ti0 2 polymorphs are stable at room pressure, and can be more easily
studied than stishovite. Although infrared and Raman data are available for all
of these oxides, inelastic neutron scattering data are available only for a-quartz
and rutile.
The heat capacity at 1 atm pressure has been calculated for quartz with a
number of different models, each accounting for the optic modes in slightly
different ways. It is possible to enumerate the zone-center mode frequencies
6.5.2 Lattice Dynamics and Thermodynamic Properties of Minerals 425
for all optic modes, and the various models that have been presented in the
literature differ only in the way in which the dispersion in the modes is treated to
obtain an assumed g(ro). Most models give heat capacities that are within 1-2%
of calorimetric values at temperatures above 298 K.
Measurements of the infrared and/or Raman spectra as a function of
pressure have allowed a number of new kinds of thermodynamic calculations
based on vibrational spectroscopy to be introduced. Measurement of the shift of
spectral lines as function of pressure allows calculation of the mode Gruneisen
parameters. Variations in the spectra with temperature allow modeling of
anharmonic contributions to the thermodynamic functions. Models that take
account of the anharmonicity (both the pure-volume contribution that arises
from the change in bond length with pressure and temperature and the volume-
independent contribution arising from the higher-order anharmonic terms in
the potential energy function) reproduce the calorimetric results for Cp very well.
Comparison of the thermodynamic properties obtained from high-pressure and
high-temperature spectroscopy with range of experimentally measured phase
boundaries for the coesite-stishovite transition suggests that the most current
"best guess" for the phase boundary is 8 ± 0.3 Gpa at 300 K and that the
boundary has a slope of 2 x 10- 3 Gpa K - 1.
Measurement of the change of vibrational band frequency upon isotopic
substitution allows calculation of isotopic fractionation. Oxygen fractionation
has been calculated for at least a dozen minerals - including calcite - in this way
and the results agree with experimentally determined values to within a few
parts per million. Such calculations have not yet been carried out for silicon
fractionation, although 28Si/30Si vibrational data are now available.
In quartz, the 207 cm - 1 mode broadens and shifts rapidly to lower fre-
quency with increasing temperature. This is known as soft mode behavior. The
atomic displacements of this mode mimic those of the 1Y.-f3 phase change, and
thermal excitation of the anharmonic mode is responsible for the displacive 1Y.-f3
phase transition in quartz. The mode at 517 cm - 1 in Ge0 2 shows a lesser, but
still appreciable, degree of anharmonicity. The vibrational spectra of stishovite,
tetragonal Ge0 2 , and Ti0 2 rutile all show interesting and significant mode
anharmonicity. Studies of the so-called soft-modes in these minerals, as well as
in cassiterite (Sn0 2, rutile structure) have led to increased understanding of the
mechanisms of phase transitions.
Large mode Gruneisen parameters represent a challenge in attempts to
relate mode Gruneisen parameters (Yi) to thermal Gruneisen parameters (Yth).
Mg2 Si04 Forsterite and its High-Pressure Spinel and Spinelloid Polymorphs. A
particularly well-examined problem has been that of the thermochemical prop-
erties and phase relations of forsterite [1Y.-Mg 2 Si0 4 ] and its high-pressure
polymorphic modifications [f3- and y-Mg 2Si0 4 ], from a combination of ther-
modynamic calculations, calorimetry, and high pressure synthesis and phase
equilibrium experiments. The results of these experimental and theoretical
studies have been combined with work on MgO and Si0 2 and MgSi0 3
426 Chapter 6. Properties of Minerals
All the mode Gruneisen parameters were found to be positive and to lie
between 0.382 and 2.09. The averaged mode Gruneisen parameters give a mean
of 1.09, in reasonably good agreement with the macroscopic thermal Gruneisen
parameter Ylh of 1.17.
The phonon density of states functions for the high-pressure Mg zSi0 4
phases (p and y) are less well constrained from experimental data, although zone
center (infrared and Raman) data and elasticity measurements are available, and
rigid ion model lattice dynamic calculations have been carried out. The entropy
and heat capacity for these phases have been calculated using vibrational
models like that shown in Fig. 107, constrained by the experimental vibrational
spectra and elastic constants. The calculations support experimental results that
P-Mg zSi0 4 is intermediate in lattice entropy and energy to the oc and Y forms.
The calculated entropies were combined with calorimetric measurements of
enthalpies to examine the stability fields of the three polymorphs. The entropy
differences among the phases allows determination of the oc-P, p-y, and oc-y
phase changes. These were compared with AS,,_p and AS p _ y as determined from
the slopes of monovariant equilibria lines on the Mg zSi04 phase diagram:
AS = AV*(ap/aT).
The differences in slopes were about ± 30% and the differences in positions
of curves, about 2.5 Gpa (25 kbar) [at approximately 17 Gpa (170 kbar)], but
such differences are plausible when limits of experimental and model errors are
considered. Phase relations to 30 Gpa (300 kbar) and to melting temperatures
have been reproduced.
6.5.2 Lattice Dynamics and Thermodynamic Properties of Minerals 427
In a different treatment, the lattice dynamics of IX-, f3- and y-Mg 2 Si0 4 were
calculated using an empirical rigid ion treatment, which was used to construct
theoretical g( w) curves for the three polymorphs. The density-of-state spectrum
for forsterite was very close to those obtained by optic and inelastic neutron
methods. The elastic and shear moduli as well as Cp , S~, IX, and Ylh were
calculated. The calculations of the harmonic properties of specific heat and
entropy were in excellent agreement with corresponding calometric data, but the
anharmonic parameters IX and Ylh were approximately 30% lower than meas-
ured values. An attempt was carried out to compute the mono variant equilibria
for the 1X-f3-y phases of Mg 2 Si0 4 using this Born ion model. The P-T slopes for
the 1X-f3 and f3-y transitions corresponded to the experimental slopes; however,
the curve positions differed from the experimental phase equilibrium data:
- 15 kbar for 1X-f3 and + 40 kbar for the f3-y transitions. Thus, the error using
g(w) functions determined from empirical lattice dynamical calculations within
the ionic model is comparable to that using the Kieffer model.
Al2 Si0 5 Polymorphs. Calculation of the phase boundaries between the poly-
morphs of Al 2 Si0 5 provides a sensitive test of the vibrational approach to
thermodynamic calculations. The computed and calorimetric C p and S¥ agreed
at the level of ± 1% at 298 K because the spectral assignments can be made
quite accurately. Modeling of the phase boundaries requires calculation of
differences in the free energy AG p •T at the phase boundaries, and also requires
incorporation of the thermochemical heat of solution calorimetry data. The
different calculations done constraint the triple non-variant point of kyanite- and
alusite-sillimanite at 477-557°C and 3-4.6 kbar (compare with 430 ± 10 K, 3
± 0.1 kbar originally in Salje and Werneke 1982b). Although this may seem like
a large range, it should be remembered that the free-energy surfaces intersect at a
very shallow angle and that experimentally determined values span a similar
range.
Summary
References
Chopelas A (1990a) Thermal expansion, heat capacity, and entropy of MgO at mantle
pressure. Phys Chern Mineral 17: 142-148
Chopelas A (1990b) Thermal properties of forsterite at mantle pressures derived from
vibrational spectroscopy. Phys Chern Mineral 17: 149-156
Clayton RN, Kieffer SW (1991) Oxygen isotopic thermometer calibrations. In Taylor HP,
O'neil JR, and Kaplan IR (eds) Stable Isotope Geochemistry: a tribute to Sam Epsten.
Geochemical Society spec. Publ. No.3, Sanantonis, Texas, pp 3-10
Fei Y, Saxena SK, Navrotsky A (1990) Internally consistent thermodynamic data and
equilibrium phase relations for compounds in the system MgO-Si0 2 at high pressure and
high temperature. J Geophys Res 95: 6915-6928
Ghose S, Hastings JM, Corliss LM, Rao KR, Chaplot SL, Choudhury N (1987) Study of
phonon dispersion relations in forsterite MgSi0 4 by inelastic neutron scattering. Sol State
Commun 63: 1045-1050
Gillet PH, Guyot F, Malezieux JM (1989) High pressure and high temperature Raman
spectroscopy of Ca 2 Ge0 4 : some insights on anharmonicity. Phys Earth Planet Int 58:
141-154
Gillet PH, Le Cleac'h A, Madon M (1990) High temperature Raman spectroscopy ofSi0 2 and
Ge0 2 polymorphs: anharmonicity, thermodynamic properties and phase relations among
the Si0 2 polymorphs at high temperatures. J Geophys Res 95: NB13 21, 635-21, 655
Hemley RJ, Chen RE, Yeganeh-Haeri A, Mao HK, Weidner DJ, Ito E (1989) Raman
spectroscopy and lattice dynamics of MgSi0 3 -perovskite at high pressure. In: Navrotsky A,
Weidner DJ (eds) Perovskite: a structure of great interest to geophysics and material science.
Geophys Union, Washington DC, pp 35-53
Hemly RJ, Jackson MD, Gordon RG (1987) Theoretical study of structure, lattice dynamics,
and equation of state of perovskite-type MgSi0 3 and CaTi0 3 . Phys Chern Mineral 14: 2-12
Hofmeister AM, Hoering TC, Virgo D (1987) Virbrational spectroscopy of beryllium alu-
minosilicates: heat capacity calculations from band assignments. Phys Chern Mineral 14:
205-224
Ito E, Navrotsky A (1985) MgSi0 3 ilmenite: calorimetry, phase equilibria, and decomposition
at atmospheric pressure. Am Mineral 70: 1020-1026
Kieffer SW (1979a) Thermodynamics and lattice vibrations of minerals: 1. Mineral heat
capacities and their relationships to simple lattice vibrational modes. Rev Geophys Space
Phys 17: 1-19
Kieffer SW (1979b) Thermodynamics and lattice vibrations of minerals: 2. Vibrational
characteristics of silicates. Rev Geophys Space Phys 17: 20-34
Kieffer SW (1979c) Thermodynamics and lattice vibrations of minerals: 3. Lattice dynamics
and an approximation for minerals with application to simple substances and framework
silicates. Rev Geophys Space Phys 17: 35-59
Kieffer SW (1980) Thermodynamics and lattice vibrations of minerals: 4. Applications to
chain and sheet silicates and orthosilicates. Rev Geophys Space Phys 18: 862-886
Kieffer SW (1982) Thermodynamics and lattice vibrations of minerals: 5. Application to phase
equilibria, isotopic fractionation, and high-pressure thermodynamic properties. Rev Geo-
phys Space Phys 20: 827-849
Kieffer SW, Navrotsky A (eds) (1985) Microscopic to macroscopic: atomic environments to
mineral thermodynamics. Reviews in Mineralogy, vol 14, Mineral Soc Am 428 pp
Lazarev AN (1988) Vibrational spectra, lattice dynamics and chemical constitution of oxides.
Phys Chern Mineral 16: 61-72
Lazarev AN, Shchegolev BF, Smirnov MB, Dolin SP (1988) Quantum chemistry of molecular
systems and the crystal chemistry of silicates. Nauka, Leningrad (in Russian)
McMillan PF, Hess AC (1990) Ab initio valence force field calculations for quartz. Phys Chern
Mineral 17: 97-107
McMillan PF, Ross NL (1987) Heat capacity calculations for AI 2 0 3 corundum and MgSi0 3
ilmenite. Phys Chern Mineral 14: 225-234
Navrotsky A (1987) Silicate and germanate garnets, i1menites and perovskites: thermo-
chemistry, lattice vibrations, and spectroscopy. In: Manghnani MH, Syono Y (eds) High-
pressure research in mineral physics, pp 261-268
Navrotsky A (1989) Thermochemistry of perovskites. In: Navrotsky A, Weidner DJ (eds)
430 Chapter 6. Properties of Minerals
The lattice thermal conductivity is defined as the ratio of heat flow density to
temperature gradient. Since it is related to lattice properties, the thermal
conductivity is sensitive to variations in temperature and pressures, as are the
lattice properties. At temperatures above the Debye temperature, a relationship
for isotropic single crystals has been deduced as:
A = ~ cyvaO
3 oeyvT'
where Cy = specific heat capacity at constant volume, v = mean sound velocity,
a o = lattice constant, oey = volumetric thermal expansion coefficient, v = Griin-
eisen parameter, T = temperature.
If the equation of heat conduction is divided by the thermal capacity (pc), the
thermal diffusivity a further thermal property is defined as:
A
a=-.
pc
The commonly used methods may be divided into two classes, i.e., steady state
and transient techniques. The steady state methods are usually comparative
432 Chapter 6. Properties of Minerals
techniques where the one dimensional heat flows along the unknown specimen
and a reference disc. The heat flow density Q is determined at the reference
probe and with the measured temperature gradient across the specimen, the
thermal conductivity of the specimen is determined. Using different fluids or
diamond powder and an uniaxial pressure in addition, the contact resistances
are small enough to be negligible, so that
A. s = Q/(dT/dx}s where Q = ).r(dT/dx}r'
sand r refer to specimen and reference probe, respectively.
An absolute method is the cylindrical heat flow technique. A long heating
wire supplies thermal energy radial-symmetrically into the specimen whereby
the temperatures are monitored at two points, r 1 and r 2' When the stationary
state is reached, the thermal conductivity can be determined by:
A. = Q In(r 2/r 1}
2n T1 - T 2 '
where Q is the energy per unit time and unit length and T 1 - T 2 is the
temperature difference between the radii r 1 and r 2' The transient state can be
used to determine the thermal diffusivity. The previously described heat flow
a) Polycrystalline
Flourite (CaF 2) 9.5
Quartz (Si0 2) 7.7
Dolomite (CaMg(C0 3}z) 5.5
Grossularite (Ca3AI2Si3012) 5.5
Forsterite (Fo 9S Fa 2) 5.1
Diopside (CaMgSi 20 6) 5.1
Enstatite (En 9s Fs 2) 4.3
Calcite (CaC0 3) 3.6
Pyrope (Mg 3AI 2Si 30 12 ) 3.2
Muscovite (K3AI4Si6AI2020(OH)4) 2.3
Orthoclase (KAlSi 30 s ) 2.3
Albite (Ab 99 An l ) 2.3
Anorthite (Ab 4An 96 ) l.7
b) Single crystals
Corundum (AI 20 3) 27
Diamond (C) 120-160
Graphite (C), parallel (001) 355
Graphite (C), perpendicular (001) 89
Quartz, direction of optical axis c 12.0
Quartz, perpendicular of optical axis c 6.0
Muscovite, parallel (001) 0.8
Muscovite, perpendicular (001) 5.0
6.5.3 Heat Flow in the Earth's Crust and Mantle 433
meter method is also applicable for determining the thermal diffusivity, if the
temperature is varied at one face of the bar.
A rapid method to determine the thermal diffusivity is the "flash" method
where heat pulses, usually from a laser or a xenon lamp, are absorbed at one face
of a thin specimen, and the temperature rise is measured at the other face as a
function of time. This method is applied up to 1800°C.
The values of the thermal conductivity of most common crustal rocks at near
surface conditions vary between 2 and 5 W jmK. The range is due to the thermal
conductivity of the poor heat conducting but very abundant feldspars and
to the, in general, better conducting chain silicates (Table 33). An exception
is quartz, whose content in crustal rocks determines its total conductivity.
Forsterite, which is abundant in the upper mantle, also conducts heat well.
From the viewpoint of mineralogy, an attractive way to determine the
distribution of thermal parameters for different mineralogical mantle models is
10
~_~1 ___
Fig. 108. Temperature dependence
of thermal conductivity for some
minerals (average values). 1 pyro-
phillite; 2 fused quartz; 3 forsterite;
4 quartz (010); 5 quartz (001); 6
MgO; 7 AI 2 0 3
600 1200 1800
T, K
434 Chapter 6. Properties of Minerals
to use the methods of estimating thermal properties from mineral content. The
theories which may be used are based on a statistical approach or on the
consideration of specific simple structural models of rocks. The experimental
data on the thermal conductivity of some minerals (the average values) at
elevated temperatures are shown in Fig. 108. The influence of pressure can be
taken into account by the use of empirical linear or quadratic relationships
between the thermal conductivity and pressure. There are minerals with very
unusual, extremely high, thermal conductivities such as diamond (120
- 160 W m - 1 K - 1 at 0 0c) and, in particular, sapphirine, whose conductivity at
very low temperatures is comparable with the conductivity of metallic materials.
These features find applications in material science.
The average HFD is equal to 57 mW/m2 for continents and 99 mW/m2 for
oceans. There are differences in the average HFD for different continents, i.e., the
lowest value is reported for Africa, 49.8 mW/m2, and the highest for Australia,
63.6 m W /m 2. The continental crust contains a significant amount of radioactive
heat sources the most important being U 235 , U 238 , Th 232 , and K 40 , which are
associated mainly with acidic rocks. They contribute for different tectonic
structures from 1/3 to 1/2 of the observed HFD. The rest is due to the heat
supplied to the base of the lithosphere. At oceans almost the total HFD is
related to the convective processes in the mantle and the cooling of the
lithospheric plates spreading from the mid-ocean ridges.
6.5.3 Heat Flow in the Earth's Crust and Mantle 435
One of the actual problems lying at the boundary between geophysics and
geochemistry is to find a way to reconstruct the thermal evolution of the
lithosphere. There are a number of methods for paleotemperature estimations
for sedimentary basins, based on the data on the maturation of organic
materials.
Several attempts have been made to reconstruct the evolution of mantle heat
flow during continental rifting based on petrochemical data and on the solution
of the nonsteady state boundary value problem.
References
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Nature 298: 734-736
436 Chapter 6. Properties of Minerals
W.O'REILLY
All materials respond in some way to a magnetic field so that all minerals have
magnetic properties. Minerals which contain no ions with uncompensated spins
(e.g., an absence of, notably, the transition series elements) are diamagnetic.
Those containing transition elements in low concentrations are paramagnetic.
The ratio of the magnetic susceptibilities of these two categories of mineral can
be high enough ( ~ 10 2 ) that magnetic methods can be employed to physically
separa·te, e.g., the desirable (diamagnetic) fraction from the undesirable (para-
magnetic) fraction of the raw material used for porcelain manufacture. Thus
even diamagnetism can be usefully exploited.
Minerals with high concentrations of transition elements may be ferrimag-
netic, antiferromagnetic, or ferromagnetic at ambient temperatures. Sometimes
the magnetic properties of these minerals are directly useful in, for example,
refining ores, including the separation of coal from stone. Sometimes the
magnetic properties are used less directly; for example, a magnetic survey reveals
magnetic ore which in turn indicates the probable presence of more valuable
minerals, such as gold.
Ferrimagnetic minerals are widely dispersed in the rocks of the Earth's crust
in concentrations rarely exceeding 10%. Just as is the case with the more
abundant rock-forming minerals, the state of the magnetic minerals reflects the
physical and chemical history of the host rock. The state of the minerals can be
inferred from the magnetic properties of the bulk rock, and magnetic measure-
ments can therefore reveal information about the state or history of the rock.
Thus anisotropy of magnetic susceptibility is used to determine rock fabric; or
Curie point temperature measurements indicate the degree of oxidation of a
submarine basalt. Although an indirect method compared to optical study, the
magnetic method does have the advantage of sampling vast numbers of mineral
grains.
The presence of ferrimagnetic minerals in crustal rocks has had monumental
importance in leading to the study of paleomagnetism, by which the history of
the geomagnetic field and motions of the crust can be traced over geological
time. This is possible because the ferrimagnetic mineral fraction can acquire a
record of the direction of the geomagnetic field at more or less the time of
formation of the rock. The consequent study of the relationship between the
magnetism of minerals and their chemical composition, crystal structure, micro-
structure, the effect of transformations (e.g., oxidation), and of elevated tem-
peratures and pressures, and the mechanisms (thermoremanence, chemical
remanence, depositional remanence, piezoremanence) by which they may acquire
6.6.1 Magnetic Minerals 437
a magnetic record which can survive more or less intact over geological time, has
evolved into the field of study known as rock and mineral magnetism. One goal is
to provide theory and practice which underpins the paleomagnetic method, and
which may lead to an understanding of the magnetism of the Earth's crust at a
profound level. The theoretical and experimental work that is inspired by
observations of the magnetism of rocks, also leads to new science by attacking
problems which otherwise might not have been recognized. Nature's recording
medium is imperfect and problems of unsuitable compositions, nonideal particle
size and shape, and complex recording processes, which can be avoided by the
designers of man-made recording media, must be confronted by rock magnetism
researchers, and science (and technology) profits. Thermoremanence, the mech-
anism hypothesized and studied to explain the stable remanent magnetization of
igneous rocks, now finds application in the replication of prerecorded video
tapes.
Magnetic minerals also figure in the human and animal worlds. A record of
human activity (e.g., the Industrial Revolution) is found in the magnetic
properties of soils, sediments, and peats; and the magnetic properties of artefacts
may allow events in antiquity to be dated, or provide details of human practices
(e.g., how the pots in a kiln were stacked during firing). Magnetite occurs as
a biomineral in many species, from bacteria to whales, where it appears to
provide a means of navigation.
The Titanomagnetites
Fig. 109. The FeO-Ti0 2 -Fe 2 0 3 ternary diagram on which many of the more abundant
magnetic minerals can be located (species other than Fe and Ti generally occur in small
concentrations only). Primary magnetic minerals in igneous rocks can be modeled by
Fe2.4TiO.604 (TM60) or Fe 3 0 4 (magnetite). Oxidation of primary minerals is common and
results in movement to the right in the diagram. Hematite (IXFe 2 0 3 ) is the ultimately stable
oxidized magnetic mineral (see also Fig. 125)
experimental time is of the same order as T. This may explain why direct attempts
to observe the temperature-dependent cation distribution in titanomagnetites
have failed. If reliable values for the potentials of Fe 2 + , Fe 3 +, and Ti4 + in oxides
are available, a computational approach might be fruitful and illuminating.
The observed variation in Ms of the synthetic titanomagnetites must still be
explained, and one possibility may be in a variable concentration of vacant
lattice sites ("high temperature nonstoichiometry"). High temperature non-
stoichiometry certainly appears to have a strong (but unexplained) influence on
T c such that Tc(x,z) = T c(x,o) + 700 z, where z is an oxidation parameter. The
limiting value for z is temperature-dependent, but can be as large as ~ 0.1. Thus
Tc may vary by about 70°C for a given x.
The spin structure-dependent properties (Ms' K 1 , A) depend on temperature
and vanish at the Curie point. The temperature variation of K1 and A can be
quite complex. The variation of K1 with temperature for some titanomagnetite
compositions is shown in Fig. 110. The zero point in K1 indicates a switch in the
preferred direction of spontaneous magnetization from [100] (K1 > 0) to [111]
(K1 < 0). K1 results from the individual, "single-ion", contributions of Fe 2 + and
Fe 3 + in the octahedral and tetrahedral sites. The temperature dependence of the
Fe2+ contribution (in octahedral sites in near-Fe 3 0 4 compositions) is the most
c0
iii
c:
0
u
>-
Go
~
0III
c:
<{
complex and may be directly responsible for the zero point in K t . Magnetocrys-
talline anisotropy and magnetostriction are related, and the increasing concen-
tration of highly anisotropic Fe2+ in higher x-value compositions (say, TM60)
is believed to be responsible for the "giant magnetostriction" found at low
tern perature.
The room temperature values of the composition-related intrinsic magnetic
properties result from an interplay between the changing composition (increas-
ing Fe2+, decreasing Fe3+), and the consequences of the changing composition
on Curie point temperature. Thus the introduction of Fe 2 +, which being an
anisotropic ion is expected to increase the anisotropy of the material, may bring
about a decrease in anisotropy at some specific temperature (say room temper-
ature), because the exchange interaction has also been weakened and the Curie
point temperature lowered (to, say, even below room temperature). The sys-
tematic variation of the intrinsic properties with temperature and composition is
often best revealed by replacing temperature, T, by the dimensionless magnetic
temperature, T/Tc.
The magnetization process parameters - susceptibility (X), remanence, etc. -
are extrinsic, depending on microstructure, in addition to their dependence on
the intrinsic properties. Their connection to the intrinsic properties takes the
5 ~ 10
I
x 10-2 I x 10-10
• X I Ms
I
I
I
0 I K11 1Ms I
I
4 I
8
I
I K11 I
I
X
Ms I
I Ms
I
I
3 I
6
I
I
I
I
I
I
2 I
I
4 Fig. 111. The room temper-
I ature values of the ratios
I
IKII/Ms and IAI/Ms of titan-
.,- ...
A omagnetites as a function of
.,- ...
.,-
composition. These ratios in-
,; dicate the compositional in-
,, 2 fluences on the magnetization
process parameters. The po-
,,:.1>----0-- _--000-- --- __
.AI
"d
tf'
---0...
-----0 tential via IAI/Ms for high
magnetic "hardness" due to
stress in x = 0.6 (TM60) is
evident
0 0.4 0.6 0
Composition, x
6.6.1 Magnetic Minerals 441
form ofa dependence on the ratios IK11/Ms or IAI/M s. A high Ms means that even
a small applied field will couple strongly with the magnetization and make the
material "soft" (e.g., a high X). On the other hand, a high IK11 or IAI indicates a
strong coupling of the magnetization to the crystal axes or a strain direction,
making the material "hard" (low X). The room temperature values for the
hardness parameters of the titanomagnetites is shown in Fig 111. The variation
of IAI/Ms with composition is striking. The value achieved for TM60, when
combined with the stress which may be incorporated into the crystal structure -
by laboratory pulverization, say, or by compositional gradients in naturally
occuring crystals - results in the highest magnetic hardness (highest coercive
force, most stable remanence etc.), so for observed, for any mineral at room
temperature.
The Titanomaghemites
0<t
Q/
N
1/1
Q; 6.40
u
6.36
•
6 32 L-_--'-_-1.._----l_ _.L..-_....I
o 0.2 0.4 0.6 0.6 1.0
Oxidation paramE'tE'r, Z
Hematite (a-Fe 2 0 3 ) has the corundum structure which leads to (an imperfect)
antiferromagnetism. The ilmenite structure is essentially similar to the
6.6.1 Magnetic Minerals 443
corundum structure, but has basal plane cation layers occupied alternately by
Fe2+ and by Ti4+. The hematite-ilmenite solid solution Fez _yTiy03 (0 < Y < 1)
(Fig. 109) may have ordered or disordered distributions of FeZ +, Fe 3+, and Ti 4 +
between the cation layers. An ordered distribution could have layers with
(1-y)Fe3+ and yTi4 + alternating with layers containing (l-y)Fe3+ and yFe2+. If
the layers are oppositely coupled by exchange interactions, the spontaneous
magnetization would be 4y Bohr magnetons per formula unit at low temper-
ature. Moments approaching these values have been found for slow cooled
samples of composition y = 0.6-0.8. These strong magnetizations cannot persist
up to y = 1, regardless of the degree of order produced by slow cooling. One
sublattice becomes totally populated by nonmagnetic Ti 4 + ions, and the spin
structure must be organized by the separated Fe2+ -rich layers. This results
in antiferromagnetism and the low Neel point temperature (TN = 55 K) of
ilmenite.
At the other end of the series, the abundant mineral hematite is an
antiferromagnet, at least in mm-size crystals and at low temperature, when the
moments of the Fe 3+ ions lie perpendicular to the basal planes and the
magnetization of alternate layers is precisely antiparallel. The orientation of the
spin structure is governed by the sign of the anisotropy constant Ku' This
consists of two terms due to the competing single-ion and dipolar contributions
to the anisotropy, which may cancel at a Ku = 0 point (the Morin transition).
The dipolar term falls less quickly as T rises and dictates the sign ofK u above the
compensation point. Thus above about - 10 °e, the spin structure switches to
lie within the basal planes of the crystal structure (Fig. 113). The two magnetic
sublattices of the antiferromagnetic structure no longer lie closely antiparallel.
This is accounted for by a antisymmetric exchange interaction described by a
term - D· Ml X M z in the expression for the free energy. The vector D, lying
along the trigonal axis of the structure, represents the exchange energy constant
(in appropriate units) and Ml and M z are the sublattice magnetizations. The
combination of this antisymmetric exchange interaction with the interaction
The Pyrrhotites
Troilite, FeS, which crystallizes in the NiAs structure has, like hematite above
the Morin transition temperature, magnetized layers lying in the basal planes
with alternating orientation. The spin structure is colinear and has only
antiferromagnetic susceptibility. Monoclinic pyrrhotite (Fe 7 SS ) is cation-defi-
cient and, below the f3 transition, the vacancies are located in layers which
alternate with completely filled layers. This gives rise to a strong ferrimagnetism
of about 30 A m 2 kg-I confined to lie in the basal plane by a strong crystal
anisotropy (Ku '" 10 5 J m - 3).
The hexagonal pyrrhotites (Fe 9 S IO ' FelOS ll and Fe ll S 12 ) have fewer vacan-
cies. Ordered arrangements, which may consist of layers which contain 25%
vacancies (like Fe 7 SS ) separated by different numbers of filled layers, as appro-
priate to the compositional formula, are ferrimagnetic. The ferrimagnetic or-
dered arrangement is stable between about 200°C (T y) and the T c of about
250°C. The ferrimagnetism of about 10 A m 2 kg-I can be preserved at room
temperature by quenching from above Ty- The anisotropy within the basal plane
of Fe 7 SS seems to be triaxial with magnitude 3 x 10 3 J m - 3.
The iron sulfide Greigite, Fe 3 S4 , which is ferrimagnetic with spontaneous
magnetization of 20-30Am2 kg- 1 and a Tc of about 300-340°C is probably
structurally metastable but may be widespread in low-temperature environ-
ments like lake sediments.
When magnetic particles are small enough ( < 111m or thereabouts), they are
monodomain; each particle has a magnetization equal to the spontaneous
6.6.1 Magnetic Minerals 445
right angles. Such calculations again show that a particle of nominally 2D size
could be largely filled by an incoherent spin structure (a "wall"), and in addition
have the angles by which the spins rotate with increasing distance coordinate
going beyond 180 in one "domain" and below 0° in the other. These "over-
0
shoots" reduce the domain wall moment. A further result of such calculations is
that, although a given multiplicity of domains may represent the lowest possible
energy for the particle, the particle may be in different stable state (say with fewer
domains) with higher energy. The particle cannot achieve the lower energy
minimum because a potential barrier (the work done to construct a domain wall
at the surface) must first be overcome (Fig. 114). After the nucleated wall has
Wall position
6.6.1 Magnetic Minerals 447
propagated into the interior, the reduction in Eself brings about a net saving in
energy. Thus a particle of a given size may be found in one of several energy
minima, each corresponding to a certain number of domains, separated by
potential barriers from each other and from the lowest energy state.
Finally, using supercomputers, it is possible to carry out unconstrained
calculations of the free energy of small crystals. These calculations produce a
variety of different nonuniform structures with energies and magnetic moments
much less than lamellar structures.
a b c d
Fig. lIS. Observations of domain structure is a small pyrrhotite particle. a In the state of
natural remanent magnetization (NRM) the particle accommodates a domain wall pre-
sumably nucleated at high temperature. b After application and removal of a saturating field,
the particle is unable to nucleate domain walls and is left in the monodomain state. c A back
field of - 43 kA m - 1 causes a domain wall to nucleate and cross the particle in a single jump
to produce a reversed magnetization. d Relaxation of the back field to a value of - 40 kA m - J
allows a domain wall to nucleate and migrate into the particle. (After Halgedhal and Fuller
1983)
448 Chapter 6. Properties of Minerals
•
'0
t
0
u
20
o 3 4 5
Root mean grain size L1/2 (~m 1/2 )
and Lc is the critical size for the monodomain/multidomain transition, then the
number of particles in the monodomain state, in a saturated assemblage of
particles, is proportional to exp{ - (L/Lc)1/2}. The form of the grain size
dependence of magnetization process parameters in pyrrhotite fine particles
(Fig. 116) may, therefore, be suggestive of the importance of domain wall
nucleation in the magnetization process of this mineral.
Application to the Magnetism of the Earth's Crust. The submarine crust reveals
an interesting and fruitful convergence of geomagnetism and tectonics. One
aspect which has intrigued rock magnetists is the decay in amplitude of the
magnetic stripe anomalies, and the directly observed fall in remanence intensity
of recovered basalts, with increasing age. The source of the decay is believed to
be submarine weathering (maghemitization), but the precise connection between
the course of alteration and the decrease in magnetization is uncertain. The
effect of compositional change on the intrinsic properties (principally Ms) seems
unable to account for the 90% fall in remanence intensity. The effect of the
microstructural consequences of maghemitization on the spin structure within
the particles must therefore be invoked as the cause of the fall in remanence
intensity. Maghemitization results in a decrease in lattice parameter (Fig. 112)
and overall shrinkage of the crystal lattice. A heterogeneously maghemitized
titanomagnetite, therefore, acquires an outer oxidized mantle stretched over an
un oxidized core. The mechanical failure of the mantle results in the shrinkage
cracks observed in the larger ( > 5.um) titanomagnetite grains of submarine
6.6.1 Magnetic Minerals 449
a b
ttttttttt
t t t t t 1t t t t t t t
t t t 1 t 11t 1 t 1 t t 11
11111 t t t 1 t 1 t 11t
tttt1ttt111t1t1
11t11t1ttt1tt
t1tttttt11
Fig. 117a, b. Postulated spin structure in a model titanomagnetite grain which has undergone
partial maghemitization to produce a strained outer mantle. The incoherent spin structure (a)
may have a reduced energy compared to the coherent monodomain structure (b) especially in
grains which lie just below the monodomain/multidomain transition before the growth of the
strained mantle
basalts. Smaller grains, which include the most potent carriers of the paleo-
magnetic record, accommodate the shrinkage-induced strain without cracking.
The strained mantle of the grain now carries induced magnetic anisotropy -
strain anisotropy - and a homogeneously magnetized monodomain grain now
has increased magnetic energy. Other, incoherent, spin structures with sym-
metry in harmony with the mechanical state of the strained grain may now have
lower energy than the monodomain structure. Figure 117 shows a hypothesized
spin structure for a model, heterogeneously maghemitized, grain. Calculations
show that this structure will have lower energy than the coherent spin structure,
especially for large monodomain particles. The falling magnetic moment of the
progressively smaller coherently magnetized core provides a plausible explana-
tion for the fall in intensity of submarine basalts with increasing age and degree
of maghemitization.
References
Dunlop OJ (1990) Developments in rock magnetism. Rep Prog Phys 53: 707-792
Halgedahl S, Fuller M (1983) The dependence of magnetic domain structure upon magnetization
state with emphasis upon nucleation as a mechanism for pseudo-single-domain behavior.
J Geophys Res 88: 6505-6522
Moon TS, Merrill RT (1985) Nucleation theory and domain states in muItidomain magnetic
material. Phys Earth Planet Int 37: 214-222
O'Reilly W (1984) Rock and mineral magnetism. Blackie, Glasgow (Chapman & Hall/Methuen,
New York), 220 pp
450 Chapter 6. Properties of Minerals
The formation of rocks proceeds in the presence of the geomagnetic field (He)
that permeates through the Earth, ocean, and atmosphere and affects animate
and inanimate nature. In ferromagnetic minerals included in rocks, the natural
remanent magnetization (NRM) is formed under the action of He' these
minerals becoming the source of an anomalous geomagnetic field. The NRM is
carried commonly by Fe-Ti oxides such a magnetite (Fe 30 4 ) with a Curie
temperature Tc = 575°C and a spontaneous magnetization Ms = 92 Amz/kg
at room temperature, maghemite (y-Fe Z 0 3) which is unstable above 350 °C, with
an extrapolated Tc ~ 700°C and Ms = 85 A m Z/kg, minerals of the two solid
solution series: magnetite-ulvospinel (Fe 3 _ xTi x 0 4 with 0 ~ x:-:::; 1; titano-
magnetite series) and hematite-ilmenite (Fez _ y TiP3 with 0 :-:::; y :-:::; 1; hemo-
ilmenite series) whose ferrimagnetic properties are suppressed with increasing
content of titanium. Specific properties are found in anti ferromagnetic hema-
tite (IX-Fe 2 0 3) exhibiting weak ferromagnetism due to noncollinear or canted
spin arrangement in the antiferromagnetic sublattices, its Tc = 675°C, Ms ~
0.04 A m 2 /kg.
According to the basic hypothesis of paleomagnetism, the NRM of rocks
reflects the geomagnetic field polarity state at the time of the formation of a rock.
Therefore, in general, normally and reversely magnetized rocks are due to the
numerous geomagnetic field inversions which occurred during the geological
history.
Unmixing, oxidation, and ex solution complicate composition and structure
of the rock forming Fe-Ti oxides thereby changing their magnetic properties,
too. These processes take place in the ambient geomagnetic field and are called
magnetomineralogical processes. They initiate evolution of microstructures in
the Fe-Ti oxides which in turn affect the NRM formation and hence that of
anomalous geomagnetic fields. One of the possible consequences of magneto-
mineralogical processes is an anomalous magnetization of rocks which is
imprinted antiparallel with regard to He and is referred to as self-reversal of
NRM. The presence of rocks with self-reversed NRM changes the morphology
of geomagnetic anomalies and may provoke erroneous paleomagnetic inter-
pretations. In addition to the Fe-Ti oxides, Fe sulfides like greigite, smythite, or
pyrrhotite are potential candidates for self-reversing mineral properties.
It has been shown theoretically that magnetization self-reversal can occur
both in one-phase and two-phase (multi-phase) ferromagnets. The one-phase
self-reversal is realized only in ferromagnetic material with an anomalous
temperature dependence of spontaneous magnetization (N-type dependence).
When such a ferromagnetic mineral is cooled from T;:::.: T c' its Ms direction
6.6.2 Self-Reversal of Natural Remanent Magnetization 451
Heating Heating
Cooling
90,---------------------------------------.
~ 360·
.~ 270 ~ t
~~ 180-
~
90~--~------~--------~--~----~----~
o 100 165 100 11
100 200 300 400
Temperature (DC)
90
E:l 45
0
::J
QI
.E:l 0
.:::
.::
\J
-45
-90
Fig. 118. Intensity, inclination, and declination of NRM during thermal cycling in air and zero
magnetic field of an andesitic sample from the Nevado del Ruiz (Colombia) eruption in 1985
showing complete self-reversal. Heating and cooling cycles indicated
4.0
~
~
~
~
2.0
Fig. 119. Partial self-reversal of TRM in a Siberian
trapp sample. Continuous thermal demagnetization of
TRM during repeated (1-4) heating cycles. Applied
field H = 80Am- '
200 400 600
T(ee)
6.6.2 Self-Reversal of Natural Remanent Magnetization 453
400
200
60 40 20
Fe 2Ti04 (mole %)
tion, slight fluctuations of the composition appear at first. They are associated
with much less activation energy as compared to that of nucleation. The
sinusoidal waves of fluctuations simultaneously propagate through the whole
structure. With time the composition fluctuations are intensified in wavelength
and amplitude, until eventually the crests and nodes of the waves become two
separate phases. Spinodal decomposition is most likely to occur in solid
solutions with similar structures of end members, magnetite, and ulvospinel
being such members in the case of titanomagnetite exsolution. Coherent stresses
that appear during unmixing, due to the emergence of regions with slightly
different chemical composition and lattice parameters, limit the amplitude of the
composition fluctuations. In the composition-temperature diagram (Fig. 120)
the region of spinodal decomposition is to be found within the coherent spinodal
temperature range. The spinodal decomposition temperature is referred to as
the spinodal temperature Tsp"
Electron microscope studies have shown that the exsolution structures in
titanomagnetites are 3D lattices in regions (enriched or depleted in titanium) of
alternating directions [100]. The dimensions of these regions range from 10 to
1000 nm or more. There are structures of secondary finer exsolution in the
ulvospinel regions. At the early stages of unmixing, shorter periods of recurrence
and "magnetite" regions of cubic shape are observed, the latter becoming
stratified at the late coarsening stages and arranging themselves parallel to the
(100) planes.
Since spinodal decomposition proceeds very slowly, it cannot be completed
in quickly cooled geological bodies. In very slowly cooled bodies the process
goes practically to completion forming a ferromagnetic phase that is close to
magnetite and a non-ferromagnetic phase that is close to ulvospinel. In order to
promote the formation of magnetically interacting phases, the exsolved solution
should be partially homogenized. In the laboratory this homogenization is
facilitated by heating to 600 °C-700 0c. During thermomagnetization of par-
tially homogenized titanomagnetite in H ::;; 80 A m -1 a weak, probably magne-
tostatic interaction appears between the Ti poorer and Ti richer phases. The Ti
454 Chapter 6. Properties of Minerals
poorer phase with a higher T ep than T er of the Ti richer phase is the first to
become magnetized.
At T < T er the Ti richer phase is magnetized in the effective field H - Hp
which acts anti parallel to H under the condition that the field of the Ti poorer
phase is Hp > H. In titanomagnetites, Ms decreases with increasing Ti content.
Therefore during the spinodal decomposition of titanomagnetite a partial self-
reversal of TRM may be observed which in turn indicates the spinodal
decomposition. When heating to 600-700 °C is repeated many times, the self-
reversal properties disappear. This can be accounted for by the fact that the solid
solution becomes a one-phase solution as a result of homogenization. A similar
partial self-reversal was observed during spinodal decomposition of titanomag-
netites containing magnesium and chromium. The spinodal decomposition
affects the magnetic properties resulting in self-reversal and increasing stability
ofTRM due to separation of unmixing phases. Also there is an opposite effect of
ferrimagnetism of titanomagnetites on the spinodal decomposition of the latter.
This is associated with the fact that a decrease in free energy k·T sp during
ex solution is comparable to the energy of magnetic ordering k· Te. This effect is
revealed in the violation of the spinodal symmetry.
Complete and partial self-reversal of NRM has been observed in titano-
magnetites contained in continental and oceanic basalts and affected by low-
temperature oxidation. In fields H.::; 800 Am - 1, oxidized cation-deficient
titanomagnetite (titanomaghemite) with an oxidation degree z ranging from 0.52
to 0.66 (Te ~ 400°C) may acquire a CRM that is antiparallel to H due to
magnetic interaction with the primary titanomagnetite with Te around 180°C.
There may be either complete or partial self-reversal of NRM in consequence of
the ratio of the components: normal TRM and reversed CRM. When reaching a
high oxidation degree (z > 0.6), exsolution of titanomagnetite continues and
may also be accompanied by self-reversal. The transformation of titanomagne-
tite into hemoilmenite, which is found in oceanic basalts, may lead to a complete
self-reversal.
The most recent observations ofNRM self-reversal come from magnetomin-
eralogical studies of kimberlites and associated trapps of the Siberian platform
and andesitic to dacitic rocks of different provenance. In kimberlites and trapps
the NRM is carried by a variety of different minerals such as picroilmenite,
a member of the solid solution series FeTi0 3 -MgTi0 3 -Fe z0 3 with small
amounts of Cr Z 0 3 and Al z0 3 , magnetite, maghemite, titanomagnetite, chrom-
ium-bearing titanomagnetite and other ferrispinellides, as well as iron hydro-
xides (mainly goethite) and iron sulfides (pyrrhotite).
During thermal treatment in the laboratory, various transformations of the
ferromagnetic minerals contained in kimberlite and trapp samples were ob-
served: maghemite into hematite, titanomaghemite into magnetite with ilmenite
lamellae, pyrite into pyrrhotite, pyrrhotite into magnetite and partial homogen-
ization of unmixed members of the titanomagnetite series. The initial composi-
tion of the ferromagnetic minerals in kimberlites and trapps and their trans-
formation during and after rock formation can be determined by the analysis of
6.6.2 Self-Reversal of Natural Remanent Magnetization 455
References
Buddington AF, Lindsley DH (1964) Iron-titanium oxide minerals and synthetic equivalents.
J Petrol 5: 310-357
Haag M, Heller F, Carracedo JC, Soler V (1990) Remanent magnetization of andesitic and
dacitic pumice from the 1985 eruption of Nevado del Ruiz (Colombia) reversed due to self-
reversal. J Volcan Geothermal Res 41: 369-377
Haggerty SE (1975) The chemistry and genesis of opaque minerals in kimberlites. Phys Chern
Earth 9: 295-308
Heller F, Petersen N (1982) Self-reversal explanation for the Laschamp/Olby geomagnetic
field excursion. Phys Earth Planet Int 30: 358-372
Hoffman KA (1975) Cation diffusion processes and self-reversal of thermoremanent
magnetization in the ilmenite-hematite solid solution series. Geophys JR Astr Soc 41: 65-80
Kawai N (1956) Subsolidus phase relation in titanomagnetite and its significance to rock-
magnetism. Proc 20th Int Geol Congr 11 A: 103-120
Khisina NR (1987) Subsolidus transformations of solid solutions of rock-forming minerals.
Nauka, 207 pp
Lawson CA, Nord GL, Champion DE (1987) Fe-Ti oxide mineralogy and the origin of
normal and reverse remanent magnetization in dacitic pumice blocks from Mt. Shasta,
California. Phys Earth Planet Int 46: 270-288
6.6.3 Paleomagnetism, Magnetic Fields of the Ocean Floor, and Plate Tectonics 457
Pullaiah G, Irving E, Buchan KL, Dunlop OJ (1975) Magnetization changes caused by burial
and uplift. Earth Planet Sci Lett 28: 133-143
Readman PW, O'Reilly W (1971) Oxidation processes in titanomagnetites. Z Geophys 37:
329-338
Ryall PJC, Hall JM (1979) Laboratory alteration of titanomagnetites in submarine pillow
lavas. Can J Earth Sci 16: 496-504
Scherbakov YP (1988) The influence of magnetic transformations upon unmixing of titano
magnetites. Izv AN SSSR Fiz Zem 10: 50-53
Smith PPK (1980) Spinodal decomposition in a titanomagnetite. Am Mineral 65: 1038-1043
Trukhin VI, Zhil'ajeva VA, Zinchuk NN, Romanov NN (1989) Magnetism of kimberlites and
trapps. Moscow University Press, 165 pp
Uyeda S (1958) Thermo-remanent magnetism as a medium of palaeomagnetism, with special
reference to reverse thermo-remanent magnetism. Jpn J Geophys 2: 1-123
Paleomagnetism
Almost all rock types possess a natural remanent magnetization (NRM) carried
by natural ferrimagnetic minerals, the most important of which are magnetite,
titanomagnetite, hematite, and pyrrhotite. With the help of field tests and
laboratory cleaning procedures (Collinson 1983), the primary part of the NRM
can be isolated from secondary NRM overprints. The direction of the primary
NRM vector (described by its inclination or dip I and its declination D with
respect to present north) records the local geomagnetic field at the time and
place the rock formed (or was metamorphosed, in the case of high-grade
metamorphic rocks) in the geological past.
Early work in paleomagnetism investigating the geometry of the ancient
geomagnetic field showed that the field, when averaged over several tens of
thousands of years, approximated that of a geocentric dipole aligned with the
Earth's rotation axis. In this case, the geomagnetic and geographic poles
coincide and D = 0 everywhere on the Earth's surface. Field inclination I is
related to latitude A. by A. = tan - l(! tan I), allowing the paleolatitude of a site
to be calculated from the NRM inclination. Rotations of a geological unit, a
tectonic block, or even a continent are recorded by nonzero NRM declinations.
A common way of storing the NRM paleodirectional information embodied
in (D,I) is to report the computed paleomagnetic pole, which is the position, in
present geographic coordinates, of the ancient north pole or spin axis. Time
sequences of paleomagnetic poles, or simply paleopoles, form apparent polar
wander paths (APWPs), which record the drift history of rigid lithospheric
blocks relative to the spin axis. APWPs commence at the present geographic
north pole and radiate away from it along different paths. Figure 121 shows
458 Chapter 6. Properties of Minerals
simplified APWPs of the major continental blocks of the last 300 Ma, based on
the data compiled by Irving and Irving (1982).
By rotating continental blocks so as to bring the pre-180 Ma parts of their
APWPs into coincidence, one can deduce the relative positions of the different
blocks in the supercontinent Pangea, which existed until the opening of the
Atlantic Ocean. For times earlier than 300 Ma, the APWPs are more compli-
cated and are also different for subunits of the present continents, showing that
Pangea assembled from a different set of continental blocks than those we
see at present. Paleocontinental maps based on paleomagnetic data are given by
Smith et al. (1981), Irving (1981,1983), and Van der Voo (1988). The pre-300-Ma
reconstructions are tentative and uncertain.
Another important feature of the geomagnetic field is its frequent reversal of
polarity. The reversal process is brief (4-10 ka) compared to the duration of a
polarity epoch or time between major reversals ( ~ 1 Ma). The geometry of the
geomagnetic field during a reversal (switching of the dipole, growth and decay of
axial and equatorial multipoles) is still controversial (Hoffman 1988). The field
intensity during a reversal seems to decrease to 10-20% of its usual intensity;
such a reduction in geomagnetic shielding would allow an increased penetration
of solar radiation to the Earth's surface, although atmospheric shielding is more
important.
The geomagnetic polarity time scale is known with high precision for the last
5 Ma. The principal polarity epochs (or chrons), named after prominent geo-
magnetists, are interrupted by short reversal events (subchrons, named after type
localities). The most recent major reversal, about 0.7 Ma ago, marks the
transition from the Matuyama reversed chron to the (present) Brunhes normal
chrvn (Fig. 122). There are fragmentary indications of several short reversal
events and excursions (incomplete reversals) during the Brunhes. Evidence of
6.6.3 Paleomagnetism, Magnetic Fields of the Ocean Floor, and Plate Tectonics 459
Age [106 0J Events Fig. 122. Geomagnetic polarity time scale for the last 5 Ma.
0_ (After Hailwood, 1989)
-laschomp 7
0.70
0.87 Jaramillo
0.92
1.58 Gilsa
1.71
Olduvei
1.86
2.02 Reunion
2.17 T
2.41
2.84 Keena
2.92
2.99 Mammoth
3.09
3.l2
3.72
Cochiti
3.82
3.97
Nunivak
4.14
U3
Sidufjall
4.45
4.60
lhvera
4.81
5.30
460 Chapter 6. Properties of Minerals
During the 1950s and early 1960s, oceanographic research expanded dramat-
ically, in part at least because of improved instruments for geophysical remote
sensing and for positioning of research ships and aircraft. Measurement of the
geomagnetic field over the oceans with high precision and spatial resolution by
shipboard and airborne magnetometers revealed strikingly linear magnetic
anomaly patterns, particularly near mid-ocean ridges. The interpretation of
these magnetic lineations or stripes is based on the model of seafloor spreading
(Vine and Matthews 1963). Rigid seafloor plates, created at the ridge when
intrusive and extrusive magmas cool and acquire NRM in the geomagnetic field
direction, subsequently spread laterally at constant velocity (the plate velocity:
see following section), symmetrically about the ridge. Reversals of NRM due to
reversals of the field result in bands of alternately magnetized seafloor par-
alleling the ridge. The fields created by these normal and reverse bands produce
corresponding anomalies in the total field, which are linea ted parallel to the
ridge. Vine and Matthews' interpretation, which ushered in the era of plate
tectonics and was a milestone in the history of Earth Sciences, was made
possible by the developing knowledge of geomagnetic reversals, based at that
time on Kj Ar-dated lava sequences on land.
Figure 123 shows a profile oflinear magnetic anomalies across the Southeast
Indian Ridge between Australia and Antarctica, combining the observed profile
(the anomaly in the total intensity of the local geomagnetic field measured at the
sea surface), a model anomaly profile assuming a constant spreading rate of
68 mm/a, the block model for magnetization of the underlying seafloor (black:
normal polarity; white: reversed polarity), the polarity time scale (cf. Fig. 122),
and the age of seafloor and distance from the ridge. The striking coincidence
between the mostly land-based polarity time scale for this age interval (Fig. 122)
and the time scale developed from marine magnetic anomalies and their
6.6.3 Paleomagnetism, Magnetic Fields of the Ocean Floor, and Plate Tectonics 461
OBSERVED
PROFILE
SYNTHETIC
PROFILE
(assuming
68 mm/year
spreading)
MARINE MAGNETIC
• ANOMAL Y NUMBER
llT.......h_-.-.rn..-~... SEAFLOOR
.. MAGNETIC POLARITY
• REVERSAL TIME SCALE
5.4 5.0 3.0 2.0 1.0 1.0 2.0 3.0 4.0 5.05.4 AGE (Me)
I I I I II I I
I
100 o 100 DISTANCE (Km)
Fig. 123. Seafloor spreading model for a magnetic anomaly profile from the southeastern
Indian Ocean. (After Gordon and Acton 1989)
Plate Tectonics
•
Fig. 124. Mercator projection of major lithospheric plates. EUR Eurasian; IND Indian; PAC
Pacific; NAM North American; COC Cocos; NAZ Nazca; CAR Caribbean; SAM South
American; AFR African; ARA Arabian; ANT Antarctic. Open circles, triangles, diamonds
represent earthquake epicentres with increasing focal depths. Arrows with numbers are plate
velocities in em/a. (After Jacoby 1985, adapted and modified from Minster and Jordan 1978)
464 Chapter 6. Properties of Minerals
References
St.E. HAGGERTY
The magnetic signatures of igneous rocks are resident in mineral solid solutions
that are defined by the end members magnetite-ulvQspinel (Fe 3 0 4 -Fe 2 Ti0 4 )
and hematite-ilmenite (aFe 2 0 3 -FeTi0 3 ). Compositional variations along these
solid solution joins, in Fe 2 +, Fe 3 + and Ti, control the physical response patterns
which emerge in magnetic property measurements. Temperature, oxygen fugac-
ity, and bulk rock chemistry are the intrinsic parameters which define modal
abundances, the compositions of coequilibrated magnetic oxides, subsolidus
reequilibration paths, and ultimately the magnetic character of the rock.
The magnetic mineralogy of igneous rocks may be broadly defined within
three chemical systems: (1) the oxide system FeO-Fe 2 0 3 - Ti0 2 (Fig. 125); (2) the
sulfide system Fe-Ni-S; and (3) the metal alloy system Fe-Ni-Co. Solid
solutions are present among the mineral end members in each system and
6.6.4 Aeromagnetic Exploration Mineralogy 465
. r ' •constont
;:;...-- I
ox;dot;~ ~ :;;;...--- r:1I~-'----
I \
~ 600 I \
t.:5 roc \ ()
400 I ::r
\ ~
I '0
200 I \
\ "...,
I I I
/--. 40 60 ."
'"...,
600 o
"- -g
/ '" \ ::l
400 I \ ,,''"
I \ o
200 .....,
/ I ~
20 40 60 80 Mt
s·
ro
...,
, \ ), I l ' I to I I( I( I (
I' ( f ( ~-('('
( • 'I'«((~
~ft ~
Usp I Fe304 en
FeO
6.6.4 Aeromagnetic Exploration Mineralogy 467
J, = saturation magnetization emu/g. Tc and Tn are Curie temperatures and Neel temper-
atures respectively.
cooling induces mineral ex solution (Fig. 125), and this results in increases in
saturation magnetization, Curie temperature and magnetic stability. Partial
high temperature ( '" 600 0c) oxidation of ulvospinel-rich solid solutions, to
magnetite-rich solid solutions and ilmenite, yields a similar increase in magnetic
properties (Fig. 125). Advanced oxidation, on the other hand, is a magnetically
destructive mineral transformation process which activates the inversion of
ferrimagnetic minerals into minerals having antiferromagnetic and paramagne-
tic properties (Fig. 126). Exsolution is characteristic of all intrusive suites; partial
oxidation is prevalent in mafic suites (extrusive and intrusive) and less common
in felsic suites (extrusive and intrusive). Although advanced oxidation is typical
of subaerial basalts, high deuteric temperatures ( > 600 0c) are attained and
olivine and pyroxenes are oxidized to form single domain sized particles of
magnetite. Silicate decomposition is prevalent in medium to high grade meta-
morphic rocks and aeromagnetic signatures may be due entirely to secondary
rather than primary magnetite.
High magnetic susceptibilities and large concentrations of iron oxides are
present in Kiruna-type ore deposits, banded iron formations, and ore deposits
..
Fig. 125. Phase relationships in the system FeO-Fe 20 3- Ti0 2. Tie lines between ulvospinel
(Fe 2Ti0 4 )-magnetite (Fe 30 4 ), ilmenite (FeTi0 3)-hematite (IlFe 20 3), and ferropseudobrookite
(FeTi205)-pseudobrookite (Fe 2Ti0 5) are solid solution joins. The solvi, which define regions
of immiscibility for the spinel and ilmenite joins, are schematically shown as a function of
temperature and composition. The photomicrograph to the left illustrates the fine scale
exsolution of magnetite from ulvospinel, and oxidation to ilmenite lamellae; the photo-
micrograph to the right shows hematite (white) exsolved from ilmenite (gray), and ilmenite from
hematite; both assemblages are typical of plutonic rocks and some high grade metamorphic
assemblages. The contours are Curie temperatures. The shaded region represents the field of
titanomaghemite ('l'Fe 20 3). A typical oxidation trend is illustrated by the dashed line from
Fe 2Ti0 4 to Fe 2Ti0 5; the phases produced by oxidation are a function of temperature and
examples of these assemblages are shown in Fig. 126
.::.:...,~
~>' ~<,:~.~.',::(-..::,;~ .~~,':.~
'i~t~~~ ~
" TiOZ R4 0"-
00
f~'r_" ;t:'?:" ':i-~~,~.,~,
' ..
;~"""'" ... ..... -.,
'. '.. ' ............"'. ~ ..... ~.a1
,- ,
,.,'.:"'..:"".....:',' ,/
- '.~~"":~ , ~~-:+~ R5
R3
\
. ".",;,.,.:
\:.
.;..-, '. ......
.. ~
~
, '~~,' , .~c ,t
(J
:T
~
'0
~
?'
:3'~~;'~: I MOLE PERCENT "0
. -~ o
C2 -:-::-.: 0"', ...... - ~
C4 ::l
;;;'
en
o
....,
Fig. 126. This composite illustrates the complexities in oxide minerals and oxide mineral textures as a function of redox state, ~
Two series are illustrated: Cl to C7 represents the progressive decomposition in magnetite (cubic) series minerals; and Rl to R7 S'
<P
the corresponding trend in ilmenite solid solutions, The sequence of assemblages that form on oxidation may be traced along an ....
~
oxidation-reduction tie line (e.g" Fig. 125) of constant Fe: Ti ratio from the FeO- TiO z sideline to the Fe Z0 3 - TiO z sideline. For c;>
a complete discussion see Haggerty (1976a, b, 1991)
6.6.4 Aeromagnetic Exploration Mineralogy 469
associated with mafic and ultramafic rocks; these are all readily detected by
aeromagnetic surveys. Important advances, however, have been made in the
magnetic recognition of felsic rocks, ore mineralization, and redox states.
Granites, for example, are classified as I (igneous), S (meta-sedimentary), and A
(anorogenic) types, but are also distinguished as magnetite-series and ilmenite-
series granites. I-type granites are typically in the magnetite-series, are more
highly oxidized than S-type granites, and are hosts to Mo, scheelite, and Au
deposits. Ilmenite-series granites are more reduced, are typically graphite-
bearing, but are not necessarily of meta-sedimentary (S-type) origin; ilmenite-
series granites may host Sn and wolframite deposits. From the presence of
magnetite, the magmatic I-type granites are more responsive to aeromagnetic
detection. This response, however, as is the case for all magnetic surveys, is
directly related to magnetic contrasts between mineralized targets and barren
country rocks.
Of equal significance in the correlation of magnetic signatures and ore
deposits are those associations in which magnetite is closely linked to a central
ore-depositional process. The most prominent of these ancillary associations
are: banded iron formations with some stratiform Pb-Zn deposits; Kuroko-type
ores of volcanoclastic origin and the association of ferruginous cherts; laminated
jaspilites in some Au districts; aureole magnetite in the cores of porphyry eu
deposits, and in the outermost margins of skarn deposits. Unequivocal inter-
pretation of these associations is rarely possible but district-wide magnetic
signatures in known ore deposits have been shown to be useful.
There are at present no simple (or even complex) algorithms relating
igneous, metamorphic, and sedimentary rocks to specific types of mineral-
ization, redox state, magnetic mineralogy, and aeromagnetic response. Advan-
ces have been, and will continue to be made, but the qualitative and comparative
approach, regretably, remains in vogue.
References
P.A. CHEREMNYKH
is very limited. HGMS of Jones, Sala Magnetics, Eries Magnetics are well
known.
The second type is a volume-gradient magnetic separator (VGMS). The m.s.
in this separator is based on field distributions which produce high-gradient and
large magnetic forces over the whole working zone. It may be explained as
follows. If the conductor current is I, one can thus express the values on
the conductor surface: B = I/(2nr), VB = I/(2nr2), and Fm = I/(4n 2r 3), where r
is the conductor coil radius. These coils are placed (with period T) on
the plane or the cylinder surface of the working zones. The currents of
neighboring coils are directed in the opposite direction (line multipoles). In this
open system F m decreases with distance z from coils F mexp( - 4nz/T). The
VGMS can use either electromagnets or permanent magnets (BaFeO, SrFeO,
Fe-Ni-AI-Co, Nb-Fe-Br, and others).
Superconductors most effectively generate the VGMS magnetic field: B ::;:; 5
- 6T in the working zone volume 0.5 m 3 and fm ::;:; 108 N/m 3 without a matrix.
The particles are deflected from the main stream and trapped by the separator.
The deflection depends on B2. The separation in VGMS is close to isodynamic
m.s., therefore this device improves ore fractionation with high selectivity.
The ideal result of any m.s. is the fractionation of ore into all components. As
most components are small, there is the problem of colloidal medium separa-
tion. This process obeys the law of statistic fluctuation.
All theoretical models of m.s. based on competition between forces described
this process with fair accuracy but with some uncertainties in some parameters.
A more precise solution can be obtained with methods from nonlinear dynamic
systems. Magnetic separation is the most promising technique of ore concentra-
tion and purification. M.s. can coordinate current and future interests of
mankind in the areas of minerals, energy consumption, and environment
protection.
References
Optical Theory
For tetragonal and hexagonal minerals which have two unit cell dimensions
(a and c) and a high degree of symmetry about the c crystal axis, two indices of
refraction (nro and n.) are required to define the indicatrix whose form is an
ellipsoid of revolution whose axis is the c crystal axis. The radius along the c axis
is n. and the radius at right angles to the c axis is nro' Light propagating in a
random direction is doubly refracted. The two rays vibrate parallel to and have
indices of refraction equal in magnitude to the lengths of the semiaxes of the
elliptical section through the indicatrix which is parallel to the wave front of
the light. In hexagonal and tetragonal minerals there is one direction, along the
c crystal axis, in which the light is not doubly refracted. The section through the
indicatrix parallel to the wave front is a circle with radius nro' This direction
along the c axis is called an optic axis, and because hexagonal and tetragonal
minerals have only one optic axis, they are optically uniaxial. If n. > n ro , the
mineral is optically positive, and if n. < n ro , negative. The birefringence
(n. - nro) is a useful diagnostic value.
Orthorhombic, monoclinic, and triclinic minerals require three unit cell
dimensions to describe their crystallography and require three indices of
refraction (n" < np < ny) to describe their optical properties. The optical indi-
catrix is a triaxial ellipsoid defined by plotting the three principal indices of
refraction (n", np, ny) along orthogonal X, Y, and Z axes, respectively. The
geometry of a triaxial ellipsoid requires that there are two circular sections
which intersect in the Y axis. Directions perpendicular to the two circular
sections are the two optic axes along which light is not doubly refracted; these
minerals are optically biaxial. The size of the 2V or optic angle between the optic
axes is a useful diagnostic property as is the birefringence (ny - nIX)' If the X
indicatrix axis bisects the acute angle between the optic axes, the mineral is
optically negative, and if Z is the bisectrix, positive. As with the uniaxial case,
light entering a biaxial mineral in a random direction is doubly refracted and the
indices of refractions and vibration directions of the two rays (usually termed r:t.'
and y') are found as described above.
The orientation of the biaxial indicatrix within a mineral is constrained by
the mineral symmetry. For orthorhombic minerals, the indicatrix axes coincide
with crystal axes. For monoclinic minerals, one indicatrix axis coincides with the
b crystal axis. For triclinic minerals, indicatrix axes and crystal axes do not
coincide except by chance.
For all three optical classes (isotropic, uniaxial, and biaxial) dispersion, i.e.,
variation of index of refraction and hence dimensions and/or orientation of the
indicatrix as a function of wavelength, may also be a useful diagnostic property.
Methods
other optical elements are placed above the sample to analyze the light after it
passes through the sample. The upper polarizing filter is typically oriented so its
vibration direction is at right angles to the lower polarizer. The microscope may
be configured either for orthoscopic or conoscopic illumination.
With orthoscopic illumination, weakly converging light is used, allowing the
mineral sample to be examined directly with the upper polarizing filter either in
(crossed polars) or out (plane light) of the optical path. Isotropic minerals do not
influence the polarization of the incident light; in plane light the mineral color
will be observed, with crossed polars the mineral will appear black because the
plane polarized light passing through the mineral is entirely absorbed by the
upper polarizing filter. Light entering anisotropic minerals in most orientations
is doubly refracted. In plane light colored minerals will typically be pleochroic,
they change color as the microscope stage is rotated and the two vibration
directions are brought parallel to the vibration direction of the lower polarizer.
Between crossed polars anisotropic minerals display interference colors because
the two rays have different velocities; when they are resolved into the vibration
direction of the upper polarizing filter some wavelengths of light constructively
interfere and others destructively interfere. The complement of wavelengths that
pass is perceived as an interference color, and the mineral appears illuminated.
As the stage is rotated, the mineral will go dark, or extinct, every 90 degrees as
the mineral vibration directions are brought into coincidence with the vibration
directions of the lower and upper polarizing filters. Orientation of extinction
positions relative to cleavages and crystal outlines provides information about
the indicatrix orientation in the mineral.
Conoscopic illumination uses strongly converging light to produce optical
phenomena called interference figures which are observed at the upper focal
plane of the objective lens. The interference figure allows determination of
optical class, optic sign, dispersion characteristics, 2V angle, and indicatrix
orientation. Consult an optical mineralogy text for details of procedures.
The measurement of refractive indices is most commonly accomplished by
comparing the index of refraction of an unknown mineral with that of a known
immersion liquid. With the spindle stage method, a grain of the unknown is
mounted on a fine wire that can be rotated about a horizontal axis while holding
the unknown in a cell of immersion liquid. This allows each of the indicatrix axes
in the mineral to be placed horizontal and parallel to the lower polarizing filter
vibration direction so that the index of refraction associated with that axis can
be compared with that of the immersion oil. With the grain mount method,
loose grains of the unknown are placed in an immersion liquid on a glass
microscope slide. Grains which by chance happen to be oriented with one of the
indicatrix axes horizontal are selected based on the properties displayed in both
orthoscopic and conoscopic illumination, and the mineral index of refraction for
light vibrating parallel to that axis is then compared with that of the immersion
oil. A universal stage, which allows the microscope slide to be rotated in a wide
range of orientations, may be employed with grain mounts to allow selected
6.7.1 General Review of Optical Mineralogy 475
grains to be precisely oriented, but it is much more cumbersome than the spindle
stage. With routine work accuracy of ± 0.001 index of refraction units is
attainable. With thin sections, which are typically 0.03 mm-thick slices of
rock/mineral permanently mounted on glass microscope slides and used to
study rock mineralogy, texture, and structure, only rough estimates of index of
refraction are possible.
Other optical properties (optical class, optical sign, 2V angle, dispersion
properties, mineral color, birefringence) may also be determined with grain
mounts and the spindle stage and are the primary diagnostic properties
observed with thin sections. A universal stage may be employed to rotate a thin
section to place a selected grain in a desired orientation.
Mineral Identification
Composition Determination
It has long been recognized that optical properties of minerals vary as a function
of composition. In general, compositions with higher average electron density
have higher indices of refraction, so substitution of a higher Z element typically
results in an increase in index of refraction as, for example, the substitution of
Fe or Mn for Mg. In many cases, reasonable estimates of average index of
refraction can be obtained from knowledge of mineral composition and struc-
ture. Similarly, diagrams and equations have been developed for many minerals
and mineral groups which allow composition to be estimated based on optical
properties. While optical methods are quick and inexpensive, they have signifi-
cant limitations and are most reliable in binary systems, i.e., minerals which have
substitution of two elements in a single structural site (e.g., Fe and Mg in olivine
or orthopyroxene). In minerals which have substitutions in several structural
sites, or numerous elements in a single site, it is generally found that there are
too few optical variables to uniquely identify the composition. In an attempt to
overcome this limitation, data from X-ray diffraction has been combined with
the optical data with some success. Despite the limitations, optical estimates of
composition are quite useful and can be valuable guides in planning more
sophisticated chemical analyses.
476 Chapter 6. Properties of Minerals
Other Applications
References
Bloss FD (1981) The spindle stage: principles and practice: Cambridge Univ Press, Cambridge,
340 pp
Bulka GR, Vinokurov VM, Nizamutdinov NM, Hasanova NH (1980) Dissymetrisation of
crystals: theory and experiment. Physics and chemistry of minerals, vol 6, pp 283-293
Deer WA, Howie RA, Zussman J (1962-1986) Rock-forming minerals, 8 vols, J Wiley & Sons,
New York
Fleischer M, Wilcox RE, Matzko JJ (1984) Microscopic determination of the nonopaque
minerals. US Geol Surv Bull 1627: 453
Hauser J, Wenk NR (1976) Optical properties of composite crystals. Z Kristallogr 143:
188-219
Jaffe HW (1988) Crystal chemistry and refractivity. Cambridge Univ Press, 335 pp
MacKenzie WS, Guildord C (1980) Atlas of rock-forming minerals in thin section. John Wiley
& Sons, New York, 98 pp
Nesse WD (1991) Introduction to optical mineralogy, 2nd edn. Oxford Univ Press, New York,
335 pp
Phillips WR, Griffin DT (1981) Optical mineralogy, the nonopaque minerals. WH Freeman
and Co, San Francisco, 677 pp
Punin YuO (1989) Anomal optics of layer heterogeneous crystals. Zhapisky Vres Mineral Ob
1I8: 76-90
Su SC, Bloss FD, Ribbe PH, Stewart DB (1984) Optic axial angle, a precise measure of AI, Si
ordering in T 1 tetrahedral sites of K-rich alkali feldspars. Am Mineral 69: 440-448
Troger WE (1982) Optische Bestimmung der gesteinbildenden Minerale, Teill, Bestimmung-
stabellen (5th ed). Schweizerbart'sche Veriagsbuchhandlung, Stuttgart, 188 pp (English
translation of 4th edn available)
6.7.2 Theoretical Interpretation of Refraction 477
1. ARNDT
The starting point in the theory of refraction of light in dielectric materials is the
equation of electrostatics
eE = E + 4nP, (1)
where e is the dielectric constant and E and P are the applied electric field and
the polarization, respectively. These macroscopic quantities are related with
microscopic atomic parameters. The polarization is interpreted as the total
dipole moment per unit volume, given by the number N j of oscillators of type i
with induced dipole moment f1.i and polarizability ai per unit volume, i.e.,
(2)
~oc is the local electric field that is effective in polarizing each individual atom. It
includes in general a contribution from the polarization due to mutual inter-
actions between the induced dipoles, i.e.
E 10c = E + bP, (3)
1
Gladstone-Dale (n - 1)- = KG 2.4 2.0 1.7
P
1
Lichtenecker (log n)- = KL 5.2 4.6 4.1
P
Edwards (~)~-
n p
- KED 8.6 8.0 7.6
sequently annealed Si0 2 -glass, different refractive index values are obtained for
the same density value, depending on the initial density of the densified glass.
This indicates that the refractive index may even be not a single-valued function
of the density. Moreover, in contrast to all other crystalline materials, it is
observed for crystalline MgO and diamond that the refractive index decreases
on elastic compression and increases on thermal expansion. Similar behavior
has been found for silica glass and other glasses.
These examples clearly indicate that the Lorentz-Lorenz and Newton-Drude
formulae are based on inappropriate assumptions and that both changes in the
polarizabilities and overlap of the charge distributions of the atoms must be
accounted for. However, both effects cannot be separated from each other and
no unambiguous conclusions can be drawn about the extent of the overlap field
and the constancy or alteration of the atomic polarizabilities. Therefore, in
analyzing an experimentally determined n-p relationship, one must assume that
one of the two factors remains constant during the density change. Therefore,
two different methods of analysis have been developed. These will be outlined in
the following.
1.60
1.58
1.56
x
Q)
"0
c 1.54
Q)
->
c.l
CO
1.52
I·'"·"~"
....
'-
Q) 1.50
;' Coesite
a:
Keatite / ~uartz.
SiO glass,' Crlstoballte
1.48 ', ... /:
: Porosils
1.46
L
'/ 5 If [g/c",3j
1.44
2.2 2.4 2.6 2.8 3.0
Density [g/cm 3 ]
Fig. 127. Plots of data of refractive index versus density of the SiOz polymorphs and the
structurally altered SiOz glass and quartz.
Large diagram: Upper and lower solid lines calculated with the Lorentz-Lorenz and Newton-
Drude formulae, respectively; middle solid line calculated with the general refractivity formula
with b ,= 1.3.
For uniaxial and biaxial mineral the refractive index is represented by arithmetic mean, i.e., by
(2nD + l1e)/3 and (n. + np + n y)/3, respectively . • SiOz polymorphs (L: lechatelierite; T: low-
tridymite; CR: low-crystobalite; K: keatite; Q: low-quartz; C: coesite; + SiOz glass, densified
by static pressure; • SiOz glass, densified by dynamic pressures; 0 SiOz glass, densified by
neutron irradiation; ... quartz, neutron irradiated; • quartz, shock-loaded. (Large diagram
from Arndt and Hummel 1988; inset from Marler 1988)
solids, Mueller assumed that the Lorentz-Lorenz theory is valid but, in addition,
he assumed that the molar polarizability changes linearly with strain in isother-
mal elastic compression under hydrostatic pressures. Mueller's reasoning was
later extended to the Newton-Drude formula. Accordingly, the experimentally
observed change in refractive index with strain is the result of the change which
arises from the increase in the number of oscillators per unit volume due to the
increase in density and in addition of a change in the polarizabilities of the
atoms due to the decrease in the interatomic distances. The change in molar
polarizability due to strain S = dV/V = - dp/p is given by
I'/. = I'/.o(l + LS), (8)
where 1'/.0 and I'/. are the molar polarizabilities of the undeformed and deformed
crystal, respectively and L is the macroscopic strain polarizability parameter
6.7.2 Theoretical Interpretation of Refraction 481
defined by Mueller by
L = -- (d(J./(J./dp/p) = (d(J./(J./dVIV). (9)
The total change in refractive index with density, i.e.,
dn/dp = (on/op)~ + (on/o(J.)pd(J./dp (10)
is given according to Mueller by
dn/dp = (on/opla(1 - L). (11)
If polarizability does not change with changing density, then
dn/dp = (on/op)~ and L= 0 (12)
The theoretical value p(on/op)~ can be calculated from the partial derivatives
of the Lorentz-Lorenz or Newton-Drude formula, which are given under the
assumption that the polarizability is constant and independent of strain by
p(on/op)~ = (n 2 - 1)(n 2 + 2)/6n (13)
and
p(on/op)~ = (n 2 - 1)/2n. (14)
The proportional change in refractive index with density, p(dn/dp), can be
obtained from the slope of the curve of the experimentally observed change in
refractive index An versus the volume strain, since
p(dn/dp) =- An/(AV/V o). (15)
Values of p(dn/dp) can also be obtained from experimentally determined
elasto-optic coefficients Pij' For amorphous materials such as glasses as well as
crystals of the cubic classes with tetrads as the cube axes, i.e., the classes m3m,
43m and 432, the change in refractive index produced by a hydrostatic pressure
is given by
(16)
In Table 36 are given data of experimental p(dn/dp), of p(on/op)rz calculated
from the Lorentz-Lorenz and Newton-Drude relations and the resulting values
of the macroscopic strain polarizability parameter LLL and L D, respectively. As
is seen, the experimental values of p(dn/dp) are in general smaller than the values
calculated from the Lorentz-Lorenz formula and the Newton-Drude formula.
Mueller has related macroscopic and microscopic strain polarizability para-
meters by assuming that for a small change AV of the atomic volume the molar
polarizabilities of the atoms change also linearly with strain S = dVIV =
- dp/p, i.e.,
(17)
where (J. and (J.i are the molar polarizabilities of atoms of type i in the strained
.j:>.
Table 36. Analysis of changes in refractive index and polarizability for some cubic crystals and glasses 00
tv
Diamond 2.417 3.51 - 0.28 2.62 1.11 1.00 1.28 1.0 0.31 0.6
MgO 1.736 3.58 - 0.40 0.97 1.41 0.58 1.68 1.6 3.9 1.0
NaCI 1.544 2.16 0.24 0.66 0.58 0.45 0.38 - 3.8 12.0 - 0.7
LiF 1.392 2.60 0.1 0.44 1.00 0.34 1.00 -1.3 10.2 - 3.9
KBr 1.559 2.75 0.35 0.68 0.48 0.46 0.24 - 3.6 12.0 0.9
Si0 2 -glass 1.458 2.202 0.32 0.53 0.40 0.39 0.17 0.92 0.15 2.6
B2 0 3 -glass 1.447 1.833 0.41 0.51 0.24 0.38 - 0.08 -1.3 4.56
All data, except those for B2 0 3 -glass, from Waxler and Weir (1965).
Data for B2 0 3 -glass from K. Vedam and W.e. Schneider (1972).
(")
;:,-
~
'0
;;
....
'"d
'"...,
o
~
;::l.
en
,,'
o
-,
~
5'
n
;;l
::;;
6.7.2 Theoretical Interpretation of Refraction 483
and unstrained crystal, respectively, and Ii are their strain polarizability para-
meters.
If all atomic volumes change by an amount proportional to the total volume
change, this change is given by Eq. (11) where
(18)
where
r = - (l/p)(dp/dT) = (l/V)(dV/dT) and L = (v/rx)(arx/avh. (22)
r is the coefficient of thermal volume expansion and L is the macroscopic strain
polarizability parameter.
For the interpretation of the thermal behavior of the refractive index of
different materials one has to consider therefore the relative magnitudes of L, r,
and r. The first term in Eq. (21) represents the pure density contribution. It is
always negative. The product Lr is in general positive and r can be positive
or negative. It must be pointed out that dn/dT itself is also a function of
temperature.
Values of experimentally observed changes of the refractive index with
temperature and of the temperature-polarizability coefficient r are also given in
Table 36. As is seen, dn/dT is negative for KBr, NaCl, LiF and B2 0 3 -glass and is
positive for MgO, diamond, and silica glass. These results may be explained in
that the volume expansion leads to a decrease in the number of oscillators per
unit volume resulting in a decrease in the refractive index and, on the other
hand, it leads to an increase of the polarizabilities, resulting in an increase in
refractive index with rising temperature. The net result then depends on the
predominance of either of these effects. For example, in silica glass the thermal
expansion and thus the increase in specific volume with increasing temperature
is extraordinarily small and therefore the increase in polarizability dominates,
resulting in the observed increase in refractive index with temperature. In
contrast, the refractive index of B2 0 3 -glass decreases appreciably with rising
temperature due to its rather large thermal expansion resulting in a strong
increase in specific volume which dominates over the increase in polarizability.
\
C
\ e
:c
N
N
6 \ N e
'-
·E'" 102xt.n .9
0'"
(Linear photo-
"-
0
N
elasticity theory) - "c:
Of)
6
-=U'"
00
0
6
0 4 5 6
Shock pressure (GPa)
References
Anderson OL, Schreiber E (1965) The relation between refractive index and density of
minerals related to the Earth's mantle. J Geophys Res 70: 1463-1471
Arndt J, Hummel W (1988) The general refractivity formula applied to densified silicate
glasses. Phys Chern Mineral 15: 363-369
Ramaseshan S, Vedam K, Krishnan RS (1958) Chap V in Progress in crystal physics Vol I:
Thermal elastic and optical properties, Krsihnan RS (ed) New York, Interscience, p 139
Marler B (1988) On the relationship between refractive index and density for SiO z-
polymorphs. Phys Chern Mineral 16: 286-290
Mueller H (1935) Theory of the photoelastic effect of cubic crystals. Phys Rev 47: 947-957
Setchell RE (1979) Index of refraction of shock-compressed fused silica and sapphire. J Appl
Phys 50: 8166-8192
Vedam K, Schneider WC (1972) Variation of the refractive index of boric oxide glass with
hydrostatic pressure to 7 kbar J Appl Phys 43: 3623-3627
Waxler RM, Weir CE (1965) Effect of hydrostatic pressure on the refractive indices of some
solids. J Res Natl Bur Standards 69A: 325-333
Some have benefited from data obtained from 0-20 eV, e.g., galena, clausthalite,
altaite, molybenite, the Ag-Au alloys, sulfotellurides of Bi, etc., but for most,
measured data are available for a very much more restricted energy or wave-
length range. Many texts provide summary interpretations (with copious re-
ferences) for a wide range of metal sulfides and oxides; here we will restrict
ourselves to a single example, that of the much discussed group of semi-
conducting lead minerals: galena (S), clausthalite (Se), and altaite (Te).
In the reflectance spectra (Fig. 129) of these minerals, peaks E 1 , E z and
E3 have been interpreted as corresponding to electronic transitions from the
p-valence band of the sulfur (Se,Te) nonbonding molecular orbitals into the
p-conduction band of lead, and E 4 , and Es and E6 from lead 6s/sulfur 3p
bonding, and sulfur 3s non bonding orbitals. Such interpretations have a degree
of uncertainty even where, as in this instance, R spectra, measured and extrapol-
ated to 25 eV, permit the application of the Kramers-Kronig relations, and are
supported by ESCA spectra. These uncertainties are related primarily to the
large spin-orbit-coupling of Pb, but also to the possibility that a single peak may
disguise the presence of two or more transitions of similar energy, and that some
transitions will belong to different points within the Brillouin zone. Neverthe-
less, there is a good correlation between the transition energies, cell dimensions,
. p - Te - p - Pb s - Pb -p - Pb
Ii
L X r r
Inn
N.%(PbS)
60
60
Pble
o
20
PbSe
PbS
o , • s fj
Fig. 129. Reflectance spectra of PbS, PbSe, and PbTe, and their interpretation. (Marfunin
1979)
6.7.3 Reflectance Spectra: Their Interpretation Using Band Theory 489
and interatomic distances for these minerals. At the absorption edge (Fig. 130),
at the top of the valence and bottom of the conduction bands, the reflectance
increases dramatically. For this reason, and because, in the self-conduction
band, the reflectance is independent of admixture concentration, this region of
the spectrum is characteristic for a given species. In galena, the onset of the
absorption edge is in the far infrared at 0.37 eV (3351 nm). In general, the
position of the absorption edge determines, through its effect on the dispersion
of the reflectance, the color of the mineral: where it is in the IR, the mineral
appears white or gray, and where in the UV, the mineral is yellow, pink, or red.
Some workers describe such curves as normal and anomalous, respectively.
Although less significant than the absorption edge in determining the physical
cause of color, high energy electronic transitions, predominantly between the 3p
non bonding band and the conduction band, are marked in the spectrum of
galena at 350 nm and 670 nm. Of course, reflectance spectra in the visible region
for most ore minerals are monotonous, and without peaks, e.g., as in the shaded
region of Fig. 129, and specifically for galena in Fig. 131. Reflectance spectra
measured in the visible region are of limited use in the interpretation of
electronic structure; however, they are characteristic in themselves, and, from
data obtained by microscope-spectrophotometry, form the basis of many ore
mineral identification schemes.
The examples selected to illustrate the interpretation of electronic structure
from band theory were of isotropic minerals. In some anisotropic minerals, and
particularly in those of lower symmetry, the reflection spectra for the principal
vibration directions cross (as do those of the refractive indices and absorption
coefficients, though not usually at the same wavelength). The spectral position of
this change in optical sign is distinctive and even diagnostic for a given species:
within the visible region, the ratio R ~ 1: Eg (Eg = the width of the energy gap)
has been established for more than 70 minerals.
Recently, automated, computer-controlled, microscope-spectrophotometers
(MSP) have been introduced which are capable of measuring from 230 nm
(5.4 eV) to 2,100 nm (0.59 eV) relative to one or more of the internationally
Gr.cm-I R.%
5QfI(J() 70
1IJfI(J()
IOfl(J() 60
IfI(J()
I()(J
40
approved and directly calibrated reflectance standards: WC, (W,Ti)C, Si, and
SiC. Instruments such as the Zeiss (Oberkochen Ltd) MPM 400/800, and those
produced by Leitz, Polyspec, Nanospec, MSFU-L-312, etc. are capable of a
relative accuracy of 1% down to beam spots of 0.5 j1.m. Refractive indices and
absorption coefficients may be calculated, using the Koenigsberger equations,
from reflectances measured in two media (usually air and oil, nD = 1.515, but
glycerine/glycol for UV measurement), and these are physically significant for
isotropic and crystallographically orientated sections of uniaxial, orthorhombic,
and for the unique twofold axis of monoclinic crystals. Alternative approaches
require a much wider spectral range for measurement, e.g., Kramers Kronig, and
Fourier transform analysis, which can be used to derive near-approximations
for the optical constants from randomly orientated sections of a mineral. In
addition to specular reflectance, modern MSP can be used to measure diffuse
reflectance and transmission/absorption spectra for transparent or especially
thinned absorbing minerals. For isotropic minerals of sufficiently large grain size
and homogeneity, wavelength scanning ellipsometers, including the Laser ellip-
someters Ll16-B-85B, Ll26B, Ll06B, are an alternative to MSP. Measuring
phase and amplitude, they directly provide the dielectric constants 8 1 and 8 2 , n
and k, from which the intensity R is derived. Other, recently developed
instrumentation, including IR-microscopes, scanning-tunnelling microscopes,
ultrasound- and laser-scanning microscopes, provides additional information
on the surface or body properties of a material.
With a new stimulus being provided by the need for noninvasive measure-
ment techniques in the electronics and materials sciences industries, it can be
anticipated that further advances will be made in the spectral range and
sensitivity ofMSP. Already, curve-fitting algorithms have been developed which
enable the structure and composition of complex rn,ulti-Iayer structures, e.g.,
SIMOX, AIGaAs and other III-V compounds, to be reliably determined from
R spectra. With the continuing development of the theoretical basis of polarized
specular reflectance at near-normal incidence, we can expect to better under-
stand the electronic properties and their structural significance for a wide variety
of minerals and synthetic materials.
F or now, and to return to the limited spectral range required for ore mineral
identification - the visible spectrum - we note the application of the Com-
mission Internationale de I'Eclairage (CIE) system for the quantification of
color, widely applied in identification schemes and recommended by the Com-
mission on Ore Mineralogy of the International Mineralogical Association
(COM-IMA). The CIE system, based on RGB (red, green and blue) primaries
transformed to trichromatic coefficients x, y, and z, and the reflected intensity, or
luminance, Y%, also contains information which can be computed (e.g., using
affine geometry), or graphically plotted on a chromaticity diagram to provide
quantitative equivalents for the subjective phenomena of color saturation
(excitation purity) and hue (dominant wavelength). Color values have a role to
play in identification schemes based on R spectra, particularly those using
computerized databases. In addition, the color of anisotropic minerals between
6.7.3 Reflectance Spectra: Their Interpretation Using Band Theory 491
crossed polars (anisotropic rotation tints) have recently been investigated and a
unifying theory, bringing together these colors and those perceived in plane-
polarized light, based on dielectric tensors, and consistent with the electronic
properties of a mineral, has been developed to account for the physical causes of
color phenomena arising from specular reflectance.
Many "stand-alone" ore mineral identification schemes now exist using
reflectance data as the primary parameter. These are often supplemented by
color values and micro-indentation hardness data. The most effective are those
for which the optical data correspond to minerals of known (pre- or post-
determined) chemical composition and crystallographic symmetry. At present
there are few inter-active identification schemes: a good example is that of the
MSFU-L-312, in which the measured values are automatically compared with
those from a pre-established database containing R data for more than 800
minerals. More, and more complete schemes are being developed.
References
Atkin BP, Harvey PK (1979) The use of quantitative color values for opaque mineral
identification. Can Mineral 17: 639-647
Chvileva TN, Bessmertnaya MS, Spiridonov EM (1988) Ore mineral identification in reflected
light. Kedra, Moscow
Criddle AJ, Stanley CJ (eds) (1986) The quantitative data file for ore minerals. 2nd issue,
IMA/COM. British Museum (Natural History), London
Gerlitz CN, Leonard BF, Criddle AJ (1989) QDF Database System. Reflectance of ore
minerals - a search-and-match identification system for IBM compatible microcomputers
using the IMAICOM Quantitative Data File for ore minerals, 2nd issue. US Geol Surv
Open-File Rep 89-0306A-89-0306E
Jambor JL, Vaughan DJ (eds) (1990) Advanced microscopic studies of ore minerals. MAC;
Commission on Ore Mineralogy Short Course Handbook, 17. Mineralogical Association of
Canada, Nepean, Canada
Marfunin AS (1979) Physics of minerals and inorganic materials. Springer, Berlin Heidelberg
New York
Peckett A (1992) The colors of opaque minerals. John Wiley & Sons, Chichester, England
Phillips JC (1966) The fundamental optical spectra of solids. Sol State Phys 18: 55-164
Reeson KJ, Criddle AJ, Pearson P, Chater RJ, Chrisstensen K, Alderman J, Booker GR,
Kilner JA (1991) Microscope-spectrophotometric analysis to determine the origins of the
color variations on SIMOX wafers. Nucl Instr Meth 55: 718-724
Criddle AJ, Pearson PJ, Reeson KJ, Robinson AK, Hemment PLF, Marsh CD, Booker CG
(1992) Non-destructive characterization of thin film SIMOX structures using microscope
spectrophotometry. Materials Sci Eng B12: 185-190
Shuey RT (1975) Semiconducting ore minerals, Developments in Economic Geology 4.
Elsevier, Amsterdam
Strens RGJ (1979) Determining the optical constants of opaque minerals. Bull Mineral 102:
308-313
Strens RGJ, Freer R (1978) The physical basis of mineral optics. Mineral Mag 42: 19-30
Tossell JA, Vaughan DJ (1991) Theoretical geochemistry: applications of quantum mechanics
in the Earth and mineral Sciences. Oxford Univ Press, England
Vaughan DJ, Craig JR (1978) Mineral chemistry of metal sulfides. Cambridge Univ Press,
England
492 Chapter 6. Properties of Minerals
References
Azzam RMA, Bashara NM (1977) Ellipsometry and polarized light. North-Holland Publ Co
Amsterdam
Cardona M (1969) Modulation spectroscopy. Academic Press, New York
Proc 2nd, 3rd, and 4th Int Conf on Ellipsometry (1969, 1976, 1980) Surf Sci vols 16, 56,96,
North-Holland, Amsterdam
Pollak FH, Cardona M, Aspnes DE (eds) Proc Int Conf on Modulation spectroscopy. SPIE
Proc, 1990, vol 1286. SPIE, Bellingham, Washington
6.7.5 Nonlinear Optical Characteristics of Minerals 495
Proc Int Con on Ellipsometry and other optical methods for surface and thin film analysis
(1983) ] Phys vol 44, Colloq CIO, Les Editions de Physique Les Ulis, France
Proc 1st Int Conf on Spectroscopic ellipsometry (1993) Thin Solid Films, vols 233 and 234.
Elsevier, Amsterdam
Proc 1st Int Conf on Modulation spectroscopy (1973) Surf Sci vol 37 North-Holland,
Amsterdam
L.B. MEISNER
The study of nonlinear optical characteristics began in 1961 when Franken and
his collaborators in the USA first observed how the red beam of the ruby laser
with the frequency w (Al = 694 nm) partly transformed to ultraviolet with the
frequency 2w and A2 = Al/2 after its passage through quartz crystal. Such an
effect, known as the second-harmonic generation (SHG), represents a nonlinear
optical effect, since the optical polarization of the medium depends on the
square of the optical electric field. The lack of an inversion center which permits
second-harmonic production is just that condition which permits piezoelec-
tricity.
After the first SHG observation, a number of other nonlinear optical effects
were discovered: third-harmonic generation, forced Raman scattering, and self-
focusing and defocusing of the laser light. The appearance of tunable lasers led
to the original revolution in the spectroscopy of liquids, gases, and condensed
media: the methods of saturation, absorption, and two-photon excitation, free of
Doppler broading, the spectroscopy of the coherent anti-stokes, Raman light
scattering, and other methods appeared.
The physical reasons for the appearance of nonlinear optical phenomena are
sufficiently obvious and allow the application of a classical treatment. In the
intense light fields (which have the magnitude of intra-atomic fields), outer
electrons of highly polarizable atoms behave as anharmonic oscillators (dipoles),
and the field of light reradiated by them differs in frequency from incident light.
The optical polarization is a nonlinear function of the applied optical electric
field. Therefore, the optics of high intensity light is called nonlinear optics. The
optics of weak light flows, when the outer electrons behave as harmonic
oscillators and the optic polarization of the medium is a linear function of the
applied optical electric field, is called linear or common (pre-laser) optics.
Studies of the nonlinear optical characteristics of minerals also consider the
SHG effect, since most minerals are available as small grains. For such materials
to determine the noncentrosymmetric structure, based on the coherence of the
second-harmonic electromagnetic wave, coherent microscopy is used. The
essence of this method is as follows: a single grain of the mineral or
a powder specimen is placed in front of the objective of the microscope and
496 Chapter 6. Properties of Minerals
irradiated by the focused beam of a Nd 3 + laser (AI = 1064 nm). If the laser
induces SHG in the grain, in the field of vision in the eyepiece of the microscope,
a speckled (interference) image is formed, consisting of green (SH wavelength
A2 = 532 nm) and black spots; if the mineral has a centro symmetric structure,
the speckled image is absent.
In applied nonlinear optics a method for estimating the value of the
quadratic nonlinearity of powder materials (method of Kurtz) and a device for
its realization were developed.
The combined application of coherent microscopy and the method of Kurtz
eliminates many difficulties and makes it possible to identify noncentrosym-
metric structures, which are characterized by the extremely low integral level of
the SH signal, and to estimate the nonlinearity. At present the space symmetry
groups for 50 mineral species, have been refined; it was established that for
samples of micas (for example, lepidolite) the same polytype may double the
frequency of the laser beam (the absence of an invasion center) or may not. The
quadratic nonlinearity of 27 mineral species was determined. It was shown that
its variation in the samples of different genesis reaches a factor of 100-150 (for
example, nepheline); the prospective mineral for quantum electronics, shortite,
was also revealed. A laser method for the rapid determination of the concentra-
tion of a quartz and other noncentrosymmetric mineral phases in (1) powder
samples and (2) thin sections was developed. Based on the integral principle, the
first method involves the measurement two parameters: the relative intensity of
the SH radiation of the sample and the relative transparency at the SH
wavelength. Using these parameters, the concentration of the noncentrosym-
metric phase in the sample is calculated. The second method is based on a
differential principle and requires the determination of the relative number of
video impulses at a frequency different from the laser radiation frequency (for
example, SH impulses, photoluminescence impulses) on the condition that the
mean differential amplitude of the impulses reaches a predetermined level. This
method has no sensitivity restrictions and allows the analysis of any form of
sample (luminescence mineral phases are used).
New possibilities have appeared in the area of mineral separation. For
example, minerals of the feldspar group do not double the frequency of the laser
radiation, but quartz does. It should thus be possible to use this principle to
remove feldspar from quartz-feldspar raw material. Quartz which contains gas-
liquid inclusions and quartz which does not differ both in the intensity of the SH
and in the angular distribution of this intensity. This phenomenon can be used
in quartz separation. Certain perspectives are gained for the gold-containing
ores i.e., those in which gold associates with quartz.
The study of SHG effects in minerals provides new information and allows
one to choose new methods for a number of traditional mineralogical and
technological tasks. Although the investigation of the frequency dispersion of
cubic nonlinearity is very difficult, it actually opens boundless possibilities for
obtaining spectroscopic information on minerals.
6.8 Technological Mineralogy and Technological Properties of Minerals 497
References
Guggenheim S, Schulze WA, Harris YA, Jiunn-Chorng L (1983) Noncentric layer silicates:
an optical second harmonic generation, chemical, and X-ray study. Clays Clay Miner 31(4):
251-260
Meysner LB, Golubnichiy VV (1988) Theoretical principles of laser optics - geometrical
method of mineralogical analysis. Miner J 10(6): 90-96 (in Russian)
Meysner LB, Kuzmin VI (1986) Theoretical aspects of nonlinear optical methods of separa-
tion. Obogashenie rud 5: 22-25 (in Russian)
Zernike F, Midwinter JE (1973) Applied nonlinear optics. John Wiley and Sons, New York
The constantly rising demand for mineral-bearing materials has led to the
exhaustion of rich, accessible, and easily processable ore reserves. The demand is
currently satisfied by open-pit mining and large scale processing of low-grade
finely disseminated, complex-composition, and difficult-to-enrich ores. The ore
volume processed has doubled in the last 10 to 15 years, with the current
amount being tens of billions tonnes per year. Similarly, the amount of mining
wastes increases by more than 5000 tonnes per minute in the USSR and
probably tenfold in the world. The mining wastes contain deleterious elements
and pose a threat to the environment because processing low grade mineral-
bearing materials entails enormous losses of major and minor valuable com-
ponents.
The extensive development using traditional technological principles has
probably exhausted most possibilities for improving recoveries from low grade
ores. Consequently there is a need for new technological approaches and
processes which will improve recoveries of metal and nonmetal constituents
from mineral-bearing raw material. The need for technological approaches can
be met by technological mineralogy.
Technological Mineralogy
balancing techniques provides the basis for predicting the feasibility and
economic practicality of ore enrichment while conducting geological pros-
pecting; for defining comminution requirements and ore enrichment potential
while performing laboratory testing; and for improving comminution and
enrichment operations at mining and concentrating plants.
Ore Sorting
Luminescence Properties
The luminescence properties of minerals are employed in the lump separation
of scheelite ores, fluorites, and diamond kimberlites. Luminescence is excited
by ultraviolet radiation or X-rays. The difference in the kinetic parameters of
luminescence (build-up and quench rates) is effective for the X-ray luminescence
separation of scheelite and diamond ores. In this case it becomes possible to
separate scheelite from calcite, fluorite from wollastonite, and diamond from
calcite, apatite, and zircon.
The luminescence separation of cassiterite with the use of an UV laser as
the exciter has been established. Novel nonlinear optical technique has been
developed for separating nepheline-feldspar from a quartz-feldspar raw mater-
ial. These techniques are based on the ability of crystalline structures of minerals
without the inversion centers to generate the second harmonic on their exposure
to laser radiation.
6.8 Technological Mineralogy and Technological Properties of Minerals 501
Photometric Properties
The color contrast of the minerals to be separated is used in the photometric
separation of gold-bearing white quartz from enclosing black shales, and white
magnesite from green serpentinite.
Bulk Separations
Gravitational Methods
The density of minerals is employed as a separation technique during benefi-
ciation and during concentrate enriching operations with ores of noble (Au,Pt),
rare (W,Mo,Sn,Zr,Ti,Ta,Nb), nonferrous (Pb,Zn,Cu) metals, and diamonds.
Techniques using density of minerals include mechanical methods such as
tabling, jigging, spirals, cones, hydrocyclones, and heavy media suspension
(mainly magnetic fluids).
Skarn-carbonate W-Mo ores of the Tyrnyauz deposit (USSR) have been
enriched in heavy media suspensions by separating heavier skarn pieces with
scheelite from light marble calcite. The Altai disseminated polymetallic ores in
the USSR are separated from metamorphosed enclosing rock by the difference
in density between the ore minerals and rock. The magnetite and hematite
in iron ores in Canada are separated from silicate and carbonate gangue with
large scale spirals in concentrators that process over 100 000 tonnes of iron ore
per day.
The efficiency of gravitational enrichment is influenced by the mass, size, and
morphology of mineral particles to be separated, and by the change in the
density of variable-composition minerals as well as intergrowths containing
mineral inclusions. Process Mineralogy investigations may define the optimum
degree of comminution for maximum possible yield of liberated and unliberated
mineral grains.
Magnetic Properties
The magnetic properties of magnetite and maghemite are employed for dry
lump separation of iron ores in weak magnetic fields. Wet electromagnetic
separation in fields of up to 1000 oersteds is used to separate magnetite from
quartz and other minerals in finely disseminated ores. Process mineralogy
investigations have shown a relationship between the quality of ore concentrates
and the amount of intergrowths of quartz with magnetite, as well as the presence
of isomorphous impurities of magnesium, titanium, and other elements. The
recovery of iron is also influenced by the natural magnetization of magnetite and
the decreasing amount of isomorphous impurities as well as oxidation and
pseudomorphous substitution by maghemite and hematite. Recent develop-
ments on high intensity magnetic separation (over 10000 oersteds) have made it
possible to recover hematite from iron ores.
The differences in magnetic properties are also useful in enriching tungstate
from tantalite--columbite ores, and in separating pyrrhotite from copper-nickel
and polymetallic ores.
502 Chapter 6. Properties of Minerals
Flotation
The flotation properties of minerals are used for enriching almost 80% of rare
minerals, nonferrous metal-bearing minerals, and finely disseminated ores.
Flotation is based on the differences in the surface properties of minerals, their
hydrophobicity or water receptivity, as well as on their different abilities of
reacting with flotation agents. Apolar and polar organic molecules play the role
of collectors, and salts of inorganic acids represent depressors. The flotation
properties of minerals are determined by the chemical bond type and by the
degree of compensation of comminuted particles on the surface. They also
depend on the crystallographic orientation of cleavage splitting, isomorphous
impurity content, and on the presence of structural imperfections and mineral
inclusions.
The natural floatability in water and oil-receptivity are exhibited by native
metals with metallic bonds, nonmetals with covalent and molecular bonds,
sulfides and oxides with donor-acceptor, covalent and molecular bonds, and
layered silicates such as talc and pyrophyllite with Van-der-Waals bonds on the
surfaces of cleavage flakes. Most oxides, oxygeneous salts, and silicates with
prevailing ionic bonds are hydrophillic and therefore unfloatable. If polar
molecule collectors are adsorbed on the surfaces of such minerals, the latter
manifest floatability. The induced flotation properties of minerals depend on the
degree of attachment of flotation agents on their surfaces. Their adsorption may
be prevented by surface pretreatment with depressors. The process mineral-
ogical study of ores from various deposits has shown a strong variability of the
flotation properties of many minerals.
The natural floatability of the minerals of the scheelite-molybdoscheelite-
powellite series is proportional to the amount of isomorphous molybdenum
which increases the degree of covalence of the chemical bond. The induced
floatability due to formation of hydrophobic calcium oleate on the surfaces of
cleavage splitting along a dipyramid and a prism is inversely proportional to the
molybdenum content. This may be accounted for by the processes of concentra-
tion ordering and decomposition of the solid solution with the formation of
oriented powellite micro-inclusions. Variations of the floatabilities of fluorite
modifications differing in the color and luminescence are caused by different
concentrations of structural-chemical defects on the particle surfaces. These
defects are mainly represented by anion vacancies and rare-earth ions with
locally uncompensated excessive positive charges which provide the stable bond
with the oleinic acid molecules.
The variability of the flotation properties of minerals is also dependent on
the flotation agent conditions and the salt composition of the flotation pulp. In
real flotation conditions the salt composition is determined by the presence in
ores of readily oxidizable, easily solvable minerals, as well as minerals with
a high specific surface area and a crystalline structure which ensures a high
adsorptivity and the ion-exchange properties. The dissolution of the products of
oxidation of pyrrhotite and chalcopyrite, i.e., melanterite, chalcanthite, gypsum,
and calcite, leads to the continuous presence of ions of calcium, iron, copper,
6.8 Technological Mineralogy and Technological Properties of Minerals 503
sulfate and bicarbonate in the pulp. It is known that the adsorption of copper
ions on the surface of sphalerite intensifies its flotation by xanthogenate, but the
effect can be reduced or eliminited by conditioning with Na cyanide. The joint
flotation of fluorine-containing biotite with scheelite, fluorite, and calcite, which
worsens the quality of the scheelite concentrate, is explained by the activation of
the cleavage plane of this mineral by calcium ions with which the hydrophobic
molecules of oleinic acid form stable bonds.
Induced Properties
An intentional change in the technological properties of minerals, aimed at
intensification of ore processing, may be achieved by radiation, thermal, chem-
ical and mechanical actions on minerals. A study is also being carried out on the
influence of the laser, electron beam, plasma, ultrasonics, electric pulses, and
other techniques on the technological properties of minerals.
References
Physical Properties
Physicochemical Properties
Mechanical Properties
Applications
References
Bates RL, Jackson JA (eds) (1979) Glossary of geology. Am Geol Inst, Falls Church, Virginia,
751 pp
Beck BF (ed) (1989) Engineering and environmental impacts of sinkholes and karst, AA
Balkema, Rotterdam, 384 pp
Clark SP (ed) (1966) Handbook of physical constants. Geol Soc Am Mem 97, 587 pp
Fleming RW, Ellen SD, Algus MA (1989) Transformation of dilative and contractive landslide
debris into debris flows - an example from Marin County, California. Eng Geo127: 201-223
Gillott JE (1987) Clay in engineering geology. Elsevier, Amsterdam, 468 pp
Grabowska-Olszewska B (1988) Engineering-geological problems of loess in Poland. Eng
Geol 25: 177-199
Gray DE (ed) (1972) American Institute of Physics Handbook. McGraw-Hill, i~ew York,
3rd edn. vii + 2442 pp
Handy RL (1973) Collapsible loess in Iowa. Soil Sci Am Proc 37: 281-284
Knight K (1963) The origin and occurrence of collapsing soils. Proc 3rd Regional Conf for
Africa on Soil Mech Found Eng 1: 127-130
Kutepov VM, Kodgevnikova VN (1989) Stability of karst territories. Science, Moscow, 150 pp
(in Russian)
Landolt-Bornstein (1950) Euken A, Hellwege KH (eds) Landolt, Hans Heinrich, Zahlenwerte
und Functionen aus Physik, Chemie, Astronomie, Geophysik und Technik, Sechste Auflage.
Springer, Berlin Heidelberg, New York
Lutenegger AL, Hallberg GR (1988) Stability of loess. Eng Geol 25: 247-261
Lynch CT (ed) (1974) Practical Handbook of materials science. CRC Press, Boca Raton,
Florida. 1989, 636 pp
Osipov VI, Babak VG (1987) Nature and mechanism of clay swelling. Eng Geol 5: 18-27
(in Russian)
Povarennih AS (1963) Strength of minerals. Academy of Sciences of the Ukrainian SSR, Kiev,
304 pp
National Research Council Advisory Board on the Built Environment Reducing losses from
land sliding in the United States. National Academy Press, Washington, D.C. 1985,41 pp
Sergeev EM, Golodkovskaya GA, Ziangirov RS, Osipov VI, Trophimov VT (1983) Terrain
science. Moscow State Univ, 388 pp (in Russian)
Smalley IJ (1966) The properties of glacial loess and the formation ofloess deposits. J Sediment
Petrol 36: 669-676
CHAPTER 7
The next step in developing an understanding of solids is connected with the use
of extremely diverse, special manifestations of the properties of materials, with
their innumerable applications in many completely different fields. Moreover,
a transition from general theories to the most detailed elaborations of particular
theories regarding structural types families of materials has taken place.
Technical parameters describing the properties of modern materials reflect
the much more complicated characteristics of solids used as materials. This
applies not only to the use of materials in electronics, but also the consideration
of many kinds of mechanical, thermal, optical, and magnetic properties in
various technical devices.
All the properties of materials are electronic properties. Consequently,
calculations of chemical bonding (or electronic structure) in solids are necessary
to understand the theories of particular parameters describing the action of
materials in devices.
In the interrelations: crystal structure-electronic structure-solid state spec-
troscopy-electronic properties, these properties have provoked radical changes
in the approach to solids and consideration of them as material.
It is in this area that the most sophisticated understanding of matter and its
most intricate applications in new branches of technical methods and electronics
are being developed.
A general overview of solids as possible materials can be represented by
structure types (as in Chap. 2.3) or (taking chemical substitutions into account)
by families of materials. Many of the materials and families of materials are
designated by title compounds represented by minerals, e.g.:
garnets M3M2 T 3012 (silicate garnets, rare earth garnets, Y-AI garnets, etc.),
tourmalines MM3M6 T 601SB03X3+ 1, zeolites (M +, 1/2M2+)TxSi 1_x 0iH 20)n,
sodalite Na sCI 2AISi0 4, petalite LiAISi0 4, spodumene LiAISi 20 6, wollastonite
CaSi0 3, beryl Be3A12Si601s,
quartz SiOrberlinite AIP0 4, corundum-ruby-sapphire A1 20 3, chrisoberyl
A1 2Be0 4, rutile Ti0 2, wiistite Fe 1- xO, ferrites-spinels MM 20 4, hematite
Fe 20 3, ilmenite FeTi0 3, perovskites CaTi0 3, paratellurite Te0 2, sillenite
Bi 20 3, apatites Ms[T04]3X, alunites M+M~+[T04]2X6' boracites
M3B7013X, calcite CaC0 3, scheelites CaW0 4, powellites PbMo0 4, anhydrite
CaS04,
pyrites, marcasites MS 2, arsenopyrites FeAsS, nickeline NiAs, pyrrhotite Fe 7SS,
molybdenite MoS 2, cinnabar HgS, sphalerite ZnS, galena PbS, proustite
Ag 3AsS 3, pyrargyrite Ag 3SbS 3, stanosulites (berndtite) SnS 2-SnSe2' stibnite
7.1 Concept of Materials as a New Approach to Solids and Minerals 513
coefficient (TFC, the best value is zero), and indices offrequency stability (10- 5
to 10- 12 , from some milliseconds to several years) are used in the needed ranges
of frequencies and temperatures. In some particular devices the combinations of
the nonoptimal values ofk 2 and TFC are necessary (for example, in devices with
broad frequency bands).
Piezoelectric devices with frequencies of some kHz to hundreds of MHz are
made of single crystals with low k 2 < 2% ("weak" piezoelectric materials) as
well as of piezoceramics. The single crystals are quartz ((X-Si0 2), tourmaline,
XY 3Z 6 (B0 3hSi 6 0dOH,F)4' where X stands for Na+, Ca2+, K +, Mg2+; V-for
Mg2+, Fe2+, Fe3+, Li +, AP + and Z-for AP +, Fe 3+. An example of the
"strong" piezoelectric material for this frequency range is Rochelle salt,
KNaC 40 6 H 4 '4H 20 with k 2 = 65%. The popular and inexpensive PZT
ceramics (PZT = PbZr 1 _ xTix 03) have a basic working range of 1 kHz to
1 MHz and k 2 values up to 50%. Piezoelectric ceramic materials must be
carefully poled to align the ferroelectric domains.
Both "weak" and "strong" materials (k 2 > 2 %) are used in the manufacture
of devices for the MHz range. Single crystals of quartz, LiNb0 3, LiTa0 3,
berlinite (AIP0 4), and lithium tetraborate (Li 2B40 7 ) are utilized by the elec-
tronics industry. Similar characteristics are shown by perovskite ceramics
(AB0 3) and most especially by modified lead zirconate-titanate compositions.
Melt grown LiTa0 3 is a reasonably strong piezoelectric material with k 2
values up to 4% and special orientations with resonant frequencies that are
temperature-insensitive. LiNb0 3 has larger values of the piezoelectric coeffi-
cients but the thermal instability of resonant frequency is troublesome.
Phosphates and borates have lower k 2 though the frequencies are stable over
broad temperature ranges. Berlinite (AIP0 4) is representative of phosphate
materials of the type MeP0 4 (Me = AI, Ga, Mn, Fe) and is a promising material
for the electronics industry. It is a structural analog of quartz with a temperature
r
coefficient near zero (10- 9 C), and it surpasses (X-Si0 2 with k 2 = 2.3%. Uses of
berlinite are restricted because of hydroxyl groups incorporated in crystals
during hydrothermal growth.
Lithium tetraborate also surpasses quartz in some piezoelectric properties.
Cuts of 0°, 78°, 90° with temperature coefficients approaching zero have k33 four
times greater than kll of quartz. Crystals are grown by the Czochralski method.
This material would be used more widely were it not so hard to cut and polish
because of its solubility in acids.
In microwave piezodevices for GHz frequencies, the materials with high k 2
values are mainly piezoceramic materials and thin film piezoelectric structures.
Thin films of zincite (ZnO) deposited on insulating substrates such as glass,
sapphire, and silicon are good piezoelectric materials.
the intrinsic interaction of different types of acoustic waves with the electron-
phonon system of the material. Acoustoelectric materials are used in com-
munication and information systems, instrumentation engineering, and in
various other systems for generating and filtering signals and controlling their
frequencies.
Requirements for material properties depend on the type of wave propaga-
tion: bulk acoustic waves (BA W), surface acoustic waves (SAW), magnetostric-
tion waves (MSW) and subsurface acoustic waves (SSA W).
For signals generated in piezoelectric materials, the basic parameters include
elastic wave velocity, intrinsic loss, insertion loss, thermal variations in velocity,
and time delay. Important characteristics of acoustoelectric materials are
flatness, cleanliness, and cost.
The acoustic velocity is very slow in acoustoelectric devices used for low
frequencies such as bismuth germanate (v = 1680 m/s) and very fast in crystals
used at high frequencies, such as diamond with its record v = 12100 m/s.
The group of "slow" materials includes bismuth germanate and silicate
(Bi 1z GeO zo , Bi 12 Si0 2o ) and thallium sulvanite (TI3BX4)' These materials are
used for broad band filters with low frequencies and for delay lines because of
their low acoustic wave velocity and high k 2 values. The drawback of these
crystals is the large temperature dependence of SAW propagation and time
delay. Thallium sulvanites are not widely used because of ecological problems
encountered during production.
The "slow" crystals, ceramics and quartz glass, are used mainly as low
frequency acoustoelectrics. Devices working at 150 MHz are manufactured
from crystalline quartz, lithium tetraborate, berlinite, and piezoelectric ceramics
of lead zirconate-titanate, LiNb0 3 is superior to quartz in some applications
because of its high k 2 (6%), easy production and rapid wave propagation up to
3488 m/s in YZ-cuts.
Ruby and rare earth-doped garnets are used as substrates. Sound waves
travel in yttrium aluminum garnet (YAG) at 8563 mls in the [001] direction and
at 5029 m/s along [110]. Control of the acoustic velocities and insertion losses is
achieved by means of different rare-earth dopants. Lutetium doped garnet has
much lower damping than ruby. Current industrial practice utilizes piezoelectric
semiconductors such as GaAs on glass or sapphire substrates for devices in the
high frequency range. They are manufactured in the form of laminar or layered
systems. Materials with high k 2 and high propagation velocities are used in the
form of thin films (ZnO, AIN, Li 2 B40 7 , Ta 2 0 s, Ba 2 Si 2 TiO s).
minerals and their synthetic analogs (CaC0 3, NaN0 3) having the best polari-
zing properties are not very hard, making it difficult to obtain polished surfaces.
Yet another group of optical crystals is composed of materials capable of
rotating the plane of polarization under an applied magnetic field (Faraday
Effect). These materials are used in fast-latching optical switches, modulators,
and as optical isolators in communication lines. They are characterized by an
angle of rotation per unit path length. Included in this group are garnets
(Me 3AI s0 12 -type), fluorides (CeF 3, LaF 2' EuF 2, LiTbF 4), and selenides (ZnSe).
Y3FeSOlZ: Bi-substituted garnets produces 45° rotation for 2 mm microwaves.
Electro-optic crystals change their refractive index under applied electric
fields. Materials which change their optical activity under field (electro gyration)
also are part of this group. It is necessary to distinguish between linear changes
in the refractive indices in noncentrosymmetric crystals (Pockels effect) and
quadratic changes (Kerr effect). The electro-optic materials find applications in
the modulation and control of laser beams in signal processing devices and in
the holographic storage of information. Electro-optic materials are character-
ized by a half-wave voltage, (V;'/2 - the lower, the better) or by an electro-optic
efficiency factor (I:·V . . /2)-1. The possibility of optically induced changes of
refraction must be also taken into account.
Representative electro-optic materials are synthetic lithium tantalate,
lithium niobate, potassium dihydrogen phosphate, potassium titanyl phosphate,
bismuth silicate, bismuth germanate, bismuth titanate, and zinc telluride.
LiTa0 3, LiNb0 3 and KTiOP0 4 have V;'/2 values of 2.5 kV, 3.5 kV, and 2.0 kV
in the range of 0.35-4.5 !lm. The best electro-optic properties are those of
(Ba,Sr)Nb 20 6 (BSN) and K(Ta,Nb)03 (KTN). Although difficult to obtain,
large BSN crystals have VAj2 as low as 0.45 kV in the range 0.4 to 4.5 !lm.
In acousto-optic materials, acoustic waves produce a diffraction grating for
incident light, causing changes in frequency, amplitude, and direction ofthe light
beams. These materials are used in high resolution processors of optical
information, principally in communication optoelectronics as well as in micro-
scopes. Selection of acoustic materials is not an easy problem because high
acousto-optic efficiency must be accompanied by low acoustic losses.
In the visible spectrum proustite (Ag 3AsS 3), lithium niobate (LiNb0 3), para-
tellurite (Te0 2), lead molybdate (PbMo0 4 ), germanosillenite (Bi 12 Ge0 2o), and
lithium iodate (a-LiJ0 3) are used. The synthetic materials have somewhat better
properties compared to natural crystals and are more reproducible technolo-
gically.
Devices for the infrared range incorporate complex halides, chalcohalides,
and chalcogenides that have high indices of refraction. Materials in this
group include cinnabar (a-HgS), calomel (Hg 2 CI 2), thallium phosphoselenide
(Ti 3PSe4)' and thallium arsenoselenide (TI3AsSe3)' Cinnabar has a damping
coefficient of 7dB/(s MHz2) for }, = 1.153!lm along [001]. Its transparency
range is from 0.62 to 16!lm and n = 2.705. TIAsS 4 has n = 2.626 and is
transparent from 2 to 35!lm with a damping coefficient of 6.2 dB/s'MHz 2 at
Ii = 1.153 !lm along [001].
7.2.4 Laser Materials 519
Nonlinear optic devices are used to generate second harmonic waves, and to add
and substract the frequencies of two optical fields. These devices place strict
requirements on crystals with quadratic nonlinearity: they must be transparent
for all of the interesting frequencies, as well as highly nonlinear and mechan-
ically strong.
Among the nonlinear materials are the synthetic analogs of the minerals
proustite, pyrargyrite, cinnabar, and quartz. The first three are used to trans-
form infrared laser radiation, while quartz being a universal material of excellent
optical quality is used as a standard for the relative assessment of nonlinear
susceptibility. Many other minerals analogs have been tested including bromel-
lite, sphalerite, and zinc tellurite, but the properties are not strong enough for
applications in quantum electronics. The only exception may be shortite
(Na 2Ca 2C 30 9 ), which has shown a high quadratic nonlinearity coefficient when
exposed to a Nd laser beam.
7.3 Multifunctional Minerals 521
A.S. MARFUNIN
Type I accounts for about 95-98% of all natural diamonds, while only 2-3%
belong to type II.
The next step in distinguishing diamonds of type I is related to the structural
position of the nitrogen impurities:
Of all these types of centers, only Nand N3 are paramagnetic, and can be
observed directly by optical and luminescence spectra, while the A and B centers
(most usual in natural diamonds) are non-paramagnetic and optically non-
active. However, the contents of A and B centers correlate with conjugated
7.3.1 Diamond: the Mineral-Absolute. Applications in Electronics 525
References
Bachman PK, Collins AT, Seal M (eds) (1993) Diamond 1992. Elsevier Sequoia, Lausanne
Davies G (1984) Diamond. A Hilger, London
Diamond Films-90 (1990) First Eur Conf on Diamond- and Diamond-like Carbon Coatings.
Crans-Mon
Field J (ed) (1979) Properties of diamond. Acad Press, New York
Kvaskov VB (ed) (1990) Diamond in electronics. Energoatom, Moscow
New Diamond (1988) First lnt Conf on the New Diamond Science and Technology, Tokyo
Quartz (ex-Si0 2 ) occupies a special position among the minerals because of its
wide geological distribution and its numerous applications.
Single crystals and polycrystalline quartz are used as a final product and also
as a raw material in the production of silicates, glass, porcelain, ceramics,
gaseous silanes, and in the growth of high quality single crystals. Quartz is a
useful material for many technical applications because of its excellent techno-
logical properties: hard but brittle, insoluble in acids (except in hydrofluoric
acid) and its availability and relative cheapness. The world output of quartz
exceeds 10000 tons yearly. Since natural high quality crystals are scarce and
their characteristics variable, and demand is rising, industries of a number of
countries have begun synthetic production. During the 1950s, the USA, Ger-
many, the USSR, Japan, and Great Britain began to develop synthetic quartz
crystals by hydrothermal processes. Technologies differed in vessel design,
solution compositions, as well as in temperature, pressure, and kinetic factors.
Modern-day synthetic quartz production satisfies 95 to 98% of the industrial
demand for electronic grade material.
In addition to technical quartz, a number of colored varieties with excellent
gem qualities have been obtained: amethyst, citrine, and blue quartz, a Co-
7.3.3 Corundum - Ruby -Sapphire 527
References
Genmuller P (ed) (1985) Inorganic solid fluorides: chemistry and physics. Academic Press,
Orlando
Jaffe B, Cook W, Jaffe H (1971) Piezoelectric ceramics. Academic Press, New York
Japan Electronics Industry Development Association (JEIDA) (ed) (1985) Future of electronic
parts and materials. Tokyo, pp 231~255
Kamada N, Gomi T, Shindo M (eds) New materials developed in Japan 1987. Toray Research
Center, Tokyo
Kaminskii AA (1980) Laser crystals, Springer ser in optical sciences 14. Springer, Berlin
Heidelberg New York
Lemanov VV (1988) Acousto-optic devices and materials for IR. In: Acoustic devices of
radioelectronic systems. Nauka, Leningrad (in Russian)
Macleod HA (1985) Thin film optical filters. Adam Hilger, Boston, Matthews H (1977) Surface
wave filters: design, construction and use. Wiley and Sons, New York
Moulson AJ, Herbert JM, Electroceramics. Chapman and Hall, London
Musikant S (ed) (1990) Optical materials: a series of advances vol I. Marcel Dekker, New York
Oliner AA (1978) Acoustic surface waves. Springer, Berlin Heidelberg New York
Salt D (1987) Hy-D handbook of quartz crystal devices. Van Nostrand Reinhold (UK),
Wok ingham, Berkshire (England)
Savage JA (1985) Infrared optical materials and their antireflection coatings. Adam Hilger,
Bristol
Stwalley WC, Marshall Lapp (cds) (1986) Advances in laser science. Proceedings of the First
Intern Conference, Dallas, Texas
Suprigo D (1986) Surface acoustic wave devices. Prentice-Hall, Englewood Cliffs
Synthesis of minerals (1987) Vol 1, 2. Nedra, Moscow (in Russian)
Zelenka J (1986) Piezoelectric resonators and their applications. Academia, Elsevier, Prague
The first zeolite mineral was discovered in 1756 and over the next two centuries
zeolites remained the subject of intensive field and laboratory investigations.
Ion-exchange properties of zeolites were recognized in 1858 and adsorption of
7.3.4 Natural and Synthetic Zeolites 529
gases by dehydrated chabazite was observed in 1909, but the first industrial
application commenced as late as 1954 with the production of oxygen-enriched
air by the selective adsorption of nitrogen and the purification of the gasoline
fraction from normal paraffins on CaA zeolite.
Since then, these microporous solids have been developed into key materials
in oil processing and in the petrochemical and chemical industries. Only a few
hundred tons of zeolites were produced in the late 1950s, about 60000 t in 1975
and in 1987 the production of zeolites had increased to 460000 t worldwide.
Hundreds of thousand tons of natural zeolites are mined as components of
volcanic tuffs, sedimentary and low-grade metamorphic rocks. Workable depos-
its of zeolite-containing rocks were discovered in the USA, Japan, Cuba, Russia,
Italy, Hungary, Bulgaria, and in other countries, where zeolite minerals often
occur in megaton quantities at high purities.
Increasing production of zeolites was a response to the growing need of these
solids as ion exchangers, adsorbents, and catalysts. Following their rapid
introduction as commercial, molecular sieve adsorbents, zeolites came to dom-
inate the petroleum refining industry. In the United States, approximately one-
third of all processed crude oil is catalytically converted over zeolite-containing
catalysts. Over 500 t of catalyst are required daily. In future years the worldwide
sales of zeolite catalysts to the petroleum, petrochemical, and chemical in-
dustries are expected to exceed 5 billion dollars.
The estimated annual use of A zeolites as builders of detergent comes close
to 400 000 t. Natural high silica zeolites were recognized as unique materials
for removing 137CS, 90Sr, and 90y from liquid nuclear effluents, for soil
enrichment, and even for preparing animal feed supplements. The advent of
zeolites as commercial inorganic materials helps to solve three major problems
encountered in our century: the development of effective industrial technologies,
the improvement of agricultural productivity, and the reduction of environ-
mental damage created by industrial and municipal effluents.
Comprehensive information on the industrial application of zeolites can
be found in excellent books compiled by Breck (1974) and Rabo (1976). Here,
we give only some typical examples of the uses of zeolites as ion exchangers,
sorbents, and catalysts.
Zeolites display outstanding properties in separation, purification, and
molecular rearrangements, which can be attributed to a unique combination of
strong active sites and spatial selectivity. The reasons for this behavior lie in the
topologies of the anionic frameworks of zeolites.
As in other tecto silicates, the main building unit in zeolites is the T0 4
tetrahedron, where T may be Si, AI, or some other element capable of forming a
tetrahedral coordination with oxygen. The T0 4 units are linked with other T0 4
tetrahedra through shared oxygens. In contrast to other tecto silicates, the
zeolites have, however, a well-developed intracrystalline channel system. At
present, 39 naturally occurring zeolite minerals and more than 100 synthetic
species are available, among which about 40 different topologies can be
identified.
530 Chapter 7. Mineralogical Material Science
Finally, very high silica zeolites can now be readily synthesized, whereby the
content of Al and cations is so low, that they have lost much of their polar
character and show the properties of hydrophobic rather than hydrophilic
sorbents. These solids retain the full power of molecular sieving, but cannot sorb
small polar molecules such as water at low and moderate external pressure.
In summary, the separation of the complex mixtures in the presence of
zeolites can be due to many factors. The most important factors governing the
selective behavior of zeolites in separating the different substances can be
described as follows:
1. Molecular sieving with the adequate shape and size differences between the
molecules to be separated based on the different accessibility of the intra-
crystalline pores.
2. Interaction of the adsorbed molecules with the electrostatic fields of the
cations.
3. Unequal distribution of the negative charge among the framework oxygen
and the energetic heterogeneity of the ion-exchange and adsorption sites.
4. Hydrophobization of the zeolite surfaces.
The versatility of these general principles is used in the application of zeolite as
ion exchangers, sorbents, and catalysts.
The ion-exchange capacity and selectivity to the given ion characterize the
replacement of the zeolite cations by the ions present in the external solution.
The exchange capacity of a zeolite depends on the chemical composition and
increases with the decreasing Si/Al ratio. The selectivity is estimated by the
distribution of the exchange cation between the exchanger and the external
solution.
Zeolite A (Si/ Al = 1) has the highest exchange capacity among the known
zeolites. In a typical sample all divalent cations can be favorably accommodated
near the centers of the six rings. For divalent ions in zeolite A the order of
decreasing selectivity is:
Zn > Sr > Ba > Ca > Co > Ni > Cd > Hg > Mg.
This zeolite is very selective toward Ca2+ in comparison to Na + and to a
lesser extent to Mg2 +. Small crystallites of synthetic zeolite A (2-10 jlm), which
have no natural counterpart, ensure the high rate of exchange. They form
a stable suspension in water and have proven to be an ideal scavenger of Ca 2+
in hard water. Zeolite is used as a builder in detergent powders to replace
phosphates, which are banned in many countries throughout the world. The
large role played by phosphates in the autrophication of stagnant or slowly
flowing surface waters led to extensive research into the problem of finding
suitable substitutes for phosphates in detergents. When combined with small
7.3.4 Natural and Synthetic Zeolites 533
1. Manufacturing of detergents
Zeolites NaA;NaX
Advantage in using zeolite based materials Effective removal of Ca2+ - and Mg2+ -ions
2. Treatment of nuclear waste
Zeolites Natural clinoptilolite, mordenite, chabazite
Advantage in using zeolite sorbents Selective removal of 137CS and 90Sr
3. Treatment of waste waters
Zeolites Natural mordenite, clinoptilolite, phillipsite,
chabazite, and zeolite-containing tuffs
Advantage in using zeolite sorbents Removal of NH 4 + -ions, traces of Fe, Zn, Cu,
caprolactam, and lubricants
4. Soil benefication
Zeolites Synthetic A zeolite, natural clinoptilolite, and
mordenite
Advantage in using zeolites Stabilization of soil pH, moisture contents and
manure malodour
5. Animal feed supplementation
Zeolites Synthetic A zeolite, natural clinoptilolite and
mordenite
Advantage in using zeolite-containing diets Beneficial weight gain, control of ammonium
level, regulation of blood protein levels
534 Chapter 7. Mineralogical Material Science
The selective and rapid uptake of the bulky, monovalent cations from
aqueous solutions by clinoptilolite and mordenite was used for the decontami-
nation of radioactive effluents (Table 38) and the treatment of wastewaters. The
use of these minerals for soil improvement is related to the ability of these
zeolites to improve nitrogen retention in the soil. Zeolite addition to the growing
media has a beneficial effect on the production of vegetables. The beneficial
effects of 5-6% supplementation to the diet of animals is also attributed to the
ion-exchange control of ammonium levels.
Zeolites as Adsorbents
Sorbex processes exceeds 8 million t year. All these processes are based on the
sieving properties of large and small port zeolites.
Finally, another large-scale sieving operation, involving zeolite adsorbents,
is the production of oxygen-enriched air by selective adsorption of nitrogen on
various zeolites. This process uses the selective uptake of nitrogen, due to
quadrupole interaction.
Zeolites as Catalysts
Catalysts for modern chemical processes (Table 40) have to show excellent
activity and selectivity and also have to satisfy purely practical considerations in
their use and performance, such as thermostability and resistance to attrition.
Most of the synthetic zeolites meet all these requirements. These crystalline
aluminosilicates in appropriate ion-exchanged forms can offer sizeable activity
I. Catalytic cracking oflarge petroleum molecules into smaller hydrocarbons, primarily in the
gasoline range to produce gasoline
Zeolites Rare-earth, ammonium, magnesium, ex-
changed Y zeolites or mixed REHY and
MgHY zeolites embedded in a matrix of dense,
amorphous silica-alumina
Advantage in using zeolite catalysts Increased gasoline yield, enhanced gasoline
octane number, stable performance in the hy-
drothermal stability of the catalysts in the re-
generators
2. Hydrocracking of heavy gasoils to producce gasoline, central heating oil, jet diesel fuels,
and petrochemical feedstocks
Zeolites Faujastite, mordenite or HZSM-5 loaded with
transition metals ions
Advantage in using zeolite catalysts Resistance to metals (like N;, Y, Cu, and Fe)
contaminants in the feed, versatility in pro-
cessing crude oils of different nature, favorable
time on stream behavior
3. Selectoforming of reformer product streams to produce low paraffin gasolines
Zeolites Synthetic or natural erionites and c1inoptil-
olites containing N;
Advantage in using zeolite catalysts Selective uptake of the unbranched paraffins
from the feed eliminating low octane rating
fractions can be achieved only by zeolites with
narrow channels ( < 5 A)
4. Paraffin isomerization to produce components of higher octane numbers
Zeolites Synthetic mordenite, containing noble metals
Advantage in using zeolite catalysts Conversion of low octane pentane and hexane
feeds to higher octane yields
7.3.4 Natural and Synthetic Zeolites 537
The site densities of zeolites are 10 to 100 times greater than those of silica-
alumina. Such effects are explained by the following factors:
1. Greater concentration of active sites;
2. Greater effective concentration of hydrocarbons in the vicinity of a site,
resulting from strong adsorption in the fine micropore structure;
3. Electric fields in the zeolite pores may enhance the formation and reactions of
carbonium ions through polarization of C-H bonds.
Cracking, i.e., the conversion of large petroleum molecules into smaller
hydrocarbons, primarily in the gasoline range, is one of the largest scale catalytic
processes. The most important advance in cracking technology in the last three
decades has been the development of zeolite catalysts. The most significant
improvement offered by zeolites over silica-alumina is better selectivity. Zeolite-
containing catalysts provide more products in the CS-C 10 range and fewer in
the C 3 -C 4 range. The yields of gasoline are thus improved and the formation of
light gases reduced. In the United States more than 250000 t of crude oil is
processed every day over zeolite-containing cracking catalysts.
Selectoforming is another industrial use of shape selectivity, involving the
selective uptake of C S-C 9 n-paraffins from the crude oil distillates. The selecto-
forming catalyst selectively cracks these n-paraffins to liquid propane gas. In this
way the selectoforming increases the octane number of gasoline (Fig. 133).
Benzene alkylation and xylene isomerization were traditionally performed
with aluminum chloride and BF-HF catalysts, which are corrosive and produce
product contamination. New zeolite-based processes help to avoid the problems
of corrosion and improve the selectivity for cumene, styrene, and p-xylene,
which are valuable chemicals for polystyrene, phenol, acetone, and polyester
production.
Molecular sieving can be observed in the catalytic transformation of meth-
anol to gasoline. This new industrial process uses high silica ZSM-5 type
zeolites. Among the products formed from methanol only those with proper
dimensions can diffuse out and appear as gasoline hydrocarbons. Bulky pro-
ducts are then retained in the pores until converted to less bulky molecules.
Methanol to gasoline conversion is a promising way to produce fuel from coal
and natural gas.
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References