AGU

Reference

Shelf

AGU

Reference

Shelf

Mineral
Physics
&Crystallography
AHandbook
ofPhysical

Published under the aegis of the AGU Books Board

Library of Congress Cataloging-in-Publication Data

Mineral physics and crystailography: a handbook of physical constants/

Thomas J. Ahrens, editor.

p. cm. -- (AGU reference shelf ISSN 1080-305X; 2)

Includes bibliographicalreferencesand index.
ISBN 0-87590-852-7 (acid-free)
I. MineralogymHandbooks, manuals, etc. 2. Crystallography---Handbooks, manuals, etc.
I. Ahrens, T. J. (Thomas J.), 1936II.

Series.

QE366.8.M55

1995

549'. I--de20

95-3663
CIP

ISBN

0-87590-852-7

ISSN

1080-305X

Thisbookisprinted
onacid-free
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Copyfight 1995 by the American Geophysical Union

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Washington, DC 20009

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Published by
American Geophysical Union

Printed

in the United

States of

CONTENTS

Preface

Thomas

J. Ahrens

vii

Crystallographic Data for Minerals (2-1)

Joseph R. Smyth and Tamsin C. McCormick

Thermodynamic Properties of Minerals (2-2)

Alexandra Navrotsky
18
Thermal Expansion (2-4)
Yingwei Fei
29

Elasticity of Minerals, Glasses, and Melts (2-5)

Jay D. Bass
45
Elastic Constants of Mantle Minerals at High Temperature (2-5a)
Orson L. Anderson

and Donald

G. Isaak

64

Static Compression Measurements of Equations of State (2-6a)

Elise

Knittie

98

Shock Wave Data for Minerals (2-6b)

Thomas J. Ahrens and Mary L. Johnson

143

Electrical Properties of Minerals and Melts (2-8)

James A. Tyburczy and Diana K. Fisler
185
Viscosity and Artelasticity of Melts (2-9)
Donald B. Dingwell
209

Viscosity of the Outer Core (2-9a)

R. A. Secco

218

Models of Mantle Viscosity (2-9b)

Scott D. King
227

PlasticRheology
of Crystals
(2-10)
J.P.

Poirier

237

Phase Diagrams of Earth-Forming Minerals (2-11)

Dean

C. Presnall

CONTENTS

Diffusion Data for Silicate Minerals, Glasses,and Liquids (2-12)

John B. Brady
269
Infrared, Raman, and Optical Spectroscopyof Earth Materials (2-13)
Q. Williams
291
Nuclear Magnetic ResonanceSpectroscopyof Silicatesand Oxides in
Geochemistryand Geophysics(2-14)
Jonathan

F. Stebbins

303

M6ssbauer Spectroscopyof Minerals (2-15)

Catherine
Index

McCaramon

332

PREFACE

The purposeof this Handbookis to provide, in highly accessibleform, selected

critical data for professionaland studentsolid Earth and planetary geophysicists.
Coverageof topicsand authorswere carefully chosento fulfill theseobjectives.
Thesevolumesrepresentthethirdversionof the "Handbookof PhysicalConstants."

Severalgenerations
of solidEarthscientists
havefoundthesehandbooks'to
be themost
frequentlyuseditem in their personallibrary. The first versionof thisHandbookwas
editedby F. Birch, J. F. Schairer,and H. Cecil Spicerand publishedin 1942 by the
GeologicalSocietyof America(GSA) as SpecialPaper36. The secondedition,edited
by SydneyP. Clark, Jr., was alsopublishedby GSA as Memoir 92 in 1966. Since
1966, our scientificknowledgeof the Earth andplanetshasgrown enormously,spurred
by thediscoveryandverificationof platetectonics
andthesystematic
explorationof the
solar system.
The presentrevisionwas initiated,in part, by a 1989 chanceremarkby Alexandra
NavrotskyaskingwhattheMineral Physics(nowMineral andRockPhysics)Committee
of the American GeophysicalUnion could producethat would be a tangible useful
product. At the time I responded,"updatethe Handbookof PhysicalConstants."As
soon as thesewords were uttered, I realized that I could edit sucha revised Handbook.

! thank RaymondJeanlozfor his help with initial suggestions

of topics,the AGU's
BooksBoard, especiallyIan McGregor, for encouragement
and enthusiasticsupport.
Ms. Susan Yamada, my assistant,deserves special thanks for her meticulous
stewardshipof thesevolumes. I thank the technicalreviewers listed below whose
efforts, in all cases,improvedthe manuscripts.
Thomas J. Ahrens, Editor

California Instituteof Technology

Pasadena

Carl Agee

Thomas

Thomas

Thomas Herring

George Rossman

Joel Ira

John Sass

Andreas K. Kronenberg
Robert A. Langel
John Longhi
Guenter W. Lugmair
Stephen Mackwell

Surendra

Gerald

Maureen

J. Ahrens

Orson

Anderson

Don Anderson

George H. BrimhaH
John Brodhok

J. Michael
Brace

Buffett

Robert
Clement

Robert

Brown

Butler
Chase

Creaser

Heaton

M.

Mavko

Ricardo

Schwarz

Doug E. Smylie
Carol

Stein
Steiner

Herbert

Edward Stolper
Stuart Ross Taylor
JeannotTrampert

Palme

Alfred

Larry Finger
Michael Gaffey
Carey Gazis

RichardH. Rapp
JustinRcvcnaugh
Rich Reynolds
Robert Reynolds

Michael

Yanick

William W. Hay

K. Saxena
Schmucker

Lars Stixrude

Dean

Gumis

Ulrich

Walter D. Mooney

Veronique Dchant
G. D uba

William I. Rose, Jr.

Frank

Presnall

Ricard
Richter
oo

Marius
Richard
John M.

Yuk

Vassiliou
P. Von Herzen
Wahr

CrystallographicData For Minerals

JosephR. Smyth and TamsinC. McCormick

b,andcinngstrom
units(10-l m)andinter-axial
angles
ct,[3,indegrees,
unitcellvolume
in/k3,molarvolume
in
cm3, calculated
densityin Mg/m3, anda reference
to the

With the adventof modemX-ray diffractioninstruments

and the improving availability of neutron diffraction

instrumenttime, therehasbeena substantial

improvement
in the numberandqualityof structuralcharacterizations
of
minerals.Also,thepast25 yearshasseengreatadvances
in
high pressuremineralsynthesistechnologyso that many
new high pressuresilicate and oxide phasesof potential
geophysical
significancehavebeensynthesized
in crystals
of sufficientsizefor completestructuralcharacterization
by
X-ray methods.The objectof this work is to compileand
presenta summaryof thesedataon a selectedgroupof the
more abundant,rock-forming mineralsin an internally
consistentformat for use in geophysicaland geochemical

completecrystalstructuredata.
To facilitategeochemical
andgeophysical
modeling,data
for pure synthetic end members are presented when
available. Otherwise, data are for near end-member natural

samples.
For manyminerals,structure
data(or samples)for
pure end membersare not available,and in thesecases,
indicatedby an asteriskafter the mineralname,datafor an
impure, natural sample are presentedtogether with an
approximateidealformulaand formulaweightand density
calculated from the ideal formula.

studies.

composing
the crustof theEarthas well as highpressure
synthetic
phasesthatarebelievedto compose
thebulkof the

In orderto conservespacewe haveomittedthe precision

given by the original workers in the unit cell parameter
determination.However,we havequotedthedatasuchthat
the statedprecisionis lessthan5 in the lastdecimalplace
given. The cell volumes,molar volumesand densitiesare
calculatedby usgivensothattheprecisionin thelastgiven
place is lessthan5. The formulaweightspresentedare
calculatedby us and given to one part in approximately

solid Earth. The data include mineral name, ideal formula,

20,000 for purephasesand onepart in 1000 for impure

idealformulaweight,crystalsystem,spacegroup,structure
type,Z (numberof formulaunitspercell),unitcelledges,a,

naturalsamples.

Using mostly primary referenceson crystal structure

determinations
of theseminerals,we havecompiledbasic
crystallographic property information for some 300
minerals. Thesedataare presentedin Table 1. The minerals
were selectedto representthe most abundantminerals

J. R. Smyth,and T. C. McCormick,Departmentof Geological

Sciences,University of Colorado,Boulder,CO 80309-0250
Mineral Physicsand Crysta!!ography
A Handbook of Physical Constants
AGU

Reference

Shelf 2

Copyright1995by theAmericanGeophysical
Union.

CRYSTALLOGRAPHIC

DATA

FOR MINERALS

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Acknowledgements.
The authorsthankStephenJ. Guggenheim
(University of Illinois) and two anonymousreviewersfor con-

AND

McCORMICK

11

NationalScienceFoundation
GrantEAR 91-05391andU.S. Dept.
of EnergyOffice of BasicEnergySciences.

structivecriticismof themanuscript.
This workwassupported
by
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refinement

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in sub-

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1158-1167, 1977.

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221. Taylor, L. A., Smythite,Fe3+xS4,and

associated

minerals

from

the

Silverfields Mine, Cobalt, Ontario, Am.

Mineral., 55, 1650-1658, 1970.

222. Taylor, M., and R. C. Ewing, The

crystal structures of the ThSiO4
polymorphs:
huttonireandthorire,Acta
Cryst.,B34, 1074-1079, 1978.
223. Thompson, R. M., The telluride
minerals

and

their

occurrence

in

Canada, Am. Mineral., 34, 342-383,

1949.

tallstrukturund magnetischenstruktur
des ferberits FeWO4, Z. Krist., 124,
192- 219 1967.

226. Vezzalini, G. and R. Oberti, The

crystalchemistryof gismondines:
the
non-existenceof K-rich gismondines,
Bulletin de Mineralogie, 107, 805812, 1984.

227. Vogel, R. E. and C. P. Kempter,

Mathematical technique for the
precision determination of lattice
constants, U. S. Atomic Energy
Commission, LA-2317, 30, 1959.

228. Wainwright,J. E., and J. Starkey,A

refinementof the crystal structureof
anorthite, Z. Krist., 133, 75-84, 1971.
229. Wechsler, B.A. and C.T. Prewitt,

Crystal structureof ilmenite at high

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Mineral., 69, 176-185, 1985.
230. Wechsler, B. A., C. T. Prewitt, and J. J.

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Planet. Sci. Lett., 29, 91-103 1976.
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232.Willis,
B.T.M.,Anomalous
behavi
ur
of the neutron reflexions of fluorite,

219. Tagai,Y., H. Ried, W. Joswig,andM.

Korekawa,Kristallographische
untersuchungeines petalits mittels neutronenbeugungund transmissionselektronmikxoskopie,
Z. Kristal., 160,

axinite

225. Olkti,D., Untersuchungen

zur Kris-

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expansionandhightemperature
crystal
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Am. Mineral., 64,573-586, 1979.
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Am. Mineral., 64,409-423,

1979.

235. Wyckoff, R. W. G. CrystalStructures,

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Crystal structures of spinel polymorphsof Fe2SiO4 and Ni2SiO4,Am.
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SMYTH

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AND McCORMICK

17

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ThermodynamicPropertiesof Minerals

AlexandraNavrotsky

1. INTRODUCTION

(}V/}P)T.
Forsolids,
Cp - Cvisontheorder
ofa few
percent of Cv, and increaseswith temperature. The

Thermochemicalpropertiesof mineralscanbe usedto

calculate the thermodynamic stability of phases as
functionsof temperature,pressure,componentfugacity,
and bulk composition. A number of compendia of

vibrationalheatcapacitycanbe calculated
usingstatistical
mechanicsfrom the densityof states,whichin turncanbe
modeledat variousdegreesof approximation[20]. The
magneticcontributions,importantfor transitionmetals,
play a major role in iron-bearing minerals [32].
Electronictransitionsare usuallyunimportantin silicates
but may become significant in iron oxides and iron
silicatesat high T and P. Order-disorder
is an important
complicationin framework silicates(A1-Si disorderon

thermochemical data [4, 5, 7, 9, 10, 13, 15, 16, 18, 19, 31]

containdetaileddata. The purposeof this summaryis to

give, in shortform, usefuldata for anhydrousphasesof
geophysicalimportance. The valuesselectedare, in the
author'sopinion,reliable,but no attempthasbeenmadeto
systematicallyselectvaluesmost consistentwith a large
set of experimental observations. When possible,
estimatesof uncertaintyare given.
2. HEAT

tetrahedral
sites),
in spineIs
(M2+-M
3+ disorder
over
octahedral and tetrahedral sites) and in olivines,

CAPACITIES

The isobaricheatcapacity,
Cp, is the temperature
derivative
of theenthalpy,
Cp= (dH/}T)p.
Forsolids,
Cp
is virtually independentof pressurebut a strongfunction

pyroxenes,amphiboles,and micas(cationdisorderover
severalinequivalentoctahedralsites). Thesefactorsmust
be consideredfor specificmineralsbut detaileddiscussion
is beyondthe scopeof thisreview.

AsT--> 0 K, Cp --> 0 (seeFig.1). At intermediate

temperatures,Cp increases
sharply. The Debye
temperatureis typically 800-1200 K for oxides and
silicates. At high temperature,the harmoniccontribution
toC v approaches
the DulongandPetit limit of 3nR (R the

of temperature
(seeFig. 1). Contributions
to Cp arise
from latticevibrations,andfrom magnetic,electronic,and
positional order-disorder. The relation between heat

capacity
at constant
pressure,
Cp, andthatat constant

volume,
Cv = (}E/}T)v,
isgiven
byCp- Cv=TVo2/B,
where T = absolutetemperature,V = molar volume, o =

thermalexpansivity
= (l/V) (}V/}T)pand 13=
compressibility = inverse bulk modulus = -(l/V)

gasconstant,
n thenumber
ofatoms
performula
unit).Cp
is then 5-10% larger than 3nR and varies slowly and
roughlylinearlywith temperature
(seeFig. 1).
Table 1 lists heat capacities for some common
minerals. The values at high temperature may be
compared with the 3nR limit as follows: Mg2SiO4

(forsterite)
3nR= 175J/K.mol,Cp at 1500K = 188
J/K-mol;
MgAI204(spinel)
3nR= 188J/Komol,
Cpat
1500 K = 191 J/Komol. Thus the Dulong and Petit limit
givesa usefulfirst orderestimateof the hightemperature
heat capacityof a solid, namely 3R per gram atom,
irrespective
of structural
detail.
The entropy,

A. Navrotsky,PrincetonUniversity,Departmentof Geological
and GeophysicalSciencesand PrincetonMaterials Institute,
Guyot Hall, Princeton,NJ 08544

Mineral Physicsand Crysta!lography

A Handbookof PhysicalConstants
AGU

Reference

ST=IoT(Cp
/ T)dT

Shelf 2

Copyright1995 by the AmericanGeophysical

Union.

18

(1)

NAVROTSKY

T(K)
0

400

19

Any "zero point" entropy, arising from "frozen in"

800

1200

configurational disorder, must be added to this

calorimetricentropy. Emropiesof somecommonphases

1600

200

are also shown in Table 1.

160

Thesharpdependence
of Cp on T at intermediate
temperature
makesit difficultto fit Cp by algebraic

120

equationswhichextrapolateproperlyto high temperature

and suchempiricalequationsalmostnever showproper
low temperature behavior. At 298 - 1500 K, an

express.
ionof theMaier-Kelley
form,[31]
i

Cp=A+BT+CT-0-5
+DT-2

(2)

givesa reasonablefit but mustbe extrapolatedwith care.

A form whichensuresproperhigh temperature
behavior,
recommendedby Fei and Saxena[8] is

,40

Cp=3nR[
1+kI T-1+k2T'2+k3T-3]+

lOO

(3)

A + BT+ Cp (disordering)

200

'r(K)

Because
differentauthorsfit Cp datato a varietyof

Fig. 1. Heat capacityof Mg2SiO4 (forsterire)from 0 to

equations and over different temperature ranges, a

tabulationof coefficientsis not givenherebut the reader

1800 K, data from [31].

is referred to Robie et al. [31], Holland and Powell [ 15-

Table 1. HeatCapacities
andEntropies
of Minerals(J/(K-mol))
298 K

Cp

1000K

1500 K
O

S
,

MgO (periclase)
A1203 (corundum)
"FeO" (wustite)
Fe203 (hematite)
Fe30 4 (magnetite)
TiO2 (ruffle)
FeTiO3 (ilmenite)
Fe2TIO4 (titanomagnetite)
MgA1204 (spinel)
Mg 2SIO4 (forsterire)
MgSiO3 (enstatite)
NaAISi308 (low albite)
KAISi 308 (microcline)
Mg 3AI2Si3012 (pyrope)
Ca3AI 2Si3012 (grossular)
CaSiO3 (wollastonite)
CaSiO3 (pseudowollastonite)
CaMgSi206 (diopside)
Mg 2AI2Si5018 (cordierite)
CaCO3 (calcite)
MgCO 3 (magnesite)
CaMg(CO3)2 (dolomite)
Dala from [5,311.

37.8
79.0

26.9
50.9

51.2
124.9

82.2
180.2

53.1
132.1

103.5
232.3

48.12
103.9

57.6
87.4

55.8
148.5

121.4
252.7

63.6
144.6

145.3
310.5

150.8

146.1

206.0

390.2

201.0

471.5

55.1

50.3

73.2

129.2

79.5

160.1

99.5

105.9

133.7

249.3

155.0

307.4
463.4

142.3

168.9

197.5

375.1

243.2

115.9

80.6

178.3

264.5

191.3

339.5

117.9

95.2

175.3

277.2

187.7

350.8

127.6

243.5

269.1

82.1

67.9

121.3

192.9

205.1

207.4

312.3

530.1

202.4

214.2

310.3

533.8

325.5

222.0

474.0

730.8

330.1

255.5

491.7

773.0

85.3

82.0

123.4

213.4

86.5

87.5

122.3

217.6

132.3

166.5

143.0

248.9

401.7

269.7

506.3

452.3

407.2

698.3

1126.6

753.6

1420.9

220.2

83.5

91.7

124.5

76.1

65.1

131.5

190.5

157.5

155.2

253.1

406.0

20

THERMODYNAMICS

600

I i . i . i

IJq

500

400-

liquid
Tg

300

.'

200

la

20O

'""''
100'

0
300

.-',,,
.- 600 9{0crystal
12'00
15'00

400

Temperature

1800

800

12'00 16'00

Temperature

(K)

(K)

Fig. 2. Enthalpyandheatcapacityin CaMgSi206,a glass-forming

system,
datafrom[21].

Table

2.

HeatCapacities
of Glasses
andLiquidsandGlassTransition
Temperatures
,

Composition

SiO2

Cpglass
298K

Cpglass
(atTg)

J/mol-K

J/mol-K

38[311

74[28,291

Tg
(K)

Cpliquid
J/mol-K

1607128,291

81128,291

CaMgSi206

170a

256[28,291

1005[28,29]

335128,29]

NaAISi308

2101311

321128,291

1096128,291

347128,291

KAISi308

209[31!

316128,291

1221128,291 338128,291

CaAI2Si20
8

2111311

334128,29]

1160128,29!

Mg2SIO4

424128,29]
268/11,12l

Na2Si205

217128,291

703128,291

263128,29]

K2Si205

226128,29!

770128,29!

259128,29!

CaSiO
3

871301

131128,29,301

1065

167128,29]

Mg3AI2Si3012

330a

516128,291

1020

679128,29]

Mg2A14Si5018

460a

731128,291

1118

928128,29]

aEstimated
from highertemperature
dataandfrontcomparison
withc7stalline
phases.

2000

NAVROTSKY

16], Berman [5], JANAF [18], and Fei et al. [9] for such

where i is takenover the oxide componentsof the glassor

liquid [22, 33]. The partial molar heat capacitiesof the

equations.
In glass-formingsystems,seeFig. 2, the heatcapacity
of the glassfrom room temperatureto the glasstransition
is not very different from that of the crystallinephase.

oxide
components
in glasses
andmelts,
Cp,.,aregiven
in
Table 3.

ForCaMgSi206Cp, glass
= 170J/moloK
at298K, 256
J/moloK
at 1000K; Cp,crystal
= 167J/moloK
at298K,
249 J/moloKat 1000K [21]. At Tg, the viscosity

3. MOLAR

VOLUME,

ENTROPY,

ENTHALPY

Table 4 lists enthalpiesand entropiesof formationof

selected

minerals

from

the elements

and the oxides at

severaltemperatures.Theserefer to the reaction

aA + bB + cC + n/2 02 = A aBbCcOn

(5)

and

aAO1+ bBOm + cCOn = A aBbccOn

(6)

respectively,where A, B, C are different elements(e.g.

Ca, AI, Si), O is oxygen,andreferencestatesare the most
stableform of the elementsor oxidesat the temperaturein
question. The free energyof formationis then givenby

(4)

Table 3. PartialMolar HeatCapacitiesof OxideComponents

in Glassesand Melts (J/K.mol)

Glass
[291
298 K

OF

FORMATION

decreases,and the volume and heat capacity increase,

reflectingthe onsetof configurational
rearrangements
in
the liquid [27]. The heat capacityof the liquid is
generally larger than that of the glass(see Table 2) and,
except for cases with strongstructuralrearrangements
(suchas coordinationnumberchanges),heatcapacitiesof
liquidsdependonly weakly on temperature.
For multicomponent glasses and liquids with
compositions relevant to magmatic processes,heat
capacitiescan, to a useful approximation,be given as a
sum of terms dependingon the mole fractionsof oxide
components, i.e., partial molar heat capacities are
relativelyindependentof composition.Then

Cp=X
i 2p
i

21

Liquid122,2833!
400 K

1000 K

1500 K

SiO2

44.04

52.39

70.56

82.6

TiO2

44.92

58.76

84.40

109.2

A1203

79.22

96.24

124.98

170.3

Fe203

94.89

115.74

143.65

240.9

FeO

43.23

47.17

70.28

78.8

35.09

42.89

56.60

94.2

CaO

43.00

45.67

57.66

89.8

Na20

74.63

79.09

96.64

97.6

K20

75.20

79.43

84.22

98.5

B203

62.81

77.67

120.96

H20

46.45

62.04

78.43

22

THERMODYNAMICS

ii
i

i I

ii

i
i

NAVROTSKY

AG = AH - TAS. Fig. 3 showstheequilibriumoxygen

fugacityfor a seriesof oxidationreactions

----_.,.
(i) .....---"'"'"
2)

A+ 02=AO

(7)

C;u ..-."""" ........

......
......,.-'"'"

_.., 3)

-:too
..............
-,-,
.,.o.'.
..........
::5;
.........
s_.....-t16)
','.s'"" '"

and

23

...C."""

. .....

. ..........

.,,.,,

AOn+- 02=AOm+
n

(8)

-40O

as a function of temperature. These curves (see Fig. 3)

are the basisfor various"buffers"usedin geochemistry,

e.g.QFM (quartz-fayalite-magnetite),
NNO (nickel-nickel

state transitions) in either the reactants (elements) or

products(oxides).

The enthalpiesof formation of ternaryoxides from

binary oxides are generally in the range +10 to -250
kJ/mol and become more exothermic with greater
difference in "basicity" (or ionic potential =
charge/radius)of the components.Thus for AI2SiO5,

(andalusite)
AI-I,ox,
298=-1.1 kJ/mol;for MgSiO3
(enstatite)
AI-I,o,298
= -35.6kJ/mol,andfor CaSiO3
(wollastonite)
AI-f,
ox,
298= -89.4kJ/mol.Entropies
of
formationof ternaryoxidesfrom binarycomponentsare
generallysmall in magnitude(-10 to +10 J/moloK)unless
majororder-disorder
occurs.
4. ENTHALPY
AND
TRANSFORMATION

ENTROPY
OF PHASE
AND MELTING

AG,
=0=AH,
- TAS,

(9)

At constanttemperature,a thermodynamically
reversible
phasetransitionoccurs with increasingpressureif the
highpressurephaseis denserthanthelow pressure
phase

.O

:..-'

,-'
O?-

-looo

""
-. ......
%!-%'"'"_)4.o,
o_-__

...........

,_., _o..

o.o.ooo---"
..,,oO

(3) 2Co02' 2CoO

........
_

(4)
2H2
* 02'2H20
(S) 6FeO * 02- 2Fe304

-1200 ".C,o

(6)
(7)

2C0 - 02. ' 2C02

:3/2Fe - 02-1/2Fe:04

(:e) 2Fe
9)

300

8(0

,3)0

02 - FeO

C + 02

- C02

,8;0

Temperature (K)

Fig. 3. Gibbs free energy for oxidation-reduction

equilibria,permoleof 02, datafrom[4, 18,31].

and the following balance of enthalpy, entropy, and

volume terms is reached

AG(P,T) = 0 = AIT- TAS+

At
constant
(atmospheric)
pressure, a
thermodynamically
reversiblefirst orderphasetransition
occurswith increasingtemperatureif both the enthalpy
andentropyof the hightemperature
polymorphare higher
than thoseof the low temperaturepolymorphand, at the
transformation
temperature

..........'::.,.,:::_

..............................

.............
ro' .............

oxide) and IW (iron-wurstite).

The free energies of formation from the elements

becomeless negativewith increasingtemperature,and
more reduced species are generally favored as
temperatureincreases. This reflectsthe large negative
entropyof incorporationof oxygengasin the crystalline
phase.Thusthe equilibriumoxygenfugacityfor a given
oxidation-reduction
equilibriumincreases
with increasing
temperature. Changesin slope (kinks) in the curvesin
Fig. 3 reflectphasechanges(melting,vaporization,solid-

flP AV(P,T)dP

(1o)

atm

An equilibriumphaseboundaryhasits slopedefined
by the Clausius- Clapeyronequation

(dP/dT)equi
I = AS/AV

(11)

Thus the phaseboundaryis a straightline if AS and

AV are independent(or only weakly dependent)of P and
T, as is a reasonablefirst approximationfor solid-solid
transitionsover moderateP-T intervals at high T. A
negativeP-T slopeimpliesthatAS and AV haveopposite'
signs. Melting curvestend to showdecreasing(dT/dP)
with increasingpressurebecausesilicateliquidsare often

24

THERMODYNAMICS

Table 5. Enthalpy,EntropyandVolumeChangesfor High PressurePhaseTransitions

AH (kJ/mol)

AS(J/mol
K)

AV(cm3/mol)

Mg2SIO4 (a =

30.0 + 2.8a I21

-7.7 + 1.9a [21

_3.16a [21

Mg2SIO4( ot= hi)

39.1+ 2.6121

-15.0+ 2.4[2]

-4.14[2]

Fe2SIO4(or= [)

9.6+ 1.3121

-10.9+ 0.8[2]

-3.20[21

Fe2SiO4(or= h,)

3.8+ 2.4121

-14.0+ 1.9121

-4.24[21

MgSiO3(px= il)

59.1+ 4.3131

-15.5+ 2.0[31

-4.94131

MgSiO
3 (px= gt)

35.7+ 3.0191

-2.0+ 0.5[9!

-2.8319!

MgSiO3(il = pv)

51.1+ 6.6//7/

+5+ 4[/71

-1.89/17/

Mg2SiO40/)=MgSiO3(pv)+MgO

96.8 + 5.81/71

+4 + 41171

-3.791171

SiO2(q = co)

2.7+ 0.5l/1

-5.0+ 0.4l/1

-2.05lll

SiO2 (co= st)

49.0+ 1.7lll

-4.2+ 1.7III

-6.63[11

a zll-IandASarevalues
at1 attonear1000K,AVisAV298,for
alllistings
intable,oc= olivine,
fi = spinelloid
orwadsleyite,
y=
spinel,px = pyroxene,il = ilmenite,gt = garnet,pv = perovskite,q = quartz,co = coesite,st = stishovite

Table6. Thermodynamic
Parameters
for OtherPhaseTransitions
Transition

AH o

(kJ/mol)
SiO2 ( a-quartz= [3-quartz)
SiO2 ( [3-quartz= cristobalite)

0.47a,b
2.94[5]
5.6[23]
5.0[311
3.88[5!
-8.13[5!
-0.37[5]
1.59151
-0.17[251

2
(mtile = quartz)
CaSiO3 (wollastonite= pseudowollastonite)
AI 2SiO 5 (andalusite= sillimanite)
AI 2SiO5 (sillimanite= kyanite)
MgSiO3 (ortho= clino)
MgSiO3 (ortho= proto)
FeSiO3 (ortho= clino)
0.25[251
MnSiO3 (rhodonite= pyroxmangite)
MnSiO3 (pyroxmangite= pyroxene)
13.5/311
NaAISi30 8 (low albite= highalbite)

14.0

KAISi 309 (microcline= sanidine)

11.1[5]

- 1.03

0.88125!

a Treatedasthougit
allfirstorder,though
a strong
higher
ordercomponent.

bAHandASarevalues
near
1000
K,AVisAV298
foralllistings
intable.

AS o

(J/K-mol)
0.35
1.93
4.0
3.6
4.50
-13.5
O.16
1.27
-0.03

AV o

(cm3/mol)
0.101
0.318
11.51
0.12
-0.164
-0.571
-0.002
0.109
-0.06

-0.39

-0.39

-2.66

-0.3

0.40

15.0

0.40

0.027

Table 7. Enthalpiesof Vitrification andFusion

'Compound

Vitrification

Fusion

All (kJ/mol)

Melting Point

All(T)

(kJ/mol)

T(K)
MgO
CaO

107.5+ 5.4[28]
9.4 + 1.01281
8.9 + 1.01281
31.3 + 0.21281

2323

A1203 SiO2 (quartz)

SiO2 (cristabalite)
"FeO" (wustite)
Mg2SiO4 (forsterite)
MgSiO3 (enstatite)
Fe2SIO4 (fayatite)

1700b
1999
1652

42 + 11281

2163

114+

1834a

77 + 5 [281
89 + 10[28]
62+ 41281
57+ 31281
138+ 2128]
63 + 201281
56 + 4128]
134+ 41281
20+ 4[ 28]
243 + 81281
346+ 101281

1490

25.5+ 0.41261

CaSiO3 (wollastonite)
CaSiO3 (pseudowollastonite)
CaMgSi206 (diopside)
NaAISi308 (highalbite)
KAISi308 (sanidine)
CaAI2Si208 (anorthite)
I(2SiO 3
Mg 3AI 2Si3012 (pyrope)
Mg2AI4Si.5018(cordierite)

1770b
1817

85.8+ 0.8[241
51.8+ 08[241

1665
1373
1473 a

77.8+ 0.8[241
9 + 1128!

1830
1249
1500 a

209+ 2161

1740

20 a

aEstimated
roetastable
congruem
melting.
bMelting
ofroetastable
phase.
I

ROCKSALT

PEROVSKITE

+ RUTILE

(OR a-PbO OR FLUORITE)

18
NTO3,22

Fe2SO4.23

MgTO3
22

C oaSO4.17

COT,O3.22
LITHIUMNIOBATE

N2SO4.15

'--'"'/-M

ZnTO3.22
CoGeO3.22

N2GeO4.20

ILMENITE

14

GARNET

CaGeO3.9
03

BaGeO3.9

NTERMEDIATE

z
uJ

STRUCTURES

o IsPINEL
+RUTILE
z

MgSO3,17ZnSO3,12

-[

uJ

FeSO3,8 MgGeO3.3

f-)

CoSO3.9

MgSO3.16
MnSO3.12
PYROXENE

FeSO3,1

MnSO3.7

COS,O3,2

PYROXENOID

OLlVINE
+QUARTZ
I
Fig. 4. Schematic diagram showing phase transitions
observedin analoguesystemsof silicates,germanates,
andtimnates. Numbersrefer to pressurein GPa.

- Fe
600

'-Ni2S104
1000

1400

T(K)

Fig. 5. Phase relations in M2SiO4 systemsat high

pressureand temperatures[25].

26

THERMODYNAMICS

o
o

o
o
o

(edg)

anssed

(ed9)

anssad

NAVROTSKY

substantiallymore compressiblethan the corresponding

crystals.For reactionsinvolvingvolatiles(e.g. H20 and
OD2), phaseboundariesare stronglycurvedin P-T space
becausethe volume of the volatile (gas or fluid) phase
dependsvery strongly on P and T. The section by
Presnallgivesexamplesof suchbehavior.
Table 5 listsentropy,enthalpy,and volumechangefor
high pressuretransitionsof geophysicalsignificance.
Table 6 listsparametersfor someotherphasetransitions.
Table 7 presentsenthalpiesof vitrification (crystal
glass, not an equilibrium process) and enthalpies,
emropies, and volumes of fusion at the equilibrium
meltingpointat oneatmosphere.
A numberof silicates,germanates,and othermaterials
showphasetransitionsamongpyroxene,garnet,ilmenite,
perovskite,andrelatedstructures,
as shownschematically
in Fig. 4. Phaserelationsamongolivine,spinel,andbeta
phasein severalsilicatesare shownin Fig. 5. Relationsat
high P and T for the systemFeO-MgO-SiO2 at mantle
pressures
are shownin Figs. 5-7. The wealthof phasesin
theH 20 phasediagramis shownin Fig. 8.

VIII

Vl

200

LIQUID
-

300

27

400

TEMPERATURE (K)

Fig. 8. Equilibriumphaserelationsin H20. Compiled

from various sources [ 14].

Acknowledgments. I thank RebeccaLange and Elena

Petrovicova
for helpwith tablesandfigures.

REFERENCES

H20-CO 2, J. Petrol., 29, 445-522,

Akaogi, M. and A. Navrotsky,The

quartz-coesite-stishovite
transformations:
measurements

New calorimetric
and calculation

6.

of

phasediagrams,Phys.Earth Planet.
Inter.,36,

measurenents,

Carpenter,M. A., A. Putnis , A.

Navrotsky, and J. Desmond C.

Cosmochim. Acta, 47, 899-906,

1983.

7.

Fei,

Y.

and S. K.

Saxena, A

calculation,
and geophysical
application,J. Geophys.Res., 94,

equilibriain thesystemFe-Mg-Si-O

15,671-15,686, 1989.
Ashida, T., S. Kume, E. Ito, and A.

Phys.Chem.Miner., 13, 311-324,

Navrotsky,MgSiO3 ihnenite: heat

capacity, thermal expansivity,and
enthalpy of transformation,Phys.
Chem. Miner., 16, 239-245, 1988.
Barin,
I.
and O. Knacke,

Thermochemical properties of
inorganic substances, pp. 921,
Springer-Verlag,New York, 1973.
Berman,R. G., Internally-consistent
thermodynamicdata for mineralsin
the systemNa 20-K 20-CaO-MgOFeO-Fe2O3-A1203-SiO2-TIO2-

Mineral. Petrol., 71,323-342,

1986.

Fei, Y.

and S. K. Saxena, An

12.

equationfor the heat capacityof

Fei, Y.,

S. K. Saxena, and A.

Mineral., 17, 467-499, 1987.

13.

Navrotsky, Internally consistent

thermodynamic
data
and

equilibrium phase relations for

compoundsin the system MgOSiO2 at high pressureand high
temperature,
J. Geophys.Res.,95,
6915-6928, 1990.

1980.

Ghiorso, M. S., I. S. E. Carmichael,

Modeling magnatic systems:

petrologic applications, Rev.

solids, Geochim. Cosmochim. Acta,

51, 251-254, 1987.

9.

Ghiorso, M. S., I. S. E. Carnichael,

A regular solutionmodel for metaluminous

silicate
liquids:
applications to geothermometry,
immiscibility, and the source
regionsof basicmagmas,Contrib.

at high pressureand temperature,

8.

Mao, and B. O.

1991.
11.

thermochemicaldata basefor phase

thermochemical

Fei, Y., H.-K.

Mysen,Experinentaldetermination
of element partitioning and
calculationof phaserelationsin the
MgO-FeO-SiO2 system at high
pressureand high temperature,J.
Geophys. Res., 96, 2157-2169,

McConnell,
Enthalpy effects
associatedwith A1/Si ordering in
anhydrousMg-cordierite,Geochim.

124-134, 1984.

Akaogi, M., E. Ito, and A.

Navrotsky,Olivine-modifiedspinelspinel transitions in the system
Mg 2SiO4-Fe2SIO4: Calorimetric

10.

1988.

Helgeson,H. C., J. Delany, H. W.

Nesbitt, and D. K. Bird, Summary
and critique of the thermodynamic
propertiesof rock-formingminerals,
Ant. J. Sci., 278A, 1-229, 1978.

14.

Hemley, R. J., L. C. Chen, and H.

K.

Mao,

New

transformations

betweencrystallineand amorphous

28

15.

THERMODYNAMICS

ice, Nature, 338, 638-640, 1989.

Holland, T. J. B., R. Powell, An

internallyconsistent
thermodynamic

measurement of heat capacity

during incongruent melting of
diopside,Arner. Mineral., 76, 904-

dataset

912,1991.

with

uncertainties

and

correlations: 2. Data and results,J.

22.

Metamorphic Geol., 3, 343-370,

1985.
16.

Holland, T. J. B., R. Powell, An

enlarged and updated internally

23.

the systemK20-Na20-CaO-MgO-

Navrotsky, A., Enthalpies of

transformation
among
the
tetragonal, hexagonal, and glassy
modificationsof GeO2, J. Inorg.

MnO-FeO-Fe2O3-A1203-TiO2-

Nucl. Chern. 33, 1119-1124, 1971.

with uncertainties and correlations:

SIO2-C-H2-O2,J. Metamorphic

24.

Geol., 8, 89-124, 1990.

17.

Ito, E., M. Akaogi,L. Topor, andA.

Navrotsky, Negative pressuretemperature slopes for reactions
forming MgSiO3 perovskitefrom
calorimetry, Science, 249, 12751278, 1990.

18.

JANAF,Thermochemical
Tables, 25.
Third Ed., edited by American
Chemical Society and American

19.

20.

Institute
ofPhysics,
1986.

Kelley, K. K., High-temperature

heat content, heat capacity, and
entropy data for the elementsand
inorganic compounds,U.S. Bur.
Mines Bull., 584, 232 pp., 1960.
Kieffer, S. W., Heat capacity and
entropy: systematic relation to
lattice vibrations, Rev. Mineral., 14,

65-126,1985.

21.

Lange,R. A., J. J. DeYoreo,andA.

Navrotsky, Scanningcalorimetric

Navrotsky,A., R. Hon, D. F. Weill,

and D. J. Henry, Thermochemistry
of glassesandliquidsin the systems
CaMgSi2 O6-CaAI2Si208 NaAISi308, SiO2 -CaAI2Si208 NaAISi308 andSiO2- A1203Na20, Geochirn.Cosrnochim.
Acta,

Richet, P., and Y. Bottinga,

Thermochemical properties of
silicate glasses and liquids: A
review, Rev. Geophys., 24, 1-25,

29.

Richet, P., Heat capacityof silicate

glasses,Chern.Geol., 62, 111-124,

30.

Richet, P., R. A. Robie, and B. S.

1986.

1987.

Hemingway, Thermodynamic
properties
of wollastonite,
pseudowollastonite and CaSiO3
glassandliquid,Europ.J. Mineral.,
3, 475-485, 1991.
31.

Robie,R. A., B. S. Hemingway,and

J. R. Fisher, Thermodynamic
propertiesof mineralsand related
substances at 298.15

K and 1 bar

44, 1409-1423, 1980.

(105 pascals)and at higher

Navrotsky, A., High pressure

transitionsin silicates,Prog. Solid

temperatures,U.S. Geol. Surv.

Bull., 1452, 456 pp., 1978.

St.

26.

28.

Lange, R. A. and A. Navrotsky,

Heat capacitiesof Fe203-bearing
silicate liquids, Contrib. Mineral.
Petrol., 110, 311-320, 1992.

consistentthermodynamicdataset

melts, Geochirn.Cosmochirn.Acta.,
48, 471-483, 1984.

Chern.,

17,

53-86,

1987.

32.

Oestrike,

and

P.

ManJar,

Calorimetry of silicate melts at

1773K: Measurementof enthalpies
of fusion and of mixing in the
systems diopside-anorthite-albite
and anorthite-forsterite, Contrib.
Mineral. Petrol., 101, 122-130,
1989.

27. Richet,

P., Viscosity
and
configurationalentropy of silicate

Robie, R. A., C. B. Finch, and B. S.

Hemingway, Heat capacity and

entropy of fayalite (Fe2SiO4)
between5.1 and383 K; comparison
of calorimetric and equilibrium
values for the QFM buffer reactor,

Navrotsky, A., D. Ziegler, R.

33.

Arner. Mineral, 67, 463-469, 1982.

Stebbins, J. F., I. S. E. Carmichael,

and L. K. Moret, Heat capacities

andentropiesof silicateliquidsand
glasses,Contrib. Mineral. Petrol.,
86, 131-148, 1984.

Thermal Expansion

Yingwei Fei

SinceSkinner[75] compiledthethermalexpansiondata
of substances of geological interest, many new

V(T)
=-[1+2.k(1-4kE/Q0)l/2
]

(l)

measurementson oxides, carbonates, and silicates have

where E is the energy of the lattice vibrations. The

constantQo is related to volume (Vo) and bulk modulus
(Ko)at zeroKelvin, andtheGriineisenparameter(y) by Qo
= KoVdy. The constantk is obtained by fitting to the
experimentaldata. In the Debye model of solids with a
characteristictemperature, 0o, the energy E can be
calculatedby

been made by x-ray diffraction, dilatometry, and

interferometry.With the development
of high-temperature
x-ray diffraction techniquesin the seventies,thermal
parameters of many rock-forming minerals were
measured [e.g., 14, 22, 28, 45, 68, 77, 97, 99].
Considerable thermal expansion data for important
mantle-related minerals such as periclase, stishovite,
olivine, wadsleyite,silicate spinel, silicate ilmenite and
silicate perovskitewere collectedby x-ray diffraction
methods [e.g., 4, 39, 42, 71] and by dilatometric and
interferometrictechniques[e.g.,54, 86, 88, 89]. While the
data set for 1-bar thermal expansionis expanding,many
efforts have recently been made to obtain the pressure
effect on thermal expansivity[e.g.,9, 19, 21, 36, 51]. In
studyof liquid density,a systematic
approachis takento
obtaindensityand its temperaturedependence
of natural
liquids[e.g., 11, 12, 16, 44, 46, 48].
The thermal expansioncoefficient a, defined by a =
1/V(OV/OT),,is usedto expressthe volume changeof a
substancedue to a temperaturechange.In a microscopic
sense,thethermalexpansionis causedby the anharmonic
natureof the vibrationsin a potential-wellmodel [103].
The Griineisentheory of thermal expansionleads to a
usefulrelationbetweenvolumeandtemperature
[90],

E=9nRT
I v/r
x3 dx

(2)

where n and R are the number of atoms in the chemical

formulaandthegasconstant,respectively.
In this model, four parameters,0o, Qo,/, and Vo, are
required to describethe thermal expansionof a solid.
When the thermalexpansionis accuratelymeasuredover
a wide temperaturerange,the four parametersmay be
uniquelydefinedby fitting the experimentaldata to the
model.Furthermore,measurements
on heatcapacityand
bulk moduluscan provide additionalconstraintson the
model.A simultaneous
evaluationof thermalexpansion,
bulk modulus,andheatcapacitythrougha self-consistent
model suchas the Debye model [e.g., 81] is, therefore,
recommended,especiallywhen extrapolationof data is
involved.

Y. Fci, Carnegie Institutionof Washington,Geophysical

Laboratory,5251 BroadBranchRoad,NW, Washington,DC
20015-1305

In many casesthe above model cannotbe uniquely

defined,eitherbecausetheaccuracy
of thermalexpansion
measurementis not sufficiently high or because the

MineralPhysicsand Crysta!!ography

temperature range of measurementis limited. For the

A Handbookof PhysicalConstants

purpose of fitting experimental data over a specific

temperature range, a polynomial expression for the

AGU

Reference

Shelf 2

Copyright1995 by the AmericanGeophysicalUnion.

29

30

THERMAL

EXPANSION

thermalexpansioncoefficientmay be used

a(T) = ao+ al T + a2T'2

93] are alsorecommended

asdatasources.
The pressure
effecton thethermalexpansion
coefficient
may be described
by the Anderson-Griineisen
parameter

(3)

where ao, a,, and a2 (< O) are constantsdeterminedby

fitting the experimental data. The measuredvolume
aboveroom temperaturecanbe well reproduced
by

a(r,r)/a(r)=[v(r,r)/v(r)]ar

V(T) = Vr,exp

The thermal expansion coefficient as a function of

pressurecanbe calculatedfrom equation(7) andthe third
orderBirch-Murnaghanequationof state,

a(T)d

(4)

where Vrr is the volume at reference temperature(T,),

usually room temperature.When the thermalexpansion
coefficient is independent of temperature over the
measuredtemperaturerange,

V(T) = Vr, exp[ao(T- Tr)]

(7)

(8)
and

(5)
2LV(P,T)

The commonlyusedmean thermalexpansioncoefficient

Ca-) can be related to equation (5) by truncating the
exponentialseriesof exp[ao(T- T,)] at its secondorder,

whereKr andKr' are the bulk modulusand its pressure

derivative,respectively.Table 2 liststhe valuesof
and 6r for somemantle-relatedminerals.
The liquid molarvolume of a multioxideliquid can be
calculatedby

i.e.,

V(T) = Vrr [1 + (T- Tr)]

(6)

Table 1 lists thermalexpansioncoefficientsof solids.

The coefficientsfor most substanceswere obtainedby
fitting the experimentaldatato equations(3) and(4). The
mean coefficient ca-), listed in the literature, can be
convertedto a0, accordingto equations(5) and(6).
Thermal expansioncoefficientsof elementsandhalides
(e.g., NaC1, KCI, LiF, and KBr) are not includedin this
compilation because the data are available in the
American Institute of PhysicsHandbook [41]. Volumes
12 and 13 of ThermophysicalPropertiesof Matter [92,

Viiq(T)
-- Xiii,n[1
+ (T- Tr)] +Vcx

(lO)

where Xi andi are the mole fraction and mean thermal

expansioncoefficientof oxide componenti, respectively.
Vi,rr is the partial molar volume of componenti in the
liquid at a referencetemperature,T,, and V' is the excess
volume term. Recent measurements on density and
thermal expansion coefficient of silicate liquid are
summarized

in Tables 3a-3d.

TABLE 1. ThermalExpansionCoefficientsof Solids

a(T) = ao+ al T + a2T'2

Names

T range

0.o(10
'6)

ao(104)

a! (10'8)

a2

ref.

[2]
[2]
[2]

Oxides

(I.AI2 O3, corundum

293-2298

7.3

0.0758

0.1191

-0.0603

293-2298

8.3

0.0773

0.1743

0.0000

293-2298

23.0

0.2276

0.4198

-0.0897

FEI

TABLE 1. (continued)
Names

BeAI204, chrysoberyl

ao(10'6)

T range

ao(10-)

a1(10's)

a2

298-963

6.6

0.0250

1.3569

0.0000

298-963

8.7

0.0490

1.2777

0.0000
0.0000

298-963

7.6

0.0540

0.7315

298-963

23.8

0.1320

3.5227

0.0000

BeO

292-1272

17.8

0.1820

1.3933

-0.4122

CaO

293-2400

33.5

0.3032

1.0463

0.0000

3CaO-A!203
17CaO-7AI203
CaO-AI203
CO304,normalspinel
Cr203, eskolaite
FeA!204, hercynite
FeCr204, chromite

293-1473

19.5

0.2555

0.7564

-0.7490

298-1073

12.3

0.1230

0.0000

0.0000

10.5

0.2232

0.0259

-1.0687

14.8

0.0631

2.8160

0.0000

FeO, wiistite

Fe203, hematite

293-1473

301-995

293-1473

18.6

0.2146

0.1154

-0.2904

293-1273

15.6

0.0977

1.9392

0.0000

293-1273

9.9

0.0513

1.5936

0.0000

V
a

293-873
293-673

K
K

33.9

0.3203
0.0350

0.6293

0.0000

7.9

1.4836

0.0000

293-673

8.0

0.0559

0.7904

0.0000

293-673

23.8

3.8014

Fe304, magnetite

293-843

20.6

0.1238
-0.0353

8.0591

0.0000
0.0000

843-1273

FeTiO3, ilmenit

0.5013
0.1006

0.0000

297-1323

50.1
10.1

0.0000

0.0000

0.0000

7.6

0.0638

0.4031

0.0000

27.9

0.2689

0.3482

0.0000

c
V

297-1323

HfO2
MgAI204, normalspinel
MgA1204,disorderedspinel
MgCr204, picrochromite
MgFe204, magnesioferrite
MgGeO3, ilmenite
Mg2GeO4,olivine
Mg2GeO4,spinel
MgO, periclase
MnO, manganosite
ThO2, thorianite

297-1323
293-1273

293-873

993-1933

15.8

0.1264

1.0368

0.0000

24.9

0.2490

0.0000

0.0000

29.4

0.2940

0.0000

0.0000

293-1473

16.5

0.1430

1.1191

-0.1063

293-1473

20.5

0.3108

1.2118

-1.2773

299-1023

22.4

0.2244

0.0000

0.0000

298-1273

41.1

0.4110

0.0000

0.0000

298- 1273 K

32.1

0.3210

0.0000

0.0000

303-1273

31.6

0.3768

0.7404

-0.7446

V
V

293-1123
293-1273

K
K

34.5
28.5

0.3317
0.2853

1.2055

-0.2094

0.0000

0.0000

TiO

293-1073

22.3

0.1832

1.3236

0.0000

TiO2, rutile

298-1883

8.9

0.0890

0.0000

0.0000

298-1883

11.1

0.1110

0.0000

0.0000

298-1883

28.9

0.2890

0.0000

0.0000

293-1273

24.5

0.2180

1.2446

-0.0920

293-1273

21.2

0.2042

0.2639

0.0000

100-530

9.7

-0.0048

3.4000

0.0000

100-530

25.3

-0.0232

9.2000

0.0000

100-530

0.7

0.0005

0.2000

0.0000

100-530

35.7

-0.0275

12.8000

0.0000

U02.o3, uraninite
Zr02, baddeleyite

K
K

ref.

[30]
[30]
[30]
[30]
[93, cf. 29]
[93]
[75]a
[151
[75]
[49]
[751
[75]
[75]
[75]
[75]
[75]
[75]
[751
[75]
[951
[95]
[95]
[75]
[102]
[102]
[75]
[75]
[3]
[72]
[72]
[86]
[90]
[75, cf. 96]
[75]
[851
[851
[85]
[75, cf. 96]
[751

Hydrous minerals
AIOOH, boehmite

[71
[71
[7]
[71

31

32

THERMAL

EXPANSION

TABLE 1. (continued)
Names

Ca2MgSi802(OH)2
tremolite

KAI2(AISi30lo)(OH)2
muscovite

Mg(OH)2, brucite

T range

ao(10'6)

ao(10'4)

a(10-8)

a2

297-973

12.0

0.1202

0.0000

0.0000

b
c

297-973 K
297-973 K

11.7
5.8

0.1167
0.0583

0.0000

0.00

0.0000

0.00

/ 297-973 K

-2.7

-0.0266

0.0000

0.00

V
a

297-973 K
293-1073 K

31.3
9.9

0.3131
0.0994

0.0000

0.00

0.0000

0.00

b
c

293-1073 K
293-1073 K

11.1
13.8

0.1110
0.1379

0.0000

0.00

0.0000

0.0000

d001

293-1073 K

13.7

0.1367

0.0000

0.0000

V
a

293-1073 K
300-650 K

35.4
11.0

0.3537
0.1100

0.0000
0.0000

0.00

300-650 K

59.0

0.5900

0.0000

0.0000

300-650 K

80.0

0.8000

0.0000

0.00

0.0000

ref.

[83]
[83]
[83]
[83]
[83]
[25]
[25]
[25]
[25]
[25]
[191
[19]
[19]

Carbonates

BaCO3(hexagonal)

1093-1233

-102.0

-1.0200

0.0000

0.0000

1093-1233

297.0

2.9700

0.0000

0.0000

V
a

1093-1233 K
293-673 K

93.0
8.3

0.9300
0.0833

0.0000

0.0000

0.0000

0.0000

b
c

293-673 K
293-673 K'

18.6
35.2

0.1862
0.3520

V
a

293-673 K
297-1173 K

62.2
-3.2

0.6221
-0.0315

0.0000

0.0000

CaCO3, calcit

0.0000

0.0000

297-1173

13.3

0.1922

2.5183

-1.2140

297-1173 K
293-593 K

3.8
-5.6

0.0713
-0.0560

3.3941

CdCO3, otavite

V
a

-1.2140
0.0000

293-593 K

22.7

0.2270

0.0000

0.0OOO

293-593 K
297-973 K

11.5
3.2

0.1150
0.0271

0.0000

0.0000

CaMg(CO3)2,dolomite

V
a

0.6045

-0.1152

297-973

15.6

0.1233

2.2286

-0.3089

V
a

297-973
297-773

K
K

22.8
2.2

0.1928
0.0775

3.1703

-0.5393

MgCO3, magnesite

0.2934

-0.5809

297-773 K
297-773 K
297-773 K

13.2
18.2
1.8

0.0037
0.1686
0.0180

4.2711

0.0000

4.7429

MnCO3, rhodochrosite

c
V
a

0.0000

-1.1618
o.oooo

297-773 K
297-773 K
297-773 K

19.2
22.8
5.4

0.1920
0.2280
0.0540

0.0000

o.oooo

0.0000

o.oooo

FeCO3, siderite

c
V
a

0.0000

0.0000

297-773

16.1

0.1610

0.0000

0.0000

297-773 K
293-1073 K

26.9
7.1

0.2690
0.0508

0.0000

0.0000

SrCO3, strontianite

V
a

0.6630

0.0000

b
c

293-1073 K
293-1073 K

12.1
36.5

0.1107
0.2629

0.3362

0.0000

3.4137

0.0000

293-1073

59.2

0.4982

3.1111

0.0000

CaCO3, aragonite

0.0000

0.0000

0.0000

0.0000

0.0000

[43]
[43]
[43]
[7s]
[75]
[75]
[75]
[53]
[53]
[53]
[5]

[5]
[5]
[70]
[70]
[70]
[53]
[53]
[53]
[69]
[69]
[69]
[64]
[64]
[64]
[75]
[75]
[75]
[75]

FEI

TABLE 1. (continued)
Names

Su!fides

ao(10-6)

T range

ao(10'4)

a (10'8)

a2

ref.

and Sulfates

FeS2, pyrite
PbS, galena
ZnS, sphalerite

293-673

25.7

0.1256

4.3873

0.0000

293-873

58.1

0.5027

2.6125

0.0000

293-1273

17.8

0.2836

0.0000

-0.9537

ZnS, wurtzite

293-1273

6.7

0.0763

0.3815

-0.1885
-0.1274

BaSOn, barite

K2SO4

293-1273

6.5

0.0762

0.1134

293-1273

19.0

0.2136

1.0938

-0.5061

298-1158

20.7

0.2070

0.0000

0.0000

298-1158

25.5

0.2550

0.0000

0.0000

298-1158

17.2

0.1720

0.0000

0.0000

V
a

298-1158 K
293-673 K

63.7

0.6370

0.0000

0.0000

15.5

-0.1713

10.8705

0.0000

293-673

33.4

0.3337

0.0000

0.0000

293-673

42.6

0.1628

8.7701

0.0000

293-673

91.4

0.3252

19.6406

0.0000

293-693

10.7

0.1065

0.0000

0.0000

293-693

5.9

0.0346

0.8280

0.0000

V
a

293-693

27.1

0.2453

0.8700

0.0000

298-1273

12.5

0.1223

0.0963

0.0000

298-1273

8.1

0.0753

0.1918

0.0000

298-1273

2.3

0.0233

0.0000

0.0000

298-1273

22.8

0.2181

0.3261

0.0000

298-1073

2.6

0.0260

0.0000

0.0000

298-1073

-2.9

-0.0290

0.0000

0.0000

298-1073

2.3

0.0230

0.0000

0.0000

293-1473

33.1

0.2883

1.4106

0.0000

293-1473

31.4

0.4601

0.0158

-1.3157

[75]
[75]
[75]
[75]
[75]
[75]
[73]
[73]
[73]
[73]
[75]
[75]
[75]
[75]

Silicates

Akermanite,Ca2MgSi207

Andalusite,A!2SiO5

Beryl, Be3A!9_Si608

Calcium

[31]
[31]
[31]
[97]
[97]
[97]
[97]
[58]
[58]
[58]

silicates

Ca3Si207,rankinite
lS-Ca2SiOa
Ca3SiO5
Cancrinite

293-1273

25.7

0.1852

2.4073

0.0000

298-673

7.0

0.0034

2.2150

0.0000

298-673

16.1

0.0328

4.2629

0.0000

298-673

29.9

0.0364

8.7589

0.0000

[75]
[75]
[75]
[75]
[75]
[75]

Cordierite

Mg2A14Si5O18
(hexagonal)

[5-Eucryptite,LiAISiO4

Feldspars
Celsian,BaAI2Si208
High Albite, NaAISi308

298-873

2.2

0.0220

0.0000

0.0000

298-873

-1.8

-0.0180

0.0000

0.0000

[35]
[35]

298-873

2.6

0.0260

0.0000

0.0000

[35,cf.67]/'

296-920

8.6

0.0860

0.0000

0.0000

296-920

-18.4

-0.1840

0.0000

0.0000

296-920

-1.2

-0.0120

0.0000

0.0000

[66]
[66]
[66]

8.7

0.0605

0.8692

0.0000

9.6

0.0716

0.8114

0.0000

6.6

0.0656

0.0000

0.0000

5.2

0.0523

0.0000

0.0000

293-673

297-1378

297-1378

297-1378K

[75]
[68]
[68]
[68]

33

34

THERMAL

EXPANSION

TABLE 1. (continued)
Names

o0O)

T range

0.1603

-6.0284

0.0000

297-1378 K
297-1378 K

-2.3

-0.0197

-0.1120

0.0000

-2.6

-0.0252

-0.0252

0.0000

297-1378

26.8

0.7621

298-1243

11.7

0.2455
0.0882

0.0000
0.0000

0.9479

ref.

a2

-2.1

298-1243

4.7

0.0371

0.3400

0.0000

298-1243

0.3

-0.0113

0.4618

0.0000

298-1243

0.0000

-2.7

0.0263

-1.7927

298-1243 K
298-1243 K

-5.2

-0.0547

0.0987

0.00

-0.5

0.0061

-0.3641

0.00

298-1243 K

0.1737

22.6
11.2

0.1846

1.7276
0.5719

-0.80

293-1273

15.6

0.1297

0.8683

293-1273

9.7

-0.0097

3.5490

0.0000

293-1273

15.4

0.2199

1.0271

-0.8714

293-1273

8.9

0.1612

0.7683

-0.83

293-1273

10.6

0.1524

0.5038

-O.555O

293-1273

14.1

0.1394

0.0597

0.0000

293-1273

Adularia, Or88.3Ab9.3An2.
4
Microcline, Or83.sAb6.5
Orthoclase,Orr.6Ab32.sAno.6
Plagioclase,Ab99An
Plagioclase,Ab77An23
Plagioclase,Ab50,n
Plagioclase,AbsAn95

a (10's)

297-1378

Low Albite, NaAISi3Os

ao(10'4)

0.0000

0.0000

[68, cf. 991

[981
[98]
[98]
[98]
[98]
[98]
[98]
[75]
[75]
[75]
[75]
[751
[75]

[75,

24c]

Garnets

Almandite,Fe3A12Si3012
Andradite,Ca3Fe2Si3012
Cacium-richgarnet
Grossularite,Ca3A12Si3012
Pyrope,Mg3AI2Si302
Spessartite,Mn3AI2Si302
Natural garnet(pyrope-rich)
Gehlenite,Ca2AI2SiO7

294-1044

294-963

15.8

0.1776

1.2140

-0.5071

20.6

0.2103

0.6839

-0.2245

20.2

0.2647

0.3080

-0.6617

16.4

0.1951

0.8089

-0.4972

19.9

0.2311

O.5956

-0.4538

17.2

0.2927

0.2726

-1.1560

K
K

23.6
24.0

0.2880
0.2320

0.2787
0.2679

-0.5521
o.oooo

300-1000

292-980

283-1031

292-973

V
V

298-1000
293-1473

K
K
K

Hornblende

293-1273

23.8

0.0000

298-1073

7.5

0.2075
0.0749

1.0270

Kyanite, AI2SiO5

0.0000

o.oooo

298-1073

6.6

0.0661

0.0000

0.0000

298-1073

10.9

0.1095

0.0000

o.oooo

V
V

298-1073
293-1473

K
.

25.1

0.0000

29.8

0.2505
0.2521

1.5285

o.oooo
o.oooo

17tJK

3.9

0.0390

0.00

o.oooo

73K

7.0

0.0700

0.0000

o.oooo

o.oooo

Merwinite, Ca3Mg(SiO4)2

[75]
[75]
[381
[751
[751
[751
[87]
[75]
[75]
[97]
[97]
[97]
[97]
[75]

Mullite,

A!2O3(71.2%)SiO2(28.6%)

53
5--1'

A1203(.o%)SiO2(28.4%)Cr

Al 2O3(62.1%)Si02
(27.4%)Fe

73-[173

5.8

0.0580

0.00

573-1173

16.7

0.1670

0.00

o. oooo

573-1173

3.1

0.0310

0.0000

o.oooo

573-1173

6.2

0.0620

0.0000

o.oooo

573-1173

5.6

0.0560

0.0000

o.oooo

573-1173
573-1173

K
K

14.9

0.1490

0.0000

o.oooo

3.3

0.0330

0.0000

o.oooo

573-1173

7.0

0.0700

0.0000

o.oooo

573-1173

5.6

0.0560

0.0000

o.oooo

573-1173

15.9

0.1590

0.0000

o.oooo

[74]
[74]
[74]
[74]
[74]
[74]
[74]
[74]
[74]
[74]
[74]
[74]

FEI

TABLE 1. (continued)

Nephelines
(Nao.78.22)SiO4

(Nao.59Ko.41)AISiO4

ao(10'6)

T range

Names

ao(10-4)

a1(10'a)

a2

293-1073

11.1

0.0512

1.9931

0.0000

293-1073

8.3

0.0665

O.5544

0.0000

V
a

293-1073
293-1073

K
K

31.3

0.1889
0.1952

4.1498

0.0000

19.5

-0.0211

0.0000

293-1073

19.8

0.2627

-2.1428

0.0000

293-1073

58.5

0.6515

-2.2071

0.0000

CaMgo.97Feo.o7SiO4

298-1068

6.4

0.0855

0.1308

-0.2331

monticellite

298-1068

7.4

0.0965

0.1806

-0.2575

ref.

[75]
[75]
[75]
[75]
[75]
[75]

Olivines

CaMn(MgZn)SiO4
glaucochroite

Mg2SiO4, forsterite

Mg2SiO4, forsterite
Mg2SiO4, forsterite
Mg2SiO4, forsterite
Mn2SiO4, tephroite

Ni2SiO4, Ni-olivine

Fe2SiO4,fayalite

298-1068

10.3

0.1235

0.4236

-0.2891

V
a

298-1068
298-1073

K
K

24.2

0.6733
0.2233

-0.8133

6.5

0.3114
0.0976

298-1073

6.4

0.0953

0.2091

-0.3536

298-1073

7.2

0.1055

0.2783

-0.3852

V
a

298-1073
303-1173

K
K

20.3

0.3007

0.7192

6.6

0.0663

0.3898

-1.1080
-0.0918

303-1173

9.9

0.1201

0.2882

-0.2696

303-1173

9.8

0.1172

0.0649

-0.1929

V
V

303-1173
296-1293

K
K

26.4
30.6

0.3034

0.7422

0.2635

1.4036

-0.5381
0.0000

298-1273

28.2

0.3407

0.8674

-0.7545
-0.3842

-O.3605

300-1300

27.3

0.2854

1.0080

298-1123

5.8

0.0397

0.5249

0.0621

298-1123

8.8

0.1042

0.2744

-0.2188

298-1123

8.0

0.0807

0.3370

-0.0853

V
a

298-1123

K
K

22.6
9.5

0.2307
0.1049

1.0740
0.2093

-0.2898

298-1173

298-1173

8.9

0.0990

0.1746

-0.1387

298-1173

9.0

0.1004

0.1827

-0.1396

V
a

298-1173
298-1123

K
K

27.3

0.3036

0.5598

-0.4204

5.5

0.1050

0.0602

-0.4958

-0.1409

298-1123

7.9

0.0819

0.1629

-0.0694

298-1123

9.9

0.1526

-0.1217

-0.4594

V
a

298-1123 K
297-983 K

26.1

(Mgo.7Feo.3)2SiO4

6.1

0.2386
0.0610

1.1530
o.oooo

-0.0518
0.0000

hortonolite

297-983

9.6

0.0960

o.oooo

0.0000

297-983

9.7

0.0975

o.oooo

o.oooo

297-983

25.5

0.2557

o.oooo

o.oooo

Mgo.75Fel.loMno.15SiO4

296-1173

9.2

0.0916

0.0000

0.0000

hortnolite

296-1173

11.1

0.1109

0.0000

0.0000

296-1173

14.6

0.1456

o.oooo

0.0000

296-1173

35.0

0.3504

0.0000

o.oooo

77-298

8.4

0.0840

o.oooo

o.oooo

0.0000

o.oooo

o.oooo

[45]
[45]
[45]
[45]
[45]
[45]
[45]
[45]
[86]
[86]
[86]
[861
[541
[40]

[61]
[61]
[61]
[45]
[451
[45]
[45]
[911
[911
[91]
[91, 76, 27]
[13]
[13]
[13]
[13]
[27]
[27]
[27]
[27, cf. 79]

Perovskite

MgSiOa

77-298

0.0

[71]
[71]

35

36

THERMAL

EXPANSION

TABLE 1. (continued)
Names

(Mgo.9Feo.1)SiO3

(Mgo.9Feo.1)SiO3
Phenakite,Be2SiO4

Pseudowollastonite,
CaSiO3
Pyroxenes
CaAI2SiO6, CaTs

a1(10-s)

a2

77-298

5.9

0.0590

0.0000

0.0000

77-298

14.5

0.1450

0.0000

0.0000

22.0

298-381K

0.0000

100-250

5.8

0.2200
0.0580

0.0000

0.0000

0.0000

100-250

5.2

0.0520

0.0000

0.0000

100-250

4.5

0.0450

0.0000

0.0000

100-250

15.5

0.1550

0.0000

0.0000

250-373

8.1

0.0810

0.0000

0.0000

250-373

5.4

0.0540

0.0000

0.0000

250-373

5.4

0.0540

0.0000

0.0000

250-373

18.9

0.1890

0.0000

0.0000

V
V

150-373
298-840

K
K

19.0

0.1900

0.0000

0.0000

30.7

0.3156

0.9421

-0.3271

298-963

5.2

0.0520

0.0000

0.0000

298-963

6.4

0.0640

0.0000

0.0000

298-963

16.8

0.1680

0.0000

0.0000

293-1473

27.8

0.2474

1.0096

0.0000

298-1473

8.8

0.0882

0.0000

0.0000

298-1473

12.0

0.1204

0.0000

0.0000

298-1473

8.9

0.0888

0.0000

0.0000

298-1473

27.8

0.2780

0.0000

0.0000

297-1273

7.8

0.0779

0.0000

0.0000

297-1273

2O.5

0.2050

0.0000

0.0000

297-1273

6.5

0.0646

0.0000

0.0000

d100

297-1273

6.1

0.0606

0.0000

0.0000

V
a

297-1273
293-1123

K
K

33.3

0.3330

13.5

0.1350

0.0000
0.0000

0.0000

293-1123

14.5

0.1450

0.0000

0.0000

293-1123

15.4

0.1540

0.0000

0.0000

V
a

293-1123 K
293-973 K

43.8

0.4380

0.0000

0.0000

16.2

0.1620

0.0000

0.0000

Cao.o15Mgo.3osFeo.SiO3
ferrohypersthene

Cao.o15Mgo.3osFeo.SiO3
clinohypersthene

0.0000

293-973

10.4

0.1040

0.0000

0.0000

293-973

13.8

0.1380

0.0000

0.0000

d100

293-973

8.3

0.0830

0.0000

0.0000

293-973

32.7

0.3270

0.0000

0.0000

297-1273

7.2

0.0724

0.0000

-0.0000

297-1273

17.6

0.1760

0.0000

0.0000

297-1273

6.0

0.0597

0.0000

0.0000

297-1273

d100

Cao.15Feo.85SiO3,
FsWo

ao(10'4)

CaMgSi206,diopside

CaFeSi20,hedenbergite

aoO0)

T range

4.8

0.0483

0.0000

0.0000

V
a

297-1273 K
297-773 K

29.8

0.2980

0.0000

0.0000

18.9

0.1890

0.0000

0.0000

297-773

13.3

0.1330

0.0000

0.0000

297-773

15.2

0.1520

0.0000

0.0000

d100

297-773

8.9

0.0893

0.0000

0.0000

297-773

37.6

0.3760

0.0000

0.0000

ref.

[71]
[71]
[71]
[62]
[62]
[62]
[62]
[62]
[62]
[62]
[62]
[62]
[42]
[30]
[30]
[30]
[75]
[26]
[26]
[26]
[26]
[14]
[14]
[14]
[14]
[14, cf. 22]
[78]
[78]
[78]
[78]
[77]
[77]
[77]
[77]
[77]
[14]
[14]
[14]
[14]
[14]
[6o]
[6o]
[6o]

[6o]
[6o]

FEI

TABLE 1. (continued)
Names

FeSiO3, orthoferrosilite

LihlSi206, spodumene

Mgo.sFeo.2SiO3,
bronzite

MgSiO3, enstatite
MgSiO3, protoenstatite
MnSiO3, pyroxmangite

NaAISi206, jadeite

NaCrSi206, ureyite

NaFeSi206, acmite

Silicateilmenite,MgSiO3

Silicatespinel
-Mg2SiO,
-Ni2SiO,
-Fe2SiO
4
-Fe2SiO
4
Sillimanite,AI2SiO5

aoOO)

T range

ao(10'4)

a1(10's)

a2

297-1253

11.2

0.1120

0.0000

0.0000

297-1253

10.9

0.1090

0.0000

0.0000

0.0000

297-1253

16.8

0.1680

0.0000

297-1253

39.3

0.3930

0.0000

0.0000

297-1033K

3.8

0.0380

0.0000

0.0000

297-1033

11.1

0.1110

0.0000

0.0000

297-1033

4.8

0.0475

0.0000

0.0000

d100

297-1033

6.0

0.0600

0.0000

0.0000

297-1033

22.2

0.2220

0.0000

0.0000

298-1273

16.4

0.1640

0.0000

0.0000

298-1273

14.5

0.1450

0.0000

0.0000

298-1273

16.8

0.1680

0.0000

0.0000

298-1273

47.7

0.4770

0.0000

0.0000

293-1073

24.1

0.2947

0.2694

-0.5588

1353-1633

297-1073

16.7

0.1670

0.0000

0.0000

7.6

0.0760

0.0000

0.0000

297-1073

13.8

0.1380

0.0000

0.0000

297-1073

6.7

0.0670

0.0000

0.0000

297-1073

28.1

0.2810

0.0000

0.0000

297-1073

8.5

0.0850

0.0000

0.0000

297-1073

10.0

0.1000

0.0000

0.0000

297-1073

6.3

0.0631

0.0000

0.0000

all00

297-1073

8.2

0.0817

0.0000

0.0000

297-1073

24.7

0.2470

0.0000

0.0000

297-873

5.9

0.0585

0.0000

0.0000

297-873

9.5

0.0946

0.0000

0.0000

297-873

3.9

0.0390

0.0000

0.0000

d100

297-873

6.9

0.0691

0.0000

0.0000

297-873

20.4

0.2040

0.0000

0.0000

297-1073

7.3

0.0727

0.0000

0.0000

297-1073

12.0

0.1200

0.0000

0.0000

297-1073

4.5

0.0450

0.0000

0.0000

d100

297-1073

8.0

0.0804

0.0000

0.0000

297-1073

24.7

0.2470

0.0000

0.0000

298-876

7.1

0.0707

0.0000

0.0000

298-876

10.0

0.0996

0.0000

0.0000

298-876

24.4

0.2440

0.0000

0.0000

297-1023

18.9

0.2497

0.3639

-0.6531

298-973

26.8

0.2680

0.0000

0.0000

0.0000

K
K

298-673

27.0

0.2697

0.0000

298-673

23.0

0.2300

0.0000

0.0000

298-1273

1.0

0.0231

0.0092

-0.1185

298-1273

7.4

0.0727

0.0470

0.0000

298-1273

4.2

0.0386

0.1051

0.0000

298-1273

13.3

0.1260

0.2314

0.0000

ref.

[]
[]
[4]
[]
[141
[14]
[14]
[14]
[14]
[23]
[23]
[23]
[23]
[75]
[59]
[65]
[65]
[65]
[65]
[14]
[14]
[14]
[14]
[14]
[14]
[14]
[14]
[14]
[14]
[14]
[14]
[14]
[14]
[14]
[4]
[4]
[4]
[88]
[lOl]
[lOl]
[521
[971
[971
[971
[971

37

38

THERMAL

EXPANSION

TABLE 1. (continued)

T range

Names

ao(11Y
a)

ao(10.4)

a (10.8)

a2

ref.

SiO 2 group
Coesite

293-1273

6.9

0.0597

0.7697

-0.1231

Cristobalite, low

301-491

19.5

0.1950

0.0000

0.0000

301-491

52.7

0.5270

0.0000

0.0000

301-491

91.7

0.9170

0.0000

0.0000

[75]
[63]
[63]
[63]

Cristobalite,high

673-1473

6.0

0.0600

0.0000

0.0000

[75]a

a-Quartz

298-773

24.3

0.1417

9.6581

-1.6973

O-Quartz

848-1373

0.0

0.0000

0.0000

0.0000

1473-1673

-4.4

-0.0440

0.0000

0.0000

Stishovite

291-873

7.8

0.0758

0.0656

0.0000

291-873

0.9

0.0060

0.6553

-0.1500

[1]e
[1]
[1]
[39]
[39]
[39]
[181
[18]

Stishovite

Spodumene,t-LiAlSi206
Topaz, AI2SiOn(F,OH)2

Wadsleyite(O-phase)
Mg2SiO4

Zircon, ZrSi04

K
K
K

291-873

16.4

0.1574

0.7886

-0.1500

300-693

7.5

0.0750

0.0000

0.0000

300-693

3.8

0.0380

0.0000

0.0000

300-693

18.6

0.1860

0.0000

0.0000

0.0758

1.1542

0.0000
0.0000

293-1073

11.0

[75]
[75]
[75]
[75]
[75]
[89]
[89]
[89]
[89]
[6]

293-1273

4.6

0.0316

0.4698

293-1273

3.6

0.0245

0.3795

0.0000

293-1273

6.3

0.0485

0.4924

0.0000

293-1273

14.8

0.1098

1.2700

0.0000

293-1073

6.0

0.0851

0.1388

-0.2662

293-1073

5.6

0.0791

0.1165

-0.2487

293-1073

9.3

0.1196

0.3884

-0.3412

293-1073

20.9

0.2893

-0.8903

293-1293

3.4

0.0340

0.5772
0.0000

293-1293

5.6

0.0560

0.0000

0.0000

293-1293

12.3

0.1230

0.0000

0.0000

[6, cf. 82]

293-873

20.6

0.2060

0.00

0.0000

295-520

13.8

0.1380

0.00

0.0000

[104]
[50]
[50]
[50]
[50]
[50]
[50]
[50]
[50]
[105]
[105]
[105]
[105]
[105]
[32]
[32]
[32]

0.0000

Perovskites

BaZrO3, perovskite
CaGeO3, perovskite

NaMgO3, perovskite

NaMgO3, cubic
ScAIO3, perovskite

295-520

6.8

0.0680

0.0000

0.0000

295-520

10.5

0.1050

0.00

0.

295-520

31.1

0.3110

0.0000

0.0000

520-673

12.1

0.1210

0.00

0.0000

520-673

12.1

0.1210

0.0000

0.0000

520-673

10.5

0.1050

0.00

0.0000

0.0000
0.0000

520-673

35.0

0.3500

0.0000

298-873

40.4

0.4040

0.0000

298-873

15.3

0.15300

0.0000

0.0000

298-873

30.6

0.3060

0.00

0.0000

288-873

88.0

0.0000

1038-1173

94.9

0.8800
0.9490

0.0000

0.00

0.0000

293-973

10.0

0.1000

0.00

0.00

0'.0700

0.00

0.00

0.1000

0.00

0.

K
K

b 293-973 K
c

293-973

7.0
10.0

FEI

TABLE 1. (continued)
Names

SrZrO3, perovskite

V
a

T range

ao(10)

283-1373 K
293-973 K

27.0
12.4

ao(10'n)
0.2700
0.1240

a Offs)

a2

ref.

0.0000
0.0000

0.0000
0.0000

[32]
[]o4]
[104]
[104]
[104]
[104]
[104]
[104]
[104]
[104]
[lO41
[104]

293-973

7.5

0.0750

0.0000

0.0000

293-973

9.7

0.0970

0.0000

0.0000

293-973

973-1123

29.8

0.2980

0.0000

0.0000

7.6

0.0760

0.0000

0.0000

973-1123

16.1

0.1610

0.0000

0.0000

973-1123

8.2

0.0820

0.0000

0.0000

973-1123 K
1123-1443 K

32.4
14.9

0.3240
0.1490

0.0000
0.0000

0.0000
0.0000

a
c

1123-1443

6.8

0.0680

0.0000

0.0000

1123-1443

37.5

0.3750

0.0000

0.0000

aFordatacitedfrom[75], see[75]for originaldatasources.

bSee
[56]fororthorhombic
cordierite
and[33]forhydrous
Mg-andFe-cordierites.
CSee
[24]for plagioclases,
An100,
Ab9An9
, Ab7An93
, Ab75An22Or3,
Ab63An36Orl,
AbnAn57Or2,
andAb23An76Or
1.

dinversion
at491K.Alsosee[75]fordataontridymite.
ea-andO-quartz
transition
at846K; see[1]fordiscussion
onthermal
expansion
nearthetransition.

TABLE 2. PressureEffect on ThermalExpansionCoefficientof SelectedSubstances

Phases

Fe(bcc)
Fe(hcp)
Fe(fcc)
NaCI
LiF

MgO, periclase
(Mgo.6Feo.4)O,
magnesiowiistite
Mg(OI-I)2
Mg2SiO4, olivine
[5-(Mgo.sFeo.16)2Si04
MgSiOn, spinel
(Mgo.9Feo.
1)Si03, perovskite

Kr, OPa

KT'

fit

165.0
212.0
167.0
24.0
65.3
160.3
157.0
54.3
129.0
174.0
183.0
261.0

5.30
4.00
4.00
5.01
5.10
4.13
4.00
4.70
5.37
4.00
4.30
4.00

6.5
6.5
6.5
5.8
5.4
4.7
4.3
4.5
5.5
5.1
5.8
6.5

references

[34]
[34]
[9]
[10{3]
[10]
[36]
[20]
[19]
[37]
[21]
[55]
[51]

39

40

THERMAL

TABLE

EXPANSION

3a. Partial Molar Volume and Mean Thermal

TABLE

3b. Partial Molar Volume

and Mean Thermal

ExpansionCoefficientof Oxide Components

ExpansionCoefficientof Oxide Components

[46]

in Al-Free Melts [11]

Viiq(r)
-- XiVii,Tr[
1+ i(T-Tr)]+XNa2OXTiO2
VNa20-TiO2
a = Yiai

64liquids
b

iron-freesilicateliquida

Oxides

Vi,1673

ai (x105)
,

Oxides

Vi,1773
K ai (x105) Vi,1573
K ai (x105)

SiO2
TiO2
AI203
FeO3

26.88
23.98
37.52
-

FeO

-1.2
36.5
2.0
-

26.92
22.43
36.80
41.44

0
32.3
7.1
21.9

13.35

21.9

MgO

11.85

: 0.7

11.24

23.3

CaO

16.84

25.1

16.27

17.9

NaeO
KeO
Li20
NaeO-TiOe

29.53
47.10
17.42
20.10

26.8
72.8
33.4

28.02
44.61
16.19
20.33

26.4
26.7
32.4

a Data were derivedfrom densitymeasurements

of meltsin ironfree system[8, 46, 80]. Unitsarein cc/moleand1/K.

SiO2
TiO2
Fe203

26.75
22.45
44.40

0.1
37.1
32.1

FeO

13.94

34.7

MgO

12.32

12.2

CaO

16.59

16.7

Na20
K20

29.03
46.30

25.9
35.9

Li20

17.31

22.0

MnO

14.13

15.1

NiO

12.48

24.9

ZnO

13.64

43.0

SrO

20.45

15.4

BaO

26.20

17.4

PbO

25.71

16.1

54.22
68.33

61.3
71.4

b Datawerederivedfromdensity
measurements
of 64 meltsil

Rb20
the systemNa2C,-K20-CaO-MgO-FeO-Fe203-AI203-TiO2-SiO2 Cs20
[8, 46, 57, 801.

a Data were derivedfrom densitymeasurements

of AI free
melts.See[11] for datasources.
Unitsarein cc/moleand1/K.

TABLE

3c. Partial Molar Volume and Mean Thermal

ExpansionCoefficientof Oxide Components

in CaO-FeO-Fe203-SiO2 Melts [/]
TABLE

Fiq(T)
= X,r[1+ i(r- T0]+Xs,oXo
Vs,o-cao
> 20 wt% silica a

Oxides Vi,1673
I
25.727
37.501

FeO

14.626

21.0

CaO

18.388

12.1

low silica

0
9.2

and Mean Thermal

Yiiq(T)
= Xiii,r[1
+ i(TOxides

Vi,1573
26.60
41.39

ai (x105)

27.801
35.770

0
13.3

13.087

19.4

SiO2
F203

21.460

10.5

FeO

13.61

18.7

Na20

28.48

23.2

-11.042

a Datawerederivedfromdensitymeasurements
of 30 meltsin
the systemCaO-FeO-Fe203-SiO
2 [16, 57]. Unitsarein cc/mole
and 1/K.

Volume

ai (x105) Vi,1673 ai (x105)

SiOe
FeeO3

SiOe-CaO

3d. Partial Molar

ExpansionCoefficientof OxideComponents
in NaeO-FeO-Fe203-SiO2 Melts [47]

0.3
12.9

a Datawerederivedfromdensitymeasurements
of 12 meltsin
the system Na20-FeO-Fe203-SiO [17] and ferric-ferrous
relations[47]. Unitsarein cc/moleand1/K.

FEI

41

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THERMAL

EXPANSION

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Elasticity of Minerals, Glasses,and Melts

Jay D. Bass

INTRODUCTION

talline aggregate. The isotropicmoduli listed are are

In this chapter I present a compilation of the elastic

moduli of minerals and related substanceswhich may be
of use in geophysicalor geochemicalcalculations. The
disciplineof elasticity is a mature one. Laboratory measurementsof elasticity have been actively investigated
for a number of years for a wide variety of materials.
Consequently,there are several excellent compilations
of elastic moduli available, notably those of Hearmon

[46, 47], in the Landolt-BSrnstein

tables,and Sumino
and Anderson[118] (for crystallinematerials), and of
Bansaland Doremus[6] (for glasses).Here are summarized elastic moduli of most direct geologicimportance. Included are many important results published
in the last few years which are not available in other
summaries.

The main

content

of the tables consists of elastic

moduli, cij, which are stiffnesscoefficients

in the linear stress-strain
relationship[80]:

trij = cij,e

(1)

wheretYijand e are the stressand strain tensors,respectively.We usethe standardVoigt notation'J80],to

representthe moduli as componentsof a 6 x 6 matrix

cij wherethe indicesi andj rangefrom I to 6. Also

listed for each material

are the adiabatic bulk modulus

and shear modulus for an equivalent isotropic polycrys-

J. D. Bass, Department of Geology, University of Illinois,

1301 West Green Street, Urbana, IL 61801

Mineral Physicsand Crystallography

A Handbook of Physical Constants
AGU

Reference

Shelf 2

Copyright 1995 by the American GeophysicalUnion.

Hill averages
of the Voigt and Reussbounds[135]. In
conjunctionwith the density,the moduli can be used
to calculateacousticvelocitiesusing standard relations

[16].
This chapter is not meant to be either historically
completenor encyclopedicin scope. In caseswhere a
material hasbeen the subjectof severalstudies,we have

cited the averagemoduli computedby Hearmon[46,

47], whereavailable.Thus,the resultsfrom manyolder
studiesare not individually listed, especiallywhere they
have been supercededby experiments using more modern techniques. This has made the present summary
far more compact than it would otherwise be. However, elastic properties reported after the compilations

of Uearmon[46, 47], and by Bansaland Doremus[61,

are included as separate entries. Except in a few important cases, only results from single-crystal studies are reported. Results from experiments on polycrystalline sampleswere uniformly excluded unlessno
single-crystaldata were available.

Sincethe earliercompilationby Birch[16],the quantity of data related to the equation of state of rocks
and minerals has grown considerably. For many materials, complimentary results on the equation of state
of minerals from static compressiondata are found in
the chapter by Knittle, with which there is a degreeof
overlap. Likewise, the chapter by Anderson and Isaak
present considerablymore detail on the high temperature elasticity of minerals.
The results in this chapter derive from a variety of
techniqueswhich have a broad range of precision. We
have not made any attempt to assessthe relative accuracy of results from different laboratories on a given
material.

46

ELASTICITY

The number of independent elastic constants appropriate to a materiM dependson the symmetry of that

material [80], rangingfrom two for a noncrystalline

substance,to threefor an cubic(isometric)crystal,to
twenty one for a triclinic crystal. Tables are therefore
organized on the basis of crystallographicsymmetry,

with materialsof a similar nature (e.g. elements,garnets,etc.) groupedtogether.

The notation usedthroughout the tables is as follows:

GPa

Mg/ms

Units

Description

cij

GPa

Single-crystalelastic stiffness

GPa

Adiabatic

bulk modulus

Ks,o

GPa

Adiabatic

bulk modulus

GPa

Shear modulus

Vr

m/s

Kelvins

Longitudinal wave velocity

Temperature

moduli

Ks

at zero

frequency

Density
Superscripts

Indicates

Indicates constant electric displacement

constant electric field

Note that for melts, we have cited the zerofrequency,or

relaxed, bulk modulus where possible.It is not possible
within

Symbol

Pressure

the framework

of this review

to summarize

the

frequencydependenceof the elastic propertiesof melts

or glassesat high temperature. In caseswhere the dispersivepropertiesof liquids were investigated,we have
listed the results obtained at the lowest frequency.
Most of the entries are for minerals,althoughsome
chemically and structurally related compoundsof interest are included. In all of the tables, the compositions
of solidsolutionsare givenin terms of molepercentages
of the end-members,indicated by the subscripts,except
where specificallynoted.

Table 1. Elastic Moduli of Cubic Crystals at Room P & T

Material

p
Mg/ms

Subscriptij in moduluscij (GPa)

11
44
12

Ks

GPa

GPa

171.7
102.0

27.6
29.2
535.7

ences

Elements, Metallic Compounds

Au, Gold

Ag, Silver
C, Diamond
Cu, Copper
Fe, a-Iron
Feo.94Sio.06
Feo.94Sio.06
Fe0.91Sio.o9
BaO

CaO, Lime
CoO

re0.92O, Wutite
Fe0.9430
Fe0.9sO
MnO, Manganosite

MgO, Periclase

NiO, Bunsenire

19.283
10.500
3.512
8.932
7.874
7.684
7.675
7.601

191
122

1079
169
230
221.0
222.3
216.4

42.4
45.5
578

162
92
124

75.3
117
122.3
123
124.6

122
135
135.1
135.5
134

443.0
137.3
166.7
163.7
164.4
161.4

45
60

70.7
114.7

36.0
81.2

47, 126
46, 111

80.59
71.3
46.1
46.4
46.8
68.1

81
47
120
56
15
47

5.992
3.346

Binary Ozides
122
34.4
224
80.6

3.349
6.438
5.681
5.708
5.730
5.365

220.5
260
245.7
218.4
217
227

80.03
82.4
44.7
45.5
46
78

57.7
145
149.3
123.0
121
116

112.0
183.3
181.4
154.8
153.0
153.0

5.368

223.5

78.1

111.8

149.0

5.346
3.584
3.584
3.584
6.828

226.4
294
296.8
297.8
344.6

79.0
155
155.8
155.8
40

114.9
93
95.3
95.1
141

152.1
160.0
162.5
162.7
205

46.9
81.5
80.40
81.1
80.1

68.3
68.7
130.3
130.8
131.1
58.8

47
47
77

46
47
103
72
72

89
138
46
57
152
134

BASS

47

Table 1. (continued)
Material

Mg/ms
SrO

UO2, Uraninite

5.009

10.97

Subscript
ij in moduluscij (GPa)
11

44

12

Ks

GPa

GPa

ences

87.3

58.1

46, 116

170

55.6

46

389

59.7

119

209

83

35

104

161.0

91.4

47

162.0

91.2

47

203.3

104.9

47

46, 24

Spinel Structured Ozides

Fe304

Magnetite
FeCr:O4, Chromite
MgAI204,
Spinel
MgO-2.6AI03
MgO.3.5AI03

5.206

275

95.5

270
5.09

98.7

322

117

144

3.578

282

154

154

196.7

108.3

3.578

282.9

154.8

155.4

197.9

108.5

152

153.7

202.0

115.3

106

153.7

202.6

116.4

126

168

216.0

114.8

46

158

206.3

114.7

46

97

130

3.619

3.63

298.6

157.6

300.5

158.6

312

157

303

M go.75Feo.36
AI .90O4,

108

156

3.826

269.5

143.5

163.3

198.7

4.280

266.0
327
366
300

133.5
126
106
126

182.5
112
155
118

210.3
184
226
179

84.5
119
106
110

33.6
-44

142.7
104.7
58.6
77.1

125.7
149.7
31.9
31.5

108

57.8

25.1

46

86.3

42.4

46

24.9

14.7

46

18.1

9.4

46

172.8

92.0

85

177

89

67

108.9

11

162

92

10

178.8

96.3

11

Pleonaste

FeAI204, Hercynite

-Mg2Si04, Pdngwoodite

3.559

Ni2SiO4

5.351

MgGeO4

4.389

FeS, Pyrite

5.016

PbS, Galena
ZnS, Sphalerite

7.597
4.088

BaF, Frankdicksonite
CaF2, Fluorite
NaCI, Halite
KC1, Sylvite

4.886
3.181
2.163
1.987

130
144

13

140

Sulphide.
s
361
402
127
102

105.2
114
23
44.6

24.4
64.6

47
47

47

Binaqt Halides

90.7
165
49.1
40.5

25.3
33.9
12.8
6.27

41.0
47
12.8
6.9

91.6
90
104.6

111.1
117
91.2
91

Garnels

Pyrope(Py),
MgaAISiaO
Grossular,(Gr99)

3.567
3.563
3.602

296.2
295
321.7

3.850

304

84

4.195

309.5

95.2

H ibschite

3.13

187

63.9

57

100

64.3

86

Ca3Al ( SiO4).74(H40 ).28

Andradite(An96)

3.836

289

85

92

157

90

10

An7oGr2Alm4Pys
Gr4sPysAlmsSp
Alm4Py2GrSpAnda
AIm74PyoGrsSps

3.775
3.741
4.131
4.160

281.2
310.2
306.7
306.2

87.9
99.5
94.9
92.7

80.4
100.4
111.9
112.5

147.3

92.7

170.4

101.6

84

176.8

95.9

177.0

94.3

111

Py73Alm16And4Uv
Py6Alma6Gr

3.705
3.839

296.6
301.4

91.6
94.3

108.5
110.0

171.2

92.6

121

173.6

94.9

136

168.4

CasAl:SisOl:t

Uvarovite(Uv)
CaaCr2SiaO

Spessartite(Sp95)

113.5

MnsAISiaO

CasFe2+3Si3012

48

ELASTICITY

Table 1. (continued)
Material

p
Mg/ma

Sp54AIm46

Subscript
ij in modulus
cij (GPa)
11
44
12

Ks

Refer-

GPa

GPa

ences

177.7

96.1

3.555

164

89

12

3.545
3.527
3.606

170
172
174

92
92
115

150
150
90

4.249

308.5

94.8

112.3

132

Majorde (Mj) - GarnetSolidSolutions

Mj41PY59

Mgs(Mg,Si).s:AI1.18Sis01:
MjssPy6?
Mj6PY34
Nal.s7Mgl. 18Si4.94012

329

114

96

Abbreviations:
Py,pyrope;
Aim,almandite;
Gr,grossular;
Uv,uvarovite;
An,andradite;
Sp,spessartite;
Mj, majorite(Si-richandAl-poorgarnet).

Table2. ElasticModuliof Hexagonal

Crystals
(5 Moduli)at RoomP & T

Material
BeO, Bromellite
Beryl
BesAlSi018
C, Graphite

Ca,0(PO4)(OH),

Mg/ms
3.01
2.724
2.698
2.26
3.146

11
470
304.2
308.5
1060
140

Subscript
ij in modulus
cii (GPa)

Ks

GPa

GPa

119
114.5
118.5
15

251
176
181
161.0

162
78.8
79.2
109.3

69

80.4

45.6

47

46

56

212.3

101.8

47

38

21

48.9

30.7

46

33
494
277.6
283.4
36.5
180

44
153
65.3
66.1
.3
36.2

12
168
123.8
128.9
180
13

177

44.3

125

37.2

13

ences

14

153
153

18

Hydroxyapatite

Ca10(PO4)F2,

3.200

141

Fluorapatite

Cancrinite
2.6
79
(NaCa)4(AI,SiO4)aCOs.nH20
CdS, Greenockite
4.824
86.5

cD
cz
H20, Ice-I (257K)
Ice-I (270K)
NasKA14Si4016,

0.9175
2.571

94.4

15.0

54.0

47.3

62.7

16.9

47

83.8
83.1

96.5
94.8

15.8
15.3

51.1
50.4

45.0
46.2

60.7
60.7

17.5

61

13.5
13.70
79

14.9
14.70
125

3.09
2.96
37.2

6.5
6.97
38

5.9
5.63
21

8.72
8.73
48.9

117
209

110
218

36
44.1

16
120

33
104

207.0
209.6

209.5
221.0

44.8
46.1

117.7
120.4

106.1 142.6
101.3 142.9

122

138

28.7

17.1

3.48
3.40

61
46

37

30.7

47

41.4

47

Nepheline

-SiO2 (873K)
ZnO, Zincite

5.675

cz
cD
Wurtzite, ZnS

4.084

58

42

56.4
143.5

74.0

46.8

46

46.3

61

48.2

61

33.3

46

BASS

Table 3. ElasticModuli of TrigonalCrystals(6 Moduli) at RoomP & T

Mineral

p
Mg/m3

A12Os,Sapphire,
Corundum

Subscriptij in moduluscii (GPa)

33
44
12
13

11

14

Ks
GPa

Refer-

GPa

ences

3.999

495

497

146

160

115

-23

251.7

162.5

46

3.982

497

501

146.8

162

116

-21.9

253.5

163.2

83

ALPO4, (cE)
Berlinire, (c)

2.620

64.0
69.8

85.8
87.1

CaCOs, Calcite
Cr2Os, Eskolaite
Fe2Os, Hematite
MgCOs, Magnesite
NaNOs, Nitratine
AgsAsSs,

2.712
5.21
5.254
3.009
2.260
5.59

144
374

259
54.6
59.5

156
34.9
39.8

54.8
11.3
9.97

75.6
18.9
31.7

58.8
19.3
29.6

73.3
234.0
206.6
-19.0
114.0
7.5
28.2
0.18 36.8

2.648
2.648
2.648
3.100

86.6
86.74
86.47
305.0

106.1
107.2
107.2
176.4

57.8
57.9
58.0
64.8

6.7
6.98
6.25
108

12.6
11.9
11.9
51

-17.8
-17.9
-18.1
-6

84.0
362

43.2
42.2
33.5
159

7.2
10.6
53.9
148

9.6
14.9
51.1
175

-12.4
13.4

29.3
33.9

-20.5
-19

33.0

25

32.7

32

32.0

46

123.2

1, 46

91.0

69

68.0

46, 50

12.0

46

11.0

47

44.3

46

44.4

46

44.5

46

81.5

87

Proustite

SiO2, c-Quartz
cz
cD
Tourmaline,

37.8
37.8
37.5
127.2

(Na)(Mg,Fe+2,Fe+,Al,Li) Al6(BO)s(Si6018)
(OH,F)4

Table 4. ElasticModuli of TrigonalCrystals(7 Moduli) at Room P & T

Material

Subscriptij in moduluscij (GPa)

Dolomite,

Mg/ms

11

33

3.795

205

113

2.960

341.9

391.0

3.795

472

382

44

12

13

39.8

71.0

57.4

91.4

148.0

136.0

14

-19.5

15

Ks

GPa

GPa

References

13.7

94.9

45.7

46, 50

3.5

212.8

98.9

148

CaMg(COs)
Phenacite

0.1

BeSiO4

MgSiOs
Ilmenite

structure

106

168

70

-27

24

212

132

141

49

50

ELASTICITY

Table5. ElasticModuliof TetragonalCrystals(6 Moduli) at RoomP & T

Material

p
Mg/ms

11

Subscriptij in moduluscij (GPa)

33
44
66
12

13

Ks
GPa

Refer-

GPa

ences

316

220

Ru tile-St ru ctu red

Si02,

4.290

453

776

252

302

211

203

143

Stishovite

Si02,

2.335

59.4

42.4

67.2

25.7

3.8

6.975

261.7

449.6

103.1

207.4

177.2

6.02

55.7

105.8

26.5

65.9

5.99

53.2

108.5

24.4

55.2

269
337.2

480
599.4

124
161.5

192
258.4

177
188.2

-4.4

16.4

39.1

151

155.5

212.3

101.8

22

51.2

21.8

45.0

20.4

93

48.6

21.2

43.7

19.0

122

a-Cristobalite

SnO2,
Cassiterite

TeO,
Paratellurite

TiO, Rutile
GeO

4.260
6.279

146

215.5

112.4

47

187.4

257.6

150.8

131
46

Other Minerals

Ba2Si2TiOs,

140

83

33

59

36

24

56.9

42.1

166

100

31.7

69.4

58

44

77.6

43.3

46

99

113

15.6

22.9

35.1

35.4

58.0

23.1

47

102
102

140
140

23.0
23.0

30.4
30.4

38.9
38.9

43.3

65.3

29.1

47

43.3

65.3

29.1

47

153

166

55.8

54.0

48

44

82.6

55.5

47

4.675

424.3

489.3

149

227.9

109.0

88

4.70

256

372

214

223.9

66.6

47

Fresnoite
(cr)
Scapolite,

(Na,Ca,K)4Als(AI,Si)s
Si6024(CI,SO4,COs)
Vesuvianite

Ca0Mg2A14(SiO4)5(Si2O7)2(OH)4
ZrSiO4 a,
Zircon

131.1
73.5

48.3
116

69.7
175

a nonmetamict.

Table 6. ElasticModuli of TetragonalCrystals(7 Moduli) at RoomP & T

Material

CaMo04,

Subscriptij in moduluscij (GPa)

11

33

4.255

144

127

6.119

141

6.816

109
108

Mg/ms

44

Ks

GPa

GPa

Refer-

66

12

13

16

36.8

45.8

65

47

-13.5

81.0

39.9

46

125

33.7

40.7

61

41

-17

76.5

37.4

46

92
95

26.7
26.4

33.7
35.4

68
63

53
51

-13.6
-15.8

72.4
70.8

24.5
25.0

46

ences

Powellite

CAW04,
Scheelite

PbMo04,
Wulfenite

46

BASS

o o

51

52

ELASTICITY

BASS

o
o

I'--,

t.c'D

.,,.

C'4" C"'q

53

54

ELASTICITY

BASS

Table 9. Elastic Moduli

Composition

CaAISiOs (An)

kg/ms

2490
3950
1833

6.54
5.54
2.56

1893
An ,

Ans6Di4
AnsDi4 '
AnsoDiso
AnsoAbso
AbsoDiso

AbzsDis

AbssAnssDias

BaSiOs
CaSiOs
CaTiSiOs
CsSiOs

CaMgSi2Oa(Di)
Di

Fe.22Sio.s9Oa
Fe2SiO4
K2Si2Os

K9.SiOs
LiSi2Os
Li2SiOs

MgSiOs
NaCI

(SO)(^O)(SiO)
(SO)
Na2Si205
NaSiOs

O) (SiO)

and Velocities in Melts

Ks,co

Vp

GPa

m/s

94.8
52.4
20.6

3808
3075
2850

20.4

Refer enc es

48
48

3.529
3.0

100
107

1923
1677
1673

2.61

17.9
23.0
24.2

1673
1573
1753
1698
1598
1753
1648
1698
1583
1793
1693
1836
1753
1653

2.60
2.61
2.44
2.45
2.46
2.39
2.40
2.49
2.50
3.44
3.47
2.65
2.96
3.01

21.6
22.1
17.8
18.2
19.3
16.4
16.7
19.5
19.8
19.5
20.2
27.1
19.9
20.0

1693

3.14

6.4

1450

3.854

100

1208

3.34

8.8

2345

4.023

100

1773

2.61

22.4

1758
1698
1693
1598
1653
1503
1693
1408
1698
1498
1693
1411
1543
1913
1094

2.60
2.61
3.48
3.51
3.71
3.76
2.16
2.22
2.10
2.17
2.12
2.17
2.08
2.52

24.2
24.1
19.2
20.6
21.4
22.6
10.3
11.9
7.5
8.5
15.0
16.3
20.7
20.6

3040
3020
2345
2450
2400
2450
2190
2600
1890
1970
2670
2740
3160
2860
1727

3.842
3.83
3.665
3.680
7.65
8.67
3.955
3.951
4.909
5.242
4.100
3.852
3.712
4.040
8.61

100

1540
2653
2695
2835
2525
2680
2663
2752

8.61
3.707
3.764
5.558
3.934
3.990
10.1
8.4

1322
1684
1599
1690
1693
1408
1573
1458

2.55

Frequency
106s-

2.20
2.26
2.22
2.25

15.8 a
16.4 a
18.6
14.0
16.2
15.7
17.0

99
107
98

2885
2910
2850
2735
2830
2800
3400
2805
2880
2390
2410
3120
2590
2580

3.635
3.922
3.858
3.662
3.943
3.565
3.833
3.803
3.944
3.906
3.652
3.484
4.014
4.013

100
100

100

100
100
100
100

100
100
100
100
100

100
100

99
100
100

100

100

100
100
100
100
100
100
100
100

100
63
63

63
63
63

100
100

100
100

55

56

ELASTICITY

Table 9. (continued)
Composition
Or7sAn22
Or61Di39
Rb2Si205
SrSi205
Tholeitic

Basalt

Basalt-Andesite
Andesite

Ryolite

kg/ma

K,,oo

V,

GPa

m/s

Frequency
106s-1

References

1783

2.33

13.8

4300

3.836

lOO

1598

2.35

14.1

5200

3.923

lOO

1768

2.38

16.0

2795

3.656

lOO

1578

2.40

16.5

3470

3.673

lOO

1693

2.78

7.8

1678

3.945

lOO

1408

2.88

9.9

2130

3.974

lOO

1758

3.02

19.6

2550

3.690

lOO

1653

3.04

20.1

2570

3.833

lOO

1708

2.65

17.9

2600

3.839

lOO

1505
1803

2.68
2.55

18.3
18.6

2610
2700

3.909
3.790

lOO

1503

2.59

19.4

2980

3.863

lOO

1783

2.44

16.1

2775

3.827

lOO

1553

2.46

16.6

3850

3.889

lOO

1803

2.29

13.0

4350

3.664

lOO

1553

2.31

13.5

5280

3.723

lOO

lOO

Abbreviations: An, CaAI2Si208; Di, CaMgSi2Oa, Or, KA1SiaOs; Ab, NaA1SiaO8.

a From shock wave experiments.

Table

10. Elastic

Moduli

of Glasses
Refer enc es

Composition

kg/m3 GPa

GPa

MPa g -1

SiO2

2.204

36.5

31.2

MgSiO3

2.761

78.8

41.8

129

CaSiOs

2.880

69.2

36.3

129

CaMgSi206

2.863

76.9

39.7

129

2.847

74.1

38.8

113

CaA12Si2Os
Na2Si206

2.693
2.494

69.2
41.9

38.7
24.1

129

(Na20)as(Si02)s'

2.495
2.369

41.0
39.1

23.0
29.2

4.6

2.490
2.749

45.1
50.0

30.2
30.2

2.4
4.9

-0.35
0.5

-7
-8.1

-9
-7.1

2.42

30

21

to +4

- 1

- 2.4

- 3.4

Obsidian

2.331

37.8

30.1

Andesire

2.571

52.5

33.6

Basalt

2.777

62.9

36.5

NaA1SiaO8
Na2A128i208

(NaeO)ao(TiO2)20(SiO2)so

-6

-3.4

16

MPa g -1
4

38, 79

129

0.7

-12.2

-10.7

75

129

-4

-1.8

44
74

75, 36

-1.7

79

0.6

-0.8

79

2.1

-0.3

79

a Compositiongiven as mole percentagesof oxide components.

BASS

Table 11. P and T derivativesof Isotropic Elastic Moduli

Material

tKs/tip

5G/SP

5Ks/tit
MPa/K

tG/ST
MPa/K

AT

References

Elements,Metallic Compounds
Ag, Silver

6.09

1.68

-21.5

-12.7

79-

298

Au, Gold
C, Diamond

6.13

1.27

-31.0

-8.4

79-

298

4.0

2.3

-8.7

-5.7

223-

ct-Fe,(bcc)

323

17
17
77

5.29

1.82

-31

-27

25-

5.97

1.91

-43

-33

300-

5.13

2.16

-51

-47

500-

700

4.3

3.4

-43

-43

800-

900

-18

-14

77-

300

71

-19

-17

80-

298

103

-33

-30

298-

Feo.94Sio.o

300
500

900

29, 42
29, 102
29, 128
29, 49

103

Simple Oxides
A1203, Corundum

BaO

4.3

5.52

1.12

-15

-27

@296

-23

-24

@1ooo

40

-19

-24

@1825

40

-23.9

-12.0

-7

CaO, Lime

195-

293

5.23

1.64

-14.3

-13.8

283-

303

6.0

1.7

-I9.2

-15.0

195-

293

-14.1

-14.7

4.83

1.78

-12.8

-14.9

20

112

CoO

Feo.9O, Wiistite
Feo.9430, Wiistite
Fe203, Hematite
GeOa,

281 - 298

-20

5.1

0.71

4.5

0.73

6.2

1.2

12.4

300-

1200

281 - 298
293-

303

@298

39, 40

26

127
112

8, 114
81
26

120
120
56
69

-36

-12

293-

-20.3

-11

273-473

373

131

(futile structure)
MnO, Manganosite

5.28

1.55

4.7

1.2

138
-21

MgO, Periclase

SrO

3.85

-15.3

89

@298

120

300 - 800

115

4.5

2.5

4.13

2.5

-14.5

-24

@300K

4.27

2.5

-22.5

-26

@1200K

-21.3

-21

5.18

1.61

-17.8

-12.6

-7.1

-11.9

195-

293

5.50

0.61

-19

-6.7

298-

373

6.4

0.46

-8.5

-0.8

6.76

0.78

-48.7

-21.0

6.0

SnO:, Cassiterite
SiOn, Quartz
TiO., Rutlie
UO., Uraninite

14.6

4.69

52, 57
23, 52

@1800K

52

281 - 298

26

@293
298 - 583

1.42

8, 114
22

78, 110,118
34, 73, 76
35

Spinel Structured Oxides

fl-Mg9.Si04, Wadsleyite
MgAI9.O4, Spinel
MgAI9.O4
MgO-2.6AleO3

4.8

5.66

1.7

43
-15.7

-9.4

293 - 423

70,152

4.89

24

4.18

106

57

ELASTICITY

Table 11. (continued)

alf'

MateriM

Mg0.?5Feo.36
All.9o04,

4.92

a:slT
MPa/K

References

AT
K

MPa/K

130

0.29

Pleonaste

Sulphides

PbS, Galena
ZnS, Wurtzite

6.28

BaF2,

5.05

4.37

77-

-39.0

0.00

-9.56

0.00

300

91, 94

298-

373

21

195-

298

145

195-

298

145

195-

295

300-

800

116
147

Binary Halides
-14.5

Frankdicksonite

CaF2, Fluorite
NaCl, Halite

-17.5

4.92
5.27

-10.8

2.14

-11.13

5.256

KCI, Sylvite

5.0

-9.9

2.0

-10.5

-8.2

294-

338

-15.2

-9.5

745-

766

-7.2

-3.2

-8.7

-5.6

300-

1000

147

7, 28, 30

294-

865

146

298 -

1000

121

298-

338

Garnets

Py?aAlm16And4Uv6
Py62AIm36Gr2
Py61AIma6Gr2
Sp,4AIm46
Alm, Py Gr AndsSpa

-19.5
4.93
4.95

1.44

5.43

1.40

Other

MgSiO4

Olivine, Fo90
Fo93Fa7
Fo91Fa9
Fo9oFalo
Fo92Fas

(Mg.sFe0.2)SiOa
ALPO4, Berlinite
Beryl, BeaAISi60 s
Calcitea, CaCOa
Nepheline,

2O
132

288 -

313

111

-20.1

-10.6

-14.9

-12.5

300 -

1350

54

-14.7

-12.5

300 -

1250

54

41

Minerals

4.97

1.82

-17.6

-13.6

300 -

700

5.37

1.80

-15.0

-13.0

298 -

306

65

-16.0

-13.5

293 -

673

119

-15.7

-13.5

4.56
5.13
4.6

1.71
1.79
1.9

FayMite(Fa),
Fe2SiO4
Orthopyroxene

137

-18.8

4.74

Gr9sAnPyl
Gr?6An2Spl

Forsterite(Fo),

-10.2

1.56

10.8

2.06

9.6

2.38

300 -

1700

53
154

-15.6

-1.30

298- 306

65
136

-18.0
-16.9

-13.6
-13.8

300- 1500
300- 1500

51

-24

- 13

300- 500

55

51

137

-26.8
-7

- 11.9
-2

298- 623

33

180- 298

25

153

3.90
4.83

58

-3.7

1.6

298- 353

19

298- 573

88

NaaKAI4Si406

Zircon, ZrSiO4

6.5

0.78

-21

-9.4

Abbreviations: Py, Pyrope MgaAlaSi3012; Aim, Almandite Mg3A12Si302; Gr, GrossularCaaA12Si3012;Uv, Uvarovite
Ca3Cr2Si3012; And, Andradite Ca3Fe2Si3012; Sp, SpessartiteMn3A12Si3012;Fo, Forsterite Mg2SiO4; Fa, FayMite
Fe2SiO4.

a Pressurederivative of KT is given.

BASS

59

Table 12. Higher Order Pressureand TemperatureDerivatives

Composition

52K/SP2
GPa-1

SiOe Glass
Grossular

52G/Sp

52K/ST

52G/ST

GPa-1

kPa K -2

kPa K -

2.9

38

Garnet

CasA12SisO12
Pyrope Garnet
MgaAlSiaO
Forsterire,
T < 760
MgSiO4
T > 760
Olivine,

References

-0.28

-0.08

-1.8

-1.1

54

-1.8

-1.1

136

-5.2
-0.7

-2.6

53
53

-0.15

-0.11

136

(Mg,Fe)SiO4

-0.05

-0.06

154

MgO, Periclase
Fe0.s4sO,Wiistite
CaO, Lime
Orthopyroxene,

-0.03
-0.07

-0.10

57
56

-1.4

- 1.6

0.3

81

-0.12

137

(Mg,Fe)SiOs
MgAI204, Spinel

0.5

24

Acknowledgments:
Thisworkwassupported
in part by the NSF undergrantno. EAR-90-18676.
The review of O.L. Andersonis appreciated.
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Elastic Constants of Mantle Minerals at High Temperature

Orson L. Anderson

1.

and Donald

G. Isaak

ABSTRACT

The techniques
of RUS do not lendthemselves
to pressure measurement.

Data

on elastic constants and associated thermoe-

lastic constants at high temperatures for 14 solidsof

significanceto geophysicsare presentedand discussed.

nique(RPR) pioneeredby Ohno [44] and Sumincet

al. [60] (seeShanklandand Bass[49]for a reviewof
techniques).
We presentthe elasticconstants,Cij versusT, at
high T for fourteensolidslisted in Tables 1-14; in-

A synopsisof quasiharmonic
theory in the high temperature limit shows that anharmonic corrections to

the quasiharmonicdeterminationof thermal pressure

are not neededin the equationof statethroughoutconditionsof the lowermantle. Equationsfor extrapolating the bulk andshearmodulito temperaturesbeyond
the limit of experimentalmeasurement
are givenand

cluded are silicates,oxides, and two alkali halides. In

Tables15-28, we presentisotropicthermoelasticproperties, including the adiabatic bulk modulus Ks and
the shearmodulusG obtainedby appropriateaveraging schemes
(SeeSection4). Valuesof thermalexpansivitya andspecificheat (at constantP) Cp, coupled
with the elasticity data, allow the computationof the

evaluated.
2.

INTRODUCTION

Though compendiumsof elastic constant data for

Griineisen ratio 7 and then values for the isothermal

mineralsexist [11, 50, 59], they are restrictedto tem-

bulk modulusKT (computedfrom Ks) and the specificheat at constantV Cv (computedfromCr). The
densityp is computedfrom a, whichallowsthe respective isotropiclongitudinaland shearsoundvelocities,
vp and v, to be computedfrom Ks and G.

peratures at or near room temperature. Current prob-

lemsin mantlegeophysics
and geochemistry
oftenrequire valuesof elasticconstantsat temperaturesfound
in the lowercrustandmantle(1000to 1900K).
Using the techniquesof resonantultrasoundspectroscopy(RUS) [6, 7], elasticconstantdatahavebeen

From the values of properties in Tables 15-28 the

temperaturederivativesare calculated,thus defining

severalimportant dimensionless
thermoelasticparam-

taken above the Debye temperature of mantle minerals, often as high as 1825 K, which is of the order

eters that are presented in Tables 29-42. We list the

of T = 20, whereO is the Debyetemperature[13].

Anderson-Griineisenparameters, /s and /T; the dimensionlessratio of changeof G with T, r; and the

measureof the rate of changeof shear sound velocity with the longitudinal velocity, v. We also list the
Debye temperature, O, determined from sound velocities; Poisson'sratio, r; and rKT and s integrated
value APTf, which is the changeof thermal pressure
relative to the pressureat 300 K.

O. L. Andersonand D. G. Isaak,Centerfor Chemistryand

Physicsof Earth and Planets,Instituteof Geophysics
and
PlanetaryPhysics,UCLA, Los Angeles,CA 90024
Mineral Physicsand Crysta!lography
A Handbook of PhysicalConstants
AGU

Reference

Shelf 2

Copyright1995 by the AmericanGeophysicalUnion.

We note that of the several RUS

techniques,the predominanttechniqueusedto obtain

the data here is the rectangularparallelepipedtech-

64

ANDERSON

AND

ISAAK

Table 1. MgO' Measuredsingle-crystal

Table 3. Pyrope-rich garnet: Measured single-

elastic
moduli
(GPa)from300to 1800
K

crystal
elastic
moduli
(GPa)from300to

(max. measuredvalueof T/O' 2.22)

1000K (max. measuredvalueof T/O: 1.62)

T (K)
300

Cxx

Cx

C44

C$

T (K)

Oil

Cl

C44

Cs

300

296.6

108.5

91.6

94.0

.+1.5

.+1.4

.+0.2

.+1.0

299.0

96.4

157.1

101.3

+0.7

.+0.6

.+0.3

.+0.2

400

292.9

97.0

155.8

98.0

350

294.6

107.6

91.2

93.5

500

296.9

97.6

154.3

94.6

400

292.7

106.9

90.8

92.9

600

280.6

98.0

152.8

91.3

450

291.0

106.5

90.4

92.3

700

274.5

98.4

151.3

88.0

500

289.2

105.9

90.0

91.7

800

268.2

98.5

149.7

84.8

550

287.3

105.2

89.6

91.1

900

261.9

98.6

148.1

81.7

600

285.5

104.6

89.1

90.5

1000

255.7

98.7

146.5

78.5

650

283.8

104.2

88.7

89.8

1100

249.5

98.6

144.8

75.5

700

282.1

103.7

88.3

89.2

1200

243.3

98.4

143.1

72.5

750

280.3

103.2

87.8

88.6

1300

237.2

98.1

141.3

69.6

800

278.5

102.6

87.4

88.0

1400

231.0

97.6

139.5

66.7

850

276.7

102.1

86.9

87.3

1500

224.9

97.1

137.9

63.9

900

274.8

101.5

86.5

86.7

1600

219.0

96.4

136.2

61.3

950

273.1

101.0

86.0

86.1

1700

213.4

95.7

134.7

58.9

1000

271.2

100.3

85.5

85.5

1800

208.2

95.0

133.1

56.6

.+2.0

+1.9

.+0.2

.+1.4

.+1.2

.+0.5

.+0.2

:::1:1.2

Cs - (1/2)(C

- C).

Cs - (1/2)(Cll - Cid).

AfterSuzuki
& Anderson
[65].

From
Isaak
etal.[34].

Table 2. CaO' Measured single-crystal

Table 4. Grossulargarnet' Measuredsingle-

elastic
moduli
(GPa)from300to1200
K

crystal
elastic
moduli]
(GPa)from300to

(max. measuredvalueof T/O' 1.61)

1350K (max. measuredvalueof T/O: 1.89)

T (K)

Cll

Cl

C44

Cs

300

220.5

57.67

80.03

81.43

.+0.1

.+0.08

.+0.02

.+0.04

400

215.7

57.96

79.35

78.85

500

210.7

58.23

78.70

76.25

600

205.9

58.44

77.94

700

201.2

58.66

77.18

800

196.6

58.81

900

192.0

58.98

1000

187.2

58.98

1100

182.7

1200

178.1

.+0.3

.+0.24

T (K)

Cll

300

318.9

92.2

102.9

113.4

.+0.8

9:0.7

.+0.2

400
500

315.2
311.7

91.8
91.5

101.4
100.4

.+0.3
111.7
110.1

73.72

600

307.8

91.1

99.8

108.4

71.28

700

303.8

90.5

98.7

106.6

76.46

68.88

800

97.6

104.9

66.52

74.92

64.13

58.96

74.17

61.89

900
1000
1100

300.2
296.5
292.7
289.1

90.4

75.72

90.2
89.9
89.8

96.5
95.3
94.2

103.2
101.4
99.7

58.99

73.48

59.56

.+0.09

.+0.09

1200
1300
1350

284.8
280.5
278.8

89.1
88.6
88.7

93.0
91.8
91.2

97.8
96.0
95.0

4-1.4

9:1.2

9:0.3

.+0.4

Cs - (1/2) (C - C).

From
Odaetal.[43].

C12

Cs - (1/2)(C - C).

After
Isaak
etal.[36].

C44

Cs

65

66

HIGH

7' ELASTICITY

OF MANTLE

MINERALS

Table 5. MgA1204: Measuredsingle-crystal

Table 7. KCI: Measured single-crystal

elastic
moduli
(GPa)from300to1000K

elastic
moduli$
(GPa)from300to850K

(max. measuredvalueof T/O: 1.20)

(max. measured
valueof T/O: 4.42)

T (K)

Cll

300

400

292.2
4-5.2
290.1
288.6

168.7
4-5.2
167.2
166.3

156.5
4.1.0
155.0
155.3

450
500

286.2
284.4

164.8
163.7

154.4
153.6

60.7
60.3

550
600

282.8
281.1

162.8
161.9

152.9
152.2

60.0
59.6

650

297.1

160.8

151.5

59.1

700

277.2

159.8

150.7

58.7

750
800
850

275.3
273.3
271.1

158.8
157.7
156.5

149.9
149.2
148.5

58.2
57.8
57.3

350

C12

44

$
61.8

T (K)
300

4.0.3

61.5
61.1

900

269.2

155.5

147.7

56.9

950

267.3

154.4

146.9

56.4

1000

266.0
4.6.5

154.0
4.6.5

146.1
4-1.3

56.0
4-0.4

350
400
450
500
550
600
650
700
750
800
850

C'

C'

C44

Cs

40.1

6.6

6.35

16.7

4-0.4

4-0.5

4-0.02

4-0.3

38.4
36.9
35.4
33.8
32.3
31.1
29.7
28.2
26.6
25.2
23.5
4-0.5

6.8
7.0
7.1
7.2
7.3
7.5
7.7

6.28
6.21
6.15
6.11
6.05
5.96
5.87

7.7
7.7
7.8
7.7
4-0.5

5.79
5.69
5.57
5.57
+0.02

15.8
15.0
14.1
13.3
12.5
11.8
11.0
10.2
9.5
8.7
7.9
4.0.4

Cs = (1/2)(C'n - C').

AfterY,mamoto
& Anderson
[76].

Cs = (1/2)

AfterCynn
[19].

Table 6. MnO: Measured single-crystal

Table 8. NaCI: Measured single-crystal

elastic
moduli
(GPa)from300to500K

elastic
moduli
(GPa)from300to750K

(max. measuredvalueof T/O: 0.96)

(max. measuredvalueof T/O: 2.84)

T (K)
300

T (K)

Cn

C44

223.5

111.8

78.1

55.9

4-4.5

4-3.1

4-0.9

4-2.7

300

C'

C'

C44

Cs

49.5

13.2

12.79

18.1

4-0.4

4-0.4

4-0.02

4-0.3
17.1

350

220.4

111.8

78.1

54.3

350

47.6

13.3

12.62

400

217.2

111.8

77.8

52.7

400

45.8

13.4

12.43

16.2

450

214.1

111.7

77.3

51.2

500

210.9

111.7

76.5

49.6

4-4.5

4-3.1

4-0.9

-/-2.7

450
500
550

44.1
42.4
40.5

13.5
13.6
13.5

12.26
12.09
11.90

15.3
14.4
13.5

600
650

38.7
37.0

13.2
13.1

11.71
11.52

12.7
11.9

700

35.4

13.1

11.31

11.2

750

33.7

12.9

11.10

10.4
:::i:0.3

Cs = (1/2)(Cn -- C'2).

AfterPacalo
& Graham
[47].

:::i:0.4

+0.4

Cs -- (1/2) (Cn - Cid).

AfterYamamoto
etal.[77].

:9:0.02

ANDERSON

AND

Table9. Mg2SiO4'
Measured
single-crystal
elastic
moduli
(GPa)from300to 1700K
(max. measuredvalueof T/O: 2.1)

300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700

330.0
4-0.7
326.3
322.4
318.6
314.5
310.3
306.3
302.0
297.4
292.8
288.3
283.8
279.1
274.4
269.8
4-1.1

200.0
4-0.4
197.2
194.2
191.2
188.0
184.8
181.5
178.3
175.1
171.8
168.7
165.1
162.2
159.0
155.6
+0.8

236.0
+0.6
233.1
230.1
226.8
223.6
220.3
216.9
213.5
209.8
206.1
202.7
199.2
195.5
192.0
188.2
+1.0

67.2
4-0.1
65.9
64.4
63.0
61.6
60.1
58.8
57.4
56.1
54.7
53.3
51.9
50.6
49.3
48.0
4-0.2

81.5
4-0.2
80.1
78.7
77.2
75.8
74.3
72.8
71.3
69.9
68.3
66.9
65.4
64.0
62.5
61.0
4-0.2

81.2
+0.2
79.6
78.0
76.3
74.6
73.0
71.3
69.6
67.9
66.2
64.6
62.9
61.4
59.9
58.4
4-0.3

72.1
+0.4
71.6
71.1
70.4
69.7
69.1
68.3
67.8
67.2
66.6
66.0
65.2
64.6
64.0
63.3
4-0.7

68.0
+0.5
67.0
66.1
65.1
64.3
63.3
62.5
61.5
60.5
59.4
58.5
57.6
56.7
55.8
54.9
4-0.9

66.2
+0.5
65.2
64.0
62.9
61.8
60.7
59.4
58.4
57.3
56.3
55.3
54.2
53.2
52.1
51.0
4-0.8

t Fzom
Isaak
etM.[35].

Table10. Olivine
Fo90Fam:
Measured
elastic
moduli
(GPa)from300to 1500K
(max. measuredvalueof T/O' 2.26)

T (K)

300

320.6

197.1

234.2

+0.4

+0.3

+0.5

400

316.8

194.1

231.0

62.37

76.3

76.61

74.4

70.3

68.6

500

313.0

190.9

227.6

61.05

74.9

74.97

73.7

69.3

67.4

600

309.0

187.7

224.1

59.73

73.6

73.33

73.0

68.3

66.2

700

305.0

184.6

220.6

58.45

72.3

71.73

72.3

67.2

65.0

800

300.7

181.5

217.2

57.23

71.0

70.17

71.6

66.1

63.6

900

297.0

178.3

214.3

55.91

69.9

68.59

71.2

66.0

62.8

1000

293.1

175.3

210.4

54.68

68.5

67.07

70.3

64.7

61.8

1100

289.0

172.3

206.6

53.47

67.1

65.53

69.4

63.4

60.5

1200
1300
1400

285.1
280.9
276.6

169.2
166.1
163.0

202.9
199.3
195.6

52.28
51.06
49.83

65.8
64.5
63.2

64.01
62.51
61.02

68.6
67.8
67.0

62.4
61.4
60.5

59.4
58.2
57.2

+0.5

4-0.4

4-0.7

1500

272.0

159.8

192.1

+0.07
48.57

4-0.2
62.2

+0.11
59.52

4-0.5
66.4

+0.5
59.8

+0.4
56.2

tFzom
Isaak
[32].

C:2

Caa

C44
63.72
+0.05

C55
77.6
+0.1

C6s
78.29
+0.08

Cs
74.8
4-0.3

Cs
71.2
+0.4

C2
69.8
+0.2

ISAAK

67

68

HIGH

T ELASTICITY

OF MANTLE

MINERALS

Table11. Fe2SiO4:
Measured
single-crystal
elastic
moduli
(GPa)from300to
700 K (max. measuredvalueof T/O' 1.41)
T (K)

C22

Css

C44

C55

C66

C23

C12

C31

300

266.9

173.5

239.1

32.4

46.7

57.3

97.9

98.7

95.1

350
400

J:1.9
264.5
262.2

J:1.1
171.8
170.1

J:1.4
237.0
234.7

J:0.1
31.9
31.7

+0.1
46.2
46.0

J:0.1
56.3
55.3

J:1.2
97.7
97.4

J:1.6
98.2
97.7

J:1.5
94.3
93.4

450
500

260.7
258.8

168.4
166.6

232.4
229.9

31.4
31.4

45.8
45.8

54.5
53.7

97.2
96.8

97.5
97.0

92.8
91.9

550
600
650
700

257.0
255.0
252.8
251.0
J:2.2

164.9
162.8
160.9
159.0
:]:1.3

227.5
225.1
222.7
220.5
J:l.6

31.4
31.5
31.5
31.6
:]:0.1

45.7
45.6
45.6
45.5
J:0.1

52.9
52.3
51.6
51.0
J:0.2

96.5
96.0
95.4
94.8
:]:1.3

96.6
96.1
95.5
94.9
4-1.8

91.0
90.0
88.9
87.7
:]:1.7

AfterSumino
[58].

Table12. Mn9.
Si04:Measured
single-crystal
elastic
moduli
(GPa)from300to
700 K (max. measuredvalueof T/O: 1.28)
T (K)

Cll

C44

C55

C66

C23

C31

12

300

258.3

165.5

206.7

45.3

55.6

57.8

91.7

95.2

87.1

400

J:l.9
254.8

+1.0
162.7

:]:1.3
203.9

:]:0.1
44.4

:]:0.2
54.4

:]:0.2
56.4

:t:l.0
90.6

:]:1.5
93.8

J:l.3
85.5

251.3

201.0
198.2
195.3

89.5

92.3

83.8

42.5

52.0

53.7

244.3

159.8
157.0
154.2

41.5

51.8

52.4

43.4
88.3
87.2

53.2
90.9
89.4

55.1
82.2
80.6

4-2.4

4-1.3

4-1.7

4-0.1

4-0.2

4-0.2

4-1.3

4-1.9

4-1.6

500
600
700

247.8

C22

33

AfterSumino
[58].

Table13. Co2SiO4:
Measured
single-crystal
elastic
moduli
(GPa)from300to
700 K (max. measuredvalueof T/O: 1.25)
T (K)

Cll

C22

C33

300

307.7
4-1.2

194.7
4-0.7

400
500

304.0
301.1

192.6

230.7

190.5

600

297.8

700

294.5
4-1.7

C55

C66

46.7

63.9

64.8

4-0.1

4-0.1

4-0.1

227.4

46.2
45.7

62.9
61.9

188.8

224.0

45.2

186.2
4-1.2

220.6
4-1.4

44.7
+0.1

AfterSumino
[58].

234.1
4-0.9

C44

C23

C31

C12

103.2
4-0.7

105.0
4-1.0

101.6
4-0.8

62.8

101.8
100.5

103.6
102.3

99.8
97.9

60.8

61.8

99.1

100.9

96.1

59.8
+0.1

60.8
4-0.2

97.8
4-1.1

99.6
4-1.3

4-1.3

63.8

94.3

ANDERSON

AND

ISAAK

Table14. AleOs'
Measured
single-crystal
elastic
moduli
(GPa)
from 300 to 1800K (max. measuredvalueof T/O' 1.95)

T (K)
300

400
500
600

Cxx

Caa

C44

C2

Cxa

497.2

500.8

146.7

162.8

116.0

+1.5

:!:1.8

+0.2

:!:1.7

+1.0

494.7
490.6
486.0

497.2
493.6
489.2

144.4
141.8
139.2

163.8
163.7
163.1

115.3
114.4
113.0

C14
-21.9
4- 0.2

-22.5
-23.0
-23.3

700

481.5

484.9

136.5

162.9

111.9

-23.4

800

476.8

480.4

133.9

162.4

110.6

-23.7

900

472.3

476.0

131.2

162.4

109.6

-23.9

1000

467.4

471.2

128.6

161.8

108.2

-24.1

1100

462.5

466.4

125.8

161.4

107.1

-24.2

1200

457.3

461.1

123.2

160.7

105.4

-24.3

1300

451.9

456.2

120.4

160.0

104.1

-24.4

1400

446.7

450.8

117.7

159.5

102.4

-24.5

1500

442.2

446.4

115.1

159.4

101.6

-24.5

+1.9

+2.1

4-0.2

+2.2

4-2.1

1600

437.2

441.3

112.5

159.0

100.5

-24.6

1700

432.3

436.5

110.0

158.4

99.4

-24.5

1800

427.2

432.5

107.4

158.0

99.1

-24.5

+ 0.2

t From
Goto
eta].[26].
Table15. MgO:Thermal
expansivity,
specific
heat,isotropic
elastic
constants
andvelocities$

Ks

Cp*

9/

J/(gK)

K.

vr

GPa

km/s

V$

g/cma

10-5/K

3.602

0.63

165.7

132.0

0.194

1.59

0.194

165.6

9.80

6.13

200

3.597

2.24

164.6

130.3

0.662

1.55

0.658

163.5

9.78

6.10

300

3.585

3.12

163.9

131.8

0.928

1.54

0.915

161.6

9.73

6.06

+0.6

+0.5

:t:0.6

4-0.01

4-0.01

+0.06

GPa J/(gK)

Cv

100

4-0.005

GPa

4-0.03

km/s

400
500

3.573
3.559

3.57
3.84

162.3
160.7

129.4
126.9

1.061
1.130

1.53
1.53

1.048
1.098

158.9
156.1

9.68
9.63

6.02

600

3.545

4.02

158.9

124.4

1.173

1.54

1.131

153.2

0.57

5.92

700
800
900

3.531
3.516
3.501

4.14
4.26
4.38

157.1
155.1
153.1

121.8
119.2
116.7

1.204
1.227
1.246

1.53
1.53
1.54

1.153
1.166
1.175

150.4
147.4
144.3

9.51
9.45
9.39

5.87

1000

3.486

4.47

151.1

114.1

1.262

1.54

1.181

141.4

9.33

5.72

1100

3.470

4.56

148.9

111.5

1.276

1.53

1.185

138.3

9.26

5.67

1200

3.454

4.65

146.7

109.0

1.289

1.53

1.188

135.1

9.19

5.62

1300
1400
1500
1600
1700
1800

3.438
3.422
3.405
3.388
3.371
3.354
4-0.007

4.71
4.80
4.89
4.98
5.04
5.13
4-0.10

144.4

106.4
103.8
101.3
99.0
96.7
94.5
+1.6

1.301
1.312
1.323
1.334
1.346
1.358

1.52
1.52
1.52
1.51
1.50
1.50
+0.03

1.190
1.191
1.191
1.191
1.193
1.193

132.1

9.13
9.05
8.98
8.92
8.85
8.78
4-0.04

5.56

142.0

139.7
137.3
134.9
132.7
4-1.1

$Computed
from
Table
1;t Suzuki
[64];
'Garvin
etal.[25].

128.1

125.7
122.5
119.6
116.6
4-1.1

5.97

5.82
5.77

5.51

5.46
5.41
5.36
5.31
4-0.05

69

70

HIGH

T ELASTICITY

OF MANTLE

MINERALS

Table16. A12Os'
Thermal
expansivity,
specific
heat,isotropic
moduli
andvelocities

T
300

Ks

1.62
4-0.03
1.99
2.23
2.40
2.51

253.6
4-1.7
252.6
250.9
248.6
246.6

163.0
4-2.8
161.1
158.8
156.6
154.2

0.779

700

3.982
+0.009
3.975
3.966
3.957
3.947

800

3.937

2.59

244.4

151.9

900

3.927

2.66

242.4

1000

3.916

2.73

1100

3.906

2.80

1200

3.894

1300

Cg
0.774

1.148

1.32
4.0.03
1.34
1.36
1.37
1.36

1.180

1.36

149.5

1.205

1.36

240.0

147.1

1.223

237.8

144.6

1.244

2.88

235.2

142.2

3.883

2.96

232.6

1400

3.872

3.03

1500
1600

3.860
3.848

1700
1800

400
500
600

Ka,vp

1.121

252.0
4-1.7
249.9
247.1
243.8
240.8

10.88
4.0.05
10.84
10.80
10.75
10.70

1.148

237.7

10.65

6.21

1.167

234.8

10.61

6.17

1.37

1.179

231.4

10.55

6.13

1.37

1.194

228.2

10.50

6.09

1.257

1.38

1.199

224.5

10.44

6.04

139.7

1.267

1.40

1.203

220.8

10.39

6.00

230.0

137.2

1.277

1.41

1.205

217.1

10.33

5.95

3.09
3.15

228.1
225.9

134.8
133.5

1.286
1.296

1.42
1.43

1.207
1.209

214.0
210.7

10.28
10.23

5.91
5.86

3.835

3.20

224.8

131.2

1.306

1.43

1.212

207.5

10.17

5.82

3.823

3.25

221.8

127.5

1.318

1.43

1.216

204.7

10.12

5.78

4-0.009

4-0.06

4-2.3

4-4.8

4-2.2

4-0.009

4-0.11

0.943
1.040
1.103

0.933
1.024
1.082

4-0.03

6.40
4-0.06
6.37
6.33
6.29
6.25

Computed
from
Table
14;White
& Roberts
[75];
*Furukawa
etal.[24];
Dimensions
asinTable
15.

Table17. MgA1204'
Thermal
expansivity,
specific
heat,isotropic
moduli$
andvelocities$

T
300
350
400
450
500

550
600
650
700
750

at

Ks

C'p*
0.819

3.576
4-0.005
3.572
3.568
3.564
3.560
3.555

2.11
+0.04
2.18
2.25
2.32
2.38
2.45

209.9

108.2

+5.2
208.2
207.1
205.3
203.9
202.8

4-2.5
107.7
107.2
106.6
106.0
105.5

3.551

2.51

201.6

104.9

1.088
1.115

3.547
3.542

2.57
2.63

200.3
199.0

104.3
103.6

1.139
1.160

1.28
1.27

0.899

0.963
1.014
1.055

1.51
4.0.05
1.41
1.36
1.32
1.30
1.28

Cg
0.811
0.889

0.952
1.001
1.039

Ka.
207.9

vp

4-5.2
205.9
204.6
202.5
200.8
199.4

9.95
4.0.09
9.92
9.91
9.87
9.85
9.83

5.50
4.0.06
5.49
5.48
5.47
5.46
5.45

197.8

9.81

196.1
194.4

9.78
9.76

5.45
5.42
5.41

3.537

2.69

197.7

103.0

1.179

1.27

1.069
1.094
1.115
1.133
1.149

192.7

9.73

5.40

800

3.532

2.74

196.2

102.4

1.180

1.27

1.164

190.9

9.71

5.38

850
900

3.528
3.523

2.80
2.85

194.7
193.4

101.8
101.1

1.213
1.229

1.27
1.27

1.178
1.190

189.0
187.3

9.68
9.65

5.37
5.36

950

3.518

2.90

192.0

100.5

1.243

1.27

1.201

185.5

9.63

5.34

1000

3.512

2.94

191.3

99.8

1.253

1.28

1.208

184.4

9.61

5.33

4.0.005

4-0.06

4-6.5

4-2.7

4-6.3

4-0.11

4-0.07

1.28

4-0.05

$Computed
from
Table
5;tTouloukian
etal.[69];
*Robie
etal.[48];
Dimensions
asinTable
15.

ANDERSON

AND

ISAAK

Table18. Mg2SiO4'
Thermal
expansivity,
specific
heat,isotropic
moduli
andvelocities

T
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700

p
3.222
-4-0.007
3.213
3.203
3.192
3.181
3.170
3.159
3.147
3.135
3.122
3.109
3.096
3.083
3.069
3.055
4.0.008

at
2.72
-4-0.05
3.03
3.22
3.36
3.48
3.59
3.70
3.81
3.92
4.05
4.16
4.27
4.39
4.50
4.62
4.0.08

Ks

128.6
-4-0.4
127.1
125.4
123.7
121.9
120.2
118.3
116.6
114.8
112.9
111.1
109.2
107.5
105.6
103.7
4.0.5

81.6
-4-0.3
80.3
78.9
77.4
76.0
74.5
73.1
71.6
70.1
68.6
67.1
65.6
64.1
62.7
61.2
4-0.3

C*
0.840
0.990
1.068
1.119
1.156
1.186
1.211
1.235
1.256
1.277
1.296
1.315
1.334
1.352
1.370

7
1.29
-4-0.02
1.21
1.18
1.17
1.16
1.15
1.15
1.14
1.14
1.15
1.15
1.15
1.15
1.15
1.14
4-0.02

Cv
0.831
0.976
1.048
1.093
1.124
1.148
1.167
1.183
1.197
1.210
1.220
1.231
1.240
1.249
1.257

KT
127.3
4-0.4
125.2
123.1
120.8
118.6
116.3
114.0
111.7
109.4
106.9
104.6
102.2
99.9
97.6
95.2
4-0.5

v,
8.58
4-0.01
$.54
8.48
8.43
8.38
8.32
8.27
8.21
8.15
8.09
8.03
7.97
7.91
7.85
7.79
4-0.02

V$

5.03
4-0.01
5.00
4.96
4.93
4.89
4.85
4.81
4.77
4.73
4.69
4.65
4.60
4.56
4.52
4.48
4-0.01

[Computed
from
Table
9;tKajiyoshi
[38];
*Barin
& Knacke
[15];
Dimensions
asinTable
15.

Table19. Olivine
Fo9oFalo'
Thermal
expansivity,
specific
heat,isotropic
moduliandvelocities

T
300

400
500
600
700
800
900
1000
1100

1200
1300
1400
1500

at

Ks

3.353
4-0.004
3.343
3.333
3.322

2.66
4-0.05
2.99
3.21
3.35

129.3
4-0.3
127.7
125.9
124.1

78.1
4-0.2
76.8
75.3
73.9

0.816

3.311
3.299
3.287
3.275
3.263
3.251
3.238
3.225
3.212
4-0.004

3.46
3.55
3.64
3.71
3.79
3.86
3.93
4.00
4.07
4-0.08

122.2
120.3
118.9
117.0
115.1
113.2
111.4
109.6
107.8
4-0.5

72.5
71.2
69.8
68.5
67.1
65.8
64.4
63.1
61.7
4-0.3

0.957
1.032
1.080
1.112
1.145
1.171
1.194
1.216

1.236
1.256
1.275
1.294

7
1.25
4-0.02
1.19
1.17
1.16

1.14
1.13
1.12
1.11
1.10
1.09
1.08
1.07
1.06
4-0.02

Cv

KT

0.808

128.0
4-0.3
125.9
123.6
121.2

8.34
4-0.01
8.29
8.24
8.19

4.83
4-0.01
4.79
4.75
4.72

118.2
116.6
114.7
112.1
110.0
107.8
105.6
103.4
101.3
4-0.5

8.13
8.07
8.03
7.97
7.92
7.86
7.81
7.75
7.69
4-0.01

4.68
4.65
4.61
4.57
4.54
4.50
4.60
4.22
4.38
4-0.01

0.944
1.013
1.055
1.086
1.109
1.129
1.147
1.163

1.177
1.191
1.203
1.216

Computed
from
Table
10;tSuzuki
[64];
*Barin
&Knacke
[15];
Dimensions
asinTable
15.

V$

71

Table20. Fe2SiO4'
Thermal
expansivity,
specific
heat,isotropic
moduliandvelocities:

T
300
400
500
600
700

'

Ks

Cr*

4.400
4.0.009
4.388

2.61
4.0.05
2.74

138.0
4.0.8
135.9

51.0
4.0.5
49.7

0.673

4.375
4.362
4.348
4-0.009

3.00
3.12
3.22
4-0.06

134.0
131.8
129.3
4-0.9

48.8
48.0
47.4
4-0.4

0.793
0.830
0.863

0.746

C,

1.21
4-0.03
1.18

0.667

1.16
1.13
1.11
4-0.03

0.779
0.813
0.842

0.736

K.

vp

V$

136.7
4-0.8
134.1

6.84
4-0.02
6.79

3.40
4-0.02
3.37

131.7
129.0
126.1
4-0.8

6.74
6.70
6.65
4-0.02

3.34
3.32
3.30
4-0.02

Computed
from
Table
11;Suzuki
etal.[67];
*Watanabe
[72];
Dimensions
asinTable
15.
Table21. Mn2SiO4:
Thermal
expansivity,
specific
heat,isotropic
moduli:
andvelocities

T
300

at

Ks

Cr*
0.666

4.129

2.27

128.9

54.5

4-0.005

4-0.05

4-0.6

4-0.3

1.06

400

4.119

2.57

127.0

53.5

0.736

1.08

500
600
700

4.108
4.096
4.084
4-0.005

2.77
2.91
3.03
4-0.06

125.0
123.0
121.1
4-0.8

52.5
51.4
50.4
4-0.3

0.781
0.818
0.850

1.08
1.07
1.06
4-0.03

Cg
0.661

KT

vp

V$

128.0

6.99

3.634

4-0.6

4-0.01

-90.009

0.728

125.6

6.94

3.604

0.770
0.803
0.831

123.1
120.8
118.4
4-0.8

6.89
6.84
6.79
4-0.02

4-0.03

3.573
3.543
3.512
4-0.011

Comruted
from
Table
12;Okajima
etal.[46];
*Barin
& Knacke
[15];
Dimensions
asinTable
15.
Table22. Co2SiO4'
Thermal
expansivity,
specific
heat,isotropic
moduliandvelocities;

af

300

4.706
4-0.009

2.27
4-0.05

148.2
+0.5

62.0
4.0.3

0.640

1.12
4-0.03

0.636

147.1
4-0.5

7.00
4-0.01

3.621
4-0.009

400
500
600
700

4.695
4.682
4.669
4.655
4-0.009

2.57
2.77

146.2
144.3
142.3
140.4
4-0.7

61.4
60.7
59.9
59.1
4.0.3

0.747
0.803

1.07
1.06

0.739
0.791

144.6
142.2

6.97
6.93

3.611
3.594

0.840
0.868

1.06
1.05
4.0.02

0.825
0.849

139.8
137.3
4.0.6

6.89
6.86
4-0.01

3.557
4-0.010

2.91
3.03
4-0.06

Ks

C*

Cg

KT

vp

Us

3.575

Computed
from
Table
13; (assume
Mn2SiO4);
*Watanabe
[72];
Dimensions
asinTable
15.
Table23. MnO'Thermal
expansivity,
specific
heat,isotropic
moduli:
andvelocitiesJ:

T
300

Ks

(7

C*

3.46
4-0.07
3.58

149.0

350

5.378
4-0.001
5.369

4-2.6
148.0

68.3
4-1.5
67.6

0.632

400

5.359

3.68

146.9

66.7

0.653
0.669

450
500

5.349
5.339

3.77
3.85

145.8
144.8

65.6
64.4

0.682
0.692

4-0.001

4-0.08

4-2.6

4-1.6

?
1.51
4-0.04
1.51

Cg
0.623

1.51

0.641
0.655

1.51
1.51

0.665
0.673

4-0.04

K.
146.7

vp

Us

+2.5
145.2

6.68
4.0.05
6.66

143.7

6.63

3.53

142.2
140.7

6.60
6.57

3.50
3.47

4-2.5

4-0.05

4-0.04

Computed
from
Table
6;Suzuki
etal.[66];
*Barin
& Knacke
[15];
Dimensions
asinTable
15.

3.57
4.0.04
3.55

Table24. CaO'Thermal
expansivity,
specific
heat,isotropic
moduli$
andvelocities

300

Ks

C
0.752

3.349

3.04

112.0

80.59

4-0.001

4-0.06

4-0.1

4-0.02

7
1.35

Cv
0.743

4-0.03

K,

vr

V$

110.6

8.094

4.905

4-0.1

4-0.002

4-0.001

400

3.338

3.47

110.5

79.15

0.834

1.36

0.819

108.5

8.045

4.869

500

3.327

3.67

109.1

77.71

0.880

1.37

0.858

106.4

7.996

4.834

600

3.314

3.81

107.6

76.22

0.904

1.37

0.877

104.3

7.946

4.796

700

3.301

3.92

106.2

74.76

0.921

1.37

0.888

102.3

7.897

4.759

800

3.288
3.275

4.01

104.7
103.3

73.33
71.90

0.933
0.943

1.37

0.894
0.898

100.3

900

98.4

7.848
7.799

4.723
4.686

1000

3.262

4.14

101.7

70.40

0.952

1.36

0.901

96.3

7.745

4.646

1100

3.248

4.20

100.2

68.99

0.959

1.35

0.903

94.3

7.693

4.609

1200

3.234

4.26

98.7

67.56

0.965

1.35

0.903

92.3

7.640

4.571

4-0.002

4-0.09

4-0.2

4-0.08

4-0.3

4-0.006

4-0.003

4.08

1.36

4-0.03

Computed
fromTable
2; Odaetal.[43];
'Garyin
etal.[25];
Dimensions
asinTable
15.
_

Table25. Grossular
garnet:
Thermal
expansivity,
specific
heat,isotropic
moduli
andvelocities

T
300

400
500
600
700
800
900
1000
1100
1200

1300

al

3.597

1.92

167.8

106.9

0.736

1.22

4-0.006

4-0.05

4-0.7

4-0.2

3.589

3.532
3.522

2.28
2.49
2.61
2.71
2.78
2.83
2.88
2.92

166.2
164.9
163.3
161.6
160.3
158.9
157.5
156.2

105.7
104.5
103.1
101.8
100.5
99.1
97.7
96.4

.0.865
0.945
0.995
1.028
1.052
1.072
1.092
1.113

1.22
1.21
1.20
1.19
1.19
1.19
1.18
1.16

0.855
0.931
0.977
1.006
1.025
1.041
1.056
1.073

3.512
3.501
4-0.006

2.97
3.00
4-0.07

154.4

94.9

1.139

1.14

1.095

148.3

152.6
4-1.2

93.4
4-0.2

1.170

1.12
4-0.03

1.121

146.2
4-1.2

3.581

3.571
3.562
3.552
3.542

Ks

Cu
0.730

4-0.03

K,

vr

166.6

9.29

5.453

4-0.7

4-0.01

4-0.006

164.4

9.25
9.22
9.18
9.14
9.10
9.06
9.03
8.99

5.427
5.401
5.373
5.346
5.318
5.289
5.259
5.230

8.94
8.90
4-0.02

5.198
5.165
4-0.008

162.5

160.3
158.1
156.2
154.3

152.3
150.6

J;Computed
from
Table
4;Isaak
etal.[36];
*Krupka
etal.[39];
Dimensions
asinTable
15.
Table26. Pyrope-rich
garnet:
Thermal
expansivity,
specific
heat,isotropic
moduli;
andvelocities:

T
300

400
500
600
700
800
900
1000

p
3.705

at
2.36

171.2

Ks

92.6

0.726

1.50

4-0.005

4-0.04

4-0.8

4-0.4

3.696
3.686
3.675
3.664
3.653
3.642
3.631
4-0.005

2.64
2.80
2.90
2.97
3.03
3.07
3.11
4-0.06

168.9
167.0
164.9
163.2
161.3
159.3
157.3
4-1.1

91.6
90.6
89.7
88.7
87.6
86.5
85.5
4-0.6

Cg

1.34
1.29
1.26
1.24
1.23
1.22
1.21
4-0.02

vr

169.4

4-0.8

0.02

4-0.01

0.889
0.964
1.010
1.040
1.057
1.068
1.076

166.5
164.0
161.4
159.1
156.6
154.1
151.6
4-1.1

8.87
8.84
8.80
8.76
8.72
8.68
8.64
4-0.03

4.98
4.96
4.94
4.92
4.90
4.87
4.85
4-0.02

4-0.03
0.902
0.981
1.032
1.067
1.088
1.104
1.116

K,

0.718

Computed
from
Table
3;t Suzuki
&Anderson
[65];
*idare;
Dimensions
asinTable
15.

8.92

5.00

74

HIGH

T ELASTICITY

OF MANTLE

MINERALS

Table27. NaCI:Thermal
expansivity,
specific
heat,isotropic
elastic
moduliandvelocities

T
300

350
400
450
500
550
600
650
700
750

p
2.159
4-0.005
2.146
2.132
2.118
2.104
2.089
2.074
2.059
2.043
2.026
4-0.006

at

Ks

11.8
4-0.2
12.2
12.7
13.2
13.7
14.3
14.8
15.4
16.0
16.6
4-0.3

25.3
4-0.3
24.8
24.2
23.7
23.2
22.5
21.7
21.1
20.5
19.8
4-0.3

14.71
4-0.08
14.27
13.81
13.39
12.96
12.53
12.11
11.68
11.25
10.80
4-0.11

C'*
0.868

0.883
0.897
0.910
0.923
0.937
0.950
0.964
0.979
0.997

7
1.59
4-0.04
1.60
1.61
1.62
1.64
1.64
1.63
1.63
1.63
1.63
4-0.04

C'v
0.822

0.826
0.829
0.830
0.830
0.830
0.830
0.829
0.828
0.829

Ka.vp
24.0
4-0.3
23.2
22.4
21.6
20.8
19.9
19.0
18.1
17.3
16.5
4-0.3

4.56
4-0.02
4.52
4.47
4.43
4.39
4.33
4.27
4.22
4.17
4.11
4-0.02

2.610
4-0.008
2.579
2.545
2.514
2.482
2.449
2.416
2.382
2.346
2.309
4-0.012

Computed
from
Table
8;tEnck
&Dommel
[22];
*Stull
&Prophet
[57];
Dimensions
asinTable
15.

Table28. KCI:Thermal
expansivity,
specific
heat,isotropic
elastic
moduli;andvelocities;

T
300
350
400
450
500
550
600
650
700
750
800
850

at

Ks

1.982
4-0.005
1.971
1.959

11.0
4-0.2
11.3
11.7

17.8
4-0.4
17.3
17.0

9.47
4-1.03
9.18
8.91

1.948
1.935
1.923
1.910
1.897
1.883
1.869
1.855
1.840
4-0.005

12.1
12.6
13.2
13.7
14.2
14.7
15.2
15.7
16.2
4-0.2

16.6
16.1
15.7
15.4
15.0
14.5
14.0
13.6
12.0
4-0.4

8.64
8.39
8.13
7.85
7.57
7.29
6.98
6.67
6.41
4-0.13

C*
0.689
0.701
0.713
0.724
0.735
0.745
0.756
0.767
0.778
0.791
0.806
0.823

7
1.44
4-0.04
1.42
1.42

1.42
1.43
1.44
1.45
1.46
1.46
1.44
1.43
1.39
4-0.04

C'v
0.657
0.664
0.669
0.672
0.674
0.675
0.676
0.676
0.677
0.679
0.683
0.691

Ka.vp
17.0
4-0.3
16.4
15.9

3.92
4-0.09
3.88
3.84

2.19
4-0.12
2.16
2.13

15.4
14.7
14.2
13.7
13.2
12.6
12.0
11.5
10.9
4-0.3

3.80
3.75
3.71
3.68
3.64
3.59
3.53
3.48
3.42
4-0.03

2.11
2.08
2.06
2.03
2.00
1.97
1.93
1.90
1.87
4-0.02

Computed
from
Table
7;tEnck
etal.[23];
*Stull
&Prophet
[57];
Dimensions
asinTable
15.

ANDERSON

AND

Table 29. A12Os: Dimensionlessparameters,Debye temperature and thermal

pressure

300
400

1034
1029

r
0.235
0.237

$
3.30
3.16

$T

(ZT-Zs) v

5.71
5.16

5.71
5.16

1.82
1.49

1.60
1.52

aKT
MPa/K

GPa

4.08
4.98

0.00
0.45
0.98

500

1022

0.239

3.20

5.03

6.27

1.35

1.46

5.53

600

1015

0.240

3.31

5.08

6.09

1.29

1.42

5.85

1.55

700

1008

0.241

3.43

5.17

6.05

1.28

1.40

6.03

2.15

800

1001

0.243

3.55

5.29

6.06

1.28

1.38

6.15

2.76

900
1000
1100
1200
1300
1400
1500
1600
1700
1800

994
986
979
971
963
955
947
939
932
924

0.244
0.246
0.247
0.248
0.250
0.251
0.253
0.255
0.257
0.259

3.62
3.66
3.65
3.60
3.51
3.39
3.24
3.06
2.85
2.60

5.37
5.42
5.42
5.39
5.32
5.22
5.08
4.92
4.73
4.50

6.08
6.09
6.07
6.03
5.98
5.93
5.87
5.80
5.74
5.66

1.28
1.29
1.29
1.30
1.29
1.30
1.30
1.30
1.32
1.32

1.36
1.36
1.36
1.37
1.38
1.40
1.43
1.47
1.52
1.58

6.24
6.30
6.40
6.45
6.52
6.57
6.62
6.64
6.64
6.66

1.43
4.01

Calculated

from Tables

4.64
5.93

5.93
6.59
7.24
7.91
8.57
9.24

14 & 16.

Table 30. MgO' Dimensionlessparameters,Debye temperature and thermal

pressure

300

800
900

945
937
928
920
911
902
894

0.183
0.185
0.188
0.190
0.192
0.194
0.196

2.83
2.79
2.81
2.86
2.92
2.98
3.04

1000
1100
1200
1300
1400
1500
1600
1700
1800

885
875
806
857
847
838
828
820
811

0.198
0.200
0.202
0.204
0.206
0.208
0.209
0.211
0.212

3.12
3.21
3.30
3.41
3.47
3.50
3.46
3.36
3.12

400
500

600
700

Calculated/tom

5.26

1.57
1.33
1.23
1.18
1.16
1.15
1.13

1.40
1.40
1.38
1.37
1.35
1.34
1.32

5.04
5.67
6.00
6.16
6.23
6.28
6.32

0.00

4.74
4.78

5.73
5.34
5.17
5.08
5.05
5.03
5.02

4.84
4.92
4.99
5.08
5.12
5.13
5.07
4.95
4.66

5.05
5.08
5.09
5.10
5.04
4.92
4.75
4.56
4.34

1.12
1.12
1.11
1.10
1.09
1.07
1.07
1.06
1.03

1.31
1.30
1.28
1.26
1.24
1.22
1.21
1.20
1.23

6.32
6.31
6.28
6.22
6.19
6.16
6.13
6.03
6.00

4.24

4.83
4.69

4.67
4.70

Tables I & 15. Dimensions as in Table 29.

(ZT--ZS) v
0.54
1.12

1.73

2.35

2.98
3.61
4.87

5.50
6.12

6.74

7.36
7.97

8.58

9.20

ISAAK

75

Table 31. CaO' Dimensionless

parameters,
Debyetemperatures
andthermalpressure

(9

6s

6T

300
400
500
600
700
800
900
1000
1100
1200

671
666
660
654
649
643
637
631
625
619

0.210
0.211
0.212
0.213
0.215
0.216
0.218
0.219
0.220
0.221

4.15
3.75
3.60
3.54
3.52
3.53
3.55
3.58
3.62
3.65

6.19
5.54
5.27
5.14
5.07
5.03
5.01
5.00
5.01
5.01

6.00
5.38
5.13
5.01
4.99
4.95
4.93
4.94
4.96
4.99

(zT-zs) v
1.51
1.31
1.22
1.17
1.13
1.10
1.07
1.05
1.03
1.01

1.24
1.24
1.23
1.23
1.23
1.23
1.22
1.22
1.22
1.22

cKT
3.36
3.73
3.90
3.98
4.01
4.02
4.01
3.99
3.96
3.93

0.00
0.36
0.74
1.13
1.53
2.34
2.34
2.54
3.13
3.53

Clculated from Tables 2 & 24. Dimensions as in Table 29.

Table 32. Grossular

garnet:Dimensionless
parameters,
Debyetemperatures
and
thermal pressure

(9

I'

300
400
500
600
700
800
900
1000
1100
1200
1300

824
820
816
811
806
801
796
791
786
780
715

0.237
0.238
0.239
0.239
0.240
0.241
0.242
0.243
0.244
0.245
0.246

4.64
3.93
3.64
3.49
3.41
3.35
3.31
3.29
3.27
3.26
3.25

6.30
5.36
4.98
4.80
4.70
4.64
4.60
4.58
4.57
4.57
4.58

6.09
5.27
4.97
4.87
4.84
4.86
4.90
4.96
5.03
5.11
5.20

(z'-zs)
1.36
1.17
1.11
1.08
1.08
1.08
1.08
1.09
1.11
1.15
1.18

trKT

APTIt

1.22
1.23
1.24
1.25
1.26
1.27
1.28
1.29
1.30
1.31
1.32

3.21
3.74
4.03
4.18
4.28
4.34
4.36
4.38
4.41
4.40
4.38

0.00
0.36
0.75
1.16
1.57
1.98
2.40
2.83
3.25
3.69
5.40

Calculated from Tables 4 & 25. Dimensions as in Table 29.

Table 33. Pyrope-rich

garnet:Dimensionless
parameters,
Debyetemperatures
and
thermal pressure
7

300
350
400
450
500
550
600
650
700
750
800
850
900
950
1000

779
777
775
773
771
769
767
765
764
761
759
757
755
753
751

0.271
0.271
0.270
0.270
0.270
0.270
0.270
0.270
0.270
0.270
0.270
0.270
0.270
0.270
0.270

4.81
4.52
4.36
4.24
4.16
4.11
4.07
4.05
4.01
4.00
3.98
3.98
3.98
3.97
3.97

6.27
5.90
5.70
5.55
5.46
5.41
5.35
5.34
5.30
5.29
5.28
5.29
5.30
5.30
5.32

4.29
4.07
3.96
3.90
3.86
3.86
3.86
3.88
3.89
3.92
3.94
3.98
4.02
4.06
4.10

Calculated from Tables 3 & 26. Dimensionsas in Table 29.

0.97
1.00
1.00
1.00
1.00
1.02
1.04
1.04
1.04
1.05
1.06
1.07
1.09
1.10
1.11

0.88
0.89
0.90
0.92
0.93
0.94
0.96
0.97
0.98
1.00
1.01
1.02
1.04
1.05
1.06

4.00
4.25
4.40
4.51
4.59
4.64
4.68
4.69
4.72
4.74
4.74
4.74
4.73
4.73
4.71

0.00
0.21
0.42

0.65
0.87
1.10
1.34
1.57

1.81
2.04
2.28
2.52
2.75
2.99

3.23

ANDERSON

AND

Table 34. Mg2SiO4:Dimensionless

parameters,Debyetemperatureand thermal
pressure

300

0.238
0.239
0.240
0.241
0.242

4.45

5.94

6.07

1.16

1.20

3.46

4.20

5.58

5.66

1.14

1.21

3.80

0.36

500
600
700

763
757
751
744
738

4.15
4.15
4.16

5.49
5.48
5.49

5.54
5.50
5.46

1.14
1.14
1.15

1.20
1.20
1.20

3.97
4.07
4.13

0.75

800
900
1000
1100

731
724
718
711

0.243
0.244
0.245
0.246

4.13
4.08
4.05
4.00

5.47
5.46
5.47
5.46

5.45
5.44
5.45
5.43

1.17
1.20
1.25
1.28

1.18
1.20
1.22
1.20

4.18
4.22
4.26
4.31

1200
1300
1400
1500
1600
1700

704
697
689
682
674
668

0.248
0.249
0.250
0.251
0.252
0.254

4.02
3.97
3.90
3.92
3.93
3.96

5.49
5.44
5.37
5.38
5.40
5.42

5.38
5.32
5.24
5.22
5.19
5.16

1.28
1.28
1.28
1.27
1.28
1.28

1.21
1.20
1.21
1.23
1.19
1.20

4.33
4.36
4.37
4.39
4.40
4.39

400

Calculated

tr

a"F

from Tables 9 & 18. Dimensions

(r-s)

as in Table

aKr
0.00

1.16

1.57

1.98
2.40

2.83
3.25

3.69
4.13
4.5O

5.07
5.43
5.87

29.

Table 35. Olivine Fo90Fa0:Dimensionless

parameters,Debye temperaturesand
thermal pressure

300
400

731
725

0.249
0.250

5.24
4.70

6.59
5.95

500
600
700
800

719
713
706
700

0.251
0.252
0.252
0.253

4.46
4.33
4.25
4.21

900
1000

699
688

0.255
0.255

1100

681

1200
1300
1400
1500

675
669
662
665

Calculated

a"F

(r-s)

6.56
5.92

1.07
1.03

1.17
1.17

3.37
3.76

0.00

5.65
5.51
5.44
5.40

5.63
5.50
5.42
5.38

1.02
1.02
1.04
1.06

1.17
1.18
1.18
1.18

3.97
4.05
4.11
4.14

0.75

4.16
4.14

5.36
5.36

5.36
5.35

1.07
1.10

1.18
1.18

4.18
4.17

2.38

0.256

4.13

5.37

5.35

1.13

1.18

4.17

3.22

0.257
0.258
0.259
0.260

4.12
4.07
4.10
4.10

5.38
5.35
5.41
5.43

5.36
5.32
5.39
5.41

1.16
1.18
1.23
1.26

1.18
1.18
1.19
1.19

4.16
4.15
4.14
4.13

3.63

from Tables 10 & 19. Dimensions

as in Table

29.

aKr
0.36
1.15
1.56

1.97

2.80

4.05
4.46
4.88

ISAAK

77

78

HIGH

7' ELASTICITY

OF MANTLE

MINERALS

Table 36. Fe2SiO4: Dimensionlessparameters, Debye temperaturesand thermM

pressure

300
400
500
600
700

511
506
501
497
494

0.336
0.337
0.338
0.338
0.338

5.99
5.56
5.35
5.24
5.18

7.34
6.85
6.62
6.50
6.45

9.34
7.49
6.02
4.69
3.43

Calculated

from Tables

11 & 20. Dimensions

as in Table

(zT-ss) v
1.12
1.09
1.09
1.11
1.14

1.54
1.33
1.09
0.85
0.60

aKT
3.56
3.82
3.95
4.02
4.06

0.00
0.37
0.76
1.16
1.56

29.

Table 37. Mn2SiO4: Dimensionlessparameters,Debye temperaturesand thermal

pressure

300
400
500
600
700

535
530
525
520

0.315
0.315
0.316
0.317

515

0.317

6.66
5.95
5.61
5.43
5.31

8.19
7.35
6.96
6.76
6.63

8.43
7.57
7.17
6.97
6.84

Calculated

from Tables

12 & 21. Dimensions

as in Table

(sT-Zs) ,
1.44
1.30
1.25
1.24
1.25

1.19
1.19
1.19
1.19
1.20

aKT
2.90
3.23
3.41
3.52

0.00

3.59

1.34

0.31
0.64
0.99

29.

Table 38. Co2Si04: Dimensionleas

parameters,Debyetemperaturesand thermal
pressure

I'

300
400
500
600
700

551
548
545
541
538

0.317
0.316
0.316
0.316
0.316

5.81
5.19
4.88
4.71
4.60

7.32
6.56
6.19
6.01
5.88

5.51
4.91
4.62
4.46
4.35

Calculated

from Tables

13 & 22. Dimensions

as in Table

(Sr-Ss)
1.35
1.27
1.23
1.22
1.21

0.96
0.96
0.96
0.96
0.96

aKT
3.34
3.72
3.94
4.07
4.16

APTH
0.00
0.35
0.74
1.14
1.55

29.

Table 39. MnO: Dimensionless

parameters,Debyetemperaturesand thermal pressure

300
350
400
450
500

534
531
527
523
519

0.301
0.302
0.303
0.305
0.307

4.14
4.03
3.94
3.88
3.83

5.96
5.82
5.71
5.64
5.58

8.33
8.14
8.01
7.95
7.94

Calculated

from Tables

6 & 23. Dimensions

az in Table

(z,-Ss)
1.20
1.18
1.17
1.16
1.16
29.

1.56
1.57
1.57
1.57
1.58

aKT
5.07
5.20
5.29
5.36
5.41

APTH
0.00
0.26
0.52
0.79
1.05

ANDERSON

AND

Table 40. MgA1204: Dimensionlessparameters, Debye temperature and thermal

pressure

(r

6s

(zT-zs)

aKT

APTH

300

862

0.280

6.03

7.73

5.30

1.12

0.90

4.38

0.00

400

858

0.279

5.72

7.36

5.01

1.20

0.90

4.60

0.45

500
600

854
850

0.279
0.278

5.49
5.27

7.07
6.82

4.78
4.59

1.22
1.21

0.90
0.90

4.79
4.97

0.92
1.41

700

845

0.278

5.10

6.62

4.43

1.20

0.90

5.11

1.91

800

840

0.278

4.96

6.47

4.30

1.19

0.90

5.24

2.43

900

835

0.277

4.85

6.35

4.20

1.18

0.90

5.33

2.96

1000

830

0.278

4.74

6.24

4.11

1.17

0.90

5.43

3.49

Calculated

from

Tables

5 & 17. Dimensions

as in Table

29.

Table 41. NaCI: Dimensionlessparameters,Debye temperature and thermal pressure

6s

(8-s)

rKT APTH

300

304

0.256

3.47

5.56

5.05

1.32

1.29

2.82

0.00

350
400

300
296

0.258
0.260

3.56
3.65

5.62
5.69

5.00
4.95

1.29
1.27

1.26
1.23

2.83
2.84

0.14
0.28

450
500
550
600
650

291
287
283
278
274

0.262

0.266

3.72
3.80
3.91
4.03
4.14

5.74
5.82
5.95
6.10
6.24

4.90
4.86
4.83
4.79
4.77

1.25
1.24
1.25
1.27
1.29

1.20
1.18
1.16
1.13
1.11

2.86
2.86
2.84
2.81
2.78

700
750

269
264

0.268
0.270

4.23
4.34

6.37
6.53

4.76
4.76

1.31
1.35

1.10
1.08

2.77
2.73

Calculated

0.264
0.265

0.265

from Tables

8 & 27. Dimensions

as in Table

0.43
0.57
0.71

0.85
0.99
1.13
1.27

29.

Table 42. KCI: Dimensionlessparameters,Debye temperatureand thermal pressure

(9

er

300
350
400
450
500
550
600
650
700
750
800
850

230
227
224
221
218
214
211
208
204
200
196
192

0.274
0.275
0.277
0.278
0.278
0.279
0.282
0.284
0.285
0.286
0.289
0.288

3.77
3.86
3.92
3.97
4.02
4.05
4.06
4.09
4.18
4.27
4.34
4.50

Calculated

5.84
5.88
5.88
5.88
5.88
5.87
5.84
5.83
5.90
5.98
6.04
6.19

from Tables 7 & 28. Dimensions

(r-s)

4.66
4.77
4.86
4.93
4.97
5.02
5.10
5.19
5.30
5.44
5.61
5.76

1.34
1.34
1.32
1.30
1.28
1.26
1.23
1.21
1.23
1.25
1.27
1.33

1.17
1.17
1.17
1.17
1.17
1.17
1.18
1.18
1.18
1.18
1.19
1.19

as in Table 29.

cKT APH
1.87
1.86
1.86
1.86
1.86
1.87
1.88
1.88
1.86
1.83
1.81
1.77

0.00
0.09
0.19
0.28
0.37
0.47
0.56
0.65
0.75
0.84
0.93
1.02

ISAAK

79

80

HIGH

T ELASTICITY

OF MANTLE

MINERALS

The appropriateequationsusedin preparingthe tables are presented in Section 2. The various correlations between the thermoelastic constants are pre-

Mie-Griineisenequationof state).

sentedin Andersonet al. [13] and reviewedin Sec-

A well-known thermodynamic identity is that the

temperature derivative of the pressureat constant V is
exactly equal to aKt by meansof calculusdefinitions,

tion 3.

so that

The

mineral

data

are set forth in Section

4.

Theory appropriate to the high temperature trends of

the data is presentedin Section5. Extrapolation equations are reviewed

3. EQUATIONS
OF

PHYSICAL

Once

the elastic

in Section

- v

6.

USED IN TABLED

VALUES

PROPERTIES

constants

have been determined

over a wide range in T, the four dimensionlessther-

moelasticparametersat eachT are computed[7]using

the following nomenclature:
a Ks

OT v

where//is
the thermal pressure.Thus alCT is the
slope for the PT/versus T curve at constant V.

Using (6) for an isochore,

-f

tiT,

(7)

which is equivalent to the statement that

a KT

(1)

- - ( ) (Ks
OT
) --(OlnKs
6T
----(o
f,'
) (O
KT
)r _(O
OT
0n
inK,
p )r
r- - (a--J-)
(-)p
OG

Ptl-/(OT)v
dT.
If alCT is independentof T at constant V and also
independent of volume, then aKT comes out of the

(3) integralshownby (7), giving

(4)

The parameter 7 is known as the Griineisen ratio. The

parameters 5T and 6s are often called the Anderson-

Griineisenparameters[17]. The dimensionless

temperaturesreachedby someof thesedata (MgO, A12Os,
Mg2SiO4, KCI, NaCl) either exceedor are closeto
those of the lower mantle, which are in the neighborhoodof T/O = 2.3 [4]. The measurements
must
be done at sufficiently high temperature so that one
is justified in speaking of observationsin the hightemperature region. The definition of used is

PTH(T) -- PTH(O) = KT(T-

O).

(s)

As an empirical finding, APt/is linear in T down to

much lower temperatures than O, and we usually find
empirically that the data satisfy

APTH -- aKt(T-

300).

(9)

The measured Cp data can be used to find Cv from

Cv =

1 -F a7T

(10a)

once 7 has been determined. Similarly,

(9-

Ks

4rM (vS
+2v-S)-/s' (5) KT-- 1+a7T'

Since vp and v, decreasewith increasingT, O also

decreaseswith increasingT.
Since the value of O for most mantle minerals is 600-

900 K, measurementshave to be taken up to the 1300

to 1800 K range so that the high-temperaturetrends
are clearly discernible. Such high T data permit the
verification of classicalequations. For example, one

can test whether Cv is independentof T (as in the

Dulong-Petit limit) and whether 7 at constantV is
independentof T (as requiredin the derivationof the

(lOb)

In isobaric high-temperaturecalculationsthe thero

moelasticparametersgivenby (2) and (3) are useful

for many thermodynamicapplicationsrelating sound
speed or bulk modulus to temperature, the adiabatic
case arising from adiabatic elastic constants and the
isothermal case arising from isothermal elastic constants.

We list our experimentalvaluesfor the dimensionless

parameter y defined by

ANDERSON

AND

ISAAK

81

ues in the integrand are positive). This behaviorof

/0n
v/

(c9-r/OT)vhas an importanteffecton the validityof

(11) the
Mie-Griineisen formulation of the thermal pres-

v-- /9n
vp p'

whichis of interestin seismictomographycalculations

[1, 20, 37]. We alsolist valuesof the adiabaticPois-

sure.

son's ratio r given by

als with higher densityhave higher valuesof Oac. We

know that when the averagemass is constantfrom
material to material, the valueof Oacrisesas the 4/3
power of the density [2]. We would thereforeexpect
that Oac for perovskitewill be high, in the neighbor-

3Ks - 2G

a - 6Ks+ 2G'
4. SOME
CORRELATIONS
PROPERTIES
IN THE

(12)
FOUND
TABLES

FOR

Oac shows that miner-

hood of that found for AIOs.

The value of Oac for perovskite at ambient condi-

This section deals with relationships between the

thermoelasticdimensionless
parameters.The equation

showingthe relationship
between/a,/s and-r is [10]'

tionscalculated
by (5) is 1094K. The valuesvp- 10.94
kin/s, vs - 6.69 km/s, and p0 - 4.108g/cma usedin
the calculationare givenby Yeganeh-Iiaeriet al. [78].
Oac for corundumis 1033 K, and p0 - 3.981. This
similarity in valuesof Oac and p0 suggeststhat the

OnT
p OnTP1}
{1+ [(o')na)(On-r)
(1+
. (13)

measuredthermal pressureof corundum couldbe used

as a guide for that of perovskite at mantle temperatures and pressures. The expected variation of Oac

- -

The acoustic version of ,

If the relative increasein a with T nearly compensatesfor the relative decreaseof -r with T taking into
accountthe changein the denominatorof (13), then
we may expect that /T- /s is closein value to 'rSince the rate of changeof 7 with T is seldom the
same as the rate of changeof a with T, we see that
tT--S = -r may be an approximationvalid onlyovera
limited range of temperatures,usuallynear and above

with T for perovskiteis shownin Figure 1, whereOac

of perovskiteis comparedto that of forsteriteandpericlase.

Debye Temperature (four minerals)

1200

1100

O.

In somethermodynamics
manipulations,the approximation/a,-s = -r is useful.In Tables29-42, we show

the variationof (a, - s)/'r with T/O for ourfourteen

minerals.Thus an empiricallydeterminedapproximation whereactual high-temperature
data are lacking

_.perovskite
.

lOOO

900

is
8OO

/a,-/s - -r.

a-Mg SiO
4

(14)

Equation(14) is seldoma goodapproximationbelow

T = O. We note, however,that evenin somehightemperatureregions,(14) is in error, especiallyfor
A12Oa.

7OO

600

Whilethe valueof (0-r/0T)p at highT is closeto

zerofor manyminerals,thevalueof (O-r/i9T)vis less
andis alwaysa negativenumbernot closeto zero(be-

cause
thecorrection
involves
- f a-rq
dT,and
allval-

I
200

The variation of -r with T for all fourteen minerals

is listedin Tables29-42. For somesolids,-r decreases

with T at high T, but for CaO, A12Oa,and Mg2SiO4,
it appearsthat (O-r/0T)p is closeto zeroat highT.

,
600

1000

I
1400

1800

Temperature (K)

Fig. 1. Plots of O (acoustic)versusT. Solid lines

showdata on O from Tables 29, 30, and 34. The A is

data for O (acoustic)for perovskiteat roomtemperature. The dashedline showsthe expected variation
of O (acoustic)with T, yielding a value near 900 at
1900 K.

82

HIGH

T ELASTICITY

OF MANTLE

MINERALS

Another significantcorrelationfound for most minerals is

The errors indicated in Tables 15-28 for Ks and G

are propagatedby standard error techniquesin which

two sources of error are considered.

which allows one to calculate G for KT in high temperature ranges where G is not known. It immediately followsfrom (15) that, becauseG is lessthan

mus
5.

Goto et M. [26],whichare basedon the VRH scheme.

PRESENTATION

I.
OF

MINERAL

DATA

We tabulate the adiabatic single-crystMelasticmod-

at 300 K and proceedingin intervals of either 50 or

100K. The errorsindicated at selectedtemperatures
in Tables 1-14 are those listed in the original refer-

ences.The (7ij data for thirteenof the fourteenminerals in Tables 1-14 were retrieved by the already defined

RUS method(either rectangularparaHelepipeds

or res-

onantspheres).The tabulatederrorsin the Cij from

termined

minerals

are the standard

from the difference

deviations

of each measured

errors in-

Cp (at constantP) data with Ks and G andcalculate

uli (Cij) for 14 mineralsin Tables 1 to 14 starting

these thirteen

These

clude both the uncertainty with which the midpoints

of the upper and lower boundsof Ks and G are known
and the differencebetweenthe midpoints and the upper bounds.
We couple thermal expansiona and heat capacity

de-

the values for several other thermoelastic quantities

given in Tables 15-42. We assumea is accurate to

2% (unlessspecified
otherwisein the originalreference
from whichthe a data are obtained)and rigorously
propagateerrorsto p, Cv, K., %, and v, at highand
low temperaturesin Tables 15-28. The uncertainty in
the dimensionless
quantities5s, gT, I', and v shouldbe

taken as5% or more,sincethe valuesof theseparameters can dependsomewhat on the order of polynomial

fit usedwhen determiningthe T derivatives.

modal

frequency with that modal frequency value calculated

5a. MgO

from the final set of Cij. Thus the listeduncertainties

ing Cij valuesfor a particularspecimen.The MnO

Prior to the workof Isaaket al. [34],highT data on

the elasticmoduliof single-crystalMgO wereavailable
up to 1300K. Spetzler[55] usedan ultrasonicpulse-

data and their uncertainties

echo method

reflect how consistentthe frequencydata are in providare not from RUS mea-

to obtain

ambient

P data at 300 and

surements,but are those recommendedby Pacalo and

800 K and providesa table listing T derivativesof elas-

Graham[47]from a weightedlinearregression
analyses
togetherwith the PacaloandGraham[47]temperature

ticity at thesetwo temperatures.Suminoet al. [63],

usingthe rectangularparallelepiped
resonance
(RPR)
method, extendedthe T range for which data were
availableup to 1300K. Isaak et al. [34] (RPR) and
Zouboulisand Grimsditch[80] (Brillouinscattering)
report Cij data for MgO up to 1800and 1900K, re-

derivatives.

The isotropic adiabatic bulk Ks and shear G mod-

uli computedfrom the Cij in Tables1-14 are included

in Tables 15-28. For minerals with cubic crystal sym-

metry,Ks is givenby (1/3)(Cll + 2C12).We usethe

Hashin-Shtrikman
(HS) [29,30, 73]scheme
to compute
G for cubic minerals(MgO, MgA1204, MnO, CaO,
garnet, and NaCI) and both Ks and G for minerals
with orthorhombic
symmetry([Mg,Fe,Mn, Co]2SiO4).
Very small variations(typically_<0.1 GPa) between
our tabulated values of Ks and G for the orthorhorn-

bic mineralsand the valuesfound in the originalreferencesare due to the differences

in Ks (or G) that
resultwhenusingthe HS andVoigt-Reuss-Hill
(VRH)
schemes. However, the HS schemeusually provides
significantlynarrower bounds and is preferred. The
valuesin the tables are the averagesof the upper and
lower bounds found with the HS scheme. We use the

VRH schemeto determinethe isotropicG for KC1 becauseof difficultiesin interpreting the HS upper and

lowerbounds(seeSectiong. below). For corundum

(A1203) we use the Ks and G valuestabulatedby

spectively.

We list the Cij valuesasreportedby Isaaket al. [34]

in Table

1 and note that

an alternative

source for

high T data can be found in Zouboulis and Grims-

ditch [80]. In their Table 2, Zouboulisand Grimsditch [80]report Cu(T), C44(T), and the combined
moduli(Cll --C12--2C44)/2and (Cll -C12)/2 versusT. However,there is more scatter(especiallyin
the C44modulus)in the data of ZouboulisandGrim,sditch[80]thanin the dataof Isaaket al. [34].We find
excellentareement
in (oCij/c?T)p
valueswhencomparingthe resultsof Spetzler[55],Suminoet al. [63],
and Isaaket M. [34]in their T rangeof overlap.The
high T (i.e., T > 1400K) Zouboulisand Grimsditch
[80] data haveT dependence
nearlyidenticalto that
of the Isak et al. [34]data up to 1800K.
The valuesof the dimensionless
parameters,s, T,
F, and v, in Table 30 are foundusingsixth orderpoly-

ANDERSON

AND

ISAAK

83

nomial fits to the Ks, KT, G, vv, and v resultsas

doneby Isaak et al. [34]. We find very little difference

pyrope,1.2%;lessthan 0.5%almandineor spessartine)

in the value of these dimensionlessparameters, other

than a slightly lessrapid decreasewhen T > 1500 K,
when a lower order of fit, such as 3, is used.

and C44of Isaak et al. [36] as primary data. C' and

5b.

CaO

The appropriate thermoelastic quantities for CaO

[43]re listedin Tbles 2, 24, nd 31. Od et 1. [43]

used the resonantspheretechnique(RST) to reach
1200 K. We includethe c data of Okajima [45] as
tabulatedby Oda et al. [43] in our Table 24. The dimensionless
parametersin Table 31 are obtainedfrom
a secondorder polynomialfit of the Ks, KT, G, v,
and v, [43].
5c. Pyrope-lich

Garnet

Suzuki and Anderson[65] provideCij for pyrope-

to 1350 K. Table 4 is constructedusing the Ks, Cs,

C'2 and their errors are calculated from these primary

data. The Cij valuesin Table 4 are plottedby Isaak

et al. [36],but not explicitlytabulatedin their presentation. We followIsaak et al. [36] in the order of fit
used to calculate

the T derivatives

for the dimension-

lessparameters. The parameterss and T are found

using first order fits to the Ks and KT data. Second
order fits were applied to the G data to obtain F and

to the vp andv valuesto obtain,. Isaaket al. [36]

also provide new c data for grossular-richgarnet and

point out the possibilitythat the Skinner[51]thermal

expansionvaluesfor garnets may be low.

5e. Spinel (MgAI204)

Cynn [19]providesCij for single-crystal

MgA1204
over the range 298-999 K at irregular intervals of T.

rich garnet over the temperature range 298-993 K at

irregular intervalsof T. The specimenusedby Suzuki

There are data [19]up to 1060K, but a suddenchange

and Anderson[65] is a single-crystalnatural garnet

with composition:pyrope, 72.6%; almandine,15.7%;
uvarovite,6.1; androdite,4.3%; spessartine,0.7%; and
grossular,0.6%. We usethe Ks, C', and C44values
givenby Suzukiand Anderson[65](seetheir Table 1)

the primary data sourceand interpolate to obtain the

as the primary data sourceand interpolate to obtain

these moduli given in Table 3 at 100K incrementsof
T. The C44 value at 638 K given by Suzuki and An-

derson[65]seemsunusuallylow and is excludedin our

fit for interpolating. All errors in Table 3 are either

thosegivenby Suzukiand Anderson[65] (i.e., errors

for Ks, C', C44)or are propagatedfrom the errorsin
Ks, C', and C44(i.e,errorsin C'2andCs). We extrapolate(linearin Ks andC'; quadraticin/3'44)the
Suzukiand Anderson[65]Cij data oversevendegrees

in the slope of the data near 1000 K is attributed to

the effect of cation disordering. We use the Ks, Cs,

and C44valuesfrom 298-999K givenby Cynn [19]as

Cij in Table5 at regular50Kincrements
of T. Errors
in Table 5 are either thosegivenby Cynn [19]or are
propagatedfrom the errors in Ks, Cs, and C44. The

uncertaintyin p at 300 K (Table 17) is assumedsince

it is not reportedby Cynn [19]. The uncertainties
in
the Cij for MgA1204are largerelativeto mostother
resonancedata; thus we present the dimensionless
rameters in Table 40 based on linear fits of Ks,

G, vp, and v0 with T.

5f.

MnO

by a linear fit of the Ks and KT values in Table 26.

Pacaloand Graham [47] presentnew data on MnO

from 273-473 K. We constructTable 6 usingthe Gij
and (OGij/OT),valuesrecommended
by Pacaloand
Graham[47](seetheir Table 10) for MnO. For G44we

We find that G and v, have noticeable curvature, so

use a secondorder polynomial to interpolate at inter-

that secondorder fits are preferred when calculating

F and . It is worth noting that tends to increase
graduallyfrom about 0.88 to 1.06 overthe 300-1000 K

valsof50Kwherethenonzero
valueof (O:Cij/OT:)r
recommendedfirst temperature derivatives are based

rangewhensecondorderfits to v, andvv versusT are

on both ultrasonicpulse-echo
[47] and resonant[62]

used. If first order fits are assumed, is constant with

a value of 0.97 over the 300-1000 K range in T. Thermal expansion a data on pyrope-rich garnet are also

measurements. For minerals of cubic symmetry there

are only two independent moduli among Ks, C1, and
C12. The recommended values for Ks, Cll, and

providedin the Suzukiand Anderson[65]paper.

in Table 10 of Pacaloand Graham [47] are not self-

to include the 1000 K values in Table 3. The dimen-

sionlessparameters5s and 5, (Table 33) are found

is foundin Table 6 of Pacaloand Graham [47]. The

consistent. We take C'1 and C'12 from Pacalo and

5d.

Grossular

Garnet

Isaak et al. [36]provideelasticitydata for near endmembergrossular(grossular,96.5%; andradite,1.6%;

Graham [47] as the primary data and use theseto

computeKs for Table 23. Thus a small differenceappears between the 300 K value for Ks in our Table 23

84

HIGH

T ELASTICITY

OF MANTLE

MINERALS

(149.0:t:2.6 GPa) and that givenby Pacaloand Graham [47](150.64-2.5GPa). The valuesat 500 K in our
Table 6 require an extrapolation of 27K beyond the

al. [771is -0.012 GPa/K. The Yamamotoet al. [77]

resultstend to favorthoseof Spetzleret al. [56],who
obtained elasticity data to 800 K for NaCl. Spetzler

maximum T measured, but are below the Nel tem-

et al. [56]find (OKs/OT)p to be -0.011 GPa/K from

300-800K. The Yamamotoet al. [77]data are out to

perature (522 K for MnO). Temperaturederivatives

of Ks, KT, G, vp, and vo are donewith a linear fit
in T when calculatingthe dimensionless
parametersin
Table

39.

5g. KCI

Table 7 showsCij for KCI wherewe use the Yamamotoand Anderson[76]data to interpolateat even
intervalsof 100K. The C, C2, and C44 [76] are

a slightlylower maximumtemperaturethan Spetzler

et al. [56],but containa muchdenserset of tabulated
Cij values.
We interpolate the C, Ca, and C44 found in Table 2 of Yamamotoet al. [77] to regularintervalsof
50K for our primary elasticitydata sourcein Table 8.
The uncertaintyin the densityof the specimenusedby

Yamamoto
et al. [77]is assumed
to be 0.005gm/cms

taken as the primary data from which Cs and Ks

at 300 K (Table27), sincethis is not providedby Ya-

(Table28) andtheir errorsare derived.In determining

mamoto et al. We calculate the dimensionlessparam-

the isotropicshearmodulusG we usedthe VRH rather

than the HS scheme.When attempting to use the HS

eters in Table 41 using a secondorder fit in T to the

scheme[30], we foundthat the resultingupperbound

that this resultsin 5T at 300 K having a value near 5.6

for G is less than the lower bound for temperatures

in the range of 300-450 K. We are unable to resolve
this difficulty. This seeminglycontradictoryresult is
likely related to the fact that the shear modulus Cs
is very near to the value of the bulk modulus Ks at
the lower temperatures. In any casewe must defer to

rather than 5.3 as indicatedby Yamamotoet al. [77].

the VRH

scheme for this materiM

and note that there

are relativelywideboundson G (thusalsoon vp and

vo), especiallyso at lower temperatures. Statistical

Ks, KT, G, vp, and vovaluesin Table 27, and note

We also find that above 600 K, 5T increasesgradually from 6.1 to 6.5, rather than having a value nearer
5.8-5.9 in this temperature range. These differences
are due to the difference in method

used to calculate

the T derivatives. We fit the data over the T range

of measurement
to a polynomial;Yamamotoet al. [77]
find T derivativesby taking a finite differencebetween
two adjacent data points.

analysis indicates that a secondorder polynomial fit

of Ks, G, vp, and vois warrantedwhendetermining

5i. MgaSiO4

the T derivatives, whereasa linear fit of Ka, with T is

adequate.

Followingthe workof Suminoet al. [61]to 670K and

Suzukiet al. [68]to 1200K, the MgaSiO4(forsterite)
dataof Isaaket al. [35]to 1700K extendthe T limit for

5h.

whichelasticitydata are available. Prior to bhesestud-

NaCI

Yamamotoet al. [77]reportelasticitydatafrom294-

ies the available

data were limited

to T near ambient

766 K for NaCl. Elasticity data up to the melting

[27,40].Thereis general
agreement
between
thedata

temperatureof 1077 K for NaC1 [31] were obtained

wheretheyoverlap.Suminoet al. [61]provideschemes

for extrapolatingthat are generallyconfirmedby the
highertemperaturemeasurements
of Suzukiet al. [68]
and Isaaket al. [35](SeeFigures3 and 5). We con-

with the compositeoscillatormethod. To find accu-

rate Vii resultswith the compositeoscillatorrequires

that the resonant frequenciesof quartz and silica rods
that are coupled to the NaC1 specimenbe known in

structTable9 fromtheCijreportedbyIsaaket al. [35].

requires a large volume to be heated when increasing temperature. For these reasonswe prefer the data

The thermal expansionresultsof Kajiyoshi [38] are

used(seeour Table 18) to calculatethe thermoelastic
properties
of Mg2SiO4(seelsaaket al. [35]for a comparisonof the Kajiyoshi[38] valuesof a with other

of Yamamoto et al. [77], but emphasizethat Hunter

and Siegel[31] report data 300K higherin T than
do Yamamotoet al. [77]. There are relativelysmall

VRH schemeto calculate isotropic Ks and G moduli,

whereas Table 18 lists Ks and (7 obtained from the

order to reduce the NaCl

data.

We also note that

the

experimentalarrangementof Hunter and Siegel[31]

but measurable differencesin the T dependenceof the

elasticmoduli betweenthesetwo data setswhere they
overlap. For instance, from 300-700 K the average

value of (OKs/OT)r from Hunter and Siegel[31] is

-0.015 GPa/K, whereasthat foundby Yamamotoet

values
in the li,terature).Isaaket al. [35]usedth
HS averagingscheme.There is only a smalldifference
(< 0.1 GPa) betweenthe two approaches.Isaak et
al. [35] showthat fits of the Ks, K., G, v, and vs
data with T imply that third order polynomialsare
appropriateto describethe data. Thus we use third

ANDERSON

order fits for all T derivativesrequired to determine

dimensionlessparameters in Table 34. There are some
small differencesin the s, T, and F between our Ta-

ble 34 and Table 5 of Isaak et al. [35]due to different

methods used in calculating the T derivatives. Isak

et al. [35]usedthe intervalbetweenthe two neighboring points to calculatethe derivative at a particular T;

here we apply polynomial fits over the whole temperature range from which the derivativesare obtained.
The present approachproducessmoother variations in
s, T, F, and , with T.

5j. Olivine (Fo0Fa0)

Isaak [32]reportsdata to 1400and 1500K, respectively, on two natural olivine samples with compositions of Fo92.xFa7.7and Fo90.sF9.5. Previously available T data on the elasticity of iron-bearing minerals

werelimitedto temperatures
nearambient[40]. We includethe Cij for Fo90.sFa9.5
(referredto hereasolivine
Fo90Fax0)in Table 10. There are somedifferences
betweenthe Cij of the twoolivinesreportedby Isaak[32]

AND

ISAAK

85

Mite (seeGrahamet M. [28],IsaakandAnderson[33],

and Wang et al. [71]). As an exampleof the effect
of uncertainties in the derivative values, Graham et

al. [28]report (c9Ks/i3T),=-0.050 GPa/K, whereas

Sumino[58]reports-0.0205 GPa/K. The reasonsfor
these types of discrepanciesare under investigation.
At present,we deferto the data of Sumino[58] since
they involvea significantlywider rangein T (up to
673 K) than the maximum temperatureof $15 K used
by Graham et al. [28]. However,no compellingreasonsexistto suggestthat the Sumino[58]fayMitedata
shouldbe preferredoverthoseof Grahamet al. [28].
From Figure 2 of Sumino[58] it is clear that Ks
is linear in T, whereasG requiresa higher order T
dependence
(at least a fourth order polynomial). In
calculating the dimensionlessparameters for fayMite
in Table 36 we use linear fits in T for Ks and K,

and fourthorderfits for G, vp , and v,. Sumino[58]

attributes the strong nonlinear behavior of the shear
modulusto influencesof the antiferromagnetic
to paramagnetic transition, even though this transition occurs

that do not appear to be due to fayMite content. The

differencesare small, but caution should be used when
interpolating betweenspecimenswith small differences

at a muchlowertemperature(65 K).
Sumino[58] alsoreportselasticitydata on single-

in chemistry.The uncertainties
in Ks and G (and in
all propertiesthat dependon Ks and G) aresomewhat
smallerin Table 19 than foundin Isaak [32]for these
quantities. Isaak [32] estimatedthe uncertaintyby

ino [58]indicatesthat all the C'ij of Mn2SiO4and

simply adding the uncertaintywith whichthe HS averagevalueis known to the distancebetweenthe average
value and the HS high value. Here we squareboth the
uncertainty of the HS averageand the distance from
the HS averageto the HS high value, add the squares,
and take the root. We use linear fits in T to the Ks,

tures of 100Kfor Mn2SiO4 and Co2SiO4,using the

KT, G, vp,andv datawhenobtainingthe dimensionlessparameters 5s, T, F, and y. We start our olivine

tables by interpolating the T = 296 and 350 K data

of Isaak [32]to 300 K. This shift in startingT causes

minor differencesin the T derivatives;hencethe slight
differences between 5s, 5,, and F in Table 35 and in

Table 6b of Isaak [32].

5k. Fe2SiO4, MnSiO4, CoSiO4

Sumino[58]presents
T datafrom25-400C(398673 K) on the elasticityof single-crystal
Fe2SiO4(fayMite). We interpolatethe Sumino[58] fayMite data
(seehis Table 3, specimen
TA) so as to provideCij
from 300-700 K in regular 50K intervals in Table 11.
A small extrapolation over 27K is required to extend
the values represented in Table 3 to 700 K. It should
be noted that there are questionsregardingthe values

of someof the Cij andsomeof the T derivativesof fay-

crystal Mn2SiO4 and Co25iO4 at 300 and 673 K. Sum-

Co2SiO4are linearly dependenton T with the exception of (744 for Co2SiO4. We construct Tables 12 and

13, whichshowvaluesof C'ijat incremental

temperaC'ij and the (c9C'ij/e9T)p
givenby Sumino[58]in his
Tables 4a,b. We assumea linear T dependenceof the
C02SIO4C44 modulusin constructingTable 13 since
the presenceof nonlinearity in this modulusis asserted
by Sumino[58]but no quantitativeresultis provided.
As with Fe2SiO4,we must performa small extrapolation outside of the maximum

T measured in order to

include the T = 700 K valuesin the tablesfor Mn2SiO4

and Co2SiO4.When calculatingthe dimensionless

pa-

rametersall T derivatives
areassumed
linearin T (see
Figure2 in Sumino[58]).
51. Corundum (AI2Oa)
The C'ij(Table14), Ks, and(7 (Table16) for AlaO3
are thosefound in Goto et al. [26]. The Ks and G
givenby Goto et al. [26] are foundby the the VoigtReuss-Hill averaging scheme. Full account is made of

the differencebetweenthe Hill (averagedVRH) valuesfor Ks and G and the Voigt (upperbound)values
when assigningerrors to Ks, (7, and other isotropic
quantitiesderivedfrom them. This accountsfor larger
errors being assignedto the G valuesin our Table 14

than are foundin Table 2 of Goto et al. [26]. Appar-

86

HIGH

T ELASTICITY

OF MANTLE

MINERALS

ently Goto et al. [26]assigned

errorsin G that include
only the uncertainty in the Hill averageitself, but do
not consider the difference from the Hill average to

number;and p is the numberof atomsin eachcell (or

molecule).The first term on the right is the zeropoint
vibrational energyEgg given by

the upper (or lower) bound. We interpolatethe Cij,

Ks, G, and p provided at 296 and 350 K to start our
Tables

14 and 16 at 300 K.

We use a from White and Roberts[75]rather than

the a preferredby Goto et al. [26], i.e., thosefrom
Wachtmanet al. [70].
We use a third order polynomial fit to determine

the T derivativesfor eachof Ks, KT, G, vp, and v,

required for the dimensionless
parametersshownin Table 29. This order of fit seemsappropriate from a sta-

tisticalconsideration,
i.e., an Fx test [18]. Thus,the

Ezv-

(17)

j=l

Note that, unlike the last term in (16), there is no

T in Ezv. This term arose by summing the allowed
quantum state levelsto find the energyof eachnormal

mode,accordingto the Hamiltonian[42].

We replace :v with y, the dimensionlessfrequency,
so that

s, ', and v found in our Table 29 for AI2Os may

differ somewhat at a particular T from those given by

Yi= hwJ
kT'

Goto et al. [26] in their Tables 4 and 5. The Goto

et al. [26] s, T, and v valuesare calculatedfrom

Thus (16) canbe givenin termsof the thermalenergy

derivatives found by using a finite interval from the

two nearest data points. Thus, we find considerably

4VIB = Ezv + .4TIt,

(18)
(19)

more scatterin the Goto et al. [26] s and T values

than in Table

where

29.

8pN

6.

THEORETICAL

PROPERTIES

BASIS

AT

HIGH

FOR

OBSERVED

8pN

AT,-- kT n
(1- e-yj)-- kT .ATIt.
i.

TEMPERATURE

j=l

Most, but not quite all, of the high temperature

properties of the solids reported here are consistent
with the high temperature limit of the quasiharmonic
approximationof the statistical formulation of the free
energy.

6a. The Helmholtz Free Energy

The expressionfor the Helmholtz energy for an in-

sulatoris [41]

4TH the energy arising from temperature excitation, called the thermal energy. Ezv is not affected
by T, as shownin (17). Thus 4TH --* 0 as T --. 0.
However, Avlr --* Ezv as T .- O, and Ezv is a nonzero number. Ezv is sufficiently small that for most
numerical evaluations it could be dropped, but it is
useful to keep this term in Av.r for algebraicmanipulations

done later on.

The expressionfor the Helmholtz energy for an insulator

is thus

4 = EST + Ezv + 4TH.

where electronicand magneticeffectsare ignored. EST

is the potential of a static lattice at absolute zero, and
4VlB is the vibrational energy due to motion of the
atoms as each is constrained

to vibrate

We need to divide (21) into temperature-dependent

and nontemperature-dependentparts, so we use

.A = ET=o + .ATH,
statistical

mechanical

definition

(21)

around a lattice

point.
The

(20)

j=l

of the vibra-

tional contribution to the Helmholtz energy arising

from 3pN independent oscillatorsis

(16)

(22)

where

ET=O = EST + EZV.

(23)

Dividing (21) into its vibrational and nonvibrational

parts, we define

wherewj is the jth modalfrequency;N is Avogadro's

A = EsT + Aver,

(24)

ANDERSON

where4viB is givenby (16).

AND

ISAAK

Cv
-k (e,Yse';),
= Cvs.

6b. The Quasiharmonic Approximation

Before we can find thermodynamic properties such

asP and Cv from (20), wemustmakedecisions

on the
volumeand temperaturebehaviorof wj. In the quasiharmonic approximation, w is assumed to be dependent upon V but not upon T. This makes all the thermodynamic properties directly dependent on V. The
temperature behavior of the thermodynamic properties is indirect; it comes from the fact that while wi is

not dependentupon T, the sum n(1- e-ys) dependsuponT. When wj are different,then Yi are also
different, and the sum above becomesT-dependent,
especially at low T.'
The internal energy/g is found by applying the for-

87

(31)

Entropyis foundby applyingthe operator(O/OT)v to

A, obtaining

$-kyi(ey' _1)-k n
(1-e-")

(32)

The expression
for aKw isfoundby applying02/OTOV
to (22), yielding

aKw
- -.
y (e',1)]'

(33)

mulaLI = -T 2 ((O.A/T)/OT) [41],yielding

Yi --Ew=0
+ kTZ Ewts.
/g--ET=0
+kTj=lZeY,_l
j=l

To get a we divideaKw (givenby (33)) by Kw, defining Kw =-V(OP/OV)w, and usingP givenby (26).
Using(30), wefind that oKw= 7Cv IV, and equating this to (33), we find that [16]

The pressureP is foundby applying-(O]OV)T to

(21), yielding
kT

kT

p__(OEs
+- . 7jeS- 1,
OV )+- Z 7jYj

Y-

Cv '

(34)

The bar over 7 indicates that this result is an approximationof 7 = KTV/v

resultingfrom invok-

where

ing the quasiharmonicapproximationto the Helmholtz

n
wI
7.= 0
OtnV

(27)

and where7j are calledthe modegammas.Thus

=

(2s)

wherethe thermal energy(20) effecton the pressure,

called the thermal pressure,is

Y'
Pw,- kF 7ieys
- 1'

(29)

Comparing(29) with (20), we seethat

energy.

6c. The High-Temperature Limit of the Quasiharmonic Approximation

At sufficientlyhigh temperatures, the expressionfor
4TH can be simplified due to the convergenceof cer-

tain seriesexpansions.
The argumentin (16) becomes
small sincehwj << kT, that is, Yi is small. At high
temperatures,wetake advantageof the expansion[79],

n
(1-e
-y')--n
yj-(-y]
+...)
n
(1-1
---nyj+
vs).

(35)

By replacing the last logarithmic term above with its

argument,whichis valid for low valuesof YJ,we find

1

PT,--F .Aws.

(30)

that
1

In (1- e-y')_In7j- 7j.

The specificheat is formedby applying-(O/OT)v to
(25), yielding

(36)

Thus the high-temperaturerepresentation

of (20) is

HIGH

T ELASTICITY

OF MANTLE

at

MINERALS

.A.ar
- kT (n
y,- yj).

(37)

By using(21) and (34), the high T Helmholtzenergy

for insulators at high T is

elude that insofar as specific heat is concerned, the

quasiharmonicapproximation is not adequate for some
solids up to T 20, but is adequate for other solids
up to T 20.
The high temperature Grtineisenparameter is found

from (34), and considering

that as T oo, C -- k,
1

Aht-Es+Ez+kT(n-Ej). (38)
J

We see that the lt

term above just cancelsthe zero

Yht
- (T-oo)
= 3pN
y"7j,

(44)

temperatureenergygivenby (17), so that

which is independent of T. The data on 7 is found in

Za'- Es+ kT (lnh)- InkT).

(39)

j=l

This can be simplifiedby definingan averagekequency

, ven by
1

In- 3pN
Inj,

(40)

in which ce (20) becomes

- 3pNT ( in h-

in kT).

(41)

6d. Thermodynic
Properties in the High T
Lit
of the Quasiharmonic Approximation
At high T, A includesonly the static potential and
the thermal energy in the quiharmonic approxima-

Tables 15-28.

We see that there is an approximate trend for 7 to

be independentof T at high T. For these solidswhen
d7/dT is not zero, it is also true that Cv doesnot
obey the Dulong and Petit limit. Thus departures
from quasiharmonictheory in Cv create a departure
from the quasiharmonictheory of 7- Above T = O,

thedeparture
from(07/OT)p: 0 is slight,however.
Applyingthe operator-(O/OV)a. to (38), we find
thehighT pressure,
pat, whichbyusing(44)becomes

" v) - r(0, v) +

Hht- Esw+ 3pRT,

(45)

P't -

3pR
V

7at T.

(42)

whereR the g constant,kN. Equations(41) and

(42) are important resultsfor the high temperature
limit in the quiharmonic approximation.

Taking the temperaturederivativeof H to find specific heat,

Chw
t -- 3pR.

V 7atT.

Thus the thermal pressureis

tion. Usingthe equation

we find the high temperature internal energy to be

3pR

(43)

Equation (43) is knownas the Dulongand Petit limit.

Thus the high temperature quasiharmonicapproximation leads to the classicallimit in specificheats. If at
high T the experimentallydeterminedCv is not parallel to the T axis, we must concludethat the quasiharmonic approximationis not adequatefor this property,

V is a functionof T, and it is alsoequalto M/p where

M is the molecular weight, so that the above is

3R7ht
p0(1
--aT)T.
PT.- (M/p)

(46)

We see that the quasiharmonic theory allows for

Pa,t to be virtually linear in T: at the highest measured T, aT _ 0.05. But 7ht is not, as we shall see,
exactly independent of T, though close to it. Thus
there are counter effects in T, and the I- aT term
is often obscured.Thus to a very good approximation
PTt is proportional to T under the quasiharmonicapproximation.
The thermal pressurerelative to T = O for T > O

and anharmonic terms must be added to A.

is given by

From Figures 14-26, where the data for specificheat

versus T are listed, we see that for several solids of

APa-. -Pa"

(T, Vo)- Pa" (e, Vo).

(47)

interestto geophysicists
(OCv/OT)r = 0 at high T.
This is true for MgO, CaO, and A12Oaand NaCI, but
not for olivine, garnets, spinel, or KCI. We must con-

As shownin Tables 15-28, we seethat APa.a, is indeed

linear with T (for T/0o > 1). (Seealso Figure2).

ANDERSON
10

Using the operator--V(O/OV)T on (45), we find

that the bulk modulusKT alongan isochoreis

/ /

//

CaO
' 6.0 67FeSiO,
/// /

4.0

v) =

8NaCL

<:1
0'00

v)

3Rp
qht
(M/p)7a,(1)T,

(49)

whereqat= (Oin 7ht/Oin V).

6 8

2.0

Thus at high T, the isochoricbulk modulus is decreasingwith T accordingto the slope

(OK
3Rp
aTt)v-_- (MIr--
7t(1
- qh,)
.

T/o

Fig. 2. AP-H versusT/0o for nine mineralsshow-

ing: 1) APTH is linearin T/O0; and 2) the slope

of the AP,Ar--T/0o line decreases
aspo/(M/p) decreases.
Valuesof po/(M/p) in ascending
order(1-9)
are: 0.195, 0.178, 0.176, 0.160, 0.160, 0.151, 0.119,
0.073, and 0.053. (9o is the acoustic (9 at T = 300 K.

This meansthat for the thermalpressure

property,the
quasiharmonic
approximationappearsquite adequate
up to relativetemperaturesof T/O0 2.0. This range
coversvaluesof T/0o for the mantleof the earth. The
linearity of PTH with T is not unique to silicatesand

alkalihalides;it is alsofoundfor gold(seeFigure10

of Andersonet al. [12]).
The slopeof the APTH- T curvefrom (47) is em-

piricallya constant.SincePTH = f aKT dT, thenwe

can definean averagevalueof aKT, aKT, goodfor T
above , such that

(OAPTH
--(M/r)
3R7ht
aT )r - aKT
po(1-aT)- const.,
(48)

whereM/p is themeanatomicweight(peratom). For

non iron-bearingsilicate minerals,M/p varieslittle
from mineralto mineraland is nearthe value21 [74].
Also 7ht does not vary greatly from mineral to mineral. Thus from (48) for M/p = constantthe slope
increases from mineral to mineral as the ambient den-

sity increases.The data in Tables27-30 bear this out,

as shownin Figure 2. Sinceto a goodapproximation

for silicates
of constant
M/p, !3 = const
p4/S[2],we
seethat (OP.f/OT)rshould
increase
ass/4: In general,the mineralwith the highestvalueof po/(M/p)
will havethe highestslope,according
to (48), andthat
is borneout by the experimentalresultsshownin Figure 2.

89

6e. The Bulk Modulus at High T

3 Spinel
4 Grossular

5Mg2SiO4

'

ISAAK

AI203
8.0

AND

(50)

For qat = 1, (OK,/OT)v vanishes,

so the determination of (50) ordinarilyyields a small quantity. To
obtainthe isobaricderivative,(OK,/OT)p, weusethe
calculus expression:

(OKT)
(O'T)
(51)
OT p _(OKT)
OT v --aKT
OP T '
Thus at high T, alongan isobar,

OTp-- (M/p)
7ht
(1--qht)
_aK.
,OP.'
The term on thefar right of (49) is the thermalbulk
modulus,KTH. Using(48) in (52), we have

OKT
(qta_
1)--aKT
k,aPT'
OT p --aKT
Letting aKT:

aKT in the above

(53)
(01)
OT r __aKT(K,+qt_i).

We thus see that the thermal bulk modulus,KTH,

contributesa minoramountto (OK/OT)p.
We evaluate(53) for the caseof MgO from the data
as an example. The average value of aKT is found
from the valuesof APTH between 1000 K and 1800 K
listed in Table 30. In this table aKT is shown to be
0.0064GPa/K, closeto actualmeasuredvaluesof aKT

at high T. The high T valueof K' - 4.5 [8], and

qht= 1.4 [8]. Thuswefindfrom(53) that a predictedvalueof (OKT/OT)p = 0.031 GPa/K. This
result agreeswell with the measurementsfound in Ta-

ble 16 showing
(OKs/OT)pto be 0.03GPa/K in the
high T range.

90

HIGH

T ELASTICITY

6f. Entropy

OF MANTLE

MINERALS

and

in Cw, but evenso,thiseffectdoesnot appearin prop-

Applyingthe operator(0/0T)w to (38), the entropy

is found

Sat- -3pR(n
kT- n
h + 1).

(54)

The entropyincreaseswith nT in the quasiharmonic

approximationat high T. In contrast,Cv is independent of T in this approximationat high T, as shown
by (43).

We note that if P is linearin T, then (OP/OT)v

is independentof T. From experiments,
however,we
find that aKT is independent
of T (or approximately
so) only at T above. The functionalform of aKT
resembles a Cv curve.

Applyingtheoperator(0/c9T)gto thepressure
given

erties that are controlled by the volume derivativesof

4 as describedabove. Further, we also showedthat
there is no evidenceof anharmoniceffectsin PTn be-

causeit is linearin T. Thus (OP/OT)w shouldbe es-

sentially
independent
of anharmonicity.
If (OP/OT)v
is independent
of T, then a is controlled
by (57), a
strictly quasiharmonicequation.

6h. $2'and q 'omthe QuasiharmonicTheory

Fromthe definition
of ST,(3), andusing(51), (52)
and (53), we find

5T=(qat_
1)+(OKT
k,Op)

by (45), we havefor isochores,

The above equation tells us that 5T should be virtu-

(aKw)at
= 3pRyat
V -_ Ctyat
(M/r)p0(1-aT)

in Tables29-43, whichshowthat roughlyspeaking,

ally independentof T at high T. This is demonstrated

(55)

T is parallel to the T axis. We also note that if

determinedfrom PTn. Nevertheless

to a fair approximation aKT is parallelto the T axisfor T > O, as

(OKT/OP)T -- K is virtuallyindependent
of T, and
theexperimental
evidence
isin favorofthis,5T at high
T shouldbe slightlyhigherthan K, providingq > 1.
We deriveda relationshipbetweenthreeimportant
dimensionless
thermoelastic
constants
at highT. The

Tables

aboveequationcan be expressedas

Equation(55)is to be compared
to (48). The actual
measuredaKT will have more structure than aKT

29-42

show.

qat_ 5T- K q-1.

6g. a Versus T at High T Along Isobars

Usingtheexpression
forK t versus
T, (49),andthe
expression
for aKT givenby (48), we have
aKT

a-KTo+ (OK"t
OT)r T'

(58)

Equation(58)isappropriate
forhighT only,arisingas
it doesfrom the high temperaturelimit of the quasiharmonicapproximation. For the low temperature
equationcorresponding
to (59), we takethe logarithmic derivativeof 7, as definedby (1), yielding

(56)

whichis closeto, andfor somesolidsexactlyequalto,

const

q-- (On)
0tn T_&r_K,+l_(OnCv)
'0n
V T. (59)

(57)

At highT andP = O,(59) reduces

to (58)because
Cv

fortheP - 0 isobar
andwhere
a - (OKt/OT)p,

6i. Summary of the Quasiharmonic Approximation Effects Upon Physical Properties

The data presentedhere stronglysuggestthat the

a-- KTo
--aT

givenby (53). We note that (57) resultsfrom the

quasiharmonicapproximation.

is independent
of V abovethe Debyetemperature.

Examinationof (57) showsthat at high T we may

quasiharmonicapproximation is valid for the follow-

expect a to increasewith T at high T even under the

ing propertiesat leastup to T = 20: P, KT, aKT,

quasiharmonic
approximation.This steadyincreaseof
a with T at high T doesnot necessarily
requirethe

a, and all the respective volume derivativesof these

assumption of additional anharmonic terms in .A be-

fourproperties.They alsosuggest
that the quasiharmonicapproximation
may or may not be validfor Cg

yondthe quasiharmonic
highT approximation,
(41).
It arisesbecause
the denominator
in (57) hasa term

means that equations of state should not be corrected

that decreases
withT evenin the quasiharmonic
approximation.
Wesawsomeevidence
of anharmonicity

for anharmonic
effectsfor pressures
andtemperatures
corresponding
to mantleconditions.For an explana-

and entropy for temperaturesup to T - 20. This

ANDERSON

AND

ISAAK

91

could be used to find Ks vs. T, becauseV is a func-

tion of why P, KT, aKT and a do not require anharmonic correction, while at the same time Cv and S
may require anharmoniccorrection,see Andersonet

tion of T. Anderson[3] used (61) in a more convenient form, which followswhen 5s is independentof

al. [13].

T. Along isobars,

7.

HIGH

TION

TEMPERATURE

EXTRAPOLA-

[v(:r)]

FORMULAS

7a. Introductory

Comments

Knowledge of the high temperature thermoelastic

properties permits one to generate extrapolation formulasfor estimatingKs and G at temperatureshigher
than measured. We have seenthat at high temperature (aboveO), 7 and 5s are virtually independentof
T for someminerals, and nearly so for others. By assuming that 7 and 5s are exactly independentof T,
good estimatesof Ks are found using the definitions
of 7 and 5s. Sincethe valuesof 5s and 7 are oftennot
steadyfor T < O, it is not safe to usethe extrapolation formulas describedbelow when only low T data
for 5s and 7 are available. This is true especiallyfor
minerals,for in this caseambientvaluesof 5s and 7
are measured at temperatures much lower than O.

7b. Extrapolations for Ks Using ? Constant

With

Ks--Kso
L Vo

L Po J

Using(62)heestimated
Ks forMgOupto 2000C(see
Figurei andEquation(21) of Anderson[3]). Sumino
et al. [61] used(62) to extrapolatevaluesof Ks for
forsterite

from 700 K to 2000 K.

Duffy and D.L. Anderson[21]presenta generalformulafor extrapolatingelasticconstants,

in which(62)
is a specialcase.Duffy and D.L. Anderson'sequation
for G(T) in terms of the nomenclature
usedin this
paper is

act)- ao
Knowledgeof Co(T) is not requiredfor (62) and
(63), but someknowledge
of a(T) at highT isrequired
to get p(T) at high T. The appropriateequationrelating p and a is

If 7 is independent
of T, asin the caseof MgO, CaO,
andMg2SiO4at highT, andif a(T) andCp(T) data

p(T) - 0exr -

a(T) d

(64)

are availableat high T, then the followingformula,

determined
from (1), is useful.Using(1)

[c"]
Cro J

For somesolids,p(T) at high T may not be known.

However there is another method

(6o)

Ks(T)-[a(T)V(T)]
aoo

that minimizes

the

dependence
of Ks upona(T) and p(T).
Combining(1) and (2), wehave

whereKso, Cpo, a0, and V0 all refer to valuesof these

quantities at somereferenceT beyond which 7 is approximatelyconstant.Suminoet al. [61] and Sumino
et al. [63], respectively,
used(60) to extrapolateKs
from 700 to 2100 K (forsterire)and 1300 to 3100 K

(MgO). We emphasize
that reliableextrapolations
using (60) requirethat a be knownat high T and the

OKs
aKs
- .
s.Cr(65)
OT )p - -s
Integrating(65) with respectto T

Ks(T)- Ks(To)
- -

V dT.
f Ss7CP

(66)

assumptionthat 7 is constant.

Assuming now that the product 5s7 is independent of

7c. Extrapolations for /rs Using $$ Constant

T at high T, and taking V = V0(1+ aT), we find to a

very goodapproximation[54]

With

Andersonand Nafe [9] pointedout that if 5s is independent of T along isobars, then

nKs = -8s nV + constant

(61)

tCs() -

78s

oo
[H(T)-H(To)]

[1_a(TTo)]
2

'

(67)

92

HIGH

T ELASTICITY

OF MANTLE

MINERALS

whereH(T) - f Cp dT is theenthalpy.
Equation(67) showsthat Ks(T) shouldbe linear in
H(T). This wasprovenexperimentallyfor three mineralsfor 300 < T < 1200 K by Sogaet al. [54], and

used for one extrapolation and an equation involving

linearity in Poisson'sratio is also used

for the same three minerals for 300 < T < 1800 K by

0)P To(T-To).
o'(T)
--o'o
+ ('

Anderson[5]. The term a(T-

Both extrapolation equationsgive reasonablygoodre-

T0)/2 is of little con-

sequencein the calculation and can be ignored. Anderson[5] used (67) to extrapolatethe velocitiesof
soundfrom O to the melting point. Equation (67) is

very usefulbecausea(T) is not neededto find Ks(T),

and there is much enthalpy data published listing H
to temperatures about or greater than 2500 K.

7d. Extrapolations of Ks by Sumino et al. [61]

Suminoet al. [61]measuredthe elasticconstantsof
forsterite between -190C and 400C. They then ex-

trapolatedthe valuesof Ks up to 2200K using(60),

(62), and (67) assuming7 and 5s constantin the high

_----

130

(69)

Isaakel al. [1989b]

Surmno
elal.[1977]

z:x,,.

......... Extrapolation
(Eq.
60)

--

Extrapolation
(Eq62)

_,.'.-.....
-....
'--_......Extrapolatio
(Eq
67)

.. 120

110

-.

temperature regime. The extrapolation to 2000 K is

shownin Figure 3. Isaak et al. [35] reportedmea-

100

sured values of Ks up to 1700 K, and their values are

II

400

However,Figure3 illustratesthe pointthat (60) is not

a good extrapolation formula, at least for forsterite.

Suminoet al. [63]measuredthe elasticconstantsof

MgO from 80 to 1300 K. They usedequation(60) to
extrapolate values of Ks above the maximum mea-

surement(1300 K) up to 3000 K. This is shownin

Figure4, in whichthe measuredvaluesof Ks [35]up
to 1800 K are alsoplotted. It is clear that the extrapolationformulagivenby (60) is reasonablysuccessful
in the caseof MgO.

and A12Oa up to 1200 K and found that G was linear

Fig. 3.

150

140

120
11o

(68)

Suminoet al. [61] measuredG for forsteriteup to

to 2200K. Isaaket al. [35]measured

G up to 1700K.
Theseresultsare plotted in Figure5. Equation(68) is

.".J

2000

Isaak et al. [1989a]

Sumino
et
al.
[1983]

MgO
,

500

1000

1500

2000

2500

3000

T (K)

to estimate shear velocitiesup to 2500 K.

400C and reported e.xtrapolated values from 700 K

1600

100

To

&&&,.

Ks up to 1100 K for Mg2SiO4 and MgSiOa and also

found linearity for G and Ks. They usedthe empirical

(a.- a")

170

130

Observedand extrapolated valuesof Ks ver-

in T above800 K. They [53] later measuredG and

formula

susT for forsterire. Experimental(plotted symbols):

Isaak et al. [35]; Suminoet al. [61]. Extrapolations
by Suminoet al. [61]: (a) usingEquation(60) where
600K is the reference
T; (b) usingEquation(62); and
(c) usingEquation(67). Two extrapolations
madeby
Suminoet al. [61]are confirmedto within 2% out to
1700K by the measurements
of Isaak et al. [35].

160

7e. Extrapolation of to High T

Sogaand Anderson[52]measuredK and G for MgO

1200

T (K)

alsoplottedin Figure3. Equations(62) and (63) gave

good results for extrapolations, since the actual measured values are quite closeto the extrapolated ones.

800

Fig. 4.

Observedand extrapolatedvaluesof Ks ver-

susT for MgO. Experimental(plottedsymbols):Isaak

et al. [34];Suminoet al. [63].Extrapolation
by Sumino
et al. [63]usingEquation(60).

ANDERSON

AND

ISAAK

93

suits when comparedwith the later measurementsof

9O

Isaak et al. [35]

Suminoet al. [1977]

Isaak et al. [1989b]

The equation of G is

Extrapolation(Eq. 68)
Extrapolation(Eq. 70)

8O

Ks(T).
G(T)
- 3(1
(1-+2r(T))
r(T))

70-

(70)

7f. Extrapolations for v, and v to High T

If K and G are successfullyextrapolated, then v0

andvpareextrapolated.
Sumino
et al. [61]gavevalues
for the extrapolatedvaluesof v, andv for forsteritcup

Mg2Si04
50

'
0

400

800

1200

1600

2000

T (K)
Fig. 5.

Observed and extrapolated values of G ver-

susT for forsteritc. Experimental(plotted symbols):

Isaaket al. [35];Suminoet al. [61]. Extrapolationsby'
Suminoet al. [61]' (a) usingEquation(68); (b) using
Equation (70). The extrapolationsmade by Sumino
et al. [61]are confirmedto within 1.5% out to 1700K
by the measurements
of Isaak et al. [35].

to 2200 K using their 100 K to 200 K measurements.

These are shownin Figure 6. Comparisonwith the

actualmeasurements
of v, andv by Isaaket al. [35]
and presentedin Table 15 are alsoplotted. It is clear
that the extrapolations
by Suminoet al. [61]werequite
successful.

170

,i

Cossular
(GGD)

",'.

8.8

8.6

TS1

160 -

8.4
8.2

k'%
,,.//6,
at
high
T

' A

7.8

'.

150

7.6

Suminoet al. [1977]

- -- - Extralat
(Sumino
elal.[1977])
5

6s at lowT

140

4.8

4.6
4.4

130

4.2 -

200

500

1000

15oo

20oo

T (K)
Fig. 6. Observedand extrapolatedvaluesof vp and
v, versusT for forsteritc.Experimental(plottedsymbols):Suminoet al. [61]up to 700 K; Isaak et al. [35]
up to 1700K. Extrapolationsby Suminoet al. [61]are
from 700 to 2200 K and are confirmed to within

1.5%

at 1700K by the measurements

of Isaak et al. [35].

600

1000

1400

1800

Temperature
(K)
Fig. 7. Observedand extrapolated valuesof Ks vs. T
for grossulargarnet. Experimental points shown with

symbols[36]. Extrapolations:TS1 refersto first order

Taylor expansionusing lower temperature data; long
dashedline usingEquation(62) with low temperature
valueof/is; shortdashedlineusingEquation(62) with
high temperature values of s.

94

HIGH

T ELASTICITY

OF MANTLE

MINERALS

7g. The Importance of Using High T Values of

110

8s and I

Grossulor(GGD)

Isaak e al. [36] reported Ks and (7 for grossular

garnetup to 1550K, measuring/sand F overa wide
T range.Figures7 and 8 showthe extrapolations
presentedby hem up to 000 K, with 4 methods.They
tried both a first order polynomial and a secondorder polynomial. The fits were marginally successful,
as shownin Figures7 and 8. They alsofound Equations(6e) and (63) to be a muchbetterrepresentation
of G(T) providedtha the exponents,/s and F, are
the averagehigh temperaturevalues,and no the low
emperaturevaluesof F (T O). Thereforewe recommendEquation(62) for extrapolationsof Ks and
Equation(63) for extrapolations
of G, providedthat

105 -

100 \

95TS1

F af low T

90-

F at highT

valuesof/s and F measured above O axe used in the

85-

equations. If enthalpy daa axe available,we recommend(67) for extrapolationsof Ks.

80-

Acknowledoements. The authors thank former members of the mineral physicslaboratory who contributedto
the dt bnk published here, including M. Kumazwa,
I. Ohno, Y. Sumino, I. Suzuki, S. Yamanoto, T. Goto,
tt. Oda, S. Ota, and H. Cynn. We acknowledgewith
thnks the works of E. K. Graham, N. Sog, R. Liebermnn, H. Spetzler, D. L. Weidner, J. Bass,I. Jckson,and
M. Mnghnni that affectedour researchprograms.Sung
Kim of Azusa Pacific University provided much help in the
statistical analysisrequired to arrive at valuesfor the variousdimensionless
parameters.The salary of one of us was
providedby grantsfrom the LLNL-IGPP branchunderthe
auspicesof the Department of Energy under contractW7405-ENG 48. Support for Mr. Kim w provided by the
Office of Naval Research through Grant no. N00014-93-

75

200

600

1000

1400

1800

Temperalure
(K)
Fig. 8. Observedand extrapolatedvaluesof G (GPa)
versus T for grossular garnet. Experimental points

shownwith symbols[36]. Extrapolations:TS1 and

TS2 r.cferto first and secondorder Taylor expansions
usinglowT data;longdashedlinesusingEquation(63)
with low T valuesof F; short dashedlines using Equa-

tion (63) with high temperaturevalueof F.

10544.

IGPP

contribution

no. 3849.

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1.

2.

Anderson, D. L., A seismic equation of state. II. Shear properties

and thermodynamics of the lower
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edited by W. P. Mason, pp. 43-

95, Academic Press, New York,

5.

Anderson, O. L., The relationship

1965.

between

Anderson, O. L., A proposed law

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Phys. Chern. Miner., 16, 559-562,

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Grfineisen

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earth's lower mntle, J. Geophys.

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modulus

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6.

Anderson, O. L., Evidence supporting the approximation TP for

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of

resonant

ultrasound

and

its

applications to the determination

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Acoust. Soc., 91, 2245-2253, 1992.

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The

bulk

modulus-volume

relatedgeophysical
problems,jr.
Geophys. Res.,

Sciences, 2nd Edition, 328 pp.,

McGraw-Hill, New York, 1992.
19. Cynn, H., Effects of cation disor-

70, 3951-3963,

deringin MgA1204 spinelon the

1965.

Anderson, O. L., and S. Yamamoto, The interrelationship

of thermodynamic properties obtained by the piston-cylinderhigh
pressure experiments and RPR
high temperature experiments for
NaCI, in High Pressure Research
in Mineral Physics, Geophys.
Monogr. Set., vol. 39, edited by
M. H. Manghnani and Y. Syono,
pp. 289-298, AGU, Washington,
D.C., 1987, 486 pp.
Anderson, O. L., E. Schreiber, R.
Liebermann, and N. Soga, Some
elastic

constant

data

rectangular parallelepiped resonance and Raman measurements

of vibrational spectra, Ph.D. thesis, 169 pp., UCLA, Los Angeles,
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21.

H. Oda, High temperature

elastic
relevant

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14.

Anderson,
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15.

Prototype Set of Tables, 356 pp.,

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26. Goto, T., S. Yamamoto, I. Ohno,
and O. L. Anderson, Elastic constants of corundum up to 1825 K,
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1989.

27. Graham, E. K., Jr., and G. R.

Barsch, Elastic constants of
single-crystal forsterite as a function of temperature and pressure,
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28. Graham, E. K., J. A. Schwab,

S. M. Sopkin, and H. Takei, The
pressure and temperature dependence of the elastic properties of

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Phys Ghem. Miner., 16, 186-198,
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1993.

10, 335-342, 1962a.

miner-

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Enck,F. D., and J. D. Domreel,

Behaviorof the thermal expansion
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23. Enck,F. D., D.G. Engle,andK.I.

Marks, Thermal expansionof KC1
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24.Furukawa,G. T., T. B. Douglas,

R. E. McCoskey, and D.C. Ginning, Thermal properties of alu-

neisen ratio at extreme

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MgO as an example, Phys. Chem.

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Mixtures:

Duffy,T. S., andD. L. Anderson, 30. Hashin, Z., and S. Shtrikman,

Chopelas, and D. Isaak, A thermodynamic theory of the Grficonditions:

and Related

On some variational principles in

anisotropic and nonhomogeneous
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Sound velocities in mantle

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Calcium

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Anderson, O. L., D.G. Isaak, and

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20. Duffy, T. S., and T. J. Ahrens,

phys., 6, 491-524, 1968.

12.

Reduction and

Error Analysisfor the Physical

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9S

Anderson, O. L., and T. Goto,

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10.

AND ISAAK

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Barin,
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Thering- 25.Garvin,

D., V. B. Parker, and

A variational approach to the

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Hunter,
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variation with temperature of the
principal elastic moduli of NaC1
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32. Isaak, D. G, High temperature

elasticity of iron-bearing olivines,
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33. Isaak, D.G., and O. L. Anderson,

Elasticity of single-crystalfayalite
(abstract), Eos Trans. A Gif, 70,
1418, 1989.

34. Isaak, D.G., O. L. Anderson, and

T. Goto, Measured elastic modulus of single-crystal MgO up to

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HIGH

T ELASTICITY

OF MANTLE

1800 K, Phys. Chem. Miner., 16,

703-704, 1989a.

35. Isaak, D. G., O. L. Anderson,

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36. Isaak, D. G., O. L. Anderson,
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44. Ohno, I., Free vibration of rectangular parallelepiped crystal and

its applicationto determinationof

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45. Okajima, S., Study of thermal

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39. Krupka, K. M., R. A. Robie,
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dence of the elastic properties

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pyrophyllite, KA1SisOs glass,
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40. Kumazawa,M., and O. L. Anderson, Elastic moduli, pres-

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50. Simmons,G., and H. Wang, Single Crystal Elastic Constantsand

sure derivatives,and temperature

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Calculated AggregateProperties,
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51. Skinner, B. J., Physical properties of end-members of the garnet
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52. Soga, N., and O. L. Anderson,

High temperature elastic properties of polycrystalline MgO and

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355-359,

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53. Soga, N., and O. L. Anderson,

High temperature elasticity and

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Estimation

of bulk

modulus and sound velocities at

very high temperatures, J. Geophys. Res., 71, 5315-5320, 1966.

55. Spetzler, H., Equation of state of
polycrystalline and single-crystal
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56. Spetzler, H., C. G. Sammis, and

R. J. O'Connell, Equation of
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Ultrasonic

mea-

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The

elastic con-

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Fe2SiO4,

and CO2SIO4 and the elastic

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59. Sumino,Y., and O. L. Anderson,

Elasticconstantsof minerals,in
Handbook
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BocaRaton, Fl., 1984.
60. Sumino,Y., I. Ohno, T. Goto, M.
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and internal

friction

on single-crystal MgO by rectangular parallelepiped resonance, J.

Phys. Earth, , 263-273, 1976.
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Temperature variation of elastic constants of single-crystal
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The elastic constants of single
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the elasticity of stoichiometric

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Elasticity and thermal expansion
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AND

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Static CompressionMeasurementsof Equationsof State

Elise Knittle

1.

INTRODUCTION

pressuresmaintainablefor long periodsof time. The bulk

modulidatahavebeencollectedusingprimarilyeitherx-ray
diffraction or piston displacementin conjunctionwith a
high-pressure
apparatus
to measurethechangein volumeof
a material as a function of pressure. In general, high
pressureapparatuses
are optimizedfor either: 1) allowing

Generation of high pressuresand temperaturesin the

laboratoryis essentialin exploringthe behaviorof solids
andliquidsat thepressureandtemperature
conditions
of the
Earth'sinterior. Indeed,the primary insightsinto magma
genesis,phasetransitions
and theequations
of stateof deep opticalaccessto the samplewhile held at high pressures
(diamond-anvilcells); or 2) maintaininglarge sample
Earth constituents,as well as the geochemicalbehaviorof
volumes(large-volumepresses).
materials at depth in the planet have been derived from
experimentsinvolving staticcompression.
In this chapter,
the emphasisis on static-compression
measurements
of the
2.1.
Diamond-Anvil
Cell
equations of state of minerals, elements and related
The most widely used high-pressureapparatus for
materials. To date, the vast majority of staticcompression
measuring
staticequationsof stateis the diamond-anvilcell
experiments have focused on measuring isothermal
coupled
with
x-my diffraction. There are severalexcellent
equations of state (P-V measurements at constant
recentreviews on the use of the diamond cell [88, 97, 215],
temperature), in order to determinethe isothermalbulk
modulus(KOT= -lfV(/dT)
and its pressurederivative and thusno detailsof its operationare presentedhere. For
(dKoT/dP = KOT') as well as characterizingthe pressure equation-of-statemeasurements,two basic diamond cell
designsare used(seeFigure 1). The Merrill-Bassett-type
conditions of structuralphase transitions. With the bulk
diamondcells are commonlyusedfor single-crystalx-ray
modulus and its pressure derivative, it is possible to
diffraction measurements, as their small size makes them
extrapolate the density of a material to any pressure
convenientfor mountingon a goniometerto obtainsinglecondition. Here, I tabulatebulk modulidatafor a varietyof
crystalx-ray patterns. In general,thesediamondcells are
minerals and related materials.
used for pressuresbelow about 10 GPa. However, for
single-crystalmeasurements,
it is necessaryto maintainthe
2. EXPERIMENTAL
TECHNIQUES
samplein a hydrostaticenvironment.Sinceliquid pressure
media (such as 4:1 methanol:ethanolmixtures)are only
There are a numberof differentexperimentaltechniques
hydrostatic to-12 GPa, the pressurelimitation of the
and apparatusesfor achievinghigh pressuresstatically,or
diornondcell is not a limiting factorfor theexperiment.
The second type of diamond cell, a Mao-Bell or
"megabar"-type
diamondcell, is optimalfor obtainingx-ray
diffractiondata to pressuresup to 300 GPa. Usually, in
E. Knittie, University of California, Santa Cruz, Instituteof
Tectonics,Mineral PhysicsLaboratory,SantaCruz, CA 95064
thistypeof diamondcell, the sampleis a powderandthexray
diffraction data collected is directly analogousto a
Mineral Physicsand Crysta!lography
Debye-Scherrer
powder pattern. A typical sample
A Handbookof PhysicalConstants
configurationin thediamond-cellis shownin Figure2.
AGU Reference Shelf 2
Copyright1995 by the AmericanGeophysicalUnion.

98

KHE

99

A schematic diagram of the geometry of an x-ray

diffraction experimentin shownin Figure 3. Usually,
MoK(x x-raysare passethroughthe diamondsand sample
along the axis of force of the diamond cell. X-ray
diffractionfroma crystaloccurswhentheBraggequationis

Optic Access

satisfied:

g = 2dsin0

S_ple

lcm
on

Cylinder

Sample

2 cm

Lever
Arm

Fig. la. The Mao-Bell-type diamond cell capable of

generatingpressuresup to 550 GPa. The diamondsare
glued onto half-cylindersof tungstencarbide which are
mountedin a pistonandcylindermadeof hardened
tool steel
(shownherein a cutawayview at the top). The diamonds
can be translationallyalignedby meansof set screwsand
tilted with ret
to eachother by rockingthe WC halfcylinders.The pistonandcylinderareplacedin a leverarm
assemblyCoottom)designedto advancethe pistonwithin
the cylinder, apply force uniformly to the sampleheld
between the diamonds, and exert a minimum amount of

torqueon the piston.

(1)

whereJ[is the wavelengthof the incomingx-ray, 20 is the

anglebetweenthediffractedx-raybeamandthetransmitted
beam,and d is the d-spacingor the distancebetweenthe
diffracfingsetof atomicplanesin thecrystal.Thediffracted
x-rays, either Laue spotsfor single crystal samplesor
diffracted conesof radiation for powdered samples,are
detectedby a solidstatedetectoror on film. The setof dspacingsfor a crystal is used to determinethe lattice
parameters
andthusthevolumeof thecrystallographic
unit
cell as a functionof pressure.The relationshipbetweendspacingsand lattice parametersfor the various lattice
symmetriesare given in most standardtexts on x-ray
diffxacfion[e.g.,36].
Pressurein the diamondcell is usuallymeasuredusingthe
ruby fluorescence
technique[20, 128, 129]. Here, the R1
and R2 fluorescence bands of ruby, at zero-pressure
wavelengthsof 694.24 nm and 692.92 nm, are excitedwith
blue or greenlaserlight (typically He:Cd or At-ion lasers
are used). These fluorescence bands have a strong
wavelengthshift as a function of pressure. This shift has
been calibrated using simultaneous x-ray diffraction
measurements
on metalswhoseequationsof state(pressurevolumerelation)are independently
knownfrom shock-wave
measurements
(seeChapteron Shock-waveMeasurements).
Therefore, the accuracy of the pressuremeasuredin the
diamondcell is ultimately determinedby the accuracyof
measurements
of shock-waveequationsof state. In addition
to average pressuremeasurements,ruby can be finely
dispersedin the sample(fluorescence
measurements
canbe
obtainedfor ruby grainsless than 1 gm in diameter),thus
enabling pressuregradientsto be accuratelydetermined
within diamondcell samples.
Becausediamondsare transparent
andallow opticalaccess
to the stunpie,other methodsfor measuringequationsof
stateare possible.For example,the changesin the volume

of the samplechamberas a functionof pressurecan be

directly measured[cf., 139], or changesin the sample
dimensionswith pressuremay be directly measured[cf.,
143]. Additionally, accurateadiabatic moduli and their
derivativesmaybe obtainedusingBrillouinspectroscopy
in
conjunctionwith the diamond cell (see the chapter on
Elasticity).

100

STATIC

COMPRESSION

Alignment

Sample

et
Screw
Chamber
i

I_

2.2. Large-Volume Presses

Equationof statemeasurements
havealsobeencarriedout
usinga varietyof large-volume,high-pressure
apparatuses:
piston-cylinder
devices,Bridgman-anvilpresses,
Drickamer
presses,cubicand tetrahedral-anvil
pressesand multianvil
presses(Figure4). For recentreviewsof thedesignanduse
of large-volumepresses
seeGraham[59] andHollowayand
Wood [85].

One of the mostwidely usedhigh-pressure,

large-volume
devicesfor equationof statemeasurements
is the pistoncylinder (Figure 4a), where the pressure is applied
uniaxiallyby a pistonon a sampleembeddedin a pressure
medium and containedby the cylinder. As the sampleis
compressed its volume decreases, and by careful
measurementof the resulting piston displacementas a
function of pressure,the P-V equation of state can be
determined. The routine pressure limit of the pistoncylinderat roomtemperature
is betweenabout3 and5 GPa.
Other types of high-pressure, large-volume devices
utilizing opposedanvilsfor equationof statemeasurements
are Bridgman anvils and the Drickamer press. In these
devices,two tungstencarbideanvils are driven togetherto

Plate

AlignmentPin

uniaxiallycompress
a samplecontainedwithina large
retainingring whichactsas a gasket. If all or a portionof
theretainingring is madeof a materialtransparent
to x-rays
(suchas B or Be), diffractionmeasurements
canbe madeon
a sampleheld at high pressures.The pressurelimit of the
Bridgman-anvil press is about 10-12 GPa at room
temperature,and the limit of the Drickamerpressis about
BackingPlate

30-35 GPa.

Hole to Diamond Back

andOpticAccess

Bolts for Pressure

Application

A second family of large-volume apparatusesis the

multi-anvil press. Rather than uniaxially compressing
the
sample, these devices compress simultaneously from
several directions.

Fig. lb. Merrill-Bassett-typediamond-anvilcell shownin

schematicfrom both side (top) and top views (bottom).
This devicecan be usedto generatepressures
of-- 30 GPa.
The single-crystaldiamondsare glued on flat, circular
backingplatestypically madeof hardenedsteel,tungsten
carbide or copper-berylliumalloy. Holes or slits in the
backingplatesprovideopticalaccessto the sample,which
is containedbetweenthe diamondsin a metalgasket. The
backingplatesareheldin placein recesses
in largersteelor
inconelplates by meansof set screws,and also allow the
diamonds to be translationally aligned relative to one
another.Alignmentpins ensurethatthe the top and bottom
halvesof the cell arecorrectlyoriented.Pressureis applied
by sequentiallyturningthe threeboltswhich compressthe
top and bottomplatestogether.

Such instruments are more difficult

to

use than a piston-cylinder,as the anvils mustbe carefully

alignedandsynchronized
to compressthesampleuniformly
and thus prevent failure of the anvils; however, much
higherpressurescan be attainedin multi-anvildevices. A
number of designsexist for multi-anvil pressesof which
the ones most commonly used for equation of state
measurements

are the tetrahedral-anvil

and cubic-anvil

presses(Figure4b), and multiple-stagesystems.

In tetrahedraland cubic-anvil presses,as their names
imply, the samplesare typically containedwithin either a
tetrahedron
or a cubecomposed
of oxides,with the sample
occupying a cylindrical cavity inside the cube or
tetrahedron. The sample assembly, which varies in
complexitydepending
on the experiment,is compressed
by
four hydraulicramsin the caseof the tetrahedralpress,or
six hydraulicrams for the cubic press. As illustratedin
Figure 4c for a cubic-anvilpress,in-situ x-ray diffraction

KNITTLE

measurementscan be made through these pressesif the

sample is contained in an x-ray-transparent material.
Equationof statemeasurements
havetypicallybeenmadeto
pressuresof about 12 GPa in the cubic-anvil press. To
achievehigher pressures,the sampleassemblyin a cubicanvil press can be replaced by a second, pressureintensifying stage. Such a multi-anvil design can reach
typical pressuresof about25 GPa.
The pressureinsidea large-volumedeviceis determined
either by including an internal stressmonitor within the
sample, or by calibration of the external load on the
sample. In the latter case, which representsthe most

III
Upper Diamon(

RubyGrains

Gasket

Sample

Culet Face

ure Medium

Lower

101

Dia

commonmethodfor estimatingthe pressurein all largevolume devices,the oil pressureof the pressis calibrated
against a series of materials or fixed points, with wellcharacterized
phasetransformations,
suchasthoseoccuring
in Bi (the I-II transition at 2.5 GPa and V-VI transitionat
7.7 GPa). Specific disadvantagesof x-ray diffraction
measurements
in large volumepressesinclude: 1) indirect
pressure calibration; 2) an inability to accurately
characterizepressuregradients;and 3) the small volumeof
the sample relative to the containing material, which
necessitates
both careful experimentaldesignand a high
intensityx-ray source. Furthermore,the diffractionangles
availablethroughthe apparatusmay be limited, producing
few redundancies
in the measurement
of latticeparameters.
3.

ANALYSIS

OF

THE

DATA

To determinethe valuesof K0T andKOT'from pressurevolume data, an equationof stateformalismmustbe used.

Here, I summarize the most common methods for data

Fig. 2. Schematicview of the sampleconfigurationin the

diamondcell. A hole is drilled in a metal gasket(here a
typicaldiameterof 0.10 mm is shown),and the gasketis
centeredbetweenthe diamondanvils(shownwith a typical
culetdiameterof 0.30 mm). The sampleis placedin the
holein thegasketalongwith a pressure
medium(generally
eitheran alcoholmixture,or a noblegassuchas argon)and
smallruby chipsfor pressurecalibration.The transparent
diamonds allow for a wide range of different in situ
experiments
to be performedon the samples.For equation
of state measurements,x-ray diffraction patternscan be
obtained at high pressurealong the axis of force of the
diamondcell for either single-crystals
or powders.(From
[215]).

reduction.A linear fit to pressure-volume

datais oftenused
for staticcompression
datalimited to low pressures
(small
compressions). The bulk modulusis calculatedfrom the
thermodynamicdefinition: KOT = -1/V(dP/dV)T, where
KOT is the isothermalbulk modulus, V is the volume and
P is the pressure.This analysisimpliesthatKOT' = 0, and
thus is at best approximate,and is most appropriatefor
rigid materialsovernarrowpressure
ranges(preferablyless
than 5 GPa). In general,becauseKOT' is usuallypositive,
this analysismethodwill tendto overestimateKOT.
An equationof stateformalismusedextensivelyprior to
1980 and sporadicallysince is the Murnaghanequation
[153], in which:

P = KOT/KOT'{
(Vo/V)KoT
' -1}

(2)

The Murnaghanequationis derivedfrom finite straintheory

with the assumption that the bulk modulus is a linear
function of pressure. At modest compressions,this

102

STATIC

COMPRESSION

assumptionis sufficiently accurate that the Murnaghan

equationaccuratelyfits staticcompression
data.
One of the most widely used equations of state in
reducingstaticcompression
datais theEulerianfinite-strain
formalism proposedby Birch, and referredto as the BirchMurnaghan equation [25]. This equation has been
empiricallyshownto describethebehaviorof a widevariety
of materialsover a largerangeof compressions.Pressureis
expresseM
as a Taylor seriesin strain:

P = 3f(l+2f)5/2KOT(1
+ xlf + x2f2 + ...)

<--40-->

((
Film
,r Solid
State Detector

(3)

X-rays
Sam

wheref is theEulerianstrainvariabledefinedas

Diamond
Anvil Cell

f: 12[(V/Vo)2/3
-]
and the coefficientsin (3) are:

irect X-ray

Xl = 3/2(KOT' - 4)

Beam

x2 = 3/2 [KoTKOT"+ KOT'(KOT'-7)+ 143/9].

Note that KOT' = 4 reducesequation(3) to a secondorder

equationin strain. Indeed,KOT' is closeto 4 for many

materials, and in the reductionof pressure-volume
data,is
oftenassumedto equal4. In addition,mineralsare seldom
compressible
enoughfor KOT"to be significant;
therefore,
thex2 termis usuallydroppedfrom theequation.
Recently, anotherequationof stateformalismhas been
proposed by Vinet et al. [205] and is known as the
Universalequationof state. Here:

Fig. 3. Schematicof an x-ray diffraction experiment

throughthe diamondcell. MOK x-raysare passedthrough
the sampleand the diffractedx-raysare recordedeitheron
film (shown here) or by a solid-statedetector. Here the
schematicx-ray pattern is that of a powder diffraction
experiment,where the film intersectsdiffracted conesof
radiation.

The

maximum

distance

between

the

corresponding
x-ray line on eithersideof the transmittedxray beam is 40, which is used in the Bragg equation to
determine the set of d-spacingsof the crystal at each
pressure.

P = 3 KOT(VoIV)2/311-(VIVo)
/3
exp{3/2(KOT'1) [1-(V/Vo)13]}.

(4)

This equationis successfulin describingthe equationof

stateof a material at extremelyhigh compressions
and is
beingusedwith increasingfrequencyin staticcompression

mineral or native element. Oxides, sulfides, halides and

hydrides were included which are useful as mineral

analogues,either due to structuralsimilaritiesto minerals,
studies.
or to provide the systematicsof the behaviorof a given
structuraltype. Specificallynot includedare datafor non4.
EXPLANATION
OF THE
TABLE
mineralIII-V compounds
andothernon-naturallyoccurring
semiconductors.All the KOTand KOT' data listed are for
the structure of the common room-temperature,
The Table lists the isothermalbulk moduli (KOT) and
atmospheric-pressurephase, except where noted. In
pressurederivatives(dKoT/dP=KoT) for minerals,mineral
particular, the structuresof the high pressurephasesare
analogues and chemical elements studied using static
explicitlygiven, asare thespecificstructurefor solidswith
compressiontechniques (i.e. x-ray diffraction, piston
displacementmeasurements
or directvolumemeasurements morethanonepolymorphat ambientconditions.It should
be notedthat entrieswith no errorssimplyreflect thaterror
at high pressures). All the data reported is from the
barswerenotreportedin theoriginalreferences.
literaturefrom 1966 to the present:staticcompression
data
The silicate minerals are categorizedfollowing Deer,
from before 1966 canbe foundin thepreviousHandbookof
Howie and Zussman's An Introduction
to the RockPhysical Constants. Not every entry in the Table is a

KNrFrLE

lOB

Feedthrough

ressure Medium

X-Rays

Sample
!

5cm
I

pie
Assembly

2cm
Fig. 4a. A piston-cylinder apparatus shown in crosssection. Here, a uniaxialforce is usedto advancea piston
into a cylinder, compressinga pressuremediumand thus
applying hydrostatic or quasi-hydrostaticpressureto a
sample contained within the medium. The piston and
cylinder are usually made of tungstencarbide and the
maximum routine pressurelimit of this deviceis 5 GPa at
room temperature.The feedthroughinto the cylindergives
a way of monitoringthe sampleenvironment.For example,
electricalleadscanbe introducedinto thesampleto measure
temperatureor as a pressuregauge. Another use of the
feedthrough is to provide current to a resistanceheater
surroundingthe sample (not shown). Equation of state
measurementscan be made in this device by determining
the piston displacementas a functionof pressure.(From
[215]).

Fig. 4b A cubic-anvilpressin which six, synchronized

ramsare usedto compressa cubic sample. The rams are
usuallymadeof steel with tungstencarbideor sintered
diamondtips. The samplegeometriescan vary from
relativelysimple,with thesampleassembly
embedded
in a
cubeof pressuremediumwhichis directlycompressed
by
the rams, to a sample contained in a second, cubic,
pressure-intensifying
set of anvils (a multi-anvilpress).
Electricalleadscan be broughtin betweenthe ramsof the
pressto heatthesample,monitortemperature
andpressure,
and measure pressure-inducedchanges in electrical
conductivity.In addition,by usinga low-atomicweight
pressuremediumsuch as B or Be, x-ray diffraction

FormingMinerals[38].The datafor high-pressure

phases
are given in the samecategoryas for the low-pressure
phase. For example,the bulk modulifor perovskitestructured silicates are given with the data for the
pyroxenes,
whichhavethesamestoichiometry,
underthe

(Fe203)andmagnetite(Fe304) arelistedwith theoxides.

Also, measurements
are not given which clearly seemed

"ChainSilicates"category.

The data for the iron polymorphsand iron alloyswhich

are importantas possiblecoreconstituents
arelistedin a
separate
category
("IronandIronAlloys").Therefore,
iron
sulfides,Fel_xO,ironhydride,andiron-silicon,
iron-nickel
andiron-cobaltalloysarefoundin thisportionof theTable,
while more oxidized

iron minerals such as hematite

measurementscan be obtained on samplesheld at high

pressures.
(From[215]).

to be incorrect, based on comparisonwith other static

compressionmeasurements,ultrasonicdata or Brillouin
spectroscopicresults. Finally, I note that a range of
materialshavebeenstaticallycompressed
with the primary
motivationbeingto characterize
thepressure
at whichphase
transitionsoccur. Such studiesoften do not report either
bulk moduli or the numericalstaticcompressiondata, and
are accordinglynot includedin the Table (an exampleof
this type of studyare severalstaticcompression
resultsfor
C,e).

104

STATIC

COMPRESSION

Table 1. Bulk Moduli from Static CompressionData

Chemical
Formula
1 Density Isothermal
Bulk
(Mg/m
3)
Modulus
(GPa)
2
Framework

dKOT/dP
3
Technique
andNotes
4

Ref.

Silicates-

SiO2

2.65

Quartz

37.1 + 0.2

6.2+

DAC, scXRD, P < 5

GPa, B-M EOS

115

6.3 + 0.4

PC, ND, P < 2.5 GPa,

98

(fixedfrom
ultrasonicdata)

SiO2
Quartz

2.65

36.4 + 0.5

SiO2

2.65

38.0

5.4

BA, XRD, P < 12

GPa, O-H method

157

2.92

96 + 3

8.4 + 1.9

D AC, scXRD, P < 5.2

GPa, B-M EOS

113

4.29

313 + 4

1.7 + 0.6

DAC, scXRD, P < 16

GPa, B-M EOS

176

306 (fixed from

Brillouin data)

2.8 + 0.2

M EOS

Quartz

SiO2
Coesite

SiO2
Stishovite

SiO2

4.29

300 + 30

TAP, XRD, P < 8.5

GPa, linPVfit

21

4.29

288 + 13

BA, XRD, P < 12

GPa, O-H method

158

4.29

281

CAP, XRD, P < 12

GPa, B-M EOS

179

2.62

70

DAC, scXRD, P < 5

GPa, linPVfit

14

KAISi30 8
High Sanidine

2.56

67

DAC, scXRD, P < 5

GPa, linPVfit

14

CaA12Si208

2.76

94

DAC, scXRD, P < 5

GPa, linPVfit

14

2.76

106

DAC, scXRD, P < 5

GPa, linPVfit

14

3.12

159 + 3

4 (assmed)

DAC, scXRD, P < 5

GPa, B-M EOS

77

2.61

70 + 3

5.3 __+1.5

DAC, scXRD, P < 5

GPa, B-M EOS

63

Stishovite

SiO2
Stishovite

SiO2
Stishovite

NaA1Si308
Low Albite

Anorthite

(low-pressure
phase)
CaAI2Si208
Anorthite

(high-pressure
phase)
BeAISiO4OH
Euclase

Be4Si2(O2
Betrandite

KNITE

Table 1. Bulk Modulifrom StaticCompression

Data {cont'mued
)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus
12NaAISiO4

2.44

-27H20
Zeolite

21.7 (in glycerol)

ReL

dIT/dp3

Technique
andNotes
4

4 (asstuned)

DAC, scXRD, P < 4

GPa, B-M EOS

73

DAC, scXRD, P < 3

GPa, linPVfit

69

DAC, scXRD, P < 5

GPa, B-M EOS

76

142.8 (in water)

4A
2.24

40 + 1

2.30

52 + 8

0.17(Ca4AI6Si6024
CO3) 0.83(Na4AI3
Si9024C1)
Scapolite

2.54

60

DAC, scXRD, P < 3

GPa, linPVfit

33

0.68(Ca4AI6Si6024
CO3) 0.32(Na4AI3
Si9024C1)
Scapolite

2.66

86

DAC, scXRD, P < 4

GPa, linPVfit

33

0.88(Ca4AI6Si6024
CO3) 0.12(Na4AI3
Si9024C1)
Scapolite

2.71

90 + 12

DAC, scXRD, P < 5

GPa, B-M EOS

76

CaMgSi206
Diopside

3.22

114 + 4

4.5 + 1.8

DAC, scXRD, P < 5.3

GPa, B-M EOS

112

CaMgSi206
Diopside

3.22

113 + 2

4.8 + 0.7

DAC, scXRD, P < 5.3

GPa, B-M EOS

116

CaMgSi206
Diopside

3.22

122 + 2

4 (asstuned)

DAC, scXRD, P < 6

GPa, B-M EOS

142

CaFeSi206
Hedenbergite

3.56

119 + 2

4 (asstuned)

DAC, pXRD, P < 10

228

Ca(Mg0.4F.6)
Si206
Hedenbergite

3.42

(Caa)(Mg,Fe,Al)
Si206
Omphacite
(vacancy-rich)

3.26

NaAISi206'H20
Analcite

Na4AI3Si3012CI

4 (asstuned)

Sodalite

Chain

4 (asstuned)

silicates'

GPa, B-M EOS

82.7 + 1

4 (assumed)

DAC, pXRD, P < 10

228

GPa, B-M EOS

129 + 3

4 (assumed)

DAC, scXRD, P < 6

GPa, B-M EOS

142

105

106

STATIC

COMPRESSION

Table1. BulkModulifromStaticCompression
Data(continued)
Ref.

Chemical
Formula
1 Density Isothermal
Bulk
(Mg/m
3)
Modulus

andNotes
4
dKOT/dp3 Technique

(Ca,Na)(Mg,Fe,AI)
Si206
Omphacite
(vacancy-txr)

3.29

139 + 4

4 (assumed)

DAC, scXRD, P < 6

GPa, B-M EOS

142

MgSiO3

3.22

125

5 (assumed)

B A, XRD, P < 6.2

GPa, O-H method

159

3.52

161

4 (assumed)

DAC, pXRD, P < ?,

223

{GPa)
2

Enstatite

MgSiO3

B-M EOS

(high-pressure
tetragonal-garnct
structure)

(Mg4Si4012)0.6
(Mg3AI2Si3012)0.4
Majorite

3.55

159.8 + 0.6

4 (assumed)

CAP, XRD, P < 6

GPa, B-M EOS

224

(Fe4Si4012)0.2
(Fe3AI2Si3012)0.8

4.41

164.6 + 1.1

4 (assumed)

CAP, XRD, P < 6

GPa, B-M EOS

224

Mg0.79Fe0.21SiO3
Majorite

3.74

221 + 15

DAC, XRD, P < 8

GPa, B-M EOS

90

MgSiO3
(high-pressure
perovskitestructure)

4.10

247

DAC, scXRD, P < 10

GPa, B-M EOS

106

MgSiO3
(high-pressure
perovskitestructure)

4.10

254 + 4

4 (assumed) DAC, scXRD, P < 13

173

MgSiO3
(high-pressure
perovskitestructure)

4.10

Mg0.88Fe0.12SiO3
(high-pressure
perovskitestructure)

4.26

M g 1.0-0.8Fe0-0.2
SiO3
(high-pressure
perovskitestructure)

4.10 -

CaSiO3
(high-pressure
perovskitestructure)

4.25

Majorite
4.4 + 4.8

4 (assumed)

GPa, B-M EOS

258 + 20

4 (assumed)

D AC, pXRD, P < 7

220

GPa, B-M EOS

266 + 6

3.9 + 0.4

DAC, pXRD, P < 112

102

GPa, B-M EOS

261 + 4

4.33

4 (assumed)

DAC, pXRD, P < 30

138

GPa, B-M EOS

dIT/dT = -6.3 (+0.5)

x 10-2 GPa/K
281 + 4

4 (assumed) DAC, pXRD, P < 134

GPa, B-M EOS

133

KNITFLE

Table 1. Bulk ModulifromStaticCompression

Data (continued)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus
CaSiO3
(high-pressure

4.25

325 + 10

andNotes
4
dKoT/dp3 Technique

4 (assumed)

DAC, pXRD, P <

Ref.

199

31.5 G Pa, B-M EOS

perovskitestructure)
CaSiO3
(high-pressure
perovskitestructure)

4.25

275 + 15

ZnSiO3
(ilmenitestructure)

2.96

216 + 2

2.99

Na2Mg3A12Si8022
(OH)2
Glaucophane

4 (assumed)

DAC, pXRD, P < 85

200

GPa, B-M EOS

CAP, XRD, P < 10

GPa, B-M EOS

184

85

DAC, scXRD, P < 4

GPa, linPVfit

35

3.10

96

DAC, scXRD, P < 4

GPa, linPVfit

35

NaCa2Mg4AlSi6A12
O22(OH)2
Pargasite

3.10

97

DAC, scXRD, P < 4

GPa, linPVfit

35

(Na,K,Fe,Mg,A1)7
(Si,A1)8022
(OH,F,CI)2

3.50

50 + 1

13 + 1

DAC, scXRD, P < 5.1

GPa, B-M EOS

229

135.7 + 1.0

3.98 + 0.1

DAC, pXRD, P < 30

214

Ca2Mg5Si8022
(OH)2

4 (assumed)

Tremolite

Grunerite

Ortho- and Ring Silicates:

Mg2SiO4

3.22

G Pa, M EOS

Forsterite

3.22

120

5.6

BA, XRD, P < 10

GPa, O-H method

159

3.22

122.6

4.3

DAC, scXRD, P < 15

GPa, B-M EOS

105

Fe2SiO4
Fayalite

4.39

123.9 + 4.6

5.0 + 0.8

DAC, pXRD, P < 38

216

Fe2SiO4
Fayalite

4.39

Mg2SiO4
Forsterite

Mg2SiO4
Forsterite

GPa, B-M EOS

119 + 10

124+2

7+4

5 (assumed)

CAP, XRD, P < 7

GPa, B-M EOS

222

107

108

STATIC

COMPRESSION

Table1. BulkModulifromStaticCompression
Data(continued)

Chemical
Formula
1 Density Isothermal
Bulk
(Mg/m
3)
Modulus
(GPa)
2
Fe2SiO4
Fayalite

4.39

Fe2SiO4
Fayalite

4.39

Fe2SiO4

4.39

124 + 2

diT/dp3

Technique
andNotes
4

Ref.

4 (assumed)

DAC, pXRD, P < 30

131

GPa, B-M EOS

Fayalite

134

4 (assumed)

DAC, scXRD, P < 14

GPa, B-M EOS

104

168

103.8

7.1

DAC, pXRD, P < 8.0

(at 400 C)

(at400 C)

GPa at 400 'C, dK/dT=

-5.4x 10-2 GPa/K

CaMgSiO4

3.05

113 + 3

4 (assumed) DAC, scXRD, P < 6.2

ZrSiO4

4.65

227 + 2

3.53

174 + 3

Zircon

(Mg0.84Fe0.16)2
SO4

186

GPa, B-M EOS

Monticellite

4 (assumed)

DAC, scXRD, P < 5

GPa, linPVfit

67

DAC, pXRD, P < 27

52

GPa, B-M EOS,

Wadsleyite
or[J-Phase

168+ 4

4.7(fixedfrom dKOT/dT= -2.7 + 0.3

ultrasonic
data)
x 10-2 GPa/K

3.53

164 + 2

4 (assumed)

DAC, scXRD, P < 5

GPa, B-M EOS

78

(MgFe)2SiO4

3.47 -

171 + 0.6

4 (assumed)

Re-analysisof [78]

92

1.00>Mg/(Mg+Fe)>

3.78

(Mg0.84Fe0.16)2
SiOn
Wadsleyite

or Phase

0.75

Wadsleyite

or fl-Phase
3.47

166 + 40

MAP, XRD, P < 10

GPa, linPVfit

151

Mg2SiO4
Ringwoodite
or ?Phase
(spinelstructure)

3.55

213 + 10

MAP, XRD, P < 10

GPa, linPVfit

151

(Mg0.6Fe0.4)2SiO4
Ringwoodite
or ?Phase
(spinelstructure)

4.09

183 + 2

DAC, pXRD, P < 50

227

Mg2SiO4
Wadsleyite

or -Phase

Fe2SiO4
(spinelstructure)

5.38 + 0.24

GPa, B-M EOS

4.85

196 + 6

DAC, scXRD, P <_4

GPa, linPVfit

56

Table 1. Bulk Modulifrom StaticCompression

Data{continued)

Chemical
Formula
1 Density Isothermal
Bulk
0Vlg/m
3)
Modulus

diT/dp3

Technique
andNotes
4

ReL

(OPa)
2

Fe2SiO4
(spinelstructure)

4.85

197 + 2

4 (assumed)

CAP, XRD, P < 8

GPa, B-M EOS

178

Fe2SiO4
(spinelstructure)

4.85

212

4 (asstuned)

DAC, pXRD, P < 26

131

Ni2SiO4
(spinelstructure)

5.35

227 + 4

Ni2SiO4
(spinelstructure)

5.35

227 + 4

Ni2SiO4
(spinelstructure)

5.35

214

Co2SiO4
(spinelstructure)

5.17

Co2SiO4
(spinelstructure)

5.17

206 + 2

Ca3AI2(O4H4)3

2.52

66 + 4

Katoite

GPa, B-M EOS

DAC, scXRD, P < 4
GPa, linPVfit

56

4 (asstuned)

CAP, XRD, P < 8

GPa, B-M EOS

178

4 (asstuned)

DAC, pXRD, P < 30

127

GPa, B-M EOS

210 + 6

4.0 + 0.6

DAC, pXRD, P < 30

123

GPa, B-M EOS

4 (assumed)

4.1 + 0.5

CAP, XRD, P < 8

GPa, B-M EOS

178

DAC, pXRD, P < 43

156

GPa, B-M EOS

or

Hydrogrossular

Ca3A12Si3012

3.59

168 + 25

6.2 + 4

168A (fixed from

Brillouindam)

Ca3A12Si3012

Mg3AI2Si3012

3.59

139 + 5

4.19

171.8

DAC, scXRD, P < 6

GPa, linPVfit
7.4 + 1

Pyrope

108

174.2 (fLXedfrom
ultrasonicdam)

7.0 + 1.0

3.58

175 + 1

4.5 + 0.5

DAC, scXRD, P < 5

GPa, B-M EOS

114

3.58

171 + 3

1.8 + 0.7

CAP, XRD, P < 8

GPa, B-M EOS

183

3.58

212 + 8

3.5 + 0.6

D AC, XRD, P < 30

GPa, B-M EOS

195

Pyrope

Mg3AI2Si3012

DAC, pXRD, P < 25

GPa, B-M EOS

Pyrope

Mg3AI2Si3012

156

6.1 __ 1.5

Grossular

Mn3AI2Si3012
Spessartine

DAC, pXRD, P < 19

GPa, B-M EOS

Grossular

110

STATIC

COMPRESSION

Table1. BulkModulifromStaticCompression
D,ata(.ontinu.,.ed)

Chemical
FormulalDensity Isothermal
Bulk
(Mg/m
3)
Modulus
(GPa)
2
Mg3A12Si3012

3.58

179+ 3

dKOT/dp3 Technique
andNotes
4
4 (assumed) DAC, scXRD, P < 6

Pyrope
Mg3A12Si3O12
Pyrope

Fe3AI2Si3Oi2

3.58

175 + 0.3

3.3 + 1
3.8 + 1

4.32

175 + 7

1.5 + 1.6

CAP, XRD, P < 8

GPa, B-M EOS

183

4.32

190 + 5

3 + 0.5

DAC, pXRD, P < 30

195

GPa, B-M EOS

3.83

162

4.7 + 0.7

3.86

159 + 2

4 (assumed)

3.15

135+ 10

4 (assumed) DAC, scXRD, P < 3.7

3.68

Be3AI2Si6018
Beryl
(Mg,Fe)2A14Si5018

108

DAC, scXRD, P < 5

GPa, B-M EOS

75

169

GPa, B-M EOS

Andalusite

Mg 1.3Fe0.7Al2Si2
OI0(OH)4
Magnesiochloritoid

DAC, pXRD, P < 25

GPa, B-M EOS

Andrad/te

AI2SiO5

108

172.8 (fixed from

Brillouin data)

Uvarovite

Ca3Fe2Si3O12

DAC, pXRD, P < 25

GPa, B-M EOS

Almandine

Ca3Cr2Si3O12

75

GPa, B-M EOS

Almandine

Fe3AI2Si3Oi2

Ref.

148 + 5 GPa

170 + 5
2.63

4 (assumed)

110

n(H20, CO2; Na+,

K+)

DAC, scXRD, P < 4.2

GPa, B-M EOS

34

DAC, scXRD, P < 5

GPa, B-M EOS

77

D AC and PC, XRD

and PD, P < 3 GPa,

150

linPVfit

Cordierite

Be2SiO4

2.96

201 + 8

2.75

58.5 + 2

Phenakite

Sheet

2+

DAC, scXRD, P < 5

GPa, B-M EOS

63

D AC, scXRD, P < 4.7

GPa, linPVfit

65

silicates:

KlVlg3AISi3010
(F,OH)2
Phlogopite

111

Table 1. BulkModulifromStaticCompression
Data(continued)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus
(Mg,Fe,AI)6(Si,AI)4
Oo (F,OH)2

2.65

55.0 + 10

2.80

61.4 + 4.0

dKOTMP3 Technique
andNotes
4

Ref.

DAC, scXRD, P < 4.7

GPa, linPVfit

65

DAC, pXRD, P < 18

49

Chlorite

KAI3Si3010(OH)2

6.9 + 1.4

GPa, B-M EOS

Muscouite

BaFeSi4010
GillespiteI
(low-pressure
tetmgonalsn'ucture)

3.72

62 + 3

4 (assumed)

DAC, scXRD, 0 <

P<l.9 GPa, B-M EOS

71

BaFeSi4010
GillespiteII
(high-pressure

3.76

66 + 3

4 (assumed)

DAC, scXRD,
1.9<P<4.6 GPa,

71

M EOS

orthorhombic

smctt)

Oxides and Hydroxides:

BeO
Bromellite

3.01

212+3

MgO

3.56

156 + 9

4 (assumed)

4.7+2

3.56

178

4.54

157

4.0

Periclase

(Mg0.6Fe0.4)O
Magnesiowastite

74

DAC, pXRD, P < 95

126

GPa, M EOS

Periclase

MgO

DAC, scXRD, P < 5

GPa, B-M EOS

4 (assumed)

DP, XRD, P < 30

G Pa, M EOS

41

DAC, pXRD, P < 30

51

GPa, B-M EOS, T <

800 K, dKT/dT)p =-

2.7+ 3 x 10-2 GPa/K

111 + 1

4.2 + 0.2

CaO
Lime

3.38

CaO

3.38

112

3.9

3.79

130 + 20

3.5 _+ 0.5

DP, XRD, P < 30

GPa, M EOS

41

DAC, pXRD,

170

55<P<135 GPa,

(high-pressure
B2 slxucttm:)
SrO

170

GPa, B-M EOS

Lime

CaO

DAC, pXRD, P < 55

B-M EOS
4.70

90.6 + 2.4

4.4 + 0.3

DAC, pXRD, P < 34

GPa, B-M EOS

120

112

STATIC

COMPRESSION

Table1. BulkModulifromStaticCompression
Data(continued)

Chemical
FormulalDensity Isothermal
Bulk
(Mg/m
3)
Modulus
SiO

6.14

160 + 19

diT/dp3 Technique
andNotes
4

4 (assumed)

(high-pressure
B2 structure)

B-M EOS

6.09

66.2 + 0.8
33.2 + 1.9

5.7 (fixedfrom

DAC, pXRD, P < 10

ultrasonics)

GPa, B-M EOS

6.02 + 0.3

DAC, pXRD,

(high-pressure
PH4I

18<P<60.5 GPa, B-M

structure)

EOS

MnO

5.46

162 + 17

4.8 + 1.1

Manganosite
MnO

DAC, pXRD, P < 60

211

211

93

GPa, B-M EOS

5.46

144

3.3

DP, XRD, P < 30

GPa, M EOS

41

6.67

199

4.1

DP, XRD, P < 30

GPa, M EOS

32

190 (fixed from

ultrasonics)

5.0

Manganosite
NiO
Bunsenite

182

36<P<59 GPa,

5.72
BaO

DAC, pXRD,

Ref.

CoO

6.45

190.5

3.9

DP, XRD, P < 30

GPa, M EOS

41

CdO

8.15

108.0

9.0

DP, XRD, P < 30

GPa, M EOS

41

9.63

22.7 + 6.2

17.8 + 1.6

DAC, scXRD, P < 5

GPa, fit to Hooke's

Monteponite
PbO
Massicot

Law

EuO

8.25

97.0

4 (assumed) DAC, pXRD, P < 13

231

GPa, B-M EOS

Cu20
Cuprite

5.91

GeO2

4.23

131

5.7

DAC, pXRD, P < 10

208

GPa, M EOS

63.9 + 0.7

4 (assumed) DAC, pXRD, P < 5.7

(quartzslxucture)

225

GPa, B-M EOS

GeO2
(quartzslxucture)

4.23

GeO2
(quartzsu'ucture)

4.23

39.1 + 0.4

2.2 + 0.5

PC, ND, P < 2.5 GPa,

98

M EOS

26.5
34.3

16.8

BCAC, EXAFS, P <

6 GPa, M EOS

86

KNITTLE

Table1. BulkModulifromStaticCompression
Data(continued)

Chemical
Formula
1 Density Isothermal
Bulk
(Mg/m
3)
Modulus

...

diT/dp3

Technique
andNotes
4

Ref.

4 (assumed)

DAC, pXRD, P < 9.6

225

(GPa)
2
GeO2
Argutite
(rutile smcmre)

6.24

GeO2
Argutite
(rutile structure)

6.24

TiO2

394.9 + 0.2

GPa, B-M EOS

258 + 5

7 (assumed)

265 + 5

4 (assumed)

216 + 5

7 (assumed)

222 + 5

4 (assumed)

203

4 (assumed)

197

6.8 (fixed from

ultrasonics)

4.24

187

7.00

4.24

DAC, scXRD, P < 5

GPa, B-M EOS

70

DAC, scXRD, P < 5

GPa, B-M EOS

70

CAP, XRD, P < 12

GPa, B-M EOS

178

4 (assumed)

DAC, scXRD, P < 9

GPa, B-M EOS

104

218 + 2

7 (assumed)

DAC, scXRD, P < 5

GPa, B-M EOS

70

224 + 2

4 (assumed)
DAC, pXRD, P < 25

119

Rutde

TiO2

4.24

Rutile

TiO2
Rutile

SnO2
Cassiterite

6.26

44.4 + 1.6

5.8 + 0.5

GPa, B-M EOS

Paratellurite

(tetragonalsxucture)
10.96

207

7.13

230 + 10

7.2

Uraninite

CeO2

4 (assumed)

7.84

304 + 25 GPa

4 (assumed)

270 + 6

ZrO2
Baddeleyite

5.81

95 + 8

ZrO2
(high-pressure

6.17

phase)

45

DAC, pXRD,

45

B-M EOS

6.97

orthorhombic-I

DAC, pXRD, P < 31

3 l<P<70 GPa,

(high-pressure
ot-PbCl2-type
stmcture)
RuO2

24

GPa, B-M EOS

Cerianite

CeO:

DAC, XRD, P < ?

GPa, B-M EOS

4 (assumed)

DAC, scXRD, P < 5

GPa, B-M EOS

4-5 (assumed) DAC, pXRD, 0<P< 10

70

110

GPa, B-M EOS

220

5 (assumed) DAC, pXRD, 10<P<25

GPa, B-M EOS

110

113

114

STATIC

COMPRESSION

Table1. BulkModulifrom StaticCompression

Dam,(continued)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus
HfO2

9.68

145

andNotes
4
dKoT/dp3 Technique

5 (assumed) DAC, pXRD,0<P< 10

ReL

109

GPa, B-M EOS

HfO2
(high-pressure

10.14

210

5 (assumed) DAC, pXRD, 10<P<26

109

GPa, B-M EOS

orthorhombic-II

phase)
10.98

475

5 (assumed) DAC, pXRD,26<P<42

109

GPa, B-M EOS

(high-pressure
orthorhombic-HI

phase)
HfO2
(high-pressure
tetragonal
phase)

11.88

550

269 + 3

V305
(highpressure
phase)

5.39

175 + 11

ALPO4

2.57

36

MgAI204
Spinel

3.55

3o4
Magnetite

5.20

DAC, scXRD,0<P<
5.5 GPa, linPVfit
DAC, scXRD,6.3<P<
7.5 GPa, linPVfit

16

4 (assumed)

DAC, scXRD, P < 8.5

GPa, B-M EOS

190

194 + 6

4 (assumed)

DAC, scXRD, P < 4

GPa, B-M EOS

55

186 + 3

4 (assumed)

DAC, scXRD, P < 4

GPa, B-M EOS

55

183 + 5

5.6 (from
ultrasonics)
DAC, scXRD, P < 4.5
GPa, B-M EOS

154

DAC, pXRD, P < ?

212

Berlinite

Fe304

5.20

181 + 2

5.20

155 + 12

5.5 +__15

Magnetite

Fe304

4 (assumed)

5.20

183 +_10

4 (assumed)

4.83

137.0 + 3.8

4 (assumed)

slxucture)

130

DAC, pXRD, 0<P<10

163

GPa, B-M EOS

Hausmannite

Mn304
(high-pressure
marokite-type

DAC, pXRD, P < 32

GPa, B-M EOS

Magnetite

Mn304

16

GPa, B-M EOS

Magnetite

Fe304

109

GPa, B-M EOS

4.73

V305

5 (assumed) DAC, pXRD,42<P<50

5.33

166.6 + 2.7

4 (assumed)

DAC, pXRD, 10<P

<39 GPa, B-M EOS

163

KNeE

Table1. BulkModulifromStaticCompression
Data(continued)

Chemical
FormulalDensity Isothermal
Bulk
(Mg/m
3)

Modulus

diT/dp3

Technique
andNotes
4

4 (assumed)

DAC, scXRD, P <

6.3 GPa, B-M EOS

62

see reL, P < 0.5 GPa,

23

Ref.

(pa)2
AI2BeO4
Chrysoberyl
ReO3

3.70

242 + 5

6.9

200 + 4

linPVfit

LiNbO3

4.63

134 + 3

CaTiO3

3.98

210 + 7

2.9 + 0.5

5.6 (assumed)

5.12

Tausonite

SrTiO3

174.2

5.3

(fixed from
ultrasonicvalue)

5.12

176

4.4

218

DAC, pXRD, P < 20

57

DAC, pXRD, P < 20

47

GPa, M EOS

4.72

170 + 7

8+ 4

llmenite

177 + 3
(Fe,Mg)TiO3

DAC, pXRD, P <

GPa, B-M EOS

Tausonite

FeTiO3

37

10.4 GPa, B-M EOS

Perovskite

SrTiO3

DAC, XRD, P < 13

GPa, B-M EOS

4.44

168 + 13

DAC, scXRD, P < 5

GPa, B-M EOS

207

DAC, pXRD, P < 28

123

4 (assumed)
5+ 1

llmenite

GPa, B-M EOS

MnTiO3-I
Pyrophanite

4.54

70 + 9

4 (assumed)

DAC, scXRD, P < 5

GPa, B-M EOS

175

MnTiO3-II
(LiNbO3 structure)

4.68

158 + 9

4 (assumed)

DAC, scXRD, P < 3

GPa, B-M EOS

175

4.88

227 + 4

4 (assumed)

DAC, scXRD, 2.4

<P<5 GPa, B-M EOS

175

MnSnO3
(perovskitestructure)

6.12

196 + 20

4 (assumed) DAC, pXRD, 7<P<20

MgGeO3

4.97

187 + 2

4.97

195

MnTiO3-III
(perovskitestructure)

4 (assumed)

(ilmenite structure)

MgGeO3

3.6

CAP, XRD, P < 8

GPa, B-M EOS

184

DAC, pXRD, P <

17

22.5 GPa, B-M EOS

(ilmenite structure)

CuGeO3

111

GPa, B-M EOS

5.11

67.8

DAC, pXRD, P < 7.3

GPa, linPVfit

11

116

STATIC

COMPRESSION

Table 1. Bulk Moduli from StaticCompression

Data (continued}

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus
...
(GPa)
2

diT/dp3

Technique
andNotes
4

Ref.

Na0.55WO3
(perovskitestructure)

7.23

105

DAC, scXRD, P < 5.3

GPa, linPVfit

72

Na0.62WO3
(perovskitestructure)

7.44

119

DAC, scXRD, P < 5.3

GPa, linPVfit

72

Na0.70WO3
(perovskitestructure)

7.61

91

DAC, scXRD, P < 5.3

GPa, linPVfit

72

5.25

225

4 (assumed)

DAC, scXRD, P < 5

GPa, B-M EOS

54

5.25

199 + 6

4 (assumed)

DAC, pXRD, P < 30

212

Fe203
Hematite

Fe203

GPa, B-M EOS

Hematite

5.25

228 + 15

4 (assumed)

DAC, XRD, P < 30

GPa, B-M EOS

22

5.25

178 + 4

4 (assumed)

CAP, XRD, P < 12

GPa, B-M EOS

181

A1203
Ruby

3.98

253 + 1

DAC, pXRD, P < 65

171

A1203

3.98

Fe203
Hematite

Fe203
Hematite

5.0 + 0.4

GPa, B-M EOS

226 + 2

4 (assumed)

Corundum

239 + 4

A1203
Ruby

3.98

257 + 6

A1203

3.98

254.4 + 2.0

4.87

171 + 1

4 (assumed)

4.275 + 0.006

4 (assumed)

Karelianite

175 + 3

V203

DAC, scXRD, P < 10

GPa, B-M EOS

40

CAP, XRD, P < 12

GPa, B-M EOS

181

195 + 6

4 (assumed)

DAC, scXRD, P < 5

GPa, B-M EOS

54

5.21

222 + 2

4 (assumed)

CAP, XRD, P < 12

GPa, B-M EOS

181

DAC, scXRD, P < 5

GPa, B-M EOS

54

231+5

Cr203

53

4.87

Eskolaite

Eskolaite

DAC, scXRD, P < 5

GPa, B-M EOS

3.1 + 0.7

Karelianite

Cr203

181

0.9 + 0.8

Corundum

V203

CAP, XRD, P < 12

GPa, B-M EOS

5.21

238 + 4

2.0+

1.1

4 (assumed)

KNeE

Table1. BulkModulifromStaticCompression
Data{continued)

Chemical
FormulalDensity Isothermal
Bulk
(Mg/m
3)
Modulus
(GPa)
2

diT/dp3

Technique
andNotes
4

Ref.

KVO3

84.7

DAC, scXRD, P < 5

GPa, linPVfit

RbVO3

42.9

DAC, scXRD, P < 5

GPa, linPVfit

CsVO3

62.9

DAC, scXRD, P < 5

GPa, linPVfit

NaNO2

2.17

21.9 + 0.2

4.3 + 0.8

DAC, scXRD, P < 2.6

GPa, B-M EOS

68

NaNO3

2.26

25.8 + 0.6

6.6 + 1.5

DAC, scXRD, P < 2.6

GPa, B-M EOS

68

2.39

54.3 + 1.5

4.7 + 0.2

DAC, pXRD, P < 35

50

Nitratine

Mg(OH)2

GPa, B-M EOS

Brucite

dKT/dP= -0.018_+0.003
GPa/K

Ca(OH)2

2.24

37.8 + 1.8

5.2 + 0.7

Carbon-Bearing

SiC
Moissonite

CaMg(CO3)2

144

Minerals:

3.22

227 + 3

4.1 + 0.1

D AC, XRD, P < 43

GPa

2.86

94

4 (assumed) DAC, scXRD, P < 4.7

174

GPa, B-M EOS

Dolomite

CaMg0.3Fe0.7
(CO3)2

DAC, pXRD, P < 11

GPa, B-M EOS

Portlandite

3.05

91

4 (assumed) D AC, scXRD, P < 4.0

174

GPa, B-M EOS

Ankerite

BaCO3

4.30

50 + 3

4 (assumed)

DAC, DVM, I<P 6.5

GPa, B-M EOS

139

3.73

58 + 5

4 (assumed)

DAC, DVM, I<P 6.5

GPa, B-M EOS

139

3.67

95 + 9

4 (assumed)

DAC, DVM, 2.5<P

4.5 GPa, B-M EOS

139

2.71

71.1

PC, PD, P < 1.5 GPa,

189

Witherite

SIC03
Strontianite

MnCO3
Rhodocrosite

CaCO3
Calcite

4.15

polyPVfit

117

118

STATIC

COMPRESSION

Table1. BulkModulifromStaticCompression
Dam{continued)

Chemical
Formula
1 Density Isothermal
Bulk
(Mg/m
3)
Modulus
(OPa)
2
CaCO3
CalciteII

2.71

CaCO3
CalciteIII

2.85

CaCO3

2.85

diT/dp3

and

Ref.

189

32.7
(at 1.4 GPa)

4.4
(at 1.4 GPa)

PC, PD, 1.4<P< 1.7

75.2
(at 1.7 GPa)

PC, PD, 1.7<P<4

84.0+ 8

GPa, polyPVfit
189

GPa, polyPVfit

4 (assumed) DAC, DVM, 3<P< 5

Calcite III

Sulfides

Technique
andNotes
4

139

GPa, B-M EOS

Te!!urides-

HgS

8.13

19.4 + 0.5

11.1

Cinnabar

HgTe

8.09

16.0 + 0.5

7.3

56.7

4.9

DP, XRD, P < 30

GPa, M EOS

41

4.82

86.7

4.36

DAC, pXRD, P < 55

192

GPa, B-M EOS

4.82

94.0

7.6

DP, XRD, P < 30

GPa, M EOS

41

3.99

81.0

3.3

DP, XRD, P < 30

GPa, M EOS

41

3.99

72 + 2

4.2 + 1.3

DAC, pXRD, P < 21

140

Greenocla'te

MnS
Alabandite

MnS

210

2.50

Greenocla'te

CdS

DAC, pXRD, P < 24

GPa, B-M EOS

Oldhamite

CdS

210

GPa, B-M EOS

Coloradoite

CaS

DAC, pXRD, P < 24

Alabandite

GPa, B-M EOS

NiS
(NiAs-typestructure)

5.50

BaS

4.25

156 + 10

4.4 + 0.1

DAC, pXRD, P < 45

27

GPa, B-M EOS

55.1+ 1.4

5.5(assumed)DAC, pXRD, P < 6.5

211

GPa, B-M EOS

BaS

4.67

21.4 + 0.3

7.8 + 0.1

(highpressureB2structure)
ZnS

DAC, pXRD,
EOS

4.02

76.5

4.49

Sphalerite
ZnS

(high-pressure
phase)

211

6.5<P<89 GPa, B-M

230

4.72

85.0 + 3.8

4 (assumed) DAC, pXRD, 11<P<45

GPa, B-M EOS

230

KNFI'rLE

Table1. BulkModuiifromStaticCompression
Data(continued)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus
YbS

7.38

60 + 3

dKOT/dp3 Technique
andNotes
4

4 (assumed)

D AC, pXRD, P < 8

Ref.

194

GPa, B-M EOS

CeS

5.93

82

2.2

DAC, pXRD, P < 25

204

GPa, B-M EOS

ErS

8.38

101.5 + 1.0

5.4 + 0.2

see ref., P < 3 GPa,

89

lsqPV fit
ThS

9.56

145 + 6

5 A + 0.1

DAC, pXRD, P < 45

160

GPa, M EOS
US

10.87

92 + 9

9.1 + 0.2

DAC, pXRD, P < 45

160

G Pa, M EOS

NiS2

4.45

109 + 6

B A, XRD, P _<4 GPa,

NiS2
(high-pressure
metallicphase)
MnS2

4.91

141 + 11

3.46

76.0

BA, XRD, 4<P<11

GPa, linPVfit

5.4

Hauer/te

MnS2
(high-pressure

48

linPVfit

Vaesite

DAC, pXRD, 0<P<10

48

30

GPa, B-M EOS

4.02

213.8

5.0

DAC, pXRD, 10

30

<P<35 GPa, B-M EOS

orthorhombic

marcasite-type
structure)
4.27

118.3

DAC, scXRD, P< 3.6

GPa, linPVfit

4.50

29

DAC, scXRD, P < 5

GPa, linPVfit

As4S3
Dimorphite

3.58

17.0

CuFe2S3

4.11

55.3 + 1.7

4.36

96 + 10

4.70

60 + 8

CoS2
'Cattierite

SnS2
Berndtite

Cubanite

CuGaS2
Gallite

AgGaS2

5.5

BA, XRD, P < 12

GPa, M EOS

4 (assumed) DAC, scXRD, P < 3.7

GPa, B-M eqn
6.5

58

31

141

DAC, XRD, P < 16

GPa, M EOS

209

DAC, XRD, P < 5

G Pa, M EOS

209

119

120

STATIC

COMPRESSION

Table 1. Bulk ModulifromStaticCompression

Dam(continued)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus

diT/dp3

Technique
andNotes
4

Ref.

(GPa)
2

La6CoSi2S14

4.37

79.2 + 0.4

DAC, scXRD, P < 5

GPa, linPVfit

145

La6NiSi2S14

4.37

75.5 + 0.5

DAC, scXRD, P < 5

GPa, linPVfit

145

Halides-

LiF

2.64

66.5

3.5

CAP, XRD, P _< 9

GPa, B-M EOS

219

LiF

2.64

62.7

6.8

PC, PD, P < 4.5 GPa,

202

M EOS

LiF

2.64

65.0

4.7

DP, XRD, P _<30

GPa, M EOS

41

LiCl

2.07

31.9

3.4

PC, PD, P _<4.5 GPa,

202

M EOS

LiBr

3.46

24.3

3.5

PC, PD, P < 4.5 GPa,

202

M EOS

LiI

4.08

16.8

4.3

PC, PD, P _<4.5 GPa,

202

M EOS
NaF
Villiaumite

2.56

45.9

4.4

CAP, XRD, P < 9

GPa, B-M EOS

219

NaF
Villiaumite

2.56

46.4 + 6.2

4.9 + 1.2

DAC, pXRD, P < 23

180

NaF
Villiaumite

2.56

NaF
Villiaumite

2.56

NaF

3.16

GPa, B-M EOS

46.7

5.2

PC, PD, P _<4.5 GPa,

202

M EOS
45.6

103 _+19

5.7

4 (assumed)

DP, XRD, P _<30

GPa, M EOS

41

DAC, pXRD,

180

23<P<60 GPa, B-M

(high-pressure,
B2
structure)

EOS

NaCI
Halite

2.17

26.4

3.9

DP, XRD, P _ 30
GPa, M EOS

41

NaCI
Halite

2.17

23.2

4.9

PC, PD, P < 4.5 GPa,

202

NaCI
Halite

2.17

M EOS

23.8 + 7.5

4.0 + 3.9

DAC, pXRD, P _<29

GPa, B-M EOS

180

KNI'FFLE

Table1. BulkModulifromStaticCompression
Data(continued)

Chemical
Formula
1 Density Isothermal
Bulk
(Mg/m
3)
Modulus

dKOT/dp3 Technique
andNotes
4

Ref.

(GPa)
2

NaCI

2.34

36.2 + 4.2

4 (assumed)

DAC, pXRD,

(high-pressure
B2

25<P<70 GPa, B-M

structure)

EOS

NaBr

3.20

20.3

4.2

PC, PD, P < 4.5 GPa,

80

202

M EOS
NaBr

3.20

18.5 + 3.4

5.8 + 1.1

DAC, pXRD, P < 39

180

GPa, B-M EOS

NaI

3.67

15.0

4.1

DP, XRD, P < 30

GPa, M EOS

41

NaI

3.67

14.7 + 1.1

5.7 + 0.5

DAC, pXRD, P < 36

180

GPa, B-M EOS

NaI

3.67

15.1

4.2

PC, PD, P < 4.5 GPa,

202

M EOS
KF
Carobbiite

2.48

29.3

5.4

CAP, XRD, P<

9
GPa, B-M EOS

219

KF

2.87

37.0

5.4

CAP, XRD, P < 9

GPa, B-M EOS

219

1.98

37.0

5.0

DP, XRD, P < 30

GPa, M EOS

41

2.34

28.7 + 0.6

(high-pressure,
B2
structure)
KC1

Sylvite
KCI

4 (assumed) DAC, pXRD, P < 56

(high-pressure
B2

GPa, B-M EOS

structure)
CsCl

3.99

18.0

4.8

DP, XRD, P < 30

GPa, M EOS

41

CsCl

3.99

18.2

5.1

CAP, XRD, P < 9

GPa, B-M EOS

219

CsCI

3.99

17.1

5.1

PC, PD, P < 4.5 GPa,

202

M EOS

CsBr

4.44

14.4

5.3

PC, PD, P < 4.5 GPa,

202

M EOS
CsBr

4.44

19.1 + 0.9

5.0 + 0.1

DAC, pXRD, P < 53

103

GPa, B-M EOS

CsI

4.51

13.3 + 2.3

5.9 + 0.9

DAC, pXRD, P < 61

GPa, B-M EOS

101

121

122

STATIC

COMPRESSION

Table 1. BulkModulifromStaticCompression
Data(continued).

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus

diT/dp3

Technique
and
Notes4Ref.

(GPa)
2

CsI

4.51

12.5

4.5

PC, P D, P < 4.5 G Pa,

202

M EOS

CsI

4.51

13.5 +_ 0.2

5.45 +_ 0.06

DAC, pXRD, P < 100

137

GPa, V EOS

AgCl
Cerargyrite

5.56

AgBr
Bromyrite

6.47

CuBr

41.5

6.0

PC, PD, P < 4.5 GPa,

202

M EOS

38.2

5.9

PC, PD, P < 4.5 GPa,

202

M EOS

4.98

36.2

2.9

PC, P D, P < 4.5 G Pa,

202

M EOS

MnF2

3.98

94 +_3

4 (assumed)

DAC, scXRD, P <

5 GPa, B-M EOS

70

CaF2

3.18

81.0 +_1.2

5.22 + 0.35

DAC, scXRD, P <

9 GPa, B-M EOS

13

4.24

69.1

5.2

PC, PD, P < 4 GPa,

149

Fluorite

SrF2

M EOS

BaCI2

3.87

69.8 +_0.5

1.40 +_0.05

DAC, XRD, 0<P< 10

GPa, B-M EOS

107

BaCI2
(highpressure
hexagonalphase)

4.73

69.3 + 2

8.6 +_ 0.1

DAC, XRD, 10<P<50

GPa, B-M EOS

107

0.362 + 0.003

4.71 +_ 0.03

(4K)

(4K)

DAC, scXRD,
5.4<P<26.5 GPa, B-M

83
136

Group I Elements:

H2

0.088

EOS

H2

D2

0.172 +__
0.004

7.19 +__0.04

(4K)

(4K)

0.088

0.166

7.3

PC, PD, P < 2 GPa,

(4K)

(4K)

(4K)

lsqPVfit

0.20

0.46 + 0.05

5.2 +__0.2

DAC, scXRD,
6.5<P<14.2 GPa, B-M

V EOS

EOS

83

KNITrLE

Table 1. BulkModulifromStaticCompression
Data{continued)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus

diT/dp3

Technique
andNotes
4

Ref.

(GPa)
2

0.35 + 0.03

6.6 + 0.2
v EOS

Li

0.53

11.556 + 0.033

3.51 + 0.06

PC, PD, P < 2 GPa,

11

lsqPVfit
Na

0.97

6.06 + 0.02

4.13 + 0.04

PC, PD, P < 2 GPa,

10

lsqPVfit
K

0.86

2.99 + 0.02

4.15 + 0.10

DAC, XRD, P < 12

GPa, B-M EOS

118

0.86

2.963 + 0.001

4.208 + 0.003

PC, PD, P < 2 GPa,

10

lsqPVfit
K

0.86

3.10 + 0.01

3.91 + 0.01

see ref., P < 0.7 GPa,

99

M EOS

Rb

1.53

2.301 + 0.003

4.15 + 0.1

PC, PD, P < 2 GPa,

10

lsqPVfit
Rb

1.53

2.61

3.62

DAC, pXRD, P < 11

197

GPa, B-M EOS

Cs

1.90

1.698 + 0.006

3.79 + 0.02

PC, PD, P < 2 GPa,

11

lsqPVfit
Group II

Mg

Elements:

1.74

33.6

4.8

PC, PD, P < 4.5 GPa,

203

M EOS

Ca

1.54

18.7

2.5

PC, PD, P < 4.5 GPa,

201

M EOS

Ca

1.54

17.4 + 0.1

3.7 + 0.1

PC, PD, P < 2 GPa,

12

lsqPVfit
Sr

2.60

12.1

2.5

PC, PD, P < 4.5 G Pa,

203

M EOS

Sr

2.60

11.83 + 0.07

2.47 + 0.07

PC, PD, P < 2 GPa,

12

lsqPVfit
Ba

3.50

9.4

2.1

PC, PD, P < 4.5 GPa,

201

M EOS

Ba

3.50

8.93 + 0.6

2.76 + 0.05

PC, PD, P < 2 GPa,

lsqPVfit

12

123

124

STATIC

COMPRESSION

Table1. BulkModulifromStaticCompression
Data(continued

Chemical
Formula
1 Density Isothermal
Bulk
(Mg/m
3)

Transition

Modulus

diT/dp3 Technique
andNotes
4

Ref.

Metals:

Ti

4.51

109.4

3.4

PC, PD, P < 4.5 GPa,

203

M EOS

6.10

154 + 5

4.27 (fixed
from

D AC, XRD, P < 10

GPa, B-M EOS

147

D AC, XRD, P _<60

GPa, B-M EOS

19

PC, PD, P < 4.5 GPa,

203

ultrasonics)
V

6.10

6.10

176.4

+ 3.0

139.4

18.2

M EOS

Cr

7.19

253.0 + 11.0

8.9

DAC, XRD, P < 40

GPa, B-M EOS

19

Cr

7.19

193 + 6

4.89 (fixed

DAC, XRD, P < 10

GPa, B-M EOS

147

D AC, XRD, P < 42

GPa, B-M EOS

198

PC, PD, P < 4.5 GPa,

203

from

ultrasonics)
Mn

7.43

131 + 6

Co

8.90

167.1

6.6+7

17.3

M EOS

Ni

8.92

190.5

4.0

PC, PD, P < 4.5 GPa,

201

M EOS

Cu

8.96

162.5

4.24

pPC, PD, P < 4.5

201

GPa, M EOS

Cu

8.96

137.4

5.52

DAC, XRD, P < 10

GPa, B-M EOS

124

Zn

7.14

59.8

4.4

PC, PD, P < 4.5 GPa,

201

M EOS

4.46

44.9

2.2

PC, PD, P < 4.5 GPa,

203

M EOS

Zr

4.46

104

2.05

D AC, XRD, P < 30

GPa, B-M EOS

217

Zr

6.49

102.8

3.1

PC, PD, P < 4.5 GPa,

203

M EOS

KNITLE

Table 1. BulkModulifromStaticCompression
Data(continued)

.,

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus

Nb

diT/dp3

Technique
andNotes
4

Ref.

PC, PD, P < 4.5 GPa,

203

(GPa)
2

8.41

144.2

14.5

M EOS

Nb

8.40

171 + 7

4.03

DAC, XRD, P < 10

GPa, B-M EOS

147

Nb

8.40

175.7 + 2.7

D AC, XRD, P < 60

GPa, B-M EOS

19

Mo

10.20

266.0

3.5

PC, PD, P < 4.5 GPa,

201

M EOS

Mo

10.20

267 + 11

4.46 (fixed
from

DAC, XRD, P < 10

GPa, B-M EOS

147

D AC, XRD, P < 60

GPa, B-M EOS

19

ultrasonics)
Pd

12.00

128.0 + 5.0

Ag

10.50

103 + 5

5.6 + 0.8

D AC, XRD, P < 25

GPa, B-M EOS

Ag

10.50

116.7 + 0.7

3.4

DAC, XRD, P < 10

GPa, B-M EOS

124

Ag

10.50

120.9

5.2

PC, PD, P < 4.5 GPa,

201

M EOS

Ag

10.50

106.1

4.7

TCOA, XRD, P < 12

GPa, B-M EOS

193

Cd

8.65

44.8

4.9

PC, P D, P < 4.5 G Pa,

201

M EOS

La

6.17

24.5

1.6

PC, PD, P < 4.5 GPa,

201

M EOS

Ta

16.60

205.7

3.7

PC, PD, P < 4.5 GPa,

201

M EOS

Ta

16.60

194 + 7

3.80 (fixed
from

D AC, XRD, P < 10

GPa, B-M EOS

147

PC, PD, P < 4.5 GPa,

203

ultrasonics)
W

19.30

300.1

19.1

M EOS
W

19.30

307 + 11

4.32 (fixed
from

ulxasonics)

D AC, XRD, P < 10

GPa, B-M EOS

147

125

126

STATIC

COMPRESSION

Table1. BulkModulifromStaticCompression
Data(continued)

Chemical
FormulalDensity Isothermal
Bulk
(Mg/m
3)
Modulus
(GPa)
2
Au

19.30

Au

19.30

166.4 + 2.6

163.5

8.3

dKOT/dP3 Technique
andNotes
4

7.3

D AC, XRD, P < 10

GPa, B-M EOS

124

DAC, XRD, P < 20

GPa, B-M EOS

148

5.5 _+ 0.8

DAC, XRD, P < 70

GPa, B-M EOS

81

5.31-6.43

D AC, XRD, P < 20

GPa, B-M EOS

148

PC, PD, P < 4.5 GPa,

201

4.42-5.16

(fixed from
ultrasonics)
Au

Group III

19.30

166.6 _+ 10.8

2.70

71.7 _+3.6

Ref.

Elements:

AI

(fixed from
ultrasonics)
Al

2.70

77.9

4.6

M EOS

AI

2.70

72.7

4.3

TCOA, XRD, P < 12

GPa, B-M EOS

193

In

7.31

39.1

5.2

C, PD, P < 4.5 GPa,

201

M EOS

In

7.31

38 + 2

5.5 + 0.3

D AC, XRD, P < 67

GPa, B-M EOS

185

TI

11.85

36.6

3.0

PC, PD, P < 4.5 GPa,

201

M EOS

Group IV Elements:

3.51

444 + 3

1.9 + 0.3

D AC, XRD, P < 42

GPa, M EOS

2.25

33.8 + 3

8.9 + 1.0

D AC, XRD, P < 14

GPa, M EOS

61

2.25

30.8

D AC, XRD, P < 11

GPa, V EOS

226

DAC, scXRD, P < 20

GPa, B-M EOS

44

Diamond

Graphite
C

4 (assumed)

Graphite
C60
Fullerite

1.67

18.1 _+1.8

5.7 _+ 0.6

KNI'I.,E

Table 1. BulkModulifromStaticCompressio
n Data(continued)

Chemical
Formulal Density Isothermal
Bulk
0Vlg/m
3)
Modulus

diT/dp3

Technique
andNotes
4

4.7

PC, PD, P < 4.5 GPa,

Ref.

(GPa)
2

Si

2.33

100.8

203

M EOS

Si

2.33

97.9

4.16

DAC, XRD, P < 15

191

GPa. B-M EOS

Si

3.09

72 + 2

3.91 + 0.07

DAC, XRD, 42<P<79

GPa, B-M EOS

43

3.25

82 + 2

4.22 + 0.05

DAC, XRD,
79<P<248 GPa,

43

(high-pressure
hcpphase)
Si

(high-pressure
fccphase)

Sn

B-M EOS

7.30

54.9

4.8

PC, PD, P < 4.5 GPa,

201

M EOS
an

7.30

50.2 + 0.5

4.9

DAC, XRD, P < 10.3

GPa, B-M EOS

121

Sn

7.30

56.82 + 2.19

2.3 + 0.8

DAC, XRD, P _<9.5

GPa, B-M EOS dK/dT

28

=-1.38(+_
0.13)x 10'2
GPa/K
Sn

7.49

(high-pressure,
!xxly
tetragonalstructure)

Sn

7.49

82.0 + 1.2

5.5

(at 9.5 GPa)

(at 9.5 GPa)

56.65 + 9.04

4.53 + 0.81

(high-pressure,
body-ctexed
tetragonalstructure)

DAC, XRD, 9.5<P<

53.4 GPa, B-M EOS

121

DAC, XRD, 9<P<17

GPa,

167

B-M EOS

dIdT = -4.63 (+ 1.24)

x 10-2 GPa/K
an

7.49

76.4

4.04

(high-pressure,
body-centered
cubic
structure)
Pb

DAC, XRD,
45<P<120 GPa, B-M

39

EOS

11.40

40.0

5.8

PC, PD, P < 4.5 GPa,

201

M EOS

Pb

11.40

43.2

4.87

D AC, XRD, P < 10

GPa, B-M EOS

206

127

125

STATIC

COMPRESSION

Table 1. Bulk ModulifromStaticCompression

Data(continued)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus

diT/dp3

Technique
andNotes
4

Ref.

(GPa)
2

Pb

11.62

39.9+

0.2

6.13 +_ 0.10

DAC, XRD, 15<P<

238 GPa, V EOS

134

(combinedhcpand
bcc high pressure
phases)
Pb

11.57

46.63

5.23

DAC, XRD, 10<P<

100 G Pa, B-M EOS

206

11.66

29.02

7.16

DAC, XRD, 100<P<

272 GPa, B-M EOS

206

1.03

2.69

3.93

DAC, XRD, 5<P< 16

GPa, O-H method

155

1.21

2.98

3.78

DAC, XRD, 16<P<44

GPa, O-H method

155

2.70

36 + 2

4.5 + 0.5

DAC, pXRD,

98a

(high-pressure
hcp
phase)
Pb

(high-pressure
bcc
phase)
Group V Elements:
N2

(cubic8-phase)
N2

(hexagonale-phase)
P

(orthorhombic)
P

0<P<5.5 GPa, M EOS

2.97

46 _+4

3.0 + 0.6

DAC, pXRD, 5.5

98a

<P<10 GPa, M EOS

(high-pressure
rhombohedml

structure)
P

3.08

95 + 5

2.1 + 0.8

(high-pressure
simple

DAC, pXRD, 10

98a

<P<32 GPa, M EOS

cubic structure)
P

3.08

114

6.62

40.4

(high-pressure
simple

DAC, XRD, 1 l<P<60

GPa, B-M EOS

187

PC, PD, P < 4.5 GPa,

203

cubic structure)
Sb

4.3

M EOS

Bi

9.80

29.7

2.4

PC, PD, P < 4.5 GPa,

201

M EOS

Group VI Elements:
02
(high-pressure
phaseindexedas
monoclinic)

1.32

37.5

3.31

DAC, XRD, 10<P<62

GPa, B-M EOS

177

KNITLE

Table 1. BulkModulifromS,tatic.Compression
Data(continued)

Chemical
Formula
1 Density Isothermal
Bulk
(Mg/m
3)
Modulus

diT/dp3

Technique
andNotes
4

Ref.

(GPa)
2
02
(high-pressure
ephaseindexedas
orthorhombic)

1.32

16.7

4.09

DAC, XRD, 10<P<62

GPa, B-M EOS

177

2.07

8.8

6.5

PC, PD, P < 4.5 GPa,

203

M EOS

2.07

14.5

DAC, XRD, 0<P<5

GPa, B-M EOS

125

2.72

17.3

DAC, XRD, 5<P<24

GPa, B-M EOS

125

Se

4.79

48.1 + 0.2
(at 7.7 GPa)

4.33 + 0.04
(at 7.7 GPa)

DAC, XRD, 0<P<12

GPa, M EOS

165

Se

4.79

7.9

5.8

PC, PD, P < 4.5 GPa,

203

(high-pressure
phase)

M EOS

Te

6.24

18.2

8.4

PC, PD, P < 4.5 GPa,

203

M EOS

6.24

Group VII

24 + 2

2.3 + 0.2

(at 2 GPa)

(at 2 GPa)

DAC, XRD, 0<P<4

GPa, M EOS

164

D AC, XRD, P < 45

46

Elements:

C12

2.09

11.7 + 0.9

5.2 (assumed)

GPa. B-M EOS

Br2

4.10

13.3 + 0.7

5.2 (assumed)

D AC, XRD, P < 45

46

GPa. B-M EOS

I2

4.94

8.4

6.0

PC, PD, P < 4.5 GPa,

203

M EOS

I2

4.94

13.6 + 0.2

5.2 (assumed)

DAC, XRD, P < 45

46

GPa. B-M EOS

Noble

GasesHe

(solid)

0-0.43
GPa:
0.23

0.085

>0.18
GPa:
0.21

0.082

see reference

42

129

130

STATIC

COMPRESSION

Table 1. Bulk ModulifromStaticCompression

Data(continued)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus

andNotes
4
dKoT/dp3 Technique

ReL

(GPa)
2
He

(solid)
Ne

(solid)

0.23

P-V data tabulated

D AC, XRD, P < 24

(0 K)

only

GPa

1.51

1.097

9.23 _+ 0.03

DAC,XRD,4.7<P<
110 G Pa, B-M EOS

(4 K)

Ar

1.73

2.86

7.2

PC, PD, P < 2 GPa,

(solid)

(4 K)

(at 4 K)

(at 4 K)

lsqPVfit

1.65

1.41

8.4

(77 K)

(at 77 K)

(at 77 K)

1.73

P-V data tabulated

D AC, XRD, P < 80

(solid)

Ar

(0 K)

only

GPa

Kr

2.317

1.41

4.3 + 0.1

DAC, XRD, P < 32

GPa, M EOS

(solid)
Kr

3.09

3.34

7.2

PC, PD, P < 2 GPa,

(solid)

(4 K)

(at 4 K)

(at 4 K)

lsqPVfit

Xe

(solid)
Xe

(solid)

2.82

1.58

7.6

(110 K)

(at 110 K)

(at 110 K)

3.78

5.18 + 0.32 GPa

5.48 + 0.24

(0 K)

(0 K)

(0 K)

DAC, XRD, P < 32

GPa, B-M EOS

3.78

3.63

7.2

PC, PD, P < 2 GPa,

(4 K)

(at 4 K)

(at 4 K)

lsqPVfit

3.41

1.48

8.8

(159 K)

(at 159 K)

(at 159 K)

6.77

30.2

1.6

135

172

166

15

Lanthanides:

Pr

PC, PD, P < 4.5 GPa,

203

M EOS

Nd

7.00

32.6

3.0

PC, PD, P < 4.5 GPa,

203

M EOS

Gd

8.23

35.5

4.8

PC, PD, P < 4.5 GPa,

203

M EOS

Gd

8.23

22.71 + 2.07

4.31 + 0.29

D AC, XRD, P < 106

GPa, B-M EOS

Dy

8.78

40.3

5.1

PC, PD, P < 4.5 GPa,

M EOS

203

KNFI'rLE

Table 1. BulkModulifromStaticCompression
Data{continued
)

Chemical
Formula
1 Density Isothermal
Bulk
(Mg/m
3)
Modulus
Er

9.37

44.9

dKOT/dp3 Technique
andNotes
4

3.5

PC, PD, P < 4.5 GPa,

ReL

203

M EOS
Actinides'

Th

11.70

54.0

4.9

PC, PD, P < 4.5 G Pa,

203

M EOS

Pa

15.40

157

1.5

DAC, XRD, P < 38

GPa, B-M EOS

Iron and Iron Alloys:

Fe
a (bcc)phase
Fe

7.86

164 + 7

7.86

175.8

4 (assumed)

3.7

212

PC, PD, P < 4.5 GPa,

201

M EOS

a (bcc)phase
Fe

D AC, XRD, P < 16

GPa, B-M EOS

7.86

162.5 + 5

5.5 + 0.8

D AC, XRD, P < 30

GPa, B-M EOS

196

7.88

156 +7

4.2 + 0.8

DAC, XRD, P < 30

GPa, B-M EOS

196

7.88

153 + 7

5.7 + 0.8

D AC, XRD, P < 30

GPa, B-M EOS

196

7.39

175 + 8

4.3 + 1.0

DAC, XRD, P < 23

GPa, B-M EOS

188

7.35

174.0

4.6

DP, XRD, P < 30

GPa, M EOS

41

6.77

214 + 9

3.5 + 0.8

D AC, XRD, P < 23

GPa, B-M EOS

188

6.58

250.0

-2.0

DP, XRD, P < 30

GPa, M EOS

41

Fe
e (hcp)phase

8.30

208 + 10

D AC, XRD, P < 30

GPa, B-M EOS

196

Fe

8.30

192.7 + 9.0

4.29 + 0.36

D AC, XRD, P <

78 GPa, B-M EOS

96

8.30

164.8 + 3.6

5.33 + 0.09

DAC, XRD, P < 300

GPa, B-M EOS

132

a (bcc)phase
Fe-5.2 wt. % Ni

R (bcc)phase
Fe-10.3 wt. % Ni

a Cocc)phase
Fe-7.2 wt. % Si

a (bcc)phase
Fe-8 wt. % Si

R (bcc)phase
Fe-25 wt. % Si

a Cocc)phase

Fe3Si
Suessite

4 (assumed)

e (hcp) phase
Fe

e (hcp) phase

131

132

STATIC

COMPRESSION

Table1. BulkModulifromStaticCompression
Data(continued)

Chemical
FormulalDensity Isothermal
Bulk
(Mg/m
3)

Modulus

diT/dp3

Technique
andNotes
4

Ref.

(GPa)
2
Fe0.8Ni0.2
e (hcp) phase

8.37

171.8 + 2.2

Fe-5.2 wt. % Ni

8.41

212 + 15

8.42

4.95 + 0.09

DAC, XRD, P < 260

GPa, B-M EOS

132

4 (assumed)

DAC, XRD, P < 30

GPa, B-M EOS

196

215 + 25

4 (assumed)

D AC, XRD, P < 30

GPa, B-M EOS

196

7.76

188 + 14

4 (assumed)

DAC, XRD, P < 23

GPa, B-M EOS

188

Fe-10 wt. % Co

7.93

171+ 6

4 (assumed)

D AC, XRD, P < 30

GPa, B-M EOS

162

Fe-20wt. % Co

7.98

169+ 6

4 (assumed) DAC, XRD, P < 30

162

e (hcp) phase

Fe-10.3 wt. % Ni
(hcp)phase

Fe-7.2 wt. % Si
(hcp) phase

GPa, B-M EOS

Fe-40 wt. % Co

8.08

166+ 6

4 (assumed)

DAC, XRD, P < 30

GPa, B-M EOS

162

Fe0.980

5.87

169 + 10

4 (assumed)

(ideal)

DAC, XRD, P < 14

GPa, B-M EOS

221

Wiistite

157 + 10

4 (assumed)

DAC, XRD, P < 12

GPa, B-M EOS

94

142 + 10

4 (assumed) DAC, pXRD, P < 26

131

Fe0.9450

5.87

Wtistite

(ideal)

FeO

5.87

Wiistite

(ideal)

FeO
W 'astite

5.87
(ideal)

Fel_xO
x = 0.055, 0.07,

5.87

GPa, B-M EOS

150 + 3

3.8

155 + 5

(ideal)

DAC, XRD, P < 8.3

GPa, B-M EOS

122

DAC, scXRD, P < 5

GPa, linPVfit

91

DP, XRD, P < 30

GPa, M EOS

41

D AC, XRD, P < 20

GPa, B-M EOS

213

D AC, XRD, P < 45

GPa, M EOS

87

DAC, scXRD, P < 3.4

GPa, B-M EOS

100

0.10
W 'tistite

FeO

W 'tistite

5.87

154.0

Fe0.9410
Wastite

5.87
(ideal)

154 + 5

Fe2U

13.19

239

FeS
Troilite

3.4

(ideal)

4.74

82 + 7

4 (assumed)

-5 + 4

KNrrlE

Table1. BulkModulifromStaticCompression
Data(continued)

Chemical
Formulal Density Isothermal
Bulk
(Mg/m
3)
Modulus

dKOT/dp3 Technique
andNotes
4

Ref.

(GPa)
2
FeS

4.77

35 + 4

5 + 2

(high-pressureMnPtype structure)

DAC, scXRD,
3.6<P<6.4 GPa, B-M

100

EOS

DAC, XRD, P < 70

GPa, B-M EOS

95

DP, XRD, P < 30

GPa, M EOS

41

DAC, scXRD, P < 4.2

GPa, linPVfit

58

5.5

D AC, XRD, P < 34

GPa, B-M EOS

29

146.5 + 0.6

4.9

D AC, XRD, P < 34

GPa, B-M EOS

29

3.21

121 + 19

5.31 + 0.9

DAC, XRD, P < 62

GPa, V EOS

18

CO2

1.40

2.93 + 0.1

7.8

DAC, XRD, P <50

GPa, B-M EOS

117

NH3

0.86

7.56 + 0.06

5.29 + 0.03

DAC, XRD, 3<P<56

GPa, B-M EOS

161

H20
(cubicphaseVII)

1.46

22.3 + 1.0

4.9+0.7

DAC, XRD,

152

FeS2
Pyrite

4.95

143

FeS2
Pyrite

4.95

148

FeS2
Pyrite

4.95

157

FeS2
Pyrite

4.95

215.4 + 0.2

FeS2

4.87

Fell

4 (assumed)

5.5

Marcasite

Ices:

(P0 = 2.3 GPa)

(P0 = 2.3 GPa) 2.3<P<36 GPa, Avg.

of several EOS

D20
(cubicphaseVII)

1.48

30.0 + 1.5

(P0 = 2.9 GPa)

4.1+0.5

DAC, XRD,

152

(P0 = 2.9 GPa) 2.3<P<36 GPa, Avg.

of several EOS

H20
(cubicphaseVII)

1.46

23.7 + 0.9

4.15 + 0.07

DAC, XRD
2.3<P<128, B-M EOS

82

VH0.5

---5.73

193.5 + 4.0

D AC, XRD, P < 35

GPa, B-M EOS

19

NbH0.75

6.60

202.3 + 3.0

DAC, XRD, P < 35

GPa, B-M EOS

19

Hydrides'

133

134

STATIC

COMPRESSION

Table1. BulkModulifromStaticCompression
Data(continued)

Chemical
Formula
1 Density Isothermal
Bulk
0Vlg/m
3)
Modulus

diT/dp3

Technique
andNotes
4

Ref.

(pa)2

PdH

-10.2

130.0 + 5.0

4.8

DAC, XRD, P < 35

GPa, B-M EOS

19

PdD

-10.2

135.0 + 5.0

4.7

DAC, XRD, P < 35

GPa, B-M EOS

19

CrH

-6.23

248.0 + 9.3

11.0

DAC, XRD, P < 35

GPa, B-M EOS

19

AIH 3

-1.50

47.9 + 1

3.3 + 0.2

DAC, XRD, P < 35

GPa, B-M EOS

19

H(AIH3)

-1.28

30.9 + 2

3.2 + 0.4

DAC, XRD, P < 35

GPa, B-M EOS

19

Cull

6.38

72.5 + 2

2.7 + 0.3

DAC, XRD, P < 35

GPa, B-M EOS

19

-5.42

22.2 + 2

3.6 + 0.3

D AC, XRD, P < 35

GPa, B-M EOS

19

H(CuH)

Amorphous

Materials:

Fe2SiO4

liquid

3.747

24.4

10.1

PC, sink/float

(1773K)

( 1773K)

(1773K)

measurements,

1.0<P<5.5 GPa, B-M

EOS

SiO2 glass

2.21

37.0 + 5.5

-5.6 + 6.2

DAC, length-change

143

measurements, P <10
GPa, B-M EOS

Ca-Mg-Na glass

35.5 + 3.7

-2.9 + 4.1

DAC, length-change
measurements, P <_10
GPa, B-M EOS

Mineralnames
aregivenin italicswhereapplicable.
All values
areatambient
pressure
androomtemperature
except
where
noted.
A dash
implies
a linear
fit tothepressure-volume
data(implies
thatKOT'=
0) oranunstated
KOT'.
Thetemperature
derivative
of thebulkmodulus
(dKot/dT)
isgivenwhereavailable.
Key: DAC = diamond-anvil
cell. BA = Bridgrnan
anvilpress.DP = Drickamerpress.
CAP = cubic-anvil
press.TAP = tetrahedral-anvil
press.MAP = mulianvilpress.
TCOA = tungstencarbideopposedanvils,BCAC = boroncarbideanvil cell.

XRD = x-raydiifraction.scXRD= single-crystal

XRD. pXRD = powderXRD.
PD = pistondisplacement.DV = directvolumemeasurement.

ND = neutrondiffraction.EXAFS = extended
x-rayabsorption
f'mestructure.
P = pressurein GPa.

B-M EOS= Birch-Murngahan

equation
of state(includes
a varietyof Birchequations).
M EOS = Murngahanequationof state.

V EOS =Vinet et al. ("universal")

equationof state.
linPVfit = linear fit to the pressurevolumedata.
lsqPVfit = leastsqaresfit to the pressurevolumedata.

O-H method= Olinget-Halleck

methodof reducingP-V data(seereference).

143

KNI'I'IE

Acknowledgements.
This work was supportedby NSF andthe
W34. Keck Foundation.I thankT.J. Ahrensandan anonymous
reviewer for helpful comments. I'm sure references were
missed,for whichI apologizein advance.This papercouldnot

135

have been completedwithout the help of Quentin Williams.

Institute of Tectonics (Mineral Physics Lab)contribution
number

208.

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Shock Wave Data for Minerals

ThomasJ. Ahrensand Mary L. Johnson

1. INTRODUCTION

[13,14] is in the mechanics of both the continued

bombardmentand hence cratering on planetary objects

Shock compressionof the materials of planetary

interiors yields data, which upon comparisonwith
density-pressure
and density-soundvelocity profiles of
both terrestrialplanetary mantles and cores [4,5,94], as
well as density profiles for the interior of the major
planets [148], constrain internal composition and
temperature.Otherimportantapplications
of shockwave
data and related properties are found in the impact
mechanicsof terrestrialplanetsand the solid satellitesof
the terrestrialand major planets. Significantprocesses
which can, or have been, studiedusingshockwave data
include: (1) the formation of planetary metallic cores
duringaccretion[ 169,192], and (2) the productionof a
shock-melted "magma ocean" and concurrent impact
volatilizationversusretentionof volatilesduringaccretion

throughgeologictime [170], aswell as theeffectsof giant

impactson the Earth [183,185]. Finally, recoveryand
characterization of shock-compressedmaterials have
provided important insights into the nature of shock
deformation mechanismsand, in some cases, provided
physicaldataon the natureof eithershock-induced
phase
changesor phasechangeswhich occur upon isentropic
releasefrom the high-pressure
shockstate(e.g., melting)

[1]. Also of interest are the shock-induced chemical

reactions betweenmeteoriticcomponents(e.g. H20 and
Fe: [ 111]). The formationof primitive atmospheres,
for
example,containinga largefractionof H20 andCO2 is
also addressable using shock wave and other
thermodynamicdata for volatile-bearing minerals(e.g.
[110,112]).
A related application of both shock
compressionand isentropic release data for minerals

al. [24] and Trunin [203].

[193,194].

As indicatedfor the data summaryof Table 1, a very

large data setexistsdescribingthe Hugoniotequationof
state of minerals.

Whereas some earlier summaries have

provided raw shock data [47,121,213], the present

summary provides fits to shock wave data. Earlier
summariesprovidingfits to dataare givenby Al'tshuleret
Hugoniot data specifythe locus of pressure-density
(or specificvolume) stateswhich can be achievedby a
mineral from some initial state with a specified initial
density. An analogous summary for rocks, usually
describedas a mixtureof mineralsare given in Chapter34.

Three pressureunits are commonly in use in the

shockwave literature: kilobar (kbar), gigapascal(GPa),

andmegabar
(Mbar).These
areequal
to109,1010,
and
1012dyne/cm
2, respectively,
or 108,109,and1011

T. J. Ahreas and M. L. Johnson,SeismologicalLaboratory,

252-21, California Institute of Technology, Pasadena,CA

pascalsin SI units.

91125

2.

PresentAddress:M. L. Johnson,GemologicalInstituteof

SHOCK WAVE EQUATION OF STATE

America, 1639 Stewart Street, Santa Monica, CA 90404

The propagationof a shockwave from a detonating

explosive or the shockwave inducedupon impact of a
flyer plateaccelerated,
via explosivesor with a gun,result

Mineral Physicsand Crystallography

A Handbook of PhysicalConstants
AGU

Reference

Shelf 2

Copyfight1995 by the AmericanGeophysicalUnion.

143

144

SHOCK WAVE DATA FOR MINERALS

c:Sd

oo

AHRENS

dddd

ddd

o
o

ooc
o
,---

AND

JOHNSON

145

146

SHOCK WAVE DATA FOR MINERALS

'.-1

..=

AHRENS

ot,'

0,

AND

JOHNSON

147

148

SHOCK

WAVE

DATA

FOR

MINERALS

AHRENS

.,

AND

JOHNSON

149

lS0

SHOCK

WAVE

DATA

FOR MINERALS

AHRENS

AND

JOHNSON

151

152

SHOCK

WAVE

DATA

FOR MINERALS

('",1 Oh 0

c',1 u" c',1

AHRENS

AND

JOHNSON

153

154

SHOCK WAVE DATA FOR MINERALS

o. o o. o.

oc5ooc5c5

,, c5

o c',!.

'.

AHRENS

AND

JOHNSON

155

156

SHOCK WAVE

DATA

FOR MINERALS

AHINS

'"'4' 0

AND $OHNSON

17

158

SHOCK WAVE DATA FOR MINERALS

AHRENS

AND JOHNSON

159

160

SHOCK

WAVE

DATA

FOR

MINERALS

oo

c5o

c5

c5

c5 ,,o

AHRENS

AND

JOHNSON

0' oo0oo 0 ,---'-

C',I

("',1

0
!

C',I
.

161

162

SHOCK

WAVE

DATA

FOR MINERALS

AHRENS

AND

JOHNSON

163

164

SHOCK

WAVE

DATA

FOR

MINERALS

AHRENS

AND

OHNSON

165

0,'

166

SHOCK

WAVE

DATA

FOR MINERALS

AHRENS

oO

ocTc

,--

AND

JOHNSON

167

168

'I

'{::

SHOCK WAVE DATA FOR MINERALS

AHRENS

AND

JOHNSON

169

1'70

SHOCK WAVE

DATA

FOR MINERALS

AHRENS

AND JOHNSON

171

172

SHOCK

WAVE

DATA

FOR

MINERALS

Ts

US
A

Po

FIG. 1. Profileof a steadyshockwave,rise time 'cs,

impartinga particlevelocityUl pressureP1, and internal
energy densityEl, propagatingwith velocity Us into
materialthat is at restat densityPo and internalenergy
densityEo.

in nearly steadywavesin materials. For steadywavesa

shockvelocityUs with respectto the laboratoryframecan

The key assumption

underpinning
the validityof Eqs.(1)(3) is that the shockwave is steady,so that the rise time
zs, is shortcomparedto the characteristic
time for which
the highpressure,density,etc. are constant(seeFig. 1).
Upon driving a shockof pressureP1 into a material,a
final shockstateis achievedwhichis describedby Eqs.
(1)-(3). This shockstateis shownin Fig. 2, in relationto
otherthermodynamic
paths,in thepressure-volume
plane.
HereV o = 1/PoandV = 1/p. In thecaseof the isotherm
andisentrope,it is possibleto follow,as a thermodynamic
path,the actualisothermalor isentropiccurveto achievea
stateon the isothermor isentrope.A shock,or Hugoniot,
stateis different,however.TheHugomotstate(P1,V1) is
achieved via a a shock front. The initial and final states

are connectedby a straightline called a Rayleigh line

(Fig. 2). Thussuccessive
statesalongthe Hugoniotcurve
cannotbe achieved,onefromanother,by a shockprocess.
The Hugomotcurveitself thenjustrepresents
the locusof
final shockstatescorresponding
to a giveninitial state.
It has long been recognized that the kinematic
parameters
measuredin shockwaveexperiments
U s and

be defined. Conservation of mass, momentum, and

energyacrossa shockfrontcan thenbe expressed
as

Up canempirically
be described
in regionswherea

P = Po (Us-uo)/(Us-u)
P1 - Po = Po(Ul-Uo)(Us-uo)

()
(2)

Us= Co+ S Up

E1- Eo= (P1+ Po)(1/po-1/p

1)/2= 1/2(Ul- Uo)
2

(3)

where p, u, P, andE are density,particlevelocity,shock

pressure, and internal energy per unit mass and, as
indicatedin Fig. 1, the subscripts
o and 1 refer to thestate
in front of and behindthe shockfront, respectively. In
Table 1, shock velocity and particle velocity are

substantialphasechangein the materialdoesnot occuras:

(4)

As further discussed in several review articles on

shockcompression[22,59,136], and a recent book [40],

Isentrope

Hugoniot

designated
asUsandUl. Thusfora single
shock
Up= Ul.
In thecaseof multiple
shocks,
thevalues
of Up andUs
given in the Table are for the final (highestpressure)
shock state. Equations (1)-(3) are often called the
Rankine-Hugoniotequations.It shouldbe understoodthat
in this sectionpressureis usedin place of stressin the

indicatedwavepropagation
direction. In actuality,stress
in the wavepropagation
directionis specifiedby Eq. (2).
A derailedderivationof Eqs. (1), (2), and (3) is given in
Duvall and Fowles[70]. Equation(3) alsoindicatesthat
the matehalachievesan increasein internalenergy(per
unitmass)whichis exactlyequalto thekineticenergyper
unit mass.

Isot

Vo

In the simplestcase, when a single shock state is

achieved via a shock front, the Rankine-Hugoniot

FIG. 2. Pressure-volumecompressioncurves. For

isentropeandisotherm,the thermodynamic
pathcoincides

equations
involvesixvariables
(Us,u1, Po,P1, E1 - Eo,

with the locus of states, whereas for

and P1); thus,measuring

three,usuallyUs, u1, andPo,
determinesthe shockstatevariablesp 1, E1-Eo andP1.

thermodynamicpath is a straightline to point P1,V1, on

the Hugoniotcurve,which is the locusof shockstates.

shock, the

AHRENS

Hugoniotdata for mineralsandothercondensed

media
may be describedover varyingrangesof pressureand
densityin termsof a linearrelationof shockandparticle
velocityin Table 1. This tablewasassembled
usingthe
MicrosoftExcel, version3.0, (Redmond,WA 1993)
programandthe least-square
fits to the shockwavedata
with standarderrors were derivedby usingthe LINEST
function. The equationsemployedfor line slopesand
interceptsare identicalto thosegiven in Bevington[46]

KH = -V (3P/3V)H.

(5)

173

(11)

The isentropeand the Hugoniot and isentropicbulk

modulus are related via:

KS

(12)

- [PH- PS][+1- qo(1-q'q+...)]

TheUs-Updatafora widerangeof minerals

are

Co= x/ICs/po,

JOHNSON

The analogous
bulkmodulusalongtheHugoniotis:

(Eq. 6-9, p. 104;Eq. 6-21, p. 114for errorsin slopes;and

Eq. 6-22, p. 114 for errorsin intercepts).

given in Table 1. Here Co is the shockvelocity at

infinitesimally small particle velocity, or the ambient
pressure
bulk soundvelocitywhichis givenby

AND

Here we assumea volumedependenceof the Gruneisen

parameter

7= V (3P/3E)v= 70(V/Vo)q,

(13)

where

whereKs is the isentropicbulk modulus,

Ks = -V (dP/dV)sin the absence
of strengtheffect (see
Sect.3).. Upon substituting
Eq. 4 intoEq. 2, anddenoting
theshockpressureasPH, thisis givenby:

= poUp(o+ s Up)

(6)

Thus, from the form of Eq. 6, shockpressureis given as

the sumof a linear and quadraticterm in particlevelocity,
basedon the data of Table 1. A pressure-volume
relation
canbe obtainedby combiningEq. 6 with Eq. 1 to yield:

PH= PoCo2q/(1-Sq)
2

(7)

where

rI = 1 - V/Vo= Up/Us.

q = d n7/d nV andq'= d nq/cten

V

(14)

Tois theGriineisenparameterunderstandard
pressure
andtemperatures
and is givenby

7o= crKT Vo/Cv= orKsVo/Cp,

(15)

where c is the the thermalexpansioncoefficient,KT is

the isothermal
bulkmodulus
andCp and Cv are the
specificheat at constantpressureand volume. We note
thatthe Ps and PH can be relatedby assumingthe MieGriineisen relation

PH-Ps
=V(EH-Es)'

(16)

(8)

Eq. 7 is oftencalledthe "shockwaveequationof state"

sinceit definesa curvein thepressure-volume
plane.
The isentropic pressure can be written (e.g.
[93,98,171])by an expressionanalogousto Eq. 7 as a

if is independent
of temperature,
whereEH = El-E0 is
givenby Eq. 3 andE s is givenby
V

Es=-- I PsdV.
Vo

series

(17)

Because the Griineisen ratio relates the isentropic

Ps= PoCo2 (q+ 2Sq

2+ '"),

(9)

which upon differentiationyield the isentropicbulk

modulus

Ks= PoCo2 (1+ (4S-1)

q + -..)

(10)

pressure,Ps, and bulk modulus,K s, to the Hugoniot

pressure,
PH, and Hugoniotbulk modulus,K H, it is a key
equationof stateparameter.
The shock-velocityparticlerelationof Table 1 can be
used to calculate the shock pressurewhen two objects
impact. If (A) the flyer plateand(B) the targetare known
andexpressed
in the form of Eq. (7), the particlevelocity

174

SHOCK WAVE DATA FOR MINERALS

Ul and pressureP1 of the shockstateproducedupon

impact
of a flyerplateat velocity
Ufpona stationary
targetmaybe calculatedfrom thesolutionof theequation
equating
theshockpressures
in theflyeranddriverplate:

PoA(ufp-Ul)(CoA+ SA(p- Ul))=

PoBu I (CoB + SB u 1)-

HEL

(18)

That is;

u1=(-b- qb2-4ac)/2a,

(19)

where

ParticleVelocity

a = SA PoA- PoBSB,

b= CoAPoA- 2SAPoAUfp- PoBCoB,

(20)
(21)

and

c=Ufp(CoAPoA+ SAPoAUfp).
3. SHOCK-INDUCED
PHASE

DYNAMIC

YIELDING

(22)

3
2

AND

HEL

TRANSITIONS

Bothdynamicyieldingandphasetransitions
giverise
to multipleshockwaveprofileswhenpressure
or particle
velocityversustimeis recorded.Virtuallyall nonporous
mineralsand rocksin whichdynamiccompression
has
beenstudieddemonstrate
phenomenon
relatedto dynamic
yielding,in which materialstransformfrom finite elastic
strainstatesto statesin which irreversibledeformationhas

occurred.Moreover,mostminerals
anda largenumberof
compounds,
elements,
andorganicmaterialsdemonstrate
shock-induced
phasechanges.
The dynamicyieldpointundershockcompression,
the Hugoniot elastic limit, or HEL, is defined as the

maximum
shockpressure
a materialmaybe subjected
to
withoutpermanent,
massive,
microscopic
rearrangement
takingplaceat theshockfront. As shownin Fig. 3a, the
shockvelocityof theHEL stateremainsnearlyconstant
and for non-porousmedia is usually equal to the
longitudinal
elasticwavevelocity.Viscoelasfic
polymeric
mediagenerallydo not displaythe HEL phenomenon.
Wedenotefiveregimes
in Fig. 3 for thecaseof dynamic
yielding and phasetransitionand the available shock
wave data are separatelyfit to linear relationsin these
regimesin Table 1. For some minerals there are more
than four regimes indicated, for reasons such as

crystallographic
controlof compression
at low pressures

Volume
FIG.3. Sketch
of shockvelocity-particle
relation
(a)and
corresponding
pressure-volume
Hugoniotcurves(b) for a

mineralwhichundergoes
dynamic
yieldinganda phase
change.

0: compression
upto theHugoniot
ElasticLimit
(HEL)

1: transition
viadynamic
yieldingtoa quasihydrostaticstate

2: low pressurestate
3: mixedregion
4: highpressurestate

(suchasOa,Obforquartz),andformorethanonehighpressure
state(suchas4a, 4b, and4c for halite).
The crystallographicor atomisticlevel natureof

shock-induced
phase
changes
variesfromsimpleaverage
coordinationchangesobservedin variousliquids,
ionization and debondingin non-metallic fluids,
electronic
transitions
in metalandnon-metals,
changes
in
crystalstructurein solidmaterials,and transitionfrom the
solid to the fluid state.

AHNS

In the caseof a phasechange,thepressurealongthe

isentropePs at the volume V1 correspondingto a
Hugoniotstate(P1,V 1) is givenby

Vo

wherethe left-handsideis the Rankine-Hugoniot

energy,
and the first and secondtermson the right representthe
gainin theinternalenergyalongthepaths1 and2 of Fig.
2 Here Voo is the specific volume of the initial material
and Vo the specificvolumeof the shock-induced
highpressure
phase,or theintrinsicvolumeof the sampleif the
initial stateis distended. Also ETR is the energyof
transitionto the high-pressure
phaseat STP. In the case
of no phasechange,ETR = 0. For zeroinitial porosity
V oo = Vo. The unknownparameterin Eq. 23 is Ps,
whichis implicit in the first integralterm on the righthand side and explicit in the secondterm. The second
term is obtainedby using the definition of the Gruneisen
parameter(Eq. 13) to calculatethe changein energy
associated
with thepressuredifference(P 1-Ps)at constant

TH

V
Ps)
= ICvdT
(PH-

(25)

Ts

It is useful to carry out both postshockand shock

temperature measurements as they provide

complementary
informationfor the thermalequationof
state,that is, ,as well as Cv. Minerals for which shock
temperatures
havebeenmeasured(usuallyvia radiative
techniques)are soindicatedin Table 1.
In the case of molecular fluids such as water, a
formulation
basedonthenearconstancy
of Cp at constant

volume.

4. SHOCK

175

initial volume,andVb = V, compressed

volume. For the
calculationof postshocktemperaturesTi = TH , the
Hugoniottemperature,
Va = VH, the volumeof the shock
state, and V b = Voo, the postshock volume
corresponding
to the postshocktemperature. For shock
compression
to a volumeV, Ps is firstobtainedby using
Eq. 23; thenT s,theisentropic
compression
temperature
at
volumeV, may be calculatedby usingEq. 24. Finally,
usingEq. 16,theshocktemperature
TH is givenby

P1(VooV1)=- V1
J'PdV
+V1(P1Ps)
+ETR (23)
2

3dqD .{OHNSON

pressureis used [41,167].

Although there have been few data collected,
postshocktemperaturesare very sensitiveto the models

TEMPERATURES

which specifyand its volumedependence,

in the caseof
the Gruneisenequationof state[49,164,165]. In contrast,
the absolutevaluesof shocktemperatures
are sensitiveto
the phasetransitionenergyETR of Eq. 23, whereasthe
slope of the TH vs. pressurecurve is sensitiveto the
specificheat.

For many condensed media, the Mie-Gruneisen

equationof state,basedon a finite-differenceformulation

of the Gruneisenparameter(Eq. 16), can be used to

describe shock and postshock temperatures. The
temperature
alongtheisentrope[224] is givenby

(24)

Acknowledgments.
Researchsupportedunder NSF,
NASA,andDoD. We appreciate
comments
onthismanuscript
fromWilliamW. Anderson,
Kathleen
Gallagher,
WenboYang,

whereTi is the initial temperature.For the principal

isentrope
centered
atroomtemperature,
Ti = To, Va = Vo,

andJ. Michael Brown. Contributionnumber5332, Divisionof

GeologicalandPlanetarySciences.

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melting and shear banding in

179

J.

Colorado, 1990.

1989.

177

muscovite,

184 Shipman, F. H., W. M. Isbell,

deformation,

phase transformation, and

melting with pressure, J.
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183 Sharpton,V. L., and P. D. Ward

(Ed.), Global Catastrophes in
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An
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glass:Implicationsfor modesof
shock-induced

state

1991.

Schmitt, D. R., and T. J. Ahrens,

Emission spectra of shock

compressedsolids, in Shock

175

Rubin, and T.

of

Waves

and the questionof potassiumin

the core, J. Geophys.Res., 85,
192

relationship to fusion curves,

Somerville, M., and T. J. Ahrens,

Shockcompression
of KFeS
2

J. Ahrens, Shock wave equation

1080, 1983.

174

Sekine, T., A.M.

191

91, 667-691, 1987.

198

Svendsen, B., and T. J. Ahrens,

Shock-induced temperaturesof

CaMgSi20
6, J. Geophys.
Res.,
95, 6943-6953, 1990.
199 Swenson, C. A., J. W. Shaner,
and J. M. Brown, Hugoniot

overtake
sound-velocity
measurements
on CsI, Phys.Rev.
B, 34, 7924-7935, 1986.

200 Syono, Y., T. Goto, and Y.

Nakagawa, Phase-transition

pressures
of Fe304 andGaAs
determined

from

shock-

compression experiments, in
High Pressure Research:
Application in Geophysics,
edited by M. H. Manghnaniand
S. Akimoto, pp. 463-476,
Academic

Press, New

York,

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1977.

210

201 Syono, Y., T. Goto, J.-I. Sato,

and

H.

Takei,

Shock

Shutov,
Dynamic
compressibility of acqueous

compression measurements of
single-crystal forsterite in the
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Geophys. Res., 86, 6181-6186,
1981.

202 Taylor, J. W., and M. H. Rice,

Elastic-plasticpropertiesof iron,
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1963.

203 Trunin, R. F., Compressibilityof

various substancesat high shock
pressures: an overview, Izv.
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solutions of salts, Izv.

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206

213

214

630-631, 1969.
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209

222

F.

Wackerle,

J.,

Shock-wave

W ackerle, J., W. L. Seitz, and J.

C. Jamieson,
Shock-wave

equationof statefor high-density

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Walsh,
J. M., and R. H.

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van Thiel, M., and B. J. Alder,

Van Thiel, M., L. B. Hord, W.

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B.

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Compendium of Shock Wave

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wave

compressionof threepolynuclear
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Watt, J.P.,

and T. J. Ahrens,

Shock compression of singlecrystal forsterite, J. Geophys.

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Vassiliou,

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S., and T. J.

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McQueen, and F. L. Yarger,

Shock-wave compressions of
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Dynamic compressionof liquids

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Shock compressionof argon, J.

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Compressibilityof porousmetals
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230

Watt, J.P.,

and T. J. Ahrens,

Shock wave equations of state

using mixed-phaseregime data,

184

SHOCK

WAVE

DATA

FOR

MINERALS

Watt, J. P., and T. J. Ahrens,

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V.

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The

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34-36, 1962.

and G.

S.

impact

Electrical Propertiesof Minerals and Melts

JamesA. Tyburczy and Diana K. Fisler

Electricalpropertiesof mineralsandmeltsaid in the

interpretationof geophysicalprobesof the Earth'sinternal

which to start a search, rather than as a source of absolute

electrical structure (see Hermance, Section 1-12). In

addition, electrical conductivities and dielectric constants

Recent previous compilationsof data on electrical

propertiesof rocks are given in references[17-19, 42].
Electricalpropertiesof elements,minerals,and rocks at
room temperatureand 1 bar pressure,and of aqueous
fluidsare treatedby Olhoeftin Section3-8 of this series

values.

of minerals are used in studies of mineral structure,

electronicand ionic transportprocesses,

defectchemistry,
and other mineral physical properties. This article
contains data and referencesto electrical properties of
minerals and related materials at elevated temperature
and 1 bar pressure,and at elevated temperatureand
elevatedpressure.Electricalpropertiesof materialscan
be very sensitive to minor chemical impurities and
variations. Cracks and other macroscopicdefects,and
microscopicdefectssuchas voids,inclusions,twins, etc.
in specimenscan complicatethe achievementof reliable
measurements.As a result,for a given electricalproperty
of a mineral, there are often a wide range of reported
values,sometimesdiffering by as much as severalorders
of magnitude. We have strivento provide reliable data
for each material

listed.

and in [42].

Electrical parameters. The electricalconductivityc

and the dielectric permittivity relate an electrical
stimulusand responsethroughMaxwell's relations. In
linear systemsit can be shownthat

JT = oE + e3Fi}t

(1)

whereJT is the total currentdensity,E is the electricfield

gradient,and t is time. The first term on the right hand
side of equation(1) is called the conductioncurrentand
the secondterm is the displacementcurrent. For a time
varying electrical field of the form E = E o exp (i0t)
equation(1) becomes

Because minor element content

and experimentalconditionsare knownto stronglyaffect

electricalproperties,we have attempted,wherepossible,
to tabulateboth chemicalcompositionand experimental
conditions for each measurement. Certain previous
compendiaof mineralelectricalpropertieshavepreferred
to give only rangesof valuesfor a givenmineral[ 17-19].
The data and tablespresentedhere may bestbe usedas a
guide to the literatureor as a sourceof referencesfrom

JT = (o + ia) Eo exp (itot)

(2)

in whichi = x/-1and0= angular

frequency.A total
complexconductivitymay be definedas

OT=IJT + ioT = O+ io

(3)

and the permittivity may also be defined as a complex

value

J. A. Tyburczy and D. K. Fisler, Departmentof Geology,

Arizona State University, Tempe, AZ 85287-1404

= '- it"
Mineral Physicsand Crystallography
A Handbook of Physical Constants
AGU

Reference

e" is alsocalledthe lossfactor,andthe losstangent5is

Shelf 2

Copyright 1995 by the American GeophysicalUnion.

(4)

defined as

185

186

ELECTRICAL

PROPERTIES

OF MINERALS

tan 15= e"/e'

(5)

The complexresistivityis definedasthe reciprocalof the

complextotal conductivity

p'-ip"=(oT+ioT)-1

(6)

The SI unit of electricalconductivityis Siemens/meter

(S
equivalentto l/fl). The $I unit of dielectricpermittivity
is Farad/meter(F/m) andis oftenexpressed
as therelative
dielectricpermittivityc
=g/Co

where

(7)

is the dielectric permittivity of a vacuum=

8.854185x 10'12 F/m. For generalreferences

see
references[20, 22, 42, 66].

conduction).Impurity atomsin low concentrations

may
have large effectson the magnitudeand mechanismsof
conductivityin insulators. In an impurity-containing
insulator, low temperature conductivity is often
dominatedby the impurity-controlledmechanisms
and is
termedextrinsicconductivity. At high temperatures
the
conductivitymay becomedominatedby the fundamental
ionic conductivityof the pure crystal, which is termed
intrinsic conduction. In geological materials the
distinctionbetween'pure'materialsand 'impure'or minorelement containingmaterialsis not always clear-cutor
useful. Conductivityvaluesfor insulatorsare generally

lowerthanabout10'13S/matroomtemperature.
Many
earthmaterials,e.g., halides,are insulators.
Effects of temperature and pressure. The NemstEinsteinrelation links the electrical conductivityto the
diffusioncoefficientof the charge-carrying
species

Types of conductors. Materialsareclassifiedon the

basis of whether they are metallic conductors,
semiconductors,or insulators.
Metallic conductors. In metallic conductors, the

Fermi level (the highestfilled energylevel) lies within the

conduction band, and the conduction electrons are not

localized or bound to any particularatom. Above the

Debye temperature, the conductivity decreaseswith
increasingT, generally decreasingas 1/T [37, 44]. At
room temperature, metallic conductors have

conductivities
of 106S/mormore.Evenattemperatures
approaching0 K metallic conductivityis very high. In
addition to metals, materials such as graphite exhibit
metallic

conduction.

Semiconductors.

Semiconductors

bottom of the empty conductionband and the top of the

filled valenceband(the bandgap). Thermalpromotionof
from the valence

to the conduction

band can

occur, leaving positively chargedholes in the valence

band. Typical energygapsfor semiconductors
are on the
order of ! eV. Some solid-solutionimpurity atoms can
donate electronsto the conductionband, resulting in ntype semiconduction;
otherscan acceptelectronscausing
electron holes in the valence band, resulting in p-type
semiconduction.

Semiconductors

(8)

in which D is the diffusion coefficient, z is the valence of

theconducting
species,e is thechargeof theelectron,n is
the concentration of the conducting species, k is
Boltzmann'sconstant,and T is temperature.Diffusionis
a thermallyactivatedprocessso that D = Do exp(-E/kT),
thereforethe temperaturedependenceof the conductivity
will be of the form
!30

13=- exp(-E/kT)

(9a)

or

are materials with

a relativelysmalldifference
in energyEg between
the
electrons

o = Dz2e2n/(kT)

have conductivities

oT = A exp(-E/k

(9b)

in which13oandA arepre-exponential
constants
andE is
the activationenergy. E is often expressedin electron

voltseV; Boltzmann's
constant
k isequalto8.618x 10'5
eV/deg. In practice,the 1/T factorin the pre exponential
termon the fight handsideof equation(9a) is notalways
used,andexpressions
of the form
o = Ooexp(-FT)

(10)

in

therange10'3 to 105 S/m. At elevated

temperatures, areemployedinstead.In thetablesthatfollow,bothtypes
many silicatesandoxidesfall into thiscategory.
Insulators. In insulators,the bandgapis large(often
5 eV or more)andpreventsthermalelevationof electrons
into the valence band. Charge transport is by ionic
movement from site to site by thermally activated
transport (ionic conduction) or by electronic charge
transfer between ions of different valence (hopping

of expressions
areused,andthereadershouldbe careful
to employ the proper form of the equationfor the
constantsgiven. Plots of the logarithm of electrical
conductivity
versus1/T thatcoveran extendedrangeof
temperature
frequentlyshowtwo or morelinearregions.
The variationsin slopecanbe causedby transitionfrom
one dominant conductingspeciesto anotheror by a

TYBURCZY

transitionfrom extrinsic(impurity dominated)to intrinsic

conductivity. Each region is then described by an
expressionof the form of equation(10). However, more
precise,and mechanistically
moremeaningfulparameters
are derived if the entire data set is simultaneouslyfit to a
singleexpressionof the form

O = Ool exp(-El/kT) + 002 exp(-E2/kT)

(11)

AND

FISLER

187

The electricalconductivityof a materialis the sumof

the conductionof each charge carrier (or defect) type
actingin parallel
o = Eoi = Eciqigi

(13)

in which ci is the concentrationof the ith type of charge

carder,qi is its effectivecharge,and gi is its mobility (in

m2 V'1 sec
'1). In general,
alldefects
arepresent
in some
In the data tablesthat follow, experimentaldata that have
been fit simultaneouslyto multiple linear segmentsare
indicatedby braces.
The effect of pressure on conductivity can be
characterizedby the inclusionof an activationvolume
term V o so that
U+ PVo.

O=ooexp(-

(12)

in which U is the activation internal energy. The

activation volume is often interpretedas indicating the
volume of the mobile species,but care shouldbe taken

when making this interpretation. When available,

activation volumes are given in the tables, but more
commonly measurementsat elevated pressures are
parameterizedisobaricallyas functionsof temperature
using equation (10) or (11). In experimentsat high
pressureit is difficult to control all thermodynamic
parameters. The valuesin Table 5 and 6 are the best
currentlyavailable. We expectthat manyof thesevalues
will be revisedasexperimentalmethodsimprove.
Point Defects and Conductivity. The electrical
conductivityof materialsis determinedby the pointdefect
chemistry. Point defectsare imperfectionsin the crystal
lattice and the types of point defects possible are
substitutions, vacancies, interstitial ions, electrons, and

electron holes (electron deficienciesin the valence band

commonlytermed'holes'). Kroger-Vinknotation[23,24]

was developed to describethe type of defect and its

effective chargerelative to a normal lattice site. Inc this

notation,
each
defect
isgiven
asymbol
oftheformAB,in

which the main symbol A indicatesthe speciesof the

defect (atom, electron,hole, or vacancy),the subscriptB
indicatesthe type of site(normallatticesiteof a particular
atom type or an interstitialsite), and the superscriptc
indicatesthe net effective chargeof the defect relative to
the normally occupancyof that lattice (dots indicate
positive relative charge, slashes indicate negative
charges). Tables 1 and 2 give thesedefinitionsand show
as an example the defect speciesin nonstoichiometric
(Mg,Fe)O. Note how defectscausedby aliovalentionsin
differentvalencestatesare writtenusingthis notation.

amountin every crystal and each contributesto the total

conductivity. Usually only one or two types of defects
dominateundera given set of thermodynamicconditions.
The concentrations
of the defect speciesare governedby
chemical reactions that lead to the production or
consumptionof each defect type. For example, the
removalof a positively-charged
ion from its normalsite
resultingin the formationof a vacancyplusan interstitial
ion (formationof a Frenkeldefect)can be written as
X

AA = VA + AI

(14)

For sucha reaction,we can write equationsfor chemical

equilibriumconstants
in the usualmanner
K=

IVA

(15)

in which K is the equilibrium constant and square

brackets indicate site fractions. the Gibbs free energy
AG for thisreactionis givenby
AG = -RT In K

(16)

in whichR is the gasconstantandT is temperature.

Reactionsinvolving oxygen from the surroundings
are of particular importancein oxide materials. For
example,the reaction

00 = 1/202(g)+
V0 +2e'

(17)

describesthereactionof oxygenon a normallatticesiteto

releasean oxygenmoleculeto the environment,leaving
an oxygenvacancyand two electronsbehind. Thus the
mineral stoichiometrydependson the chemicalpotential
of oxygen(or the oxygenfugacityfo2) in the surrounding
atmosphere. In MgO, the reaction which incorporates
oxygen from the surroundingsand forms a magnesium
vacancyis written
"

1/202=VMg+ 2h'+OO

(18)

Thus, in principle,the magnesiumvacancyconcentration

188

ELECTRICAL

PROPERTIES

OF MINERALS

Table 1. Definitionsof defectspecies(Krtger-Vink)

notation.

Symbol

form

Meaning

Main symbol Element or

speciesof defect

Subscript

Site

Atomic symbol

to normallattice

site

V (vacancy)

inwhichFeM_isthefraction
ofFeonMgsites
andn and

Normal Lattice Site

stoichiometries. For a four-componentsystemsuch as

olivine (Mg,Fe)2SiO4 an additional constraintmust be
specified; in olivine the most frequently specified
constraintis the silica activity asio2 (or equivalentlythe
enstatite activity aEn), so that the most general
conductivityrelationwouldhavethe form

x (zero)
!

(negative)

' lpositive)

in even pure MgO depends on fo2 (at constant

temperature). In the presenceof even relatively small
amountsof impurity ions, the concentrations
of defects
(and hence the conductivity) may vary widely. This
extreme sensitivityof defect concentrationto minor and
trace element concentrationsmakes it very difficult to
establishabsolutevalues for the conductivitiesof 'pure'
minerals, especially at low temperatures. The general
practice has been to try to determine which defect
dominatesconductionundera given set of conditionsby
determining conductivity under varying conditions of
temperature, oxygen fugacity, and trace element
concentration (or some subsetof these conditions). The
results are then combined

with defect reactions such as

(17) and (18) above and defect conservationlaws suchas

conservationof mass,chargeneutrality,and conservation
of lattice sitesto determinethe particulardefectreaction
that controls the concentration

oi= Ooexp(-E/kT)
(Fvlg)fo2n

I (Interstitial)

Chargerelative

e (electron)
h (hole)

(Atomic symbol)

Superscript

constraintmeans that the temperature,the pressure,the

oxygenfugacity,andthe Mg:Fe ratio in the solidmustall
be specified. Thus, the conductivitywill havethe general

of the dominant defect and

predicts the correctdependenceon other environmental

conditions(fo2 in particular). Referencessuchas [23-25]
describethis processfor manymaterials,andmorerecent
referencessuchas [9-11, 59, 60] describedefectequilibria
in some important Earth materials. To properly and
completelyspecifythe thermodynamicstateof a defectcontainingcrystal,the Gibbsphaserule mustbe satisfied.
For a three-componentsystem such as (Mg,Fe)O, this

(19)

m areconstants
arising
fromthedefect
reaction

oi=Ooexp(-E/kT)
(FeMg)fo2nasio2
p

(20)

in which p is also a constant. Where available, the

exponentsn for the dependence
of conductivityon oxygen
fugacityhave beenincludedin the tablesthat follow, but
theparametersin full expressions
of the form of equation

(20) arestill notcommonly

determined.See[23-25]for
generaldiscussions
of defectequilibriaand[8-11,58-60]
for discussions
appliedto Earthmaterials.

Table 2. Examplesof defectspeciesfor (Mg,Fe)O. Note

that Fe can be in +2 or +3 valence state.

Species
Normal

Symbols

Lattice

Substitutional

Sites

Defects

Lattice Vacancies
Interstitial

Ions

Electronic

Defects

Defect Dimers

Defect Trimers, etc.

MgMgFeMg00
Fehg
FeMg

VMgVO
MgI O FeI

ii

ii

(FeMi-VMs-FeMi
?

TYBURCZY

AND

FISLER

189

190

ELECTRICAL

PROPERTIES OF MINERALS

TYBURCZY

II

II

ee

II -

II

AND

FISLER

191

192 ELECTRICAL PROPERTIESOF MINERALS

TYBURCZY

AND

FISLER

193

194

ELECTRICAL

PROPERTIES OF MINERALS

II

II

000
--0

""0

TYBURCZY

II

II

II

II

II

000000000
UUUUUUUUU

AND

II

II

II

FISLER

II

II

oo

195

II

196 ELECTRICAL PROPERTIES OF MINERALS

oo

II

II

II

II

II II II II

< .=..=..=..=.
00000

===

TYBURCZY

AND

'!:3
0

'..q

zo

FISLER

197

198 ELECTRICAL PROPERTIESOF MINERALS

TYBURCZY

'

AND

FISLER

199

200

ELECTRICAL PROPERTIES OF MINERALS

N
0

oL 0

II

II II II

TYBURCZY

AND

FISLER

Table 8. Electricalconductivity
of anhydrous
naturally-occurring
silicatemeltsat temperatures
between
1200 and 1550C. Expressedaslog o, whereo is in S/m. Data from [45, 64, 65, 67].
Temperature,C
Melt type

1200

1250

1300

1350

1400

1450

1500

Nephelinite(C- 195)

0.59

0.91

1.15

1.27

1.35

1.43

1.48

Basanite (C-90)
Tholeiitic olivine basalt(C-50)
Olivine tholeiite (C-214)
Tholeiite (C-8)
Tholeiite (70-15)
Tholeiite (PG-16)
Quartz tholeiite (HT- 1)
Hawaiite (C-42)
Alkali olivine basalt (C-222)
Alkali olivine basalt (C-70)
Alkali olivine basalt (BCR-2)
Mugearite(C-210)
Andesite (HA)
Andesite (VC-4W)
Latite (V-31)
Trachyte(C-128)
Rhyodacite(HR- 1)
Rhyoliteobsidian(YRO)

0.41
042
0.48
0.36
0.41
0.39
0.16
0.62
0.48
0.53
0.30
0.49
0.39
0.34
0.48
0.75
0.46
0.41

0.73
0.76
0.67
0.56
0.65
0.58
0.40
0.77
0.66
0.69
0.46
0.59
0.48
0.42
0.57
0.81
0.52
0.47

1.03
0.93
0.82
0.71
0.84
0.75
0.59
0.88
0.81
0.82
0.60
0.69
0.56
0.50
0.64
0.87
0.60
0.53

1.27
1.06
0.96
0.85
1.00
0.91
0.76
1.00
0.95
0.95
0.73
0.78
0.64
0.58
0.71
0.93
0.66
0.58

1.36
1.16
1.06
0.95
1.11
1.02
0.90
1.11
1.05
1.04
0.83
0.85
0.71
0.65
0.77
0.97
0.72
0.62

1.45
1.25
1.17
1.07
1.20
1.12
1.01
1.21
1.15
1.16
0.92
0.96
0.79
0.71
0.83
1.02
0.76
0.67

1.49

1550

1.25
1.15
1.27
1.20

1.26

1.27
1.23
1.22
1.00

1.07

1.00
0.86

0.92

0.88
1.04
0.81
0.71

0.91

0.74

Table 9. Electricalconductivityof naturallyoccurringsilicatemeltsat elevatedpressures

overthe
temperature
range1200-1400C,parameters
for fits to the equationlog o = log Oo - (Ea + PAVo)/2.3kT
[64, 65].

Melt Type

kb

P range

oCt
inS/m eV

log Oo

Ea

AV

YellowstoneRhyolite Obsidian,YRO

0 - 12.8
17 - 25.5

2.19
2.77

0.50
0.76

7.9
3.2

Hawaiian Rhyodacite,HR-1

0 - 8.5
12.8- 25.5

2.36
2.75

0.55
0.74

11.1
5.3

Crater lake Andesite, VC-4W

0 - 8.5
12.8 - 25.5

3.00
3.82

0.78
1.17

17.9
3.3

Hawaiin Tholeiite

0 - 4.3
8.5 - 25.5

5.05
5.33

1.30
1.53

4.6
-0.1

cm/mol

201

zz

.
FeMg _.~

[ FeMg
._. , .-

'
18

...- .-

.----'. , _.->('Y,?.
... -') ....

II

-.. o o o o
e / o o oo;oo o o o
14

Fet

z0

-6

-1;!

-8

Log(fOz,
MPa)

Fi&re
t.Caicutat
int
cfcct
met,
lott
as
to
of
c
c[t
concentur
versus
[o
o[
oxcn
[uS
acity
Fo
olivinc
at
14'13
K
[lII.
VcC
dott
lines
prent
sbili
rc
o[
olivine.
-2

MgO:
40ppm
N

-5'

'3c

-
-9 -7 -5 -3 -
-3 - Log
P02'
P02
inMPa

Figu
2.
Log
conductivity
versus
log
f02
for
MgO
containing
40
ppm
kl.
Solid
lines
are
total
cond
das

....

'

'

'

IVlgO:
400ppm
AI fOz=
10-'3-1
)-Pa

-3

"

-3 5

-4.5

-5

-6

, , , I , , , I , , , I , , , I , , I , , , I , , , I . , ,
5.2:

5.4

5.6

5.8

6.2:

6.4

6.6

6.8

104/T (K-1)
Figure
3. Logconductivity
versus
T'l forfo2~ l0'3 to 10-4barforMgOcontaining
400ppmAI. Solidlineistotal
conductivity,whichis the sumof ionicconductivity(dashed-dotline) andthe electronicconductivity(dashedline) [54,
55].

-2.5

San Carlos

Olivine

El

T = 1473 K

]
.

-3

-4

-8

-7

-6

-5

-4

-3

-2

-1

Logfoz (Pa)
Figure4. Log conductivity
versuslog fo2 for SanCarlosolivine(1=o90)
illustratingthattotalconductivityis givenby the
sumof thetwo mechanisms
(dashed
lines)with differingoxygenfugacitydependences
[68].

'

'

'

'

'

''

'

'

'

'

Olivine Electrical Conductivity

60. -0,
')_

o (QFM) Fo (QFI)

._

' ..,.,..,.. FOo(FM

)

bar,
F)'....
-''.... ..
'-...
-.

FOso(IW)

F9o(FM)

' FO9o(IW)

-6

10

12

14

16

18

104/T(K-)
Figure5. Logconductivity
versus
T-1 at 1 GPaforolivines
of different
compositions.
Solidbufferassemblages
controllingfo2 are given in parentheses;
solidlines are QFM, dashedlines at IW. Data are from [7, 69]. SanCarlos
olivineat 1 bar(self-buffered
at QFM) is shownfor comparison.
[68].
I

Electrical Conductivity of Some Halides

NaBr

-2

LiCI

KCI, RbCI

CI

-4
NaCI

-6
TICI

-8

o.s

.5

z.5

3.s

103/T(K-)
Figure
6. Logconductivity
versus
T'1forsome
halides.
Datafrom[28,33].Thelowtemperature
conductivity
ofNaCI
andNaBr is impuritycontrolled.Conductivities
for KCI andRbCl coincide.

-1

Felds'par
aridFelcspathid'

'

'

'

Electrical
Conductivity
at.)

-2

-;

NaAISiO
4
NaAISi30
a
NaAISi308
(nat.)
CaAIzSi
z 08

-3

Adularia (nat.)

10

12

3S

104/T (K )
Figure
7. Logconductivity
versus
T'1forfeldspars
andfeldpathoids.
Alllinesrefertointrinsic
regime.
Lines
labeled
by
formulaonly aresyntheticsamples;thoselabeled'nat'arenaturalsamples.Datafrom [34, 35].

10
8

....
I ....
I ....
I ....
I ' ' ' ' I ....
Conductivity of Some Binary Oxides
-

-Fe

0.95

I ....

Mgo.a3Feo.70
(Q.FM)
CaO

cr

-4

__1 -6
-8

[' , , , , I ....
5

I ....

I [ , a , I , , , I , , , , I , , , ,

10

11

1;>

104/T (K )
Figure
8. Logconductivity
versus
T'1forsome
binary
oxides.
Datafrom[6,61,63,70]. Oxygen
buffers
areshown
in
parentheses
whereappropriate.

206

ELECTRICAL

PROPERTIES OF MINERALS

10)kba

'

30 kbar

lOO
10 kbar

10'2

10-4

EquilibriumLine
Solid-Liquid
' kba
Saturation

Line

10-6

0.5

1.0

Density(g cm-3)
Figure9. Highpressure
electrical
conductivity
of supercritical
H20 versus
density
[13].

Acknowledgements.We thank Lee Hirsch, Jeff Roberts,Tom

for errorsrestswith the authors.This work was supported

by

Shankland,
andAI Dubafor helpfulreviews.Theresponsibility

the National

Science Foundation.

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Viscosity and Anelasticity of Melts.

Donald B. Dingwell

1.

DEFINITIONS

viscosity to elastic modulus yields a quantity in units of

time.

A Newtonian

This ratio

fluid is one for which a linear relation exists

between stressand the spatial variation of velocity. The

viscosityof a Newtonian material is defined as the ratio of

(4)

stress to strain rate

is the Maxwell relaxation time [24]. This relaxation time

(1)

In contrast, the elastic modulus of a Hookean elastic

material is defined as the ratio of stress to strain

(2)

As is the casefor elastic moduli, we can, for an isotropic

medium like a silicate melt, speak of two componentsof
viscosity,a volume(rlv) and a shear(rls) component.The
combination of volume and shear viscosity yields a
longitudinalviscosity,(rls)

q= v + 4 qs
3

(3)

A comparison of longitudinal and shear viscosities

illustratesthat volume and shearviscositiesare subequalat

very low strains[9] (seeFigure 1). The ratio of Newtonian

D. B. Dingwell, BayerischesGeoint., University Bayreuth,

Posffach101251, D 8580 Bayreuth, Germany

is a convenient approximation to the timescale of

deformation where the transition from purely viscous
behavior to purely elastic behavior occurs. The purely
viscous responseof a silicate melt is termed "liquid"
behavior whereas the purely elastic response is termed
"glassy"behavior.The term silicatemelt is usedto describe
molten silicates quite generally, regardless of their
rheology.Even for the simplecaseof a Maxwell body, the
changefrom liquid to glassybehaviordoesnot occur as a
sharp transition but rather describes a region of mixed
liquid-like and solid-like behavior- a region of viscoelasticity. Deformation experiments performed in the
viscoelastic region contain three distinct time-resolved
components of deformation, instantaneousrecoverable,
delayedrecoverableand delayednon-recoverable.
Figure 2
illustrates these components for a creep experiment.
Viscousflow is the delayednon-recoverable
component,the
term anelasticityrefersto the instantaneous
plusthe delayed
recoverable deformation

and the entire deformation behavior

falls underthe headingof viscoelasticity[26].

Structuralrelaxationin silicatemelts is but one example
of a relaxationmode.It canbe mechanicallyrepresented
asa
seriescombinationof viscousdashpotand elasticspring(a
Maxwell element, see Figure 3). For more complex
materials such as crystal suspensions,foams and partial

Mineral Physicsand Crystallography

A Handbook of Physical Constants

melts, several additional mechanisms of deformation are

AGU

additional

Reference

contributed

Shelf 2

Copyright1995 by the AmericanGeophysical

Union.

209

at distinct

relaxation

timescales

of deformation

via

modes within and between the added

210

>'

VISCOSITY

AND ANELASTICITY

OF MELTS

can further distinguishbetweenthe applicationof a step

function of strain and the continuousapplicationof strain
(e.g., stress relaxation versus steady-stateflow). Stress
relaxationinvolves the recordingof stressversustime as
the stressfield decaysto zeroafter the applicationof a step
functionof strain.Steady-statestrainexperimentsrecordthe
equilibrium stress sustained by the liquid due to the
constantstrain rate being applied to the sample. We can
distinguish between experimentsperformed at low total
strains such that the perturbationsfrom equilibrium are

3.0

2.0
z

o 1.0

best fit

o
o

I,

i
1.2

0.4

LOG

small and in the linear regime of stress-strainrelations.

Such measurementsprobe the responseof the system to
stresses
withoutmacroscopicrearrangements
of the phases.

I
2.0

10 SHEARVISCOSITY

In contrast

Figure 1. The relationshipbetweenlongitudinaland shear

viscositiesin silicate melts. The solid line representsthe
correlationpredictedfrom the assumptionthat volume and
shearviscositiesare equal. The dashedline is the bestfit to
the data and lies within lo of the theoretical line.

Redrawn

from Dingwell andWebb (1989).

phases (e.g., crystal-crystal interactions, bubble

deformation, matrix compaction, etc.). These relaxation
modes involve chemical and textural equilibria and thus
occur at increasinglylonger timescales(i.e., at lower rates
of deformation).As a consequence
of the multiphasenature
of flowing magma the accompanyingmechanicalmodels
become more complex, involving additional viscoelastic
elementsin the linear regime and non-lineareffectsas well.
Inherentin theexperimentalstudyof magmarheologythen,
is the experimental deformation rate or its inverse, the
experimental timescale. It is this experimental timescale
which must mostcloselymatch the naturalprocessin order
to make secureapplicationsof the rheologicalresults.
2.

CLASSES

OF

nonlinear

measurements

can deal

with

the

redistributionof phasesduringmacroscopicflow. Finally,

we candistinguishbetweentime domainexperiments
where
a stressis applied and the time variant relaxationof the
system to the new equilibrium is measured(e.g., creep
experiments)and frequency domain experimentswhere
sinusoidalvariationsof the stressfield, small in magnitude
but up to very high frequencies(from mHz to MHz), are
applied and the magnitude and phase shift of strain is
measured (e.g., torsion, ultrasonic wave attenuation).
Implicit in considerations
of rheologicalmeasurements
is
the ratio

of deformation

rate

to the relaxation

rate

of

structuralcomponentsin the material. The characteristic

strain rate of the experiment is easily defined in most
rheologicalexperiments.For example,in Figure 4, several
experimental timescales are compared with structural
relaxation

times of silicate melts. Ultrasonic

measurements

are performedon time scalesof 1-50 ns, forcedoscillation

techniquesin the rangeof 0.01-150 s and fiber elongation

EXPERIMENTS

In principle, any experiment that records strain as a

function of time and applied stresscan be used to obtain
viscosity. Viscosity experiments can be subdivided in
several ways. We can, for example, distinguish between
those in which the strain rate is controlled

and the resultant

I RECOVER^BLE

...............
.STRAIN

stressis measured(e.g., concentriccylinder) and those in

which the stress is controlled

and the resultant strain rate is

measured (e.g., fiber elongation). We can also separate

those methods that involve only shear stresses(e.g.,
concentric cylinder) from those which involve a
combination of shear and volume (compressive or
dilational) stress(e.g., beam bendingor fiber elongation).
For any given geometrythat employscontrolledstrain we

t=0

TIME

Figure 2. The instantaneous

recoverableelasticstrain,the
delayedrecoverablestrain,and the delayednon-recoverable
viscous flow occurring in a linear viscoelasticmaterial
uponapplicationof a stepfunctionin stressat time,t=0.

DINGWELL

211

imposedon an annulusof liquid filling the gap betweenan

innercylinder(or spindle)and the outer cylinder(or cup)
which usually takes the form of a cylindrical crucible.The
strain rate is delivered to the liquid by rotating either the
inner or outer cylinder. The shear stresssustainedin the
liquid is usuallyrecordedas the torqueexertedby the liquid
on the inner cylinder. The concentric cylinder method is
commonlyusedfor viscositymeasurements
in the rangeof

qL' rl

100-105
ias.Another
formof theCouette
viscometer
is

REAL

the cone-and-plategeometry. Viscometers based on the

cone-and-plategeometryhavebeenusedin bothsteadystate
(as above) and pulse strain modes. The geometry of the
cone-and-plateviscometerallowsthe preparationof starting
materialsby pre-machiningto the final form. This avoids
the need to pour or melt the silicate material into the
cylinder and to immersethe spindleinto the liquid at high
temperature.The cone-and-platemethodfindsapplicationat
lower temperatures and higher viscosities than the
concentriccylindermethod.This methodhasalsobeenused
in the investigationof the viscoelasticbehavior of silicate
meltsat/nearthe glasstransition[41].

M o, K o0,

IMA

Shearviscosities
in the range109-1014Pas canbe
Mo,Ko,Go

A'

0
LOG

UJT

Figure 3. Calculated frequencydependentbehavior of

longitudinal,volume and shearviscosities(q 1, qv, qs) and
moduli (M, K, G) of a linear viscoelastic melt with a
relaxationtime x plotted as a functionof rtrcwhere r0 is the
angular frequency of the applied sinusoidalstress. The

subscripts"0" and "oo"indicatezero frequencyand infinite

frequencyvalues. The shearrelaxationtime = q/G is for
the mechanicalmodel of a spring and dash-potin series
(i.e., a Maxwell element).

'determined
usingfiber elongationtechniques(seeFigure5).
Glassfibers with a diameter0.1-0.3 mm and lengths10-18
mm are commonly used. In a vertically mounted silica
glassdilatometerthe silica glassholder of the dilatometer
supportsthe beadedglass fiber in a fork. A secondsilica
glassrod holdsthe lower beadof the fiber in tension.The

strain-rate
rangeis machinelimitedto 10'7-10'4 s. A
tensilestress
(-107Pa)is applied
tothemeltfiberandthe
viscosityis determinedas the ratio of the applied stressto
the observed strain-rate. In this geometry the observed

viscosity,Belong,is the elongational

viscosityandis
relatedto theshearviscosity,
rls,by

Belongfrom102to 106s.Eachstructural
orphysical
component
of the system relaxes as a distinct relaxation mode at a
distinct timescale of frequency which is a function of
pressureand temperature.Frequency-dependent
or nonNewtonian effectsare seenin frequencydomaintheological
experimentswhen the measurement
timescaleapproaches
a
relaxation

{:

(5)

[11, 15, 17] Althoughinfinite shearstrainsare possible

in a melt, volumestrainmustbe limited in magnitude[25].
The volume viscosityof a melt, therefore, approachesan
infinite value with increasingtime and Equation5 becomes

mode timescale.

T1elong=
3 rl,
3.

3rlv+ rls

(6)

GEOMETRIES

The most widely used example of controlledstrain rate

and measuredstressis the rotational(Couette)method (see
Figure 5). Ryan and Blevins [34] providea descriptionof
the physics of Couette viscometry. The strain rate is

[11, 25] for times greater than the relaxation time of the
melt. Equation6 is known as Trouton'srule.

Absolute
shearviscosities
in therange109- 1011pa
s
can be determinedusingmicropenetration
techniques(see
Figure 5). This involves determiningthe rate at which an

212 VISCOSITY AND ANELASTICITY OF MELTS

Specimen deformation rates are measuredwith a linear

VOLUME
RELAXATION
//

voltage
displacement
transducer.
Fora cylindrical
specimen
of anythickness
theshear
viscosity
canbedetermined
by

CONCENTRIC
CYLINDER
q4t'
(DENSlFIED
SIO
2)
/ )FIBER
ELONGAT;N
VISCOMETRY

SCANN,N

.lC

CAtO.,METRY rl.(Pa s) =

NORMAL
TORQUE

2mgh 5
3V 15h/St
(2rh3+ V)

(8)

TORSION

for the appliedmass,m (kg), the acceleration

due to

_ -2

gravity,
g (m2/s),
thevolume,
V (m3)ofthematerial,
the

'

height,h (m) of thecylinder,andtime,t (s) [12, 16]for the

-4,

case in which the surfacearea of contact between the melt

andtheparallelplatesremainsconstant
andthecylinder
bulgeswithincreasing
deformation.
Thisis the"no-slip"

(. -6

UL'rRASONICS-..

condition. For the case in which the surfacearea between

SHOCK

thecylinderandtheplateincreases
with deformation
andthe
cylinderdoesnotbulgetheviscosityis

WAVE

AN36DI64

qs (Pa s) =

mgh2
3V 15h/St

10,000/T(K)

Figure 4. The liquid-glasstransitionas a function of

temperature plotted for several silicate melts calculated

from Equation4 togetherwith the timescaleson which a

(9)

Thisis the "perfect

slip"condition.
Theparallelplate
methodinvolvestheuniaxialdeformation
of a cylinder
of
meltateitherconstant
strainrate[18]or constant
load[40].
Thecounterbalanced
sphere
andfallingsphere
viscometers
(seeFigure5) arebasedon Stokeslaw.Riebling[30]has

rangeof experimental
measurements
areperformed.The
describeda counterbalanced
sphereviscometerwhichhe
relaxationtimesrelatingto the variousexperimental subsequently
used
inviscosity
determinations
intheB203techniques
arediscussed
in DingwellandWebb(1989).
SiO2 [31]andNa20-A1203-SiO
2 [32] systems.
Falling
RedrawnfromDingwellandWebb(1989).

sphere
viscometry
hasbeenemployed
at 1 atmandathigh

indenter under a fixed load moves into the melt surface.

High accuracy(+0.1 log10Pa s) is obtained

by usinga
silicaglasssampleholderandpushrodfor temperatures
under1000C.Theindentermaybeconical,cylindricalor
spherical
in shape[6]. For thecasein whicha spherical
indenteris used [8] the absoluteshearviscosityis
determined from

viscosity.
Alternatively
thefallingsphere
method
maybe
usedwith inputvaluesof densityprovided
thedensity
contrastbetweenmelt and sphereis relativelylarge.
Maximizing the densitycontrastreduceserrorsassociated

with the estimation

of meltdensity.Errorsin density
contrastcan be reducedbelow the uncertaintiesinherentin

theothervariables
affecting
viscosity
determination.
Very
highpressure
measurements
of viscosity
havebeenmade

qs(Pas)= 0.1875P t
r0.51] .5

pressures
[13, 34, 36]. The fallingsphere
method
maybe
usedfor the simultaneous
determination
of densityand

(7)

[19] by imagingthefallingspherein realtimeusinga

synchrotron
radiation
source
anda MAX 80 superpress.
This method extends the lower limit of measurable

[28, 44] for theradiusof thesphere,

r (m), theapplied
force,P (N), indentdistance
1(m) andtime,t (s),(t=0 and1
=0 uponapplicationof the force).

Theshearviscosity
of largecylinders
of meltor partially
moltenmaterialcan be determinedby deformingthe
cylinderbetweenparallelplatesmovingperpendicular
to
theirplanes.
Absolute
viscosities
in therange104- 108Pa

viscosity
usingthefallingsphere
method
at highpressure

to 10-3 Pa s.

The shearand longitudinalviscositiesof a melt can be

determined
fromthevelocity,
c(m),andattenuation,
of a shearor longitudinal
wavetravelling
through
themelt;
wherethe amplitudeof thewaveis

s [12, 16] and107- 10TMPa s [2] canbe determined. A(to,t)= Aoexp'axexpim-x/c

(10)

DINGWELL

213

the temperature(1000-1500C) and frequency(3-22 MHz)

conditions required to observe the relaxed (frequencyindependent)longitudinal viscosityof most silicate melts.
In cases(basaltmelts [22], basalticandesite[35], synthetic
silicatemelts [33]) wherethe experimentalconditionswere
approaching
the relaxationfrequencyof themelt,frequencydependenceof the longitudinalviscosityhasbeenobserved.
In studieswherethe frequencyof the appliedsignalhasbeen
greater than that of the relaxation frequencyof the melt

shearwave propagation
hasbeenobserved(B20 3 [43],
Na20-B203-SiO2 [23], Na2Si205 [46]).
4.

TEMPERATURE

DEPENDENCE

OF

VISCOSITY

Figure5. Methodsof determiningviscosity: (a) falling

sphere(b) restrainedsphere(c) rotationalviscometer(d)
sinkpointmeasurement
(e) free fiber elongation(f) loaded
fiber elongation(g) beambending(h) micropenetration
(i)

The temperature-dependence
of silicateliquidviscosityhas
been describedusing a numberof different equations.The
simplest form, often valid for restricted temperature
intervals, is a linear dependence of the logarithm of
viscosity on reciprocal temperature, i.e. the Arrhenius

torsionof a cylinder. Redrawnfrom Zarzicki (1991).

equation

l'og10q
= log0q0+ 2.303 E
RT

for timet anddistance

x [27]. Smallstrains(<10-6) are

(14)

usedand linear stress-straintheory is applicable.The real

component
of the modulus,M'(to) = pc2, and the
imaginary component of the modulus, M'(co)=
M'(co)ccz/f (where the quality factor Q = M'(co)iM"(to) =
f/ct [27]. Viscosities are calculated for time, t and
distance,x [27]. The shearviscositycan be calculatedfrom
the velocity and attenuation data in that q*(co)= M
*(re)lira, or

M*(ro) = M'(ro) + iM"(co) = M"(m) + iq'(m)-co =

q"(co)-r0 + iq'(r0)-co

(11)

andthereal component
of thefrequencydependent
viscosity
is

q'(co)
- 2pc3t
to2

of the shear wave.

SiO2,however,sufficientdatanowexistto demonstrate
that, in general, silicate liquids exhibit non-Ahrrenian
viscosity temperature relationships. The degree of
"curvature"of the viscositytemperaturerelationshipplotted
as log viscosity versus reciprocal absolute temperature
varies greatly with chemical composition(see [29] for a
summary). The temperature-dependence
of non-Arrhenian
datacanbereproduced
by addinga parameterto Equation14
to yield

(12)

The shearviscositycan be calculatedfrom the velocity

and attenuation

where q is the viscosityat temperature,T, and q0 and E

are termed the frequencyor pre-exponentialfactor and the
activation energy, respectively. Quite often the data
obtained by a single method of investigation over a
restrictedtemperatureor viscosityintervalare adequately
describedby Equation 14. With the possibleexceptionof

The data from

log0q =1og0q0 + 2.303

R(T-To)

( 15)

the

propagatinglongitudinalwave resultsin the determination

of the longitudinal viscosity from which the volume
viscositycan be calculated

where To is a constant.This empiricaldescriptionof the

temperature-dependence
of liquid viscosity is called the
Fulcheror TVF (Tamann-Vogel-Fulcher)
equation[14, 15,
42, 45].

ri*l(t0) = q*k(t0) + 4 q*s(co)/3 .

(13)

Most ultrasonic studies of silicate melts are conducted at

Angell [1] describesthe concept of strong and fragile

liquids basedon the extentof nonArrheniantemperaturedependenceof viscosity.This considerationis extremely

214

VISCOSITY

AND

ANELASTICITY

OF MELTS

investigated the pressure-dependenceof silicate melt

viscosities across compositional joins exhibiting both
negative and positive pressuredependenceof viscosity.

Kushiro[21] investigated
liquidsalongtheSiO2-CaAI204

join observinga linearpressuredependence

of viscositythat

changed
froma negativevalueat molefractionCaAI204=
0.15 and 0.2 throughpressureinvarianceat CaA1204 =
0.33 to a positivepressuredependence
at CaAI204.

NOAI$308

0tl 5,206 ( 350C )

Brearley et al. [5] alsoobserveda transitionfrom positive

to negativepressuredependence
of viscosityalongthejoin

_O

0 MgO55,0 (1300C)

_o

Andesle

CaMgSi206-NaA1Si308.
Volatile-bearing
silicateliquids
have also been studied at high pressure [4, 7, 38, 49].

Figure7 summarizes
theeffectsof H20 andF20.1 on the
viscosity
of NaA1Si308liquid.

(1350*C)

No20 3S02 (1175*C)

J

Abyssal Olvne Tholeile

livine

Tholeile

6.

(1400'C)

lO

2o

Pressure

(kbor)

SCHEMES

{1300*C)

CALCULATION

A number of empirical calculation schemes for the

viscosity of silicate glass melts have been around for
severaldecades[37] but calculationmethodsfor geological
melts are a more recent phenomenon.Bottinga and Weill
[3] produceda methodfor the estimationof melt viscosities

8o

4o

Figure 6. Viscosity as a function of pressurefor various

silicate melts. Redrawn from Scarfe et al. (1989).

Albite-H20-F20-

7.Skbar

important where extrapolations of viscosity to lower

temperaturesare performed.In general,silicate melts are
strongliquids in comparisonwith nonsilicateliquids. The
extent of nonArrhenian temperature dependence varies

greatly with composition.DecreasingSiO2 content

generally leads to less Arrhenian, more fragile, behavior.
Additionally the increaseof pressurelikely leads to more
fragile behavior.
5.

PRESSURE

DEPENDENCE

OF

VISCOSITY

The falling spheremethodhas been usedto study high

pressureviscositiesof naturaland syntheticsilicateliquids
[ 10, 13, 20]. The pressure-dependence
of anhydroussilicate
liquids has been summarizedby Scarfeet al. [36]. Figure 6
illustrates the pressure dependence of silicate liquid
viscosities

to 2 GPa.

The

viscosities

of

silicate

and

aluminosilicate melt compositions with relatively low

calculated NBO/T (ratio of nonbridging oxygens to
tetrahedrally coordinated cations) values decrease with
increasing pressure. In contrast the viscosities of some
silicate liquids increasewith pressure.Two studieshave

1
6

10 4/T (K)

Figure 7. Viscositiesof melts in the systemNaA1Si308H20-F20_l with (X/X+O) = 0.1 and 0.2 plotted versus
reciprocal temperature(X = F,OH).
Redrawn from
Dingwell (1987).

DINGWELL

at I atm pressurethat was basedon the literature data for

synthetic melt compositions.Shaw [39] included water in
his

calculation

model

and

with

that

allowed

for

T(C)

N-zSi40,
z

the

calculationof granitic melt viscositiesat low pressures.No

intrinsicpressuredependence
of viscositywasincluded.
7.

NON-NEWTONIAN

MELT

The Newtonian viscosity of silicate melts is a low strain

rate limiting case.With increasingstrainrate the viscosity
of silicatemelts eventuallybecomesstrainrate dependentas
the inverseof the strain rate approachesthe relaxationtime
of the silicatemelt structure.This is the direct consequence
mode due to structural relaxation

4?4

tJ

4Z9

482

493
504

506

--

0.0

--

-0.5

--

RHEOLOGY

--:-1.5

-1.0

NaAISiO.
CaMgSIO.

-1.5

in silicate

melts. All available evidence points to a single relaxation

mode being responsiblefor the onset of non-Newtonian

1.0

:.-y.

of the relaxation

215

-4

-3

-2

-1

Figure 9. (a) A reducedplot of shearviscosityrelative to

Newtonian

versus strain-rate normalized onto the relaxation

strain-rate for Na2Si409 at temperaturesfrom 474 to

506C. (b) A reduced plot of shear viscosity versus
normalized strain-rate for a range of silicate melt
compositions.These reducedplots basedon Equation4
remove the temperature-and composition-dependence
of

12.0
"1

LGM
I 1.6

the onset of non-Newtonian viscosity of silicate melts.

Redram from Webb and Dingwell (1990a).

12.0
CLA

rheology in silicate melts. The onset of non-Newtonian

rheology has been extensivelyinvestigated[47, 48]. The
onsetof non-Newtonianrheologyfor four geologicalmelts
(a rhyolite, an andesite, a basalt and a nephelinite) is
illustrated in Figure 8. The low-strain-rate limit of

11.8
HTB

11.4

Newtonian
viscosity
is seenbelowstrainratesof 10-4
12.0

+++-Vvvw

--

v.

NEP

I 1.6
_

%
_

11.2

-5

-4

-3

logto STRAIN RATE

-2

-1

(s-')

Figure 8. Shear viscosities of Little Glass Mountain

rhyolite (LGM), Crater Lake andesite (CLA), Hawaiian
tholeiite (HTB) and nephelinite(NEP) compositionmelts

asa functionof appliedstrain-rate.With increasingstrainrate the onset of non-Newtonian(strain-ratedependent)

behavior is observed.

The arrows indicate the calculated

relaxation strain-rate for these melts.

andDingwell (1990b).

Redrawn from Webb

whereas shear thinning (a decrease in viscosity with

increasingshearrate) setsin at higherstrainrate. The onset
of non-Newtonianrheologyoccursapproximately3 1og10
units of time "above"

the relaxation

time of each silicate

melt approximated from the Maxwell relation. A

normalization of the data for several compositionsand at
several temperaturesis illustrated in Figure 9 where the
viscosities are normalized to the low-strain-rate limiting
value of Newtonian viscosity and the strain rate of the
experimentis normalizedto the relaxation frequency(the
inverse of the relaxation time), calculated from the Maxwell

relation for each melt. The composition-dependence

of the
onset of non-Newtonian rheology can be removed in large
part through this normalization. The success of this
normalization

indicates

that the onset of non-Newtonian

melt rheology in silicate melts can be easily estimated

using values for the NewtonJanviscosity and the shear
modulus.

216

VISCOSITY

AND

ANELASTICITY

OF MELTS

REFERENCES

1. Angell, C.A., Strong and fragile

liquids, in Relaxations in Complex
Systems edited by K.L. Ngai and
G.B. Wright. Naval Research Lab.,
Arlington,
VA, 3-11, 345pp.,
1984.

2.

Bagdassarov, N.S. and D.B. Dingwell, Rheological investigation of

vesicular rhyolite, J. Volc. Geotherm. Res., 50, 307-322,

1992.

3.

Bottinga, Y. and D.F. Weill, The

viscosity of magmatic silicate
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Am. J. Sci., 277, 438-475, 1972.
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effect of CO2 on the viscositiesof
silicate liquids at high pressures,
Geochim. Cosmochim. Acta, 53,
2609-2616,

1989.

8.

Geophy. Res., 81, 6347-6350,

1976.
21. Kushiro, I., Changes in viscosity

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Carnegie Inst. Wash. Yearb., 76,
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system SiO2-CaA1204, Carnegie
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203-216, 1986.
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1, 423-433,

1987.

1925a.

15. Fulcher, G.S., Analysis of recent

measurements of the viscosity of
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16. Gent, A.N. Theory of the parallel
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Ultrasonic Waves. Academic Press,
535pp., 1959.
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with

different

structural

Dingwell, D.B., R. Knoche , S.L.

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Webb,

1-6, 1989.

and M.

Pichavant,

The

effect of B20 3 on the viscosity of

haplogranitic liquids, Am Mineral,
77, 467-471,

1992.

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Structural relaxation in silicate
melts and non-Newtonian melt
rheology in geological processes,

Phys. Chem. Mineral., 16, 508516, 1989.

10. Dunn, T. and C.M. Scarfe, Varia-

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T. Kato, O. Shimomura and S.
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Manghnani and S. Syono , American Geophysical Union, Washington, DC, 195-200, 1987.

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andstructure
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composition at high pressures,J.

Katahara

and

G.R.

Olhoeft,

Ultrasonic velocity and attenuation

in basalt melt, Anelasticity in the
Earth Geodynamics Series, Volume
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1978.

28. Pocklington, H.C., Rough measurement of high viscosities, Proc.

Cambridge Philos. Soc., 36, 507508, 1940.
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Cosmochim.

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1984.

Riebling, E.F., An improved

counterbalanced sphere viscometer
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1963.

31. Riebling, E.F., Viscosities in the

B203-SIO2
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1964.

32. Riebling, E.F., Structureof sodium

aluminosilicate melts containing at

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Chem. Phys., 44, 2857-2865,
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33. Rivers,

M.L.

and I.S.E.

Carmi-

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9247-9270,

Geophys. Res., 92,

1987.

34. Ryan, M.P. and J.Y.K. Blevins,

The viscosity of synthetic and
natural silicate melts and glassesat

high tetnperaturesand at I bar

(105Pa) pressure
and at higher
pressures,
U.S.Geol.Surv.Bull.,
17864, 563pp., 1987.
35. Sato, H. and M.H. Manghnani,
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complexmodulusof basaltmelt,
Phys. Earth Planet. lnt., 41, 1833, 1985.
36. Scarfe,C.M., B.O. MysenandD.

Shaw,

H.R.,

Obsidian-H20

6337-6343, 1963.
39. Shaw, H.R., Viscosities of magmatic silicate liquids: an empirical

methodof prediction,Am. J. Sci.,

272, 870-889, 1972.
40. Shiraishi, Y., L. Granasy, Y.
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and

E.

Matsubara,

2439-2442, 1963.
Vogel, H., Das Temperaturabhingigkeitsgesetzder Viskositit
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645-646, 1921.
46. Webb,S.L., Shear and volume
relaxation in Na2Si205, Am. Mineral., 76, 451-456, 1991.
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Dingwell,

, 95, 1031-1038, 1987.

Chem. Mineral.,

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125-132,

41. Simmons,
J.H.,R. OchoaandK.D.
1990a.
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Non-Newtonian
viscous 48. Webb,S.L. and D.B. Dingwell,
flow in soda-lime-silicaglass at
forming and annealing temperatures,J. Non-Cryst. Solid., 105,
313-322, 1988.

Non-Newtonian theology of igneous melts at high stresses and

strain-rates: experimental results
for rhyolite, andesire, basalt and
nephelinite, J Geophys. Res., 95,

42. Tamann, G. and W. Hesse,Die

15695-15701,
1990b
Abhingigkeitder Viskosit[it yon
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Flfissigkeiten, Z. anorg. allg.
effect of H20 and CO2 on the

Geochemical
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Macedo, Viscous relaxationand

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non-Arrhenius
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Springer,Berlin, 1988.

45.

The onsetof non-Newtonianrheo!ogy of silicate melts, Phys.

Chem.,156, 245-257,1926.
43. Tauke,J., T.A. LitovitzandP.B.

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407pp.

organic glass, J. Phys. Chem., 67,

Viscosity of glassyNa20-B20 3SiO2 system,J. Non-Cryst.Solid.

Virgo,Pressure
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37.Scholze,
H.,Glas:Natur,Struktur

Viscoelasticpropertiesof a simple

viscosities at 1000 and 2000 bars

in the temperature range 700 to

900C, J. Geophy. Res. , 68,

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viscosity
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pressures,
J. Geophy.Res.,95,
15683-15693,1990.

50. Zarzicki,J., Glassesand the

J. Am.Cer.Soc.,51, 158-163,

vitreous
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1968.

versity
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505pp.,
1991.

44. Tobolsky,A.V. and R.B. Taylor,

Viscosity of the Outer Core

R. A. Secco

variations, and polar motion can all be accurately

measured,the outercore viscosityestimatesinferredfrom

Estimates of outer core viscosity span 14 orders of

magnitude. This wide range of valuesmay be partially

explainedby the differencein type of viscosity,molecular
viscosity(a rheologicalpropertyof the material)vis-h-vis
a modified or eddy viscosity (a property of the motion),
inferred

from

the various

observational

thesemeasurements,
rangingfrom 10- to 10poises,
suffer from long observationtimes which can introduce
largeuncertainties
from additionalenergysourcesand/or
sinks affecting the observedphenomenon. It must be

and theoretical

noted, however, that time independentfactors that affect

seismicwave amplitudessuch as scattering,geometrical

methods[24]. The motion associatedwith eddyviscosity

impliesthe possibilityof non-viscousdissipativemechanisms such as ohmic dissipation. Molecular viscosity is
separatedinto nearlyequalcomponentsof shearviscosity,
rl, and bulk or volume viscosity,rlv, dependingon the
type of strain involved [14,15]. rl is a measure of
resistanceto isochoricflow in a shearfield whereasXlvis
a measure of resistance to volumetric

spreading,radial and lateral inhomogeneitieswill be

embodied in derived attenuation values.

Confirmation

of

any observationof innercoreoscillationhasnot yet been

madeand thereforeany so-derivedviscosityestimatefrom
geodeticobservationor theory must be admittedwith
caution. Other methodsof outer core viscosityestimation
are from extrapolationslaunchedfrom experimentaldata
at low (relative to core) pressuresand temperaturesusing
various theoriesof liquid metals and from geomagnetic

flow in a 3-dimensi-

onal compressionalfield. In cases where outer core

viscosity estimates are based on observationsof the
attenuationof longitudinal waves, both rl and fly play
significant roles but only x!is importantfor damping
wholeEarth torsionalmodeoscillationandflyfor damping

field observations

at Earth's surface.

Both of these suffer

from large extrapolationsand from the lack of any

experimentalviscositydata on liquid Fe at pressuresof
even a few kilobars. Most of the experimentaldata on
liquid Fe and liquid Fe-Ni, Fe-S, Fe-O and Fe-Si alloysis
found in the metallurgical literature and they are all

radial mode oscillation [4].

The majority of estimatesof outer core viscosity is

basedon wholeEarthgeodeticandseismological
observations. In terms of the observationtimes required by a
particular method, studiesof p-wave attenuationbenefit
from their short periods(seconds)and all 7 studiescited
in Table 2 give upperboundviscosityvalueswithin a very

restrictedto measurementsat a pressureof 1 atm.

The data and references are presented in 9 tables.
Tables 1 and 2 are viscosityestimatesbasedon geodetic

confinedrangeof 108-109
poises. While long period

and seismologicalstudies,respectively. Tables 3 and 4

are viscosityestimatesfrom geomagneticand liquidmetal
theory studies,respectively. A brief descriptionof the

(minutesto years)geodeticphenomena,suchas the radial

and torsional modes of free oscillation,length of day

method

used for each estimate

or measurement

is also

Ontario, London, Canada N6A 5B7

given. Valuesof kinematicviscosity,v, reportedin some

referenceshave been convertedto dynamic viscosity,

Mineral Physicsand Crystallography

A Handbookof PhysicalConstants

The datain Tables 1-4 are graphicallypresentedin Figure

1. Table 5 containsexperimentalshearviscositydatafor

R. A. Sccco,Departmentof Geophysics,
Universityof Western

by v = Xl/p,usinga valueof 10 g/cm3for p, thedensity.

AGU

Reference

Shelf 2

Copyright1995 by the AmericanGeophysical

Union.

218

SECCO

219

TABLE 1. Dynamic Viscosity Estimatesof Outer Core from Geodetic Studies

Reference

DynamicViscosity

Methodt{

(Poises)

Sato and Espinosa(1967)

0.35 - 4.7 x 10

"Torsional

free oscillations

Verhoogen(1974)

2.6 x 10-!

Chandler

wobble

Yatskiv and Sasao (1975)

5X 109

"Chandler

wobble

Anderson (1980)

5 x 102

Dampingof free oscillationradial modes

Molodenskiy (1981 )

_<107

"Forcednutation of the Earth (value for MCB)

Molodenskiy (1981)

< lO s

Tidalvariationsin the lengthof day

Molodenskiy(1981 )

2 x 10 I

"Chandler

Gwinn et al (1986)

<5.4 x 104

Retrograde annual Earth nutation

measurements(value for MCB)

Neuberget al (1990)

<3.3 x 105

Viscousdamping only for nearly diurnal free

wobble (tidal measurements)

Smylie (1992)

7.7 x l0 s

Damping of inner core translational modes

(superconductinggravimeterdata)

Bondi and Lyttleton (1948)

<1012

'Theoretically
requiredfor seculardeceleration
of

of whole Earth

wobble
VLBI

core by viscouscoupling
Stewartson and Roberts (1963)

<10 9

tTheoryof rotatingfluids

Toomre (1966)

>6 x 105

'Theoreticallyrequiredfor steadyprecession
by
core/mantleviscouscoupling

Won and Kuo (1973)

> 10-

'Theoreticalevaluationof decay time of inner

core oscillation (value for ICB)

Toomre ( 1974)

<10 6

'18.6 year principal core nutation (value for

MCB)

Aidridge and Lumb (1987)

theory
observation

2.9 x 107

'Decayof inertial wavesin outercore

220

VISCOSITY

OF THE OUTER

CORE

TABLE 2. DynamicViscosityEstimatesof OuterCore From SeismologicalStudies

Reference

Dynamic Viscosity

Method

(Poises)

5 x 108

Jeffreys (1959)

Attenuationof p-waves

8.6 x 10 2

Sato and Espinosa(1965, 1967)

Multiplyreflecteds-wavesat mantle/core
boundary.

108

Sacks (1970)

Attenuationof p-waves

3-7 x 10

Suzuki and Sato (1970)

Attenuation

of s-waves

Buchbinder (1971)

2x

108

Attenuationof p-waves

Adams (1972)

4x

108

Attenuationof p-waves

Qamar and Eisenberg (1974)

1-2 x 108

Attenuationof p-waves

<<10

Attenuationof p-waves

Zharkhov and Trubitsyn (1978)

1.4 x 109

Anderson and Hart (1978)

Attenuationof body waves and checkedagainst

radial mode Q data

TABLE 3. Dynamic ViscosityEstimatesof Outer Core from GeomagnetismStudies

Reference

Dynamic Viscosity

Method

(Poises)

Bullard (1949)

10-2

Magnetic dampingof core fluid motions

Hide (1971 )

107

Magnetohydrodynamicinteractionsbetweenfluid motions
and bumps on MCB

Schloessin and Jacobs (1980)

2x 105

Decayof free dynamoactionduringpolaritytransitions

Officer (1986)

2x 108

Value predictscorrectorderof magnitudeof externalfield

and westward

drift

SECCO

221

TABLE 4. Dynamic Viscosity Estimatesof Outer Core from Theories of Liquid Metals

Reference

Dynamic Viscosity

Method

(Poises)

Bullard (1949)
Miki (1952)

l0 -2

From experimentalvaluesfor liquid metalsat STP

10-2_ 10'j

Quantumstatistical
thermodynamics
of liquidmetals

5X 102

Backus (1968)

From experimentalvaluesof liquid Hg at l0 kb

and 400K

3.7-18.5 x 10-2

Gans (1972)

Andfade formula for melting point viscosity

(value for ICB)

1-5 x 10-I

Leppaluoto (1972)

>10

Bukowinski and Knopoff (1976)

For a pure Fe outer core, from significant

structuretheory of liquids (value for MCB)
For a pure Fe outer core, from band structure
calculations

Schloessin and Jacobs (1980)

3.4 x 102

From experimental values for liquid Fe and

Andrade'spressureeffect on viscosity

Anderson (1980)

10 - 104

Two structurestate theory extrapolatedto core

pressures

3x

Pokier (1988)

10-2

Thermodynamicscalingrelationbetweenmelting
temperature and viscosity and diffusivity of
metals

2.5 x 10-2

Svendsen et al (1989)

Liquid statemodelfitted to highpressuremelting

data on Fe

18

OUTER

CORE

VISCOSITY

12

.m

.-

SEISMOLOGY

pure liquid Fe and Tables 6-9 containexperimentalshear

viscosity data for liquid Fe alloys, all measuredby the
oscillatingcruciblemethod. The viscositiesin Tables6-9
are presentedas either dynamic or kinematic viscosities,
as in the reference,becauseof insufficient densitydata for
many of the alloy compositions.

E
>,

GEODESY

GEOMAGNETISMTHEORY
-6

Method

Fig.1. The commonlogarithmof dynamicviscosity(poises)

of the outercoreplottedas a functionof methodusedfor its
determination.

222

VISCOSITY

OF THE

OUTER

CORE

TABLE 5. ExperimentalData of ShearDynamicViscosity(centipoises)of Liquid Fe at 1 atto

Reference

1536

1550

1600

1650

1700

1750

1800

1850

Kitchener(1955)

7.60e

6.79i

6.41

5.89i

5.70

5.48i

5.31

5.22

Thiele (1958)

4.7

4.6

4.2

3.9

3.7

3.4

Hoffman (1962)

5.42

5.30

4.90

4.55

3.98

Cavalier (1963)

4.95

4.87

4.54

4.30

4.10

3.92

Lucas (1964)

5.03

4.93

4.58

4.28

4.00

3.76

5.44 i

5.01 i

4.69 i

4.44

5.60

5.01

Barfield

T(C)

and

5.91

Vostryakov et al (1964)
5.54

Nakanishi et al (1967)

Kaplun et al (1974)
Arkharov et al (1978)

5.96
5.03

Steinberg et al (1981)

interpolated
extrapolated

TABLE 6. ExperimentalData of ShearViscosityof Liquid Fe-Ni Alloys at 1 atto

Reference

Adachi

(1973)

Composition
wt% Ni

Temperature
(C)

Viscosity
Kinematic
Dynamic
(centipoises)
(millistokes)

et al

4.9

9.7

1516

6.11

1550

5.91

1604

5.69

1633

5.54

1665

5.36

1502

6.02

1513

5.95

1550

5.72

1596

5.43

1652

5.04

1693

4.81

SECCO

TABLE 6 (continued)

Composition

Reference

wt%

Ni

CC)

Viscosity
Kinematic
Dynamic
(millistokes)
(centipoises)

1471

28.6

Arkharov

Temperature

6.15

1519

5.62

1545

5.37

1581

5.11

1615

4.91

et al
0.52

(1978)

1600

8.48

1.04

8.28

1.49

8.15

1.99

8.13

2.46

7.98

TABLE 7. ExperimentalData of ShearViscosityof Liquid Fe-S Alloys at 1 atm

Reference

Barfield

Composition
wt% S

Temperature
, (C)

Viscosity
Dynamic
Kinematic
(centipoises)
(millistokes)

and

Kitchener (1955)

1.16

(+0.02 wt%C)

Vostryakov et al
(1964)

0.39

1529

7.00

1600

6.45

1700

5.84

1800

5.41

1600

6.00

4.70

6.61

8.51

6.41

18.56

3.43

223

224

VISCOSITY

OF THE

OUTER

CORE

TABLE 8. ExperimentalData of ShearDynamic Viscosity of Liquid Fe-O Alloys at 1 atm

Reference

Composition
wt% O

Nakanishi

Temperature
(C)

Dynamic Viscosity
(centipoises)

et al

(1967)

0.012

1600

5.02

0.046

5.43

0.071

5.40

0.072

5.39

TABLE 9. ExperimentalData of ShearViscosityof Liquid Fe-Si Alloys at 1 atm

Reference

Romanov

and

Composition
wt% Si

0.1

Kochegarov (1964)

0.6

2.0

5.0

Temperature
(C)

1540

Viscosity
Dynamic
Kinematic
(centipoises)
(millistokes)

9.62

1580

8.72

1621

7.78

1668

7.55

1743

7.04

1782

6.66

1806

6.61

1549

7.70

1605

6.92

1642

6.83

1707

6.36

1756

6.15

1508

7.39

1553

6.90

1592

6.46

1654

5.85

1712

5.69

1758

5.49

1454

8.14

1508

6.78

1575

6.02

1627

5.61

1677

5.40

1716

5.37

SECCO

225

TABLE 9 (continued)

'Viscosity

Temperature
CC)

Conposition

Reference

wt% Si

Dynamic
(centipoises)

Nakanishi et al (1967)

0.9
2.9

1615

4.13
3.54

Kaplunet al (1979)

1.0

1550

5.41

2.0

1550

5.29

1600

4.89

1500

5.74

3.0

4.5

6.0

1550

5.18

1600

4.84

1500

5.51

1550
1600

4.72

Kinematic
(millistokes)

5.05

1500

5.04

1550

4.65

1600

4.35

Acknowledgements.
I gratefully
acknowledge
helpful
discussions
withH.H.Schloessin
andL. Mansinha,
comments

in reviews
byD.L.Anderson
andananonymous
reviewer,
aswellasfinancial
support
by theNatural
Sciences
and
Engineering
Research
Councilof Canada.

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Core and Mantle during the 26,000 Year
Precession,in: The Earth-Moon System,
ed.: B.G. Marsden and A.G.W. Cameron,
Plenum Press, New York, 33-45, 1966.

44. Toorare, A. On the "Nearly Diurnal

Wobble" of the Earth, Geophys.J.Rstr.
Soc., 38, 335-348, 1974.

45. Verhoogen, J. Chandler Wobble and

Viscosityin the Earth'sCore, Nature, 249,
334-335, 1974.

46. Vostryakov,A.A., Vatolin, N.A. andYesin,

O.A. ViscosityandElectricalResistivityof
MoltenAlloysof Iron with Phosphorus
and
Sulphur, Fiz.Metal. Metalloved. 18(3),
476-477, 1964.

Homogeneous-Mantle Earth with a Soft-

47. Won, l.J. and Kuo, J.T. Oscillation of the

Solid or a Viscous-Liquid Core, J.

Earth's Inner Core and Its Relation to the

Geophys.Res., 72, 1761-1767, 1967.

36. Schloessin, H.H.
and Jacobs, J.A.
Dynamics of a Fluid Core with Inward
Growing Boundaries,Can.J.Earth Sci. 17,

Generation of Geomagnetic Field, J.

72-89, 1980.

37. Staylie, D.E. The Inner Core Transla-tional

TripletandtheDensityNearEarth'sCenter,
Science, 255, 1678-1682, 1992.

38. Steinberg,J., Tyagi, S. and Lord, Jr., A.E.

TheViscosityof MoltenFen0Ni40
PnB6and
Pdg,_
Sing,
Acta Metall. 29, 1309-1319, 1981.

Geophys.Res., 78, 905-911, 1973.

48. Yatskiv, Ya.S. and Sasao, T. Chandler
Wobbleand Viscosityin the Earth'sCore,
Nature, 255, 655, 1975.

49. Zharkov,V.N. andTrubitsyn,V.P. Physics

of PlanetaryInteriors, p.59, translatedand
edited

by

W.B.

Hubbard, Pachart

Pub.House,
Tucson,388 pp., 1978.

Models of Mantle Viscosity

Scott D. King

1. INTRODUCTION

constant[c.L, 3, 43]. Viscosityis definedas

The viscosityof themantleis oneof the mostimportant,

and least understoodmaterial propertiesof the Earth.
Plate velocities,deep-earthquake
sourcemechanisms,
the

q = 2'"

stress distribution in subduction zones, and estimates of

therefore, deformationis directly related to viscosity.

.(Note the factorof 2 differencein equation(2) compared
with the definition used by experimentalists.) For
temperaturechangesof 100 degrees K, the viscosity
changesby an orderof magnitudeat constantstress[c.f.,
44]. Changesof deviatoricstressby a factor of 2 change
the viscosityby an order of magnitude[c.f., 44]. Other
factors,suchas partial pressureof oxygenand water may
alsohaveimportanteffects.
Two creep mechanismsare likely to dominatein the
manfie;diffusionalflow (correspondingto n= 1 in equation
1) and power-lawcreep(corresponding
to n>l in equation
1). A rheology with a linear stress strain-rate creep

geochemical
mixingtime scalesare all stronglyaffected
by the pattern of convectiveflow which, in turn, is
stronglyinfluencedby the viscositystructureof the
mantle. There are two approachesto understanding
the
viscositystructure
of theEarth: usingobservations
suchas
the geoid and post-glacialuplift, combinedwith flow
models;or studyingthe physicaldeformationpropertiesof
mantle mineralsin the laboratory. Both approacheshave
advantages
anddrawbacks.
Laboratorymeasurements
of deformationindicatethat
the rheology of upper mantle mineralssuch as olivine

((Mg,Fe)2SiO4)
is a strongfunction
of temperature,
grain
size and stress[e.g., 3, 24, 43, 45, 46, 61, 65]. The
deformationof mineralsundermantleconditionsgenerally

(2)

mechanism, such as diffusional flow, is referred to as a

Newtoniantheology. The questionof which mechanism

dominatesin the manfie dependson the averagegrain size
of the manfie minerals [46]. In the upper manfie, with
grain sizes greater than l mm, power-law creep should
dominate at stresses greater than 1 MPa; otherwise
O)
= A
d-m expdiffusion creep dominates [46]. A deformation map
(Figure 1) shows the predicted dominant deformation
where is the deformationrate,o is the deviatoricstress, mechanismsfor olivine with grain size 0.1mm as a
t is the shearmodulus,d is the grainsizeof therock,Q is functionof stressand depth. It shouldbe noted that the
the activationenergyfor the deformationmechanism,T is strain
ratesachieved
inthelab(typically
10-5 - 10-8 s-1)
thetemperature
in Kelvins,R is thegasconstant
andA is a are muchlargerthan_
thosepredictedin the lithosphereand

follows a flow law of the form

mantle
(~ 10-14s'1). Whilethelaboratory
measurements
S. D. King, Purdue University, Departmentof Earth and
AtmosphericSciences,West Lafayette,IN 47907-1397
Mineral Physicsand Crysta!lography
A Handbook of PhysicalConstants
AGU

Reference

Shelf 2

Copyright1995 by the AmericanGeophysical

Union.

are clearly in the power-law creep field, typical manfie

strain-rates lie close to the diffusional

flow field at this

smallgrain size.
The deformationof the major high pressuremantle

phases perovskite ((Mg,Fe)S

i03)
227

and

spinel

228

MODELS

OF MANTLE

VISCOSITY

them tractable;commonly,a linear rheology(i.e. n=l and

T constantin equation(1)), which variesonly with depth,
IO'Z

is assumed.

The classicstudiesof post-glacialreboundillustratethe

non-uniqueness of viscosity models derived from
observations
and flow models. Haskell [19, 20] proposed
thatthe uplift of Fennoscandia
wasthe resultof deepflow,

modeled
asa halfspace
witha uniform
viscosity
of 1021
10-,

Pa s (pascal secondsare the MKS units of dynamic

viscosity; I Pa s = 10 poise), while van Bemmelem and
Berlage [64 - see 5] proposedthat the uplift of central
Fennoscandia could be attributed to flow in a tOO km thick

10-6
l
o

Fig. 1. ((r-z)-deformation
map for polycrystallineolivine
with grain size 0.1 mm. Thick lines are creep field
boundaries;
thin lines,constantstrainrate contours(given
as powers of t0). C and NH denoteCoble and NabarroHerring creep,respectively[3].

((Mg,Fe)2SiO4)canbe studiedonlyby analogminerals.

Usinghightemperature
creepexperiments
on a CaTiO3
perovskite analog, Karato and Li [22] suggest the
possibilityof a weak zone at the top of the lower mantle
(due to the grain size reductionfrom the spinel to
perovskite phase change). Karato [21] showed that
olivine, spinel and perovskitehave similar normalized
flow stresses,which suggeststhat, due to the effect of
pressure,the lower mantleshouldhavea higherviscosity
thanthe uppermantle. Sincecreepparameterscan differ
greatlyeven for apparently-similarperovskites[44; Table
5], we shouldapply analog creep measurements
to the
mantle with great care.

Becauseof the difficultiesin interpreting

and applying
laboratory creep measurementsto mantle conditions,
models of mantle viscosity based on large-scale
geophysicalobservationscontinue to be important to
geophysics.The post-glacialuplift problem,as described
by Haskell[19], is a simpleillustration.If a loadis placed
on the surface of a viscous fluid and allowed to deform the

surfaceto establishhydrostaticequilibrium,the rate at

whichthe surfacedeformswill dependon the viscosityof
the fluid. Similarly, if the load is then removed,the rate
of returnis alsodependent
on viscosity.Viscositymodels
deducedfrom theseobservations
are not unique,however,
andrequireknowledgeof modelsfor the surfaceload (i.e.,
ice sheet thicknessand history), which are uncertain.
Also, the theoretical
modelsare oftensimplifiedto keep

channel,
with1.3x 1019Pas viscosity,
overlying
an
effectively rigid mantle. Haskell also showed that the
viscositydid not changeover the interval of time of the
analysis,supportingthe notation of a NewIonian, rather
thanstress-dependent
mantle.
The effectsof an elasticlithospherewere first discussed
by Daly [7], who appealed to the strength of the
lithosphereto avoid the formationof a bulge of material

squeezed
out of the low viscositychannelperipheralto the
ice load in his model. McConnell [28] and Cathies[4, 5]
showedthe strengthof the elasticlithosphereas important
only in consideringthe short wavelength harmonics.
O'Connell [33] determinedthe viscosityof the lower
mantleby lookingat changesin the ice loadandrelating
themto longwavelength
rebound.He alsousedspherical
harmoniccorrelationto look for the reboundsignalin the
geoid. The effect of phase changesin the mantle on
reboundwas consideredby O'Connell [34]. O'Connell
concludedthat the effectof boththe olivine-spinelandthe
basalt-eclogite
phasechangeon post-glacialare rebound
negligible. Peltier [37] solved for the responseof a
viscoelastic (Maxwell) spherical Earth using the
correspondence
principle, later adding the effects of
varying sea level [42]. The correspondence
principle
assertsthat onecanconstructthe Laplacetransformof the
solutionby solvinga seriesof elasticproblemsover a
rangeof complexfrequencies
andtheninvertingto getthe
time domain responsefor the viscoelasticproblem.
Cathles [4, 5] presented an alternative viscoelasfic
formulationwhichavoidsthecomplexities
of theboundary
conditionsfor long time periods when using the
correspondence
principle. Cathiesarguesfor an increase
in viscosityin thelowermanfie,whilePelfierarguesfor a

uniformviscositymanfie. Becauseno directcomparison

of the two methodshas been reported,it is difficult to
assess whether the differences between Peltier's and
Cathles' conclusions are due to their methods or ice

models.An ice sheetdisintegration

model,includingice
massesof Laurentia,Fennoscandia,
and Greenland,called

KING

ICE-l, was developedby Peltier and Andrews [40]. A

summaryof ice sheetmodelsis providedby Peltier [39].
Lambeck

and co-workers

have used far field absolute

sealevel changes,ratherthan the reboundhistoriesat sites

near formerly-glaciatedregions[26, 32]. They reasonthat
relative sea level variationsfar from ice marginsare less
influenced by poorly-constrained ice models. The
difference

between Nakada

and Lambeck's

models based

on relative sea level variations in the Pacific, and models

229

surface,
c is theradiusat thecore,8plmis thedensity
contrastat a depth r of sphericalharmonicdegree I and

order
m,andGl(rjl(r))isthegeoid
response
kernel.
Thedensity
perturbations
(Spiro)
aredetermined
by
seismic velocity perturbation models from seismic
tomographicinversionsand/or tectonic plate and slab
modelsfrom boundarylayer theory and deep earthquake
locations

in subduction

zones.

To

transform

seismic

velocityanomaliesinto densityanomalies,we assumethat

changesin seismicvelocity can be mappedinto changesin
temperatureand do not representchangesin composition.
Seismic velocity variationscan be written in terms of
elastic moduli for which the limited experimental
informationplacesreasonablebounds. Thus, the density
perturbations
in equation3 canbe written as

based on Fennoscandianand Canadian Uplift could be

interpretedas reflectinglateral variationsin uppermantle
viscosity.
Table 1 compares a number of recently published
viscositymodelsfrom post-glacialreboundwith geoidand
plate velocitystudiescompiledby Hager [14]. Becauseof
the limited power in the post-glacial rebound data set,
rebound models are usually reported in very simple
parameterizations.
The modelsstill rangefrom the nearlyuniform viscosity (Haskallian) model PT to strongly
layeredmodelsNL and HRPA (seeTable 1).
where
8p]v
sisavelocity
todensity
ratio
and8vslm
isthe
Another constraint on manfie viscosity comes from
seismicvelocityperturbationmodel.
modelingthegeoidand dynamictopographyof the surface
A simple,two-layerviscositymodel,with an increasein
and core manfie boundary, using the pattern of density .viscosityof a factor of ten at 670 km depth or 1200 km
anomaliesinferredfrom seismictomography[11, 16, 17, depth, explains the longest wavelengthgeoid from the
18, 23, 49, 50, 51]. From early seismictomography,it has inferreddensitiesin the lower mantle [ 11, 18]. This model
been observed that long-wavelength (i.e., spherical is different from the two end-member, post-glacial
harmonicdegreeI = 2,3) geoid lows are associatedwith
rebound models.
The differences between the models
long-wavelength,fast (presumablydenser)regionsin the from postglacialreboundand the geoid modelshave led
lower mantle [9]. In a staticEarth, this is oppositeof what to spiriteddebates,but until now no consensus
model.
one predicts; geoid highs should correspondto mass
The velocities of the Ea's plates are the surface
excesses(Figure2a). As shownby Pekris[36] (and others manifestations
of convectiveflow in the mantle. Hager
since), a mass anomaly will drive flow that deforms the
and O'Connell'smodel [15] showedthat densitiesfrom the
surfaceand core mantle boundary(Figure 2b or 2c). The
coolingof oceanplatesandsubducting
slabsaloneprovide
resultinggeoid is a combinationof both internal(Figure the neces buoyancyforce to drive plates at the
2a) and boundarymass anomalies(Figure 2b or 2c) and observedvelocities. Ricard et al. [50, 51], Ricard and
can be positive or negative, dependingon the viscosity Vigny [47], Forte and Peltier [10], and Forte et al. [12]
structure(compareFigure 2a + 2b versus2a + 2c).
used observed plate velocities to deduce the radial
The equationsof motion of an incompressibleself- viscositystructureof the mantle. Plate velocitiesconstrain
gravitatingsphericalshell are presentedin Richardsand the absolutevalueof the viscosityof the mantle;the geoid
Hager [54] and Ricardet al. [50]. Theseequationscan be doesnot. The platevelocitydatadoesnot havethe depth
solvedby a separationof variables(assuminga radially- resolutionof the geoid,becausea low viscosityzone can
stratifiedviscosity). The resultingODE's can be solved effectivelydecouplethe platesfrom flow in the deep

forresponse
functions
(kernels)
whichdepend
onlyonthe
viscositystructure. The geoid (V m) can then be
calculatedby convolvingthe responsefunctionswith a
disu'ibutionof densitycontrastsas follows

V = 4nTa G1

21+1[y (r,l(r))p
(r)dr

(3)

where2 is the gravitationalconstant,a is the radiusat the

interior.

In all of the studiesdiscussed,

the final viscositymodel
is dependent
uponanothermodel. In post-glacialrebound
studies,this is a modelof the ice sheet,which is only
crudelyknown. In the caseof the geoid,it is the seismic
velocity models(see equations3 and 4). Most seismic
tomographicinversionsdo not reportformal uncertainties
(which are difficult to perform and, because of the
difficulty in definingsourcesof error may have little

230

MODELS

OF MANTLE

VISCOSITY

TABLE 1. A Comparisonof RecentlyPublishedViscosityStructures

Determinedby SystematicForwardModeling (from [14])

Model

'flum

11
m

(Inn)

(Pa s)

(Pa s)

llm/lnm

PTa
MPb
LJN2c
LJN3d
LNAe
NI t'

120
120
100
150
75
50

1021
1021
3.5x 1020
3.8x 1020
2 x 1020
1020

2 x 1021
4.5 x 1021
4.7 x 1021
3.4 x 1021
7.5 x 1021
1022

2
4
15
8
40
100

RVGP
g
HGPA
h
HSi

(100)
(100)
(100)

2.6x 1020
2 x 1019
2 x 1020

1.3x 1022
6 x 1021
6 x l021

50
300
30

apeltierandTushingham
[41] model,basedon globalsealevel variations,with emphasis
on near-field
sites.

bMitrovica
andPelder
[29]model,
based
ontheassumption
thatthegravity
anomaly
overHudson
Bayis
totally due to delayedrebound.

CLambeck,
Johnston
andNakada[26] model2, basedon European
sealevelvariations
with emphasis
on
relativevariationsin sitesaway from the ice margins.

dLambeck,
Johnston
andNakada
[26]model
3,analternative
tomodel
2.
eLambexk
andNakada[25] modelfor Australia,
basedon sealevelvariations
withemphasis
onrelative
variationsin sitesspanning
thecontinental
margin.

fNakada
andLambeck
[32]model
forOceanic
response,
based
onsealevelvariations,
withemphasis
on
relative variations as a function of island size.

gRicardand Vigny [47] modelfrom the Geoidand Platevelocities. Parentheses

on (h) indicatethe
thicknessof thehigh viscositylid.

hHager
andRichards
[16]model
forrelative
manfie
viscosity
fromtheGeoid,
calibrated
forPlate
velocitiesand Advectedheat flux [14]. An additionallayer, from 400 km to 670 km depth has a

viscosity
of6 x 1020
Pas.

iAmodification
ofmodel
HRGP
that
hasanasthenospheric
viscosity
higher
byafactor
of10,asmight
be
expectedfor Shieldregions.

KING

2. RECENT

Ci

INRSION

231

RESULTS

Several recent studiesform and solve inverse problems

rather than repeatedlysolving the forward problem. In
theory,the inverseproblemprovidesnot only a model,but
alsoestimatesof the resolvingpower of the data and of the
wade-offsbetweenmodel parameters. The resolutionand
trade-off analysesare not always straight-forward. There
is a surprisingconvergenceof these results and the
resultingmodel differs from the "traditional"models. In
this paper, all of the figures will present relative
viscosities. To convert to absoluteviscosities(in Pa s),

oneshould
multiply
thehorizontal
axisscale
by1021
Pas.
static only

dynamiconly

dynamic only

Fig. 2. (a) The geoid anomaly over a positive mass

anomaly(stippled)in a staticearth. Co)The dynamicflow
driven by the mass anomaly causes negative mass
anomalies (stripped regions) at the upper and lower
boundaries,hencenegativegeoidanomalies. The sum of
(a) and Co)is a negativeanomalyin a uniformviscosity
medium. (c) With an increasexlviscosityin the lower
layer, the dynamic topographyof the surfaceis reduced
andthe sum of (a) plus(c) couldbe positive.

meaning). The use of different seismic models can

producedifferent viscositymodels [23, 51], suggesting
that crude viscositymodelsmay already be pushingthe
limit of the observations.Plate velocity modelsalso have
associated
uncertainties;
in addition,only the poloidalpart
of the plate velocitiesare drivenby viscousflow without
lateral variationsin viscosity. Becausethey are ignoredin

C,cid modelsare only sensitiveto relative viscosities,so

the absolutescale is chosento be consistentwith postglacialreboundandplate velocitystudies.
2.1 Plate Velocity Inversion
Forte et al. [12] usedthe methodof Bayesianinference
to invert for the radial viscosityprof'dewhich best fit the
observedplate velocities. Harmonic coefficientsof the
observedplate divergencein the degreerangeI = 1-8 were
used [10]. Using a tomographic shear wave model

SH425.2[62]asthedriving
force
(i.e.,$vslm
inequation
4) and Greens functions (kernels) for viscous flow
developedin Forte and Peltier [ 10], they parameterizeAthe

mantle viscosityin five layers (0-100 km, 100-400 km,

400-670 km, 670-2600 km and 26(X} km to the CMB).

Their inversionproduceda viscositymodel (i.e., the best

fitting uniform viscosityin eachof the five layers)with a
low viscosityin the transitionzone and .highviscosityin
the 100-400 km layer with a factorof 42 jump at 670 km
(seeFigure3). The plate-likedivergencepredictedby this
the viscous flow formulations, lateral variations in
modelexplains48% of the variancein the observedplate
viscositythemselvescould also introducea major source divergence(in the range1 = 1-15). Prior to the inversion,
the variance reduction with an isoviscous manfie was of error in the viscositymodels.
Studiesof Frth's rotationprovideconstraintson mantle 770%. However, there is a significanttrade-off between
viscosity. O'Connell [33] suggests
that changingpatterns the top three layers (0-100 km and 400-670 km are
of convectionwould change the principle momentsof correlated and 100-400 km is anti-correlated with the
inertia of the Earth and that his viscositymodel would others),so a model with a low viscosityin the 100-400 km
permit polar wander from convection. Sabadini and layerandhigherviscosities
in the0-100 km layerand400Peltier[57] andWu andPelfier[67] discuss
the changesin 670 km layersfits the data nearlyas well (seealsoFigure
Earth'srotation due to Pleistocenedeglaciafion. Ricard 3).
and Sabadini [48] discusschangesin rotationinducedby
Ricard andWuming [49], usingthe lower mantlemodel
densityanomaliesin the mantle. Polar wanderalso has of Dziewonski [8] and the upper mantle model of
recenfiy been demonstratedto provide constraintson Woodhouseand Dziewonski [66], invert the topography,
mantleviscosity[e.g.,53, 58]. A numberof recentpapers geoid, rotation poles, and angular plate velocities for
summarizingthese results(and the post glacial uplift, mantleviscosity. Using presentday plate geometries,the
geoidand plate velocity studies)can be foundin Glacial surfacevelocity boundaryconditionis choosento match
Isostasy,Sea-Leveland Mantle Rheology,ed. $abadini, the stressesbetweena no-slip boundaryconditionat the
Lainbeck and Boschi [59].
surfaceflow driven by the internal density contrastsand

232

MODELS OF MANTLE

VISCOSITY

670- 1800km),withveryweaksensitivity
tochanges
in
viscosity
of uptoanorder
of magnitude
below
thisdepth
or in theuppermantle.Therefore,
models
withlarge
increases
inviscosity
withdepth
cannot
beruled
outbythe

RSLdataaslongastheaverage
viscosity
in the670-1800

1000

kmdepth
range
is1021
Pas. It should
bepointed
outthat

1500

averageviscosityof the mantle.

Haskell[20] indicatedthat his resultrepresented

the
2.3 Geoid Inversion
2000

Ricard
etal.[51]considered
a three
layermantle.
They
usedL02.56[8] for thedensities
in thelowermantle,
and

M84C[66]anda slabmodelforthosein theupper

mantle;theyalso solvedforthe densitytovelocity
ratio(/5p//Jv
- seeequation
4) in the upperandlower

2500

10-

100

101

102

RelativeViscosity
Fig. 3. 1-D viscosity
modelsfrom Forteet al. [12]
determined
by inverting
observed
platevelocities
for the
bestfitting5 layerviscosity
model.Thedashed
line is the

mantle,
thedensity
coefficient
fortheslabmodel
(Pslab),

and viscositiesin 100-300, 300-670, and 670-2900 km

layers,
givingthemsixunknowns.
Theyused
theresponse
kernelsfor Newtonianviscousflow [50], andchosethe

viscosity
valuein the0-100km layerto be 1022Pas,
because
thegeoidis sensitive
onlyto relative
viscosity

preferred
model,
thesolidlineisalsoanacceptable
model. change.Theyperformeda MonteCarloinversionfor the
Theviscosities
in thisplotarescaled
by a characteristicviscosity
modelwhichbestfit boththegeoidandplate
mantle
viscosity
(q= 1021Pas).
velocities.Two classes
of modelsemerged
fromtheir
study;
onewithanincre.
asingviscosity
withdepth
(Figure
4 - solidline)andanother
withthehighest
viscosity
in the
transition
region
and
lower
viscosity
in
the
upper
100-300
flowdriven
bytheplates.Theresulting
viscosity
model

hasa continuous
increase
in viscosity
withdepth
to the
mid-lower
mantle,
thenadecrease
inviscosity
inthelower

one-thirdof the lower mantle, with no noticeable

discontinuities
orlowviscosity
zones.There
is a peak

change
inviscosity
ofabout
twoorders
ofmagnitude
from

the surfaceto the maximumin the lower mantle.

However,
thismodelprovides
poorfits to the data;
variancereductions
are 44% for geoid,58% for

topography,
and19%forpoliodal
component
oftheplate

5O0

1000

I
I
I
I
I
I
I

velocities.

1500

2000

250O

2.2 PostGlacialUplift Inversions

Therehavebeenseveral
attempts
to formandsolvean

inverse
problem
fortheviscosity
ofthemantle
using
post-

glacialupliftdata[35,38]. Ananalysis
of therelative
sea

level,
oruplift
history,
over
Hudson
Baywas
performed
by

Mitrovica
andPeltier[30,31]. Thehorizontal
extentof
theLaurentide
icesheetsuggests
thatthissubset
of the
relativesealevel(RSL)datashould
be sensitive
to the

10-2

10-1

10o

101

102

RelativeViscosity
viscosity
at greater
depths
thanother
datasubsets
[30].
Theyconclude
thatthepreference
ofa uniform
viscosityFig.4. Threerepresentative
1-Dviscosity
models
from

inthelower
manfie
of1021
Pasfrom
other
studies
[e.g., Ricard
etal.[51]fromMonte
Carlo
inversion
using
geoid
2, 4, 5, 42] is moreappropriately
interpreted
as a andplatevelocities.
Theviscosities
in thisplotarescaled
constraint
ontheuppermost
partofthelower
mantle
(i.e., byacharacteristic
mantle
viscosity
(q= 1021Pa
s).

KING

233

km and 670-2900 km regions (Figure 4 - dash dot line).

However, includingthe plate velocities,in additionto the

geoid, a third model emerged(Figure 4 - heavy dashed

line). One of their strongestconclusionsis the sensitivity
of their modelingto the assumeddensitymodel. As they
note, I-lager et al. [18] obtained better results with the
same formalism using Clayton and Comers' [6] lower
mantle and a boundary layer theory slab upper mantle.
The more interesting result is the model that emerged
when they consideredboth geoid and plate velocitiesin
the inversion(Figure 4 - heavy dashedline). In addition,
Ricard et al. [51] are the only investigatorsof the recent
group to considerchemically stratified manfie models.
Their resultssuggestthat,basedon the inversionstudy,the

1000

1500

2500

data are unable to discriminatebetween layered or whole

mantle models.

A study by King and Masters [23] consideredseveral

publishedmodels for S-wave velocity for the densities
providingthe drivingforce (Jpin equation3): MDLSH
[63]; SH425.2 [62]; and MODSH.C [27]. Using the selfgravitatingGreen'sfunctionsfor Newtonianviscousflow,
following Richardsand Hager [54] and Ricard et al. [50],
they invertedfor radial viscositymodelsthat best fit the
observedI = 2-8 geoid (1 = 2-6 for MDLSI-I) usinga nonnegative,least-squares
schemewith smoothingto inhibit

500

lOOO

1500
200O

10

15

Relative Viscosity
Fig. 6. 1-D viscositymodel from Forte tal. [13]. This
forward model provides good fits to geoid and plate
velocities. It compareswell with Figures3, 4 and 5. The
viscositiesin this plot are scaledby a characteristicmantle

viscosity
(q= 1021
Pas).
wild oscillations.All threeof the seismicvelocity models
predicta low viscositybetween400-670 km depth(Figure
5). The pattern of viscositywith depth for the three
modelsis strikinglysimilar:a high viscosityfrom 0 to 400
km depth,a low viscositybetween400 and 670 km, and
increasingviscositybelow 670 km. The largestdifference
betweenthe viscositymodelsis a factor of two difference
in the viscosityof the 400-670 km layer. It is interesting
to note that the viscosityin the lower mantle increasesby
a factor of five below 1022 km in addition to an increase

at 670 km. This resemblesthe two-layer model of Forte

and Pelfier [ 11].
Forte et al. [13] used the recent S-wave model

SH8/U4L8 which they describe. Using Frechet kernels

[Forte et al., 12], they determinethe viscosityprofile
2500 required to fit the geoid. The model, which containsa
thin, low-viscosityzone at the baseof the upper mantle
lO 1
10-2
10-1
10o
and an increasein viscosityin the lower mantle (Fige 6),
is quite similarto thosedeterminedby King and Masters
Relative Viscosity
[23] (Figure5). It may be beyondthe limit of theirdatato
Fig. 5. I-D viscositymodelsfrom King and Masters[23] constrain such a thin layer at the base of the mantle,
determinedby invertingthe seismicallydetermineddensity however; becauselayer thicknessand viscositycontrast
anomalies for the best fitting 11 layer viscosity model trade-off directly, this could possiblyrepresenta thicker,
using the geoid. The models are normalized by the less extreme layer. Forte et al. obtain a 65% variance
viscosityin the 1284 to 1555 region. The viscositiesin reductionfor the observedgeoid0 = 2-8), in additionto a
this plot are scaledby a characteristicmantleviscosity(l reasonablefit to the plate velocitieswith theseviscosity

= 1021Va
s).

and density models. They also point out that their

234

MODELS

OF MANTLE

VISCOSITY

viscositymodelis consistent
withrecentpost-glacial
uplift
analysesand mineralphysics.
3. COMPARISON

The viscositymodel from Forte et al. [12] - determined

rebound,platevelocity and geoidpredictions. Using

perturbation
theoryon a 2-D Cartesianproblem,Richards
and Hager [55] suggested
this effect would be small for
long-wavelengthstructuresin the lower mantle. Ritzler
and Jacobi [56], however, suggestthat, becauseradial
viscosity
modelsunderpredict
thegeoidcompared
to their

by inversionusingthe plate velocitydata,the viscosity lateralviscosityequivalants,

neglectinglateralviscosity
modelsfrom King and Masters[23] - determinedby variationsleads to errors in the magnitudeof radial
inversionusingthe geoiddata,and the viscositymodel viscosity
jumpsas muchas a factorof two. Zhangand
from Ricardet al. [51] - usinga Monte Carlo inversionof
geoid and plate velocity data- are remarkablysimilar.
Furthermore,the resultsof the post-glacialuplift inversion
by MitrovicaandPeltier[30] andtheexperimental
data,as
discussed
by Ranalii [46], seem compatiblewith these

observations.
Uponconsidering
boththeuncertainty
in the
internal densitiesand surfaceloads and the uncertaintiesin

Christensen [68] also find that the effects of lateral

viscosityvariationsare significant,especiallywhen the

radialviscosityis stratified.Ricardet al. [52] showedthat
a model with lateral viscosity variations between
continentaland oceanicasthenosphere
is consistent
with

theobserved
globalrotationof thelithosphere
withrespect
to thehot spotreferenceframe(i.e., the degree1 toroidal

the viscositymodelsthemselves,
it appearsthat the results component of plate velocities).
A number of
from the differentobservations
are compatible.However, investigations
addressing
lateral viscosityvariationsare
ff the transition
zoneis Ca rich,assuggested
by some[ 1], currentlyunderway.
Karato's [21] results on the strengthof garnet are
incompatiblewith this new model. Mantle modelswith a
hard transitionzone appearcompatiblewith observations
[60].
Acknowledgments.
The authoracknowledges
support
from
NSF grantEAR-9117406.Thanksto R. O'Connell,A. Forte,and
4. LATERAL

VISCOSITY

VARIATIONS

Y. Ricardfor providing
theses,
reprts, andpreprints.Thanks
also to the numerousanonymousreviewerswhosecomments

An area of increasinginterest is the role of lateral

helpedimprovethis manuscript.Specialthanksto Kathy

variationsin viscosityand their effect on post-glacial Kincade
forhelpin preparing
thismanuscript.

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I.,ambeck,

Boschi,

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426, 1973.

Plastic Rheology of Crystals

J.P.

Poirier

1. PHENOMENOLOGY
DEFORMATION

OF

PLASTIC

machine (usually in tensionor compression),at constant

strain-rate:de/dr-=; when the yield stressis reached,

stressremains constantand strain keeps increasingat rate

When crystalsare strainedabove a certain limit, they

ceasebehaving like elastic solids and become plastic.
Plastic deformation is an irreversible, isovolume process,
which results in a permanent shear strain after the shear
stressthat causedit hasbeenremoved.Hydrostaticpressure
alonedoesnot produceplasticdeformation.
A perfectly plastic solid undergoesno plastic strainif

; theyieldstress
usuallyincreases
with.Theconstitutive
equation
cantherefore
bewrittenc= f( ,T).
Plastic deformation of materials in the Earth, however,

doesnot generallyoccurat constant

strain-rate:
at high
temperatures, rocks and minerals slowly flow under
constantstress.The relevant laboratory experimentsare
then creep tests [45].In creep tests,a sampleis put under
constant stress (tensile or compressive) and strain is
recorded as a function of time; the curve e(t) is a creep
curve.In many cases,after a transientstageduringwhich it
decreases,the strain-ratebecomesapproximatelyconstant,
until eventual failure (Figurelb). The creep curve is then
approximately linear (quasi steady-statecreep ) and the
corresponding
creep-ratedependson the appliedstressand

theapplied
stress
is lowerthantheelasticlimit GEL,or
yieldstress; if c= EL' theplasticstraincantakeany
value.Any increasein appliedstresswould immediatelybe
relaxed by strain, so that the applied stresscannot be
greater than the yield stress. The yield stress usually
decreases with increasing grain size and increasing
temperature; in single crystals, it depends on the
orientationof the stressaxis with respect to the crystal
lattice. In actuality, the applied stress necessary for
continuing deformation usually increases with strain
(hardening). At high temperatures,however, many
crystallinematerialsexhibit negligiblehardeningand can
reasonablybe considered
asperfectlyplasticsolids.
For perfectly plastic solids, the stress-strain curve,

on temperature:
=f(cLT).In creeptests,thecrystals
are

o=f(e),isa straight
line,= EL' paralleltothestrainaxis
(Figure la). Time does not explicitly appear in the
constitutive equation. Standard stress-straincurves for
materialsare obtainedby straininga samplein a testing

free to deform,andtheobservedcreep-rateis thatfor which

the yield stressis equalto the appliedstress.As creeptests
are usually performed at temperatureshigh enough to
obtain a measurable creep-rate, there is very little
hardening,and, for mostmatehals,a quasisteady-statecan
be reached (if not, the creep rate would be continuously
decreasing).
It can thereforebe seenthat a soliddeformingin steadystate creep under constantstresscan be consideredas a
perfectly plastic solid, but, more interestingly, if the
variable time is introduced, it can also be considered as a

viscousfluid, sinceit flows in shearat constantrate under

applied stress. The viscosity at constant stresscan be

J.P. Poirier, Institut de Physiquedu Globe de Paris, Depart.

definedas' 1= c/d. If creep-rate

depends
linearlyon

des Geemater., 4, Place Jussieu, 75252 Paris, Cedex 05,

stress,viscosity is independentof c and it is said to be

Newtonian. However, creep-rateoften increasesfasterthan
stressand viscositydecreases
with increasingstress(nonNewtonian viscosity ). In many cases, the creep-rate

France

Mineral Physicsand Crystallosraphy

A Handbook of Physical Constants
AGU

Reference

Shelf 2

Copyright 1995 by the American GeophysicalUnion.

depends
onstress
bya power-lawd ocn, with1<n < 5.
237

238

PLASTIC

RHEOLOGY

OF CRYSTALS

const.

AH0(o)+PAV*

d=0fo2
TM
exp
(-

RT )

(1)

where
0 isa constant
thatoftendepends
ontheorientation
of thestressaxis with respectto the crystallattice.

const.

The valuesof the parametersn, m, AH 0, AV*, are

usuallyobtainedby fitting a curve to the experimental
valuesof d, determined
in a rangeof valuesof therelevant

variable
(o, l/T, P, fo2--.),all theothervariables
being
kept constant.More reliable resultsare obtainedby global
inversion of the experimental results, which
simultaneously
yieldsbestvaluesof all the parameters[51,
48].

Fig. la

Stress-strain
curveof an elastic-perfectly

plasticsolidat constantstrainrate.
Abovetheelasticlimit CEL,stress
remains
constant.

In many cases,more than one controlling processis

activein theexperimental
rangeof o, T, fo2etc.Several

processes,
withrates i' mayact concurrently
or
sequentially.The resultingcreep-ratecan be expressedas:

d=I;idi'forconcurrent
processes,
and
as:
d=[I;i di-1]-1,
The temperaturedependenceof the creep-rateusually

followsanArrhenius
law, i.e.: 0 exp(-Q/RT),whereR
is the gasconstant,T is the absolutetemperature,
andQ is
the apparentactivationenergy, determinedfrom theslope

of theIn vs 1/'I'plot, at constantstress.

The activation

for sequential
processes.
TheArrhenius
plotIn d vs 1/Tis
then usually curved and the fit of a single straightline,
when it is possible, gives only an apparentenergy Q,
which doesnot correspondto any physicalprocess,[e.g.,
2].
If, for some reason, it becomes easier to deform an

energyincreaseswith hydrostaticpressureP, throughan

apparentactivationvolume AV*. If creepis controlledby
only onephysicalmechanism,the activationenergycanbe

alreadydeformedzonefurtherthanto initiatedeformation
elsewhere,plastic instability occurs,and strainbecomes

written:
Q = AH0(c
0 + PAV*,whereAH0 andAV* arethe

situation occurs when strain-softening mechanisms

predominateover strain-hardeningmechanisms[27, 44].
The stresssensitivityof strain-raten (or stressexponentin
the creep equation) is an important parameter:if n =1
(Newtonian viscousmaterial), deformationis intrinsically
stable.If n = 2, the solids still can be deformed to very

activation enthalpy and volume respectively of the

controllingprocess.In somecases,the activationenthalpy
may depend on the applied stress(decreasingas stress
increases);then,if thelogarithmof thecreep-rateis plotted
againstthe logarithmof the stressto obtaintheexponentn
of a power law, the stressdependenceof the activation
enthalpy may appearas a spuriouslyhigh value of n (n >
5).

The creep-rateof polycrystals(and obviouslyof single

crystals)doesnotgenerallydependon grainsize,exceptfor
very fine-grainedpolycrystals
deformingby diffusioncreep

localized

in deformation

bands

or shear zones.

This

const.

(see next section).

The creeprate of pure elements(e.g., metals)is entirely

characterizedby its dependenceon stress,temperature,

pressureand grain-size.This, however,is not the casefor
ceramicsandminerals,whosethermodynamic
statedepends
on the activity of the components.
In particular,the creep

- const.

rate of oxides (which constitute most of the minerals

relevant to deformationin the Earth) often dependson

oxygen
fugacityfo2.Inaddition,
thecreep-rate
of silicates
is also sensitive to the amount of water presentas an

impurity,expressed
astheratioH+/Si.
The constitutiveequation(rheologicalequation)of pure
singlecrystaloxideminerals,if creepis controlled
by only
oneprocess,is usuallyexpressed
as:

Fig. lb

Constantstresscreepcurve.Strainrate is
approximately
constantduringquasi steadystate creep.

POIRIER

large strains in a stable manner by the so-called

superplastic
deformation,whichmayoccurin:ine-grained
materials.Non-Newtoniancreep,with n > 3, on the other
hand,is potentiallyunstableand strain-inducedstructural
changesor strainheatingmay causeshearlocalization.
Phase transformations strongly interact with plastic
deformation; the resultanttransformation plasticity [45]
appears,in creep experiments,as an important transient
enhancement
of the creeprateduringtransformation
(or as a
stressdrop in the caseof deformationat constantstrainrate).Localizedphasetransformation
undernon-hydrostatic
stresses
may causeshearfaultinginstabilities[7, 30].
2.

PHYSICAL

MECHANISMS

Plasticdeformationis the macroscopic

resultof transport
of matter on a microscopic scale, resulting from the
motion of defects:point defects,dislocations,or grainboundaries.Applied shearstressprovidesthe drivingforce
for the motion of defectsand the rate of motion usually
increases
with temperature.
Deformationat low temperature
(T/TIn < 0.3) is due to glide of dislocations on
crystallographic
slipplanesin thedirectionof theirBurgers
vector; plastic deformationoccurswhen the shear stress
resolvedon the slip plane in the slip directionis equal to
the critical resolvedshear stress(CRSS), characteristicof
the slip system.Deformationat high temperature,in most
cases, involves diffusion of point defects (usually
vacancies);it may alsodependon the interactionof several
kinds of defects: e.g., in dislocationcreep controlledby
vacancy diffusion or diffusion creep accommodatedby
grain-boundary
sliding (see[45] for a review).
In general, the shearstrain rate is given by a transport
equation, and is equal to the density of carriers of
deformationtimes the strengthof the carrierstimes their
velocity. In the most frequent case of deformation by

239

temperature),dislocationstend to remain straightin the

deep troughs along the dense rows, and the thermally
activated, stress-assistedstep of passing over the hill
betweenone row of atomsand the next (lattice friction), is
the controlling process.Creep is then said to be glidecontrolled. If the potential hills are so low, that slip
betweenlocalized obstaclesis easierthan overcomingthe
obstacles, dislocations wait in front of the obstacle until

they can circumventit by climbingout of their slip planes

and glide until they meet the next obstacle.As climb of
edge dislocationsout of their slip plane is controlledby

diffusion of point defectsto or from the dislocations,

climb-controlled creep is rate-limited by thermally
activateddiffusionand can only occurat high temperatures;
also, the activation energy does not depend on stress.In
climb-controlled creep as in glide-controlledcreep, the
strainis still due to dislocationglide, only the controlling
processesof the strain rate differ. In general,dislocation
creepis grainsizeindependent.
If one makes the reasonableassumptionthat, in steadystatedeformation,the averagedistancebetweendislocations
is determined by their long-range stress field, which
balancesthe appliedstress, the dislocationdensityp is

thenproportional
to 2. The difference
between
the

motionof dislocations,
the shearstrain-rate obeys

rheological equation for glide-controlled and climbcontrolled creep essentially comes from the physics
underlyingthe expression
of the velocity.
i) In glide-controlledcreep (Figure2a), to moveby one
Burgersvector,a dislocationmustlocally nucleatepairsof
kinks over the potential hill; sidewaysmigration of the
kinks then brings the dislocationto the next low-energy
trough. Nucleation and migration of the kinks are
thermally activatedprocesses;the applied stresshelpsin
overcomingthe energy barrier and the activationenergy
decreasesby an amount equal to the work done by the
stress.In most cases, the dependenceof the activation
energy on stresscan be assumedto be linear: AH () =

Orowan equation'

AH0- B.

= plv

(2)

where p is the densityof mobiledislocations(lengthof

dislocationline per unit volume),b is their Burgersvector
(strength),and v their velocity.Orowan'sequationis valid
whether shear strain is caused by slip or climb of
dislocations.Theoreticalrheologicalequationssuchas (1)
can be derivedfrom Orowan'sequationby expressingthe
dislocationdensityand the dislocationvelocity in termsof

therelevant
physical
parameters:
T, c,P,fo2,etc.[45].
Glide of dislocations
is drivenby theappliedshearstress;
to movealongtheir slip planedislocations
have to go over
the potentialhills betweendenserowsof atoms;they also
have to overcome localized obstacles,due for instance to

the stressfield of other dislocations.If the potential hills

are high (as they are in some minerals, even at high

Fig. 2a

Glide-controlledcreep.Dislocationstendto
lie in the potentialtroughs, overcoming of
the potentialhills is achievedby nucleation
andsidewaysspreading
of kink pairs(K).

240

PLASTIC

RIIEOLOGY

OF CRYSTALS

_L

121

121

Fig. 2b

Climb-controlledcreep.Edgedislocations
emittedby a source(S) glide on their

glideplane(G) untiltheyarestopped
in front
of an obstacle(0), they have to climb (C) to
clearthe obstacleandresumegliding(G).

A screw dislocation can in principle glide on all

crystallographic
planeswhich containit; if it is dissociated
in one plane, it can usually easily glide in this plane.
However, to cross-slip from on plane to another,which

may be neededto avoidobstacles,

thedislocation
must be
constricted.Constriction is thermally activated and the
activationenergy of cross-slipcontrolledcreepdecreases

with increasing stress. Although cross-slip helps in

overcominglocalizedobstacles,the rheologicalequationof
cross-slipcontrolledcreepis basicallysimilar to that of
glide-controlled
creep.
ii) In climb-controlled creep (Figure 2b), strainresults
from glide of the dislocationsbetweenobstacles,but the
strain-rateis controlled by the time the dislocationsmust
wait behind the obstaclesbefore circumventingthem by
climb and gliding further. Creep-rate increases with
decreasing waiting time, i.e., with increasing climb
velocity. Climb velocity dependson the diffusiveflux of
point defects to or from the dislocation,which in turn
dependson the diffusion coefficientof the relevantpoint
defects.In the caseof crystalsof elements(e.g., metals)the
activationenergyfor creepis thereforeindependent
of stress
and equalto the activationenergyof self-diffusion[45]; in
the caseof simpleionic crystals(e.g., NaC1), it is equal to
the coefficient of diffusion of the slower species,usually
the anion(oxygenfor binaryoxides).For morecomplicated
minerals,climb involvesmulticomponent
diffusionand the
activation energy for creep is not simply related to the
activationenergyof diffusionof any one species(seenext

alwaysthecase,andfor manycrystals3<n<5.
iii) In diffusion-creep (Figure 2c), diffusionof point
defectsnot only controlsthe creeprate, but alsocausesthe
creep strain: vacanciestravel down the stress-induced
chemicalpotentialgradientbetweencrystalfacesin tension
and in compression,
thusdeformingthe crystalin response
to the appliedstress.The creeprate is proportionalto the
applied stressand to the self-diffusioncoefficient;it is
inversely proportionalto the squareof the grain size if
diffusionoccursin thebulk (Herring-Nabarrocreep), and
inversely proportional to the cube of the grain size if
diffusionoccursalongthegrainboundaries
(Coblecreep).
Diffusion creep is a mechanismeffective only at high
temperaturesand in polycrystalsof small grain sizes. As
the creep rate is linear in stress(Newtonian viscosity),
diffusion creep can successfullycompete with climbcontrolledcreep only at low stresses.Deformation of the
grains of a polycrystal by diffusion creep creates
incompatibilitiesthat mustbe relievedby grain-boundary
sliding. Diffusion creep and grain-boundarysliding are
mutuallyaccommodating
processes.
Harper-Dorncreep,like diffusioncreep,is characterized
by a stressexponent n =1, but exhibits no grain-size

&

sectionand [2, 23]).

The diffusive flux of defects responsiblefor climb is

driven by a chemicalpotentialgradient,which is usually

assumedto be proportionalto the appliedshearstress.The
climb velocity is therefore proportional to the applied
stress. Since, by Orowan's equation, the creep rate is
proportionalto the product of the climb velocity by the

dislocation
density(proportional
to c2),andsincethe
activationenergyis stress-independent,
it follows that the
creep-rate at constanttemperatureand pressurecan be

theoretically
expressed
bya power
law: o,:03.Although
in manyinstancesthe stressexponentn of climb-controlled
power-law creep is indeed n = 3, this is by no means

Fig. 2c

Diffusioncreep.Vacancies(V) diffusefrom
regionsof high equilibrium concentration,
at surfacesnormal to the extensive stress,to

regionsof low equilibrium concentration,

at surfacesnormalto the compressivestress.
Atoms(A) diffusein theoppositedirection.

POIRIER

TEMPERATURE
-200

10-!

(C)

200

200

I )00

I'

'

'

--.L-LASTICITY

1400

1800

OLIVINE

d=I mm
10-3

,,, 10-2

10'2

(/) lO-3

POWER-LAW
o-
lO

(/) lO-4

nZ

PLASTICITY

OF

IMPORTANT

MINERALS

This section dealsonly with recentinvestigationson the

minerals most widespreadin the crust and mantle of the
Earth, whoseplastic deformationhas been experimentally
investigatedusing single crystals,thus allowing better
understanding
of the physicalmechanisms.The plasticity
of polycrystallineminerals,or monomineralicrocks(e.g.,
quartzite,dunite...),will be treatedin the "Rock Physics"
section.For a review of the plasticityof crustal rocksand
minerals,see [29, 27, 17]. Data on creepof ceramicscanbe

10-1

1o -6

02

04

06

10

08

HOMOLOGOUS TEMPERATURE, Trr rn

found in [8].

Deformationmechanismmap for olivin,

,Fig. 3

with grainsize 1 mm, showingiso-strain

rate contours(afterFrostandAshby,1982).

dependence.It is observedonly at low stressesand can

probably be consideredas climb-controlledcreep, with a
stress-independent
dislocation
density.
Hydrostatic pressure has little influence on plastic
deformation at low temperatureduring glide-controlled
creep. It is only in the caseof diffusion-controlledcreep
(climb-controlleddislocationcreepand diffusioncreep)that
pressurecan causea noticeabledecreasein the creeprate

throughthe activationvolume for diffusion.The role of

pressureis, of course,importantin the creepof materials
in the Earth's mantle and at the pressuresof the lower
mantle, one must considera pressuredependenceof the
activationvolume for creep [46].
determination

of

the

active

mechanism

of

deformation cannot be done entirely on the basis of the

experimentalrheologicalequation(e.g., by comparingthe
stressexponent to that of the various models and the
activationenergyto thosefor diffusionof differentspecies).
It is essential,wheneverpossible,to examinethe deformed
samplesby transmission
electronmicroscopy[40] in order
to

3.

DIFFUSION
AL
FLO
W
,__

The

constructed
(Figure3), displayingin 2-dimensionalspace
(e.g., c/t and T/Tm) the domains where various
mechanisms are dominant (e.g., power-law climbcontrolled creep, diffusion creep, etc.). The boundaries
betweendomainsare obtainedby equatingthe theological
equationsfor the mechanismsdominantin each domain.
Deformation-mechanismmaps are useful to predict the
behavior of a material only in the intervals in which the
parameters
havebeenconstrained
by experiments.

iii

: lO

241

characterize

the

dislocations

and

observe

their

configurations,
lookingfor diagnosticfeatures[e.g.,5, 22].
The parametersof rheologicalequationssuchas (1) can
be constrained by experiments for various possible
deformation

mechanisms. A mechanism is dominant over a

rangein the variablesdefiningtheexperimental

conditions

(T, c,P, grain-size,

fo2,etc.),if thecorresponding
strainrate is greaterthanthoseof competingmechanisms.
If all
variablesdefiningtheexperimentalconditions,excepttwo,
are kept constant,deformation-mechanism
maps can be

3.1. Quartz

Since the discoveryof water-weakeningby Griggs and

Blacic [20], it has been known that the plastic behaviorof
quartz is very much dependent on the nature and
concentration

of water-related

defects contained

in the

crystals. Reviews on the influence of water on the

plasticityof quartzcanbe foundin [40, 43]. Water-related

defectsmightconsist
of 4 protons
(H+) substituted
for a
Si4+ ionor oneOH2 groupsubstituted
for an oxygen;
however,recentelectronmicroscopywork identifieswaterrelated defectswith high-pressureclustersof molecular
water [41].

Natural, "dry" quartz (H/106Si< 80) is almost

impossibleto deformplasticallyin thelaboratory:it is still
brittle at 1300C, under an applied stressof 1GPa [11].
Thus, most experimental work is conductedon "wet"

(H+/106Si
> 500),oftensynthetic,
quartz
crystals.
Below a critical temperature,which decreasesas water
content increases,wet syntheticquartz is very strongand

behavesmuch as dry natural quartz. Above the critical

temperature,
thestress-strain
curves(at constantstrain-rate)
exhibita suddenstressdropat the yield stress(yield-point)
followed by a hardening stage. The creep curves
correspondingly
exhibitan initial incubationperiodduring
which the creep rate increasesto decreaselater during a
hardeningstage[11]. Dislocationglide usuallyoccurson
the basalplane(0001) in the <1120> direction(a), andon
the prism planes { 1011} in the a or c [0001] , or c+a,
directions(the indices of planesand directionsare given
using Miller-Bravais notation). At high enough
temperatures,there may exist a quasi-steadystatecreep,
following a power law whoseparametersdependon the

242 PLASTIC RHEOLOGY OF CRYSTALS

TABLE1.High-temperature
compression
creep
ofwetsingle-crystal
quartz

OH-/Si SlipSystem
(ppm)
4300
....
370

....
370
....

T
(C)

{2110}c

{2110}C
{ 1010}a

cr

(MPa)

( inbars)

400- 570 (o0

570- 800(]3)
400- 570(O0

40 - 162
"
80 - 200

570- 800(]3)
400- 570(o0
570- 800([)

"
80 - 200
"

orientationof the sampleswith respectto the stressaxis

(Table 1).

10-8-9
10-8-9
10-9-5
10-9'7

Ref.

(kJ/mol)

3.7
3.7
3.0

109

3.0
5.3
3.4

9:2

[28]

:3:3

92

[35]

213

"

117

"

ii) At higher
temperatures,
during
theincubation
period,

clusters
of watermolecules
precipitate
intowaterbubbles;
Observations
of experimentally
deformed
crystals
using theelastic
strain
around
thebubbles
isrelieved
bypunchedtransmission
electron
microscopy
[11,36, 9, 18] support outdislocation
loops,whichexpandby climbandactas
the followingmechanisms:
sources,
thusincreasing
thedislocation
density;
plastic
i) At low temperatures,
low waterfugacity,andhigh yieldoccurs
suddenly
witha stress
drop(yieldpoin0foran
strainrate,deformation
is controlled
by latticefriction,the
applied
stress
highenough
tomakemassive
multiplication
densityof grown-indislocationsis very small, the
of dislocations
possible.
FitzGerald
et al. [18]alsopoint

dislocations
arestraight
andtheirmobility
islow;quartz
is
thenvery strong.

out the role of microfractures in the nucleation of

dislocations.

TABLE2.High-temperature
compression
creep
ofsingle-crystal
olivines
Crystal

Orientation

of stress
axis

(C)

Atm.

Q
(kJ/mol)

(MPa)

(pseudo-cubic)

Ref.

Fo92

Various

1430- 1650

5- 150

CO2/H2 = 0.1

fro)

525

[31]

Fo92

<111>

1500 - 1600

10 - 40

CO2/H2 = 0.43

3.5

523

[13]

Fo92

<110>

1400- 1600

10 - 60

CO2/H2 = 0.43

3.7

523

[13]

Fo100

[101]

1550 -1650

8 - 60

CO2/H2 = 0.33

3.5

564

[14]

Fo100

[111]

1500- 1680

3- 30

H2/A

2.9

667

[16]

Fo90

[101]

1250 - 1400

100

CO22 = 2.3

536

[32]

Fo90

[101]

1250- 1400

100

C022 = 0.25

536

[32]

Fo90

[101]

1250- 1400

100

fo2= 10-6Pa

448

[32]

Fo100

[ 110]

1400-1650

10- 100 H2/CO2

2.6

460

[10]

Fo100

[101]

1400- 1600

20- 100 H2/CO2

3.6

573

[10]

Fo100

[011]

1500- 1600

30- 100

2.7

598

[10]

H2/CO2

POIRIER

243

TABLE 3. High-temperature
creeplawsfor bufferedsingle-crystal
Fo91 olivine

Orientation Buffer
of stressaxis
(pseudo-cubic)

[101]

[011]

[110]

dO

(o inMPa)

(kJ/mol)

opx

0.65

mw

5.3x1011 3.5
1.0x1014 3.5

0.06 690
0.40 700

2
1

0.16

3.5

0.05

2.1x 104

3.5

0.02 540

5.2x 105

3.5

0.23

mw

1.0x 10TM

3.5

0.40 750

opx

0.2
0.02

3.5
3.5

0.0
0.36

370
230

2
1

1.3x 1022 3.5

0.10

1000

g2

1.2

0.15

290

1.0x1022 3.5

0.2

1000

25

0.2

330

d2

opx

mw

3.5

3.5
3.5

0.33

250

300
540

After
[2].1200C
<T<1525
C'10
-12
< fo2< 10-3atm.,buffer:
opx(Mg0.9Fe0.1
$iO3)
or mw(Mg0.7Fe0.
3 O)
= 0o fo2 exp
(-Q/RT)-1
-1
-1
-1
n

in

Flow
law:[1011opx:
-1= 1 +2 ; [101]mw:
-1=1
. +2
.
-[0111opx:
= 1+2
-1=1
. -1+2
. -1 [1101opx:
.-1=1
. -1+2
. -1
[011]row:
= 1+[2 -1
+ 3-1]-1
-[110]mw:

3.2.

O!ivine

Olivine (Mg, Fe)2SiO4, the dominant mineral of the

upper mantle, has an orthorhombiclattice and a slightly
distorted hexagonal close-packedoxygen sublattice.The
common slip systemsare: at low temperature(100)[001],
corresponding
to slip on the basalplaneof the hcp oxygen
sublattice in the a direction; and at high temperature
(010)[100] (prism plane of the hcp sublattice in the c
direction), with cross-slipon other prism planessuchas
(001) and (011).
High temperaturecreep of single crystals in various
orientationsobeysa power-lawcreepequationwith n = 3.5
(Table 2), apparentlycompatiblewith dislocationcreep
controlledby climb of edge dislocations.Examinationof
deformed samplesby transmissionelectron microscopy
suggestthat creepcan be controlledby climb and/orglide,
according to the orientation [15, 21]. However, when
climb-controlwouldbe expected,the activationenergyfor

creep(of the orderof 500 kJ/mol) doesnot tally with that

for diffusionof the slowerspecies:oxygenor silicon(about
335 kJ/mol). One should however note that climb of
dislocationsshouldbe controlledby multicomponent
diffusion of all the species,ratherthanby diffusionof the
slowestspeciesalone[23].
The thermodynamic
stateof olivine with fixed Fe/Mg

ratioisnotentirely
determined
whenT, P andfo2arefixed,
the activity of one component (orthopyroxene or

magnesiowtistite)
must also be specified.Bai et al [2]
performed systematic experiments on olivine buffered
against orthopyroxeneor magnesiowiistitefor various
orientations as a function of temperature, stress, and
oxygen fugacity. The results (Table 3) show wide

variations
in activationenergyand fo2 dependence
according to the experimental conditions:two or three
power law equations are needed to
describe

244

PLASTIC

RHEOLOGY

OF CRYSTALS

TABLE 4. High-temperature
compression
creepof single-crystal
pyroxenes
Crystal

d0

T
(C)

(( inMPa)

Ref

Q
Od/mol)

Enstatite(En99)

1350-

1450

4.6 x 10TM

3.8

750

Enstatite(En96)

1350-

1450

2.1 x 1015

3.9

880

Diopside

1000-

1050

Bufferedby olivine
....

[37]
[37]

4.3

284

P = 5-15 kbar, in talc

[1]

Ar 10% H2-2% H20

[49]

Diopside
Slip on (100)

Slip on { 110}

Hedenbergite

1020 - 1137

4.9 x 103

8.1

742

1137- 1321

7.1 x 10-23

8.8

85

....

[49]

1020- 1130

4.1 x 10-4

6.5

442

....

[49]

1130- 1321

7.0 x 10-18

6.0

48

....

[49]

900 - 1100

1.2 x 108

3.6

526

phenomenologically the creep behaviorover the whole

rangeof experimentalconditions,suggesting
thatdifferent
mechanismshave to be considered.The stressexponent,
however,is equalto 3.5 in all cases(which,incidentally,is
a confirmation

of its limited usefulness as a criterion for

the determinationof the physicalmechanismof creep).

Examination of deformed samples by the oxidationdecoration technique [3] shows that different dislocation
structuresparallelthe changesin power-lawequationsand
confirmsthat severalrate-controlling
mechanismsmay be
operatingin differentexperimentalconditions.
As in the caseof quartz, water-relateddefectsincrease
olivine plasticity. For singlecrystalsof olivinetreatedin a
hydrous environment at 1300C under a hydrostatic
pressureof 300 MPa, and subsequentlydeformedin the

sameconditions
at a constant
strainrateof 10-5s
-1, the
flow stressis reducedby a factorof 1.5 to 2.5, with respect
to that of crystals treated in a dry environment [38].
Samples deformed under wet conditionsand examined in
transmissionelectron microscopyexhibited evidence of

enhancedclimbof dislocations
(dislocation
walls,etc.).
3.3.

Pyroxenes

Although orthopyroxeneMg2Si206 (enstatite)and

clinopyroxeneMgCaSi206 (diopside)are also important
mineralsof the uppermantle,theirplasticpropertieshave
been much less studied than those of olivine. The easiest

slip system of orthorhombic enstatite as well as of

monoclinicdiopsideis (100)[001],with dislocation

glide
on theplanesof thelayersof chainsof SiO4 tetrahedra,and
in the direction of the chains.

P = 10 kbar

[33]

In orthoenstatite,the glissile dislocationswith Burgers

vector [001] can dissociateon (100) [52]. During hightemperaturedeformation, the shear stress can favor the
nucleationof very fine lamella: of clinoenstatiteon (100)
planes; calcium present as a minor ion in enstatitecan
diffuse to the clinoenstatite,thus forming thin lamella:of
calcic clinopyroxene[26], which might be confusedwith
stackingfaults.High-temperaturecreepof (Mg, Fe)2Si206
enstatiteobeysa power law (Table 4); it doesnot seemto
be sensitiveto oxygenfugacitybut the creep-rateincreases
with increasingiron and aluminumcontent[37].
Mechanicaltwinning,primarily on the (100) planein the
[001] direction, is the dominant deformation mode for

clinopyroxenes at low temperatures [33]. At high

temperature,crystalsorientedin sucha way that twinning
is impossibledeform by power-law creep (Table 4). In
experimentson high-temperaturecreep of pure diopside,
Ratteron and Jaoul [49] report a drastic decrease in
activationenergyby a factor of almostten abovea critical
temperatureabout 200C below the melting point. The
crystalsthenbecomemuchmorecreep-resistant
thanwould
be expectedfrom the extrapolatedlower-temperature
creep
law. Examinationof the deformedsamplesby transmission
electronmicroscopy[13] showedthataboveandbelow the
critical temperaturedeformationtook place primarily by
{110] 1/2<110> slip, with no detectableoccurrenceof
climb. Deformationis thereforeprobablyglide-controlled,
whichaccountsfor the high valueof the stressexponent(n
-- 8). Above the critical temperature,the dislocationswere
pinnedby tiny glassyglobules(<10 nm), resultingfrom
incipientpartialmeltingwell belowthe currentlyaccepted

POIRIER

245

TABLE 5. High-temperature
compression
creepof single-crystal
oxideswithperovskite
structure

Orientation

Crystal

T/Tm

Atm

of stressaxis
(pseudo-cubic)

In0

(( in Pa)

Ref.

(kJ/mol)

BaTiO3

<110>

0.75 - 0.92

Argon

-38

3.6

469

30

[4]

KNbO3

<110>

0.84 - 0.99

Argon

-43

3.7

415

38

[5]

KTaO3

< 110>

0.87 - 0.99

Argon

- 11

292

21

[5]

CaTiO3

< 110>

0.67 - 0.78

Air

-39

2.5

274

15

[53]

CaTiO3

< 100>

0.67 - 0.78

Air

-37

3.3

444

24

[53]

NaNbO3

<100>

0.70 - 0.98

Air

-92

5.3

192

14

[53]

melting point of diopside. The fluid droplets may

effectivelyact asobstacles
to dislocation
slip,thuscausing

high pressuresand, there is as yet no high-temperature

creep apparatusoperating at these pressures;the only

theobservedhardening.

information we have so far on the plasticpropertiesof the

ilicatehigh-pressure
phases
comesfromexperiments
that
3.4. High-Pressure Mantle Minerals
Despite their importance for the rheology of the
transition

zone and the lower

mantle,

there is no

informationon the plasticityof the high-pressure

mantle

were performed at room temperature, either on the

metastablephasesat ambient pressureor in-situ in a
diamond-anvilcell. There is also qualitative information
extracted from the examination

of dislocation structures of

the phasesby transmissionelectronmicroscopy.Finally,

experiments on isostructural compounds presumably
pressure. The essential high-pressure phases are
belongingto isomechanical
groupsmayprovidesomebasis
(Mg,Fe)2SiO4[3-phase
andht-spinel,
andmajoritegarnetin
for speculation.
the transition zone, and (Mg,Fe)SiO3 perovskite and
Karato et al. [25] performed microhardnesstests on
(Mg,Fe)Omagnesiowfistite
in thelowermantle.
metastable MgSiO3 perovskitesingle crystalsat room
Magnesiowfistite
hasthe NaCI stuctureand is stableat
ambientpressure.
Therehavebeennumerous
investigations temperature;they found a high value of the Vickers
hardness
(Hv= 18 GPa), higherthanfor olivineor enstatite.
on the plastic properties of the MgO end-member
Meade andJeanloz[42] estimatedthe yield strengthat room
(magnesia
or periclase),whichis easilydeformable
evenat
low temperatures,
on the six{ 110} planesin the < 110>
temperatureof polycrystallineolivine, perovskiteand htdirections.Thereare howeverno experiments
at very high
spinel,preparedin a laser-heated
diamond-anvil
cell, from
temperaturesin controlled oxygen partial pressure
the pressuregradientin the cell. They foundthat at room
minerals in the relevant conditions of temperature and

conditions;experiments
at about0.5Tm, in air or vacuum
are compatiblewith climb-controlleddislocationcreep,
with n = 4 and Q = 400 kJ/mol [8]. Wiistite Fel-x O, the
other end-member,is always non-stoichiometric
and Fedeficient; recent high-temperaturecreep experiments

performed
at variouscontrolled
oxygenfugacities
[24] give
results (n = 4.8, -0.02 < m < 0.11, Q = 290 kJ/mol)
compatible with dislocation creep controlled by the
diffusion of oxygen-relatedpoint defects whose nature
varieswith temperature.
Therearegoodreasons
to believe
that deformation of magnesiowiistiteat lower mantle
conditions is not very difficult: crystals formed by
decomposition
of olivine at high pressurein a diamondanvil cell containa highdensityof dislocations
[47].
All phasesotherthanmagnesiowiistite
arestableonly at

temperature
perovskite
wasstrongerthanspinelor olivine.
However,it shouldbe emphasized
thattheyield strengthof
crystals
depends
onthecriticalresolved
shearstress
(CRSS)
of the available slip systems; the dependence on
temperature
of theCRSSmay differ considerably
for the
variousslipsystems
of onemineral(let alonefor the slip
systems
of differentminerals),so thatthedominantslip
systemat roomtemperature
maynot be the sameat high
temperature,
andtherankingof minerals
according
to their
yield strengths
at roomtemperature
cannotbe assumed
to
remainthe sameat high temperature.

Althoughtransmission
electronmicroscopyof phases
deformedat hightemperature,
in theirstabilityfield, does
not providequantitative
informationon their strength,
it
doesat leastprovidereliablequalitative
information
on the

246

PLASTIC

RHEOLOGY

OF CRYSTALS

dislocationstructures,density,and dissociationfrom which

educatedguesseson the deformabilitycan be attempted.
Thus, in natural ),-spinel (ringwoodite) formed at high
temperaturein shockedmeteorites,stackingfaults and
dislocationssimilar to thosefoundin MgA1204 spinelare
observed[39]. There is also evidencefor the [ 111}<110>
slip systemas in MgAI204 [12], and dislocations
are very
straight,pointingto glide controlof the deformation.
There is no information on the plasticityor dislocation
structuresof MgSiO3 perovskiteat high temperature;it is

reasonableto assumethat the slip systemsare the sameas

in other perovskites,but crystals of perovskite structure
certainlydo not constitutean isomechanicalgroup [5, 53],

probably due to the fact that the distortionsand the

dislocation
corestructures
are different:creepparameters
can
be very different even for apparentlysimilar perovskites
(Table 5). Therefore, the successof the analogueapproach
to try elucidatingthe plasticpropertiesof MgSiO3 at high
temperature is contingent on the existence of a good
analogue(yet to be identified)of MgSiO3 perovskite.

REFERENCES

1.

Av6 Lallemant, H.G., Experimental

deformation of diopside and
websteritc, Tectonophysics, 48, 1-

10. Darot, M. and Y. Gueguen, Hightemperature creep of forsteritc

single crystals, J. Geophys. Res.,

27, 1978.
Bai, Q., S.J. Mackwell and D.L.
Kohlstedt, High-temperature creep
of olivine single crystals, 1.

11. Doukhan, J.C. and L. Tr6pied,

Plastic deformation of quartz single
crystals, Bull. Mineral., 108, 97-

Mechanical

results

for

buffered

samples, J. Geophys. Res., 96,

2441-2463,

1991.

Bai, Q. and D.L. Kohlstedt, Hightemperaturecreep of olivine single

crystals, 3. Dislocation structures,
Tectonophysics,206, 1-29, 1992.
Beauchesne,

S. and J.P. Poirier,

Creep
of baryum titanate
perovskite: a contribution to a
systematic approach to the
viscosity of the lower mantle,
Phys. Earth planet. Interiors, 55,
5.

187-189, 1989.
Beauchesne, S. and J.P. Pokier, In

search of a systematics for the

viscosity of perovskites:creep of
potassium tantalate and niobate,
Phys. Earth planet. Interiors, 61,
6.

182-198, 1990.
Blacic, J.D. and J.M.

Christie,

Plasticity and hydrolyticweakening

of quartz single crystals, J.
Geophys. Res., 89, 4223-4239,
1984.

7.

Burnley, P.C., H.W. Green II and

D.J. Prior, Faulting associatedwith
the olivine to spinel transformation

in Mg2GeO4 and its implications

for deep-focus earthquakes, J.
Geophys.Res., 96, 425-443, 1991.
8.

Cannon, W.R. and T.G. Langdon,

9.

Science, 18, 1-50, 1983.

Cordier, P. and J.C. Doukhan, Water

Creep of ceramics,J. Materials

solubilityin quartzand its influence
on ductility,Eur. J. Mineralogy,1,
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1989.

86, 6219-6234,

1981.

19.

Frost, H.J. and M.F. Ashby,

Deformation mechanism maps,
PergamonPress,Oxford, 1982.
20. Griggs, D.T. and J.D. Blacic, The
strength of quartz in the ductile
regime, Trans. Amer. Geophys.
Union, 45, 102, 1964.

123, 1985.
12. Duclos, R., N. Doukhan and B.

21. Gu6guen, Y. and M. Darot, Les

Escaig, High-temperature creep

behavior of nearly stoichiometric
alumina spinel, J. Materials Sci.,

d6form6e h haute temp6rature,

Philos. Mag., A 45, 419-442,

13, !740-1748, 1978.

13. Durham, W.B. and C. Goetze, Plastic

22. Ingrin, J., N. Doukhan and J.C.

Doukhan, High-temperature deformation of diopside single-crystal.

flow of oriented single crystals of

olivine,

1. Mechanical

data, J..

Geophys.Res., 82, 5737-5753,

1977a.

14. Durham, W.B.

and C. Goetze, A

comparisonof the creep properties

of pure forsteritc and iron-beating
olivine, Tectonophysics,40, T15T18, 1977b.
15. Durham, W.B., C. Goetze and B.
Blake, Plastic flow of oriented

single crystals of olivine, 2.

Observationsand interpretationsof
the

dislocation

structure,

J.

Geophys. Res., 82, 5755-5770,

creepof pureforsteritcat low stress,

Phys. Earth planet. Interiors, 19,

la

forst6rite

1982.

2.Transmission

electron

micros-

copy investigation of the defect

microstructure, J. Geophys. Res.,
96,

14,287-14,297,

1991.

23. Jaoul, O., Multicomponent diffusion

and creep in olivine,J. Geophys.
Res., 95, 17631-17642,

1990.

24. Jolles, E. and C. Monty, High

temperature creep of Fel_ x O,
Philos. Mag., 64, 765-775, 1991.
25. Karato, S., K. Fujino and E. Ito,
Plasticity of MgSiO3 perovskite:
the results

of microhardness

tests

on single crystals, Geophys. Res.

pieces, Reviews of Geophysics

Supplement,29 , 823-843, 1991.
18. FitzGerald, J.D., J.N. Boland, A.C.
McLaren, A. Ord and B. Hobbs,
Microstructures

26. Kirby, S.H. and M.A. Etheridge,

xsolution of Ca-clinopyroxene
from orthopyroxene aided by
deformation,
Phys.
Chem.
Minerals, 7, 105-109, 1981.

1979.

17. Evans, B.and G. Dresen, Deformation of Earth materials: six easy

in water-weakened

single crystals of quartz, J.

Geophys. Res., 96, 2139-2155,
1991.

dans

Lett., 17, 13-16, 1990.

1977.

16. Durham, W.B., C. Froidevaux and

O. Jaoul, Transient and steady-state

263-274.

dislocations

27. Kirby, S.H. and A.K. Kronenberg,

Rheology of the lithosphere:
selected topics, Reviews of
Geophysics,25, 1219-1244, 1987.
28. Kirby, S.H. and J.W. McCormick,
reep of hydrolytically weakened
syntheticquartz crystalsorientedto
promote {21 10}<0001> slip: a
brief summaryof work to date, Bull.
Mineral, 102, 124-137, 1979.

POIRIER

hydrolyrically weakened synthetic

quartz crystals at atmospheric
pressure, J. Geophys. Res., 89,

29. Kirby, S.H. and J.W. McCormick,

Inelastic properties of rocks and
minerals: strengthand theology, in
Handbookof physicalpropertiesof
rocks, edited by R.S. Carmichael,

1984.

Earth's lower mantle, Phys. Earth

planet. Interiors, 35, 283-293,

4241-4255,

rheology of enstatite: implications

for creep in the mantle, Geophys.

Boca Raton, Florida, 1984.

Stern, Mantle phase changes and

38.

deep-earthquake faulting in
subducting lithosphere, Science,

Res., 79, 2045-2051, 1974.

32. Kohlstedt, D.L. and P. Hornack,

Effect of oxygenpartial pressureon

the creepof olivine, in Anelasticity
of the Earth, editedby F.D. Stacey,
M.S. Paterson and A. Nicolas, pp
101-107, American Geophysical
Union, Washington D.C., 1981.
33. Kollt,J.J., and J.D. Blacic, Deformation of single-crystal clino-

pyroxenes:1. Mechanicaltwinning
in diopside and hedenbergite,J.
Geophys. Res., 87, 4019-4034,

11319-11333,

39.

pyroxenes: 2. Dislocation-controlled flow processesin hedenbergite,

J. Geophys.Res., 88, 2381-2393,

Revcolevschi,

35. Linker,

M.F.

and S.H.

Kirby,

Anisotropy in the theology of

hydrolyrically weakened synthetic
quartz crystals, in Mechanical
Behavior of crustal rocks (The
Handin volume) , edited by N.L.
Carter, M. Friedman, J.M. Logan
and D.W. Stearns, pp 29-48,
American Geophysical Union,
Washington, D.C., 1981.
36. Linker, M.F., $.H. Kirby, A. Ord
J.M.

Christie,

Effects

of

compression direction on the

plasticity and rheology of

phase
and

1986.

48. Poirier, J.P., C.Sotin and S.Beau-

chesne, Experimental deformation

anddataprocessing,
in Deformation
processes
in minerals,ceramicsand
rocks, edited by D.J. Barber and
P.G. Meredith, pp 179-189, Unwin
Hyman, London, 1990.

66-68, 1980.
40. McLaren, A.C., Transmission elect-

ron microscopyof minerals and

rocks, CambridgeUniversity Press,
Cambridge, 1991.
41. McLaren, A.C., J.D. FitzGerald and
J. Gerretsen, Dislocation nucleation

and multiplication in synthetic

to

49. Ratteton, P. and O. Jaoul, High-

temperature
deformationof diopside
single-crystal. 1.Mechanical data,
J. Geophys. Res., 96, 14,27714,286, 1991.
50. Ricoult, D.L. and D.L. Kohlstedt,

Creep of Fe2SiO 4 and Co2SiO4

single crystals in controlled
thermodynamic
environment,
Philos. Mag., 51, 79-93, 1985.

water-

weakening,Phys. Chem.Minerals,
1989.

42. Meade, C. and R. Jeanloz, The

strengthof metal silicatesat high

pressures and room temperature:

51.

implicationsfor the viscosityof

the mantle, Nature, 348, 533-535,
1990.

1983.

olivine

structures, Nature, 321, 603-605,

olivine and pyroxene:implications

for mantle theology, Science, 207,

relevance

of

spinelinto perovskiteandrock salt

high-pressure polymorphs of

quartz:

Eutectoid

transformation

1985.

Madon, M. and Poirier, J.P.,

Dislocations in spinel and garnet

I6, 465-482,

1982.

34. Kollt, J.J., and J.D. Blacic, Deformation of single-crystal clino-

and

Res. Lett., 18, 2027-2030, 1991.

Mackwell, S.J., D.L. Kohlstedt and
M.S. Paterson, The role of water in
the deformation of olivine single

1984.

47. Poirier, J.P., J. Peyronneau, M.

Madon, F. Guyot,
and A.

crystals, J. Geophys. Res., 90,

252, 216-225, 1991.

31. Kohlstedt, D.L. and C. Goetze, Low-

stress, high-temperature creep in

olivine single crystals,J. Geophys.

46. Poirier, J.P. and R.C.Liebermann,

On the activation volume for creep
and its variation with depth in the

37. Mackwell, S.J., High-temperature

vol III, pp 139 - 280, CRC Press,

30. Kirby, S.H., W.B. DurhamandL.A.

24?

43. Paterson, M.S., The interaction of

water with quartz and its influence

on dislocation flow -- an overview,

in Rheology of solids and of the

Earth, edited by S. Karato and M.
Toriumi, Oxford University Press,

Oxford, pp 107-142, 1989.

44. Pokier, J.P., Shear localization and
shearinstability in materialsin the
ductile field, J.Struct. Geol., 2, 135142, 1980.

45. Poirier, J.P., Creep of Crystals,

Cambridge University Press,
Cambridge,1985.

Sotin, C. and J.P. Pokier, Analysis

of high-temperature creep experiments by generalized non-linear
inversion, Mechanics of Materials,
3, 311-317, 1984.

52.

Van Duysen,J.C., N. Doukhanand

J.C.

Doukhan,

Transmission

electron microscope study of

dislocationsin orthopyroxene(Mg,
Fe)2Si206, Phys. Chem. Minerals,
12, 39-44, 1985.

53. Wright, K., G.D. Price and J.P.

Poirier, High-temperature creep of
the perovskites CaTiO 3 and
NaNbO3, Phys. Earth planet.
Interiors,

74, 9-22, 1992.

PhaseDiagramsof Earth-FormingMinerals

Dean C. Presnall

The purposeof this compilationis to presenta selected

and compactset of phasediagramsfor the major Earthforming minerals and to show the presentstateof knowledge concerningthe effect of pressureon the individual
mineral stabilitiesand their high-pressuretransformation
products.The phasediagramsare arrangedasfollows:
Figure
Silica

Feldspars
Pyroxenes

2-7
8-13

elsewhere [ 13, 50, 70, 122, 154]. Other usefulreviews and

compilations of phase diagrams are Lindsley [96] for

Olivine

14-16

oxides, Gilbert et al. [60] and Huckenholz et al. [74] for

Garnet

17-20

amphiboles,Liu and Bassett[104] for elements,oxides,

and silicates at high pressures,and Phase Diagrams for
Ceramists[ 129-137]. It will be notedthat somediagrams
are in weight percentand othersare in mole percent;they
have usually been left as originally published. Minor
drafting errors and topological imperfections that were
found on a few of the original diagrams have been

Iron-titanium

oxides

Pargasite
Serpentine
Phlogopite
Iron

21-23

24
25
25
26-27

The compilationhasbeencompressed
in threeways. (1)

correctedin the redrafteddiagramsshownhere.

D.C. Presnali,University of Texas, Dallas, GeoscienceProgram, POB 830688, Richardson,TX 75083-0688

Mineral Physicsand Crysta!!ography

A Handbook of Physical Constants
AGU

For several of the mineral groups, only representative

phasediagramsare shown. (2) The presentation
of more
complex phase diagrams that show mutual stability
relationships among the various minerals and mineral
groupshas been minimized. (3) Many subsolidusphase
diagrams important to metamorphic petrology and
thermobarometry are excluded. Reviews of these
subsolidusphaserelationshipsand thermodynamicdata for
calculating the phase diagrams have been presented

Reference

Shelf 2

Copyright 1995 by the AmericanGeophysicalUnion.

248

PRESNALL

3000:

249

dodeite + I_quid
1500

1400

2000

Liquid

--

Jadeire
+

o 1300

Coesite

/I

Stishovite

1200

e +Quartz

I000

I100

Pressure, GPa
5

I0

Pressure, GPa

Fig. 1. Phase relationshipsfor SiO2. Numbers beside

curvesrefer to the following sources:1 - [178]; 2 - [168]; 3
- [160]; 4 - [4]. The melting curve is from Jackson[77] at
pressuresbelow 4 GPa, from Kanzaki [83] at pressures
between 4 and 7 GPa, and from Zhang et al. [178] at
pressuresabove 7 GPa. The temperature of the high
quartz-low quartz-coesiteinvariantpoint is from Mirwald
and Massanne [ 113]. The quartz-coesitetransitionis from
Bohlen and Boettcher [24] but note that their curve lies

toward the low-pressureside of the range of curves by

others[5, 23, 31, 62, 89, 113]. The high quartz-lowquartz
curve is from Yoder [ 172]. Boundariesfor the tridymite
and cristobalite fields are from Tuttle and Bowen [ 164]

except that the cristobalite-highquartz-liquid invariant

pointhasbeenshiftedto 0.7 GPa to accomodatethe dataof
Jackson [77]. Silica has been synthesizedin the Fe2N
structureat 35-40 GPa, T> 1000Cby Liu et al. [ 105], and
at 35 GPa, 500-1000C by Togaya [162]. However,
Tsuchida and Yagi [163] reporteda reversibletransition
between stishoviteand the CaCI2 structureat 80-100 GPa

Fig. 2. Isopleth for the composition,NaAISi30 8 [12, 16,

33]. The albite = jadeite + quartz reaction shownby Bell
and Roseboom [12] and in this figure is about 0.1 GPa
higher than the curve of Boettcherand Wyllie [22]. The
,latter passesthrough the "consensus"value of 1.63 GPa,
600C for this reaction [81]. Also, the quartz-coesitecurve
shown by Bell and Roseboom [12] and in this figure is
about0.4 GPa higherat 1300Cthanthe pressuregiven by
a linear extrapolationof the curve of Bohlen and Boettcher
[24], which is shownin Figure 1. The curve of Bohlen and
Boettcher would intersect the albite = jadeite + quartz
curve at about 1300C rather than the jadeite + quartz
(coesite) = liquid curve. At about 1000C, Liu [101]
synthesized NaAISi308 in the hollandite structure at
pressuresfrom 21 to 24 GPa, and a mixture of NaAISiO4
(CaFe204-type structure) + stishovite above 24 GPa.
Jadeite,NaAISi206; Coesite,SiO2.
1800

1600

Cor+
Liquid_
-

1400

Anorthite

1200

G+r _

liquid. Locationsof dashedlines are inferred.

- Liquid/

and T> 1000C.

Fig. 3. Isoplethfor the composition,CaAI2Si208 [67, 94].

Car, corundum;
Gr, grossular;
Ky, kyanite;Qz, quartz;Liq,

Ky

+
Oz

IOOO
o

Pressure,

GPo

i
4

2S0

PHASE DIAGRAMS

IGO0

I
--

1500

Liquid

o.,
'-

1400

--

E 1300

1200

ilOO

--

--

I
I

I
2

Pressure,

I
3

I
4

GPa

Fig.4. Isopleth
forthecomposition,
KAISi308[93,149]. At 12GPa,900C,
Ringwood
et al. [144]
synthesized
KA1Si308
in thehollandite
structure.
In experiments
from8-10GPaand700-1000C,
Kinomura

etal. [88]synthesized
theassemblage
K2Si409
(wadeite-type
structure)
+ kyanite
(A123iOs)
+ coesite
(SiO2)
fromthecomposition
KA1Si308;
andtheysynthesized
thehollandite
structure
ofKA1Si308
at900C,
12GPa,
and at 700C, 11 and 11.5 GPa.
An

CaAI2Si20e

0.1 GPa

Ab

NaAISi308

Or

Molepercent

KAISi30e

Fig.5. Compositions
of coexisting
alkalifeldspar
andplagioclase
at0.1GPaandtemperatures
from800to

900C,
asindicated
[49].Notethatthephase
boundary
isessentially
isothermal
except
intheAb-rich
portion
ofthediagram.
Manyothers
havediscussed
ternary
feldspar
geothermometry
[10,39,54,58,63,66,75,80,
139,142,151-153,
165]andternary
feldspar
phase
relationships
[68,121,156,
164,175].An,anorthite;
Ab,
albite; Or, orthoclase.

PRESNALL

1800

1700

Liquid

Liquid + Corundum

1600

1500

Liquid + Plagiocla
+

2GPa

Corundum

1400

Plagioclase
1300
1700

Liquid,+

Corunaum

? 16oo
Liquid
.--1500

Liq + Plag
+Corundum

E 1400

1300

Plagioclase
1200

I Atm

Liquid + H2!

I100

IOOO

H20-saturated,
0.5

GPa

Liquid+ Plagioclase+ H20

9OO

Plagioclase+ H20

8OO

7OO

I0

NaAISi308
Albite

20

30

40

50

60

Mole Percent

70

80

90

CaAI2Si208
Anorthite

Fig. 6. Temperature-composition
sections
for thejoin NaAISi308(albite)- CaAI2Si208(anorthite)under
anhydrous
conditions
at 1 arm[26, 117], 1 GPa,2 GPa [33, 94], andunderH20-saturated
conditions
at 0.5
GPa [79, 175].

251

252

PHASE

DIAGRAMS

1300

Liquid
1200

Leucite + Liquid
Leucite

Feldspar

+Liquid

I Atm,
I100

hydrous

Feldspar
+Liquid
'
I000

Feldspar

900

Liquid

+ Vapor

0.2 GPa,
,O-saturated

8oo

0.5

GPa,

H20-saturated

Orthoclase + Liquid + Vapor

Ab+

Liq + V
7OO
Albite

Orthoclase +Vapor

2 Feldspars

600

+ Vapor

5OO

I0

NaAISi08

20

30

40

50

60

70

Weightpercent

80

90

KAISi308

Fig. 7. Temperature-composition
sectionsfor thejoin NaA1Si308(albite)- KA1Si308(orthoclase)
under
anhydrous
conditions
at 1 atm[148],andunderH20-saturated
conditions
at 0.2 GPa [29] and0.5 GPa [119,
175]. Ab, albite;Liq, liquid;V, vapor. Locationsof dashedlinesareinferred.

PRESNALL

253

2500

Liquid

Majorire
2000

Perovskite

h
inoenstatite

Orthoenstatite

1500

Ilmenite

Protoenstatite

High-P
Modified Spinel

Clinoenstatite

Stishovite

IOOO

Spinel + Stishovite
Low
Clinoenstatite

5O0

IO
Pressure,

15
G Pa

20

25

Fig.8. Isopleth
forthecomposition
MgSiO
3 [7,9, 35,45,56,57,65,76,92, 127,140,169].Foradditional
dataatpressures
above15GPa,seealsoSawamoto
[147]. Notshown
is a singular
pointatabout0.13GPa
belowwhichenstatite
meltsincongruently
to forsterite
+ liquid[45]. Positionof dashedcurveis inferred.For
additionaldataon meltingtemperatures
up to 58 GPa,seeZerr andBoehler[177].
I

1900
-

,,oo

Fig.9. Meltingcurvefor diopside,

CaMgSi206.Curve1 is
from Williams and Kennedy [166] uncorrectedfor the

effect of pressureon thermocouple

emf, and curve2 is
from Boyd andEngland[33]. SeealsoYoder [173] for

1400
I
13001

databelow 0.5 GPa. For CaMgSi206 composition,Mao et

al. [ 110] founda mixtureof perovskite(MgSiO3) andglass
at 21.7 and 42.1 GPa and 1000-1200C.They interpreted

Pressure, GPa

the glassto be a secondperovskitephaseof CaSiO3

composition
whichinvertedto glassonquenching
[seealso
102].

254

PHASE

DIAGRAMS

1600
L

1650 C

l atm

20

,,Fo+
Liq

--

II+Gt

1,500

Liq

Pen+ F'o+ Liq

II + CoSiO3Pv
Gt + CoSi03Pv

18

,,

,Opx Opx+ Fo+

Gt

Di+
16

14oo

+ Fo+Liq

Gt+CM

+
,

CaSiOsPv

Cp Cpx
+C

x+Gt

Pig + Di

1300

Cpx+ Di
Di

12

-I-

CaSiO3 Pv

Cpx

2oo

Di

I0

Pen

+ Di
_

IlOO

Opx+ Cpx

IOOO

MgSiO3
Oen + Di

Mg2Si206 20

40

60

80 CoMgSi206

Mole percent

Fig. 10. The join Mg2Si20 6 (enstatite) - CaMgSi206

(diopside) at 1 atm [43]. Many othershave also discussed
phaserelationshipson this join [9, 14, 36, 41, 42, 56, 78,
91, 106, 170, 171]. Fo, forsterite,Mg2SiO4;Liq, liquid;
Pen,protoenstatite;
Opx, orthopyroxene;
Pig, pigeonite;Di,
diopside;Oen, orthoenstatite.

1800

20

30

40

50

Molepercent
CaSiO
3 Di

60CaSi03

----,,-

Fig. 12. Pressure-compositionsection for the system

MgSiO3-CaSiO3 at 1650C [55, 57].
Garnet and
clinopyroxene,when they are free of Ca on the left-hand
margin of this diagram, are the samephases,respectively,
as majorite and high-P clinoenstatite on Figure 7. I1,
ilmenite; Gt, garnet; Pv, perovskite;Cpx, clinopyroxene;
Opx, orthopyroxene;Di, diopside; CM, a high-pressure
phaseof unknownstructure.

Oen + Di

1600['J
5_2 ''-/53 4 5

'.10GPo _l

?Cen
I 1.5

Di

Di

Oen+Pig

Fig. 11. Thermodynamicallymodeledsubsolidusphase

relationships for the system Mg2Si20 6 (enstatite)800D

Mg2Si206 20

40
Mole

60
percent

80 CaMgSi206

CaMgSi20 6 (diopside)from 1.5 to 10 GPa [56, 44]. The

thermodynamic models are based on data from other
sources [37, 98, 118, 123, 128, 150]. See also data of
Biggar [15] from 1 atm to 0.95 GPa.

PRESNALL

Di

255

Hd

I atm

-500-
ooo---,

--

o o___._.,,o --------z.-------Z '-':---'---"

,o

, -_

--

--Polythermal
, boundary
of
"Forbidden
'

Zone"

,,oo '"'-C
,

25

en

zoo oO5oo

50

75

Es

Mole percent

Fi[.]3.Ortboyroxee
+u[ite,
ortboproxee
+[ite+pi[eoite,
d i[oit
+[iteeqilibri
armad500-]
3C [95].Pberelationships
totefi[btofthe[orbidde
zone
boudr
e roetastable
mltiv
to[ite+olivi+silicm
LiJsl[] bspeseted
teeotbe
similar
di[rms
t0.5,],
P. LiJslJ AJs [9?]sbolJ
bconsulted
forcoffectio
pocedres
equimd
before

pyroxees
othese
di[ms
for8eotbermometry.
[, estatite
(8SiO3);
Fs,[rrosilit
(FSiO);
Di,
JiosiJ
(C[Si]Of); BJ,bedebersite
(CeSiO6).

I I JI+Liquid
I I %,,
I JI I I I I
2500
I I I I JI I I I JI I Periclase
Anhydrous B + Liquid

Liquid

Modified

Spinel

Forsterite

Spinel
IOOO

50O

I0
Presse,

15

20

25

G Pa

Fig.14.Isopleth
forthe
composition
Mg2SiO4
[48,
57,141].
Additional
studies
ofthe
melting
relationships
areOhtani
and
Kumazawa
[126]
and
Kato
and
Kumazawa
[84-86].
Locations
ofdashed
lines
areinferred.

2000

1800

Lquld
_

1700

1800
%

LIQUID

1600

1600

t500

14oo

-Spinel
+Lqud
/.z'-

Enstatlte

..--'"'/
+?+L)qu)d

Pyrope

Enst+at,te
/

Sapp+h,r,ne
/
1200
S11rncimt

1400
OLIVlNE

I000e/

1300

1200

Pressure, GPo

'o o Jo ooOFS,O
Mg2SO 'o 'oWeight
percent
Fig. 15. Phase relationshipsfor the systemMg2SiO4
(forsterite)- Fe2SiO4(fayalite) in equilibriumwith Fe at 1
atm [27]. Locationsof dashedlines are inferred.

i'

Fig. 17. Isoplethfor Mg3AI2Si30]2, pyropegarnet. Phase

relationshipsat pressureslessthan 5 GPa are from Boyd
and England [32]. The melting curve at 5 GPa and above
is from Ohtani et al. [125]. Liu [99] reportedthat pyrope
transformsto perovskite+ corundumat about30 GPa,200800C. Liu [100] subsequentlyrevised this result and
found that pyrope transformsto the ilmenite structureat
about 24-25 GPa, 1000-1400C, and that ilmenite then

transformsto perovskite at about 30 GPa. Locationsof

dashed lines are inferred.

".1

_ bp
20

i '".//ooc

Sp + Mw + St

28

1600
O

,-,

Pv+Gt

[- 'v
..- Pv
+Ale0
3,
-

II

Sp

15

Mod Sp + Sp

o,oA
18

2oo c

'XNXX
x+Sp
NNN
I-

io

Mg2siO 20

40

60

/
Sp+St+Gf / /

16 .....

80 Fe2s04

Mole percent

Fig. 16. Pressure-composition sections for the join

Mg2SiO4-Fe2SiO4 at various temperatures. Phase
relationships above 21 GPa are from Ito and Takahashi
[76] and thosebelow 21 GPa are from Akaogi et al. [3].
Other references [51, 8, 15] give additional data and
discussionof these phase relationships. Pv, perovskite
(MgSiO3-FeSiO3 solid solution); Mw, magnesiowstite
(MgO-FeO solidsolution);St, stishovite(SiO2);Sp, spinel;
Mod Sp, modifiedspinel;O1,olivine.

I0
MgSiO 5

IO

15

20

25

50 A zO

Molepercent
AI20
Fig. 18.Pressure-composition
sectionfor thejoin MgSiO3A1203 at 1000 and 1650C [57, 82]. For additional data

alongthe boundarybetweenthe gnet and clinopyroxene

+ garnetfieldsat 10C, seeAkaogiandAMmoto [2]. At
11 and 1600Cfor pressuresbetween2 and 6.5 GPa, the
AI20 3 contentof pyroxene in equilibrium with gnet
increaseswith decreasingpressureto at least 15 mole
percent[30, 34].

PRESNALL

257

AI203
Corundum

1200 C,3 GPo

(CaAI2SiO6

AI2SiOl

Ca3AI2Si

Pyrope

Grossu

Mg-Gt
Ca-Gt

Di + En

Wo+Di

CaSiO
3

CaMgSi
206

Wollastonite

Diopside
Weight

MgSi03
Enstatite

percent

Fig.19.Thesystem
CaSiO3-MgSiO3-AI203
at1200C,
3GPa[30].Co,corundum;
Di,diopside'
Ca-Gt,
Cagarnet;
Mg-Gt,Mg-garnet;
Wo,wollastonite;
En,enstatite;
CaA12SiO6,
Ca-Tschermak's
molecule.
Pyrope
Gt
9, 2000-

r, Mole
i/
io,2o35-
8, 195o-

II,20651
12,21oo
1
Cpx[
50

40

:30

20

,x

IO

Enstatite

MgSiO
Diopside
Mole5/oCaSiO3
Fig.20.Compositions
(unsmoothed)
of coexisting
garnet
(Gt),Ca-rich
pyroxene
(Cpx),andCa-poor
pyroxene
(OpxorCpx)atvarious
pressures
andtemperatures
[69].Labels
ofthetype,
9, 2000,indicate
pressure
(GPa)
followed
bytemperature
(C).Pyrope,
Mg3A12Si3012;
Grossular,
Ca3A12Si3012.

258

PHASE

DIAGRAMS

LIQUID

2 LIQUI

1600

'%,

-IRON

LIQUID
OXIDE
%-6

0
HEMATITE
I 2 '%10
xo
+

'X '%
LIQUID
MAGNETITE+LIQUID
. /I

I0%

HEMATIT

+ LIQUID
AIR

1400
)"-IRON

MAGNETITE

1200

10

..

7'- IRON + WUSTITE

7'

-i-

HEMATITE

WUSTITE

__ i( 12
I000
.o

WUSTITE

800

Q-IRON+ WOSTITE

10

TI4

+ MAGNETITE

iC'--.

600

Q-IRON

+ MAGNETITE

1(20

--I( I'0

id22___.__

I(24

ld,4___._

I 26
-28
1
3o

I0-

i( '2

iL

_.
18

400

Fe 0.1 0.3

FeO 23

24

25

26

27 Fe304

29

Fe203

Weight % Oxygen
Fig.21.Temperature-composition
section
forthesystem
Fe-Oat 1 atm[46,47,64, 120,138].Lightdash-dot
lines are oxygenisobarsin atm.

PRESNALL

259

Rutile

TiO 2

80 ,/
Rutile

-8

1300C

I '+
Fpb-Psb

Fpb

One

atm

t
-3.43

I
/

/
I
i

TIrn

/IIm-Hem

I
I

-8
/

4O

Ilrn-

Us

Fpb-Psb
Hern

C02
/

/
/

/
/
-I0

Usp-Mt

/
/

-8

/
FeO

Air

-I-

Usp- Mt
+
WEs

\
-0.68

IIm-Hem

Psb

20

40

60 Mt
Mole
percent

80

I
Fe203
Hem

Fig.22.The
system
TiO2-FeO-Fe203
at1300C,
1atm
[161
]. Light
dashed
lines
areoxygen
isobars
labeled
inlogoxygen
fugacity
units
(atm).
Psb,
pseudobrookite
(Fe2TiO5);
Fpb,
ferropseudobrookite
(FeTi20$);
Ilm,
ilmenite
(FeTiO3)'
Hem,
hematite
(Fe203)
' Usp,
ulvospinel
(Fe2TiO4);
Mt,magnetite
(Fe304)'
Was,
wiistite
(Fel_xO).

26O PHASE DIAGRAMS

-IO

-2o

MT-USP

-25

500

Miscibility gap

600 700 800

900

I000 I100 1200 1300

Temperoture, C

Fig.
23.Temperature-oxygen
fugacity
(f02)
grid
forcoexisting
magnetite-ulvospinel
solid
solution
and
ilmenite-hematite
solid
solution
pairs
[155].
Lines
with
labels
ofthe
type,
1-70,
indicate
mole
%ilmenite
in
the
ilmenite
(FeTiO3)
-hematite
(Fe203)
solid
solution.
Lines
with
labels
ofthe
type,
U-70,
indicate
mole
%

ulvospinel
inthe
ulvospinel
(Fe2TiO4)
_magnetite
(Fe304)
solid
solution.
Mt,
magnetiteulvospinel' Usp,

Ilm, ilmenite;Hem, hematite.

PRESNALL

'

'

261

'

I-

3114

IOOO

15

12oo

14 o

Temperature *C
Pa-out (

Fi. 25. Pressure-temperature

projectioashowia the upper
temperaturestabilitylimits for serpeatiae,M3SiOs(OH)4
(curves 1 aad 2), and phloopite, 3AIS3010(O)
(ues 3-6). Nuabers besideurves refer to the follob
sources:1 - [28]' 2- [90]' 3-6- [115]. Curves5 and 6 ive
the aximum stability of phloopite in the preseae
5) and absence(curve 6) of vapor. Curves3 and4 ive the
eorrespo.ai. axium stability of phloopite ia the
presenceof forsterire and enstatite, and representmore
1osl th stbilit of phloopite in the mntle. Curves3-

Pc]

Pa-out
(0.3.)
---Pa-out
(0.5)
800

I000

II

1200

1300

1500

Temperature,C

Fig. 24. Pressure-temperature

projectionof pargasite,(Pa)
NaCa2MgnA13Si6022(OH,F)2,
stability limits. The
univariant curveslabeledPa-out (1.0), Pa-out (0.5), and Paout (0.3) are from Gilbert [59], Holloway [71], and Oba

[124], and give the maximumstabilityof pargasiteduring

melting in the presenceof a pure H20 or H20-CO2 vapor
with H20 mole fractions of 1.0, 0.5, and 0.3. Small
concentrations of other constituents in the vapor are
ignored. The dashed curve labeled OH I00, and the
patterned areas labeled F43OH57 and Fi00 are from
Holloway and Ford [72] and Foley [52], and show the
breakdownof pargasiteduring vapor-absentmelting for
different proportions of fluorine and hydroxyl in the
pargasite.

6 r ,ot u,ivb,t

I114]. S

Yoder aa ushiro [174]

for lir stua of the stbilit of phloopite.

ad Brerley [ 116] speubted that a siaubr poim exists
about 1.5 GPa on curve 4, so that the curve above this

pressureis

262

PHASE

DIAGRAMS

8000[ I

2000

'

,,S,
I/
I

6000k

'/'

///

40001-

ooo

100

0
0

I00

?
Pressure,

Fi. ]?. ib

(bcc)

200

500

J
,oc
,

GPa

pressure melti

curves Cot iro..

Mirwald
adKennedy
[i ]]], Budy[40],adBoebler
[17]
e usedCotthe -s-? phaserelmiosbips. Numbersbeside

50

meld curvesad brackets

reCerto thefollowi. so.roes:
45]4, ]5]. 6allaber ad Abres [54] Could that earlier
sbk data om their laboratow [] 1] e 10E too blab,

o0o

IO

ti

2o

Pressure,

$o

which
brings
thedataof Bass
etal. [11]andBrown
and

4o

GPa

Fig. 26. Low pressurephase relationshipsfor iron.

Numbers besidecurvesrefer to the following sources:1 [159]; 2- [109]; 3- [112]; 4- [103]; 5 - [6]; 6- [20, 40]; 7[107]; 8 - [73]; 9 - [17, 21]. Severaladditionalreferences
[61, 108, 179] alsodiscussthe o-
transition,.

Acknowledgements.
Preparationof this compilation was
supported
byTexasAdvanced
Research
Program
Grants009741007 and 009741-066,andby NationalScienceFoundationGrants
EAR-8816044

and EAR-9219159.

Contribution no. 738,

Geosciences
Program,
Universityof Texasat Dallas.

McQueen [38] into agreement. The shock data of Yoo et

al. [176] (not plotted but located at 6350 K, 235 GPa and
6720 K, 300 GPa) are at slightly higher temperaturesthan
the data of Brown and McQueen. (Ross et al. [145] and

Anderson[8] haveproposedthe existenceof a new phase,

oC-iron,that is stablealong the liquidus at pressuresabove
about 170 GPa. On the basis of molecular dynamics
calculations,Matsui [ 111] has also proposedthe existence
of a new phaseat 300 GPa and temperaturesabove5000 K.
Saxena et al. [146] have suggestedthat ot'-iron is the
liquidus phase down to a pressureof 60-70 GPa. CM,
core-mantle boundary (136 GPa); IOC, inner-outer core
boundary(329 GPa); C, centerof Earth (364 GPa).

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thermo-

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L.,

Bukowinski,
(Mg,Fe)SiO3

and

M.

S.

T.

Stability
of
perovskite and the

structure of the lowermost mantle,

Geophys. Res. Lett., 19, 10571060,

1992.

158. Stormer, J. C., Jr., A practical

two-feldspar geothermometer,
Am.

Mineral.,

60,

667-674,

1975.

159. Strong, H. M., R. E. Tuft, and R.

E. Hannemann,

The iron fusion

curve and the triple point, Metall.

Trans., 4, 2657-2611,

1973.

Mg2SiO 4 up to 200 kilobars, in

High-PressureResearch,editedby
H.

Manghnani

and

S.

Akimoto, pp. 255-266, Academic

Press, 1977.

161. Taylor, R. W., Phaseequilibria in

the system FeO-Fe203-TiO2 at
1300C, Am. Mineral.,
1030, 1964.

Homan, R. K. MacCrone, and E.

Whalley, 373-376, 1984.
163. Tsuchida, Y., and T. Yagi, A new

post-stishovite high-pressure
polymorph of silica, Nature, 340,
217-220,

1989.

Origin of granite in the light of

experimental studies in the system NaA1Si308-KAISi308-SiO 2H20, Geol Soc. Am. Mem. 74,
153 pp., 1958.
165. Whitney, J. A., and J. C. Stormer,
Jr., The distributionof NaAISi30 8
between coexisting microcline
and plagioclase and its effect on
geothermometric calculations,
Am. Mineral,

49, 1O16-

162. Togaya, M., High pressure

generation
and
phase
transformations of SiO 2 and

silica at atmospheric pressure,

Am. J. Sci., 273, 488-497,

1973.

171. Yang, H.-Y., and W. R. Foster,

Stability of iron-free pigeonite at
atmospheric
pressure, Am.
Mineral.,

57, 1232-1241,

1972.

172. Yoder, H. S., Jr., High-low quartz

inversion up to 10,000 bars,
Trans. AGU, 31, 827-835, 1950.

164. Tuttle, O. F., and N. L. Bowen,

62, 687-691,

1977.

166. Williams, D. W., and Kennedy,G.

C., Melting curve of diopside to
50 kilobars, J. Geophys. Res.,

173. Yoder, H. S., Jr., Change of

melting point of diopside with
pressure, J. Geol., 60, 364-374,
1952.

174. Yoder, H. S., Jr., and I. Kushiro,

Melting of a hydrousphase:phlogopite, Am. J. Sci., 267-A, 558582,

1969.

175. Yoder, H. S., Jr., D. B. Stewart,

and J. R. Smith, Ternary feldspars, Carnegie Inst. Washington
Year Book 56, 206-214, 1957.
176. Yoo, C. S., N. C. Holmes, M.
Ross, D. J. Webb, and C. Pike,

Shock temperaturesand melting

74, 4359-5366, 1969.

167. Williams, Q., R. Jeanloz, J. Bass,
B. Svendsen, and T. J. Ahrens,

of iron at Earth core conditions,

Phys. Rev. Lett., 70, 3931-3934,

The melting curve of iron to 250

gigapascals: A constraint on the
temperature at Earth's core,

177. Zerr, A., and Boehler,R., Melting

of (Mg,Fe)SiO3-perovskiteunder

Science, 236, 181-183, 1987.

168. Yagi, T., and S. Akimoto, Direct

determination

160. Suito, K., Phase relations of pure

M.

GeO2, in High Pressurein Science

and
Technology, Mat.
Res.
Symp. Proc., 22, edited by C.

of

coesite-

stishovite transition by in-situ Xray measurements, Tectonophys.,

35, 259-270, 1976.
169. Yamamoto, K., and S. Akimoto,

The system MgO-SiO2-H20 at

high pressuresand temperaturesStability field for hydroxyl-chondrodite, hydroxy-clinohumiteand

10 ]i-phase,Am. J. Sci., 277,

288-312,

1977.

170. Yang, H.-Y., Crystallization of

iron-free pigeonite in the system
anorthite-diopside-enstatite-

1993.

hydrostatic, inert conditions to

580 kbar (abstract), Eos Trans.
AGU,
74, No. 16, 168-169,
1993.

178. Zhang, J., R. C. Liebermann, T.

Gasparik, C. T. Herzberg, and Y.
Fei, Melting and subsolidus
relations of SiO2 at 9-14 GPa, J.
Geophys. Res., 98, 19,78519,793, 1993.
179. Zou, G., P.M.

Bell, and H. K.

Mao, Application of the solid-helium pressuremediumin a studyof

the -; Fe transitionunderhydrostatic pressure, Carnegie Inst.
Washington Year Book 80, 272274,

1981.

Diffusion Data for SilicateMinerals,Glasses,and Liquids

John B. Brady

1.

INTRODUCTION

energy. For example, the movementof Ani moles of

chemical componenti from a region (II) of high

Diffusion is an integralpart of many geologicprocesses and an increasing portion of the geologic

chemicalpotential(gi ) to a region (I) of lower

chemicalpotential(gi ) will causethe systemGibbs
energy(G) to fall since

literature is devoted to the measurement, estimation,

andapplicationof diffusiondata. This compilationis

intended to be a guide to recent experimentallydetermined diffusion coefficients and, through the
paperscited,to importantolderliterature.To provide
a contextfor the tables,a brief summaryof the equationsrequiredfor a phenomenological
(macroscopic)
descriptionof diffusionfollows. Althoughthe equations for well-constrainedexperimentsare relatively
straightforward,
theapplicationof the resultingdiffusion coefficients to complex geologicproblemsmay
not be straightforward.The readeris urgedto read

and usingthe definitionof gi [139, p.128],

one or more diffusion texts [e.g., 99, 121, 32, 147,

135] beforeattemptingto usethe datapresentedhere.

odynamicforce for atom movement.

2. FORCES

AND

)G
II)P,T,
AG
+AG
ll-Ani[.ni
P,T,nj
Ani
hni
nj
-

AGTtal
_ Ani g _ [[i < 0 .

(1)

(2)

Thus,a chemicalpotentialgradientprovidesa therm-

On a macroscopic
scale,linear equationsappearto
be adequatefor relating eachdiffusive flux to the set
of operative forces [137, p.45]. The instantaneous,

FLUXES

one-dimensional,
isothermal
diffusive
flux Ji (moles
of i/m2s) of componenti in a single-phase,
n-

Diffusion is the thermally-activated,relative movement (flux) of atoms or molecules that occurs in

responseto forces such as gradientsin chemical

potentialor temperature.Diffusionis spontaneous

componentsystemwith respectto referenceframe R

may be describedby

and, therefore, must lead to a net decrease in free

(3)

where
x (m)isdistance
andthen2termsLi(moles

J. B. Brady, Departmentof Geology, Smith College,North-

of i/m.J's) are "phenomenological

diffusion coefficients"[36]. Becauseeachcomponentof the system

ampton, MA 01063

Mineral Physics and Crystallography

A Handbook of Physical Constants
AGU

Reference

may move in responseto a gradient in the chemical

potentialof any othercomponent,the complexityof

describing
diffusionin multicomponent
systemsrises

Shelf 2

Copyright 1995 by the American GeophysicalUnion.

269

270

DIFFUSION

DATA

rapidly with the numberof components.Two important resultshelp limit this complexity. First, the isothermal, isobaric Gibbs-Duhemequation [139, p.
134]

3. FICK'S

LAWS

Adolf Fick's [50] empiricalequationswere usedto

describebinarydiffusionexperimentslongbeforethe
moregeneralequations(3) and (6) were developed.
Fick's First Law

Ji =

-Lij

(4)

for the single phase in which the diffusion occurs

reducesthe numberof independentgradientsto (n-1)
and the number of diffusion coefficientsto (n-l)2.
Second, Onsager [132, 133] showed that if the
forces, fluxes, components,and referenceframe are
properlychosen,thematrixof coefficients
relatingthe
forcesandfluxesis symmetrical
R

Lj = Lj,

(5)

Ji--Di(
dCi

,dxJ

(7)

relatesthe instantaneous
flux Ji (moles of i/m2s) of
componenti to the one-dimensionalgradientof the
concentrationof i, dCi/dx (moles of i/m4), and
definesthediffusioncoefficientD i (m2/s). However,
unlessthe experimentattainsa steadystate,time (t) is
also a variable and a continuity equation (Fick's
SecondLaw)

(8)

reducing the number of independentdiffusion

coefficients to (2n- 1).

Althoughequations(3)-(5) are theoreticallysatisfying, they are not generallyusedto describediffusion

experiments, in part becausechemical potential
gradientsare not directly measurablein most cases.
Fisher [51], Joesten[94, 96, 97], and others [e.g.,
55, 98, 16, 1] have appliedtheseequationssuccessfully in modelingthe diffusion evolutionof coronas
and other textures in some rocks. However, most

mustbe solved. If D i is not a functionof composition

(Ci) and, therefore,not a function of position(x),

thenequation(4) maybe simplifiedto

--tJx- Dix2t'

(9)

workers use empirical equationsrelated to (3) that

involvemeasurable
compositions
Cj (molesofj/m3)
(6)
j=l

whichhasmanyanalyticalsolutions[6, 99, 17, 32].

Somecommonlyusedsolutionsto (5) for planar
geometriesare given in Table 1 and two of theseare
showngraphicallyin Figure 1. All of the equations
(7)-(13) implicitly assumeconstancyof volume, for
which the fixed laboratoryreferenceframe is a rman

[ 134]. Only (n- 1) compositions

are independent,but

volume reference frame, and must be modified if the

unfortunately
DiDi so that (n-l)2 diffusion

samplevolumedoeschange[10]. Similaranalytical
solutionsexistfor relatedboundaryconditionsand/or
other geometries,notably sphericaland cylindrical
cases. More complicatedboundaryconditionsand
geometries
may requirenumericalapproximation[32,
Chap. 8].

e (m2/s)areneeded
for (6).
coefficients
Dij

The mostobvioussimplificationof (6) is to limit the

numberof componentsto 2 and, therefore,the number of required diffusion coefficients to 1. Most
experimentalists
achievethis by their experimental
design. The nexttwo sectionspresentdefinitionsand
equationsused to describethese binary (2-component) experiments. Additional ways to simplify the
treatmentof multicomponent
systemsare addressedin
Section 5.

It is clear from Table 1 and Figure 1 that the

parameter
x/-t maybeused
tocharacterize
theextent
of diffusion. In semi-infinite casessuchas (10) and
(11), the distancex that hasattaineda particularvalue

ofCi aftertimet isproportional

to x/Dt. In finite

BRADY

271

Table I. Commonly-used
solutionsto equation(9)
Solution

BoundaryConditions
Thin-film

Solution

Ci-->CO
for
Ixl>0
as
t->0
/
Ci-->oo for x=0 as t-->0 J

-CO=
c

exp

2x/Dt

where
c--I)(Ci-C0)dx

4Dt

(10)

Semi-infinite Pair Solution

(11)

CI-C0=erfc
2Dit

,Ci=C1 for x<0 at t

Finite Pair Solution

ICi=Cl
for
0<x<h
att=0/

Ci=C0tbrh<x<Latt=0?
(aci/ax),
=0 forx=O&L J

]-CO
L
=n
(Ci-CO)
h ;21

sin

exp L2

cos(-)

(12)

Finite Sheet- Fixed SurfaceComposition

('.
=CO
for
-L<x
<Latt=0}
C=CI for x=0&L

at t>0

=1---

casessuchas (12) and (13), the fractionalextentof

completion
of homogenization
by diffusion
ispropor-

tional
to x/-it.These
x/-itrelations
provide
importantteststhatexperimental
datamustpassif diffusion
is assertedas the rate-controllingprocess.They also

providesimpleapproximations
to the limits of
diffusion when applying measured diffusion
coefficients
to specificproblems[147].
4. DIFFUSION

COEFFICIENTS

In general,
onemustassume
thatDi isa function
of
Ci. Therefore,equations
(9)-(13) maybe usedwith
confidence
only if Ci doesnot changeappreciably
duringtheexperiment.Thisis accomplished
either
(a) by usinga measurement
technique
(typically
involvingradioactivetracers)that candetectvery
smallchangesin Ci, or (b) by usingdiffusional
exchange
of stableisotopes
of the sameelement
that
leave

the element concentration unchanged.

Approach
(a)yieldsa "tracer
diffusion
coefficient"
for
the elementthat is specificto the bulk composition

studied.Approach
(b) yieldsa "self-diffusion
coeffi-

4L
cos 2L
-Di(2n
+21)22t)((2n
+1)x)
(13)

exp

assilicateminerals,glasses,
andliquids.
If Ci doeschangesignificantlyin the experiment

andDi is a functionof Ci, observedcompositional

profiles
mightnotmatchtheshape
ofthose
predicted
by (9)-(13). In suchcasesthe Di calculated
with
these equationswill be at best a compositional
"average"andequation(8) shouldbe considered.
Experimentsin which compositiondoes change
significantlyare often termed "interdiffusion"
or
"chemicaldiffusion"experiments.A commonly-used

analyticalsolutionto (8), for the sameboundary

conditionsas for equation(11), was obtainedby
Matano [122] usingthe Boltzmann[8] substitution

lcCi=C2

Di(C2)t 'i

i=C0
XClLi
.

(14)

C i =C2

Equation
(14)canbeevaluated
numerically
orgraphically from a plot of (Ci - C0)/(CI - CO) versusx,
wherethe point x = 0 (the Matano interface)is
selected such that

cient"for theisotopicallydopedelementthatis also

specificto the bulkchemicalcomposition.

Both
approaches
generally
ignoretheopposite
orexchange
flux that mustoccurin dominantlyionicphasessuch

IC
Ci=Cl
xdC
i- 0
i=CO

(15)

272

DIFFUSION

DATA

0.0

1.0

(A)

(B)

0.8

-0.5

0.6
0.6
0.8

0.4

0.8

1.0

0.2

0.2
0.0

-2.0

0.2

0.4

0.6

0.8

1.0

0.0

0.2

0.4

x2

0.6

0.8

1.0

x/L

Figure
1. Graphical
solutions
toequation
(9).(A)The"thin
film"solution
ofequation
(10)is

shown
with(z=lforvarious
values
ofi t (labels
onlines).
Plotting
ln(Ci- CO)asafunction
of

x2atany
time
yields
astraight
line
ofslope
-1/(4Dit).
(B)The"finite
pair"
solution
ofequation
(12)isshown
forh/L=0.4
and
various
values
ofDt/L
2(labels
oncurves).
Plotting
(Ci-C0)/(C1
CO)
asafunction
ofx/Lnormalizes
allcases
toasingle
dimen
sionless
graph.
Theinitial
boundary
between
thetwophases
ismarked
bya dashed
vertical
line.
[32, p.230-234]. For binary,cationexchange

betweenionic crystals,the Matano interfaceis the

originalboundary
between
thetwocrystals.Diffusionexperimentsthat follow theBoltzmann-Matano

approach
havetheadvantage
of determining
Di asa

function
of Ci andthedisadvantage
of riskingthe

complicationsof multicomponent
diffusion, for
whichneither(8) nor(14) is correct.

independent
fluxes and, therefore,the "tracer"
diffusion
coefficients
of Cu andZn canbedetermined

inaddition
totheinterdiffusion
coefficient
Dczn_,.

A similaranalysis
for binarycationinterdiffusion

(AZ BZ whereAZ represents

Az+Z
andBZ
represents
Bz+Z
) inappreciably
ionicmaterials
such
assilicate
minerals
yields[5, 112,113,10]:

Darken[35] andHartleyandCrank[83] showed

thatforelectrically
neutral
species,
thebinary
(A<--B)

interdiffusion
coefficients
(DAB_,)
obtained
in a

Boltzmann-Matano
typeexperiment
andthetracerdif-

fusion
coefficients
(D andD) fortheinterdiffusing
species
arerelatedby

DAB_
-- NBDA+ NADB 1+

(Dkz)(D3z)(a
+bNBz)
2[

DAUB_,
= (a2NAzD
Z+b2
NBzDBz)
. 1

[)lnNaz
)In
AZ
)P,T]'
()lnYA
) ],(16)
c]lnNAP,T

whereNA isthemolefraction
andAthemolaractiv-

itycoefficient
ofcomponent
A. Darken
developed
his
analysis
inresponse
totheexperiments
of Smigelskas
and Kirkendall [148], who studiedthe interdiffusion

of CuandZn between
Cu metalandCu?0Zn
3obrass.
Smigelskasand Kirkendall observedthat Mo wires

(inertmarkers)
placedat theboundary
between
theCu

andbrass
moved
in thedirection
of thebrass
during
theirexperiments,
indicatingthatmoreZn atomsthan

Cuatomscrossed
theboundary.Darken's
analysis
showedthat in the presenceof inert markersthe

(17)

whichrequires
vacancy
diffusion
if a;e:b.
If a=b,then

(17) simplifiesto

DAZ DBZ

DAB_,
DAZ
= (NAZ
, +NBzDBz
, 1

[)In
AZ
)]
)InNAZP,T

(18)

[121]. Thisexpression
permitsinterdiffusion
coeffi-

cientsto becalculated
frommore-easily-measured
tracerdiffusioncoefficients.
For mineralsthatarenot

BRADY

2'73

ideal solutions, the "thermodynamic factor" in

brackets on the right side of (!6)-(!8)
can

coefficients
D to calculatemulticomponent
interdif-

significantlychangethe magnitude(and even the

sign!) of interdiffusioncoefficientsfrom those
expected
for an idealsolution[12, 25].

mosthopefor diffusionanalysisof multicomponent

problems[115, 19, 20]. It shouldbe notedin using
equations(16)-(!9) that the tracer diffusivities
themselves
maybefunctionsof bulkcomposition.

5. MULTICOMPONENT

fusion coefficient matrices, and its inverse offer the

DIFFUSION
6. EXPERIMENTAL

Rarely is diffusionin geologicmaterialsbinary.

Multicomponent
diffusionpresents
thepossibility
that

few

additional

DESIGN

considerations

should

be

diffusive fluxes of one component may occur in

mentioned
regarding
thecollectionandapplication
of

response
to factorsnotincludedin (7)-(!8), suchas
gradients
in thechemicalpotentials
of othercomponents,couplingof diffusingspecies,etc. In these
cases,equation(6) or (3) mustbe used. The off-

diffusion

diagonal
(i-j)diffusion
coefficients,
Di or Li!,are

The form of this tensoris constrainedby point group

unknown for most materials and most workers are

forced to assume(at significantperil!) that they are

zero.

Garnet is the one mineral for which off-

diagonaldiffusivities
areavailable[19, 20] andthey

data.

In anisotropiccrystals, diffusion may be a

function of crystallographicorientationand the
diffusion coefficient becomes a second rank tensor.

symmetryandthe tensorcan be diagonalized

by a
properchoiceof coordinate
system[ 131].
Vacancies,dislocations,and othercrystaldefects

mayhaveprofoundeffectson diffusionrates[e.g.,
121, 164]. Therefore,it is essentialthat the mineral

werefoundto be relativelysmall.

Oneapproach
usedby manyistotreatdiffusion
that
is one-dimensionalin real spaceas if it were onedimensionalin compositionspace. This approach
was formalized by Cooper and Varshneya[28, 30]

beingstudiedis we!l-characterized.
If the mineral,
liquid,or glasscontains
a multivalent
element
likeFe,
then an equilibriumoxygenfugacity shouldbe
controlled or measured because of its effect on the

who discussdiffusion in ternary glassesand present

criteria to be satisfiedto obtain "effective binary diffusion coefficients"from multicomponentdiffusion

vacancyconcentration.
Diffusion in rocks or other polycrystalline
materialsmay occurrapidly alonggrainboundaries,

experiments. In general,diffusioncoefficients

crystalinterfaces,or surfacesandwill notnecessarily

record intracrystallinediffusivities. Experiments
involvinggrain-boundarydiffusion [e.g., 102, 103,

obtainedwith this procedureare functionsof both

compositionand directionin compositionspace.

Anotherapproach,developedby Cullinan[33] and
Guptaand,Cooper[75, 29], is to diagonalizethe
diffusion coefficient matrix for (6) through an

11, 47, 49, 95, 154, 13, 158] are beyond the scope
of this summary. If polycrystallinematerialsare
usedin experimentsto measure"intrinsic"or "vol-

eigenvector
analysis.Althoughsomesimplification
in datapresentation
is achievedin thisway, a matrix

ume" diffusion coefficients, then the contributions of

of diffusion coefficients must be determined before

theanalysiscanproceed.

to be negligible.
Water can have a major effect on diffusion in

Lasaga[105, see also 161] has generalizedthe

relationship
(17) to multicomponent
minerals. The
full expression
is quitelong,butsimplifies
to

many geologicmaterials,even in small quantities

[e.g., 73, 150, 46, 167, 71]. If water is present,
water fugacities are an essential part of the

Dij- Difiij- n

Dj- Dn

(19)

"extrinsic"grain-boundary
diffusionmustbe shown

experimentaldataset.
Because many kinetic experimentscannot be
"reversed," every effort should be made to
demonstrate that diffusion is the rate-controlling

process.
Important
testsinclude
the x/-itrelations
noted in equations (10)-(13) and the "zero time

experiment."
Thei t testcanbeusedif dataare
(19)zi isthecharge
oncationi, 15i.i-I if i=j, andij

gatheredat the samephysicalconditionsfor at least

two times,preferablydifferingby a factorof four or

= 0 if i:j. This approach,using tracer diffusion

more. The often-overlooked"zerotime experiment,"

if the solid solutionis thermodynamicallyideal. In

2?4

DIFFUSION

DATA

which duplicatesthe samplepreparation,heatingto

the temperatureof the experiment, quenching(after
"zero time" at temperature),and data analysisof the
other diffusion experiments, commonly reveals
sourcesof systematicerrors.
These and other important features of diffusion
experimentsare describedin Ryerson[141].
7. DATA

TABLE

Due to spacelimitations,the data includedin this

compilation have been restrictedto comparatively
recentexperimentalmeasurements
of diffusioncoefficients for silicate minerals, glasses,and liquids.
Many good,older data have beenleft out, but can be
foundby followingthe trail of references
in the recent
papersthat are included. Older data may also be
found by consultingthe compilationsof Freer [56,
57], Hofmann [86], Askill [2], and Harrop [81].
Somegooddata also exist for importantnon-silicate
mineralssuchas apatite[ 157, 23, 45] andmagnetitetitanomagnetite
[65, 136, 59], butthe silicateminerals
offeredthe clearestboundaryfor this paper.
Almost

all of the data listed are for tracer or self-

diffusion. Interdiffusion (chemicaldiffusion)experiments involving minerals are not numerous and

interdiffusion

data sets do not lend themselves

AH (J/mole) is the "activationenergy." Do and AH

have significancein the atomic theory of diffusion
[see32, 121] andmay be relatedfor groupsof similar
materials [ 162, 82, 106].
Diffusiondataarelisted in termsof AH and log Do
and their uncertainties. In many cases data were

converted
totheunits(kJ,m2/s)andform(logDo) of
thiscompilation.Logarithmsare listedto 3 decimal
places for accurate conversion, even though the
original data may not warrant such precision. No
attemptwasmadeto reevaluatethedata,the fit, or the
uncertainties
given(or omitted)in the originalpapers.
Also listedare the conditionsof the experimentas
appropriate
includingthetemperature
range,pressure
range, oxygen fugacity, and sample geometry.
Extrapolation of the data using (20) to conditions
outsideof the experimentalrange is not advisable.
However, for easeof comparisonlog D is listedfor a
uniformtemperature
of 800C(1200Cfor the glasses
and liquids), even thoughthis temperaturemay be
outside of the experimental range. Use these
tabulatedlog D numberswith caution.
Finally, a sample "closuretemperature"(Tc) has
been calculated for the silicate mineral diffusion data.

The closure temperaturegiven is a solution of the

Dodson[38] equation

to

compactpresentation.Interdiffusiondata for silicate

liquidsandglassesare more abundant,but are not in-

(21)

cluded [see 156, 3, 4]. Neither are non-isothermal

(Soret)diffusiondata[see108]. Diffusiondatalisted
for silicate glassesand liquids have been further
restrictedto bulk compositions
thatmaybe classified
as eitherbasaltor rhyolite.
Because diffusion is thermally activated,
coefficientsfor diffusion by a singlemechanismat
different temperatures may be described by an
Arrheniusequation

D- DOexp-AH)
RT

for a sphereof radiusa=0.1 mm and a coolingrate

(dT/dt) of 5 K/Ma. The exampleclosuretemperatures
were included becauseof the importanceof closure
temperatures
in the applicationof diffusiondata to
petrologic[107] and geochronologic
[123, Chap.5]
problems. Note that other closuretemperatures
wouldbecalculated
for differentcrystalsizes,cooling
rates,and boundaryconditions.

(2O)

andfit by a straightline on a graphof logD (m2/s)as

a functionof 1/T (K -) [147, Chap. 2]. Log Do

(m2/s)is the interceptof the line on the log D axis

(I/T = 0). AH/(2.303.R) is the slope of the line
where R is the gas constant(8.3143 J/mole. K) and

Acknowledgments.This paperwasimprovedby helpful commentson earlier versionsof the manuscriptby

D. J. Cherniak,R. A. Cooper,R. Freer, J. Ganguly,B. J.
Giletti, S. J. Kozak, E. B. Watson, and an anonymous
reviewer. N. Vondellprovidedconsiderable
helpwith the
library work.

BRADY

2'75

2'76 DIFFUSION DATA

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277

278

DIFFUSION DATA

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279

280

DIFFUSION

DATA

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103, 228-

Infrared,Raman and Optical Spectroscopy

of Earth Materials

Q. Williams

or crystals.Here, threeseparatetypesof light-mediated

spectroscopies
of interest to geophysicsand mineral

commonlyproducethe colorsof manyminerals:theseare

dictatedby the localbondingenvironments
andelectronic
configurations of different elements in crystals or
molecules.The role of electronictransitionsin controlling
the electrical conductivityand in reducingthe radiative
thermalconductivityof mineralsat high temperaturesis
briefly reviewed, and their relation to spectroscopic
observationssummarized.Additionally, observationsof
opticaltransitionsmay be usedto constrainthe energetic
effectsof different electronicconfigurationson element
partitioningbetweensitesof different symmetriesand

sciencesareexamined:1) infraredtroscopy;

distortions.

1.

INTRODUCTION

There are a numberof ways in which light interacts

with condensed matter. In most cases, these are associated

with the electric field of an incident photon interacting

with the vibrational or electronic states of materials. The

presence
andstrength
of theseinteractions
areprincipally
dependenton bondingproperties,the configurations
of
electronicstates,and local symmetryof ions, molecules

2) Raman

spectroscopy;
and3) opticalabsorption
spectroscopy.
Each of these techniquesprovides complementary
informationon the vibrationaland electronicpropertiesof
Earth materials.The bondingpropertieswhich produce
infrared and Raman-activevibrationalbandsprovide not

2.

VIBRATIONAL

INFRARED

AND

SPECTROSCOPY:

RAMAN

TECHNIQUES

The primary feature of importance in vibrational

spectroscopy
is the interactionbetweenthe electricfield
associated with a photon and changes induced by
vibrational motions in the electronicchargedistribution

only a usefulfingerprinting
techniquefor determiningthe
presence
or abundance
of differentfunctional
groups,such
as hydroxylor carbonateunits,but also(in a bulk sense)
fundamentallycontrol a variety of thermochemical
propertiesof materials,includingtheir heat capacity.
Moreover, the vibrational spectrum provides basic
information on the bond strengths present within a
material.Electronictransitionsmay occurin the infrared,

within

a material.

The most common

unit utilized

to

describethe frequencyof these vibrational motions (as

well as, in many cases,electronictransitions)is inverse

centimeters,
orwavenumbers
(cm-1):
these
maybereadily
convertedto Hertz by multiplyingby the speedof light, c

visible or ultraviolet region of the spectrum, and

(2.998x 1010cm/sec),
tothewavelength
of light(incm)
by taking its inverse,and to energyby multiplyingby c

andPlanck's
constant,
h (6.626x 10-34J-sec).
Here, we focus on infrared and Raman spectroscopic
characterization of vibrational states: in this discussion,

Q. Williams,Universityof California,SantaCruz, Instituteof

we explicitly treat only normal Raman scatteringand

disregard
non-vibrational
effectssuchasRamanelectronic
and magnonscatteringandnon-lineareffectssuchas the
hyper-Ramanandresonance
Ramaneffects,noneof which
havehad significantimpactto date in the Earth sciences

Tectonics,Mineral PhysicsLaboratory,SantaCruz, CA 95064

Mineral Physicsand Crysta!iosraphy

A Handbook of PhysicalConstants
AGU

Reference Shelf 2

Copyright1995by the AmericanGeophysical

Union.

291

292

INFRARED,

RAMAN

AND OPTICAL SPECTROSCOPY

(see [ 10] for discussionof theseeffects).

In the caseof infraredspectroscopy,
a photonof energy

below~14000cm-1 (andmostoftenbelow5000cm-1) is
either absorbed or reflected from a material through
interaction with interatomic vibrations. The primary
measurementis thus of the intensity of transmittedor
reflected infrared light as a function of frequency.With
Raman spectroscopy, a photon of light interacts
inelasticallywith an optic vibrationalmodeand is either
red-shiftedtowardslower frequency(Stokeslines) or blueshifted to higher frequency (anti-Stokes lines) by an
amount correspondingto the energy of the vibrational
mode. When such an interaction

occurs with an acoustic

mode (or sound wave), the effect is called Brillouin

spectroscopy
(see the sectionon elasticconstantsin this
volume). Notably, Raman measurements rely on
monochromaticlight sources(which, since the 1960's,
have almost always been lasers) to provide a discrete

frequencyfromwhichtheoffsetvibrationalmodesmaybe
measured. Furthermore, the Raman effect is rather weak:

onlyabout1 in 105to 106incident

photons
areRaman
scattered, necessitating relatively high powered
monochromatic
sources,sensitivedetectiontechniques,
or
both.

The vibrational

modes measured in infrared and Raman

spectroscopy
may be describedas a functionof the force
constant of the vibration

or deformation

and the mass of

the participating atoms. For the simplest case of a

vibratingdiatomicspecies,thisrelationmay be described
usingHooke'sLaw, in which

v,a,=

(0

whereK is the forceconstantassociated

with stretchingof
the diatomic bond, and / is the reduced mass of the
vibrating atoms. Clearly, a range of different force
constantsare required to treat more complex molecules,
which have more possible vibrational modes beyond
simple stretchingmotions(seeFigure 1): becauseof the
morecomplexinteratomicinteractions,
differentstretching
andbendingforceconstants
are necessitated.
Approximate
equationsrelatingtheseforceconstantsto the frequencies
of vibrationfor different polyatomicmoleculeshavebeen
reviewedanddevelopedby Herzberg[12], while a detailed
review of the frequencies of vibrations of different
moleculesis givenby Nakamoto[18]. Figure 1 showsthe
vibrational modes expected for an isolated silicate
tetrahedra,which comprisesymmetricandantisymmetric
stretchingand bending vibrations. That different force
constantsare required to describe these vibrations is
apparentfrom the atomic displacementsillustrated:for

example,the symmetricstretchof the tetrahedron

depends
predominantlyon the strength of the Si-O bond. For
comparison,
thesymmetricbendingvibrationis controlled
principallyby the O-Si-O angle bendingforceconstant,
the magnitudeof which is dictated in turn largely by
repulsive interactions between the oxygen anions.
Considerableinsightin distinguishingvibrationssuchas
those shown in Figure 1 from one another has been
derived from isotopic substitutionexperiments,which
effectively alter the masses involved in the vibration
withoutsignificantlyaffectingthe forceconstants.
Within crystalline solids, the number of vibrations
potentially accessiblethrougheither infrared or Raman
spectroscopy
in 3n-3, where n is the numberof atomsin
the unit cell of the material.This simply resultsfrom the
n atomsin the unit cell having 3 dimensionaldegreesof
freedom during displacements,with three degreesof
translational freedom of the entire unit cell being
associatedwith acoustic(Brillouin) vibrations.These3n-3
vibrationsrepresentthe maximumnumberof observable
vibrationalmodesof a crystal,as somevibrationsmay be
symmetrically
equivalent(or energetically
degenerate)
with
one another, and others may not be active in either the
infraredor Ramanspectra.Becausethe wavelengthof even
visiblelight is long relative to the size of crystallographic
unit cells,bothinfraredand Ramanspectroscopy
primarily
sample vibrations which are in-phase between different
unit cells (at the center of the Brillouin zone).
Characterizingvibrationalmodesthat are out-of-phaseto
differentdegreesbetweenneighboringunit cellsrequires
shorter wavelengthprobes, such as neutron scattering
techniques.These shorterwavelengthprobesare usedto
characterize the dispersion (or change in energy) of
vibrationsas the periodicityof vibrationsbecomeslonger
than the unit cell length-scale (that is, vibrations
occurringaway from the center of the Brillouin zone).
Suchdispersionis characterized
by vibrationsof adjacent
unit cellsbeingout-of-phasewith one another[6].
For crystals,a range of bondinginteractions(and thus
force constants), the crystal symmetry (or atomic
locations), and the massesof atoms within the unit cell
are generallyrequiredto solvefor the differentvibrational
frequencies occurring in the unit cell. Broadly, the
calculationof the vibrationalfrequenciesof a latticeentail
examiningthe interchange
betweenthe kineticenergiesof
theatomicdisplacements
andthepotentialenergyinduced
by the bonding interactionspresentin the crystal. The
primary difficulties with such calculations lie in
determiningadequatepotential interactions,and in the
number of different

interatomic

interactions

included in

thesecalculations.Suchcomputationsof latticedynamics

WILLIAMS

v 1-symmetric
stretch
800-950cm-1
Raman(often strong)

v2-symmetric
bend
300-500cm-1
Present in Raman

293

bend
v3-asymmetric
stretch v4-asymrnetric
400-600cm'1
850-1200cm-1
Infrared (strong),Raman

Infrared, Raman

Fig.1.Thenormal
modes
of vibration
of anSiO4-tetrahedra.
Withinisolated
tetrahedra,
allvibrations
are
Raman-active,
whileonlythev3 andv4 vibrations
areactivein theinfrared.
However,
environments
with
non-tetrahedral
symmetries
frequently
produce
infraredactivityof theVl andv2 vibrations
in silicate
minerals[modifiedfrom [ 12] and [ 1811.

havecontributed
majorinsightinto thecharacterization
of
differenttypesof vibrationalmodesin complexcrystals:
the precise equationsand means by which such
calculations are carried out have been reviewed elsewhere

[3, 91.

Whether

given

vibrational

motion

is

motionproducesa changein the polarizabilityof a

material, then the vibration is Raman active. Notably,
while the induceddipoleis a vector,thepolarizabilityis a
secondrank tensor,and it is the symmetricpropertiesof
this tensorwhich allow the predictionof which families
of modeswill be active when observedalong different

of the unit cell occurs during the vibration. It is this

crystallographic
directions.
Thus,bothRamanandinfrared
activitiesare govemedby interactions
of theelectricfield
of theincominglightwith vibrationally
producedchanges
in the chargedistributionof the moleculeor unit cell.
Yet, despite Raman active vibrationsdependingon
changesin the polarizabilitytensorandinfraredactive
vibrationsbeing generatedby changesin the dipole

changein the electricfield associated

with theunit cell

moment, the two sets of vibrations are not always

which interacts with the electric field of the incident

photons.Becauseof this dependence

on vibrational
changesin the chargedistribution,highly symmetric

mutuallyexclusive:for non-centrosymmetric
molecules
(or unit cells), somevibrationscan be both Ramanand
infrared-active. Finally, the intensities of different

vibrations are often inactive or weak in infrared spectra:

vibrationsin the two differenttypesof spectroscopy

may

for example, within isolated tetrahedra, both the

symmetricstretching
andsymmetric
bendingvibrations
shownin Figure1 areinfrared-inactive.
The physicalorigin of Raman scatteringmay be
viewedfrom a simpleclassicalperspectivein which the

be relatedto themagnitude
of thechanges
producedin the
dipole moment or polarizability tensor in a given

electric field associatedwith the incidentlight interacts

with the vibratingcrystal.In particular,this interaction

the lattice which enables different vibrations

occursthroughthepolarizabilityof the material:that is,

itsabilitytoproduce
aninduced
dipolein anelectricfield.

with possiblecrystallographic
directionalityfor the

spectroscopically
activeunderinfrared
orRamanexcitation
is governedby selectionrulesassociated
with a given
crystal structure.These selectionrules are primarily
governedby the symmetryof the unit cell, and the
differingproperties
of Ramanandinfrared
activity.Infrared
activityis produced
whena changein thedipolemoment

It is the oscillationsin the polarizability producedby

vibrationswhichcauseRamanscattering:if a vibrational

vibration.

It is the relation of the changein the polarizability

tensorandshiftsin the dipolemomentto the symmetryof
to be

associatedwith different symmetryspecies,as well as

infrared and Raman modes. The way in which this
characterization of vibrational mode symmetries is

conducted
is throughan application
of grouptheorycalled

294

INFRARED,

RAMAN AND OI:'TIC

SPECTROSCOPY

factorgroupanalysis.This is a meansof utilizingthesite

symmetries
of atomsin theprimitiveunitcell of a crystal
(as given,for example,in The International
Tablesof Xray Crystallography),
coupledwithcharacter
tablesof the
site symmetry and crystal symmetry group, and
correlation tables between different symmetrygroupsto
determinethe number,activity, and symmetryof infrared
and Raman vibrationsof a crystal. Charactertables for

differentsymmetries
aregivenin manytexts(for example,
5), andcorrelationtablesaregivenin [7] and[8]: thelatter
text providesa numberof workedexamplesof factor
groupanalysis
appliedto mineralsandinorganic
crystals.
Infraredspectramay be presentedfrom two different
experimental
configurations:
absorption
(or transmission),
or reflection.Sampleabsorbanceis dimensionless,
and is
defined as

A = -1og(I/1o),

(2)

where I is the intensity of light transmittedthroughthe

sample, and Io is the intensityof light transmitted

througha non-absorbing
referencematerial.Frequently,
suchdata are reportedas per centtransmittance,
whichis
simply the ratio I/Io multiplied by 100 (note that
vibrationalpeaksare negativefeaturesin transmittance
plotsandpositivefeaturesin absorbance).
Because
of the
intensity of many of the absorptionsin rock-forming
minerals (greater than -2 gm thicknessesin the mid-

infrared(>-400 cm-1) oftenrendersamples

effectively
opaque),suchabsorbance
or transmission
dataare often
generatedfrom suspensionsof powderedminerals or
glasseswithinmatriceswith indicesof refractionwhich
approximate
thoseof minerals.Typicalexamples
of such
matricesare pressedsalts(typically KBr, KI or CsI) and
hydrocarbons
(for example,Nujol (paraffinoil) or teflon).
While relative absorptionintensifiesand locationscan
often be accurately determined using these techniques
(highlypolarizablecrystalscanpresentdifficulties:seepp.
183-188 of [7]), absolute absorption intensity is
compromised
andorientationinformationis lost.
A secondmeansby which infraredspectraare measmexl
is throughmeasurementof reflectionspectra.Reflection
spectra of crystals sample two componentsof each
vibrationalmodes:transverseoptic and longitudinaloptic
modes, while absorptionspectroscopyideally samples
only the transversemodes.That thereare two typesof
modes in reflection

is because each vibrational

motion

may be described either with atomic displacements

orientedparallel (longitudinalmodes)and perpendicular
(transversemodes)to the wavevectorof the incoming
light. Those with their atomic displacements
oriented

parallel to the wavevectorof the incominglight can be

subject to an additional electrostatic restoring force
producedby thedifferingdisplacements
of planesof ions
relative to one another,an effect not generatedby shear.
Suchtransverseandlongitudinalmodesare thusseparated
from one anotherby long-rangeCoulombicinteractions
in
the crystal [3, 6].
In practice, reflection spectra generally have broad
flattenedpeaks,with the lowest frequencyonsetof high
reflectivity of a peak corresponding
approximatelyto the
transverse
opticfrequency,
while thehigherfrequency
drop
in reflectivity of a peak is near the frequency of the
longitudinal optic vibration. These data are generally
invertedfor TO andLO frequencies
andoscillatorsuengths
(a measureof the intensityof the reflectionof the band)
using one of two typesof analyses:Kramers-Kronig,or
an iterative classicaldispersionanalysis.Suchanalyses,
describedin [17] andelsewhere,are designedto modelthe
extremechangesin the opticalconstants(expressed
as the
frequencydependentandcomplexindex of refractionor
dielectricconstant)occurringover the frequencyrangeof
an opticallyactivevibration.
For many minerals,the types of vibrational modes
may be divided into two loose categories:internal and
lattice modes. Internal modes are vibrations which can be

associatedwith those of a molecular unit, shifted (and

possibly split) by interaction with the crystalline
environment

in which the molecular

unit is bonded: the

vibrationsof the silica tetrahedrashownin Figure 1 are

typical examplesof the typesof motionswhich give rise
to internal modes. Such internal modes are typically
associated with the most strongly bonded units in a
crystal,andthuswith thehighestfrequencyvibrationsof a
given matehal.We notealso that even the simplepicture
of molecular vibrations is often complicatedby the
presenceof interactingmolecularunits within a crystal.
For example,it is difficult to associatedifferentbandsin
feldsparswith stretchingvibrationsof distinct AIO4 or
SiO4 tetrahedra:becauseof the interlinking tetmhedra,a
silica symmetricstretchingvibrationsuchas is shownin
Figure 1 will involvea stretchingmotionof the adjoining
AIO4 tetrahedra,andvibrationsof thesetwo speciesmust
be viewedascoupledwithin suchstructures.
Lattice modes comprise both a range of (often
comparatively low-frequency) vibrations not readily
describable in terms of molecular units, and so-called
external modes. External

modes are those which involve

motions of a molecular unit against its surrounding

lattice:for example,displacements
of the SiO4 tetrahedra
against their surrounding magnesium polyhedra in
forsterite

would

constitute

an external

motion

of the

WILLIES

tetrahedralunit. Typically, suchlattice modesare of

critical importancein controllingthe heat capacityof
minerals at moderatetemperatures(of order less than
-1000 K). As it is the thermalexcitationof vibrational
modeswhichproducesthetemperature
dependence
of the
latticeheatcapacity,considerable
effort hasbeendevoted
to designing methods to extract thermochemical
parameters
suchas the heatcapacityand the Griineisen
parameter
(theratioof thermalpressure
to thermalenergy
per unit volume)from vibrationalspectraat ambientand
high pressures[13]. A fundamentallimitation on such
techniqueslies in that infraredandRamanspectraaccess
only vibrationswhichhavetheperiodicityof the unitcell
(thatis, effectsof dispersionare ignored).
Representative
Ramanspectraof quartzandcalciteare
shown in Figure 2, along with a powder infrared
absorption
spectrumof quartzandan unpolarized
infrared
reflectancespectraof calcite.The factorgroupanalysisof
quartzpredicts16 total opticallyactivevibrations,with
fourbeingRaman-active
(AI symmetry
type),fourbeing
infrared-active (A2 symmetry), and eight being both

295

Figure3 showsrepresentative
vibrationalfrequencies
of different functional, or molecular-like groupings,in

mineral spectra.In the case of many mineralswith

complexstructures,
normalmodesinvolvingmotionsof
the entire lattice, or coupled vibrations of different

functional
groupsmayoccur,andthesearenotincludedin
Figure3. As expected
fromEquation1, thereis a general
decrease
in frequencywith decreases
in bondstrength
for
differentisoelectronicand isostructuralgroupings,suchas
occursin the PO4-SiO4-AIO4 sequenceof tetrahedral
anions.

While both infrared and Raman spectroscopyrepresent

usefultechniques
for characterizing
bondingenvironments,
vibrationalmodefrequenciesand the molecularspecies
presentwithinminerals,infraredspectroscopy
hasbeen
extensively utilized as a quantitative techniquefor
determining
the concentration
and speciation
of volatile
components
within samples.Specificexamplesinclude
the determination of the dissolved molecular water and

hydroxylcontentof glassesand crystals,the amountof

dissolved
CO2relative
toCO32- groups,
andtheamount

Raman and infrared-active (E symmetry: doubly

of impurities
withincrystalssuchasdiamondanda range

degenerate).For calcite, suchan analysispredictsfive

of semiconductors.Such determinationsdepend on an

Raman
active
vibrations
(1Algandfourdoubly
degenerate
Egsymmetry
modes)
andeight,infrared-active
vibrations

applicationof the Beer-LambertLaw, in which the

amountof absorptionis assumedto be proportionalto the

(3A2u and 5 doubly degenerateEu). Two featuresare

immediately apparent from these spectra: first, the
differences
betweenthe vibrationsof the silicategroupand
thoseof the carbonategroupare immediatelyapparent:in
the infrared,the asymmetricstretchingand out-of-plane
bendingvibrationsof the carbonategrouparepresentnear

number of absorbing species present in the sampled

region.This maybe expressedas

1410and870cm-1, whilethestrongest
highfrequency

vibrations
in quartz
lienear1100cm-1 (theasymmetric
stretches
of the silicatetrahedra)
and 680-820cm-1
(corresponding
to Si-O-Si bendingvibrations).Moreover,
the LO-TO splitting of the asymmetric stretching
vibration of the carbonategroupis clearly visible in the
reflectancespectrum.Within the Raman spectrum,the
most intense vibration of calcite is the symmetric

stretching
vibration
ofthecarbonate
group
at~1080
cm-1,
while that within quartz is predominantlya displacement

of thebridging
oxygens
between
tetrahedra
at464cm-1.
Atlowerfrequency
(below
400cm-1),thespectrmn
ofthe
carbonate

has Raman

bands associated with external

vibrationsof the carbonategroup relative to stationary

calcium ions. At lower frequenciesthan are shown in
Figure 2 in the infrared spectrum,both lattice-type
vibrations

of the calcium ions relative to the carbonate

groupsanddisplacements
of thecarbonategroupsandthe
calcium ions both against and parallel to one another

c = (M.A)/(p.

d. e),

(3)

in whichc is theweightfractionof a dissolvedspecies,

M
is themolecularweightof thedissolvedmaterial,A is the
absorbance
of a diagnostic
bandof thedissolved
species,
p
is the density of the matrix in which the speciesis
suspended,
d is thepathlengththroughthesample,ande
is the molar absorptioncoefficient of the suspended

species,with units of length2/mole.

It is the
determination of this last parameter on which the

quantitative
application
of Equation3 depends:
typically,a
non-vibrationalmeansof analysisis usedto quantifythe
amountof dissolvedspecieswithina sequence
of samples
in order to calibratethe value of e. Severalcomplications
exist in the straightforwardapplicationof Equation 3:
fu'st,theextinctioncoefficientcanbe frequency-dependent,
in that the amount of absorption can depend on the
structuralenvironmentin which a given speciesoccurs.
Second,for someapplicationsa moreappropriatemeasure
of the numberof speciespresentis not the amplitudeof
absorption,but ratherthe integratedintensityunderneath
an absorption
band(see[21] for a mineralogically-odented
discussion
of eachof theseeffectsin hydratedspecies).

296 INFRARED, RAM

AND OPTICAL SPECTROSCOPY

WILLIAMS

297

Cation-Oxygen

I<I I I I I
IStretches
I I I IA1I4A106
I'r[
i

ig(6[

CO
I
I III(K,Na)O1
lFe3+O6 Fe2+O6

IH-O-HI [2800-3700
]O-H
stretch
=1] I
cm-

In-Plane

Out-of-Plane
I

O-H Bends

bends

AsymmetricStretches

Bends

Bends

',

Stretches

Bends/Stretches SiO6-octahedra
I

Silica Networks

Carbonates

Symm. Out-of-Plane In-Plane

stretches

Polymerized

Hydroxides

O-H Bends

s:o'-si:

v3

bends symm. stretchbends

Inosilicates

tridgin
OIv3&Iv1 I Si-O_SI
Io_si_o
I
& Non-Bridging O

bends bends

Orthosilicates
v 3 Vl

Sulfates

v3

Orthophosphates
I

1600

'

1400

Vl

v3

1200

v4

v4

v2

V , I ,
II , , , I 'I V4, , 2/

1000

8 O0

600

400

200

Frequency
(cm-1)
Fig. 3. Approximate
frequency
rangeof commonvibrations
of silicates,
oxidesandotherfunctionalgroups
withinminerals.For tetrahedral
species,
the modedesignations
are identicalto thoseshownin Figure1.
Most of the spectralrangesare derivedfrom [3]; thatfor octahedralsiliconis from [24].

The applicationof Ramanspectroscopy

to quantitative
measurementof molecular species is complicated by
practicaldifficultiesin determiningthe absoluteRaman
scattering cross-sectionof different species, and in
maintaininga constantvolumeof Ramanexcitationfrom
which scatteredlight is collected.Its utility hasthusbeen
principallyin determiningwhat speciesare presentin a
sample,as opposedto their quantitativeabundance.
Yet,
for analysisof sampleswhosesizesare of the orderof the
wavelength of infrared light (such as some fluid
inclusions),diffractionof incidentinfraredlight limits the
usefulnessof infraredtechniques.Considerableeffort has
thus been devoted to characterizingRaman scattering
cross-sections of gas-bearing mixtures, with the
motivation of establishing Raman spectroscopyas a
quantitative,non-destructive
compositional
probeof fluid
inclusioncompositions[e.g., 20].

3.

OPTICAL

SPECTROSCOPY

Thereare a numberof differentprocesses

whichmay
generateoptical absorption(see [19] for a discussionof
different causesof color) in the visible and ultraviolet

wavelength range. The three processesof primary

importance
for mineralsare: 1) crystal-fieldabsorptions;
2) intervalencetransitions;and 3) charge transferor
absorptioninto the conductionband (4, 15, and Bums in
[2]). The first of theseprocesses
involvesan ion with a

partiallyfilledd- (or in somecasesf-) electronshellbeing

incorporated into a crystalline environment whose
symmetryproducesa differencein energy betweenthe
different orbitals. A representativeexampleof this
phenomenonis shownin Figure 4: when the five atomic

d-orbitals
areoctahedrally
coordinated
byanions,
thedx2_

y2anddz2orbitals,
which
have
lobes
ofelectron
density

298 INFRARED, RAMAN AND OPTICAL SPECTROSCOPY

0-5

/10
Y
dx2y
2 '-t
,0' x --

'

eg

dz2

10Dq
IZ

9 dxy

Energy

Iz

o'
dyz

.oG
-:

t2g

dxz

Fig.
4.The
effect
ofoctahedml
coordination
onthedifferent
d-orbitals
ofatransition
metal
cation
(labelled
M).Thesurfaces
ofthed-orbitals
represent
contours
ofconstant
probability
that
anelectron
lieswithin
the

boundaries.
Therepulsive
effect
produced
byclose
proximity
ofthenegatively
charged
oxygen
cations
to

the
dx2_y
2and
dz
zorbitals
separates
these
inenergy
from
the
dxy,
dyz
and
dxz
orbitals
byanamount

referred
toasthecrystal
fieldsplitting
energy
(also
as10DqorAo).
oriented
towards
theanions,
lieathigher
energy
thanthe
remaining
threeorbitals
because
of thelarger
repulsive

interactions
between
thedx2_y
2and
dz2orbitals
andtheir
neighboring
anions.
Thus,optical
absorption
maybe

produced
byexcitation
of electrons
intoandbetween
these

separated,
orcrystal-field
split,
energy
levels,
theenergetic
separation
between
which
isoften
referred
toas10Dqor

Ao. Such crystal-fieldeffects are observedwithin

compounds
containing
suchtransition
metalionsasFe2+,

Fe3+,Mn2+,Ti3+,Cr3+,andisassociated
withboth
the
colors
andfluorescent
properties
ofa range
of minerals,
gemsand lasercrystals,includingforsteriticolivines

(peridot:
Mg2SiO4
withFe2+),
ruby
(A1203
withCr3+)
andbothsilicate
andaluminate
garnets
(whichmay
contain
a range
of transition
elements).
Thepreferential
occupation
of thelowerenergylevelsproduces
a net
crystal field stabilizationenergy(CFSE) which
contributes
tothethermochemical
energetics
of transition
metal-bearing
crystals.
Thecharacteristic
magnitude
ofthe

coordinated
cations,
thusproducing
a netpreference
of
many transitionmetal ions for octahedralsites.For

comparison,
characteristic
cohesive
energies
of divalent

transition
metal
ionsoctahedrally
coordinated
byoxygen

areontheorderof 3000-4000
kJ/mole
[4, 15,16].
Furthermore,
aseachorbitalcancontain
twoelectrons

of opposite
spins,two possible
configurations
are

possible
foroctahedrally
coordinated
cations
containing
between
threeand eightd-electronshighspin
configurations,
in which
theenergy
required
topairtwo
electrons
within
anorbital
isgreater
thanthecrystal
field
splitting
energy,
andelectrons
enter
intothehigher
energy

unoccupied
dx2_y
2and
dz2orbitals
(egstates)
rather
than
pairing
inthelower
energy
three-fold
t2gstates.
For
comparison,
electrons
in lowspinconfigurations
fully

occupy
thet2gstates
before
entering
theeglevels.
Among
major
transition
elements,
ironessentially
always

occurs
in thehighspinconfiguration
in minerals:
thisis

simply
aconsequence
oftheenergy
required
topairspins
CFSEfor Fe2+ (d6 configuration)
in octahedral in divalentironbeinglargerthanthe crystalfield
coordination
in mineralsis betweenabout40 and 60
stabilization
energy.
Estimates
ofthespin-pairing
energy
ld/mole;
that
foroctahedral
Cr3+(d3)isgenerally
between in iron-bearing
minerals
arepoorlyconstrained,
but
200 and275 kJ/mole.Characteristic
octahedral
CFSE

values
forother
transition
metal
cations
withunpaired
delectrons
generally
lie in between
theseextremes;
tetrahedrally
coordinated
cationstypicallyhaveCFS
energies
between
-30 and-70%thatof octahedrally

representative
values
forthisquantity
aregenerally
greater
than100kJ/mole
atambient
pressure.
Historically,
the
highspinto lowspintransition
of ironin crystalline

silicates
hasbeen
frequently
invoked
asa possible
high

pressure
phenomena.
Essentially
noexperimental
evidence

WILLIAMS

299

exists, however, that indicates that such an electronic

transition occurs over the pressureand compositional

rangeof theEarth'smantle.
The valuesof the crystal-field splitting,discussedin
detail elsewhere[4, 15, 16], clearlydependon the valence
of the cation(as thiscontrolstheamountof occupancyin
the d-orbitals, as well as contributingto the amount of
cation-anioninteraction,throughthe cation-anionbond
strength),the anionpresent(as thechargeandradiusof the
anion will also control the amount of crystal field
splittingwhichtakesplace),and thetypeandsymmetryof
the site in which the ion sits. Sucheffectsof symmetry
are demonstrated
by a comparisonbetweenoctahedraland

tetrahedral
sites:
intetrahedral
sites,
thedx2_y
2 anddz2
orbitals lie at lower energy than the threeremainingdorbitals.In more complex environments,suchas distorted
octahedraor dodecahedral
sites,a largernumberof crystal
field bandsmaybe observedbecause
of furthersplittingof
the d-levels.An exampleof spectraproducedby different
polarizations of light incident on Fe2SiO4-fayalite, a
materialwith distortedoctahedralsites,is shownin Figure
5, combinedwith an interpretationof the differentcrystal
field transitionspresent in this material [4]. The lower
than octahedral symmetry of the M1 and M2 sites
producesmore extensive splitting of the energy levels
thanoccursin sitesof idealoctahedralsymmetry.
The intensitiesof crystal-field absorptionbands can
vary over four orders of magnitude:theseare governed
both by the abundanceof the absorbingcation, in a
manner directly analogous to Equation 3, and by a
combinationof the symmetry of the cation environment
and quantummechanicalselectionrules. For example,
non-centrosymmetricenvironments(e.g. tetrahedrally
coordinated cations) generally produce more intense
absorptions.
The primary selectionrulesare relatedto spin
multiplicity (involving conservationof the number of
unpairedelectronsbetweenthe groundand excitedstate)
and to conservationof parity (or, transitionsbeing only
allowedbetweenorbitalswhich differ in the symmetryof
their wavefunction: the Laporte selection rule). These
selectionrules may be relaxed througha rangeof effects
which include orbital

interactions, vibrational

and

magneticperturbations,
and lack of a centrosymmetric
ion
site, producingboth weak spin-forbiddenand Laporteforbiddentransitions.Indeed, suchcrystalfield bandsare
frequently orders of magnitude less intense than the
vibrational bands discussed above.

Inter-valence,
chargetransfer,andvalenceto conduction
band transitionsare all termsusedto describeabsorption
mechanismsof similar origins:the transferof electrons
betweenions in non-metalsvia an inputof energyin the

Frequency
25 000 15,000
J

l,

I'l=l

J I

10,000
I

1.0

Octahedrai

Splitting

M1 Site

Splitting

Octahedrai

Splitting

M2 Site

Splitting

0.5

500

Wavelength (nm)
Fig. 5. Polarized crystal field absorption spectra of
Fe2SiO4-fayalite in three different crystallographic
orientations, combined with an interpretation of the
observed transitions in terms of the M1 and M2 cation

sitesof Fe2+in olivine[from4]. Thedotted

spectrum
is
takenparallel to the b-axis of this phase,the dashedline
parallel to c, and the solid line parallel to a. As the M1
and M2 sites are each distortedfrom perfect octahedral
symmetry, additional splitting beyond that shown in
Figure 4 occurs for the d-orbitals of iron ions within
fayalite: this is shown in the insets. Short arrows in

insets
represent
electrons
occupying
eachd-orbital
(Fe2+
hassixd-electrons).
Thesharp
bands
above20,000cm-1
are generatedby spin-forbidden
transitions.

300

INFRARED,

RAMAN

AND OPTICAL SPECTROSCOPY

form of a photon. The term inter-valence transition is

generally used to describeprocessesassociatedwith the
transfer of an electron between transition metal ions,

especiallythosewhichare ableto adoptmultiplevalence

statesin minerals, suchas Fe (+2,+3) and Ti (+3,+4).
Characteristically,
thesebandsoccurin thevisibleregion
of the spectrum,and are most intensein those minerals
which have large quantities of transition metals, and
relatively short metal-metal distances.As such, these
transitionsproduce the colorationof many iron and
iron/titanimn-rich
oxidesandhydroxides.
Charge transfer transitionsnot only occur between
transition metal ions, but also occur in excitation of

frequentlysmall),and represents
the interceptof a plot of
thelog of theconductivityandtheinverseof temperature.
Absorptionsgeneratedby such cation-anioncharge
delocalization
processes
are commonin ore mineralssuch
as sulfidesandarsenides,
andproducetheopacityor deep
red color in the visible of many such minerals.
Furthermore,they also induceeffective opacityof most

and
Band-Gap rystm-em
Absorptio,ns bsorptons
1.0

charge transfer between anions and cations is often

'

I'

4000"-",,,_
Biack-l)d--

electronsbetweencationsand anions.Within oxides,such

oxygen-to-metal
chargetransfer
absorption
bandstypically
occurat highenergies
in theultraviolet,
andareextremely
intense:often three to four ordersof magnitudemore
intensethan crystalfield transitions.Effectively,such

Vibrational
, Absorptions

rmal

Radiation

O.OLO

associated
with delocalization
of an electron,or photoexcitation of an electron into the conduction band of a

material:the separation
in energybetweenthe valenceand
conductionband of materialsis commonlyreferredto as
thebandgap.Withinmanymaterials,
suchchargetransfer
bandsappearas an absorptionedge,ratherthana discrete

band:thisedgeis simplygenerated
becauseall photons
with an energy above that of the edge will produce
electrondelocalization.
Thisedgemaybeaccompanied
by
discretebandsat slightlylowerenergythantheedge:such
bandsare often associated
with a binding,or attractive
force between the photo-excitedelectronand its ion of
origin. These bound electron states are referred to as
excitons,and are discussedin greaterdetail in solid state
physics texts [e.g., 1]. There is an intimate association
betweensuchprocesses
of electrondelocalizationand the

high-andmoderate-temperature
electrical
conductivity
of
insulators and semiconductors:in materials in which the

lO-,
1

10

Wavelength ( lam)

Fig. 6. The dependenceof blackbody emission on

wavelength
at differenttemperatures,
with thewavelength
rangesof electronic and vibrational absorptionswhich
inhibit radiative heat transport in mantle minerals
illustrated. Vibrational absorptions (both single
vibrationaltransitionsand overtones)absorbstronglyat
wavelengthslonger than about 5 gm; if hydroxyl or
carbonate units are present, then such vibrational
absorptions
mayextendto 3 pm. Crystalfieldabsorptions
of divalent iron in distorted octahedral sites, such as the

22]. Thepre-exponential
factor,or0,isgenerallytreatedas
a constant(althoughbothit and thebandgap may be

M2 site in pyroxenes,can occurat wavelengthsabove4

!xm;similarly,iron in thedodecahedral
siteof garnetscan
absorbat longer wavelengthsthan 2 gm (see Bums in
[2]). Amongthe mostintensecrystalfield absorptions
of
iron in mineralsare thoseoccurringnear 1 m, suchas
are shownin Figure5. Suchcrystal-fieldabsorptionbands
tendto broadenmarkedlyat hightemperatures,
increasing
the efficiency with which they prevent radiative heat
transport.The locationof charge-transferbandsis known
to be highlysensitiveto pressure,
with bandsin relatively
iron-rich phases(such as magnesiowtistite)shifting
stronglyto longer wavelengthwith increasingpressure.
Suchabsorptions
generate
an effectivemeansof impeding
radiativeconductivityunder lower mantle pressureand

temperature
dependent:
thesedependences
are, however,

temperatureconditions.

electricalconductivityis notdominatedby defect-related

processes,the thermal excitation of electrons into the

conduction
bandrepresents
the primarymeansby which
charge
carriers
aregenerated.
Thisrelationship
isexpressed
through

o'= o'0exp(-Eg/2kT),

(4)

in whichcris the electricalconductivity

of the material,

Eg is the energyof the bandgap,k is Boltzmann's

constant
(1.381
x 10-23J/K),andT istemperature
[e.g.,

WILLIAMS

301

silicatesin the far ultraviolet. The role of pressure(in

mostcases)is to decreasethe energyat which suchbandgaprelatedabsorptions
occur(thatis, it becomeseasierto

conductivity of mantle materials naturally incorporates

both a frequency-dependent
absorptioncoefficient and

delocalize

greybodyemissionof Equation 5 [23]. Figure 6 shows

representativevaluesof emitted intensityfor a range of
temperatures,
alongwith the wavelengthrangeof ddferent
absorptionmechanismsoccurringin mineralsrelevantto
the Earth'suppermantle.Among lower mantleminerals,
no opticalabsorptiondata havebeenreportedfor silicate
perovskite;however,theabsorption
of magnesiowtistite
at
both ambient and high pressures has been wellcharacterized[ 14]. Not shownin Figure 6 are the grain
boundaryscatteringeffectswhich may also act to reduce
radiative conductivity over a broad frequency range.
Clearly, given the wavelengthrangesover which crystalfield absorptions (which broaden in width at high
temperatures)
andcharge-transfer
bandsoccurin transitionmetal bearingminerals,radiativeconductivityis unlikely
to providea rapid mechanismof heat transportwithin the
deep Earth. Thus, the optical properties of mantle
mineralsplay a passivebut seminalrole in the thermal
and tectonic evolution of the planet: were radiative
conductivityan efficient meansof heat transportthrough
the deep Earth, thermal convection(and its geochemical
andgeodynamic
consequences)
wouldnotbe necessitated.

electrons

as the

distance

between

ions

decreases).It is generally believed that among relevant

deepEarthconstituents
only relativelyiron-richmaterials
(suchas FeO) will have absorptionedgeswhich decrease
to zero energy and metallize over the pressure and
temperature
intervalof the Earth'smantle.However,the
effect of a lower energy absorptionedge in compressed
magnesiowiistite(MgxFel_xO) may have a significant
effect on the electricalconductivityof the deepmantle,in
additionto producingan absoluteimpedimentto radiative
thermalconductivityat thesedepths.
This effect is illustratedin Figure 6; the intensityof
radiative thermal emission is describedby the Planck
function,

l(v) = 2ffehc2v5(exp[hv/kT]
- 1)-1

(5)

in which the emitted intensity, I, is a function of

frequency(v), e representsthe emissivityof the material
(assumedto be unity in the caseof a blackbody,and to lie
at a wavelength-independent
valuebetweenzero and one
for a greybody),and c, h, k and T are the speedof light,
Planck'sconstant,Boltzmann'sconstantand temperature,
respectively. Figure 6 shows representativevalues of
emitted intensityfor a range of temperatures,along with
absorptionmechanisms
of mineralsrelevantto the Earth's

upper and lower mantle. The actual radiative thermal

index of refraction of the material, as well as the black- or

Acknowledgments.I thankthe NSF for support,and

an anonymousreviewer, T.J. Ahrens and E. Knittie for
helpful comments. This is contribution #207 of the
Institute of Tectonics at UCSC.

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Cotton,

Applications of Group Theory,

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An

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RAMAN AND OPTICAL SPECTROSCOPY

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Res., 92, 8116-8128, 1987.
12. Herzberg,G., Molecular Spectra
and

Molecular

Structure:

H.

Infrared and Raman Spectraof

PolyatomicMolecules,632 pp.,
Van Nostrand Reinhold, New
York, 1945.

13. Kieffer, S.W., Heat capacityand

entropy: Systematicrelations to
lattice vibrations, Rev. Mineral.,
14, 65-126, 1985.

14. Mao, H.K., Charge transfer

processesat high pressure,in The
Physics and Chemistry of
Minerals and Rocks, editedby
R.G.J. Strens, pp. 573-581, J.

Wiley, New York, 1976.

15. Marfunin, A.S., Spectroscopy,

Luminescence

and

Radiation

Centers in Minerals, 352 pp.,

Springer-Verlag, New York,
1979.

16. McClure,D.S., Electronicspectra

of molecules
andionsin crystals.
Part II. Spectra of ions in
crystals, Solid State Phys., 9,
399-525, 1959.
17. McMillan,
P.F. and A.M.
Hofmeister, Infrared and Raman

Spectroscopy,
Rev.Mineral., 18,
99-159, 1988.

18. Nakamoto, K., Infrared and

RamanSpectraof Inorganic and
Coor-dination Compounds,4th
edition, 484 pp., WileyInterscience,New York, 1986.

19. Nassau, K., The Physics and

Chemistryof Color: The Fifteen
Causes of Color, 454 pp., J.
Wiley, New York, 1983.
20. Pasteris,J.D., B. Wopenkaand
J.C. Seitz, Practical aspectsof

quantitative

laser

Raman

spectroscopy
for thestudyof fluid
inclusions, Geochim. Cosmo-

chim.Acta., 52, 979-988, 1988.

21. Paterson,M., The determination

of hydroxylby infrared
absorption
in quartz, silicate glassesand
similarmaterials,Bull. Mindral.,
105, 20-29, 1982.

22. Solymar, L. and D. Walsh,

Lectures

on

the

Electrical

Propertiesof Materials,5th Ed.,

482 pp., Oxford Univ. Press,
New York, 1992.

23. Siegel, R. and J.R. Howell,

Thermal
Radiation
HeatTransfer,
3rd Ed., 1072 pp., Hemisphere,
Washington,D.C., 1992.
24. Williams, Q., R. Jeanlozand P.
McMillan, Vibrationalspectrum
of MgSiO3-perovskite: Zero
pressure Raman and infrared

spectrato 27 GPa,J. Geophys.

Res., 92, 8116-8128, 1987.

NuclearMagneticResonance
Spectroscopy
of SilicatesandOxides
in Geochemistryand Geophysics

Jonathan F. Stebbins

I.

INTRODUCTION

The purposeof thischapteris to verybrieflysummarizetheapplications

andlimitations
of NMR spectroscopy
in the studyof the silicatesandoxidesthatmakeup the
earth's crust and mantle, and to tabulate the most useful

data.More extensivereviewshavebeenpublishedrecently

ciesandcorrespondingly
broadNMR spectra.Potentially
interestingnuclidesare listedin Tables I and 2, which
containa simplecomparison
of therelativeeaseof observation in a liquid sample,basedon resonantfrequency,
spin quantumnumber,and abundance.Thesedata serve
only for rough comparison,however (especiallyfor
solids), becausethey containno material-specificinformation on relaxation rates and line widths.

thatgive background
onthe fundamentals,
aswellas details of applications [2,11,29,33,34,42,61,62,88,116,
141]. Extensive tabulationsof NMR data on silicates
havealsobeenpublished[34,43,56,78,118,128,161].
The utilityof NMR in understanding
thechemistry
and

physicsof materialscomesfromthesmallperturbations
of nuclearspinenergylevels(non-degenerate
only in a
magnetic
field) thatarecaused
by variations
in localelectrondistributions,
by thedistributions
of otherneighboring spins(electronic
or nuclear),andby thetimedependenceof theseinteractions.
Any nuclidewith non-zeronuclear spinthuscan, in principle,be observedby NMR,
butthepracticality
of theexperiment
variestremendously.
Detectionof signalsfrom nuclideswith low naturalabundanceandlow resonantfrequencyis often difficultor im-

possible,
although
isotopic
enrichment
canbeuseful.The

NMR is an elementspecificspectroscopy,
and spectra
are primarily sensitiveto short-range
effects.Thus,like
techniques
suchas x-ray absorption
andM0ssbauerspectroscopy,NMR is a good complementto diffraction
methods,andis particularlyusefulin amorphous
materials
andliquids.NMR canbe highlyquantitative,
with a 1 to
1 correlationbetweensignalintensityand the abundance
of a nuclidein a given structuralsite,regardless
of the
structure.In practice,of course,experiments
mustbecarried out carefully to be accuratelyquantitative.A major
drawbackof NMR is its low sensitivitywhencomparedto
spectroscopies
involvinghigherenergytransitions
(e.g.
visible,infraredandRaman).Interpretations
of solid-state
NMR spectrastill rely primarily on empiricalcorrelations,but theseare now well understoodin a qualitative
sense. Another limitation of NMR is a severe one for the

samecanbe truefor evenabundantnuclidesof heavyelements,whichmayhaveextremelywiderangesof frequen-

MineralPhysicsandCrystallography
A Handbookof PhysicalConstants

studyof naturalsilicateminerals:paramagnetic
ionsin
abundances
greaterthana few tenthsof onepercentcan
broadenNMR spectrato the pointof beingimpossible
to
obsee or interpret[87].
Most of the data reportedin the tableshasbeencollectedby high resolutionmagicanglesspinning(MAS)
techniques,with importantcontributionsfrom the new
techniqueof dynamicanglespinning(DAS), and from
singlecrystalandstaticpowderspectra.Figure1 suggests,

AGU

however, that someof the orientationalinformationthat

J. F. Stebbins,StanfordUniversity, Departmentof Geology,

Stanford, CA 94305-2115

Reference Shelf 2

Copyright1995by theAmericanGeophysical
Union.

303

304

NMR

OF SILICATES

AND

OXIDES

TABLE 1. NMR parametersfor somenuclidesof interestin geochemistry:

spin 1/2 nuclides

Isoiope
1H
13C
15N
19F
29Si
31p
57Fe
77Se
89y
103Rh

Natural

NMR
frequency

Receptivity

abundance,
%

at 9.4T, MHz

relative
to 29Si

99.99

1.1
0.4
100
4.7
100
2.2
7.6
100
100

400.0

2700

100.6
40.6
376.4
79.5
161.9
12.8
76.3
19.7
12.7

0.48
0.010
2252
1
180
0.002
1.43
0.32
0.09

109Ag

48.2

18.6

0.13

113Cd
19Sn
25Te
129Xe
69Tm
171yb
183W
195pt

12.3
8.6
7.0
26.4
100
14.3
14.4
33.8

88.7
149.2
126.2
-111.2
33.1
70.4
16.6
85.6

3.7
12.2
6.1
15.4
1.5
2.1
0.03
9.1

99Hg

16.8

205T1
207pb

70.5
22.6

71.6

2.7

230.5
83.7

377
5.4

Notesfor Tables1 and 2:

Data are primarilyfrom tabulationin [49]. Noble gasses,lanthanides,
lessfavorableisotopesof elementslisted,andunfavorableradioisotopes
areexcluded.Relativereceptivityis
calculatedfor low-viscosityliquid samples.Line width and relaxationbehaviorin solid
samplescan make this estimatesquite misleading.In particular, nuclideswith large
quadrupolarmoments(Table 2), and heavynuclideswith very largechemicalshiftranges
may be difficult to observein solids.

is lost in MAS may prove to be usefulin characterizing

anisotropicmaterials.
Quantitative local structural information on minerals
and melts is importantto many problemsin geochemistry and geophysics.
NMR hasprovento be very useful

inthisarea.A second
nearly
unique
utililyofMR, that
is just beginningto be applied in the geosciences,is in

studyingdynamicsat the time cale of seconds

to
nanoseconds.For many geochemicallyinterestingpro-

cesses,suchas diffusion,viscousflow, and displacive

phase transitions, the fundamentalrate may be within
this range.
1.1.

Definitions

The chemicalshift 5is the perturbation

in theresonant (Larmor) frequencyv of a nuclidein a particular
chemicalenvironment,
causedby screening
of theexternal
magneticfieldby thesurrounding
electrons.
5is generally

STEBBS

TABLE 2. NMR parameters

for somenuclidesof interestin geochemistry:
quadrupolarnuclides.SeeTable
1 for notes.

Isotope

Spin

Natural

abundance,
%
0.02
7.4

Quadrupolar

NMR frequency

Receptivity

moment
x1028,

at 9.4T, MHz

relativeto 29Si

m-2

2H
6Li

1
1

7Li
9Be

3/2
3/2

10B
11B
14N

3
3/2
1

19.58
80.4
99.6

170
23Na

5/2
3/2

0.04
100

25Mg

5/2

0.22

24.5

27A1
33S
35C1
37C1
39K
43Ca
45Sc
47Ti
49Ti
51V
53Cr
55Mn
59Co
61Ni
63Cu
65Cu
67Zn
71Ga
73Ge
75As
81Br
87Rb
87Sr
91Zr
93Nb
95Mo

5/2
3/2
3/2
3/2
3/2
7/2
7/2
5/2
7/2
7/2
3/2
5/2
7/2
3/2
3/2
3/2
5/2
3/2
9/2
3/2
3/2
3/2
9/2
5/2
9/2
5/2

100
0.8
75.5
24.5
93.1
0.15
100
7.3
5.5
99.8
9.6
100
100
1.2
69.1
30.9
4.1
39.6
7.8
100
49.5
27.9
7.0
11.2
100
15.7

0.15
-0.055
-0.10
-0.08
0.05
0.2
-0.22
0.29
0.24
-0.05
0.03
0.4
0.38
0.16
-0.21
-0.20
0.16
0.12
-0.18
0.29
0.31
0.13
0.3
-0.21
-0.22
+0.12

104.3
30.7
39.2
32.7
18.7
27.0
97.3
22.5
22.6
105.4
22.6
98.8
94.4
35.8
106.1
113.7
25.1
122.2
14.0
68.7
108.4
131.3
17.4
37.3
98.2
26.2

99Ru

5/2

12.7

0.08

18.4

0.4

101Ru

5/2

17.1

0.44

20.7

0.7

92.6
100

10.13

0.0028
-0.0008

-0.04
0.05

61.4
59.0

0.004
1.7

155.6
56.2

737
37.5

0.085
0.041
0.01

43.0
128.4
28.9

10.6
360
2.7

-0.026
0.10

54.2
105.9

0.03
250

0.7
560
0.05
9.6
1.8
1.3
0.02
819
0.4
0.6
1035
0.23
475
750
0.11
174
96
0.32
152
0.30
69
133
133
0.51
2.9
1320
1.4

305

306

NMR

OF SILICATES

AND

OXIDES

TABLE 2 (continued)

Isotole

Spin

105Pd 5/2
115in
121Sb
127I
133Cs
137Ba
139La
177Hf
181Ta
187Re
189Os
193Ir
197Au

9/2
5/2
5/2
7/2
3/2
7/2
7/2
7/2
5/2
3/2
3/2
3/2

201Hg

3/2

209Bi

9/2

Quadrupolar

NMR
freqlencyReceptivity

abundance,

moment
x1028,

at 9.4T, MHz

m-2

22.2

0.8

Natural

95.7
57.3
100
100
11.3
99.9
18.5
99.99
62.9
16.1
62.7
100

13.2
100

18.4

relativeto29Si
0.7

0.83

88.1

910

-0.28

96.2

251

-0.79

80.5

257

-0.003

52.8

130

0.28

44.7

0.22

56.8

2.1

163

4.5

16.2

48.0

99

238

2.2

91.8

0.8

31.4

0.7

1.0

1.0

7.6

0.06

0.59

6.9

0.07

0.44

26.6

-0.38

64.9

0.5
381

expressedin partsper million relativeto a standard,with

= 106(samplestandard)/standard.
Thechemical
shift is orientationdependent,and is describedby the
chemicalshift anisotropy(CSA) tensor,whoseprinciple
components
are usuallydenoted511,22, and33 and
which has a unique orientationwith respectto the local
structure(or with respectto crystallographicaxes in a
crystallinematerial).The isotropicchemicalshift,Siso,
is
the averageof thesethreecomponents.For spin1/2 nuclides,5isois observedexperimentally
in liquidswhere
molecularrotationproduces
rapidisotropicaveraging,
and
in solidsby rapid samplespinning(MAS NMR) at the
"magic" angle 0 with respectto the externalfield (0 =

54.7, 1-3cos20
= 0).
For nuclideswith spin I > 1/2, a total of 21 transitionsmay be observable.The frequenciesof thesetransitionsare controlledby the energyof interactions
with the

Fig.1. Static
(non-MAS)
29Sispectra
forquartz.
Top

.-80

-100

-120

spectrumshowsthreemagneticallyinequivalentSi sites;
bottom spectrumshows spectrumfor randomlyoriented
powder;centerspectrumshowseffectof strongpreferred
orientationin a quartz mylonite [132]. Scalesin this and
otherfiguresare in ppm.

STEBBINS

electric field gradient,often summarizedby the nuclear

quadrupolar
coupling
constant
QCC=e2qOJh.
Here,eQis
the nuclearquadrupolarmoment,and qis the principle
component
of theelectricfield gradientat thesiteof interest.The full description
of thequadrupolar
interactionrequirestheelectricfield gradienttensorandits orientation
relative to the structure.The deviation from cylindrical
symmetryof this tensoris given by the asymmetryparameterq, which variesfrom 0 to 1. In liquidswith sufficientlyrapidisotropicrotationof molecules,
thefield gradient and the quadrupolarinteractionaverageto zero and
/Sisois observed.In MAS NMR, the central 1/2 to -1/2
transitionremainsshiftedandbroadened
by a secondorder

quadrupolar
interaction;
in DAS NMR,/Sisois shiftedby

307

amongnumberof AI neighbors,
bondangles,and have
beendevelopedthatallow ratherpreciseestimates
of 8 for
tectosilicate structures[34]. A few correlationshave been

developedfor SiO4 groupsin generalthat allow estima-

tionof 8 for mostsilicatestructures

[56,118].Similarapproacheshavebeentakenfor SiO6 groups[47,146].
Structure45 correlations have been used to derive im-

portantconstraints
on AI/Si orderingin a numberof minerals.The greatesteffortshavebeenon syntheticzeolites,
becauseof their tremendoustechnologicalimportance
[34,72]. In geochemistry,the most importantexamples
have been in determiningthe orderingstatein feldspars
[64,102,103,120,127,169],
other tectosilicates
[12,53,95,104,117,148], cordierite [107] and sheet sili-

listedin Tables3 through5. In silicates,the largesteffect

cates[5,20,52,60,74,112,160]. In severalcases,discrepanciesin thermodynamic

datathathadbeententativelyascribedto underestimates
of theentropyof disordered
syntheticphaseshavebeendisplacedto otherpartsof thedata
baseby findingsof nearlycompleteorder,suchas for sillimanite [59,140] and prehnite[139]. For a few systems,
carefulcombinationof NMR spectroscopy
with calorimetric observationhas providednew insightsand detailsof
the energeticcontroland consequences
of Si/AI disorder

of structure on chemical shift is that of coordination num-

[17,53,103,106].

theisotropicaverageof the secondorderquadropolar

interaction, but is not broadened.
2. APPLICATIONS
SILICATES
AND

TO CRYSTALLINE
OXIDES

2.1. 29S i

Isotropic
chemical
shiftsfor29SiandCSAdataare
ber.Thus, for SiO6groups
is therangeof about-180
to -220 ppm relativeto tetramethylsilane(TMS), andis
in nearlyall casesbetweenabout-65 and -120 ppm for
SiO4 groups. Signals near to -150 ppm are probably
from SiO5 groups [58,166].
The secondmostimportanteffectis thatof the number
andidentityof firstcationneighbors.
If bridgingoxygens

Veryrecently,
29SiMASNMRhasbegun
tobeapplied to high pressuremantle phasesthat contain SiO6

groups.In MgSiO3 ilmenite and perovskite, and [5Mg2SiO4, Mg/Si disorderhasnotbeendetected[63,146],

but both Mg/Si and Si/AI disorderare significantin majorite and majorite-pyropesolid solutions,as shownin
Figure 2 [101,146].

are consideredas thosesharedwith tetrahedralSi or AI (or

B or P) neighbors,and non-bridgingoxygensto be those

sharedwith larger and/or lower chargedM cations,an
SiO4 site can be labeledas Qn, wheren designates
the
numberof bridgingoxygens(andQ standsfor quaternary).
For a fixed M cation type, decreasingn by one tendsto
increaseJby about10 ppm to lessnegative,higherfrequencies.EachQn speciesthushasa distinct,but somewhat overlappingrangeof 5.In a similarfashion,the
substitution
of tetrahedralAI for a tetrahedralSi neighbor

tendsto increase
5 byabout5 ppm.Asa result,
295i
MAS NMR spectraof aluminosilicates
oftenhavemultiple, partiallyoverlappingpeaksfor $i sites with varying numbersm of A1neighbors
[Qn(mA1)].Thiseffectis
particularlyobviousand well-exploitedin tectosilicates,
where it has often providedthe key to unravelingquite
complexAI/Si orderingpatterns.Thebondanglebetween
tetrahedrahasa relatedeffect, againbestcalibratedfor tec-

tosilicates.Increasingthe meanSioO-T anglesystemaftcallydecreases/5.

A numberof semi-empirical
correlations

2.2.

27A i

NMR studies
of 27A1in minerals
havebeenreviewed
recently[66], and dataare listedin Tables6 and7. Most
early studiesof this nuclidewere of singlecrystals,with
complete determinationsof quadrupolarcouplingconstants,asymmetryparameters,and electricfield gradient
tensors,but without preciseisotropicchemicalshifts.
The quadrupolar parameters have been shown to be
roughlycorrelatedwith the extentof distortionof the AI
site for both octahedraland tetrahedralgeometries[43].
Single-crystal
work on MgAI204 spinelallowedquantificationof octahedral
andtetrahedral
AI siteoccupancies
and
orderingstate[14].

Asfor29Si,isotropic
shifts
for27A1in oxides
(now
determined most commonly by high resolutionMAS
NMR) are most strongly influencedby coordination
number.Jvaluesfor AIO4 groupsfall roughlyin the

range
of 50to90 ppmrelative
toaqueous
Al(H20)63+,
and for AIO6 groupsin the range of-10

to 15 ppm.

308

NMR OF SILICATES AND OXIDES

TABLE
3.29Si
NMRdata
forQo,Q1,and
Q2sites
incrystalline
silicates.
mineral

(s)=synthetic
Qosites:

nominal
formula

chondrodite
forsterite(s)

Mg5(SiO4)2(OH,F)2
Mg2SiO4

(s)
monticellite(s)
(s)

Li2SiO4
CaMgSiO4
NaH3SiO4

(s)

Na2H2SiO4-8.5H20

majorite
garnet(s)g Mg4SiVlsilV3012e
(s)
(s)

-Jiso
a
60c
61.9
64.9
66
66.4
67.8

-/511

CSA b
-/522

-J33

reft

[78]

38.8d

55.3

95.4

44

60

94

[78,159]
[78]
[128]
[78]
[78]

68to90f

[101,146]

Ba2SiO4
ot-Ca2SiO4

70.3
70.3

[78]

afwillite

Ca3(HSiO4)2-2H20

71.3,73.3

[34]

larnite(s)
pyrope(s)
Ca-olivine(s)
(s)
(s)
phenacite
ruffle
titanite
andalusite
kyanite
zircon
piemontiteg

I-Ca2S
iO4
Mg3AI2Si3Oi2
e
-Ca2SiO4
Ca3SiO5
CaNaHSiO4
Be2SiO4
<1% SiO2in TiO2
CaTiSiO5
AI2SiO5
AI2SiO5
ZrSiO4
Ca2(AI,Mn,Fe)3

71.4
72.0
73.5
69 to 75h
73.5
74.2
77.2
79.6
79.8
82.3,83.2
81.6
81.9

[78]

grossu
lar
topaz

(Si207)(SiO4)OH
Ca3AI2(SiO4)3
AI2SiO4(OH,F)2

83.4
85.6

(s)
(s)
gehlenite(s)
akermanite(s)

Na6Si207
Li6Si207
Ca2AI2SiO7
Ca2MgSi207

68.4
72.4
72.5
73.7

mnkinite(s)
hemimorphite

Ca3Si207
Zn4Si207(OH)2-H20

74.5,76.0
77.9

[I-Mg2SiO4

79.0

CaA12Si207(OH)'H20
o-Y2Si207

81
81.6,83.5

(s)

o-La2Si207

83.2

(s)

Ca6Si207(OH)6

82.6

[78]

[101]
[78]

[78,124]
[78]

[78]
[139]
[118]
45

78

116

[78,128]

50

79

120

[118,128]
[78]
[118]
[56]
[78]

Q1sites:

(s)

lawsonite
(s)

[78]
[34]
122

74

20

[56]

134

84

[56]
[78]
[78]
[146]

123

92

28

[128]
[34]
[78]

109

109

35

[34,46]

STEBBINS

TABLE 3 (continued)

CSAb
-822

mineral

(s)=synlhetic

nominal formula

-Siso a

-833
[118]

86.4,90.4

(s)

Ca2(AI,Mn,Fe)3
(Si207)(SiO4)OH
In2Si207

87.7

[78]

(s)

piemontiteg

[5-Y2Si207

92.9

[78]

thortveitite

Sc2Si207

95.3

[78]

zunyiteg

AI13Si5020(OH)
14F4
Cli

91.2,96.9

Li2SiO3

74.5

Na2SiO3
BaSiO3

76.8

18

59

156

[78,36]

80

29

71

140

[128]

SrSiO3

85

30

71

154

[128]

Mg2Si206
Mg2Si206
CaMgSi206

82 c

81.8,84.2

73

132

[56,128]

84.8

73

148

[118,128]

(Ca,Na)(Mg,AI)Si206
i

85.4

81

142

[118]

Q2sites:
(s)
(s)
(s)

(s)
orthoenstatite

clinoenstatite(s)

diopside
omphacite
spodumene
jadeire

pyroxene
phase(s)g
alamosite

LiAISi206
NaA1Si206

NaMg0.5
SivI0.5SiTM
206
Pb{ 2Si{ 2036

[781

[78]

91.4

[118]
53

[118]

[78]

91.8

[146]

92.1,97.6

[34]

84.1,86.5,
94.3

prehniteg
tchermakitic

amphibole(s)g
triple-chain
phase(s)g
Sc-Fpargasite(s)

(Q2+Q3)
tremoliteg

hillebrandite(s)

pectolite(s)
foshagite(s)
xonotlite(s)g
walstromitephase

Ca2AI2Si3010(OH)2
Ca2(Mg4AI)(AISi7022)(oI-I):
Na2Mg4Si6016(OH)2

84.6k

NaCa2Mg4ScSi6AI2022F2
Ca2Mgs(Si4Oll)2(OH)2
Ca2SiO3(OH)2
Ca2NaHSi309
Ca4Si309(OH)2
Ca6Si6017(OH)2
Ca3Si309

[139]

83.4,87.4

[18]

85.3

[18]

86 m

[108]

87.2

5O

77

137

[18,128]

86.3

[78]

86.3

[78]

84.8,86.4
86.8

[78]

73.8,78.5,

[58]

79.0

wollastonite

Ca3Si309

87.6,91.71

[5-wollastonite(s)

[-Ca3Si309

89.0

24

85

158

[118]

[78]

309

TABLE 3 (continued)

mineral
(s)=synthetic

nominal formula

-6iso a

Q2sites,
rings:
ps-wollastonite(s) x-Ca3Si309
83.5
(s)
K4H4Si4012
87.5
tourmaline
Na(Mg,Li,A1)3AI6Si6018-88.1
(BO3)3(OH,F)4
i
(s)
Ba7Si7021'
10BaCI2
92.5
benitoite
BaTiS
i309
94.2

wadeite
phase(s)g K2S
iVlsilV309

95.0

-$11

63

CSAb
-i22

63

-/533

141

ref.

[78]
[71,78]
[118]
[34]
[78]

[146]

High P phases,uncertainstructure:

"phase
E"(s)

"phase
Y"(s)g
(s)

Mg2.3Sil.3H2.406

75.7TM

(CaO)xSiVsilVo4

80

-Na2Si205

80.6,81.8

[58]

[146]
ee

(s)g

CaSiVIsiIVo5

88.9

[146]

(s)g
(s)g

Na2S
ivISiTM207
-Na2
SiVIsilVo5

94.4
97.9

ee
ee

(s)g

Na2(S
iVI,siTM)409

97 .0,107.7,

ee

108.9

Notesfor Tables 3, 4, and 5:

'{'Mostintensepeak.

Si-O-B
bonds
areconsidered
as"bridging",
placing
theSisites
inberyl
anddatolite
intheQ4andQ3groups,
respectively.
(a)Chemical
shifts
areinppmrelative
totetramethylsilane.
(b)Unless
otherwise
noted,
principle
components
of

CSAtensor
arederived
fromfitting
spinning
sidebands,
andareofrelatively
lowprecision;
orientation
oftensor
withre-

spect
tocrystallographic
axes
maynotbeknown.
Insome
cases,
15iso
andCSAdataarefromdifferent
sources
andmay
therefore
appear
tobeslightly
discrepant
[/Siso
should
= (/511+/522+i33)/3].
Given
typical
errors
inCSAmeasurements,
thisisgenerally
notsignificant.
(c)Broad
peak
(atleast
5ppmwidth).
(d)CSAbased
onsingle
crystal
study.
(e)Additional
dataonsolid
solution
series
given
inreference.
(f)Multiple
peaks
duetopartial
disorder
among
octahedral
Siand
Mg.Mainpeakisat-74.3ppm.(g)Dataforanother
typeofSi sitelisted
elsewhere
intableorinTable
4 or5. (h)
NineSisites,
7 resolved
peaks.
(i) Approximate
formula.
(j) CSA dataaremeans
fortwosites.(k)Twoadditional
peaks
indicate
asmall
amount
ofSi/AIdisorder.
(1)First
peak
isforT1site,second
forT2+T3.(m)Broad
peakconsistent
with considerable
disorder.(n)
Ordering
schemes
canbecomplex,
butcanbecharacterized
fortetrahedral
SiandAI

as(1)disordered,
Al-avoidance
violated;
(2)ordered
according
toAl-avoidance
only;
(3)more
ordered
than
required
byAIavoidance;
(4)fullyordered
ornearly
so;(5)partially
disordered.
(o)Split
peak
reported
by[4].(p)CSAcomponents:
-43,-59,
-147ppm[128].(q)CSAcomponents:
-49,-83,-129ppm[128].(r)CSAcomponents:
-107,-107,-59ppm
[128].(s)small
peak
duetotriple-chain
sitein partially
disordered
phase.
(t)CSAcomponents:
-56,-72,-151
ppm
[128].(u)CSAcomponents:
-54,-70,-161
ppm[128].(v)CSAcomponents
fromsingle
crystal
study:
102.6,
107.0,
109.1
[132].(w)Approximately
5 peaks
resolved
for12sites.(x)Overlapping
peaks
duetomultiple
sites.
(y)End
member:
complex
series
ofpeaks
forintermediate
compositions.
(z)Approximately
8peaks
for15possible
sites.
(aa)8
peaks
for8 sites.
(bb)511=-173.4
ppm;
1522
= [33TM
-183.1
ppm.(cc)Narrow
peak
consistent
withcomplete
Mg/Si
order.(rid)Somewhat
broadened
peakconsistent
withsome
Mg/Sidisorder.
Reference
contains
dataonsolidsolution
withpyrope.(ee)Kanzaki,Stebbins
andXue,unpublished
data.

TABLE4. 29SiNMRdataforQ3andQ4sitesin crystalline

silicates.
Dataforsomeclayminerals
andsynthetic
silicas,
zeolites,
aswellassilicates
withorganic
ligands,
havebeenexcluded
forbrevity.
Dataforend-member
compositions
only.SeeTable3 for notes.
mineral

(s)=synthetic

nominal
formula

-Siso
a

ordering
staten

ref.

Q3sites,
layeraluminosilicates
:

margarite
CaA12(A12Si2010)(OH)2 75.5
phlogopite
KMg3AlSi3010(F,OH)2
84to87
phlogopite(s)e KMg3AISi3010(OH)2
83.2,87.0?,90.7
palygorskite MgAIS
i4010(OH)2'4H20
84.9,91.7,96.8
beidellite

Na0.3AI2(AI0.3Si2.7010)

muscovite
illitee

KAI2S
iA13010(O
H)2
KAI2SiAI3010(OH)2
i

lepidolite

KLi2AI(AISi3010)(F,OH)2

89m

dickite
kaolinite
endellite

AInSi4010(OH)8
AI4Si4010(OH)8
AI4Si4010(OH)
10'8H20

90.9
91.5
93.1

pyrophyllite

AI2Si4010(OH)2

94.0

4
5
3

88,94

[78]
[60,78]
[20]
[34]
[34]

(oI-I)2

montmorillonite (AI,Mg)2Si4010(OH)2'4H20

89,85
?,81
91rn

5
5

[112]
[60]

[78]
[34]
[78]
[78]

[112,118]

93.7

sepiolite

Mg4Si6015(OH)2'2H20

hectorite

(Mg,Li)2.7Na0.3Si4010(OH)2 95.3

[34]

92,95,98

[34]
[60]

-4H20

Q3sites,
othersilicates:
sapphirine
e
datolite

sillimanite

tremoliteg

tremolite(s)g
tchermakitic

(M g3.6AI4.4)(AI4.4S
i 1.6)020
CaOSO4(OH)
AI2SiO5
Ca2Mg5(Si4011)2(OH)2
Ca2Mg5(Si4011)2(OH)2
Ca2(Mg4AI)(AlSi7022)(OH)2

73TM

83.0P

86.4q

[19]
[128]

[59,118]

91.7 r

[18]

91.7, 96.9s

[18]

92.1

[18]

Na2Mg4Si6016(OH)2

87.8,91.4

[18]

KFCa4Si8020'H20

92.0

[78]

Mg3Si205(OH)4
Mg3Si4010(OH)2
Ca6(Si6017)(OH)2
Li2Si205
BaSi205
c-Na2Si205
K2Si205
[I-H2Si205
c-H2Si205

94.0

[78]

97.2

[118]

97.6

[78]

92.5 t

[94]

93.5

[94]

94.5 u

[94]

91.5,93,94.5

[94]

98.4,101.9,110

[34]

amphibole(s)g
triple-chain
phase(s)g
apophyllite
serpentine
talc

xonotlite(s)g
(s)

(s)
(s)
(s)

(s)
(s)

101.5

[34]

312

NMR OF SILICATES

AND OXIDES

TABLE 4 (continued)
mineral

(s)=synthetic

nominal formula

-Sisoa

ordering

reft

state n

Q4,silicapolymorphs:
quartz
coesite
cristobalite
tridymite

Si02
Si02
Si02
Si02

107.4 v

[118,126]

108.1,113.9

[126]

108.5

[118,126]

109.3-114.0 TM

[126]

Q4,feldspars
:
low albite e

high albitee
microcline e
sanidine e

anorthite e
anorthite e

NaAISi308
NaAISi308
KAISi308

92.3,96.9,104.3

[103,127]

91 to 112 x

[169]

95.6,97.6,100.6

K0.6Na0.4AlSi308
CaAI2Si208
CaAI2Si208(disordered)

97,101 m

[103,127]
[64]

82.7,84.7,89.3 x

[120]

82.5 to 104.5 x

[102]

[148]

Q4,f eldspathoids
:
camegieite(s)

NaAISiO4

82.2

sodalite

Na8AI6Si6024CI2

84.9

[118]

nepheline
e
kalsilite(s)e

Na3KAI4Si4016
i

85.1',88.4

[148]

KAISiO4

88.8

[148]

cancrinite

NasAI6Si6024CO3

86.3

[8]

scapolite
e

Na4AI3Si9024CI-

92.6,106.2Y

[117]

analcite

Ca4AI6Si6024CO3
NaAISi206-H20

91.6,96.8',102.0

[95]

leucite

KA1Si206

78.7 to 106.7 z

[95]

NaCa2AIsSi5020-6H20
CaAI2Si3010'3H20
Na2AI2Si3010'2H20
Na2AI2Si4012'6H20
CaAI2Si4012'6H20
CaAI2Si7018-7H20
BaAI2Si6016'6H20
CaAI2Si7018-6H20

86.4,89.0,91.7

[118]

86.4,88.8,95.7

[118]

87.7?,95.4

[118]

Q4,zeolites
:
thomsonite
scolectite
natrolite

gmelinite
chabazite
stilbite

harmotone
heulandite

92.0,97.2', 102.5

[72]

94.0,99.47,104.8

[72]

98,101.5'{',108

[72]

95,98.6,102.6,108
95.0 tO 108.0 aa

[72]

[118]

Q4,others:
cordierite
cordierite

petalite

Mg2AI4Si5018(ordered)
Mg2AI4Si5018(disordered)
LiAISi4010

79,1007

[107]

79 to 112 aa

[107]

87 c

[78]

STEBBINS

TABLE 4 (continued)
mineral

nominalformula

(s)=synthetic

-isoa

ref.

ordering
state n

danburite

prehnite
beryle
roedderite

zunyite

CaB2Si208
Ca2AI2Si3010(OH)2
A12Be3Si6018
Na2Mg5Si12030
AI 13Si50 20(OH) 14F4C1

89
98.6
102.3
100.6
128.5

[128]

[139]
[1191
[501

[1181

TABLE5.29SiNMRdataforSiO6andSiO5sites
incrystalline
silicates.
Dataforend-member
compositionsonly. SeeTable 3 for notes.
!

mineral

(s)=synthetic

nominal
fo.rmula

-5i,o
a

ref.

Si06, known structures:

thaumasite
ilmenite
phase(s)
stis
hovite(s)
perovskite
phase(s)
perovskite
phase(s)
pyroxene
phase(s)g
majorite
garnet(s)g
wadeite
phase(s)g
(s)
(s)

Ca3siVI(oH)6(SO4)(CO3)
15H20
MgSiVlo3
SiVIo2
MgSiVlo
3
CaSiVlo3
NaMg0.5
SivI0.5SiTM
206
Mg4SiVisiIV3012e
K2siVIsiIV309
siVI50(PO4)6
SiVIP207

179.6
bb
181.0
cc
191.3
191.7
cc
194.5
194.7
cc
197.6
dd
203.1
214.0,217.0
220c

[48,139]
[146]
[146]
[63]
[146]
[146]
[101,146]
[146]
[158]
[158]

CaSiVIsiIVo5
-Na2SiVIsiIVo5
Na2S
iVIsiTM
207
Na2(SiVI,siIV)409
(CaO)xSiVIo2

193.4
199.8
200.4
202.4
208.6

[146]
ee
ee
ee
[146]

(CaO)xSiVsiIVo4
g

150.0

[146]

Si06, uncertainstructure:

(s)g
(s)g
(s)g
(s)g
"phase
X"(s)
Si05, uncertainstructure:

"phase
Y"

313

:314

NMR

OF SILICATES

AND

OXIDES

$i TM

siVl

j
-200

Fig.2. 29SiMASspectrum
forahigh
pressure,
MgSiO3
garnet.
Themultiplicity
oftetrahedral
sites
results
frompartial
disorder
among
six-coordinated
SiandMgneighbors
[101].Blackdotmarks
spinning
side
band.

TABLE
6.27A1
NMRdata
AIO4
sites
incrystalline
silicates
and
oxides.
Data
foranumber
ofclay
minerals,
synthetic
zeolites,
sheetsilicates,
andphosphates
havebeenexcluded
forbrevity.

Mineral

nominal
formula

.(s)=synthefic
Qosites:
(s)

QCC,

MHz
Ba5AI208

Siso
a,b

ref.

ppm

2.3

0.8

5.47
6.02

0
0

80

[92]

72

[92]

76.0
72c

[43,79,129]

Qosites,
AlTMneighbors:

zunyite
AIVI12AIIVsi5020(OH)
14F4CI
garnet
phase(s)
Gd3AI2VIAI3IVo12
garnet
phase(s)
Y3AI2VIAI3IVo12
spinel
(disordered)(s)
(Mg,AI)
TM(Al,Mg)vI204

[43]

[86,92,163]

(s)
(s)
(s)
(s)

[5-A1203
y-A1203
ri-A1203
z-AI203

64
66
62
64

(s)

BaAIVI9AIVAIIV2019

70

[92]

[92]
[92]
[92]
[92]

Q1sites:
(s)

KAIO2.1.5H20

5.0

0.25

81

[92]

KAlO2'H20
0t-BaAl2On.2H20
"

6.5
3.4
5.1

0.6
0.5
0.9

83
81
80

[92]

Q2sites:
(s)
(s)

[92]

[92]

STEBBINS

315

TABLE 6 (continued)
Mineral

nominal formula

(s)=synthetic

Q3sites,
layer
aluminosilicates
:d
CaAiVI2(AI
TM2Si2010)(OH)2
margarite
phlogopite
e

KMg3AISi3010(F,OH)2

muscovite

illite e

KAIVI2S
iA1TM
3010(OH)
2
KAI2SiAI3010(OH)2
f

hectorite

(Mg,Li)3Na0.3Si4010(OH)24 H20

penninite
xanthophyllite

QCC,

Siso
a,b

MHz

ppm

4.2

2.1

ref.

76

[73]

69 c

[20,60,111]

72

[73]

72.8

[54,60]

66 c

IdOl

(Mg,AIVI)6(Si,AllV)4010(OH)8
f
Ca2(Mg,AI
VI)6(S
i,AlTM)4010(OH)4
f

2.8

72

[731

2.8

76

[73]

KAIO2-0.5H20
Ca12AI14033

5.6

77

[921

0.2

85

[92]

0.53

64.5

[43,731

75 c

[19]

Q3sites,
others:
(s)
(s)

AIVIAIIVSiO5

sillimanite

11

6.77

(Mg3.6AIVI4.4)(A1TM
4.4S
i1.6)020

sapphirine

Q4sites,
silicaanalogs:
berlinite(s)
AlPOn
tridymitephase(s)
ALPO4
cristobalite
phase(s) ALPO4

4.09

0.37

44.5

[43,93]

0.75

0.95

39.8

[93]

1.2

0.75

42.5

[931

3.29

0.62

63.0

[43,64,73,103,169

3.22

0.21

60.9

[43,64,73,103,169

62,55 c

Q4sites,
feldspars:
albite e

microcline e

NaAISi308
KAISi308
CaAI2Si208

8.5

0.66

0z00

7.4

0.76

00i0

6.8

0.65

m000

6.3

0.88

m0i0

5.5

0.42

mz00

4.90

0.75

4.4

0.53

2.6

0.66

0.94

0.32

anorthite, 0zi0

mzi0

[133]g,[64]

Q4sites,
feldspathoids:
sodalite e

NasA16Si6024CI2

nepheline
kalsilite(s)e
scapolite
e

Na3KAI4Si4016
f

analcite
leucite

62.9

61.0,63.5

[73,961
[53,73]

KAISiO4

61.7

[53]

Na4AI3Si90 24CI-Ca4AI6Si6024CO3
NaAISi206'H20
KAISi206

58.0 c

[117]

59.4

[73]

61,65,69 c

[1041

316

NMR

OF SILICATES

AND

OXIDES

TABLE 6 (continued)

Mineral
(s)=synefic

nominal
formula

QCC,
MHz

rl

Jiso
a,b
ppm

ref.

Q4sites,zeolites:
thomsonite
scolecfite
natrolite
gmelinite
chabazite
mordenite
gismondite

NaCa2AI5Si5O20'6H20
CaAI2Si3010.3H20
Na2AI2Si3010'2H20
Na2AI2Si4012-6H20
CaA12Si4012'6H20
(Na2,K2,Ca)AI 2Si 10024'7H 20
CaAI2Si208-4H20

1.66

0.50

62.7
62.5,66.4
64.0
59.9
59.4
55.8
56.4

[73]
[73]
[43,73]
[73]
[73]
[73]
[73]

Q4sites,
others:
cordierrite,T1
T5

Mg2AI4Si5018'nH20

prehnite

Ca2AlVIAIIVsi3010(OH)2

9.0

13-LiAIO2
,-LiAIO2
[3-NaA102
KAIO2
BaAI204
T1AIO2

1.9
3.2
1.4
1.1
2.4

(s)
....
(s)
....
(s)
(s)

Ca3AI206,AI(1)
, AI(2)
Ca12AI14033,Al(1)
, AI(2)
CanAI6013
CanAI6013'3H20
"

8.69
9.30
9.7
3.8
2.4
1.8
5.4

(s)

CaAI204
h

(s)
....

CaAI407, AI(1)
, AI(2)

6.25
9.55

(s)

VI
CaAI
9AIV AIIV 2019,Q0

2.0

(s)
(s)
(s)
(s)
(s)
(s)

10.6
5.6

0.38
0.34

[43]
[43]

60

[139,#179]

0.56
0.7
0.5
0.7
0.4

83.0
81.3
80.1
76.0
78.0
69

[92,125]
[92]
[921
[92]
[92]
[92]

0.32
0.54
0.40
0.70
0.95
0.5
0.45

79.5
78.25
85.9
80.2
80.3
78
79

Ca-aluminates:

[122]
[122]
[123]
[123]
[91]
[91]
[9]

2.5-4.3 0.2-1.0 81.2-86.2 [123]

0.88
0.82

4)

75.5
69.5

[123]
[123]

65

[91]

Notesfor Tables6 and 7:

a)Relative
toAI(H20)63+.
(b)Peak
positions
corrected
forsecond
order
quadrupolar
shift
have
been
included
where
possible.Wherethiscorrection
is notmade,MASpeakpositions
andwidths
will depend
somewhat
onthemagnetic
field
used.(c) MASpeakposition;
fiisoat slightly
higher
frequency.
(d)See[162]forextensive
dataonclayminerals.
(e)
Approximate
formula.(f) Reference
includes
dataonothersolidsolution
compositions.
(g)Reference
includes
highT
studyof phasetransition.(h) Rangeof damfor six sites.

STEBBINS

TABLE7. 27A1NMR dataforAIO5andAIO6sitesin crystalline

silicates
andoxides.
Datafora varietyof
syntheticzeolites,sheetsilicates,andphosphates
havebeenexcludedfor brevity.SeeTable6 for notes.

Mineral

nominal
formula

(s)=synthetic

QCC,

MHz

Siso
a,b

ref.

ppm

AI05 sites:

(s)
andalusite,
AI2
augelite
senegalite
(s)
(s)

AIV2Si207
AlVIAlVSiO5
AlVIAlV(OH)3PO4
AIVIAIV(OH)3PO4.H20
A12Ge207
LaAIGe207

vesuvianite

10.5
5.9
5.7
=2.7
8.8
7.2

0.6
0.70
0.85

29
36.0
30.9
36.0

[41]

0.4
0.3

36
35

[8O]

41.1

[100]

16.0

[43,55]

Ca19All1Mg2Si
18068(OH)
10f

[3A3,73]
[7]

[7]

[8O]

A106 sites:

corundum

ot-A1203

2.39

chrysoberyl,All
AI 2
spinel(ordered)

BeA1204

2.85
2.85
3.68

0.94
0.76
0

MgAI204

(disordered)

gahnite

ZnA1204

3.68

futile

= 1% A1203 in TiO2

2.8

1.0

(s)

A12TiO5

[43]

[43]
[43]

1lC

[86,163]

-6.5

[143]

6c

[143]

[43]

beryl

Be3A12Si6018

3.09

[43]

euclase

HBeA1SiO5

5.17

0.70

[43]

vesuvianite

Ca19AI11Mg2Si
18068(OH)
l0f

prehnite

Ca2AIVIAlIVsi3010(OH)2

<1

spodumene
kyanite,All
AI2

LiAIS i206
AI2SiO5

2.95
10.04
3.70

0.94
0.27
0.89

15
5.0

[43,129]

6.53

0.59

7.5

[43,73]

9.37

0.38

13

[43,129]

8.93
15.6

0.46
0.08

4.0
12

[43,73]

AI3

AI4

sillimanite
andalusite,
All

AIVIAIIVsio5
AIVIAlVsio5

sapphirine
garnet
(s)
garnet
"YAG"(s)

(Mg3.6AIVI4.4)(AIIV
4.4Si.6)020
Gd3A12VIA13IVo12
Y3AI2VIA13IVo12

grossular
almandine

Ca3AI2Si3012
(Fe,Mg)3AI2Si3012

pyrope
f

Mg3AI2Si30!2

<0.1 0
0.63 0
3.61
1.51

2.5

[100]

4.5

[66,139]
[43]

[43,73]

[23,43]

8c

[19]

0.8

[43,79,129]

[43]

[43]

[43]

2.4c

[82,101]

317

318

NMR

OF SILICATES

AND

OXIDES

TABLE 7 (continued)
Mineral

nominal
formula

QCC,

(s)=synelic
zoisite,AI 1,2

Ca2AI3Si3012OH

8.05

AI3

epidote,All

MHz

Ca2AI2(Fe,AI)Si3012OH

AI2

8isoa,b

ref.

ppm
0.46

[43]

18.5

0.16

[43]

9.8

0.2

[43]

4.6

0.34

[43]

0.38

[43]

topaz

AI2SiO4F2 (AIO4F2 site)

1.67

margarite

6.3

11

[73]

2.2

[73]

5.9

[54,60]

penninite
xanthophyllite

CaAl
VI2(AIIV2s
i2010)
(OH)2
KAIVI2s
iAlIV3010(OH)2
KAI2$iA13010(OH)2
f
(Mg,AI
VI)6(Si,AlIV)4010(OH)8
f
Ca2(Mg,AIVI)6
(Si,AIIV)4010(OH)4
f

1.4

10

[73]

2.0

11

[73]

kaolinite

AI4Si4010(OH)8

4c

[60]

pyrophyllite

AI2Si4010(OH)2

4c

[60]

smectite

(Ca,Na)(AI,Mg)4(S
i,AI)8020(OH)4
f

4c

[60]

muscovite

illite e

gibbsite(s)

AI(OH)3, AI(1)
"

augelite
senegalite

, A(2)

AIVIAIV(OH)3PO4
AIVIAIV(OH)3PO4-H20

1.97

0.73

10.4

[123]

4.45

0.44

11.5

[123]

4.5

1.0

0.3

[7]

=3.8

1.7

[7]

10.2

Ca-aluminates:

(s)

CaAI204' 10H20

2.4

(s)
(s)

Ca3AI206-6H2
Ca4AI207'l 3H20

0.71

(s)

CaAIVI9AIVAIIV2019

1.5

<1

ettringite(s)
(s)

Ca6AI209'3S03-32H20
Ca4AI207'SO3' 12H20

AIO5 groups in a few knownstructureshave/5valuesof

about35 to 40 ppm. The more subtleeffectsof bondanle and secondneighboridentityare similarto thosefor

9Si [2,66,88].

ManyMASNMRstudies
of 27A1of solids
havereportedonly peakpositions,whichare generallyshiftedto

frequencies
lowerthanSiso
by thesecond
orderquadrupolar interaction.Quadrupolar
shiftscanbe aslargeas20 or
more ppm for data collectedat relativelylow magnetic
fieldsand/orfor siteswith largefield gradients,
butcanbe

0.09

1.8

0.36
1.7

[123]

12.36

[123]

10.20

[123]

=0

[91]

16

[91]

13.10

[123]

11.80

[123]

0.19

almost negligible in many mineralsat high magnetic

fields.Determinationof Siso
from MAS spectracanbe
donein somecasesby detailedanalysisof spinningsidebandsfor the satellitetransitions[55,79], by collectionof
spectraat more thanone magneticfield [73,103],and,for
sites with relatively large QCC (quadrupolarcoupling
constant)values,by fitting of quadrupolarline shapes
[34]. Quadrupolareffectscan broadenpeaksto the extent
of beinginadequatelynarrowedby MAS, or evenlostentirely becauseof instrumentaldead time. MAS studiesat

STEBBINS

319

AivI

very high magneticfields (e.g.14.1 Tesla) can be very

helpful.The new techniques
of "dynamic
anglespinning"
(DAS) and "doublerotation"(DOR) NMR may proveto
be very usefulin improvingresolution[90,164].
The distinctionsamong octahedraland tetrahedralAI
havein somecasesallowedquantificationof disorderand
AI site occupancyin silicatesand oxides.In a numberof

sheet
silicates,
forexample,
27A1MASNMRdatahave
beenshownto agreewell with siteassignments
basedon
stoichiometry [5,20,52,60,162]. In MgAI204 spinel

A!TM

[45,86,163], MAS NMR has also been used to estimate

?oooc

theeffectof temperature
on disorder(Figure3).

2.3. 170

Although
170 canbeobserved
atnatural
abundance
in
liquidsand in highly symmetricalsitesin crystallineoxides[6], applicationsto silicateshavegenerallybeenlimited by the necessityof workingon isotopically
enriched
samples.The data assembledin Table 8 havebeen obtained at high magnetic fields by the fitting of MAS,
DAS spectra,or static spectra.For somematerials,the
latter can be quite informative,but neglectof chemical
shiftanisotropycanleadto discrepancies
[131].

Themostobvious
effecton 170 spectra
of silicates
with tetrahedralSi is the distinctionbetweenbridgingand
non-bridgingoxygens.Theformer generallyhave much

largerQCC values.Indeed,QCC is well correlatedwith

theelectronegativity
of the neighborcationsandthuswith
the

covalent

character

of

the

M-O

bonds

[115,152,153,154]. Isotropic chemical shifts for nonbridgingoxygensvarywidely(over1000ppm)depending

on the natureand numberof the coordinating
cations.For
groupII oxidesandbothbridgingandnon-bridging
oxygensin silicates,thereare goodcorrelations
betweenincreasingcationsize and decreasedshielding(higherfrequenciesor largerchemicalshifts)[153,154]. CP MAS
NMR hasbeenshownto work well for enhancingsignals
from oxygensnearto protons[ 157].
DAS andDOR spectrahaverecentlybeenshownto be

lZ,O0OC

250

-15o

Fig.3. 27A1
MASspectra
forMgAI204
spinel
quenched
from the two temperatures
shown.Featuresotherthanthe
two labeledpeaksarespinningsidebands.The increase
in

theintensity
oftheAITMpeakindicates
anincrease
indisorderwith temperature
[86].

made to borate and borosilicate glasses[11,155,170].

Recently,similareffectson isohavebeen detectedfor

23Nain silicates[53,103] aswell asaluminofluoride

minerals [24]. Studies of other nuclides in silicates and
oxides are too numerous to mention in detail, but have re-

centlyincluded
9Be,13C,19F,25Mg,31p,35C1
' 39K,
45Sc
' 47Ti' 51V,89y, 93Nb' 119Sn
' 129Xe
' and207pb.

remarkably
effectiveforresolving
170NMRpeaks
for
structurallysimilar but crystallographically
distinctsites
in silicates [89].

2.5. Dynamics in Crystalline Phases

In oxidesand silcates,dynamicalstudieshaveconcentrated on the mechanisms and rates of diffusion of both

2.4.

Other

Nuclides

NMR studiesof a variety of othernucleiin solid geo-

logicalmaterialshaveprovidedimportantstructuralinformation[61]. The largedifferences

betweenelecc field
gradients
for three-andfour-coordinated
boron,for exam-

ple,allowthese
sites
tobeeasily
distinguished
by 1lB
NMR. Many applicationsof this relationship,
as well as
the effect of coordinationnumberon iso,have been

cations
(especially
7Li+and23Na+)
andanions
(especially
19F-),andonphase
transitions
inmaterials
withabundant
nuclides
of highLarmor
frequency
(e.g.7Li,19F,23Na,
27A1,
93Nb)[8,109,136,138].
Thefirstof these
reports
extensivework on perovskite-structured
oxides.Most of
thesestudieshave been done at relatively low magnetic
fields and consistprimarily of relaxationtime measurements.As such,quantificationof resultsoften requires

320

NMR

OF SILICATES

AND OXIDES

TABLE
8.170 NMRdata
forcrystalline
oxides
and
silicates.
Some
data
forsynthetic
zeolites,
aswellasoxysalts
andoxide
superconductors
areexcluded
forbrevity.
Insilicates,
"BO"signifies
bridging
oxygen,
"NBO"
non-bridging
oxygen.

Mineral

nominal
formula

{s)=synthefic
miscellaneous

MHz

Siso
a,

tel

ppm

oxides:

(S)
periclase(s)
(s)
(s)
(s)
ruffle(s)
anatase(s)
(s)
baddeleyite
(s)
(s)
(s)
(s)

(s)
(s)
zincite(s)
(s)
(s)
(s)
litharge(s)
cuprite(s)
(s)
(s)

(s)

BeO
MgO
CaO
SrO
BaO
TiO2
TiO2
Ti203
ZrO2
ZrO2(tetmgonal)
87ZRO2-13MgO
(cubic)
HfO2
La203(octahedral
site)
" (tetrahedral
site)
CeO2
VO2
ZnO
CdO
HgO(yellow)
SnO
PbO
Cu20
Ag20
KMnO4

=0.02
=0.014
<.005
<.005
<.005
<1.5
< 1.1
<2.6
<0.9,1.0
< 1.4
<1.1,0.9
<1.4
<2.2
M)

--0.13
7.1
2.3
0.9
=0
=0
<0.4

K2WO4,
site1f
"
"

aluminum

QCC,

, site2
, site3

26b
47b
294b
390b
629b
590c
558c
503c
325,402
c
383c
=355
d
267,335
c
469c
590c
878c
--755,815
d
- 18b
=60
121e
251
294
-193
-277
1197

[154]
[154]
[154]
[154]
[154]
[6]
[6]
[6]
[6]
[6]
[6]
[6]
[6]
[6]
[6]
[6]
[6,154]
[154]
[154]
[6]
[6]
[6]
[6]
[115]

437

[115]

429
422

[115]
[115]

oxides:

corundum(s)
(s)
(s)
(s)
(s)

It-alumina(s)

{z-A1203,
OALisite
'-A1203,
OA!4site
q-A1203,OAI4site
5-A1203,
OAI4site
0-A1203,
OAI4site
" , OAI3site

11A1203'Na20

2.17
1.8
1.6
1.6
1.2
4.0

<2.2

0.55

0.6

75c
73c
73c
72c
72c
79c

76c

[13,156]
[156]
[156]
[156]
[156]
[156]

[6]

STEBBINS

TABLE 8 (continued)
Mineral

nominal formula

(s)=synthetic

QCC,

iisoa,

MHz

ppm

ref.

hydroxides:
boehmite(s)

bayerite(s)
brucite

1.15

0.13

70.0 c

[125,156]

5.0

0.5

40 c

[156]

AI(OH)3, A12OHsite
Mg(OH)2

6.0

0.3

40 c

[156]

6.8

0.0

25g

[157]

Mg2SiO4, NBO

3.3h
2.8h
3 .Oh
2.9h
2.7h
2.5h
2.8h

72i
64i
49i
134i

[89]

AIO(OH), OAl4 site

"
, A12OH site

orthosilicates:

forsterite(s)

lamite(s)

"

, NBO

"

,NBO

Ca2SiO4, NBO
"

, NBO

"

, NBO

"

, NBO

[89]
[89]
[89]

128i
122i
122i

[89]

86i
64i
69i
57i
61i
59i
62i
70i
70i
115i
114i
107i
97i
103i
88i
75i
75i
67

[89]

[89]
[89]

chain silicates:

diopside(s)

clinoenstatite(s)

wollastonite(s)

ps-wollastonite

(s)

CaMgSi206, NBO

2.83

0.13

"

, NBO

2.74

0.00

"

, BO

4.39

0.36

Mg2Si206, NBO
"

, NBO

"

,NBO

"

,Nito

"

, BO

"

, BO

Ca3Si309, NBO
"

, NBO

"

, NBO

"

, NBO

"

, NBO

"

, NBO

"

, BO

"

, BO

"

, BO

-CaSiO3J,
NBO

2.9h
3.6h
3.6h
4.2h
5.1h
5.2h
2.3h
2.6h
2.2h
2.0h
2.9h
2.6h
4.8h
4.8h
4.7h

[89]
[89]
[891
[89]
[89]

[891
[89]

[89]
[89]
[89]
[891

[891
[89]
[891
[89]
[89]
[89]

2.1

0.1

94 c

[153]

"

, NBO

2.3

0.1

91 c

[153]

"

, BO

3.8

0.2

75 c

[1531

2.1

0.1

108 c

[153]

-SrSiO3J,NBO
"

, NBO

2.2

0.1

105 c

[153]

"

, BO

4.1

0.4

80 c

[153]

321

322

NMR

OF SILICATES

AND

OXIDES

TABLE 8 (continued)
Mineral

(s)=synthetic

(s)

nominal formula

. .

QCC,
MHz .

BaSiO3J,
NBO

8isoa'
ppm.....

ref.

2.1

0.1

169c

[153]

....

NBO

1.6

0.1

159c

[153]

....

BO

3.7

0.4

87c

[153]

3.2

40g

[157]

5.8

50g

[157]

7.3

0g

[157]

5.3

0.13

40k

[131]

3.2
3.1
4.6

0.2
0.2
0.1

32c
31 c
44 c

[152]
[152]
[ 152]

4.45

0.35

62.5

[165]

4.90

0.2

97.0

[165]

6.50

0.13

109.5

[165]

talc(s)

Mg3Si4010(OH)2,NBO

....

BO

, MgOH site

frameworksilicates:
Na-A zeolite(s)

SiO2
(seereference),Si-O-AI, BO

Na-Y zeolite(s)

(seereference),Si-O-AI, BO

cristobalite(s)

"

, Si-O-AI, BO

highpressuresilicates:
wadeitephase(s)
K2siVIsilV309,
silV-o-siTM

"
stishovite(s)

, silV-o-si vI

SiO2

Notesfor Table 8:
a) Relative to H20.

(b) From MAS data,little or no correctionfor QCC needed. (c) From simulationof MAS
data. (d) Uncorrectedfor QCC. (e) From MAS, correctedusingQCC from staticspectrum. (f) For site 1'
c11=564,c22=530,c33=217ppm; for site2: c11=567,c22=518,c33=202ppm; for site 3:c11=561c22=497,

c33=208
ppm. (g) Basedonstaticspectrum,
CSAnotincluded.(h) QCCgivenis actuallythe"quadrupolar
prod-

uct".PQ=QCCx(l+
12/3)1/2;
0.87<QCC<PQ
[89].(i)Derived
from
DASdata
at twomagnetic
fields.
(j)More
sitesarepresentthanareresolved
in MAS spectra.(k) Fit of staticspectrum
gives311=c22=60,
333=-10ppm.

complex models.In a few recent,highresolutionstudies

of silicates,the direct observationof exchangeamong
multiple sites in a crystal offers the possibilityof simpler, more direct interpretations.
Alkali cationdynamics

informationobtainableby diffractionmethods.Becauseof
the wide and continuousrangesof compositions
studied,
andthe frequentmodel-dependent
natureof thestructural

have been studied in a number of framework silicates,for

on glasseswith the stoichiometryof end-membercrystalline phases(Table 9). Other recentreviewsdo include

example [57,144], and can have an importantinfluence

evenin ortho-andchain-silicates
[38]. Structuralanddynamicalchangesoccurringduringdisplacivephasetransitionsin silica polymorphsand their aluminumphosphate
analogshavebeenexploredin somedetail [99,130,131].

conclusions,
I havetabulated
onlya few29SiMASdata
some tabulations [34], as well as extensive discussionof

silicate, oxide,

borate, and non-oxide glasses

[10,11,29,61,62,145].These contain information on stud-

iesof nuclides
notincluded
here,especially
l lB, 19F,
23Na,and31p.

3. APPLICATIONS
TO
AMORPHOUS
SOLIDS,

GLASSES,
AND MELTS

TechniquessuchasNMR becomeparticularlyimportant when the absenceof long-rangestructurelimits the

3.1. 29S i
Therelativelyclear relationships
betweenisoand Q
speciesin crystallinesilicateshasled to a numberof attemptsto quantifytheir abundancein glasses.Separate

STEBBINS

323

TABLE9.29SiNMRdataforglasses
ofsimple,
crystalline
stoichiometry.
Composition

-fiiso, ppm
.

SiO2

111.5

FWHM,
ppm
12

[44,98]

NaAISi308

98.7

16

[98]

NaAISi206
NaAISiO4
KAISi308
CaAI2Si208
CaA12SiO6

92.8

18

[94]

86.0

13

100.5

15

Mg3A12Si3012
Ca3AI2Si3012
Na2Si409
K2Si409

87.9

15

[94,98]

83.4

11

[94,981

82.3

17

[7O]

80.1

13

[70]

105.6,92.2
105.1,94.3

Li2S i205
Na2Si205
K2Si205

102.7*,91.0,81.1*
99.5' ,88.7,77.7'
103.3* ,90.8,79.5'

N a2SiO3

84.8* ,76.0,66.8*

MgSiO3
CaMgSi206
CaSiO3

[941

[94,98]

82.3
81.3
80.6

13,11

[77,166]

11,10

[77,166]

14',12,10'

[771

12',10,8'

[771

11',11,7'

[77]

10',7,5'

[77]

20
16
14

[7O]
[7O]

[7O]

Notesfor Table 9:
Uncertaintiesare generallyat least0.5 ppmin peakpositionsandwidths.
*Partiallyresolvedshoulder

peaksfor eachQ speciesare oftenpartiallyresolvedin

MAS spectrafor alkali silicateglasses(Figure4). Quantitative interpretationshave usuallydependedon assumptions of Gaussianline shapeand curvefitting, but interpretations have converged as data improves
[26,28,32,51,134,135].It is now clear that speciationis
moredisordered
thanrequiredby simplestoichiometry,
but
moreorderedthanpredictedby randommixingof bridging
and non-bridgingoxygens[94,135]. A numberof ther-

modynamicmixing modelsfor thesesystemshave been

based on NMR

data [9,77].

In a few favorable cases,

static spectracan permit quantificationof Q speciesin

glasseswith fewer curve fitting assumptionsthan for
MAS spectra,becauseof the contrastsin chemicalshift
anisotropy[9,32,134].
In binary silicate glassesof alkaline earths, and in
aluminosilicateglasses,peaks for Q speciesare usually
unresolvedin MAS spectrabecauseof greateroveralldis-

324

NMR

OF SILICATES

AND

OXIDES

Several NMR studieshave suggestedthat opal-CT,

which is characterized
by obviousx-ray diffractionpeaks
and which thereforecontainssubstantiallong-rangeorder,

is highlydisordered
withrespect
to localstructure[ 1,22].

Siv

SiTM

12 GPa

i bar

-gO

-10

-160

-200

Fig.4. 29Si MAS spectrafor Na2Si409glasses

quenchedfrom liquidsat 12 GPa andat I bar pressures.
Signalsfrom Si with differentcoordination
numbers,and
from differenttetrahedralspecies,are labeled[ 166]. Black
dotsmark spinningsidebands.

The latterstudyusedthe CP MAS technique

to studythe
distributionof silanol groups(Si-OH), which were detectablein most of the samplesstudied.
3.2. 27Ai
As in crystallinematerials,interpretationof NMR
spectraof quadrupolar
nuclidesin glasses
is complicated
by second-order
quadrupolar
broadening
(possibly
leading
to signallossfrom highlydistortedsites).It maybe impossibleto distinguish
theseeffectsfromthosecaused
by
disordereddistributionof sites,althoughagain,studiesat
varyingmagneticfieldscanbe useful.Fittingof spinning
sidebands,whentheseare observable,canagainbe useful
in determiningisotropicchemicalshifts[79,129].Careful
quantificationof intensitiesis essentialin determining
whether all AI has been detected [65].

Themostdramatic
findings
from27A1
MASNMRin
glasses
hasbeenthecleardetection
of five andsixcoordinatedA1 in a varietyof compositions,
includingthosein
the SIO2-A1203 binary [105,110,113] and in some

order and variety of first neighborcationarrangements,

makingquantitative
derivationof speciation
highlymodel-

dependent.Studieshaveincludedextensive
workon alkali
and alkaline earth aluminosilicates [35,65,98] and Ca,

Mg silicates[70,94]. The narrowingof NMR peaksas

AI/Si is increasedto 1 suggeststhat someSi-AI ordering
occurs,probablybecauseof at leastpartial "aluminum
avoidance"[94]. For pureSiO2 glass,bondangledistributions have been derived using empiricalcorrelationsbetween{5andbondangles [44,94,98].
One approachto determiningthe effectof temperature
on liquid structureis to quenchliquidsat varyingratesto
produceglasseswith different"fictive"or glasstransition

temperatures
(Tg).Thisapproach
hasbeenusedto show
thatQ speciesdistributions,as well as overalldisorderin
bondangles,do indeedbecomemorerandomwith increasing T [9,135].
Studiesof alkali silicateglasses
quenchedfrom liquids
at pressures
to 12 GPa haveshownthepresence
of six coordinatedSi (Figure4), and for the firsttimedemonstrated
the existence of five coordinated Si [147,166,167]. The
latter

has now also been detected

phosphorus-rich
glasses
[27]and boroaluminates
[15,97].
In the CaO - A1203 - SiO2 ternary, non-tetrahedral
AI is
abundantonly in compositions
closeto the SIO2-A1203
join [ 114].In carefullyquantifiedstudies
of glasscompo-

sitions
withM+120/AI203or M+20/AI203< 1.0,it
hasbeenshownthat high coordinatedAI is undetectable
andthuscomprises
lessthana few percentof thetotalAI
[65,98]. However,high-coordinate
A1 hasbeendetectedin

onlyslightlyperaluminous
glasses
nearto theMgAI204SiO2 join [83].

3.3. 170
As in crystals,the primarydistinctionamongO sites
detectedby NMR of glassesis thatbetweenbridgingand
non-bridgingoxygens(Figure5). Staticspectracansometimes be more informative than MAS data. Systematic
compositional
effectson thechemicalshiftsfor NBO sites
have been noted [61], as have pressureeffectson O site
distribution[ 165]. Very recently,it hasbeendemonstrated

that170DASNMRcanaccurately
quantify
bondangles
andoxygen sitedistributions
[36].

at low abundance

(<0.1%) in glassesformed at 1 bar pressure[137]. High

coordinate Si has not been observedin NaAISi308 or
SiO2 glassesquenchedfrom liquidsat high P [ 150,166].
Six-coordinated
Si hasalsobeenreportedin alkali silicate
glassescontaininglargeamountsof P205 [25,27].

3.4.

Water

in

Glass

Bothstatic
"wideline"
andhighspeed
1HMASstudies
have detectedand quantified OH- and molecularH20

[30,68].
2HNMRhasdistinguished
among
water
species
in glasses,as well, and hasprovidedsomedynamicalin-

STEBBINS

formation
[31].In hydrous
NaAISi308
glass,
23Na,27A1,
and29SiMASandCPMASspectra
wereinterpreted
as
indicatingthatOH is boundsoleyto Na with thepossibility of protonatedbridging oxygens [67,69], whereasin
hydrousbinaryalkali silicateglasses[85,139]andin $iO2

[37], 29Si NMR hasclearlyshown

thepresence
of
$iOH groups.
1lB, 170,23Na
' 27A1,and29SiNMR
have been used in several studies of the interaction of sili-

cate glasseswith waterat ambientto hydrothermal

conditionsat a rangeof pH's [16,139,168,169].

325

3.5. Silicate and A!uminate Liquids

In ionic andpartiallyionicliquidssuchas silicates(at
leastat high silicacontents),flow requiresthebreakingof
the strongestbonds in the system(Si-O). As a result, at
high temperatures where viscosities are low, silicate
speciesare short lived, with all cations and artionsexchangingrapidlyamongavailablesites.Undertheseconditions, therefore,in situ, high temperatureNMR reveals

onlysingle170,23Na
' 27A1,
and29Sipeaks,
forwhich
orientationaleffectsthat lead to broadeningin a solid,includingchemicalshift anisotropyand quadrupolarcouplings, are fully averaged[38,81,121,142,149,151].The
averagepeak positioncan still give structuralinformation
however,sinceit is a quantitativeweightedmeanoverall
speciespresent.This approachhas shown,for example,
that when aluminum oxides, aluminates, and fluorides
melt, the mean AI coordinationnumberdecreases[40,81].

943 'C

A multi-nuclearhigh T NMR studyof alkali aluminosilicateliquidshasdetectedsystematictemperature

effectson
averagedchemicalshiftsthatcanbe interpreted
in termsof
structuralchanges[142]. Studieshave now been madeto

temperatures
greater
than21000
C,andhaveincluded
systematicwork on the effectsof compositionon the structure and dynamics in the CaO-AI203-SiO2 system
[21,84].
741 'C

69O 'C

639 C

85 'C

At lower temperatures,
incompleteexchangeandaveragingoccurs,and, in favorablecases,NMR line shapes
canbe analyzedto measuretheratesof exchange.The rate
of exchangeof Si amongvariousanionicspecies,andthat
of O betweenbridgingand non-bridgingsites,are fundamentallytied to diffusionand viscousflow. In K2Si409
liquid, for example(Figure 5), simulationsof high tem-

perature
170and29Silineshapes
gives
results
thatcan
be usedto accuratelypredictthe viscosity,assuminga
simpleEyring model for flow [38,145]. 2-D exchange
NMR spectroscopy
just above the glasstransitionalso
suggests
that exchangeamongQ speciesis of key importancein flow even in the very high viscosityrange[39].
A series of relaxation time measurements has shown that

25 'C

.... I'"'1'""1

4OO

.... I""l""i'r"i

Si dynamicsare greatly affectedby the transitionfrom

glassto liquid, and that the interactionof alkali cation
with the network can also be detected [38,75,76].

.... i .... ! .... I""i

40O

Acknowledgements.
I wouldlike to thankmy numerous
colleagueswho sentreprintsandpreprintsandallowedme to

Fig.5. Hightemperature
170spectra
forK2Si409liquid. "bo" and "nbo"showcontributions
from bridging
and non-bridgingoxygens[145]. Note collapseto single,
narrowline causedby exchangeof species.

include resultsprior to publication,

especially
H.J. Jakobsen, B. Phillips, J. Skibsted,and X. Xue. I thankthe editor,

T. Ahrens,andan anonymous
reviewer,andacknowledge
the
support of the National Science Foundation, grant
#EAR9204458.

326

NMR

OF SILICATES

AND

OXIDES

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MOssbauerSpectroscopyof Minerals

Catherine

1.

McCammon

INTRODUCTION

positions
andthehyperfineparameters
aregivenin Table
2. Suggested
referencesfor furtherinformationare listedin

Since the discoveryof the M0ssbauereffect in 1958,

numerous applicationsin a wide variety of scientific

Table 3.

disciplineshavebeendescribed.Of the morethan30,000

paperspublishedas of 1993, at least2000 containresults
of studieson minerals(as estimatedfrom dataprovidedby
the M0ssbauerEffect Data Center, USA). This chapter
providesa referenceto M0ssbauerdata for 108 minerals

3.

containing
57Feand18 containing
9Sn, accompanied
by

relativeto theabsorber,
shiftingtheenergyspectrum
due
to the Dopplereffect.Spectraare commonlyplottedas
percenttransmission
versussourcevelocity (energy).
Selected references to important experimental

A transmissionMOssbauerspectrometeris very
simple,and typically consistsof a y-ray source,the
absorber(sample)and a detector.The sourceis moved

referencematerialon M0ssbauerspectroscopy.
2.

EXPERIMENT

THEORY

considerations
are given in Table 4, while Table 5 lists

The M0ssbauereffect is the recoillessabsorptionand

emissionof y-raysby specific nuclei in a solid [81, 82],
and provides a means of studying e local atomic

somecommon
applications
of M0ssbauer
spectroscopy
to
mineralstudies.This chapteronly includesreferences
to
transmission
studies;howeverthe techniquecanalsobe
performedin a scatteringgeometryto studysurface
properties(e.g., [ 105, 121, 127]).

enviroment around the nuclei.

The interactions

between the nucleus and the atomic

electronsdependstronglyon the electronic,chemicaland

magneticstateof the atom.Informationfrom thesehyperfine interactionsis providedby the hyperfineparameters,
which can be determinedexperimentallyfrom the line
positionsin a M0ssbauerspectrum(Figure 1). A typical
experimentalspectrumis illustratedin Figure 2. Table 1
describes the hyperfine parameters as well as other
observables. Formulae relating the M0ssbauer line

Mineral Physicsand Crysta!!ography

A Handbook of PhysicalConstants
Reference

Shelf 2

Copyfight1995 by the AmericanGeophysicalUnion.

MINERAL

DATA

Over 100 different M0ssbauer transitions have been

observed,
althoughunfavourable
nuclearproperties
limit
thenumberof commonly
usednuclei.57Feis by far the
mostpopularisotope,followedby 9Sn. Both the 14.4
keV transitionin S7Feand the 23.88 keV transitionin

gSn involvea spinchangeof 3/2-->/2, andtherefore

havesimilarhyperfine
properties.
S7FeM0ssbauer
dataof
selected
mineralsarelistedin Tables6 through10,while
Sn data are listedin Table 11. The data were chosen
fromtheliteratureasbeingtypicalfor eachmineral;howeversincehyperfine
parameters
oftendepend
onchemical
composition,
particlesize,thermalhistoryanddegreeof
crystallinity,
thedatashouldbeconsidered
representative

C. McCammon, BaycrischcsGcoinst., Posffach 10 12 51,

D-8580 Bayreuth, Germany

AGU

4.

332

MCAMMON

(3)

(2)

(1)

(4)

excited
state

ground
state

Ire nucleus

Isomershift

Quadrupole
splitling

Magnetic
splilling
I

Eo

Fig. 1. Illustration
of hyperfine
interactions
for57Fenuclei,showing
thenuclear
energyleveldiagram
for
(1) a bare nucleus,(2) electricmonopoleinteraction(isomershift), (3) electricquadrupoleinteraction
(quadrupole
splitting),and(4) magnetic
dipoleinteraction
(hyperfinemagnetic
splitting).Eachinteraction
is
shownindividually,accompaniedby the resultingM0ssbauerspectrum.
I

1.00

0.98

0.96

0.94

0.92
-4.0

-2.0

0.0

2.0

4.0

Velocity (mm/s)
Fig. 2. M0ssbauerspectrum
of orthopyroxene
with composition
Fe0.sMg0.2SiO3
showingtwo quadrupole
doublets,
onecorresponding
to Fe2+in theM 1 site(45%of totalarea)andonecorresponding
to Fe+ in the
M2 site (55% of total area).

334

M)SSBAUER SPECTROSCOPY

only. For more complete information on specific

minerals, one should consult resources such as the

Minerals Handbook published by the Massbauer Effect

Data Center (see Table 3). Minerals are listed by name

except when part of a larger structure group, e.g.

Fe3AleSi30e is listed under garnet, not almandine.

Chemicalcompositions
are given exactlyas reportedby
the authors(even if the resulting compositionsare not
electrostatically
neutral).Data for differingcompositions
are providedfor the major mineralgroupsto illustratethe

dependence
of hyperfineparameters
on composition.
The
relative areas of subspectracan be used as a rough
approximationto relative abundance,e.g. [97], but note
thatsiteproportionsoftenvary betweendifferentsamples
of the samemineral.For example,the amountof Fe+
may depend strongly on foe conditions, and the
distribution

of

iron

cations

between

different

crystallographic sites may be a function of thermal

history.Most spectrawerefittedto Lorentzianlineshapes;
the few exceptionsare notedin the tables.

TABLE 1. Descriptionof M0ssbauerparameters

maine

Unit

Isomershift (b')

Description

Energydifferencebetweensourceandabsorber
nucleiresultingfromeffects
including differencesin valence state, spin state and coordinationof
absorberatoms.Experimentallyone observesa singleline shiftedfrom a
referencezero pointby theisomershift plusthesecond-order
Dopplershift
(SOD), a smallthemudshiftdue to atomicvibrations.

Centre shift (CS)

mm s-1

The experimental
shiftof thecentmidof a M0ssbauer
trmn froma zero
referencepoint.The contribution
from the SOD is similarin moststandard
materials,so for purposes
of comparisonthe isomershift is often takento
be equalto thecentreshift.

Quadrupolesplitting

mm s-1

Splitting of the energylevels causedby interactionbetweenthe nuclear

quadropolarmomentandan electricfield gradientat the nucleus,anddependson the valenceand spin stateof the absorberatoms,as well as the
coordination and degree of distortion of the crystallographic site.

Experimentally
oneobserves
a doubletin S7Fe
and9Sn spectra
withcomponentsof equalintensityand linewidthin the idealrandomab,sorbercase.
The quadrupole splitting is given by the energy separationbetween
components.

Hyperfinemagneticfield

Tesla

(H)

Interactionof the dipolemomentof the nucleusand a hyperfinemagnetic

field causesa splittingof the nuclearenergylevels,resultingin six peaks

forS7Fespectra
in thesimplest
case.Foranidealrandom
absorber
withno
quadrupoleinteractionthe linewidthsof the peaksare equalwith intensity
ratio 3:2:1:1:2:3. The separationof peaks 1 and 6 is proportionalto the
magnitudeof the hyperfinemagneticfield.
Line width (F)

Relative area(/)

mm s-1

Full width at half maximumof the peak height.Peakscan be broadened

beyondthenaturalline widthby effectsdueto equipment(vibrational,geometrical, thermal, and electronicproblems), the source(self-absorption
resultingfrom decay),and the sample(thicknessbroadening,next-nearestneighboureffects,anddynamicprocesses
suchasrelaxation).

Relative proportionof subspectrumarea to the total area. Each site normally contributesa subspectrum
(e.g. a quadrupoledoublet)whoseareais
approximatelyrelatedto therelativeabundance
of thatparticularsitewithin
the absorber.

MCAMMON

335

TABLE2. Determination
of linepositions
for57Fe14.4keV transition
Hyperfineinteractions
present

Line positions

- eleclricmonopole

L =CS

-eleclric monopole+ quadrupole

L1= CS+ 1/2AF-12

L2= CS- 1/2112

- electric
monopole
+ magnetic
dipole(AE2= 0)
-electricmonopole
+ quadrupole
+ magnetic
dipole
(special
caseof axiallysymmetric
electricfield
gradient
andI/4g/HI >> IAEa21)

L = /2IINH
L2= l/2#NH
La= /2I H
Ln= /21 H
Ls= /21 H
L = /2/& H

/ gm= 0.11882mms4 T-
/ gat2= 0.067899mms4 T'
- electricmonopole+ quadrupole
+ magnetic
dipole
(general
case)

( 3 gan- gm) + CS + /2AEi2

( gan- gin) + CS - 2AEi2
( gaa- o1/2
) + CS -- 1/2
( gaa+gin) + CS -/2AEQ
( - gaa+ gin) + CS -1/2AEQ
( -3gaa+ gla ) + CS + 1/2

Requires calculation of the complete interaction

Hamiltonian(e.g. [71]). Thereare eightlinesinvolving
the followinghyperfineparameters:
isomershift(6),
hyperf'me
magnetic
field(H), quadrupole
splitting(AE2),
the polar (0) and azimuthal(q0)anglesrelating the
directionof H to the electricfield gradient(EFG), and
theasymmetry
parameter
of theEFG (r/).

TABLE 3. Suggested
refereaces
for Mtlssbauer
s[troscopy
Refexence

Type
Book

Bancroft,G.M. MOssbauerSpectroscopy.
An Introductionfor Inorganic Chemistsand Geochemists.McGraw Hi!l, New York, 1973.

Cranshaw,T.E., Dale, B.W., Longworth,G.O. andJohnson,C.E. MOssbauerSpectroscopy

and
its Applications,
CambridgeUniversityPress,Cambridge,1986.
Dickson,D.P. and Berry, F.J. (eds.) MOssbauerSpectroscopy,CambridgeUniversity Press,
Cambridge,1986.
Gibb,T.C. Principlesof MOssbauer
Spectroscopy,
ChapmanandHall, London,1977.
Gonser,U. (ed.) MOssbauerSpectroscopy,
Topicsin AppliedPhysics,Vol. 5, Springer-Verlag,
Berlin, 1975.

Greenw, N,N. andGibb, T.D. MOssbauer

Spectroscopy,
ChapmanandHall, London,1971.
Gttlich, P., Link, R. and Trautwein, A., MOssbauer Spectroscopyand Transition Metal
Chemistry,Springer-Verlag,Berlin, 1978.
Hawthorne,F.C. (ed.)Spectroscopic
Methodsin Mineralogyand Geology,Rev. Mineral. Vol. 18,
MineralogicalSocietyof America, 1988. See Chapteron MOssbauerSpectroscopy,
F.C.
Hawthorne,pp. 255-340.
Mitra, S. Applied MOssbauerSpectroscopy,Theory and Practice for Geochemistsand
Archeologists,
PergamonPress,Oxford, 1992.
Robinson,J.W. (ed.) Handbbokof Spectroscopy,
Vol. 3, CRC Press,Inc., Boca Raton, USA,
1981.SeeChapteron MOssbauer
Spectroscopy,
J.G. Stevens(ed.),pp. 403-528.

336

M(SSBAUER SPECTROSCOPY

TABLE 3. (continued)
Reference

Type
Journal

Analytical Chemistry(AmericanChemicalSociety,WashingtonDC) containsbiennialreviews

(startingin 1966)of M6ssbauerspectroscopy,
seefor exampleVol. 62, pp. 125R-139R, 1990.
HyperfineInteractions(J.C. Baltzer AG, Basel) publishesproceedingsfrom variousM6ssbauer
conferences,seefor exampleVol. 68-71, 1992.
M6ssbauerEffect Referenceand Data Journal(M6ssbauerEffect Data Center,Asheville,NC) conrainsreferences
andM6ssbauerdatafor nearlyall M6ssbauerpaperspublished.

Data Resource

Stevens,J.G., Pollack, H., Zhe, L., Stevens, V.E., White, R.M. and Gibson, J.L. (eds.) Mineral:

Data and Mineral: References,M6ssbauerHandbookSeries,M6ssbauerEffect Data_Center,

Universityof North Carolina,Asheville,North Carolina,USA, 1983.
MfssbauerMicro Databases(M6ssbauerEffect Data Center,Asheville,NC) covermanytopicsincludingMinerals.Databasesare set up to run on IBM-compatiblemicrocomputers
andcanbe
searchedusingvariousoptions.
M6ssbauerEffect Data Center M6ssbauerInformation System (maintainedby the M6ssbauer
Effect Data Center,Asheville,NC) containsextensivebibliographicand M6ssbauerdataentries
compiledfrom the M6ssbauerliterature. Searchesof the databaseare possible;contactthe
M6ssbauer Effect Data Center for details.

TABLE 5. Applicationsin mineralogy

TABLE 4. MethodologyReferences

Experimentalaspect

Reference

Absorber thickness

[74, 99]
[16, 28]
[18,50]
Absorberhomogeneity
Preferred orientation of absorber
[95, 96]
Saturation effects
[97, 99, 120]
Isomer shift reference scales
[6]
Goodness of fit criteria
[31, 37, 58, 103]
Conventionsfor reportingM6ssbauerdata [117]
Geometric effects

Application

Reference

Oxidation state,including
intervalence
chargetransfer
Site occupancies,

[10, 15, 20]

[14, 32, 97, 114]

includingFe3+/Fe
Site coordination

[15, 22]
[13,85]
[66, 108]
[23, 25]

Semi-quantitative
phaseanalysis
Phase transitions

Magneticstructure

TABLE 6. 57FeM6ssbauerdata for selectedsilicateminerals

Absorber

Amphibolestructure
Mgs.7Fe.3Si8022(OH)2

Fe6.2Mgo.
sSi8022(OH
h

RT

RT

AEa

mm s-

CS(Fe)

mm s-

Tesla

1.16(1)
1.13(1)
1.16(1)
1.07(1)

2.76(1)
1.81(1)
2.79(1)
1.55(1)

0.07
0.93
0.69

0.31

site

VlFe2+
XaFe2+
XaFe2+
VFe+

Ref

[107]
[53]

MCAMMON

TABLE 6. (continued)

CaXSisOz(OH)ff

AFQ

1.27(1)
1.30(1)
1.27(1)
1.14(1)
1.12(1)
0.40(1)

3.17(1)
2.39(1)
1.86(1)
2.87(1)
2.36(1)
0.44()

RT

0.34(1)

1.76(1)

RT

1.20(1)
0.41(1)

2.44(1)
0.86(1)

0.40

1.14(3)
1.16(3)
0.23(5)

2.67(5)
2.38(5)
0.70(3)

0.70

1.15(1)
0.29(1)

2.41(1)
0.98(1)

0.98

1.22(1)
1.21(1)

2.31(1)
1.60(1)

0.94

0.36(1)
0.30(2)
1.08(1)
1.20(4)
0.35(1)

2.06(1)
1.54(3)
1.67(1)
1.90(8)
1.94(1)

0.92

0.31(5)

3.51(1)
3.46(1)
0.24(1)
3.56(1)
0.33(1)
0.55(1)
3.49(1)
0.58(1)
3.60(1)
1.39(1)
0.48(5)

1.11(1)
0.33(1)

1.73(1)
1.20(1)

1.03(2)
1.06(2)
0.48(2)

2.48(2)
2.01(2)
1.32(2)

77 K

X=Mg4.7Feo.3

Nal.sCao.
lXSisO22(OI-I)2
X=Fen.oMgo.3

CS(Fe)
mms '1

Absorber

RT

0.59
0.31
0.10

0.36
0.19

0.45

site

Ref

VXFe2+
VXFe2+
XaFe2+
XaFe2+
VFe2+
VIFe-

[113]

[4O]

Andalusite

(Alo.96Feo.
oaMno.
ol)2SiO5

[1]

Babingtonite

Ca2Fel.7Mno.aSi5014(OH)

0.60

VIFe2+
XaFe3+

[21]

rife2+
XaFe2+
Fe3+

[33]

rife2+
VIFe+

[57]

VIFe2+
channel Fe2+

[47]

VlFe3*
XaFe3*
XaFe2+
Fe 2+
XaFe3*

[36]

VllIFe2+
VmFe2+
XaFe3*
VmFe2+
XaFe3*
XaFe3+
VmFe2+
XaFe3+
VmFe2+
XaFe2*
Fe3+

[89]
[131]

VFe2+
Fe3+

[109]

WFe2*
VmFe2+
VmFe3+

[73]

Chlorite

XSiz9AIz4(OI-I)7.901
o

RT

X=Mg2.2Fe2.3Mno.
1

0.21
0.09

Chloritoid

Fe1.7Mgo.aA14Si20]o(OHh

RT

0.02

Clay minerals
Cordierite

A13Mg.9Feo.2A1SisO
Epidotestructure
Ca2XSi302(OH)
X=A12.2Feo.s

YAI.7Fe.2Si30
2(OH)
Y=Cal.2Ceo.sLao.2

RT

RT

RT

0.06

0.08

0.58
0.09
0.33

[36]

Garnet structure

FeaA12Si3012

RT

1.29(1)

Fe2+3Fe3+2Si3012

RT

1.31( 1)

quenched
from9.7 GPa,1100C
Mg2Cao.sFeo.sXSi3012
RT
X=All.sCro.5
Ca3FeaSi30
i2
RT

0.36(1)
1.28(1)
0.36(1)
0.41(1)

Ca2.sFeo.7A1].3Si3012 R'I;

1.26(1)
0.39(1)

Mgo.9Feo.
lSiO3
quenched
from 18GPa,1800C

RT

1.26(1)
1.11(1)

0.54
0.46
0.84

0.16
0.17
0.83
0.80
0.10
0.10

p]

p]
[7]

[92]

Grandidierite

Mgo.9Feo.1A13BSiO9

RT

0.94

0.06

llvaite

CaFe3Si208(OH)
a

RT

0.27
0.35
0.38

338 MSSBAUER SPECTROSCOPY

TABLE 6. (continued)
Absorber

CS(F)

AE{2

mm s-1

site

Ref

Tesla

Kyanite

(Alo.sFeo.
o2)SiO
Micagroupb
Ko.9NaoaXAISi30
o(OH
X=Al.7Feo.2Mgo.

KXAIo.sSi3Olo(OH)2
X=Mgz6Feo.6
KXAISi30o(OH)2

RT

0.38(2)

0.99(2)

RT

1.21(1)
1.14(1)
0.36(1)
1.12(1)
0.19(1)
1.02(1)
1.06(1)
0.31(1)
1.o6()
0.28(1)

2.99(1)
2.12(1)
0.86(1)
2.63(1)
0.56(1)
2.52(1)
2.08(1)
o.8o(1)
2.34(1)
0.66(1)

0.89(2)
0.95(2)
0.84(2)
0.19(4)
0.94(2)
0.99(2)
0.23(4)
1.13(1)
0.39(1)

1.91(2)
2.39(2)
1.33(2)
1.23(4)
1.98(2)
2.36(2)
0.70(4)
2.75(2)
0.91(2)

RT

0.46(1)

0.68(1)

RT

1.20(1)
1.14(1)

2.35(1)
1.86(1)

0.32

1.12(1)
0.44(5)

1.58(1)
0.98(5)

0.08

0.36(1)
0.43(4)
0.14(4)

0.18(1)
1.22(8)
0.59(8)

0.08

1.18(1)
1.13(1)
1.30(1)
1.26(2)
1.29(1)
1.28(1)
1.19(1)
0.42(1)
0.14(1)
0.39(1)

2.49(1)
1.91(1)

0.46

RT
RT

X=Mg.6Fe.2Mno.Tio.
1
CaXAIz7sil.201o(OH)2
X=Mg2.3Alo.7Feo.

RT

Olivine

Fe2SiO4
CaFeSOn

Mgo.s3Feo.7SiO4

Fe2+o.Fe3+SiO4

310 K
400 K

310 K

290 K

Orthoclase

KAlo.95Feo.
osSi3Os
Osumilite

XMgl.nFeo.9A14.4
sil 0.3030
X=Ko.9NaoA
Perovda'te structure

Mgo.95Feo.
osSiO3

RT

quenchedfrom 25 GPa, 1650C

Pyrophyllite

Fe,2Mgoa
Alo.1SiOlo(OH)
2
Pyroxenestructure
FeSiO3

RT

RT

77 K

Mgo.ssFeo.
lsSiO3c

77 K

CaFei206
CaMgo.9Feo.2Sil.906

RT

NaFei206

RT

RT

3.13(1)
2.00(1)
3.06(1)
2.16(1)
2.22(1)
1.07(1)
1.62(1)
0.30(1)

[94]
0.08

[41]

0.05
0.87

0.38

[39]

0.62

0.59

[76]

0.33
0.08

0.30

[671

0.70
0.48
0.52
0.70
0.30
0.51
0.41

0.08
0.41
0.59

0.68

0.92

0.85

0.07

0.54

rife2+
rife2+
VIFe2+
VFe3*
VFe2+
rife2+
VFea*
VIFe2+
VFe3*

[lll]

VFea*

[19]

VIFe2+
channel Fee+

[46]

XXIFe2+
Fe a*

[80]

VFea*
VFea*
VFea*

[26]

[lll]

[111]

[68]

[38]

0.50
0.50
0.20

[12]

0.80

0.50

[38]
[54]

0.50

[10]

McCAMMON

339

TABLE 6. (continued)
Absorber

CaFeAISiO6

Serpentine
(M..Ol)35i205(O4
antigorite
(Mgo.Feo.oOaSi:Os(OHh
chrysotile

(Mgo.13Feo.
g7)3Si205(OI-I)4

CS(Fe)

mm S'1

Tesla

site

Ref

RT

0.22(1)
0.35(1)

1.58(2)
0.99(2)

0.11
0.87f

IVFe3+
VIFe3+

[3]

RT

1.12(1)
0.36(4)
1.14(1)
0.38(3)
0.27(4)
1.15(2)
1.16(1)
0.36(4)

2.70(1)
0.70(5)
2.74(2)
1.08(1)
0.30(3)
2.79(1)
2.21(2)
0.70(5)

0.68
0.32
0.39
0.29
0.32
0.30
0.52
0.18

VFe2+
VFe3+
VFe2+
VFe3*
xaFe3*
rife2+
VFe2+
XaFe3+

[102]

RT

0.38(2)
0.16(50)

1.11(3)
0.5(10)

0.79
0.21

VIFe3*
IVFe3+

[101]

RT

0.37(1)
0.37(1)
0.24()
0.35(1)
0.37(1)
1.13(1)

0.23(1)
0.65(1)
0.54(1)
0.81(1)
1.35(1)
2.65(1)

0.65
0.35
0.09
0.55
0.30
0.06

XaFe3+
XaFe3+
IVFe3*
XaFe3+
VIFe3+
XaFee+

[11o]

1.09(1)
0.18(5)
1.05(1)
0.27(5)

2.62(1)
0.37(5)
2.78(1)

0.93
0.07
0.94

VFe2+
Fe3'
VFe2+

[92]

RT

0.96(1)
0.98(1)
0.92(1)
0.60(1)

2.50(1)
2.13(1)
1.17(1)
0.83(1)

RT

1.15(1)

2.63(1)

RT

0.21(1)
0.35(1)
0.48()

RT

1.06(1)
1.09(3)
0.27(5)

RT

RT

[102]

[102]

Sillimanite

(do.J%.o2hSiOs
Smectite minerals

Cao.2XSi3.6.401
o(OH)2
X=Fel.9Mgo.1

Cao.2XSi3.sAlo.3Ol
o(OH)2

RT

X=Fel.nMgl.2

Spinelstructure
y-Fe2SiO4

RT

quenchedfrom 8 GPa,1000C

y-Mgo.ssFeo.
5SiO4

RT

quenchedfrom 18 GPa,1700C

0.06

[110]

[92]

Fe 3*

Staurolite

XA19Si402o(On)2
X=Fel.1Mgo.sZno.3Tioa

0.23
0.40
0.31
0.06

rVFe2+
rVFe2+
lVFe2+
VIFe3*

[5]

1.25(1)
0.96(1)
0.81(1)

0.14
0.55
0.31

rVFe3+
XaFe3*
VIFe3*

[61]

2.76(1)
2.29(3)
0.37(5)

0.19
0.77
0.04

VFe2+
XaFee+
Fe3*

[92]

Talc

(Mgo.9Feo.)3Si40
o(OHh
Titanite

CaTio.9Feoa
SiO5

Wadsleyite

-(]V[..16)2SiO4
quenchedfrom 15.5 GPa,1800C

Yoderite(Mg2AI3.6Feo.3Mno.1)6A12S
i4015(OH)
2
RT

0.36(1)

1.00(1)

VFe'/VIFe'

a see [45] for a detaileddiscussionof calcic amphiboledata

spectral
datawerefittedusinga relaxation
model

b spectra
aremorerealistically
described
withhyperfine

site distributiondependsstronglyon thermalhistory,

see e.g. [ 112]

parameterdistributions,see [98]
c see[59] for a compilationof data

smallamountof additionalcomponent
present

340

MSSBAUER SPECTROSCOPY

TABLE7.57Fe
M6ssbauer
dataforselected
oxide
andhydroxide
minerals
Absorber

AE

mm s-

CS(Fe)

mm s-

Tesla

0.39(1)
0.38(1)

0.95(1)
0.55(1)

site

Ref

Akagandite

l-FeOOH

RT

0.39

VFe3+

0.61

rife3+

[84]

Feroxyhite
8'-FeOOH

Fem'hydrite
FesHO84H20

RT

0.4(1)
0.4(1)

- 0.1(1)
+1.1(1)

44.8(5)
39.3(5)

0.60

VFe3*

0.40

VFe3+

[35]

RT

0.35(1)

0.62(1)

RT

0.35(1)

-0.3(1)

38.4(5)

RT

0.38(5)

- 0.21(5)

52.1(5)

RT

1.07(1)

0.70(1)

VlFe2*

[44]

RT
RT

0.30(1)
1.06(1)

0.55(1)
0.53(1)

rife3+
XqFe2+

[65]
[72]

RT

0.22(5)
0.37(5)

+0.08(5)
+0.02(4)

0.33

VFe3+

[11]

0.67

rife3+

RT

0.35(5)

0.34(5)

RT

0.37(1)
0.37(1)

0.52(1)
0.90(1)

Goethite

ct-FeOOH b
Haematite

ct-Fe203c

[122]

llmenite

FeTiO3
Lepidochrocite
y-FeOOH
Magnesiowt2stite
Mgo.sFeo.20
Maghemite
y-Fe203
Perovskite

Ca.Tio.8FeoaO3

50.2(1)
50.5(1)

VFe3+

[83]

0.54

VFe3+

[29]

0.46

rife3+

Pseudobrookite

FeaTiO5
Spinelstructure
Fe3On

FeCr204
FeA12On
ZnFe2On
MgFe2On

310K

0.63(1)

0.05(10)
0.05(10)

RT

0.63(1)
0.27(1)
0.90(1)

RT
RT
RT

0.91(1)
0.33(1)
0.37(1)

1.57(1)
0.41(1)

quenchedfrom 1000C

Zno.7
Mgo.5Feo.
5A12On

Fe2TiO4
d
Tapiolite
FeTa206
Wastite

Feo.950e

51.0(2)
52.6(2)

0.48(1)

RT

0.46

XaFe2-5+ [56]

0.15
0.39

XaFe2-5+
VeFe3*

0.36

rVFe2+
IVFe2+
VFe3+
reFe3+

0.64

VFe3+

0.29(2)

0.78(2)

0.11

XaFe3+

0.92(2)
0.89(2)

0.23(2)
0.81(2)

0.76
0.13

rVFe2*
IVFe2+

RT

0.83(1)

1.91(8)

RT

1.11(2)

3.15(5)

1.00(1)

0.22(1)
0.42(1)

RT

0.93(1)
0.60(5)
spectradata were fitted with a distributionmodel

see[87]fora discussion
of theeffectofA1substitution
and
varying crystal size

see[88] for a discussion

of theeffectof A1substitution
and
varying crystalsize

45.7(1)
44.6(1)
48.9(1)

Fe2+

XaFe2+
0.43
0.48

VFe2+
VFe2+

0.09

VeFe3*

[93]
[93]
[781
[91]
[128]

[77]

[106]
[79]

octahedral
andtetrahedral
sites
inFe2TiO
4have
been
distinguished
usingextemalmagnetic
fields[123]

thereisconsiderable
controversy
overfittingmodels,
see[75]

for a review

MCAMMON

TABLE8.57FeM6ssbauer
dataforselected
sulphide,
selenide
andtellurideminerals
Absorber

site

Ref

1.15(3)

VlFe2+

[64]

0.83(2)

2.69(2)

VIFe2+

[17]

RT

0.39(1)

0.22(1)

RT

0.25(3)

RT

0.26(1)

0.45(1)

RT
RT

0.43(1)
0.72(1)
0.22(1)

1.2
0.20(1)

RT
RT

0.30(1)
0.45(1)

RT
RT
RT

RT

CS(Fe)

AE2

mm s-

mm s-

RT

0.26(3)

RT

Tesla

Arsenopyrite
FeAsS
Berthierite

FeSb2S4
Bornite

CusFeS4
Chalcopyrite
CuFeS2

[27]

35.7(5)

ntFe3+

[63]

XaFe2+

[124]

lVFe2.5+
ntFe2*
ntFe3+

[631
[491

1.65(1)
1.28(2)

VIFe2+
VlFe2+

[641
[119]

0.27(1)
0.39(1)
0.47(1)

0.51(1)
0.58(1)
0.50(1)

VlFe2+
XaFe2+
VIFe2+

[119]
[1191
[119]

0.36(1)
0.65(1)

0.32(1)

IVFcZS+?
VFca*

[69]

RT

0.31(1)

0.61(1)

VlFe2+

[119]

285 K

0.69(1)
0.68(1)
0.67(1)

RT

0.67(3)
0.67(3)

0.60(10)

RT

0.57(1)

2.90(1)

RT

0.39(2)

1.07(2)

RT

0.58(1)
0.37(1)

2.28(1)
0.33(1)

0.29(1)
0.59(1)
0.58(1)
0.55(1)
0.26(1)

0.54(1)
0.00(2)
0.70()

Cobaltite

(Co,ge)AsS
Cubanite

CuFeaSa(ortho)
CuFeaS(cubic)
L611ingitestructure
FcAs2
FSb2
Marcasite

33.1(5)
0.46
0.54

structure

FS 2
FeSea
FeTea
Pentlandite

Fe4.2Coo.lNi4.7S8
Pyrite
FeS2
Pyrrhotite
Feo.89
S

Sphalerite
Zno.95Feo.osS

0.82

0.18

- 0.48
- 0.59
-0.45

30.2(5)
25.7(5)
23.1(5)

0.41
0.36
0.23

XaFe2+
XaFe2+
XaFe2+

0.54

IVFe2+
IVFe2+

[431

lVFe2+

[491

IVFe2.5+

[129]

lVFe2+
mFe3+

[24]

VlFe2+
lVFe2+
lVFe2+
VlFeZS+?
ntFe3+

[125]
[001

0.46

Stannite

Cu2FeSnS4
Sternbergite
AgFe2S3

27.8(2)

Tetrahedrite

Cua.9Ag2Fe.
Sb4S
Thiospinelminerals
FeNi2S4
FeCr2S4
F%S4

RT
RT
RT

0.60
0.40

0.93
0.06'

31.0(5)
31.1(5)

0.66

0.34

[115]

341

342

MOSSBAUER SPECTROSCOPY

TABLE 8. (continued)
Absorber

FeIn2S4

Co2.9Feo.1
S4
Troilite
FeS

RT
RT

CS(Fe)

AEQ

mm s-1

mm s-1

Tesla

0.88(1)
0.25(1)
0.23(1)

3.27(1)
0.25(1)

RT

0.76(4)

RT

0.69(3)
0.69(3)

0.45
0.55

- 0.88

31.0(5)

site

Ref

VFe2+
VFe3+
VFe3+

[491
[130]

XaFe2+

Ds]

0.54

lVFe2+

[43]

0.46

VFe2+

Wurtzite

Zno.95Feo.osS

0.56(10)

small amountof additionalcomponentpresent

TABLE 9. S7FeM6ssbauer
datafor selected
carbonate,
phosphate,
sulphate
andtungstate
minerals

Absorber

CS(Fe)
mm s-

AEQ
mm s-

site

Ref

Tesla

Siderite

FeCO3

RT

1.24(1)

1.80(1)

VFe2+

[481

RT

1.25(1)

1.48(3)

WFe2+

[341

RT

1.11(2)

1.49(3)

rife2+

[51]

RT

0.40(5)

I. 15(5)

WFe3+

[62]

RT

1.13(2)

1.53(3)

rife2*

[51]

RT

1.21(1)

2.98(1)

0.22

rife2+

[10]

1.18(1)
0.38(1)
0.40(1)

2.45(1)
1.06(1)
0.61(1)

0.21
0.38
0.19

WFe2+
WFe3+
WFe3+

Ankerite

Ca.lX(CO3)2

X=Mgo.sFeo.3Mno.
1
Ferberite

FeWOn
Jarosite

KFea(SOn)e(OH)
6
Wolframite

Feo.sMno.sWO4
Vivianire

Feo0a)2-8H20

TABLE 10. S7FeM6ssbauer data for other minerals

Absorber

CS(Fe)
mm s-

zQ

mm s-

Tesla

site

Ref

Iron

ct-Fe

298 K

0.00

+0.001(2)

33.04(3)

Fe

[126]

33.8(7)

Fe

DO]

Fe

[41

Fe

[4]

Kamacite

~Feo.9sNio.os

RT

0.02(1)

Fe_Ni x < 0.3

RT

-0.08(1)

FeNi

RT

0.02(1)

Taenite

0.40(2)

28.9(2)

McCAMMON

343

TABLE 11. l l9Sn M6ssbauerdata for selectedminerals

Absorber

T
RT

Berndtite,$nS2
Cassiterite,SnO2

RT

CS(SnO
2)

AEi2

mm $-1

mm S-1

.03(5)
0.00

0.40(5)

site

Ref

VlSn4+
VSn4+

[8]
[132]

VlSn4+
VSSn4+
VSn2+
VlSn4+

[9]
[9]
[8]
[6]

Garnet structure
RT

CaaFei.sAlo.1Sno.1S
iaO12
YCa2Sn2Fe302
Herzenbergite,SnS
Incaite, Pb3.sFeSn4Sb2S
13.s
Malayite, CaSnSiO5
Mawsonite,Cu6Fe2SnSa
Ottemannite,Sn2S3

RT

Romarchite, SnO

RT

- 0.14(5)
0.07(5)
3.23(3)
.3(4)
3.29(5)
- 0.07(2)
1.46(5)
3.48(5)
1.10(5)
2.64(2)

Spinelstructure
Co2SnOn
Mn2SnO4
Zn2SnO4
Mg2SnO4
Stannite,Cu2Feo.9Znoa
SnS4
Stannoidite,Cus(Feo.sZno.2)aSn2S
2

RT
RT
RT
RT
RT
RT

0.30(4)
0.25(4)
0.24(4)
0.12(4)
1.45(5)
1.48(5)

RT
RT
RT

RT
RT

0.42(5)
0.42(5)
0.85(5)
0.66

0.98(5)
1.32(4)
0.00(5)
0.95(5)

Sn2+

0.34

0.29

VSn4+
reSn4+
Sn2+

0.71

VlSn4+

[104]
[132]
[8]

1.31(1)

VISn2+

[60]

0.80(8)
0.75(8)
0.75(8)
1.20(8)
0.00(5)
0.00(5)

WSn4+
VSn4+
VSn4+
VSn4+
reSn
4+
reSns+

[52]
[52]
[52]
[52]
[132]
[132]

Sn
Sn

[118]
[118]

Tin

c-Sn

300 K

2.02(2)

15-Sn

300 K

2.55(1)

Acknowledgments.I am gratefulto G. Amthauer,H. Annersten,

J. Cashion,E. Murad, G. Rossman
and
F. Seifert for valuablecomments
on the manuscript.

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61,

AGU Reference Shelf

Mineral Physics & Crystallography: A Handbook of Physical Constants

Vol. 2

Subject Index
actinides, bulk moduli, 131

activationenergy,apparent,crystals,
238

activationenergy,diffusion,274
activationvolume,apparent,crystals,
238

A1-27NMR spectra,307, 314-318,322

silicateglasses,324

temperatureand thermalpressure,

black-bodyemission,dependenceon
wavelengthat different
temperatures,300
bondingproperties,minerals,291

elastic moduli, 68
mantle mineral data, 85

borates

thermalexpansivity,specificheat,

78

elastic constants, and

velocities, 72

mineral data, 3-4

shockwave equationof state,160

albite

calcite,spectra,296

phasediagrams,249-252
viscosity,214
alkali feldspar,phasediagrams,250
alloys,shearviscosity,221-224

calcium aluminates, A1-27 NMR data, 318

Coblecreep,crystals,240
coesite,phasediagrams,249
compression
curves,shockwaves,172

calcium oxide

convective flow

76

aluminates

NMR spectra,325
See also calcium-aluminates

aluminosilicates,layer
A1-27 NMR data, 315
Si-29 NMR data, 311
aluminum

dimensionless
parameters,Debye
temperatureand thermalpressure,

oxides

dimensionless
parameters,Debye
temperatureandthermalpressure,
75

elastic moduli, 69
mantle mineral data, 85-86
O- 17 NMR data, 320

thermalexpansivity,specificheat,
elastic constants, and
velocities, 70

amorphousmaterials
bulk moduli, 134

NMR spectra,303,322-325
amphiboles
diffusion, 277

M/3ssbauer
spectra,336-337
andalusite,M/3ssbauer
spectra,337
andesite,shearviscosity,215
anelasticity,melts,209-217
anorthite,phasediagrams,249-251
Arrheniusequation,diffusion,274
Arrheniuslaw, crystals,238
asymmetryparameter,NMR spectra,307
augite,phasediagrams,255
babingtonite,
M/3ssbauer
spectra,337
basalt, diffusion, 274, 282-283
Beer-Lambertlaw, absorption,295

beta-spinel,
plasticity,245
bibliography,M/3ssbauer
spectroscopy,
335-336

elastic moduli, 65
mantle mineral data, 83

mantle, 227

mantle viscosity,229
coordinationnumber,NMR spectra,307
core,outer, viscosity,218-226
correspondence
principle,elasticity,
228

thermalexpansivity,specificheat,
elastic constants, and
velocities, 73

carbides,shockwave equationof state,

152-153

corundum

phasediagrams,251
See also aluminum

oxide

creep,climb-controlled,
crystals,

carbon-bearing
minerals,bulk moduli,
117-118

239-240

creep,glide-controlled,crystals,239
creep,power-law

carbonates

bulk moduli, 117-118

high-temperature
electrical
conductivity,189
mineral data, 3

M/Sssbauer
spectra,342
shockwaveequationof state,160
thermalexpansion,32
chain silicates

bulk moduli, 105-107

mineral data, 6
O- 17 NMR data, 321-322

chargetransferband,297
chemical diffusion, 271

chemicalshift,NMR spectra,304, 306

chemicalshift anisotropy,NMR spectra,
306

chlorite,M/3ssbauer
spectra,337
chloritoid,M/3ssbauer
spectra,337
clay minerals,M/3ssbauer
spectra,337
clinoenstatite,
phasediagrams,253-254
clinopyroxene
phasediagrams,254, 256
plasticproperties,244
closuretemperature,diffusion,274
cobalt silicate

dislocations, 240

mantleviscosity,
creep,quasisteady-state,
crystals,237
crystals,237
See also diffusioncreep;dislocation
creep;Harper-Dom creep;
Herring-Nabarrocreep
creepmechanism,mantleviscosity,227
cristobalite,phasediagrams,249
critical resolvedshearstress,yield
strength,245
cross-slip,dislocations,240
crystal-fieldabsorptions,
297
crystallographic
data,minerals,1-17
crystals
plasticrheology,237-247
Seealsocubiccrystals;hexagonal
crystals;orthorhombiccrystals;
trigonalcrystals
crystalstructure,mineraldata, 1-17
cubiccrystals,elasticmoduli,46-48
cyclosilicates
bulk moduli, 107-110
mineral data, 5-6

Seealso ring silicates

dimensionless
parameters,Debye

349

AGU Reference Shelf

350

Mineral Physics & Crystallography: A Handbook of Physical Constants

Vol. 2

INDEX

Debye temperature,mantleminerals,
75-79

electronic transitions, minerals, 29 l

deformation-mechanism
maps,plastic
deformation, 241
deformation mechanism, mantle

viscosity,227
diamond-anvil

electricalproperties,minerals,185-208

cell

equationsof state,98-101
high-pressure
minerals,245-246
dielectricpermittivity, 185
diffusion, 304

elements,GroupI, bulk moduli,122-123

elements,GroupII, bulk moduli,123

elements,
GroupIII., bulkmoduli,126
elements,GroupIV, bulk moduli,126-128
elements,GroupV, bulk moduli, 128
elements,GroupVI, bulk moduli,128-129
elements,GroupVII, bulk moduli,129
elastic moduli, 46

shockwave equationof state,146-152

enstatite

dislocations, 240
olivine, 243-244

phasediagrams,254-257
phaserelations,25
plasticproperties,244
enthalpy

silicates, 269-290
See also chemical diffusion

diffusionalflow, mantleviscosity,227
diffusion

coefficients

silicates, 270-273
See also chemical diffusion;

effectivebinarydiffusion
coefficients; interdiffusion;

multicomponent
diffusion;
phenomenological
diffusion

mantle minerals, 90
minerals, 21-23

phasetransformations,
23-27
entropy
mantle minerals, 90
minerals, 21-23

phasetransformations,
23-27
epidote,M/3ssbauer
spectra,337
equationsof state

coefficients; self-diffusion

shock waves, 143-174

coefficient;thermodynamic

staticcompressionmeasurements,
98-142

factor; tracer diffusion

coefficient

See alsoMie-Gruneisenequationof

diffusion creep
crystals,239
dislocations, 240

diopside
phasediagrams,253-257
plasticproperties,244
dislocationcreep,crystals,239
dislocations,crystals,239
dynamictopography,
mantleviscosity,
229

dynamicyielding,shockwaves, 174-175
Earth-formingminerals
phasediagrams,248-268
spectra,291-302
Earthrotation,mantleviscosity,231
effectivebinarydiffusion
coefficients, 273

elasticconstants,
isotropic,mantle
minerals, 69-74

elasticity,geologicalmaterials,45-63
elasticlimit, crystals,237
elasticmoduli, isotropic,P and T
derivatives, 57-58

crystals,46-56
mantlemineralsat high temperature,
64-97

melts, 209

electricalconductivity,185
minerals, 291

pointdefects,187-188

silicates

bulk moduli, 104-105

O- 17 NMR data, 322
See also tektosilicates

fusion,enthalpy,25

gamma-spinel,
plasticity,245-246
garnet,grossular
dimensionlessparameters,Debye
temperatureand thermalpressure,
76

multicomponent,273

diffusion

Seealsomagnesiumsilicate
framework

state

fayalite
crystalfield absorptionspectra,299
phasediagrams,256
see also iron silicate
Fe-57

line positionsfor 14.4 ke V

transition, 335

M/3ssbauer
spectroscopy,
332-335
feldspars
A1-27 NMR data, 315
diffusion, 275-276

log electricalconductivityvs.
partialpressure,205
phasediagrams,248-252
Si-29 NMR data, 312

viscosity,214

feldspathoids
AI-27 NMR data, 315
diffusion, 279

log electricalconductivityvs.
partialpressure,205
Si-29 NMR data, 312

ferropseudobrookite,
phasediagrams,259
ferrosilite,phasediagrams,255

elastic moduli, 65
mantle mineral data, 83

phasediagrams,257
thermalexpansivity,specificheat,
elastic constants, and
velocities, 73

thermoelastic
properties,93-94
garnet,majorite
phasediagrams,253
plasticity,245
garnet,pyrope-rich
dimensionless
parameters,Debye
temperatureand thermalpressure,
76

elastic moduli, 65
mantle mineral data, 83

phasediagrams,256-257
thermalexpansivity,specificheat,
elastic constants, and
velocities, 73
garnet
diffusion, 280
elastic moduli, 47-48

Massbauerspectra,337
phasediagrams,248, 256-257
gases,shockwave equationof state,
144-145

geochemistry,
304
geodeticstudies,coreviscosity,219
geoid,mantleviscosity,227
geoidanomaly,positivemassanomaly,
231

geoidinversion,mantleviscosity,
232-234

geomagnetism
studies,coreviscosity,
220

geophysics,
304
germanares,
phasetransitions,25
Gibbsfree energy,vs. temperature,23
glasses
bulk moduli, 134
diffusion, 269-290

elasticity,45-63

Fick's laws, diffusion, 270-271

elastic moduli, 56

forsterite

heatcapacity,20
NMR spectra,322-325
phasetransitions,212
shockwave equationof state,166-168

heatcapacity,19
phasediagrams,254-256
thermoelastic
properties,92-93

AGU Reference Shelf

Mineral Physics & Crystallography: A Handbook of Physical Constants

Vol. 2
INDEX

glasstransition,heatcapacity,20-21
grain-boundary
sliding,crystals,239
grandidierite,
M0ssbauerspectra,337

iron-sulfuralloys,liquid, shear
viscosity,223
iron-titaniumoxides,phasediagrams,
248, 258-260

Griineisen ratio, 173

iron

halides

bulk moduli, 131

bulk moduli, 120-122

elastic moduli, 47

hightemperatureelectrical
conductivity,189-190
log electricalconductivityvs.
partialpressure,204
mineral data, 8-9

shockwaveequationof state,153-155
hardening,crystals,237
Harper-Domcreep,crystals,240-241
heatcapacity,minerals,18-21
hedenbergite,
phasediagrams,255
Helmholtzfree energy,mantleminerals,
86-87

hematite,phasediagrams,258-260
Herring-Nabarrocreep,crystals,240
hexagonal
crystals,elasticmoduli,48
high-pressure
minerals,l.,antle,245-24,
high-pressure
silicates
mineral data, 8
O-17 NMR data, 322

hollandite,phasediagrams,250
Hugoniotequationof state,minerals,

M0ssbauerspectra,342
phasediagrams,248, 262
iron alloys,bulk moduli, 131-133
iron silicate

elastic moduli, 68
mantle mineral data, 85

isopleths,phasediagrams,249-262

deformation, 241

hydrousminerals,thermalexpansion,
31-32

hydroxides
bulk moduli, 111-117
mineral data, 3

M0ssbauerspectra,340
O- 17 NMR data, 321

shockwave equationof state,159

elastic constants, and

velocities, 69

thermoelastic
properties,92
magnesiumsilicate
dimensionless
parameters,Debye
temperatureand thermalpressure,
77

elastic moduli, 67
mantle mineral data, 84-85

thermalexpansivity,specificheat,
elastic constants,and
velocities, 71

magnetite,phasediagrams,258-260
manganese
oxide
dimensionless
parameters,Debye
temperatureandthermalpressure,
78

jadeite,phasediagrams,249

kamacite,M/assbauer
spectra,342
kinks, crystals,239
Kroger-Vinknotation,pointdefects,

elastic moduli, 66
mantle mineral data, 83-84

thermalexpansivity,specificheat,
elastic constants, and
velocities, 72

187-188

kyanite,M0ssbauerspectra,338
lanthanides, [::.,ik moduli, 130-131

leucite,phasediagrams,250, 252
liquidalloys,shearviscosity,221-224
liquidmetalstheory,coreviscosity,

143

hydrides,bulk moduli,133-134
hydrostatic
pressure,
plastic

thermalexpansivity,specificheat,

thermalexpansivity,specificheat,
elastic constants, and
velocities, 72

221

manganesesilicate
dimensionless
parameters,Debye
temperatureandthermalpressure,
78

elastic moduli, 68
mantle mineral data, 85

thermalexpansivity,specificheat,

liquids
bulk moduli, 134
diffusion, 269-290

heatcapacity,20
NMR spectroscopy,
303
phasetransitions,212
lithosphere,strength,228
longitudinalviscosity,vs.frequency,
211

lunarglass,shockwaveequationof
state, 168

351

elastic constants,and
velocities, 72
mantle

high-pressure
minerals,245-246
viscosity,227-236
mantle minerals, elastic constants,
64-97

MAS, Seemagicanglesspinning
melting,entropy,23-27
melts

elasticity,45-63
elastic moduli, 55-56

ices, bulk moduli, 133

ilmenite,phasediagrams,253, 259-260
ilvaite,M0ssbauerspectra,337
infraredspectroscopy,
Earth-forming
minerals, 291-302
insulators, 186
interdiffusion, 271
intervalence transitions, 297

inverseproblems,mantleviscosity,
231-232

iron,liquid,sheardynamicviscosity,
222

iron-nickelalloys,liquid,shear
viscosity,222-223
iron-oxygenalloys,liquid,shear
viscosity,224
iron-siliconalloys,liquid,shear
viscosity,224-225

magicanglesspinning,NMR spectra,303
magnesiowuestite
phasediagrams,256
plasticity,245
magnesiumaluminumoxide

electricalproperties,185-208
NMR spectra,304, 322-325
viscosityand anelasticity,209-217
Seealsoamorphous
materials;
glasses;liquids;silicatemelts

metal cations, effect of octahedral

dimensionless
parameters,
Debye
coordination on d-orbitals, 298
temperatureandthermalpressure,
79
metalliccompounds,elasticmoduli,46
elastic moduli, 66

thermalexpansivity,specificheat,
elastic constants, and
velocities, 70

magnesiumoxide
dimensionless
parameters,Debye
temperatureandthermalpressure,
75

elastic moduli, 65
mantle mineral data, 82-83

metallic conductors, 186

metals, transition, bulk moduli, 124-126

mica,M0ssbauerspectra,338
Mie-Gruneisenequationof state,shock
waves, 175
minerals

crystallographic
data, 1-17
elasticity,45-63
electricalproperties,185-208
equationsof state,98-142

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352

Mineral Physics & Crystallography: A Handbook of Physical Constants

Vol. 2

INDEX

M/3ssbauerspectroscopy,
332-347
NMR spectra,304
phasediagrams,248-268
shock wave data, 143-184

thermalexpansion,29-44
thermodynamic
properties,18-28
See also carbon-bearingminerals;
Earth-formingminerals;hydrous
minerals; and the different

M/3ssbauerspectra,338
phasediagrams,252
orthoenstatite,
phasediagrams,254
orthopyroxene
M/3ssbauerspectra,333
phasediagrams,254-255
plasticproperties,244
orthorhombiccrystals,elasticmoduli,
51-52

mineral groups

M/3ssbauer
parameters,
334
M/3ssbauerspectroscopy,
minerals,
332-347

molar volume, minerals, 21-23

monocliniccrystals,elasticmoduli,
53-54

native elements, mineral data, 10

nephelinite,shearviscosity,215
Nernst-Einstein relation, 186

Newtonian viscosity,crystals,240
nitrates, mineral data, 3

NMR spectroscopy,
Seenuclearmagnetic
resonance spectroscopy

noblegases,bulk moduli,129-130
nuclearmagneticresonance
spectroscopy,
minerals,303-331
nuclides,quadrupolar,NMR parameters,
305-306

nuclides,spin 1/2, NMR parameters,304

O-17 MAS NMR spectra,319
O-17 NMR spectra,silicateglasses,
324-325

olivine

phenomenological
diffusion

orthoclase

orthosilicates

bulk moduli, 107-110

mineral data, 4-5
O- 17 NMR data, 321

osumilite,M/3ssbauerspectra,338
oxidecomponents,
thermalexpansion,40
oxides,crystalline
AI-27 NMR data, 314-318
O- 17 NMR data, 320

coefficients, 269-270

phlogopite,phasediagrams,248, 261
phosphates
mineral data, 4

M/3ssbauerspectra,342

pigeonite,phasediagrams,254-255
plagioclase,phasediagrams,250-251
Planck function, minerals, 301

plasticdeformation,Seealso
superplastic
deformation
plasticinstability,crystals,238
plasticity,transformation,crystals,
239

platevelocities,mantleviscosity,229
pointdefects,electricalconductivity,
187-188

polarwander,mantleviscosity,231
post-glacialuplift, mantleviscosity,
227, 232

oxides

bulk moduli, 111-117

elastic moduli, 46-47

high temperature
electrical
conductivity,190-192
log electricalconductivityvs.
partialpressure,205
mineral data, 2-3

M/3ssbauer
spectra,
40
nucle,atmagneticresonance
spectroscopy,
303-331
partialmolarheatcapacities,
21
shockwaveequationof state,155-159
thermalexpansion,30-31
vibrations, 297
See also aluminum oxide;

potassiumchloride
dimensionless
parameters,Debye
temperatureand thermalpressure,
79

elastic moduli, 66
mantle mineral data, 84

thermalexpansivity,specificheat,
elastic constants, and
velocities, 74

power-lawcreep,plasticproperties,244
protoenstatite,
phasediagrams,253-254
pseudobrookite,
phasediagrams,259
pyrophyllite,M/3ssbauer
spectra,338
pyroxenes

diffusion, 278-279

iron-titaniumoxide;magnesium
high-temperaturecompression
creep,
244
deformation mechanism, 227-228
oxide;magnesiumaluminumoxide;
M/3ssbauerspectra,338-339
deformationmechanismmap, 241
manganese
oxide
diffusion, 279-280
phasediagrams,248, 253-255
oxygenfugacity
dimensionlessparameters,Debye
crystals,238
quadrupolarcouplingconstant,NMR
temperature
and thermalpressure,
plasticproperties,244
77
spectra,307
elastic moduli, 67
quartz
pargasite,phasediagrams,248, 261
diffusion, 275
high-temperaturecompressioncreep,
periclase,phasediagrams,255
242
phasediagrams,249
peridot,crystal-fieldeffects,298
plasticity,241-242
perovskite
high-temperature
creeplaws,243
spectra,296
high-temperature
compression
creep,
log electricalconductivityvs.
245
staticNMR spectra,306
partialpressure,202-204
mantle mineral data, 85
quasiharmonic
approximation,mantle
Massbauerspectra,338
minerals, 87-89
Massbauerspectra,338
phasediagrams,253,255-256
plasticity,245-246
phasediagrams,248, 255-256
radiativethermalconductivity,
thermalexpansion,38-39
phaserelations,26
minerals, 291
pointdefectmodel,202
phasediagrams,Earth-formingminerals,
248-268
radiative thermal emission, minerals,
point defects,188
301
thermalexpansivity,specificheat,
phasetransformations,
entropy,23-27
elastic constants, and
Ramanspectroscopy,
Earth-forming
phasetransitions,304

crystal-fieldeffects,298

velocities, 71

optical absorptionspectroscopy,
Earth-formingminerals,291-302
Orowan's equation,dislocations,239

shock waves, 174-175

silicate melts, 212

phasevelocities,mantleviscosity,
231-232

minerals, 291-302

Rankine-Hugoniot
equations,shock
waves, 172-174

reflectionspectra,minerals,294

AGU Reference Shelf

Mineral Physics & Crystallography: A Handbook of Physical Constants

Vol. 2
INDEX

relaxation mode, melts, 209

relaxation

time

melts, 209

vs. temperature,212
resonantfrequency,303
rheology,non-Newtonian,melts,215
rheology,plastic,crystals,237-247
rheology,mantleviscosity,227
rhyolite
diffusion, 274, 281-282

shearviscosity,215
ring silicates

M6ssbauerspectra,336-339
nuclearmagneticresonance
spectroscopy,
303-331
phasetransitions,19-27
shockwave equationof state,162-166
thermalexpansion,33-38
vibration of tetrahedra, 293
vibrations, 297

Seealsoamphiboles;chainsilicates;
clinopyroxene;cobaltsilicate;
feldspars;feldspathoids;
framework silicates; iron

bulk moduli, 107-110

silicate;magnesiumsilicate;
manganesesilicate;olivine;
orthopyroxene;orthosilicates;
pyroxenes;ring silicates;sheet
silicates;silicapolymorphs;

See alsocyclosilicates
ringwoodite,Seealsogamma-spinel
ruby,crystal-fieldeffects,298
rutile, phasediagrams,259

sorosilicates

sanidine,phasediagrams,250
sapphirine,
phasediagrams,256
sealevel variations, ice models, 229

seismictomography,mantleviscosity,
229

seismological
studies,coreviscosity,
220

selenides,M/3ssbauer
spectra,341-342
self-diffusion coefficient, 271
semiconductors, 186

serpentine
M6ssbauerspectra,339
phasediagrams,248, 261
shear stress,critical resolved,

crystals,239
shearviscosity,vs. frequency,211
sheet silicates

bulk moduli, 110-111

diffusion, 277
mineral data, 6-7
shock waves, minerals, 143-184

Si-29 NMR spectra,307-313

silicateglasses,322-324
silicaanalogs,AI-27 NMR data,315
silicapolymorphs
diffusion, 275

phasediagrams,248-249
shockwave equationof state,161-162
Si-29 NMR data, 312
silicate melts

hightemperature
electrical
conductivity,201
longitudinalviscosityvs. shear
viscosity,210
silicates,crystalline
AI-27 NMR data, 314-318
Si-29 NMR data, 308-313
silicates

crystallographic
properties,4-8
diffusion, 269-290

hightemperatureelectrical
conductivity,192-200

sillimanite

M6ssbauerspectra,339
phasediagrams,256
smectite,M6ssbauerspectra,339
Sn-119,M6ssbauerspectroscopy,
332-335
sodium chloride

dimensionless
parameters,
Debye
temperatureand thermalpressure,

353

climb-controlledcreep,240
plasticproperties,244
sulfates

mineral data, 4

M/3ssbauerspectra,342
shockwave equationof state,160
thermalexpansion,33
sulfides

bulk moduli, 118-120

elastic moduli, 47
mineral data, 9-10

M/3ssbauer
spectra,341-342
thermalexpansion,33
superplastic
deformation,crystals,239
taenite,M/3ssbauer
spectra,342
talc, M/3ssbauerspectra,339
tectosilicates, See tektosilicates
tektosilicates, mineral data, 7-8
tellurides

bulk moduli, 118-120

M6ssbauerspectra,341-342
temperature,shockwaves, 175
tetragonalcrystals,elasticmoduli, 50
thermalexpansion
geologicalmaterials,29-44
mantle minerals, 69-74

79

elastic moduli, 66
mantle mineral data, 84

thermalexpansivity,geological

thermalexpansivity,specificheat,

thermal pressure,mantle minerals,75-79

thermobarometry,248
thermochemicalproperties,minerals,18
thermodynamic
factor,diffusion,273
thermodynamicproperties

elastic constants, and

velocities, 74
sorosilicates

bulk moduli, 107-110

mineral data, 5-6

specificheat,mantleminerals,69-74
spinel
AI-27 MAS spectra,319
elastic moduli, 47

high temperatureelectrical
conductivity,192
mantle mineral data, 83

M/3ssbauerspectra,339
phasediagrams,253, 255-256
plasticity,245
Seealsobeta-spinel;gamma-spinel;
ulvospinel
spinquantumnumber,303
standardmaterials,shockwave equation
of state, 168-171

staticcompressiontests,equationsof
state, 98-142

staurolite,M/3ssbauerspectra,339
stishovite,phasediagrams,249, 253
strain, vs. time, 210
stress-strain

materials, 29

mantle minerals, 84-94

minerals, 18-28, 172-174

thermoelastic
dimensionless
parameters,
mantle minerals, 75-82

thermoelastic
properties,
high-temperature,mantle
minerals, 91-94

tholeiite,shearviscosity,215
tin, M/3ssbauerspectra,343
titanates,phasetransitions,25
titanite

diffusion, 281

M/3ssbauerspectra,339
tracer diffusion coefficient, 271

transmission
electronmicroscopy
high-pressure
minerals,245-246
plasticdeformation,241
quartz,242
tridymite,phasediagrams,249
trigonalcrystals,elasticmoduli,49
tungstates,M/3ssbauerspectra,342

curve

crystals,237
plasticsolid,238
stresscreepcurve,plasticsolid,238
stress exponent

ulvospinel,phasediagrams,259-260

velocity,mantleminerals,69-74
vibrationalspectroscopy

AGU Reference Shelf

354

Mineral Physics & Crystallography: A Handbook of Physical Constants

Vol. 2

INDEX

minerals, 291-297

See alsoinfraredspectroscopy;
Raman
spectroscopy

vibrational spectrum,minerals,291
virtification,enthalpy,25
viscoelasticity,melts,209
viscosity,dynamic,outercore,218-226
viscosity,Newtonian,crystals,237
viscosity,non-Newtonian,crystals,237
mantle, 227-236
mantle models, 230
melts, 209-217

pressuredependence,214
temperatedependence,213-214

Seealsolongitudinalviscosity;
Newtonianviscosity;shear
viscosity;volumeviscosity

wuestite,phasediagrams,258-260
X-ray diffractiondata,minerals,1-17

viscous flow, 304

volumeviscosity,vs. frequency,211
wadsleyite,Massbauerspectra,339
water-weakening,quartz,241

yield point, quartz,241

yield stress,crystals,237
yoderite,Massbauerspectra,339

water

zeolites

high pressureelectricalconductivity
vs. density,206
phaserelations,27
silicateglasses,324-325
wollastonite,phasediagrams,257

A1-27 NMR data, 316

Si-29 NMR data, 312
zircon, diffusion, 281