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Mineral physics and crystallography : a handbook of physical constants/ Thomas J. Ahrens, editor. p. cm. - (AGU reference shelf ISSN 3080-305X; 2) Includes bibliographical references and index. ISBN o-87590-852-7 (acid-free) I. Mineralogy-Handbooks, manuals, etc. 2. Crystallography-Handbooks, manuals, etc. I. Ahrens, T. J. (Thomas J.), 1936 II. Series. QE366.8.M55 1995 549’. l-dc20

95-3663 CIP

ISBN o-87590-852-7 ISSN 1080-305X This book is printed on acid-free paper. @

Copyright 1995 by the American 2000 Florida Avenue, N.W. Washington, DC 20009

Geophysical

Union

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in scientific books and journals

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Union

Printed in the United States of America.

CONTENTS

Preface Thomas

.I. Ahrens

vii Data for Minerals and Tamsin (2-l)

Crystallographic Joseph R. Smyth

C. McCormick (2-2)

Thermodynamic Properties of Minerals Alexandra Navrotsky 18 Thermal Yingwei Expansion (2-4) Fei 29

Elasticity of Minerals, Jay D. Bass 45

Glasses, and Melts (2-5)

Elastic Constants of Mantle Minerals at High Temperature Orson L. Anderson and Donald G. Isaak 64 Static Compression Measurements Elise Knittle 98 of Equations

(2-5a)

of State (2-6a)

Shock Wave Data for Minerals (2-6h) Thomas .I. Ahrens and Mary L. Johnson Electrical Properties James A. Tyburczy

143

of Minerals and Melts (2-8) and Diana K. Fisler 185

Viscosity and Anelasticity of Melts (2-9) Donald B. Dingwell 209 Viscosity of the Outer R. A. Secco 218 Models of Mantle Scott D. King Plastic Rheology J. P. Poirier Core (2-9a)

Viscosity 227 of Crystals 237

(2-9h)

(2-10)

Phase Diagrams of Earth-Forming Dean C. Presnall 248

Minerals

(2-11)

CONTENTS

Diffusion
John

B. Brady

Data for Silicate Minerals, 269 Raman, and Optical 291

Glasses, and Liquids

(2-12)

Infrared,

Spectroscopy

of Earth

Materials

(2-13)

Q. Williams

Nuclear Magnetic Resonance Spectroscopy Geochemistry and Geophysics (2-14) Jonathan F. Stebbins 303 MGssbauer
Catherine

of Silicates and Oxides in

Spectroscopy
McCammon

of Minerals 332

(2-15)

Index

349

PREFACE
The purpose of this Handbook is to provide, in highly accessible form, selected critical data for professional and student solid Earth and planetary geophysicists. Coverage of topics and authors were carefully chosen to fulfill these objectives. These volumes represent the third version of the “Handbook of Physical Constants.” Several generations of solid Earth scientists have found these handbooks’to be the most frequently used item in their personal library. The first version of this Handbook was edited by F. Birch, J. F. Schairer, and H. Cecil Spicer and published in 1942 by the Geological Society of America (GSA) as Special Paper 36. The second edition, edited by Sydney P. Clark, Jr., was also published by GSA as Memoir 92 in 1966. Since 1966, our scientific knowledge of the Earth and planets has grown enormously, spurred by the discovery and verification of plate tectonics and the systematic exploration of the solar system. The present revision was initiated, in part, by a 1989 chance remark by Alexandra Navrotsky asking what the Mineral Physics (now Mineral and Rock Physics) Committee of the American Geophysical Union could produce that would be a tangible useful product. At the time I responded, “update the Handbook of Physical Constants.” As soon as these words were uttered, I realized that I could edit such a revised Handbook. I thank Raymond Jeanloz for his help with initial suggestions of topics, the AGU’s Books Board, especially Ian McGregor, for encouragement and enthusiastic support. Ms. Susan Yamada, my assistant, deserves special thanks for her meticulous stewardship of these volumes. I thank the technical reviewers listed below whose efforts, in all cases, improved the manuscripts. Thomas J. Ahrens, Editor California Institute of Technology Pasadena

Carl Agee Thomas J. Ahrens Orson Anderson Don Anderson George H. Brimhall John Brodholt J. Michael Brown Bruce Buffett Robert Butler Clement Chase Robert Creaser Veronique Dehant Alfred G. Duba Larry Finger Michael Gaffey Carey Gazis Michael Gumis William W. Hay

Thomas Heaton Thomas Herring Joel ha Andreas K. Kronenberg Robert A. Lange1 John Longhi Guenter W. Lugmair Stephen Ma&well Gerald M. Mavko Walter D. Mooney Herbert Palme Dean Presnall Richard H. Rapp Justin Revenaugh Rich Reynolds Robert Reynolds Yanick Ricard Frank Richter
Vii

William 1. Rose, Jr. George Rossman John Sass Surendra K. Saxena Ulrich Schmucker Ricardo Schwarz Doug E. Smylie Carol Stein

Maureen Steiner
Lars Stixrude Edward Stolper Stuart Ross Taylor Jeannot Trampert Marius Vassiliou Richard P. Von Herzen John M. Wahr Yuk Yung

~-

~-------

Crystallographic

Data For Minerals

Joseph R. Smyth and Tamsin C. McCormick With the advent of modern X-ray diffraction instruments and the improving availability of neutron diffraction instrument time, there has been a substantial improvement in the number and quality of structural characterizations of minerals. Also, the past 25 years has seen great advances in high pressure mineral synthesis technology so that many new high pressure silicate and oxide phases of potential geophysical significance have been synthesized in crystals of sufficient size for complete structural characterization by X-ray methods. The object of this work is to compile and present a summary of these data on a selected group of the more abundant, rock-forming minerals in an internally consistent format for use in geophysical and geochemical studies. Using mostly primary references on crystal structure determinations of these minerals, we have compiled basic crystallographic property information for some 300 minerals. These data are presented in Table 1. The minerals were selected to represent the most abundant minerals composing the crust of the Earth as well as high pressure synthetic phases that are believed to compose the bulk of the solid Earth. The data include mineral name, ideal formula, ideal formula weight, crystal system, space group, structure type, Z (number of formula units per cell), unit cell edges, a, b, and c in Angstrom units (lo-lo m) and inter-axial angles cc, p, yin degrees, unit cell volume in A3, molar volume in cm3, calculated density in Mg/m3, and a reference to the complete crystal structure data. To facilitate geochemical and geophysical modeling, data for pure synthetic end mcmbcrs arc presented when available. Otherwise, data arc for near end-member natural samples. For many minerals, structure data (or samples) for pure end members are not available, and in these cases, indicated by an asterisk after the mineral name, data for an impure, natural sample are presented together with an approximate ideal formula and formula weight and density calculated from the ideal formula. In order to conserve space we have omitted the precision given by the original workers in the unit cell parameter determination. However, we have quoted the data such that the stated precision is less than 5 in the last decimal place given. The cell volumes, molar volumes and densities are calculated by us given so that the precision in the last given place is less than 5. The formula weights presented are calculated by us and given to one part in approximately 20,OflO for pure phases and one part in 1000 for impure natural samples.

J. R. Smyth, and T. C. McCormick, Sciences, University of Colorado, Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American

Department of Geological Boulder, CO 80309-0250

Geophysical

Union.

Table 1, Crystallographic Properties of Minerals.
Mineral Single Oxides Hemhxkie cuprite Monoxides Group Periclase WUStite Lime Bunsenite Munganosite Tenorite Montroydite Zincite Bromellite sesquioxide Group Corundum Hematite Eskolaite Kureliunite Bixbyite Avicennite Claudetite Arsenolite Senurmontite Valentinite Dioxide Group Brookite Anatase Rutile Cassiterite Stishovite Pyrolusite Baddeleyite Uianinite Thoriunite Multiple Oxides Chry~Yl Spin.51 Group Spine1 Hercynite Magnesiofenite Mugnesiochromite Magnetite Jacobsite Chnnnite Ulvwspinel BeAl& 126.97 Orth. Prunb 142.27 173.81 200.00 192.30 231.54 230.63 223.84 223.59 Cub. Cub. Cub. Cub. Cub. Cub. Cub. Cub. F&m F&m F&m F&m Fcdm k’&m F&m F&m Oiivine Spinet Spinet Spine1 Spine1 Spine1 Spine1 Spine1 Spinet 4 4.424 8 8 8 8 8 8 8 8 8.0832 8.1558 8.360 8.333 8.394 8.5110 8.3794 8.536 9.396 5.471 227.42 528.14 542.50 584.28 578.63 591.43 616.51 588.31 62 1.96 34.244 39.762 40.843 43.989 43.564 44.528 46.416 44.293 46.826 3.708 3.578 4.256 4.547 4.414 5.200 4.969 5.054 4.775 96 61 99 100 100 100 100 100 106 Formula Formula Crystal Space Weight System Group structure Type z a (4 B (“! Y (“) Unit Cell Molar Density Ref. Vol (K3) Vol (cm3) (calc)(h4g/m3)

h)

cuzo NsO Fe0 CaO NiO MnO cue HgO ZnO Be0
-41203 Fe203 Cr203 v203 Mnz03 T1203 AS203 AS203 SW3 Sb203

143.079 Cub. Pdm 40.312 71.848 56.079 74.709 70.937 79.539 216.589 81.369 25.012 101.961 159.692 151.990 149.882 157.905 456.738 197.841 197.841 291 A98 291.498 79.890 79.890 79.890 150.69 60.086 86.94 123.22 270.03 264.04 Cub. F&n Cub. F&n Cub. F&n Cub. F&m Cub. Fm%m Mono.C2lc Orth. Prima Hex. P63mc Hex. P63nu: Trig. R3C Trig. R% Trig. R% Trig. R% Cub. la7 Cub. 1ClS Mono. P21ln Cub. F&m Cub. F&m Chth. Orth. Ph Ten. Mtlamd Tetr. P42/mnm Tetr. P42/mnm Tea P4dmnm Ten. P42/mnm Mono.P;?t/c Cub. F&m Cub. F&m

Cuprite Halite Halite Halite Halite Halite Tencrite Montroydite Wurtzite Wurtzite

2 4.2696 4 4 4 4 4 4 4 2 2 6 6 6 6 16 16 4 16 16 4 8 4 2 2 2 2 4 4 4 4.211 4.3108 4.1684 4.446 4.8105 4.6837 6.612 3.2427 2.6984

17.833 74.67 80.11 111.32 72.43 87.88 8 1.080 128.51 47.306 26.970 254.80 302.72 289.92 297.36 834.46 1171.9 331.8 1358.19 1386.9 331.27 257.38 136.25 62.07 71.47 46.54 55.48 140.45 163.51 175.59

23.439 11.244 12.062 16.762. 10.906 13.223 12.209 19.350 14.246 a.122 25.517 30.388 29.093 29.850 31.412 44.115 49.961 51.127 52.208 49.881 19.377 20.156 18.693 21.523 14.017 86.937 21.149 24.620 26.439

6.104 3.585 5.956 3.346 6.850 5.365 6.515 11.193 5,712 3.080 3.986 5.255 5.224 5.021 5.027 10.353 3.960 3.870 5.583 5.844 4.123 3.895 4.2743 7.001 4.287 5.203 5.826 10.968 9.987

25 93
61

3.4226 5.20

5.1288 3.531 5.1948 4.2770 12.9912 13.772 13.599 14.002

99.54

235 235 195 11 12 189 189 157 23 157 157 75 167 176 177 217 216 17 105 204 15 20 121 208 126 227

Corundum Corundum Corundum Bixbyite Bixbyite Claudetite Arsenolite Arsenolite Vulentinite Brookite Anatase Rutile Rutile Rutile Rutile Baddeleyite Fluorite Fluorite

4.7589 5.038 4.9607 4.952 9.4146 10.543 4.65 7.99 11.0744 11.1519 4.911 12.464 9.184 3.7842 4.5845 4.737 4.1790 4.3% 5.1454 5.4682 5.5997 5.447

9.12

78.3

5.412 5.145 9.5146 2.9533 3.185 2.6651 2.871 5.3107

TiO2 TiO2 Ti02 SnO2 SiO2 MnO2
m2 UOZ

5.2075

99.23

Th02

M&Q
FeA120.t MgFezQ M&r204 FeFe204 MnFe204 FeCr204 TiFe204

Table 1. Crystallographic Properties of Minerals (continued).
Mineral Tilanale Group Ihnenite Pyrophanite Perovskite Armalcolite Pseudobrookite Ferberite Huebnerite Scheelite Powellitc Stolzite Wulfenite Hydroxides Gibbsite Diaspore Bochmite Brucitc Goethite Lepidoehrosite Carhonotes Magnesite Smithsonite Siderite Rhodochrositc Otavite Calcite Vaterite Dolomite Ankerite Aragonite Strontianite Cerussite Witherite Amrite Malachite Nitrates Soda Niter Niter Berates Borax Formula Fotmula Crystal Space Weight System Group
StNCtUE z 0 Y

‘be

(A)

(“)

Unit Cell Molar Density Ref. Vol (A3) Vol (cm3) (calc)(Mg/m3)

FeTiOs MnTiO3 CaTi Mg.@esTiS% FeaTi FeW04 MnW04 CaWO4 CaMoO4
Pbwo4

151.75 150.84 135.98 215.88 239.59 303.70 302.79 287.93 200.02 455.04 367.12

Trig. R? Trig. Rs
Orth. Otth. Orth. Pbnm Bbmm Bbmm

Ilmenite Ilmenite Perovskite Pseudobrookite Pscudobrookite Fe&rite Ferberite Scheelite Scheelite Scheelite Scheelite

6 6 4 4 4 2 2 4 4 4 4

5.0884 14.0855 5.137 14.283 5.3670 5.4439 7.6438 9.7762 10.0214 3.7485 9.747 9.947 3.717 4.730 4.8238 5.243 5.23 5.46 5.435 5.703 5.7504 4.952 4.9901 11.376 11.44 12.05 12.11 90.0 91.18

315.84 326.41 223.33 367.25 361.12 133.58 138.39 312.72 301.07 359.23 357.72

3 1.705 32.766 33.63 55.298 54.375 40.228 4 1.676 47.087 45.333 54.091 53.864

4.786 4.603 4.044 3.904 4.406 7.549 7.265 6.115 4.412 8.412 6.816

229 235 113 230 3 225 231 114 101 101 101

Tungstates and Molybdnks

PbMoO4

Mono. PZ/c Mono.P2/c Tetr. 141/a Tetr. 141/a Tetr. 141/a Tctr. 141/a

WW3

AID APOW MgWh FeO(OH) FeO(OH)

78.00 59.99 59.99 58.33 88.85 88.85

Mono.P2t/n
Orth. Orth. Or&. Pbnm Amam Pbnm

Gibbsite Boehmite Brucite Gocthite Boehmite

Trig. !%I orth. cmczt

8 4 4 1 4 4

8.684 4.401 3.693 3.124 4.587 3.08

5.078 9.421 12.221 9.937 12.50

9.736 2.845 2.865 4.766 3.015 3.87

9454

427.98 117.96 129.30 40.75 137.43 148.99

32.222 17.862 19.507 24.524 20.693 22.435

2.421 3.377 3.075 2.377 4.294 3.961

188 34 98 243 65 43

M&03 zatco3

FeCQ MnCOs CdCOj CaC03 CaC03 CaMgKQh
c*dco3)2

CaC03 SrC03
Pbco3

BaC03
Cu3@H)2(C03)2 Cuz@H)zC%

84.32 125.38 115.86 114.95 172.41 100.09 100.09 184.41 215.95 100.09 147.63 267.20 197.39 344.65 221.10

Trig. Trig. Trig. Trig. Trig. Trig. Hex. Trig. Trig. orth.
Orth. Orth.

R% R%
R% R% R% R?c P63hmc

d
RT Pmcn Pmcn Pmcn

orth. Pmcn Mon0.P2~/c Mono.P2t/a

Calcite Calcite Calcite Calcite Calcite Calcite Vaterite Dolomite Dolomite Aragonite Aranonite Araaonite Aragonite Amrite Malachite
Y

6 6 6 6 6 6 12 3 3 4 4 4 4 2 4

4.6328 4.6526 4.6916 4.7682 4.923 4.9896 7.151 4.8069 4.830 4.9614 7.9671 5.090 8.358 5.180 8.492 5.3126 8.8958 5.0109 5.8485 9.502 11.974

15.0129 15.0257 15.3796 15.6354 16.287 17.0610 16.937 16.0034 16.167 5.7404 5.997 6.134 6.4284 10.345 3.240

92.43 98.75

279.05 281.68 293.17 307.86 341.85 367.85 750.07 320.24 326.63 226.91 255.13 269.83 303.81 302.90 364.35

28.012 28.276 29.429 30.904 34.316 36.9257 37.647 64.293 65.516 34.166 38.416 40.629 45.745 91.219 54.862

3.010 4.434 3.937 3.720 5.024 2.7106 2.659 2.868 3.293 2.930 3.843 6.577 4.314 3.778 4.030

54 54 54 54 26 54 146 182 21 51 51 191 51 245 244

Nd%

KNOs Na2B40s(OH)4.8HaO

85.00 Trig. R% 101.11 or&l. Pmcn 381.37 Mono. C2/c

Calcite Aragonite

6 5.0708 4 5.4119 11.885

9.1567 10.654

16.818 6.5189 12.206 106.62

374.51 323.05 1480.97

37.594 48.643 223.00

2.261 2.079 1.710

198 159 128

12 13 1.62 306.879 6.185 5. Crystallographic Properties of Minerals (continued).71 6.H~O BaS04 SrS04 PbS04 CaS04 CaS042H20 KAk@0dz(0Hki KFes(S0dz(‘W6 CU3(S04)(OW4 FormulaCrystal Space Weight System Group 273.974 118.23 4. Orth. Vol (A3) Vol (cm3) (calc)(Mg/m3) 953.659 2.969 4.8 291.60 108. Pmnb Orth.371 8.41 564.904 2.04 114.595 3.12 (“) Unit Cell Molar Density Ref.760 6.x4 314.382 6. Pbnm orth.0 LiFcPOq LiMnP0.118 11.457 5.48 502. Orth.18 143.91 307.7 1661.040 3.603 46.965 8 8 161 161 161 161 69 69 69 124 50 32 165 32 Forsterite Fayalite Tephroitc Liebenbergite Ca-olivine Co-olivine Monticellite Kirschsteinite Orth.la 233.88 160.870 6.OH)POd AMOW3W Am4 6.96 209.55 Mono.08 115.0172 9.98 43.18 494.010 10.7811 4.20 490.48 MgzSiQ FqSiO4 MnzSi04 Ni2Si04 Ca2Si04 CqSiO4 CaMgSiOd CaFeSi 140.7 285.76 156. P3t21 Apatite Apatite Apatite Monazite Ziicon Wbitlockite Olivine Olivine Amblygonite Augelitc Qu== Mono.89 113.85 146.829 5.334 6.lZ/a Trig.0873 6.4788 10. Q 183. Ortb.268 11.9783 6.9 1533.763 11.959 2.42 529. P212121 Epsomite Hex.066 10.9023 4. F&ii 6.28 Mono.043 12.911 46.719 3.099 3.884 8.006 5.452 11.30 346.670 7. Pmcn Arcanite orth.036 37.8195 4.078 4.32 295.412 47.96 318.402 4.869 52.334 157.54 433.71 5.15 497.78 112.5964 10.01 298.440 147.476 6.987 5.628 6.121 4.9 1753.244 9.77 235.j LiAI(F.99 129. Pbnm 136. R3c Grth.153 3.19 500.726 5.02 282.102 4 4 4 4 4 3 3 4 8 4 4 2 2 2 4 4 3 4 4 2 4 3 7.95 232.54 3428.415 3.223 17. Mineral Kernite Colemanite Sulfates Barite Celestite Anglesite Anhydrite Gypsum Alunite* Jamsite* Antleritc Thenarditc Arcanite Epsomite Phosphates Hydroxyspatite Fluorapatite Chlorapatite Monazitc Xenotime Whitlockite Triphylite Lithiophyllite Amblygonite* AugeIite* Berlinite Orthosillcates Garner Group Almandine Spessartine Grossular Andradite Uvarovite Olivine Group P % a Y Formula Na2B406(0tI)2.172 89. P63/m Hex.70 203.74” 1I.24 209.09 183.764 6.705 2.616 118 46 145 112 91 90 142 36 214 215 137 76 123 38 237 101 16 101 206 u NqSO4 K2SG4 MgS047HzO Cag(PO&OH WPWsF Ca#O&CI ccPo4 ym4 W~~~dWQh GypSlUll Alunite Alunite Antlerite Thenardite Orb.572 160.846 9.888 44.48 188.0004 6.88 2133.533 17.81 354.40 303.21 403.913 6.80 597.90 975. RTm orth.371 47.Table 1. RTm Trig.86 110.002 m F v1 $ z 7.620 1.199 3.25 Orth.201 5.146 1501. 157. Cub. P2.859 6.838 159.2567 5.68 Orth.859 3. P63im Mono.884 6.8 289.15 508.71 43.565 4.542 3.157 6.245 46. Cub.71 142.924 46.020 7.127 2. P21k 205.693 4.58 307.19 709.124 4.953 2.939 42.045 2.21 500. l&d I&d In% IaTd IaTd IaTd Pbw?z Pbnm Ptnm Phm Pbmn Garnet Garnet Garnet Garnet Garnet Garnet Olivine Olivine Olivine Olivine Olivine Olivine Olivine Olivine 8 8 8 8 8 8 4 4 4 4 4 4 4 4 11.16 495.398 6.312 4.7534 4.280 48.42 325.C2/m Trig.46 6.482 6. Orth.302 10. Pi Mono.04 797.878 10.330 10.920 53.419 65.419 48 42 2 b F E.678 3.9 121.108 10.661 1.845 12.95 156.88 125.2 1722.531 11.361 9.P2t/n Tetr.37 735.75 385.304 8.43 117.071 12. Oh.2998 11.921 2.313 2.560 84.277 3.49 341 .822 4.21 246.17 414. Pbnm .600 3. Pmnb Tric.998 15.850 3.01 Cub. Cub.04 112.03 403.103 74.527 44.245 6.00 688.424 9.47 294.09 523. Cub.242 73.14 Orth.32 7.386 43.1902 10.988 97.201 3.493 51. Pbnm Pbnm Amma StNCtUE TYPe Kernitc Colemanitc Baritc I&rite Barite Anhydrite (A) 4 7.95 2.058 11.943 8. Cub.868 7.527 163.09 543.988 4.290 48. orth.07 67.612 11.577 5. 172.15 7.807 3.04 104.05 5. Pbnm Orth.2 1565.959 7.6114 4 8. Prima Orth.31~20 CZ~B~O~(OH)~.9 199. I4tlomd Trig.103 4.18 13.32 504.1582 15.50 172.225 10.335 146.221 4.020 44.77 201. P63lm Hex.264 6.574 58.355 5.11 5.31 520.844 10.

23 360.05 182.5566 5.67 55.6 171.9632 6.929 18.2086 9.CZlm Tric.~?$/Q Mono.473 4 4 4 4 4 2 4 2 1 4 4 7.72 346.4883 1.1900 9.+ALtaSixO&OH)2 CaBSi CaBSiOd(OH) BE$eB2SizOto FeA12Si05(OH)z MgwWit.036 10.959 91.001 5.10 109.77 101 .401 5.088 2.40 90.748 53.ooo 4 9.2718 10.09 652.6042 6.96 3. Tetr.564 50.80 257.465 52 52 53 53 70 570.566 9.1 1704.0 342.8381 10.05 90.I 484.6640 3.Sr)FeAl2Si30r~(OH) CaBE(Al.079 .8 97.5 142.7113 7.8404 20.97 orth. Orth.674 197.72 1312.341 51.11 470.30 10.6 565.1328 6.999 5.13 108.221 2.565 3.3984 8.5 413.f21/m Mono.11 3.661 3.795 9.220 92.645 2.499 19 152 45 258.4 ortb.472 18 13. Orth. funa Mono.46 90.336 3.64 Ten.f&lc Mono f&/a Tric.9796 5.616 3.73 136.668 6.00 162.0 89.?AlAiSi@ Ca2MgSi207 and Cyclosilictaes CaAizSiz07(OH)$I20 Be3Ai2SieOtx MgzA4SisOts 314.252 9. 196.4 624.74 138.5741 8. Mineral Fonnula Formula Weight Crystal System Space Group Stlucture z a Y 8.226 3.68 139.11 106.96 2 2 8.6651 4.155 10.2 212.03 1111.2 214.786 90.05 162. Tetr.150 10.486 19.221 52.36 454.f2t/m Mono.321 4. Orth.55 445.12 110.50 114.122 7.41 454.583 5.195 41.13 39.212 2 8.7104 4. R7 RI Rj Pnnm Pbam PI Pbnm fhm Wiilemite Willemite Willemite Andalusite Sillimanite Kyanite Topaz Norbergite Chondrodite Hurnite Clinohumite Staurolite Titanite Datolite Datolite Chioritoid Sapphirine Prehnite Pumpelieyite Axinite 18 12. fhm Mono.51 324.069 4.334 9.7408 4.82 593.30 210.608 7.356 615.646 8.12 3.493 2.492 3.41 302.6 569.55 88.54 2.0 343 .10 8.2539 10.6 19 2.6 1577.6560 6.832 7.60 321.995 5. Crystallographic Properties of Minerals (continued). fi 115.fZ& Orth.62 69. Tetr. Tric.0513 5.25 359.2501 16. c2/m Mo~o.565 5. Orth.197 52.662 91.0860 5.158 3.89 1554.266 2 1 2 4.69 462.61 37.7774 5.159 3.259 3.I6 203.5125 7.7284 4.8526 13.23 354.3188 6.338 108.2386 3.908 3.77 115. Trig.559 5.035 44.94 370.29 293.1426 3.06 100.19 136.894 9.916 6.006 2.0 203.10 222. fa21rn fZ21m fZ2lrn Meiilite Melilite Meiiiite 2 2 2 7.236 260. Tetr.1517 904.36 416.20 152.5 251.401 45.36 590.31 101.8 1415.945 4.6635 5. 2 lO.06 159.67 5.383 4 17.270 38.835 5.2 Tetr.636 4.53 98.99 101.185 95 212 222 115 Phenacite Willemite Eucryptite Ahminosilicate Andalusite Sillimanite Kyanite Topaz Humite Group Norbergite* Chondrodite* Humite* Clinohumite* Staurolite* Other Ortbosilicotes Titanite Datolite Gadolinite* Chloritoid* Sapphirine* Prehnite* Pumpelleyite Axinite Sorosiiicates Epidote Group Zoisite Clinozoisite Hancockite* Allanite* Epidote* Melilite Melilite* Gehlenite* Akerrnanite Olher Sorosilicates Lawsonite BUYi Cordierite’ Monof2tlb Oh.94 604.7476 7.15 9. Pztlm Mono.786 9.46 4 11.142 9.E)2 Mg3Si04F2 MgstSiOdzF2 MmMW3Fz MgdSQhFz Ee.30 97.2 454.15 3.6275 10.6808 7.960 4.Table 1.Si3)0to(OH)2 C~(Mg~eAl)AlaSi~~O~42(0H)r~l915.927 8.151 Pi Mono.57 141.9 690.56 125.696 7. fxm Mono.483 5.8877 5. f&lb Mono.831 1.502o Ca2Ai(Al.70 196.761 5.517 2. Tetr.91 307.1 HFeCa&BSbOra & Cyciosiiicates Cafil&Otz(OH) Ca2Al$Si3012(OH) Ca(Rh.44 332.7441 7.30 1014.324 241 207 97 233 233 233 242 13 74 183 186 209 213 63 148 88 149 170 172 220 183.14 77.1 330.24 537. Irlllumd 14~lumd 14tlumd 14@zd Zircon Zircon Zircon Zircon 4 4 4 4 6.9031 1.24 234.199 8.6204 8. ccmm P6lmmc ccmm Lawsonite Beryl Betyl 4 2 8.010 294.91 985.787 48.05 162.7980 1.21 423.82 126.Fe)$i30t2(0H) Ca~FeAl#i30t2(0H) Group CaNaAlSizq Ca.841 13.186 3.97 458.1262 4.48 305.51 584.140 63. orth.944 134 135 116 454. (“1 Type (A) Density Ref.971 18 13. Hex.912 3.730 5.0 412.50 14.82 614.8713 7.6344 7.391 Trig.4 114. Trig.8520 8.f 2t/m Zoisite Epidote Epidote Epidote Epidote 4 16.819 2 8. Unit Cell Molar Vol (A3) Vol (cm3) (calc)(Mg/m3) Zircon Zircon Hafnon Thorite* Coffinhe’ Wilhife Group ZrSiO4 HfSi04 ThSiO4 USi Group BezSi04 ZnzSiO4 LiAlSIO4 Group Al2SiOS AlzSi05 A12SiO5 Al$i04(OH.823 3.2580 10.83 143.

Ci 379.054 10.819 9.37 832.204 4.966 9.79 Oh.740 1725.531 18.69 939.160 5.32 102.60 438.11 Tric.8 Tric.26 Mono. (X/m Mono.533 Chain Sillfates EnstotifelFerrosilite Group EIlStatik f+ww6 Ferrosilite Fe#i& Clinoenstatite MgzSizOs Clinoferrosilite Pe2Si206 Clinopyroxme Group Diopside CaMgSi& Hedenbergitc CaPeSi Jade& Ntilsi206 Acmite NaFeSizOs Cosmochlnr NaCrsi206 Spodumene LiAlSi206 Ca-Tschennaks CaAlAlSiOs Pyroxenoid Group Wollastonite CajSi3Og Bustamite* GaPe.423 8.7 273. Crystallographic Properties of Minerals (continued).941 62.PUa 853.209 9.90 Mono Calm 864.5 Tric.039 67.2818 5.55 788.18 104.62 244.386 5.06 100.14 23 1.237 5.652 5.54 Tric.155 20.92 104.jO22(OH)2 Anthophyltite* C%sFez)Sis022(OH)2 Cummingtonite* ~MgsFez)SisOzz(OH)2 Tremolite* ~a.15 186.80 259.018 7.60 140.508 64.179 5.048 18.58 450.CZlc Mono.63 104.56 107.19 18.268 10.16 506.82 940.579 9.926 7.54 108. P4/nnc structure Type Tounnaline Vesuvianite 2 a (A) (S.6 Mono.654 128. Pi 306.261 5.992 2 15.43 105.135 197 197 150 33 39 39 39 44 39 39 164 163 163 155 155 40 163 219 169 58 60 92 185 168 202. Pbca 200.455 8.85 418.63 100.56 100.285 5.66 115.994 7.98 389. P2tlc 263.70 107. C2lc Mono.C2/c Mono.82 487.46 90.616 6.P&lc 216. C2Ic Mono.8 902. Pi 867.185 20.94 Mono.910 9.564 8.29 105.541 17.52 382.005 3.814 3. Pm 843.9 271.024 8.9 274.722 8.245 5.239 58.845 9.022 17.676 65.305 7.0 136. Pi 917.21 90.737 Orthoamphibole 4 Onhoamphibole 4 Amphibole 2 Amphibole 2 Amphibole 2 Amphibole 2 18.036 152.% 870.67 99.592 3.53 99.721 7.CZ/m 789.603 10.125 99.776 2.27 96.09 106. 3 15.116 3.67 94.892 66.14 112. Mineral Tourmaline* Vesuvianite* Fotmula Formula Crystal Space Weight System Group Trig.56 94.31 744.460 9.6 480.CUc Mono.002 3. C2Ic Mono.946 Bustantite Rhodonite Pyroxmangite Aenigmatite Pectolite Petalite 4 2 2 2 9.83 1M 1M 10.65 Talc Talc 1M IM =41 2M2 2 2 2 2 4 4 2 2 5.84 812.347 10.s(Mg$ez)A12Si.20 5.851 7.318 3.171 2 10.429 66 6 NaFe~Al&S~0~7(0H)~ 1043.324 9.184 3.3 385.09 89.076 8.173 8.9 3.111 3.9 417.308 5.231 6.899 9. Prima 843.980 11.42 107.36 437.5 144. C2lm 823. n/c Mono.427 4 9.701 17.560 9.10 Orthopyroxene Orthopyroxene Clinoenstatite Clinoenstatitc Clincpymxene Clinopyroxene Clinopyroxene Clinopyroxene Clinopyroxene Clinopymxene Clinopyroxene 8 18.35 82.0872 8.279 3.825 9.190 9.55 2.188 4.22 9.937 3. CL/c 4 4 4 4 9. Ci Tric. Ii 655.52 141.21 115.56 248.438 2.596 63.79 105. R3m Tetr.64 453.516 3. Vol (A3) Vol (cm3) (calc)(Mg/m3) 1592.44 Mono.752 3.09 218.312 5.55 113.09 10.20 427.86 Mono.35 83.825 2.863 9.72 401.30 579.CZ/m 100.295 101.2 434.227 8 18.14 909.606 63.813 7.1 Mono.28 100.656 3.04 5.30 92.176 3.93 90.CVc Mono.04 764.9 262.5 2841. Ci 360. Pi 332.190 11.09 174.tAl#i&22(OH)2 Glaucophane* Naz(FeMaAlrSisOn~OH~~ Sheet Slllctaes Talcand Pyrophyllite Talc &s%OldOH)z Pyrophyllite A12Who@H)2 Trioclohedral Mica Group An&e* KFe3(AlSi@t0(OH)2 Phlogopite* KMgfi&OldOH)2 Lepidolite* KAlLi2AISi30t0(OH)2 Lepidolite* KAU&AISi30tdOH)2 LepidolW KAlLifiISi3Oto(OH)2 Ziiwaldite* K(AlFeLi)AlSi3Otu(OH)2 200.65 1765.31 Tric.51 9.218 5.867 60.38 466.165 3.609 110.C2lm Mono.3 CatgFezMgAltoSitsqo(OH.77 425.395 8.87 95.78 103.71 62.Table 1.06 419.053 5.85 429.F)s2935.63 224.10 128.68 100.795 8.44 83.63 146. Pbca 263.15 421.778 m Y (“) Unit Cell Molar Density Ref.104 11.58 99.46 91.2 385.994 65.188 5.8 319.096 .461 9.888 2.215 2.14 3.741 18.8 265.79 Mono.290 5.274 7.341 3.01 9.~C@WWzz(OH)z Pargas&* NaCa2FeMg.023 5.251 5.60 912.87 141.2284 5.986 175 125 94 94 192 193 194 82 511.746 9.7085 9.406 2 11.872 2.13 125.626 4 4 4 4 9.296 9.2 3.294 5.445 118.23 Orth.223 5.630 5.49 875.08 227.72 Mono.01 3.C2/m 4 10.C2/m Mono.33 5.86 Orth.749 3.4 Tric.33 108.249 5.869 2.08 99.013 18.658 9.263 3.791 2.140 9.20 348.49 358.94 orth.2 385.18 98.16 Tric.124 2.dSi309 Rho&mite MqSisOts Pyroxmangite Mn7Si70a Aenigmatite’ Na@5TiTiSkOzo Pectolitc’ HNaCa&Q Petalite LiAlS&Ote Amphibole Group Gedrite* Na. 7.7 421.

625 109 108 24 22 22 86 144 Dickite Kaoiinite Amesite* Lizardite* Tektosiiicates Silica QuGroup 5.909 2.862 9.3 387.785 12.16 258.925 14.996 l2.478 25.1 Mono.C2/c 60.610 110.208 14.38 90.425 100. I4llacd Trig.132 2.33 932.045 7.221 2.832 4.C2/c Mono.70 90.558 199 2.48 719.09 5. Crystallographic Properties of Minerals (continued).75 113.194 12.587 13.085 Mono.1918 5.1464 12.627 13.36 375.61 115.937 14.0 2827.9448 7.822 329.7 1103.91 115.721 13.1 1030.028 12.CZm Mono.70 8. Tetr.688 20.4cm 158 Leucite Kaisilite Nepheiine Meionite* Marialitef Zeolite Group AnaIcime* Chabazite’ Mordenite* CIinoptiioIite* Heulandite’ Thomsonite* KAiSizOe KAiSi04 KNa@J&tOts Ct&&jSi&&@ NaqAI.2 2257.6651 8.347 103.218 2356.657 26.047 116.679 2. Unit Ceii Molar VoI (A3) Vol (cm3) (calc)(Mg/m3) Dioctahedral Muscovite* Paragonite* Margarite” Bityite* Chlorite Mica Group KAi~ISi30tc(OH)2 NaAi~AiSi~Oto(OH)~ CaAifilSi30tu(OH)2 Ca(LiAi)z(AIBeSiz)Ote(OH)2 398.34 218.215 7.7 277.2 Mono.065 2.061 3.69 8.757 2.494 4.11 115.09 Coesite Tridymite Cristobaiite Stisbovite Feldspar Group SiO2 SiO2 SiO2 SiO2 SiO2 KAISi& KAISi30s KAiSisOs NaAiSigOs NaAiSi& CaAI&Os BaAi2Si2Os Group 60. Cmcm Mono.76 2110.1554 5.4052 7.0153 20.085 Mono.374 7.898 19.167 17.4 499.325 4 4 2 4 1 8.Table 1.177 2.778 2.059 13.1790 2.621 2.173 8.058 9.561 31 2.7 671.40 332. W&nm 278.16 278.738 103.599 2.39 115.227 9.991 25.19 93.4 1698.085 Tetr.221 99. P31m Chlorite-IIb2 Chlorite-IIW Nacrite Dickite Kaolinite Amesite Lizardite IT 2 5. CZm Chth Pncn Analcime Chabazite Mordenite Heuiandite Heuiandite Thomsonite 20.C2/c Mono.085 Trig.8287 19.978 6.4 2750. Mineral Formula FomntlaCrystal Space Weight System Group structure z a Y Type (4 (“) Density Ref.25 158.33 262.8 258.3 339.283 117.01 548.16 9.23 278.159 14.054 100.060 90.Cc 60.178 5.33 278.16 258.83 116.23 262.611 17.834 2.110 7.01 115.640 2.33 96.327 14.C2/m Tric.3 88. R%I Ortb.452 loo.jO~Cl 218.8 555. Hex.831 13.9 863.735 15.283 108.557 7.54 722.319 5.68 91.12 664.8 2487.Cc Tric.636 2. Cl Trig.65 93.128 5.Cc Mono.595 8.156 15. Hex.13 129.01 90.700 104. Ci Tric.C2/c 2Mt 341 2M2 2M1 4 4 4 4 5.00 699.89 843.327 2 5.0 1263.69 107.14 210. Ci Tric.588 2. C2/c Mono.0457 8.261 1336.602 2.1 2132.C2/m Mono.4 724.48 22.1934 5. I4tla P63 P63 P42/n P42ln Leucite NepheIine Nepheiine Scapolite Scapoiite lb 2 2 2 2 1 1 1 1 1 4 13.621 89 2.993 12.941 17.373 139 178 64 131 132 NatsAIt&20g~i 6H2O Ca$i&sOw i3HzO KsAi&~Oga24H20 KNa$J+Ai&+&~24H20 Ca4Kdh%&n26H20 NaCa2AisSis02cbH20 3526.56 877.I.633 17.721 99.90 2. f4t2t2 60.61 178. Ci Mono.93 2585.869 13.89 89.4048 91.24 700.jSi. PI Tric.3 384.909 3.948 4.648 2.165 228 3. Ten.763 19.461 2.909 5.17 584.2 172.529 7.82 8.610 234 2.3796 7.46 116.318 4.O 1284.33 278.?/c Coesite Tridymite Cristobalite Rutiie Sanidine Sanidine Sanidine Albite Albite Anorthite Anorthite 3 16 48 4 2 4 4 4 4 4 8 8 4.9 3620.1829 18.161 8.332 9.33 126.35 1466. 200.17 46.94 116.CZlm Tric.264 2.3 399.358 90.192 7.179 7.24 87.287 8.111 95.35 95.599 2.017 108.430 13.19 1123.39 933.440 2.69 60.233 658.560 8.46 95.22 87.234 14.697 113.27 7.142 8.47 Mono.148 8.089 13.788 108.571 47 2.%4 12.075 7.875 12.13 720.09 338.53 94.85 99.74 94.049 187 129 83 130 Group Chlorite* Chlorite* clay Group NWXite 555.408 120.26 2.561 8.9 138 37 153 211 4 5 .803 18.96 688. Ci Tric.715 13.400 7.51 858.1038 5.75 8.5 Tetr.98 2.8 Tetr.95 662.07 667.26 2.085 Tar.3 1557.57 210. f322l 60.165 14.27 89.287 127 210 ill 173 20 Sanidine orthoclase Micro&e High Aibite Low Aibite Anorthite Ceisian Fekispathoid 90.32 140.269 2.2 2097.81 97.57 132. Pi Mono.2 2819.

030 40.097 I .40 124. Unit Cell Molar Vol (A3) Vol (cm3) (calc)(Mg/m3) 600. 2252. Ericnite* Cancrinite* Pollucite* Brewsterite* Formula Formula Ctystal Space Weight System Group structure ‘be z a (A) 14. Imma 209.622 6.93 2.508 1 13.2 90.117 17.740 18.315 2.0 996.8 2050.749 186.138 8.839 2.336 2.085 60.5591 11.868 14. Cub. Fdd2 Natrolite Cub.5 15142.09 Mono.2 NaKMgfil7Si2gQzlBH20 2590.56 558.187 20. lmmm Ferrierite Cub.340 104.5 CaA1$%401~4H~O 470.81 NgKMgAl$%3t@Zl8H20 2614.985 37.455 7.50 Cub.657 14.581 1 10.326 2 8.26 538.06 SrAlfiis01~5H20 656.638 6.668 13.6956 6.159 24.394 184 184 202 174 133 71 107 141 140 226 9 72 79 18 80 201 81 156 10 00 B 4 Ba$a.7754 6 4.02 1356. Cub.71 203. P21/m Phillipsite Mono Am Laumontite Orth.5Cal.05 96.12 2.22 Ca&IsSia032.23 NqA13Si301~CI 484.946 7.21 611.62 696.74 I 13.34 179.6 Nal.10 1458.9 1011.848 5.3 697.614 5.0449 8.810 5.4380 8 5.3796 2 4. FezSiO4 NizSi04 CqSiO4 SiO2 SiO2 741.6 423.7284 32 11.&0~16H20 1090. 172.146 2.3Ca4.5 538.252 I 12.4729 5.96 520.0894 13.44 NazA12Si30te2H20 380.182 14.445 26.6983 11. P4dmnm 16 7.9292 10.354 28. C2lc Tetr. F&m F&m Fa.017 3.h PhsB AnhB PhsB Perovskite Ilmenite Garnet Wadsleyite Wadsleyite Spine1 Spine1 Spine1 Spine1 Coesite Kutile 4 10.238 2.1 1235.12H20 1291.590 16 13. 2292.P2rla Fenierite Orth.@~~l.223 2.2 169.~AIleSi2C.073 10.6651 120.968 4 4.54 1518.236 16 24.988 58.273 2.989 2.3 26. C2lm Stilbite Mono Fd Natrolite Tetr.3 NqCaAl.764 2.8 1155.346 2.23 2. 141/a 140. hi2d Natrolite Edingtonite Tetr. Y (“) Density Ref.791 22. F&n Sodalite Hex.085 Mono.470 7. fmma 140.40 Chth. Crystallographic Properties of Minerals (continued). P21lm Brewsterite 1 9. P21/c 864.4 2561. Cub.3 1015.097 2 5.1829 2.287 59 59 166 103 102 7 104 151 196 236 236 151 210 20 Wadsleyite I%-Co$S iO4 Silicate rM8zSQ Spine1 Group 8 5.524 8 8 8 8 8.072~34H~02968.86 2210.24 1982. CaAl~Si30te~3H20 392.072 6.23 152.526 9.4 835.229 14.870 1 13.909 4. Pmcb 619. Mineral Harmotome* Phillipsite* Laumontite* Natrolite* Sodalite* StiIbite* ScoIecite* Gonnardite* Edingtonite* Gismondine* Garronite* Merlinoite+ Ferrierite* Fetrierite+ Faujasite.95 Ortb.527 14.1 203.40 90.8969 13.511 39.64 8 18.9 MgNaKZCa2AlgSi~707~18H202683.886 I 19.2 910. lzm2 olth.234 8.3 111.~Na&leSi.6 2256.34 Na&qAlgSitt0~12H~O 1626. P21/m Phillipsite Mono. P21la Gismondine Gismondine Tetr.96 618. Pnnm 100. Pbnm 100.54 N&l KCI NtiF KF 58.61 10.06 1024.490 14.5Al$itt03~12H20 1466.04 Ba2A14SisO2e8H20 997.169 1.291 4.048 8.4 702.16 1331.879 1 9.1790 7.6C02 1008. Fmh F&n Fdm Far% Halite Halite Halite Halite 4 4 4 4 5.024 1 9.2 z1 E X ii P 2 8 m 3 2 In F rA High Pressure Silicates Phase B Group Phase B Anhydrous B Superhydrous B MgSiO+roup MgSiOg-perovskite MgSiO+lmenite MgSiOs-garnet Wadsleyiie Group Ww-%%KW2 MmSidh bmWhdOW4 MgSi03 MgSiO3 MgSi03 MgzSiO4 CqSiO4 Mg#iO.549 8 18.jSireG3~13H~O 1312. la?d Analcime Mono.27 6.107 3.95 209.21 1 9.306 2.1464 12.2566 8.78 Orth.17 Mono.100 Cub. Cub.162 92.327 4.588 14.40 Grth.515 41. Cub.9266 1 14.443 2.16 162. P63 Cancrinite Cub.044 y-Fez%04 y-Ni2SiO4 *02SiO4 Silica Group f%%n Coesite Stishovite Halides Halite Sylvite Villiaumite Carobbiite 60.493 42.09 NaCa&I.116 1 18.914 2.28 2000.92 1205.9 1349.563 4.41 274.652 18. Pii3n Sodahte Mono.581 40.76 46.48 1193.567 25 1.166 1. Cub.443 74.527 6.00 360. Immm Merlinoite Mono.16Hfl 1401. PTi2lm Mono.480 8.0 90.729 94.832 10.98 98.8 124.71 orth. P63lmmc Erionite Hex.300 14.174 5.380 3.139 14.81 630.1 Car.3031 9.195 2.0 90.237 2.810 3.555 41.35 262.753 11.24 18.178 2 5.40 Tetr.40 Trig.0 570.981 8.626 14.5 609.767 90.5 CsAISi#s 312. RJ 100.22 248.92 524.383 3.978 2.601 11.12 K&afilgSi~0~24H20 2620.gAlgSit0032.501 4.7 K2.Table 1.87 210.6 599.120 2.513 3.628 39.435 3. 128.14 552.682 2 6.283 548.49 219.865 4 7.693 8.78 209.044 3.53 235 235 235 235 .

Fm%r Tetr. Ptqlmmc NiAs 2 Cobaltite 4 Onh. lm3m Argentite 2 Trig.69 229.044 5.688 24.60 159. Crystallographic Properties of Minerals (continued).84 215.49 Fe7% FeSz Cd2 NiSz Fe& FeS (kWgS11 CuFeS2 CuFezS3 cus cu2s Cut2FeZnSb& CusFeS4 Cu3AsS4 Ni4s CoAsS zns zns CdS NisFe& MnS PbS PbSe PbTe Md2 ws2 h.862 7.9 1113. P21/n orth.2607 6.801 5.571 21.5 87. Pd Pyrite 4 orth.5385 5.45 114. Fdm I talite 4 Cub.811 4.02 239.93 1013.98 123.186 4.93 157.04 696.491 335.440 11.2 2521. F&m Hex.7938 15.780 23.269 232 180 101 101 101 101 101 101 101 62 29 162 162 30 117 221 84 218 56 51 179 122 2 240 71 239 119 235 87 224 160 160 160 28 203 190 41 55 55 14 13 223 143 154 4 4 2 2 2 4 4 2 4 5. P3t Pyrrhotite 3 Cub.1532 4.076 7.92 247.822-l 4.95 104.436 5.79 881.06 159.154 5.80 393.3 183.323 9.1964 4. P42/mnm Tetr.482 32.i3m Sphalerite 4 Orth.494 24.789 4.285 8.660 4.77 227.72 9.408 7.48 11.582 6.509 35.44 92.418 Y (“1 Unit Cell Molar Density Ref.68 34.Table 1.824 20.1348 10.4541 3.28 467.06 122.65 90.475 9.32 234.129 64.407 6.43 95.294 12.884 10.199 26.676 89. PcaZl Cub. Pcmn Cubanite 4 Hex.168 5.860 30. F&-m IT&e 4 Cub.40 5.093 152.45 5. Fdm Cub.98 89.676 3. Pa3 Pyrite 4 Cub.39 28.1213 6.79 160.180 4.69 246.85 106.19 339.69 8.35 12.062 3.8613 5.14 1660.26 141.45 18.202 7.94 3.302 3. Pcmn Cub.222 4.256 90.63 57.482 40.PZt/c Chaicccite 48 Cub.222 70.15 334.467 11.18 226. P63mc Cub.95 25.95 357.447 27.77 237.619 5.453 20.853 34.464 773.189 23.950 21. Ia33m Tetmhedrite 2 Orth. Fq3m Sphalerite 4 Cub.363 5.90 23.7490 116.494 10.633 8. R3c Proustite 6 Trig. Prima Stibnite 4 Mono.436 3. Pd Pyrite 4 Cub.950 6. 14/mmm Mono.167 215.434 97.80 494.65 232.077 175.88 81.571 17.999 7.639 3.754 34.381 11.5 501.035 5.07 43.84 159.839 3.60 7.556 4. F.344 31.68 .86 10.503 7.496 125.89 1.-2H2 Mono.418 5.57 447.977 4.PZl/c Acanthite 4 Cub.80 247.730 4.17 98.98 23.97 203. Vol (K3) Vol (cm3) (calc)(h4g/m3) 162.236 7.58 5.614 8.23 99. Mineral Fluorite Frankdicksonite Sellaite CdOIllel Cryolite Neighbceite Chlorargyrite Iodyrite Nantokite Sulfides Pyrrhotite Pyrite Cattierhe Vaesite Marcasite Troilite Smythite Chalcopyrite Cubanite Covelllite Chalcocite Tetrahedrite Bon& Enargite Niccolite Cobaltite Sphalerite Wurtzite(2H) Greenockite Pentlandite Alabandite Galena Clausthalite Altaite MolyMenite(2H) Tungstenite Acantbite Argentite Proustite Pyrargyritc Cinnabar Metacinnabar Coloradoitc Stibnite Orpiment Formula CaFz BaF2 MtPz HszCh Na3AIFs NaMgF3 AgCl AsI CUCI Formula Crystal Space Weight System Group 78.861 x. Pbca Bomite 16 Orth.84 119.329 17. F&m Halite 4 Hex P63lmmc Molybdenite 2 Hex P63/mmc Molybdenite.963 3.51 136.010 4.569 88.785 7.11 173.01 4.09 486.460 6.72 541.78 5. F&m Halite 4 Cub. P&‘l Cinnabar 3 Cub.423 6.8341 11.161 4.085 4.6865 5.09 209.770 6.217 73. F&m Halite 4 Cub.44 267.058 5.903 67.097 4.246 11.069 4.33 105.37 268.550 5. lji2d Chalcopyrite 4 Orth.95 139.145 5.91 66.11 25.51 271.83 40.34 10. P21/n orpiment 4 6. Pmt12~ Enargite 2 Hex.434 144.582 27.25 98.335 4.93 79.63 165.4053 3.906 4. Pnnm Marcasite 2 Hex.44 119.8717 6.68 2190.437 4. Fz3m Structure Type Fluorite Fluorite Rut& Calomel Cryolite Perovskite Halite Wurtzite Z a (A) 5. Pbglmmc Covellite 6 Mono.537 40.289 6.024 4.309 472.s AgzS AgsAsSj has% HgS H@ HgTe SW3 As2S3 Trig.084 4.894 3.096 1.04 Cub.628 5. PT2c Troilite 12 Trig RTm Smythite 1 Tetr.911 855.1602 3.3 296.82 Il.248 34.117 3.582 5.134 4.34 62.i3m Sphalerite 4 Hex P6pc Wurtzite 2 Hex P63mc Wurtzite 2 Cub.078 10.582 5.06 920.341 13.231 16.423 34.361 30.I5 208.364 10.80 133.594 5. F.231 6.07 247.42 14i.30 143.25 286.414 4.55 232.04 169.676 5.20 361.214 5.29 202.99 647.930 4.54 171.08 291.9315 6.89 183.92 91.4651 5.021 31.422 3.65 328.270 4.953 5.526 8. R3c Proustite 6 Trig.

194 8.10 205. F&n 63.38 34. Fm% 208. F&m 190. Rsrn 118. IO7 3.1499 106. Fn&n 14.070 10.5475 3.32 212.736 6.2743 5.168 4 3. MiIlemI Re&ar Bismuthinite Hazelwoodite COOperitc Vysotskite Millerhe Linneaite Polydymite Violarite Greigite Da&reel&e Loellingite Arsenopjrite Native Elements Diamond Graphite Silicon Sulfur(a) SUWP) Kamacite Taenite Nickel Copper Arsenic Tin Ruthenium Rhodium Palladium Silver Antimony Tellurium Iridium Osmium Platinum Gold Lead Formula AsS Bi$$ Ni& PtS PdS NiS t&s4 Formula Crystal Space Weight System Group 106. F&m 121.522 8.570 21.374 181 120 832. F&m 196. Cub.15 240.? 2 bl iz C C Si S S Fe FeNi Ni CU AS Stl Ru Rb Pd 43 Sb Te Ir OS Pt AU Fb Bi 12.87 Cub.214 18.910 8. Cub.2A 129.16 68.424 11.172 8.99 514.690 Tetr. Trig.09 Cub. Mono.921 4.285 11. Pbj/mmc 28.17488 4. Cub.80 288. Fdh 12.832 205 7.967 Cub. Crystallographic Properties of Minerals (continued).175 3.891 5.456 4 3.61496 18 3.C2l/d Realgar 16 9.489 8 9.870 48 10.340 7.458 19.52 295.8898 4 4.981 11.493 10.465 Cooperite 8 6. F&m 207.011 Cub. Fdh 32.312 Y E n P) 6 $: X n” ij .329 2.064 Mono.499 4.07825 4 4.16 3299.46 90.080 998.086 Cub.093 13.41 21.76 41.43070 128 10.98 160.25 20.7598 4 5.723 49 238 %2.93 63.113 4.553 22.406 Spine1 Spine1 8 9.329 12.4163 5.4 16.500 6.82 56.23 180.731 252. P63/mmc 195.92 10.52387 4 3.94 349.268 21.521 89.790 95. f4tlamd 101.885 2 2.8197 2 2.54 27.546 9. Fmh 107.60 27.5158 2.305 89.86225 45.839 4.7056 4 3.587 11.261 12.29 3.50 40.2 62.806 235 235 235 235 78 235 235 235 235 200 235 85 235 235 235 235 235 235 235 235 235 235 .9838 Arsenopyrite 8 6.064 Orth.75 Trig.443 16. Pmcn R32 P4~mmc P42/m R3m F&n Fd%n F&m F&m F&m Pnnm StNCtUR z iJ 5~ (4 8.41 23.104 6.06 304. Fd&i 32.1 FeAs2 FeAsS Trig.456 8 5.83 121.590 7.652 4.40 Cub.3190 11.070 Hex.465 Spine1 Spine1 8 9.875 8 9.55 368.06 101.427 9.8394 2 2.15 30.459 Ni& FeNi$$ Fe& FeCrts. orth.283 9.01 60.8031 4 3.9505 6 4.20 Cub.441 8.922 Trig.459 6.059 10.281 2.655 5.075 20.746 17.189 68 26.995 Spine1 Loellingite 2 5.572 6.869 4.7352 4 3.092 10.54590 6.98 60.263 8. P63/mmc 102.557 Cub Ft&n 58.60 Trig.56679 4 2. Cub.132 49 854.321 16.011 Hex.39 301.PZl/n Orth.69 162.002 7. P3t21 192.076 2.932 17.696 24.77 305.926 10.29 22.2803 Il.467 12.6190 Milkrite 8 9.5 1276.649 Unit CeII Molar Density Ref.38 89.342 9.058 15.83 Mono. RTm 127.451 2. Tetr.016 7.412 136 91.326 49 847.873 8.26 227.0718 Hazelwoodite Cooperite 2 3.14 55.325 13.571 Stibnite 4 3.29 43.190 Cub.905 Cub.Table 1. R%n Dimmnd Graphite Diamond Sulfur Sulfur a-hm Taenite FCC FCC Arsenic Tin HCP FCC FCC FCC Arsenic Selenium FCC HCP FCC FCC FCC Arsenic 8 3.459 67.3001 5.97 72.242 22.273 18.3083 3 4.311 3.554 110 501.8665 32 7.8821 5. 6.540 Cub.368 12.710 Cub.847 Cub /m& 114. Vol (A3) Vol (cm3) (calc)(Mg/m3) 154 799.48 6.15 138.539 6.864 6.980 Trig.0862 6 4.67 75.4 64.9231 4 4.20 Hex.806 171 89. Tetr.429 9 9.50 75. P2t 55.292 35 27 273.12 107.147 4. F&m 106.38 67. Cub.910 13.611 3.

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X9-550. Heger... Monat.. 1961. 239. R. Neues J. Schuster.. 1967. 13. F. Schuster. . Zachariasen. Mineral. Zobetz. 1977. 242. 1972. T.. Se. 240. Verfeinerung der Struktur von Malachit. Joswig. 245. 1161-1166. Yamanaka. Kristallographiya. Strukturbestimmung eines OH-reichen topases. Zigan.412-426. 241.. Mineral. Tokonami. Geol. 6. Cristallogr. 1979. F.SMYTH AND MCCORMICK 17 par processus hydrothermal. Mason. B41. A. H.. 16. 1971. and H. W.D. Yund.. Zigan. and S. Voellenkle.5.. W. and M. Akad. The anharmonic thermal vibration in ZnX (X=S. Krist. 137-143. G. 298-304. and R. Z. Rothbauer.A.. Sot. Bull. CU~(OH)~(CO-&. 1273-1296. Phase relations in the system Ni-As. Be$SQ. Oest.. 94. H. Neutronenbeugungsmessungen am brucit. Te) and its dependence on the chemical-bond characters. E. 243. J. Krist. 244.D. Cuz(OH)zC03. Zigan. durch Neutronenbeugung. Wissenschajien. Econ.. 56. F. Acla Crysf. 145-147. 1985. 416436. and H. Refined crystal structure of phenacite. 1971. Z. Verfeinerung der struktur von azurit. 145. Fr. Zemann.

Cp. The purposeof this summary is to give.5. For solids. play a major role in iron-bearing minerals [321. INTRODUCTION Thermochemicalproperties of mineralscan be usedto calculate the thermodynamic stability of phases as functions of temperature. = &C. The values at high temperature may be compared with the 3nR limit as follows: Mg2Si04 (forsterite) 3nR = 175 Jmmol. amphiboles. in spinels (M2+-M3+ disorder over octahedral and tetrahedral sites) and in olivines. 1). Contributions to Cp arise from lattice vibrations. is given by Cp .Thermodynamic Properties of Minerals Alexandra Navrotsky 1. is the temperature derivative of the enthalpy. estimatesof uncertainty are given. a = thermal expansivity = (l/V) (aV/aT). / TNT (1) AGU Reference Shelf2 Copyright 1995 by the American Geophysical Union. The Debye temperature is typically 800-1200 K for oxides and silicates. Cp. Thus the Dulong and Petit limit gives a useful first order estimateof the high temperature heat capacity of a solid. 18 . Cp --> 0 (see Fig. Cp = (dH/aT)p. Cp at 1500 K = 188 J/K*mol. Department of Geological Materials Institute. Mineral Physics and Crystallography A Handbook Physical of Constants @V/aP)T. Electronic transitions are usually unimportant in silicates but may become significant in iron oxides and iron silicates at high T and P. and micas (cation disorder over severalinequivalent octahedralsites). in the author’sopinion. 2. but no attempt hasbeenmadeto systematically select values most consistentwith a large set of experimental observations. At intermediate temperatures. Cp increases sharply.electronic. irrespectiveof structural detail.Cv is on the order of a few percent of C.7. and from magnetic. 15. V = molar volume. The entropy. The magnetic contributions. where T = absolute temperature. useful data for anhydrous phasesof geophysicalimportance. namely 3R per gram atom. Cp . and that at constant volume. When possible. At high temperature. and bulk composition. Princeton University.311 contain detailed data. As T--> 0 K. The values selectedare. Table 1 lists heat capacities for some common minerals. important for transition metals.9. Cp at 1500 K = 191 J/K*mol. and increases with temperature. The relation between heat capacity at constant pressure.n the number of atomsper formula unit).. pressure. A number of compendia of thermochemicaldata [4.and positional order-disorder.Cv = TVa2/13. in short form. 19. HEAT CAPACITIES The isobaric heat capacity. Cp is then 510% larger than 3nR and varies slowly and roughly linearly with temperature(seeFig.the harmonic contribution to C v approaches Dulong and Petit limit of 3nR (R the the gasconstant. 18. For solids. s. reliable. 1). 1). 10. Order-disorder is an important complication in framework silicates (Al-Si disorder on tetrahedral sites). 16. MgA1204 (spinel) 3nR = 188 Jfimol. The vibrational heat capacitycan be calculatedusingstatistical mechanicsfrom the density of states.which in turn can be modeled at various degreesof approximation [20]. Princeton. and B = compressibility = inverse bulk modulus = -(l/V) A. Cv = (aE/aT)V. 13. Navrotsky. Thesefactors must be consideredfor specific mineralsbut detaileddiscussion is beyond the scopeof this review. pyroxenes. NJ 08544 and Geophysical Sciences Princeton and Guyot Hall. component fugacity. Cp is virtually independentof pressurebut a strong function of temperature (see Fig.

6 117.9 142.5 105.2 73.6 144.9 95. A form which ensuresproper high temperaturebehavior.3 530.0 325. must be added to this calorimetric entropy. a tabulation of coefficients is not given here but the reader is referred to Robie et al.5 190.2 82.2 82.8 26.1 145.6 124. Heat capacity of Mg2SiO4 (forsterite) from 0 to 1800K. arising from “frozen in” configurational disorder. The sharp dependenceof Cp on T at intermediate temperature makes it difficult to fit Cp by algebraic equationswhich extrapolate properly to high temperature and such empirical equations almost never show proper low temperature behavior.3 217.9 115.0 123.5 330. Entropies of some common phases are alsoshown in Table 1.4 202.9 87.2 129.5 187.4 214.3 277.1 207.2 1OOOK S” Q 51.9 80.1 155.8 146.1500 K.6 103.0 50.7 753.NAVROTSKY 19 T(K) Any “zero point” entropy.4 148. data from [311.9 698.7 206.2 133.4 243.5 253.1 103.1 55.1 157.1 50.6 243. 311.5 252.3 269.9 205. At 298 .5 87.9 48.2 131.8 474.9 180. 1311 Cp = A + BT + CT-O5 + DT-2 (2) gives a reasonablefit but must be extrapolatedwith care.1 65.Holland and Powell [ 15- Table 1.5 155. recommendedby Fei and Saxena[8] is Cp=3nR[1+klT-1+k2T-2+k3T-31+ A + BT + C p (disordering) T(K) (3) Fig. 1.0 85.2 192. Heat Capacitiesand Entropiesof Minerals (J/(K*mol)) 298K S” CP 37.2 55. an expressionof the Maier-Kelley form.7 248.7 350.8 127.1 67.3 99.0 471.5 232.4 213.5 143.5 79.0 1500K S” Q 53.9 121.3 312.6 401.8 121.0 390.9 79.4 122.2 124.5 201.5 160.5 91.2 83.1 178.1 506.0 307.3 533.8 491.4 191.5 175.3 63.5 166. [3 11.0 730. 132.5 82.7 773.5 375.6 269.2 222.12 57.9 .3 86.7 249.1 406.5 MgO (periclase) Al 203 (corundum) “FeO” (wustite) Fe203 (hematite) Fe304 (magnetite) Ti02 @utile) FeTi03 (ilmenite) Fb2TiO4 (titanomagnetite) MgAJ204 (spinel) Mg2SiO4 (forsterite) MgSi03 (enstatite) NaAlSi308 (low albite) KAtSi308 (microcline) Mg3~2si3012 @yrope) Ca3Al2Si3012 (grossular) CaSiO3 (wollastonite) CaSiO3 (pseudowollastonite) CaMgSi206 (diopside) Mg2Al2Si5018 (cordierite) CaCO3 (calcite) MgC03 (magnesite) CaMg(C03)2 (dolomite) Dalafronl [S.3 168.7 76. Because different authors fit Cp data to a variety of equations and over different temperature ranges.1 310.6 310.3 197.3 407.0 452.2 463.1 255.4 150.5 220.3 339.3 1126.3 1420.3 264.3 132.

291 347128.291 1~5PU91 1096W.291 131P&29301 5 16/m91 259/X291 167/28.291 1160~w91 -----217128. Heat Capacitiesof GlassesandLiquids andGlassTransition Temperatures Composition Cp glass 298 K J/mol*K 381311 17w 2 10[311 209[311 21 I[311 _____ --___ ----871301 33ou 460a higher temperalure data andfrom Cp glass (at Tg> J/mol*K 74 128.291 y&8.291 1065 1020 1118 731128.291 3 161XW 33~@8. a glass-forming system.291 SiO2 CaMgSi206 NaAlSi 308 KAlSi 308 CaA12Si208 MS2SiO4 Na2Si205 K2Si205 CaSiO3 Mg3A2Si3012 Mg2A4Si5018 aEstimated.291 321128.291 226/28. .from 256128.20 THERMODYNAh4ICS 500 L 400 liquid G 300 0 Tm 200 E + 0" 100 0 t 0 400 600 1200 1600 2000 4 300 600 900 1200 1500 1800 Temperature (K) Temperature (K) Fig. Enthalpy and heat capacity in CaMgSi206.291 __ __ __ __ 703/28>291 770128.291 comparison with crystalline phases.291 1221128.291 67@8>291 928[28.291 338128~291 LQL@W’I 268/11d21 263/28.291 Tg 6) 1~7128291 Cp liquid J/mol=K 8p. 2. Table 2.data from [21].

5 ----__--- .NAVROTSKY 21 161. MOLAR VOLUME.60 57. In glass-forming systems.23 35. For multicomponent glasses and liquids with compositions relevant to magmatic processes. The partial molar heat capacitiesof the oxide componentsin glassesand melts. to a useful approximation.45 400K 52. where A. 2.98 143.43 77.09 79.28 56.81 46.67 79. At Tg. and Fei et al.04 IOOOK 70.43 LiquidL22..20 62.6 98. be given as a sum of terms depending on the mole fractions of oxide components.heat capacitiesof liquids dependonly weakly on temperature.28.are given in Table 3. Si).65 70. [9j for such equations. Theserefer to the reaction aA + bB + CC + “/2 02 = AaBbCcOn and do] + bBOm +cCOn=AaBbCcOn (6) (3 respectively.96 78.and the volume and heat capacity increase. glass= 170 J/mol*K at 298 K.22 94.33I 1500K 82.64 84. Partial Molar Heat Capacities of Oxide Components in Glasses Melts (J/K*mol) and Glass/291 298 K SiO2 Ti02 A1203 R203 Fe0 MO CaO Na20 K20 B203 H20 44.22 120. For CaMgSi206 Cp.39 58. 256 J/mol=K at 1000 K.2 170. Ca. C are different elements (e.3 240. FORMATION ENTROPY.9 78. JANAF [18]. the viscosity decreases.8 97. 331. ENTHALPY OF Table 4 lists enthalpiesand entropiesof formation of selected minerals from the elements and the oxides at severaltemperatures.2 89.24 115.67 62.8 94. partial molar heat capacities are relatively independentof composition.63 75.6 109.e. The free energy of formation is then given by Table 3.74 47. Cl. reflecting the onset of configurational rearrangementsin the liquid [27].04 44. The heat capacity of the liquid is generally larger than that of the glass (see Table 2) and. 3.00 74.89 43. Al. B.92 79. 0 is oxygen. seeFig.66 96. 249 J/mol*K at 1000 K [213. Then Cp = CXi Cp i (4) where i is taken over the oxide componentsof the glassor liquid [22.. CpV.09 43.Berman [5]. the heat capacity of the glass from room temperatureto the glasstransition is not very different from that of the crystalline phase.56 84.17 42. crystal = 167J/mobK at 298 K.40 124.76 96. except for cases with strong structural rearrangements (such as coordination number changes).89 45. heat capacities can.g. and referencestatesare the most stableform of the elementsor oxidesat the temperaturein question. i.

7 151 -l9.2(181 -263.0[31] 222.1(311 4.1 1311 -4239.7 IsI -33.5f51 -1627.7 pll -3209.2[311 -50.5151 -313.4(331] -6317.4[51 -106.9[181 -173.7 (51 -81.0(31] -9200.51(181 -103.1552.8 I51 -266.6(311 -296.7 (51 -24.3L51 -X2(311 -38.0pi1 337.61311 -1211.6L5j -85.9151 -108.1 L311 .4f51 -3200.7 I51 -1176.0151 -335.6151 6.9 (311 -19.5L311 -756.9[3311 -43.9[181 410.5 1311 -321.3t311 -735.9 prl 12.01311 Fe2SiO4 (fayalite) CaSi03 CaSi03 (wollastonite) (pseudowollastonite) (diopside) CaMgSi206 NaAlSi 308 (high albite) KAlSi 308 (sanidine) CaA12Si2Og (anorthite) Mg 3N 2Si30 12 (pyrope) Mg2AlqSi5Olg Ca3Al2Si3012 (cordierite) (grossular) .9B11 -208.3[181 -J693.7151 -6632.4[311 -1624.7L311 -115.1 151 -1675.9(311 -79.61311 -3925.4 (311 24.9151 -1479.3(311 -1750.9 (3il -1472.6f51 -180.313’1 -6649.61311 -737.4151 -608.Table 4.2f51 -730.5 t51 -3924.0151 36.0 I51 -585.9 I51 400.3[181 -2182.8[311 -1.5 prl -74.1 I51 -5.0 (311 23.1 [I@ -903.5 I51 -283.41311 -60.1 1311 -764.7[31] -91.9 t311 -lOO.21311 -274.1(311 -85.8 [311 -3J9.31311 -744.0[311 -96.3 (311 -9.6L51 -70.0f1@ -174.5151 -915g.1m 39.9[51 55.4f51 -1545.3 (311 -155.9(311 4.6[18~ -332.3 1311 21.lPl -12.7 (51 -293.4(311 -4.2pI1 -67.7 I51 -6286.5[181 -634.6151 -l42.4[311 -278.1 f51 28.9 [311 0.2L311 -28.4151 -2.4[331/ -1631.4[181 -905.0L51 -1214.2[51 -33. Enthalpies and Entropies Elements of Formation of Selected Compounds and From Oxides from Compound 298 K AH kJ/mol Formation Es J/m01 K from Elements lOOOK AH AS kJ/mol J/m01 K AH kJ/mol Formation from Oxides 298 K 1000 K AS AH AS J/m01 K kJ/mol J/mol K MgO (periclase) CaO (lime) Al203 (corundum) -601.315] -1702.7 151 -907.3 i51 -2174.8[311 -3962.71311 -J214.7151 2.6[51 -146.2L311 -3959.5~5~ -635.6J311 -4228.6[31] -156.0L31] -579.7 f51 -910.9 (311 SiO 2 (quartz) SiO2 (cristobalite) “FeO” (wustite) Mg2SiO4 MgSi03 (forsterite) (enstatite) -2.8L51 -182.1 [lsl -63.5(3Jll -286.3[311 -1630.

(andalusite) A@.. for MgSi03 (enstatite) A%.298= -1. 3) are the basis for various “buffers” used in geochemistry. a thermodynamically reversible phase transition occurs with increasing pressure if the high pressurephaseis denserthan the low pressurephase Thus the phase boundary is a straight line if AS and AV are independent(or only weakly dependent)of P and T.TAS’. at the transformation temperature AG. A negativeP-T slope implies that AS and AV haveopposite signs. This reflects the large negative entropy of incorporation of oxygen gas in the crystalline phase. 02 02 2Fe304 112Fe304 .04 2NI 2co 2H2 6FeO 2C0 3/2Fe 2Fe c f * 02 f 02 . e. T) dP (10) At constant (atmospheric) pressure.Clapeyron equation (@‘/dT)equil= ASIAV (11) (9) At constant temperature.TAS.NNO (nickel-nickel oxide) and IW (iron-wurstite). Gibbs free energy for oxidation-reduction equilibria.Fe0 02 .cop 1800 800 1300 (K) Temperature Fig. and AO. . as is a reasonablefirst approximation for solid-solid transitions over moderate P-T intervals at high T.-TAS. data from [4.1 kJ/mol. 298 = -89.311.T)=O=AH. Fig.6 kJ/mol. = -35.solidstate transitions) in either the reactants (elements) or products (oxides).g. QFM (quartz-fayabte-magnetite). 4.Oz=AO. These curves (see Fig. Thus the equilibrium oxygen fugacity for a given oxidation-reduction equilibrium increases with increasing temperature. and volume terms is reached AG(P. + y O2 = AO. 02 .2CO2 02‘ . 3. entropy. The enthalpies of formation of ternary oxides from binary oxides are generally in the range +lO to -250 kJ/mol and become more exothermic with greater difference in “basicity” (or ionic potential = charge/radius) of the components. per mole of 02. Melting curves tend to show decreasing(dT/dP) with increasingpressurebecausesilicate liquids are often . Changes in slope (kinks) in the curves in Fig. . vaporization. and more reduced species are generally favored as temperature increases. a thermodynamically reversible first order phasetransition occurs with increasing temperature if both the enthalpy and entropy of the high temperaturepolymorph are higher than those of the low temperature polymorph and. 02 - 2NlO 2ceo 2&O bFc203 * 02 . An equilibrium phaseboundary has its slope defined by the Clausius. and the following balance of enthalpy. ox. Thus for A12SiO5.: ox.NAVROTSKY 23 AGo = AH’ . = 0 = AH. The free energies of formation from the elements become less negative with increasing temperature. (8) (7) 3) :6) :41 as a function of temperature. Entropies of formation of ternary oxides from binary componentsare generally small in magnitude (-10 to +lO J/mol*K) unless major order-disorderoccurs. ENTHALPY AND ENTROPY OF PHASE TRANSFORMATION AND MELTING (0 (2) (3) (4) (5) (6) (7) (8) (9) 4Fe.ox.+. 3 shows the equilibrium oxygen fugacity for a seriesof oxidation reactions A+. and for CaSi03 298 (wollastonite) AH. 3 reflect phasechanges(melting.+ P s 1 atm AV(P. .4 kJ/mol. 18.

51311 KAlSi 309 (microcline = sanidine) AH” (Wmol) 0.1 f 2.3L21 3. il = ilmenite.7 f 3.94151 561231 5:0[311 3.66 0.19[17J 30.8 f 2. pv = perovskite. y= -4.0f 2.5[11 49.0 + 0.002 0.8 + 5.47a.05[I] -6.5 f 1.39 -0.16a 12] -4.20[21 -4. /I = spinelloid spinel.06 -0.0 a Treated as though allfirst order.0 3.3 0.912J AV“ (cm3/mol) -3.39 -2.21 -0.4[1J -2.1+ 0.6 4.0 11.0[3J -2.83[9J -1. co = coesite.03 AV” (cm 3/mol> 0.109 -0.d91 51.37[51 1. AV is AV ‘298 for all listings in table.40 15.1 + 6.0 f -15. a = olivine.88[251 14.9 AZ 0.12 -0.16 1.24 THERh4ODYNAhIICS Table 5.3131 35.89[171 -3. for all listings in table.1 f 4.101 0.b 2. q = quartz.13L51 -0.l[IJ a AH and AS are values at I atm near 1000 K. gt = garnet. Enthalpy. -15. Entropy and Volume Changesfor High PressurePhaseTransitions AH’ (kJ/mol) Mg2Si04(a= Mg2SiO4(a=Y) P> AS” (J/m01K) -77*19a[21 .511 -0.03 0.164 -0.8[21 -14.4L2J 59.0 t 2.63[II or wadsleyite.40 0.35 1.0 f 1.0 * 0.l[lJ Fe2Si04(a=P) I%2Si04(a=y) MgSi03 (px = il) MgSi03 (px = gt) MgSi03 (il = pv) Ws 2siWYk MgSiWpv)+MgO SiO2 (q = co) SiO2 (co = st) 2. st = stishovite Table 6.11~2~~ -1.50 -13.027 -0.8815j -8.2 f l.5 0.93 4.d21 9.8/l 71 2. AV is AV”298. px = pyrox-ene.d171 96.318 11.24L2J -4.25Lz5J MnSi03 (pyroxmangite = pyroxene) NaAlSi308 (low albite = high albite) 13. .4L21 -10.14[21 -3.5L91 +5 + 4[171 +4 f 41171 -5.8af2] 39.6 + 1. .51 0. though a strong higher order component bAH and AY are values near 1000 K.94131 -2.1[51 -0.59[51 AS” (J/K*mol) 0. ThermodynamicParameters Other PhaseTransitions for Transition SiO2 ( o-quartz = p-quartz) Si02 ( fi-quartz = cristobalite) GeO2 (Wile = quartz) CaSiO3 (wollastonite = pseudowollastonite) Al2SiO5 (andalusite= sillimanite) Al2SiO5 (sillimanite = kyanite) MgSi03 (ortho = clino) MgSi03 (ortho = proto) FeSi03 (ortho = clino) MnSi03 (rhodonite = pyroxmangite) 0.

Table 7. Enthalpiesof Vitrification and Fusion Compound Vitrification AH (kJ/mol) Fusion Melting Point T(K) 2323 17oob 1999 1652 2163 1834a 1490 17706 1817 1665 1373 1473a 1830 1249 15@W 1740 AH(T)

(kJ/mol)
107.5rt 54281 9.4 f 1.0[287 8.9 zk1.0[281 31.3 + 0.2[2@ 114f 20a 77 f 5[281 89 k 10~28~ 62 !I 4[28j 57 f 3[281 138f 2[281 63 f 20[281 56f 4[281 134+ 4[281 20f 4[28J 243 + 8[281 346 + 10[281

M@
CaO Al203 SiO2 (quartz) SiO2 (cristabalite) “FeO” (wustite) Mg2SiO4 (forsterite) MgSi03 (enstatite) R2SiO4 (fayatite) CaSiO3 (wollastonite) CaSiO3 (pseudowollastonite) CaMgSi206 (diopside) NaAlSi 308 (high albite) KAlSi3Og (sanidine) CaA12Si2Og(anorthite) K2SiO3 Mg3~2si3012 W-w,)
h’&2&si5018
aEstinlated bMelting
(COIdiCIite)

------------------------------------------------------------_____________ _-__--------42 + 1[28l ------------25.5 f 0.4[261 ------------85.8 f 0.8[241 51.8f 08[24] 77.8 + 0.8[241 9 + 11281 -_-_--------209f 2161
melting.

metastable

congruent

of metastable phase.
PEROVSKITE

M”S03.7 CaGe03.4 PYROXENOID

OLIVINE + QUARTZ

600

1000 T(K)

1400

Fig. 4. Schematic diagram showing phase transitions observed in analogue systems of silicates, germanates, and titanates. Numbers refer to pressurein GPa.

Fig. 5. Phase relations in M2Si04 systems at high pressureand temperatures[25].

1

1

,

I

1473

KPV

15 P (GPa) 11

14 0.2 0.6 Fe/(Fe+Mg)

-I 373 K I 1 1 0.2 0.6 Fe/(Fe+Mg)

I 1.0 10 I 1000 I 1500

PX

1 2000 Temperature

I
2500 W) 3000 3500

30 19
PV + PER

15 P (GPa) SP(y)

P (GPa)&,

/

[

11
OL(a)

\

a+y
18

7

lk
i”o’o0 Fe/(Fe+Mg) 15’00 20’00 Temperature 25’00 W) 30’00 35’00

Fig. 6. Phase relations in Mg2SiO&Fe#i04 function of pressure[lo].

as a

Fig. 7. Phase relations in MgO-Si02 at high P and T. (a) Mg2SiOq composition, (b) MgSi03 composition, [9].

NAVROTSKY

27

200

300 TEMPERATURE (K)
in H20.

400

substantially more compressible than the corresponding crystals. For reactions involving volatiles (e.g. Hz0 and CQ), phaseboundariesare strongly curved in P-T space becausethe volume of the volatile (gas or fluid) phase depends very strongly on P and T. The section by Presnallgives examplesof suchbehavior. Table 5 lists entropy, enthalpy, and volume changefor high pressure transitions of geophysical significance. Table 6 lists parametersfor some other phasetransitions. Table 7 presents enthalpies of vitrification (crystal + glass, not an equilibrium process) and enthalpies, entropies, and volumes of fusion at the equilibrium melting point at one atmosphere. A number of silicates, germanates, other materials and show phasetransitions among pyroxene, garnet, ilmenite. perovskite, and related structures,as shown schematically in Fig. 4. Phaserelations among olivine, spinel, and beta phasein severalsilicatesare shown in Fig. 5. Relationsat high P and T for the system FeO-MgO-Si02 at mantle pressuresare shown in Figs. 5-7. The wealth of phasesin the Hz0 phasediagram is shown in Fig. 8.

Fig. 8. Equilibrium from various sources

phase relations [ 141.

Compiled

Acknowledgments. I thank Rebecca Petrovicova for help with tables and figures.

Lange

and Elena

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26.

27.

measurement of heat capacity during incongruent melting of diopside, Amer. Mineral., 76, 904912,199l. Lange, R. A. and A. Navrotsky, Heat capacities of Fe203bearing silicate liquids, Contrib. Mineral. Petrol., 110, 311-320, 1992. Navrotsky, A., Enthalpies of transformation among the tetragonal, hexagonal, and glassy modifications of Ge02, J. Inorg. Nucl. Chenr. 33, 1119-1124, 1971. Navrotsky, A., R. Hon, D. F. Weill, and D. J. Henry, Thermochemistry of glasses and liquids in the systems CaMgSi2%-CaAl2Si208NaAlSi308, Si02 CaAl2Si208NaAlSi308 and Si02 - Al203 -CaONa20. Geochinl. Cosmochim. Acta, 44, 1409-1423, 1980. Navrotsky, A., High pressure transitions in silicates, Prog. Solid St. Chem., 17, 53-86, 1987. Navrotsky, A., D. Ziegler, R. Oestrike, and P. Maniar, Calorimetry of silicate melts at 1773 K: Measurement of enthalpies of fusion and of mixing in the systems diopside-anorthite-albite and anorthite-forsterite, Contrib. Mineral. Petrol., 101, 122-130, 1989. Richet, P., Viscosity and configurational entropy of silicate

28.

29.

30.

31.

32.

33

melts, Geochim. Cosmochim. Acta., 48,471-483, 1984. Richet, P., and Y. Bottinga, Thermochemical properties of silicate glasses and liquids: A review, Rev. Geophys., 24, l-25, 1986. Richet, P., Heat capacity of silicate glasses, Chem. Geol., 62, 111-124, 1987. Richet, P., R. A. Robie, and B. S. Hemingway, Thermodynamic properties of wollastonite, pseudowollastonite and CaSiO3 glass and liquid, Europ. J. Mineral., 3,475-485, 1991. Robie, R. A., B. S. Hemingway, and J. R. Fisher, Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (lo5 pascals) and at higher temperatures, U. S. Geol. Surv. Bull., 14.52, 456 pp., 1978. Robie, R. A., C. B. Finch, and B. S. Hemingway, Heat capacity and entropy of fayalite (Fe2SiO4) between 5.1 and 383 K; comparison of calorimetric and equilibrium values for the QFM buffer reactor, Amer. Mineral, 67, 463-469,1982. Stebbins, J. F., I. S. E. Carmichael, and L. K. Moret, Heat capacities and entropies of silicate liquids and glasses, Contrib. Mineral. Petrol., 86, 131-148, 1984.

Thermal Expansion

Yingwei Fei

Since Skinner [75] compiled the thermal expansion data of substances of geological interest, many new measurements on oxides, carbonates, and silicates have been made by x-ray diffraction, dilatometry, and interferometry. With the development of high-temperature x-ray diffraction techniques in the seventies, thermal parameters of many rock-forming minerals were measured [e.g., 14, 22, 28, 45, 68, 77, 97, 991. Considerable thermal expansion data for important mantle-related minerals such as periclase, stishovite, olivine, wadsleyite, silicate spine& silicate ilmenite and silicate perovskite were collected by x-ray diffraction methods [e.g., 4, 39, 42, 711 and by dilatometric and interferometric techniques [e.g., 54,86,88,89]. While the data set for l-bar thermal expansion is expanding, many efforts have recently been made to obtain the pressure effect on thermal expansivity [e.g.,9, 19, 21, 36, 511. In study of liquid density, a systematic approach is taken to obtain density and its temperature dependence of natural liquids [e.g., 11, 12, 16,44,46,48]. The thermal expansion coefficient a, defined by a = ~/V(I~V/C~T)?,, used to express the volume change of a is substance due to a temperature change. In a microscopic sense, the thermal expansion is caused by the anharmonic nature of the vibrations in a potential-well model [103]. The Grtineisen theory of thermal expansion leads to a useful relation between volume and temperature [90],
Y. Fci. Carnegie Institution of Washington, Geophysical

V(T) = 31

+ 2k - (1 - 4M/Qo)‘”

]

(1)

where E is the energy of the lattice vibrations. The constant Q, is related to volume (V,) and bulk modulus (K,,) at zero Kelvin, and the Griineisen parameter (y) by Q, = K,VJy. The constant k is obtained by fitting to the experimental data. In the Debye model of solids with a characteristic temperature, 0,, the energy E can be calculated by @D/T E= 9nRT x3 (f%/T)3 I o eX - 1

(2)

Laboratory, 5251 Broad Branch Road, NW. Washington, DC 20015-1305
Mineral Physics and Crystallography A Handbook of Physical Constants

AGU Reference Shelf 2
Copyright 1995 by the American Geophysical Union. 29

where n and R are the number of atoms in the chemical formula and the gas constant, respectively. In this model, four parameters, or,, Q,, k, and V,, are required to describe the thermal expansion of a solid. When the thermal expansion is accurately measured over a wide temperature range, the four parameters may be uniquely defined by fitting the experimental data to the model. Furthermore, measurements on heat capacity and bulk modulus can provide additional constraints on the model. A simultaneous evaluation of thermal expansion, bulk modulus, and heat capacity through a self-consistent model such as the Debye model [e.g., 811 is, therefore, recommended, especially when extrapolation of data is involved. In many cases the above model cannot be uniquely defined, either because the accuracy of thermal expansion measurement is not sufficiently high or because the temperature range of measurement is limited. For the purpose of fitting experimental data over a specific temperature range, a polynomial expression for the

30 THERMAL EXPANSION

thermal expansion coefficient may be used

a(T) = a0 + a,T + azT-*

(3)

931 are also recommended as data sources. The pressure effect on the thermal expansion coefficient may be described by the Anderson-Griineisen parameter (4)9

where a,, a,, and a, (5 0) are constants determined by fitting the experimental data. The measured volume above room temperature can be well reproduced by

a(C T)/a(T)= ME WVf

(7)

v(Tj

= vT,k?Xp

I 1
T 4WT TI

(4)

The thermal expansion coefficient as a function of pressure can be calculated from equation (7) and the third order Birch-Murnaghan equation of state, P=3fil+2j)5/2KT and

where V, is the volume at reference temperature (T,), usually room temperature. When the thermal expansion coefficient is independent of temperature over the measured temperature range,
v(r) = vTr

(8)

exp[%(T -

TAI

(5)
f=i(gJ-

The commonly used mean thermal expansion coefficient (Z) can be related to equation (5) by truncating the exponential series of exp[a,(T - T,)] at its second order, i.e.,

ll

(9)

v(T) = v,, [l +a(T - T,)]

(6)

where K, and Kr’ are the bulk modulus and its pressure derivative, respectively. Table 2 lists the values of K, Kr’, and S, for some mantle-related minerals. The liquid molar volume of a multioxide liquid can be calculated by &iq(T) = 2 Xi I$,T~[1 + Ei(T - Tr) ] + V ”

Table 1 lists thermal expansion coefficients of solids. The coefficients for most substances were obtained by fitting the experimental data to equations (3) and (4). The mean coefficient @), listed in the literature, can be converted to a~, according to equations (5) and (6). Thermal expansion coefficients of elements and halides (e.g., NaCl, KCl, LiF, and KBr) are not included in this compilation because the data are available in the American Institute of Physics Handbook [41]. Volumes 12 and 13 of Thermophysical Properties of Matter 192,

(10)

where Xi and Zi are the mole fraction and mean thermal expansion coefficient of oxide component i, respectively. 6,~~ is the partial molar volume of component i in the liquid at a reference temperature, T,, and p is the excess volume term. Recent measurements on density and thermal expansion coefficient of silicate liquid are summarized in Tables 3a-3d.

TABLE 1. Thermal Expansion Coefficients of Solids

Names Oxides aA120a, corundum

T range

a, we

a0 (lo-‘?

a1 (10-p

a2

ref.

a 293-2298 K c 293-2298 K I’ 293-2298 K

7.3 8.3 23.0

0.0758 0.0773 0.2276

0.1191 0.1743 0.4198

-0.0603 0.0000 -0.0897

PI
PI PI

FBI

31

TABLE Names

1. (continued) sow-3 =o W-9 a1 w-“1 1.3569 1.2777 0.7315 3.5227 1.3933 1.0463 0.7564 0.0000 0.0259 2.8160 0.1154 1.9392 1.5936 0.6293 1.4836 0.7904 3.8014 8.0591 0.0000 0.0000 0.4031 0.3482 1.0368 0.0000 0.0000 1.1191 1.2118 0.0000 0.0000 0.0000 0.7404 1.2055 0.0000 1.3236 0.0000 0.0000 0.0000 1.2446 0.2639 ref.

T range
a c 298-963 298-963 K K K K K K

a2

BeA1204,

chrysoberyl

6.6 8.7 7.6 23.8 17.8 33.5 19.5 12.3 10.5 14.8 18.6 15.6 9.9 33.9 7.9 8.0 23.8 20.6 50.1 10.1 7.6 27.9 15.8 24.9 29.4 16.5 20.5 22.4 41.1 32.1 31.6 34.5 28.5 22.3 8.9 11.1 28.9 24.5 21.2

0.0250
0.0490 0.0540 0.1320 0.1820 0.3032 0.2555 0.1230 0.2232 0.0631 0.2146 0.0977 0.0513 0.3203 0.0350 0.0559 0.1238 -0.0353 0.5013 0.1006 0.0638 0.2689 0.1264 0.2490 0.2940 0.1430 0.3108 0.2244 0.4110 0.3210 0.3768 0.3317 0.2853 0.1832 0.0890 0.1110 0.2890 0.2180 0.2042

b 298-963 K V 298-963 K
Be0 CaO 3Ca0*A1203 17Ca0*7A120s Ca0*A1203 Co304, normal spine1 Cr203, eskolaite FeA1204, hercynite FeCrzOd, chromite FeO, wiistite Fe203, hematite v v 292-1272 293-2400 V 293-1473

0.0000 0.0000 0.0000 0.0000
-0.4122 0.0000 -0.7490 0.0000 -1.0687 0.0000 -0.2904 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 -0.1063 -1.2773 0.0000 0.0000 0.0000 -0.7446 -0.2094 0.0000 0.0000 0.0000 0.0000 0.0000 -0.0920 0.0000

[301

WI
[301 r301
[93, cf. 291

V 298-1073
v v

293-1473 K 301-995 K V 293-1473 K v 293-1273 K v 293-1273 K

V 293-873 K
a c v K K K V 293-843 K 293-673 293-673 293-673

Fes04, FeTiO,,

magnetite ilmenit

1931 r751a r151 [751 1491 [751 r751 [751 1751 1751 r751 [751 1751 :zz; [951 [951 VI PO21 WI [751 1751 [31
r74

V 843-1273
u c 297-1323 297-1323 V 297-1323 V 293-1273

Hf02 MgA1204, normal spine1 MgA1204, disordered spine1 MgCr204, picrochromite MgFe20a, magnesioferrite MgGeOs, ilmenite Mg2Ge04, olivine MgZGe04, spine1 MgO, periclase MnO, manganosite Th02, thorianite TiO Ti02, rutile

K K K K K

V 293-873 K
v v

V 293-1473 V V V V V V V 293-1073
a c

K K 293-1473 K 299-1023 K 298-1273 K 298- 1273 K 303-1273 K 293-1123 K 293-1273 K K K K K K K

993-1933

[721 WI [901
[75, cf. 961

U02.03, uraninite Zr02, baddeleyite

298-1883 298-1883 V 298-1883 V 293-1273 V 293-1273

[751 [851 1851 P51
[75, cf. 961

1751

Hydrous minerals
AlOOH, boehmite a

b

loo-530 loo-530 c loo-530 V loo-530

K K K K

9.7 25.3 0.7 35.7

-0.0048 -0.0232 0.0005 -0.0275

3.4000 9.2000 0.2000 12.8000

0.0000 0.0000 0.0000 0.0000

r71 [71 [71
[71

8 5. C~~M&%Ozz(OHh tremolite 12.1610 0.0000 0.1107 0.0000 0.1 26.9300 0.0 b 297-973 K c 297-973 /cI 297-973 QW~%W(OH)2 muscovite v a 297-973 K 293-1073 K 293-1073 K 293-1073 K 293-1073 K 293-1073 K 300-650 K 300-650 b c do01 Mg(OH)2.8000 a1 (10-y T range a 297-973 K K K a2 ref.0 11.0000 0.4 16.2 13.0000 0.8 19.2 62.0000 0.0000 0.1367 0.0 8.0000 0.0000 0.0000 0.5183 3.0000 0.1 36.0000 0.0775 0.2 15.3131 0.7 35.0000 0.2629 0.2140 -1. rhodochrosite FeCOa.0000 0.0000 0.1233 0.0000 0.0000 0.1703 0.0000 0.0000 0. magnesite a c v n c v a c a MnCOa.0508 0. 1751 [751 1751 1531 1531 [.0000 0.0833 0.2690 0.0000 0.0000 0.9700 0.9 7.0000 0.0000 0.1618 0.0000 0.0000 0.0000 0.1379 0.. WI PI WI t:.5393 -0.0000 0.).0000 0.0540 0.0037 0.1686 0.5809 0..0315 0.7429 0.3 3.4 11.5900 0.0 297.2 -3.2286 3.0266 0.1150 0.0000 0.2280 0.2140 0.0000 0.:.1110 0.0000 0.0000 0. (hexagonal) a c v 1093-1233 1093-1233 1093-1233 K K K -102.0000 0. calcit 0.6221 -0.0000 0.0000 P31 F31 1831 F31 t.1167 0.0000 0.0000 0.0200 2.0000 0.0000 -1.3941 0.1152 -0.3537 0.6 35.8 -2.0000 0.0000 0.1920 0..6 22.0000 -1.5 59.1 12.0 80.0000 0.2 1.2 -1.3 9.0000 0.0000 0.0000 2. r531 [531 [691 1691 1691 Carbonates BaCO.8 2.I [51 151 [701 [701 .1862 0. strontianite b 293-1073 c 293-1073 V 293-1073 .0271 0.:i.0000 0.0000 0. aragonite a b c v a c v a c v a c v 293-673 K 293-673 K 293-673 K 293-673 K 297-1173 K 297-1173 297-1173 293-593 293-593 293-593 297-973 297-973 297-973 K K K K K K CaCOa .0994 0.2 22.0000 0.1111 0.0000 0.5 3.2270 0.8 -5.0000 0.0000 0.9 11.0000 0.1928 0.3089 -0.0000 CdCO.6630 0.6 22. r751 [751 1751 V 297-773 K SrCOa.2 18.7 5.0000 0.3520 0.0713 -0.0180 0.0 93..7 11.0000 0. siderite K K 297-773 K 297-773 K 297-773 K 297-773 K 297-773 K 297-773 K 297-773 K 297-773 K 293-1073 K K K K 1641 rw :Gt.1922 0.2711 4.4982 CaCO.0000 0.0000 0. (continued) a0 w-3 a0 w-7 0.7 31. dolomite MgCOa.0000 0.2 13.3 18.0000 0.32 THERMAL EXPANSION TABLE Names 1.6045 2.0000 0.4137 3.0 59..0583 -0.3362 3. brucite v a c K V 300-650 K 0.0000 0.0560 0.2934 4.8 13.1202 0.1100 0. otavite CaMg(CO.0000 0. P91 P91 [431 [431 t:.0000 0.0000 -0.1 13.

2453 0.8114 0.0000 0.7589 0.7 58.0000 8.1840 -0.0938 0.0158 2. BaAi2Si208 High Albite.2883 0.0000 0.0364 0.2629 8.8 2.7 9.3252 4.SiOs Cancrinite V 293-1473 V 293-1473 V 293-1273 a c K K V 298-673 K 298-873 298-873 K 298-673 298-673 Cordierite Mg2At4SisO18 (hexagonal) a c f%Eucryptite.0000 0.8700 0.0000 0.0716 0.5 8.0000 0.4 -1. (continued) a0 (10 % WV al (10-q a2 T range ref. sphalerite ZnS.9 27.6 -18. A12SiOs b 298-1273 298-1273 V 298-1273 a 298-1073 c 298-1073 V 298-1073 c Beryl.0000 0.0000 0.7701 19.0000 0.0000 0.0000 0.A12Sib0.0 16.4 42.0000 10.1274 -0.0523 0.6 6.0000 0.5061 0.FE1 33 TABLE Names 1.0 20.0000 0.9537 -0.7 5.4601 0.5027 0.0000 0.3815 0.0000 0.0000 BaS04. galena ZnS.1 12. rankinite p-Ca2Si04 Ca.0000 0.0000 -0.0000 0.7 15.0000 0.0000 0.0000 0.1885 -0.5 33.1223 0.2836 0.0860 -0. NaAlSi$18 V 293-673 K u c 297-1378 297-1378 K K K b 297-1378 0.0000 0.0230 0.7 7.3261 0.0220 -0.7 25.8 2.0000 0.0000 0.6 -2.1713 0.0000 -1.6 91.6370 -0.0000 0.0000 0.0753 0. barite b K2S04 298-1158 K c 298-1158 K V 298-1158 K a 293-673 K b 293-673 K c 293-673 K v 293-673 K 1751 r751 [751 1751 1751 1751 [731 1731 [731 [731 [751 1751 1751 [751 1311 [311 1311 [971 [971 1971 [971 [581 [581 [581 [751 1751 r751 1751 1751 1751 [351 1351 [35. Be.1 17.0000 0.0000 0.0000 .5 17.0328 0.0000 0.4 0.1918 0. Ca2MgSi20T K K V 293-693 K a 298-1273 K a c 293-693 293-693 10. pyrite PbS.0605 0.7 6.8692 0. 671b Silicates Akermanite.1628 0.0260 0.9 2.1065 0.1720 0.0000 0.0000 0.0763 0.3 22.4106 0.0000 0.1852 0.0000 0.2 63. cf.3 33.3873 2.2 8.0000 0. Sulfides and Sulfates FeS2.0000 0.1 31.0000 0.0000 0.0000 0.8 6.0346 0.0000 0.8 K K K K K K K K K Calcium silicates Ca3Si207.0034 0.0290 0.2070 0.0180 0.0000 Andalusite.9 2.4 25.1256 0.1 2.6 5.0000 0.3337 0.5 19.0762 0.0000 1.6406 V 293-873 K 0.0260 -0.2181 0.0656 0.0000 0.6125 0.0000 0. LiAlSi04 K V 298-873 K a 296-920 K c 296-920 K V 296-920 K rw [Ml WI [751 WI WI PI Feldspars Celsian.0000 0.8280 0.0000 o.0963 0.0233 0.2550 0.0000 0.2136 0.0000 0.2 0.0000 0.6 8.8705 0.1134 1.0120 0.3157 0.oooo 0. wurtzite v v a c v a 293-673 293-1273 293-1273 293-1273 293-1273 298-1158 K K K K K K 25.2 -1.4073 2.2150 4.1 29.

0252 0.dl\b32.3 7. (continued) Names a /3 y v a b c a j? y’ V T range 297-1378 297-1378 297-1378 297-1378 298-1243 298-1243 298-1243 298-1243 298-1243 298-1243 ‘298-1243 293-1273 293-1273 293-1273 293-1273 293-1273 293-1273 293-1273 K K K K K K K K K K K K K K K K K K a0 <lo-Y -2.5956 0.Oa Adularia.7 0.5 6.1 15.2 -0.7 4.0000 o.0749 0.7927 0.8714 -0. CaJMg(Si04)2 Mullite.0000 o.0000 0.0580 0. Pyrope.0000 0.2787 0.0061 0.z.0560 0.5071 -0.3 -2.0700 0.0000 WI WI WI [68.&n2.0000 0. AbSAngS Garnets Almandite.5719 0. Low Albite.1394 0.9479 0.1603 -0. 247 r751 [751 t381 1751 1751 1751 [E..2679 1.0252 0. 1741 [741 [741 Merwinite.2455 0.3641 1.9 0. Ab7+nU Plagioclase.8 7.0000 -0.5 Orthoclase.0560 0.6 9.4972 -0.0000 o.8603 -0. ii.0000 o.0000 0. 991 P81 WI PI P81 PI [981 .oooo o. WwWi3012 Spessartite.6 10.0000 0.2199 0.0113 0.0 5. Oraa&b9.7683 0.9 25.446)Cr a 57 17’> K b F-.2880 0.1 6.2 16.7 3.2%)Si02(x646) 294-1044 K 294-963 K 300-10OOK 292-980 K 283-1031 K 292-973 K 298-1000 K 293-1473 K 293-1273 K 298-1073 K 298-1073 K 298-1073 K 298-1073 Y 293-1473 I.9 3.0284 -0.oooo 0.0000 o.1524 0.oooo 0.6 14.8 11.8 3.0882 0.3 -2.6 24.0547 0.8088 o. A1203(60.5490 1.2521 0.1560 -0. Ora3.0000 o. Mn3A12Si3012 Natural garnet (pyrope-rich) Gehlenite. Ab5&nU Plagioclase.1612 0.2 23.1846 0.6 15.7 -5.5550 0.1776 0.oooo o.0097 0.9 17.1297 -0.8 20.oooo 0. cf.0000 o.1490 0.34 THERMAL EXPANSION TABLE 1.oooo 0.2140 0.0271 0.0197 -0.5038 0.2647 0.4538 -1.4 19.0620 0.2075 0.0000 0.0 23.oooo 0.oooo 0.6 Plagioclase.0700 0.0000 0.0000 o. cf.-l 73K c >73-1173 K v 5%1173 K 573-1173 K b 573-1173 K c 573-1173 K v 573-1173 K II 573-1173 K b 573-1173 K c 573-1173 K v 573-1173 K .oooo 0.oooo o.0987 -0.5521 0.0000 0.8 16.0661 0.0000 0.0390 0.2320 0.0 5.8683 3.0000 0. A12SiOs V v V V v V V V V V v v v V V V (I b c V v -6.0371 -0. NaAlSi.7621 0.6617 -0.0000 0. [751 1751 [751 [751 [751 [75. Ab+n.0597 1.2 15.oooo o.4 8.oooo 1.9 7. Or66.Fe2Si3012 Cacium-rich garnet Grossularite.4618 -1.0000 0.1 -2.2245 -0. Ca.0330 0. 1971 1971 [971 [751 1741 [741 1741 [741 r741 1741 r741 t.5Ab16.5285 0.0000 -0.:.&.2927 0.oooo 0. Plagioclase.0263 -0.0000 0.4 Microcline.1737 0. Ca2A12Si07 Hornblende Kyanite.6 20.oooo 0.oooo o.6 26.2 5.3080 0.0000 o.8089 0.2505 0.1 29.2311 0.0000 0. Ca&Si3C11.9 10.2726 0.1590 4 w-9 02 ref.2103 0.0000 0.1095 0.0310 0.0270 0.0000 0.1951 0.6 11.1120 -0.1670 0.0000 -0.oooo 0.0%)Si02(2a.3400 0.5 22.oooo 0.6839 0.0000 0.0000 o. A1203(71.6 14. Fe3A12Si3012 Audradite.0000 o.7 15.7276 0.

6 35.0397 0.0211 -2. Mg2Si04.2 6.1049 0.0080 0.2557 0.0990 0. Ni-olivine WI [451 [451 r451 [451 WI WI WI [91.0000 0.3 6.0819 0.1498 -0.4 0.3605 -0.5 8.2854 0.0000 0.8 58.1409 -0.SiO.3114 0.2627 0.1217 1.4 7.2635 0.0 8.0621 -0.2386 0.9 9. 791 Perovskite MgSiOs 1711 [711 .6733 0.0 27.0000 0.3536 -0.0000 0.4594 -0.l&no.0953 0.0610 0.0000 0.1806 0.3407 0.6 28.0000 0.FE1 35 TABLE Names Nephelines PkdGd~SiQ T range 1. [541 1401 1611 WI 1611 CaMn(MgZn)Si04 glaucochroite Mg2Si04.5544 4. fayalite @kde&SiO4 hortonolite P31 P31 [I31 1131 ]271 Mgo.2188 -0.0000 -0.2093 0.0518 0. (10 a0 (10-4) a1 (10-y a2 ref.4 10.0000 0.0000 0.8 8.0840 o.3 31.0000 0.1396 -0.7 25.1827 0.1387 -0.2 11.0663 0.2575 -0.3036 0.5 6.1109 0.4236 0.5 6.0000 0.2898 -0. forsterite Mg2Si04.3370 1.0 0.0976 0.1004 0.3 24.0916 0.0975 0.1629 -0.1746 0.1042 0.5 7.4958 -0.0000 0.5598 0.0918 -0.2 20.3034 0.0855 0.5381 0.1172 0.9 9.diO~ hortnolite 1271 1271 [27.2071 0.4204 -0.0000 0.1952 0.4 7.9931 0.5 9.0000 0.3898 0.1050 0.2882 0.3 19.2307 0.2091 0.0649 0.1 8.diO4 monticellite WI 1451 1451 r451 1451 r451 1451 [451 WI WI F361 E.5 19.6 9.1 14.7&.0960 0. cf.0602 0.3007 0.3 5.8674 1.1308 0.4 30.7545 -0. Mg2Si04.0000 1751 [751 [751 [751 [751 [751 Olivines CaMgo.9 9.3 5.1929 -0.2 27.9 26.1055 0.2233 0.0853 -0.0000 0.0665 0.1 6.7422 1..dh.2744 0.2783 0.0807 0. Mn2Si04.3504 0. (continued) a.8 8.0000 0.1080 -0.8 26.0000 0.0 22.1526 0. forsterite forsterite forsterite tephroite Ni2Si04.5249 0.1456 0.27] Fe.0000 -0.2331 -0.2891 -0.0512 0.0694 -0.1235 0.7192 0.oooo 1.0000 0.76.1201 0.1889 0.3842 0.1 9.1428 -2.0000 0.0740 0.6 9.6515 0.0000 0.2696 -0.0000 0.1530 0.0000 0. a 293-1073 K c 293-1073 K v 293-1073 K a 293-1073 K c 293-1073 K v 293-1073 K a 298-1068 K b 298-1068 K c 298-1068 K v 298-1068 K n 298-1073 K b 2981073 K c 298-1073 K v 298-1073 K (I 303-1173 K b 303-1173 K c 303-1173 K v 303-1173 K v 296-1293 K v 298-1273 K v 300-1300 K a 298-1123 K b 298-1123 K c 298-1123 K v 298-1123 K n 298-1173 K b 298-1173 K c 298-1173 K v 298-1173 K a 298-1123 K b 298-1123 K c 298-1123 K V 298-1123 K a 297-983 K b 297-983 K c 297-983 K v 297-983 K (I 296-1173 K b 296-1173 K c 296-1173 K V 296-1173 K a b 77-298 K 77-298 K 11.0965 0.6 9.3852 -1.4036 0.0000 0.0000 0.0000 0.8133 -0.

0000 0.2200 0.0779 0.0000 0.7 5.1204 0.0810 0.5 22.0000 0. C UW@%.0000 0.0000 0.0606 0.1380 0.9 27.1760 0. clinohypersthene a CaFeSi20b.2 8.0000 0.9 19.8 18.0450 0.3270 0.0000 0.3o~Feo.0000 0.5 6. P-9 a2 ref.0000 0.0520 0.3156 0.0000 -0.0597 0.0000 0.3 32.3o~Feo.0540 0.0000 0.0000 0.1890 0.0000 0.7 7.1890 0.0000 0.0 4.0096 0.4 13.8 29.oooo o.0000 0.1 33.lFW v v a 77-298 77-298 298-381 loo-250 loo-250 loo-250 loo-250 250-373 K K K K 5.8 16.1330 0.0000 0.2780 0.0000 0.1550 0.0000 0.0000 0.1680 0.1450 0.2 6.1350 0. Be2Si04 v v a c v v a K K K K 250-373 K 250-373 K 250-373 K HO-373 K 298-840 K 298-963 K 298-963 K 298-963 K 293-1473 K 298-1473 298-1473 297-1273 K K K K K K K K K K K K K 0.3330 0.0000 0.0540 0.0000 0.0724 0.0000 0.~Si03 a 293-1123 ferrohypersthene b b 293-1123 c 293-1123 293-973 V 293-1123 Cao.0 30.0000 0.0000 0.oooo 0.0000 0.0 5.8 5.0000 0.8 8.0000 0.0000 0.0000 0.0000 1.3271 0.0000 0.0483 0.5 6.0000 0.0580 0.0000 0.0000 0.0000 0.0000 0.0000 0.2474 0.0000 0.0000 0. cf.0000 0. b c CaMgSi20b.0000 0. 221 Pseudowollastonite.0520 0.0000 0.0000 0.0000 0.3 15.9 13. EXPANSION TABLE Names 1.3760 0.0893 0.0000 0.0000 0.l)SiO3 Phenakite.oooo 0.0646 0.6 6.4 5.ol~Mgo.36 THERMAL.5 14.0590 0.9 37.0000 0.0882 0.0000 ~0.1450 0.0000 0.0000 0.1540 0.0000 0.0000 0.0888 0.0000 0.0000 o.2980 0.0000 0. hedenbergite %d-+u.0000 0.3 13.0000 0.8 7. (continued) a0 w-9 a1 (10-y T range a.0000 0.0000 0.8 27.0000 0.0000 0.5 8.&i03~ FsWo 293-973 K 293-973 K dlO0 293-973K v 293-973 K a 297-1273 K b 297-1273 K c 297-1273 K dlO0 297-1273 K v 297-1273 K a 297-773 K b 297-773 K c 297-773 K dlO0 297-773 K V 297-773 K c b [781 [781 [781 1781 [771 [771 r771 1771 [771 P41 P41 1141 P41 1141 WI WI WI [al rw .2 10.6 0.8 8.8 12.0000 b c v a b c v Wsd%.0000 0.0000 0.0000 0.0000 0.0000 0.2050 0.0000 0.0000 0.8 20.0830 0.0000 0.0000 WI 1711 1711 WI 1621 WI WI WI WI WI F21 [ii.0 8.2 4.4 16.0000 0.5 15.1040 0.5 15. CaTs CaSiO.0000 0.2 17.4 43.0000 0.0000 0.1620 0.0640 0.0000 o.~SiO.0000 0.0000 0.0000 0.1900 0.1 5.ol5M~.4 18.9421 0. diopside a 298-1473 K V 298-1473 297-1273 c 297-1273 dlO0 297-1273 V 297-1273 Cao.1520 0.0000 0.0000 0. Pyroxenes CaA12SiOs.0000 0. 1301 1301 1301 1751 PI WI WI WI 1141 1141 [I41 1141 [14.4380 0.0000 0.9 14.

0000 0.0000 0.0000 0.0000 0.5588 0.2 24.9 16.0380 0. acmite Silicate ilmenite.2497 0. spodumene Mga8Feo.0000 0.0000 0.0585 0.0386 0.3639 0. enstatite MgSiOs.0600 0.0000 0.0 1.0000 0.8 11.0000 0.9 26.2680 0.0000 0.0670 0.0000 0.0000 0.2697 0.0000 0.4 7.0946 0.0000 Silicate spine1 y-Mg2Si04 y-Ni2Si04 y-Fe.0000 0.4 14.0000 0.0000 0.1640 0.8 47.0707 0.0000 0.1090 0.0000 0.5 16. A12SiOs 297-1023 K 298-973 K 298-673 K 298-673 K 298-1273 K b 298-1273 K c 298-1273 K V 298-1273 K v v v v a 0.0000 0.0 4.0000 0. bronzite MgSiO.0000 0.8 6.3 12.0000 0.0000 0.0000 0.0000 0.1670 0.0000 0.1051 0.0 23.7 24.O.0000 0. jadeite NaCrSi20h.0000 0. ureyite NaFeSi. protoenstatite MnSiO.0000 0.0 7.2470 0.0092 0.0470 0.9 9.0000 0.0691 0.3 WI P71 .2 16.FE1 37 TABLE 1. LiAlSi.5 8.0 22.0000 0.0450 0.7 28.0000 0.0000 0.2 10.0000 0.0000 0.2810 0.063 1 0.1000 0.0000 0.0804 0.2947 0.0000 0.2440 0.0000 0.2470 0.4 18.0000 0.0000 0.0000 0.0000 0.2SiOs.0 6.4770 0.0000 0.oooo 0.0000 0.2 13.0475 0.1260 al (10-q a2 ref.0000 0.1 8.5 3.0000 0.2314 1971 1971 4.0000 0.0 24.1450 0.0000 0.9 6.7 7. orthoferrosilite T range a0 w-7 11.1 4.0000 0..0000 0.0817 0.0000 0.0000 0.SiO.0000 0. (continued) Names FeSiOs.0000 0.0000 0.7 5.0390 0.0000 0.1 10.2220 0.0000 0.0850 0.1200 0.0000 0.0231 0.1680 0.0000 0.9 20.1 16.0000 0.3 3..1680 0.0000 -0.0727 0.O.2040 0.0000 0.0000 0.2694 0.. MgSiOs a 297-1253 K 297-1253 K c 297-1253 K v 297-1253 K a 297-1033 K b 297-1033 K c 297-1033 K dlO0 297-1033 K v 297-1033 K a 298-1273 K b 298-1273 K c 298-1273 K v 298-1273 K v 293-1073 K V 1353-1633 K a 297-1073 K b 297-1073 K c 297-1073 K v 297-1073 K a 297-1073 K b 297-1073 K c 297-1073 K dlO0 297-1073 K v 297-1073 K a 297-873 K b 297-873 K c 297-873 K dlO0 297-873 K v 297-873 K u 297-1073 K b 297-1073 K c 297-1073 K dlO0 297-1073 K v 297-1073 K a 298-876 K c 298-876 K V 298-876 K b 0.0000 0.0000 0.2300 0.0000 0.6531 0.0000 0. y-Fe2SiOd Sillimanite.0000 -0.3930 0.0000 0.0000 0.0000 0.3 8.8 6.0000 0.6 13.1380 0..1110 0.1185 o.7 7.0000 0.1120 0.0000 0.8 27.4 a0 (10”‘) 0.0000 0.0727 0.0000 0. pyroxmangite NaAlSi20b.0000 [841 If341 P41 P41 P41 r141 1141 P41 P41 1231 P31 1231 ~231 [751 [591 [651 F51 [651 F51 P41 1141 P41 P41 P41 P41 1141 iI41 1141 1141 1141 1141 1141 P41 P41 /41 E41 r41 PI [1011 WI 1521 -0.0000 0.8 39.0 24.5 10.0000 0.0760 0.0996 0.

1380 0.8 0.0000 0.oooo 0. Zircon.0000 0.2060 0.0000 0.0000 0.0656 0.2700 0.0000 o.5 3.9 16.0000 0. cubic ScAlOs.0000 0.0000 -0.6 12.8800 0.0000 o.8 6.0000 0.1231 o.0000 w41 [501 r501 1501 WI 1501 r501 [501 [501 PO51 w51 r 1051 11051 PO51 [321 1321 r321 .8 18. high a-Quartz B-Quartz Stishovite Stishovite Spodumene.0H)2 Wadsleyite (p-phase) Mg2Si0.7 91.6973 0.0000 0. low T range a0 w-3 q(lo-8) a2 ref.3060 0.0 7.0750 0.0000 0.2662 -0.3500 0.8 10.3412 -0..6 9.5 35.oooo o. Cristobalite.1165 0.0000 0.8903 0.0000 0.oooo 0.0758 0.0000 0.0380 0.9170 0.8 6.1500 -0.6 88. ZrSi04 V a c V V V V V a c v a c V v a b c v a b c V a c V 293-1273 K 301-491 K 301-491 K 301-491 K 673-1473 K 298-773 K 848-1373 K 1473-1673 K 291-873 K 291-873 K 291-873 K 300-693 K 300-693 K 300-693 K 293-1073 K 293-1273 K 293-1273 K 293-1273 K 293-1273 K 293-1073 K 293-1073 K 293-1073 K 293-1073 K 293-1293 K 293-1293 K 293-1293 K 6.4 7. 821 Perovskites BaZrO.7886 0.0000 -0.2893 0.0000 o.0060 0.1000 0.0 10.3795 0.0 24.5 52.0000 0.4 15.0 -4. perovskite NaMgO.0000 0.7697 0.2487 -0.0758 0.0485 0.0000 0.0000 9.3 20.1 12.0340 0.0440 0.oooo o.3884 0.0000 0.1210 0.0000 0.0000 0. (continued) Names Si02 group Coesite Crisfobalite.3 0.5772 0.0316 0.1050 0.0000 -0.1388 0.6553 0. cf.0700 0.38 THERMAL EXPANSION TABLE 1.0000 0.0600 0.0000 0.6581 o.4040 0.0000 1751 1631 1631 F31 E751d [lle PI PI 1391 [391 1391 PI PI P81 1751 1751 E751 1751 [751 WI PI P91 WI 161 Fl [6.1500 0.1230 0.6 13. perovskite CaGeOs. A12Si04(F.1860 0.oooo 0.0000 0.0000 0.oooo 0.15300 0.1542 0.oooo 0.0000 -0.4 7.0791 0.0000 1.0000 0. a-LiAlSi20h Topaz.9 3.1950 0.0000 o.3 30.0597 0.0000 0.1574 0.0000 0.1196 0.4698 0.4924 1.0 94.0000 0.9 10.oooo 0.0000 0.0000 0.0000 0.0 4.oooo 0.0000 -1.0 0.1 10.0245 0.3 0.3110 0.0000 0.5 31.0000 0.0000 0.1000 0. perovskite NaMgOs.0000 0. perovskite V a b c v a b c V a b c V V u b c 293-873 K 295-520 K 295-520 K 295520 K 295-520 K 520-673 K 520-673 K 520-673 K 520-673 K 298-873 K 298-873 K 298-873 K 288-873 K 1038-1173 K 293-973 K 293-973 K 293-973 K 20.0000 0.9 19.1050 0.6 3.0000 0.0560 0..0000 0.1098 0.5270 0.0000 0.1417 0.0000 0.0000 0.1 12.3 14.0000 o.085 1 0.1210 0.4 5.6 11.0 40.7 6.0000 o.0680 0.0 5.9490 0.6 6.oooo 0.0000 0.

2700 0.1240 0.5 5.0000 0.7 29.0 54.0 174. 5.37 4.70 5.00 4. SrZrO.3 157.0000 0.56] for orthorhombic ‘See [24] for plagioclases.and Fe-cordierites.4 4. dInversion at 491 K. magnesiowiistite WW-02 Mg2Si04.00 4.0000 0.01 5. perovskite 27.~F%.0000 0. bSee [. Pressure Effect on Thermal Expansion Coefficient of Selected Substances Phases Fe@cc) WW Fe(fcc) NaCl LiF MgO.0 212.0000 0.0000 0.8 6.0000 0.8 7. AhbP3.oooo 0. Also Ed.5 r341 r341 PI PW WI [361 1201 rw 1371 [211 r551 r511 .0000 0.3240 0..FE1 39 TABLE 1. periclase (Mga~e0. Antoo.0000 o.6 16.30 4.0000 0.0000 0.la)2sio4 Mg2Si04. TABLE 2. and ~bh’%o~l~ see [75] for data on tridymite.8 37.0000 0.1610 0.5 0.5 6.0 12.0750 0. perovskite KT.4 7.0000 [321 PO41 PO41 r 1041 DO41 PO41 PO41 PO41 PO41 PO41 DO41 PO41 “For data cited from [75].1490 0.0 261.0000 0.0000 0.30 4. see [l] for discussion on thermal expansion near the transition.0000 0.0 167.0970 0.00 6. spine1 (Mge9Fe.0000 0.5 6. %@‘%0~1~ AWhOr2.0760 0.5 5.8 5.5 5. GPa 165. at 846 K. olivine ~-@fgO.7 4.3750 0.5 9.0000 0.r)Si0a.3 160..0000 0.10 4.1 8.9 6.2 32. (continued) Names V a b c v II b c v II c V T range 283-1373 K 293-973 K 293-973 K 293-973 K 293-973 K 973-1123 K 973-1123 K 973-1123 K 973-1123 K 1123-1443 K 1123-1443 K 1123-1443 K a0 W6) %I w-9 a1 (lo-s) a2 ref.0680 0.0 24. Ab%l.0 65. cordierite and [33] for hydrous Mg.and b-quartz transition see [75] for original data sources.0820 0.4)0.13 4.0 183.00 5.0000 0.4 14.0000 0.3 4.0 references KT' s.0000 0. Abdw.1 5.00 4.3 129.2980 0.0000 0.

1673 K OLi(X105) vi.22 68.44 13.9 22.5 2.7 23.1 37.31 14.4 a Data were derived from density measurements of Al free melts. EXPANSION TABLE 3~.24 16.13 12.1 27.75 22.2 a Data were derived from density measurements of 30 melts in the system CaO-FeO-Fe203-SiO. 1673 'i(X105) vi.3 17.9 21. TABLE 3~.4 26.59 29. Partial Molar Volume and ltiean Thermal Expansion Coeffkient of Oxide Components in CaO-FeO-Fe203-SiO2 Melts 1’ i] Vliq(T) = x Xi E.43 36.71 54.4 10. Partial Molar Volume and Mean Thermal Expansion Coefficient of Oxide Components [46] TABLE 3b.0 12.48 13.087 21.1 61.45 44.727 37.94 12.042 0 13.40 THERMAL.Tr[ 1 + Ei(T .88 23. Units are in cc/mole and l/K.53 47.27 28.9 43.l773 K ‘i (X10’) vi.9 26.388 0 0 9.10 : 0.1 24. low silica 1673 ‘i (X10’) vi.19 20.57.61 16.4 26.5 Si02 Fe203 Fe0 Na20 26..8 72.501 14.42 20.7 25.2 21. Units are in cc/mole and l/K.30 17. Units are in cc/mole and l/K.4 Si02 Ti02 Fe203 Fe0 W$’ CaO Na20 K2O ’ Data were derived from density measurements of melts in ironfree system [8.0 15.0 Fe0 MN CaO Na20 K2O Liz0 Na20-TiO. [16. Liz0 MnO NiO ZnO SrO BaO PbO Rb20 cs20 26.45 26.57].l573 K ‘i (X10’) 26.61 28.1 21. b Data were derived from density measurements of 64 melts in the system Na2@-K~0-Ca0-Mg0-Fe0-Fe203-A1203-Ti02-Si02 [8.92 22.O-FeO-Fe203-Si02 [ 171 and ferric-ferrous relations (471.64 20.80].626 18.770 13.98 37. Partial Molar Volume and Mean Thermal Expansion Coefficient of Oxide Components in Al-Free Melts [ 1l] iron-free silicate liquida Oxides SiOz TiOz M2O3 Fe203 64 liquidsb Oxides vi.46.Tr)] + XSiOryCaO V&O.801 35.48 0.1 26. 11.20 25. Units are in cc/mole and l/K.3 7.1 34.10 17.8 33.4 17.80].80 41.460 -11.85 16.40 13.7 12.9 23.02 44. 1573 25. a Data were derived from density measurements of 12 melts in the system Na. See [ll] for data sources.2 36.-CaO TABLE 3d Partial Molar Volume and Mean Thermal Expansion Coefficient of Oxide Components in Na20-FeO-FezOx-Si02 Melts [47] > 20 wt% silican Oxides Si02 Fe203 Fe0 CaO Si02-CaO vi.33 0 32.7 25.9 35.60 41.7 32.03 46.35 11.3 12.52 -1.84 29.46. .39 13.4 16.32 16.33 0.3 19.1 32.2 16.3 71.0 15.9 18.

Koto. 14. The thermal expansion of diopside to 800°C and a refinement of the crystal structure at 7OO”C.O. Cameron. Appl. 1993. Amer. and A. Akermanite: Phase transitions in heat capacity and thermal expansion. 19926. Tomii. and L. Chem. and J..1986. Prewitt. Dickinson. N. Amer... 6. 1983. 98. 1987. 1980. H.286-295. compressibility and thermal expansion coefficient of ilmenite-type MgGeO. Boehler.. Sorrell. M.4489-4495. P. F. R. R. Cryst. Gregoire.. Grebille. L. Mineral. Hazen.1976. R.O-FeO-Fe. A. 129-131. glass and pyroxene and thermal expansion of CaAl. T. Robie. High temperature X-ray study of single crystal stishovite synthesized with Li. Calculation of the density and thermal expansion coefficient of silicate liquids. Appl.2815-2825. Ito. J. G. Minerals. Jr. Aldebert.system and the partial molar volume of tetrahedrally-coordinated ferric iron in silicate melts.. B. 147-150. G.1977. Kristallogr. Hightemperature X-ray studies. Mao. 9. . Y.255-262.. Bottinga. L.SiO. Chem. 7.. T. 95. and C. Buljan. MgSiO. K. Bayer. A. R. Melt densities in the CaO-FeOFe. 30.416-422. L. Finger. and H. 481489. H. 1990.system and the compositional dependence of the partial molar volume of ferric iron in silicate melts. High Temperature-High Pressure. High-temperature crystal chemistry of phenakite (Be. J. 10.. jadeite. and D. S.. Mineral. Thermal expansion of ABO. 1984. Phys. W. 127-135. 77. Y.. PV-T equation of state of magnesiowiistite (Mg.)O. Mao. L. B. Nakamura...: A high-temperature thermal expansion standard. Bottinga... Solids. and J. 4. Cosmochim. J. S.. Brearley. 146-151. S. Weill. Melting. 27. Mineral. Weigel. and revised thermodynamic data. Phys. and C. 72. Datta. and S.875-11. compounds with zircon and scheelite structures. C. K.SiO. and enthalpy of tramsformation. D. 19. E. Hemingway. Ashida. J. O. Minerals. D. 18. Zussman. and J. 18. E..SiO. Chem.577587. Geophys.239-245.. Akahama. 299-311. Akai. 52. and J. 15. Mineral. Geophys.736..1984. 26. Kume. 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Included are many important results published in the last few years which are not available in other summaries. and Sumino and Anderson [118] (f or crystalline materials). Likewise. The discipline of elasticity is a mature one. Union. Bass. 45 WI* where Uij and ckr are the stress and strain tensors. and Melts Jay D. and of Bansal and Doremus [6] (for glasses). which are stiffness coefficients in the linear stress-strain relationship [80]: flij = cijklfkl (1) talline aggregate. We have not made any attempt to assess the relative accuracy of results from different laboratories on a given material. The isotropic moduli listed are are Hill averages of the Voigt and Reuss bounds [135]. there are several excellent compilations of elastic moduli available. Thus. Laboratory measurements of elasticity have been actively investigated for a number of years for a wide variety of materials. 471. elastic properties reported after the compilations of Hearmon [46. notably those of Hearmon [46. we have cited the average moduli computed by Hearmon [46. The main content of the tables consists of elastic moduli. cij . In cases where a . Urbana. only results from single-crystal studies are reported. Except in a few important cases. In conjunction with the density. Also listed for each material are the adiabatic bulk modulus and shear modulus for an equivalent isotropic polycrys- J. are included as separate entries. Results from experiments on polycrystalline samples were uniformly excluded unless no single-crystal data were available. 471. with which there is a degree of overlap. For many materials. 471. the chapter by Anderson and Isaak present considerably more detail on the high temperature elasticity of minerals. the quantity of data related to the equation of state of rocks and minerals has grown considerably. respectively. in the Landolt-Bornstein tables. Consequently.Elasticity of Minerals. This has made the present summary far more compact than it would otherwise be. where available. Bass INTRODUCTION In this chapter I present a compilation of the elastic moduli of minerals and related substances which may be of use in geophysical or geochemical calculations. IL 61801 Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical of Illinois. Here are summarized elastic moduli of most direct geologic importance. Glasses. and by Bansal and Doremus [6]. . complimentary results on the equation of state of minerals from static compression data are found in the chapter by Knittle. the moduli can be used to calculate acoustic velocities using standard relations This chapter is not meant to be either historically complete nor encyclopedic in scope. the results from many older studies are not individually listed. to represent the moduli as components of a 6 x 6 matrix cij where the indices i and i range from 1 to 6. We use the standard Voigt notation [80]. University 1301 West Green Street. D. However. The results in this chapter derive from a variety of techniques which have a broad range of precision.material has been the subject of several studies. Department of Geology. especially where they have been superceded by experiments using more modern techniques. Since the earlier compilation by Birch [16].

Diamond Cu.681 5. Most of the entries are for minerals.8 40 183.500 3.1 36.glSio.512 8.40 81.0 443.7 145 149. to three for an cubic (isometric) crystal.8 153.3 117 122.584 3.438 5.5 134 45 60 57.6 80.os Feo.) grouped together. we have cited the zero frequency. Bunsenit e 122 224 220.6 29.5 226.7 130.7 45.1 80.4 154.5 46 78 78.3 46. In all of the tables.59 71.8 68.7 Subscript ij in modulus cij (GPa) 11 44 12 Me2allic Compounds G GPa 27. Silver C. or relaxed.1 135.584 6.03 82.0 153.4 45.3 166.4 Binary 42.708 5.8 297. although some chemically and structurally related compounds of interest are included.&o.675 7.os BaO CaO. bulk modulus where possible. Lime 191 122 1079 169 230 221*0 222.1 93 95. garnets.0 152. Copper Fe.3 95.6 Oxides 162 92 124 I22 135 135. 326 46.365 5.o G VP T Kelvins Note that for melts.46 ELAsTlClTY The number of independent elastic constants appropriate to a material depends on the symmetry of that material [80]. Wugtite Feo.601 5. It is not possible within the framework of this review to summarize the frequency dependence of the elastic properties of melts or glasses at high temperature.368 5.0 121 116 111.7 163. cr-Iron Feo.950 MnO.5 578 75.2 535.346 3. Au.4 294 296.1 68.4 161. Table 1.2 80.828 of Cubic Crystals at Room P & T KS GPa 171. etc.g. indicated by the subscripts. ranging from two for a noncrystalline substance. Periclase NiO.0 155 155. Gold Ag.7 114.0 137.9 102.349 6. except where specifically noted. In cases where the dispersive properties of liquids were investigated.992 3. Elastic Moduli Material P Mg/m3 19.7 46.o~ Feo.920.1 46.3 123 124.7 164.9 81.94sio.0 162.8 References 47 47 77 46 47 103 72 72 47.932 7. with materials of a similar nature (e. we have listed the results obtained at the lowest frequency.7 218. Tables are therefore organized on the basis of crystallographic symmetry. The notation used throughout the tables is as follows: Symbol Cij P GPa m/m3 P E Pressure Density D Superscripts Indicates constant electric field Indicates constant electric displacement Units GPa GPa GPa GPa m/s Description Single-crystal elastic stiffness moduli Adiabatic bulk modulus Adiabatic bulk modulus at zero frequency Shear modulus Longitudinal wave velocity Temperature Ii’s ICs.8 344.3 123.3 130. the compositions of solid solutions are given in terms of mole percentages of the end-members.4 217 227 223.3 216.684 7.1 141 160.874 7.730 5.5 80.3 181.3 68.0 149.7 205 .5 162.8 114.283 10.4 70. to twenty one for a triclinic crystal.4 46.7 112.1 58. 111 81 47 120 56 15 47 89 138 46 57 152 134 Elements.6 34*4 80.0 coo Fec.8 131.5 260 245. Manganosite MgO.1 79.584 3.9430 Feo.0 81.8 155.346 3. elements.4 44.

280 3.4 14.2 306.0 47 12.5 112 155 118 33.6 59.3 184 226 179 142. Magnetite FeCr204.4 100.5 25.9 85 87.9 108.0 Mgo.8 6.2 104.5 187 289 281.5AlzOs 5.6 -44 24.4 153.75Feo.7 97 84.705 3.6 95.2 310.578 3.09 3.97 5. Chromi te M&04.5 98. Frankdicksonite CaFz.5 133. Galena ZnS.6 41.9 111.3 182.578 3.3sA11.8 40.775 3. Sphalerite BaFz.8 100 157 147.567 3.160 3.206 5. Sylvite Pyrope PY).4 84 95.163 1. ~gdWMh2 Grossular.0 203.6 304 309.3 24.8 114.5 108.9o04.9 References 46.1 172.9 94.7 210.181 2.2 173.3 .6 94.0 327 366 300 Sulphides 95.389 5.5 115. Halite KCl.5 312 303 269.1 42.5 6.2 114 23 44.28 Andradite (Anss) CasFet3SisOra AwoGmAlmd’y3 ~mJ’y2&m23Sp~ Ah&dhSpllA& Ahd’mGr&h PyrsAlmrsAnd4Uvs PYdhdh 3.7 58.4 64. (continued) Material MgTm” SrO UOz.6 295 90 321.5 119 106 110 125.6 216.7 149.1 57.74(H404)1.6 301. Uraninite Fe&.4 92.088 4.6 77. Fluorite NaCl.7 168 158 163.3 116.4 114.0 89 108.5 110.3 196.2.9 18.4 176.9 298.5 126 106 126 105.5 57 92 80.4 111.2 91 113.559 5.9 92.2 63.6 157 156 143.131 4.602 3.7 117 154 154.0 202.7 25.826 4.3 170.0 206. 116 35 47 47 47 46.3 90 92.7 Oxides 46 119 104 108 144 154 155.6 158. Hercyni te 7-MgaSiOd.9 31.9 99. Ringwoodite Ni$SiOd MgAMh Fe&.839 275 270 322 282 282.7 9.009 Subscript ij in modulus cij (GPa) 11 44 12 170 389 Spine1 Structured ITS GPa 87. 24 152 106 126 46 46 130 130 144 13 140 108 47 47 47 46 46 46 46 85 67 11 10 11 86 10 5 84 5 111 121 136 10.4 91.195 3.0 171.016 7.7 101.8 177 168.0 162.7 104. Pleonaste FeA1204.351 4.6AlaOs Mg0.8 86.1 83 91.597 4.886 3. Spine1 Mg0.BASS 41 Table 1.7 197.6 Halides 361 402 127 102 Binary 90.8 157.9 202.(Gres) CasAlsSisOr2 Uvarovite (Uv) Ca3CrzSi3012 Spessartite (Spsa) MnsAlaSiaOr2 Hibschite Ca3A12(Si04)1.6 G GPa 58. Pyrite PbS.7 306.7 104.2 91.6 300.619 3.7 153.8 177.7 91.850 4.741 4.4 162 178.63 55.6 94.3 92.987 3.3.3 64.5 266.1 117 91.5 94.3 108.9 92 96.27 Garnets 296.3 198.836 3.563 3.2 296.9 49.7 31.3 209 161.13 3.3 165 33.9 112.1 12.

2 5.96 37.7 60. Greenockite 4.9 62. grossular. almandite.3 48.40 30.i66pY34 170 92 172 92 174 115 Sp.5 180 177 125 94.3 References 14 153 153 18 47 47 46 47 61 61 46 37 47 47 46 61 61 46 HzO.724 2.48 ELA!377CITY Table 1. Mj.4 46.6 283.9 14. Alm. Graphite 2.8 46.527 Nal.0 209.5 13.1 13.5 1060 140 141 79 86.8 83.2 36 44.6 (NazCa)4(Al.698 Bea&SisGis C.0 15.70 79 117 209 207. Fluorapatite Cancrinite 2.9 5. (continued) Material MgTm3 4.1 3.8 128.249 Majorite 3. Hydroxyapatite 3.5 94.Si04)sCOs.2 308.1 50.s7Mgl.1 28.9 17.571 5. M.6 122 13 119 114.G arnet Solid Solutions Its GPa 177.084 .545 3.5 15 69 56 21 47.3 36.3 48. andradite.8 14.0 80. Bromellite Beryl 2.8 15.5 94.26 3.9175 2.7 41.5 6. Uv.675 Wurtzite. Table 2.200 Calo(P04)sFz.606 329 114 96 Abbreviations: Py.9 11 470 304.9 74.7 120.8 30.2 44.4 58 at Room P & T Ii.9 56.5 221. spessartite.lsSi4.0 46.3 42 GPa 251 176 181 161.4 96.2 15.2 109. pyrope.7 8.5 142.70 125 110 218 209.3 37.3 (Mj) .4 6.824 CD CE of Hexagonal Crystals (5 Moduli) Subscript ij in modulus cij (GPa) 33 44 12 494 277.0 G GPa 162 78. majorite (Si-rich and Al-poor garnet).8 46.nHzO CdS.2 33.0 138 153 65.7 16.8 112.94012 3.63 21 33 104 106.6 101.48 3. ZnS 4.1 101. Nepheline /3-SiO2 (873K) ZnO. Elastic Moduli Material MgTm3 3.7 168 123.1 89 References 132 12 150 150 90 3.01 BeO.5 118.555 MjdYtx Subscript ij in modulus cij (GPa) 44 12 11 308.72 8.1 .73 48.9 180 13 46 38 54.3 45.97 38 16 120 117.7 60.0 51. Ice-I (257K) Ice-I (270K) NasKAl&Cis. Gr.3 45. Zincite CE CD 0.3 66.6 142.09 2.4 212.5 83.3 3.146 Calo(P04)s(OH)2. An.4 36.5 17.1 44.8 79.4 143. uvarovite.7 164 G GPa 96.

960 BezSiOa MgSiOs 3. Nitratine Ag&%.8 87.7 6.620 2. (cD) CaCOz.5 29.8 91. 50 148 141 3.59 11 495 497 64.5 -19 K’s GPa G GPa 162.8 43.8 24 212 .0 70 -27 -19.8 37.0 206.5 References 46 83 25 32 46 1.0 68.5 Subscript ij in modulus (GPa) 33 44 12 cij 13 497 501 85.4 (Na)(Mg.9 51.6 59. Elastic Moduli of Trigonal Crystals (6 Moduli) Mineral Mgym3 A1203.1 -6 37.5 212.2 Tourmaline.0 168 57.4 -20.74 107.9 73.0 44.7 GPa 94.Fe+2.1 2.4 44.F)~ Table 4.0 362 156 34.100 305.7 32.8 -17.0 123.6 18.9 39.9 11. Eskolaite FeaOs.7 98.6 14.2 10.0 114.8 144 374 259 54.8 19.2 2.712 5.648 86.9 472 Subscript ij in modulus (GPa) 33 44 12 cij 13 14 113 391.2 CD 2.6 -19. Magnesite NaNOs. 46 69 46.8 37.25 108 at Room P & T 14 -23 -21.A1.Fe+3.5 159 54.9 58.0 148. 50 46 47 46 46 46 87 115 116 9. (cE) Berlinite.999 3.1 175 58. 3.0 12.3 234.254 3.Li)sA1s(B0s)s(Sis0~s)(OH.4 106 71.2 33.BASS 49 Table 3.260 5.5 0.795 CaMg(CO3)a Phenacite 2.4 136.795 Ilmenite structure 11 205 341.0 7. Corundum AIP04.6 11.2 91.8 -17. a-Quartz cE 3.9 51 251.97 57.0 69.7 253.0 382 39.7 6. 3.8 57.009 2.6 106.1 84.6 53.4 13.982 2.648 86.9 148 75. Proustite SiOn.3 9. Elastic Moduli of Trigonal Crystals (7 Moduli) Material MgTm3 Dolomite.18 36.5 81.0 176.648 86.6 12.9 31.9 G GPa 45.5 163.0 64. Hematite MgCOs.0 11.2 0.8 160 162 7.98 6. Calcite Cr203.1 at Room P & T IC.7 15 13.8 146 146.9 132 References 46.2 42.5 28.47 107.2 33.0 32.3 29.3 33.21 5.5 127.9 -12. Sapphire.9 -18.8 11.3 44.

2 269 337. Paratellurite Ti02.99 4.3 82.4 19.9 38.7 146 215.7 33.6 -15.4 261.675 Zircon 4.8 KS GPa 81.1 73.4 45.0 21. Elastic Moduli of Tetragonal Crystals (7 Moduli) Material MgTm3 CaMo04. Elastic Moduli of Tetragonal Crystals (6 Moduh) at Room P & T Material MgTm3 11 Subscript ij in modulus cij (GPa) 33 44 66 12 Rutile-Structured SiO2.70 ’ nonmetamict.K)4Als(AI.02 5. Presnoite (cE) Scapolite.255 6.0 140 23.4 65 61 68 63 13 47 41 53 51 at Room P & T 16 -13.1 43.7 26.8 G GPa 39.290 2. 105.4 150.3 256 776 42.8 177.5 Other Minerals 83 33 100 31.Si)s SkO24(CGO4. a-Cristobalite SnO2.1 29.1 29.7 55.4 24. (Na.119 6.1 55.2 51.9 37.5 316 16.9 223. 13 KS GPa G GPa References 4.CO3) Vesuvianite CaloMg2A4(SiO4)5(Si207)2(0H)4 ZrSiOa”.6 227.4 59 69.7 113 15.7 207.5 108.4 22.816 11 144 141 109 108 33 Subscript ij in modulus cij (GPa) 44 66 12 36.0 66.5 -17 -13.7 175 203 -4.1 38.8 33.4 43.3 372 131.5 187.975 6.8 489.4 30.8 42.2 140 166 99 102 102 153 424.9 30.0 65.5 72.5 109.2 43.335 6.6 140 23.7 35.4 212.4 54.260 6.3 116 211 3.2 192 258.3 220 39.9 Table 6.9 48 69.9 55.4 65.3 23.0 76. Powellite CaW04.8 26. Wulfenite 4. Scheelite PbMo04.6 58.8 45.2 36 58 35.279 453 59.6 252 67.50 ELA!XIClTY Table 5.0 166 55.6 143 151 22 93 122 47 131 46 46 47 47 47 47 88 47 Cassiterite TeOz. Rutile GeO2 BazSizTiOs.4 70.8 40.3 43.0 48.9 77.1 101.6 177 188.0 112.8 20.4 449.7 53.6 24 44 35. 4.7 26.3 44 149 214 56.4 155.4 161.5 25.5 24.4 480 124 599.2 103.3 65.4 257. Stishovite SiOz.5 21.Ca.2 48.1 302 25.0 References 46 46 46 46 127 125 92 95 .

3 54.029 328 266 320.5 76.7 107.4 112 52 73.8 59.7 46.6 150 238 194.2 217 66.7 324 319 258.7 83.5 74.2 81. FeSiOs Ends6 Emdh5.335 3.325 3.5 169.7 187 235 232 233.6 231.354 3.9 78.1 Fo9dh Mn2Si04.8 235.299 4.6 70.7 57.1 79.8 72 92 77 113 103 66 129.198 4.8 79.2 43.1 75.8 184 253 234.38 3.7 77.2 323.706 4.7 79.6 49.3 46. MgSiOs Ferrosilite (Fsrcc).7 198 229.0 213 22 525 147.9 78.7 210.4 215. FeaSiO4 Fog1Fag Fodb hxd’aa.7 57.5 76.0 103.7 Pyroxenes 202 44.5 77. Elastic Constants of Orthorhombic Crystals at Room P & T Material MgTm3 MgSiOs NaMgF3 Enstatite (Enloo).7 246 179 46.5 87 63.221 4. Monticellite.272 3.933 4.3 50.7 78.5 64.9 136 167.7 128 106 165 148 120 50.6 56.1 72 49.6 71.3 177.8 45.5 109.1 80.8 152 Subscript ij in modulus cij (GPa) 33 44 55 66 12 Perovskites KS 13 117 45.8 71 69 69 92 73 92 78.5 81.5 72.8 61.6 49 77.5 44 81.373 3.4 84 73.1 54.1 78.1 81.6 46.8 75.8 312 200 168 195.116 4.9 66.9 75.5 213.4 71.8 57.9 197.9 63.4 184.1 76.6 68.4 160.2 78 64.7 52.1 126.2 hd’s2o Protoenstatite.7 55 46. MgSiOa Forsterite (Force).6 71 46.1 232 238 206.0 78.9 58 76.002 3.6 196 192 165.2 63 77.316 3.0 78.3 55.9 66.3 63.0 49.2 80 62 72 46 55 136 65 82 82 117 92 13 117 140 67.1 77.311 3.6 63.9 228.4 216 340 307.1 78.5 71.3 229.6 59 79. CaMgSi04 Ni2Si04 CozSiO4 MgzGe04 4.5 75.8 81 Olivines 3.4 75.4 128.9 205.1 71.Table 7.5 59 87 59 70.8 75.129 3.7 32.0 165.4 59 23 GPa G ReferGPa ences 149 155 142 9 31 64 31 137 123 435 142.052 11 515 125.6 79.3 105.0 54 55.9 76 139 246.1 134 129.9 75.9 57 78.108 3.6 175 193.5 76 95 71 110 105 65 60 .1 70 101 102.1 67 117 49.8 82. Mg2Si04 Fayalite (Faloo).5 129.058 3.7 224.

3 107 110.2 53.4 162 94.972 2.4 160 527.7 80. Fo.9 8. 2.2 60 25.4 48.3 21.2 29.1 3. 4.1 97.8 43.0 26. forsterite. fayalite.2 89.6 15.1 91.9 19.05 CaBS&040H Staurolite.7 198 155 185 349 65. 3.8 74.8 15.6 112 129 67.9 51.7 9.Mg)2(A1.474 11 360 22 383 Subscript ij in modulus cij (GPa) 33 44 55 66 12 Other Silicates KS 13 110 23 105 GPa 174 G GPa 114 Heferences 105 Wadsleyite.5 126 126 46 46 46 45 46 46 46 46 133 46 46 46 46 47 Sulphates. 3.7 Carbonates 112.Table 7.7 167.3 18.0 29.3 16.5 6.3 28.3 38.930 233.9 78.8 104 80.9 240 91. 87.6 145.1 93.9 27.5 27.6 42.2 55.7 128 34 41 128 88 36.Fe3+)OsSiOs(0.9 27.065 4.8 48. (continued) Material P Mg/m3 3.4 Sulphides.7 151.6 13.4 114. Aragonite 273 112 118 98 75 3.6 57.4 46.3 22.6 23.2 83.2 289.6 1.4 84.9 18.4 128.4 287.8 15. Thenardite CaC03.0 25.79 (Fe.4 17.7 380.8 80.8 59.5 12.8 37. 3.3 3.1 7. .7 4.27 12.3 Minerals 8.1 388.8 50.7 158.5 77 29.6 81.145 3.473 2. Celestite Na2S04.0 58.8 Other 99.25 465.5 160 64.1 29. Fs.2 99.3 70 132 24. @-MgzSiOd AlzSiOs Andalusite Sillimanite Sulphur BaS04. Fa.663 2.4 Abbreviations: En.5 22.6 4.3 7.3 89.2 54.72 Al2 Be04 Danburite.1 46 108 19. enstatite.7 131 215 343 281 72.7 170.3 26.0 47.5 92 131 41.8 32.0 83.8 41.OH)2Si04 Natrolite. Barite CaS04.563 Alz(F.2 438.7 185 106 105 87.7 111 64 50 61 84 25.4 26.5 13.3 24 14.7 33.3 8.241 2.9 81.99 CaBzSizOa Datolite.5 14.8 23.9 20.963 3.7 62 16.0 37.0H)2 Topaz 3. Anhydrite SrS04.8 32.7 81. ferrosilite.3 125 50 44 67 125 29.4 64.0 231.8 211 110 147 294 138 144.0 11.0 95.6 116.1 Chrysoberyl. 2.8 31.7 5.5 122.1 31.

5 67.8 69.8 137 82 145 20.7 -30.5 66 50 42 -6.9 Plagioclase Solid Solution&’ 17.8 -12. NaAlSisOs Anorthite.9 52. 3.3 81 37.Al)(Si.9 222 274 245 175 171 149.6 -12.0 -19.7 51.7 217.3 26.7 14.7 27.3 113 -8.7 -6.6 46 47 47 47 47 47 47 47 13.7 112 4.6 12 4 -40 4.1 18.6 39.2 81.9 -0.7 21.6 151.3 234.4 39.1 143 123.9 26.1 31.K)AlzSizOs Labradorite”?’ KAlSisOs Microcline Oligoclase” An9 Am4 11 22 33 44 Crystals at Room P & T 25 9.8 70.1 102 -11. 3.3 23.3 114 7.7 34.0 46.4 24.3 204 223 153.7 35 21. CaAl$i20s.2 32.8 216.9 26 28 -14.1 62.5 70.0 23.4 30.3 30.2 61 85 72.5 -1 -1.33 NaAISiaOs Spodumene.32 (Ca.7 -12.4 -1.4 25.A1)20s 3.5 39.8 67 62.0 56.1 62.8 Pyroxenes 185.1 25.2 -33.7 59.0 -2.7 -2.6 -10.9 -2.5 55.2 46 KS GPa G GPa 58.9 45.4 62.5 49.9 19.0 50.4 31.1 29. 3.6 7 14.9 155.6 25.3 29.2 58.3 -23.6 19.7 28.7 -5.2 63 65 70.657 CaFeSi Jadeite.9 38.9 84.4 62.31 CaMgSizOs 3.42 AcmiteAugite Diopside.4 74.7 26.30 Hedenbergite.5 74 63.6 85 -10 120 13 -7.0 -19.4 .8 -7 -7.5 40.6 -19 -12.8 163 74.8 64.3 95 181.8 36.50 NaFeSizOs Augite.7 88 74 124 67. Hyalophane.9 67 61.8 21.5 33.2 31.9 69 94 88.0 169 80.2 -18.0 -18 -15.1 -8.6 26.1 35. (Ba.4 131 205 161 158 128 156 124 150 118 124 129 133 Feldspars 17.7 62.5 86 82 69 -19.8 28.0 46.6 32.3 17 14.3 60 94 84. Elastic Constants of Monoclinic Material MgTm3 Acmite.4 68.8 33. 3.7 37.6 176 253 199 238 235 210.5 70.1 40.2 13 14 -26.8 249 282 287 67.7 -15.8 73.19 LiAlSilOs Albite.8 48.289 Diallage 3.4 41.1 55.4 77 56.0 28.5 18.3 29.9 55 88 58.Fe.1 -1.Na)(Mg.4 -0.6 150. 3.4 -15.8 41.5 37.0 33.4 79 71 64 48.6 43 11.8 62.0 -6.2 57 30.Table 8.3 -20.0 68.7 -9.4 72.5 66 52.4 99.4 42.0 36.4 33.9 51.4 16.3 35.6 7. 3.0 References 3 3 3 3 68 3 59 60 46 Subscript ij in modulus cii (GPa) 55 66 12 13 23 15 9.0 47.4 45.1 66.8 181.

3 46 -1.3 -2.0 159.2 8.7 -1.0 42.7 71.6 61.4 10.0 43.Fe. .8 238.12 116.9 0.2 25.8 73.7 -3.1 102.7 45.0 35.3 2.7 58.6 72.6 57. anorthite.0 -2.2 -6. Or.4 31.8 2.6 -2.0 36.3 45.8 52.40 Caz(Al.9 28.2 36.9 53.5 -9.4 34.3 GPa 63.1 G GPa 31.54 2.1 -1.2 42.0 18.8 -9.6 1.6 35.5 Na-K 14.7 37.4 62.5 -1.8 -5.0 32.8 36.0 37.4 231.9 43.0 61.1 -15.1 187.8 -7.56 2.0 26.3 61.15 130.3 33.0 57.8 31.9 23.7 47.4 10. 2.6 34.3 36.6 0.3 -12.8 173 Subscript ij in modulus cij (GPa) 55 66 12 13 23 15 KS 25 -6.0 -11.1 26.7 202. (Ca.1 20.8 20. 47 124 3.0 49.9 61.0 Sulphates 41.5 87.3 37.1 38.0 -18.1 16.8 24.4 59.2 50.7 46 46 Abbreviations: Ab.1 40.9 -17.57 2.8 33.2 Feldspar Solid Solutions Ovb 22.2 77. Gypsum.2 -10. 47 2.7 -2.0 -11.2 -0.5 4.4 36.1 -39.2 43.7 72.1 163 98.317 78.1 36.9 3.8 35.7 12.Table 8.3 35.4 106.8 230.0 48.4 65.3 19.6 32.Na)2-3(Mg.3 34.0 93. An.6 -36.2 45.8 -2.4 -14.1 6.3 58.Fe)sSia012(0H) Hornblende.9 59.5 33.4 53.5 34.7 198.9 61.4 34.5 15.1 9.8 24.3 36.8 -10. b Subscripts indicate weight percentages of components.3 13.2 148 103 18.9 32.9 20.1 51.7 24.1 -4.8 82.Al)5(A1.7 191.6 158 105 20. 2.1 -12.4 51.0 -2.8 35.9 158 100 Silicates 160.911 Epidote.3 178.0 17.9 14.6 -10.1 42.2 -13.6 -2.5 65.2 61.0 70.6 67.9 10.0 36.4 57.9 113.8 21.8 21. ’ Triclinic.3 37.9 -12.2 211.4 15. albite.0 21.5 172 124 18.6 62. (continued) Material MgTm3 An29 Ana3 An56 Or79Ab 19 Ovdbz2 Or67Ab Ordb35 0mAbz7Am Omaha 2. Coesite 2.4 42.5 27.8 3.9 35.1 13.2 -7.5 -11.4 61.1 43.0 -18.Si)sO&OH)2 3.4 CaS04 94.54 2.4 9.0 39.6 9.9 49.4 -7.0 -40.6 -1.5 48.3 -6.4 -1. ’ Labradorite is a plagioclase feldspar with composition in the range 50-70% anorthite and 30-50% albite.5 -3.4 59.2 32.3 -14.4 10.0 152 118 26.2 23.4 KAlaSia01o(OH)2 Sulphides.5 66.1 -12.0 28.57 11 22 33 132 141 141 44 84.3 32.8 -15.6 -8.2 35 -18.4 33.3 23.58 2.5 -11.0 Muscovite.3 -1.4 147 99 63.2 -8.9 44.5 -6. 3. quasi monoclinic.2 References 47 47 47 47 47 47 47 47 47 139 104 SiO2.4 151 97.3 24. orthoclase.2 44.3 58.844 184.

1 17.8 19.842 3.17 2.7 17.39 2.665 3.52 fL.61 2.2 21.9 7.8 22.943 3.17 2.2 19.+a Awdh hdbo AhDko Abdh.680 7.2 20.60 2.4 8.96 3. Ab33An33DiB BaSi205 CaSiOa CaTiSiOs CszSiz05 caMgsi&& Di (Di)” (An) and Velocities in Melts T K 2490 3950 1833 1893 1923 1677 1673 1673 1573 1753 1698 1598 1753 1648 1698 1583 1793 1693 1836 1753 1653 1693 1208 1773 1758 1698 1693 1598 1653 1503 1693 1408 1698 1498 1693 1411 1543 1913 1094 1322 1684 1599 1690 1693 1408 1573 1458 kg/m3 6.4 22.0 6.10 2.61 3.8 52.955 3.9 20.aJ GPa 94.8” 16.22 2.9 23.5 20.803 3.662 3.50 3.3 11.16 2.7 19.4 24.013 3.20 2.54 5.08 2.2 15.0 100 100 63 63 63 63 63 100 100 100 100 .56 2.2 27.5 15.635 3.45 2.858 3.26 2.2 24.46 2.3 20.54 2.76 2.49 2.4 20.529 3.7 20.65 Fe&i04 KzSi205 KzSiOs Liz!%205 LisSiOs MgSiOa NaCl (Naz0)~(A1203)s(Si02)61 (Na20)32(A1203)15(Si02)52 N&$05 NazSiOs 8.4a 18.6 22.83 3.40 2.BASS 55 Table 9.* References 48 48 100 107 99 107 98 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 99 100 100 100 100 100 100 100 100 100 100 100 100 3.565 3.951 4. Elastic Moduli Composition Fe CaAl$!&Os An” Ad& h36Di6.764 5.0 16.6” 14.44 2.34 2.023 3.1 19.25 15.712 4.040 8.0 16.944 3.8 18.48 3.65 2.5 8.71 3.5 19.47 2.100 3.906 3.484 4.852 3.833 3.0 24.014 4.12 2.3 16.6 20.4 16.4 17.558 3.909 5.1 8.242 4.934 3.854 4.61 2.61 2.60 2.51 3.44 3.67 3.4 2.652 3.14 3.922 3.61 8.6 10.990 10.22 2.01 3.6 21.55 2.61 3.0 2885 2910 2850 2735 2830 2800 3400 2805 2880 2390 2410 3120 2590 2580 1450 2345 3040 3020 2345 2450 2400 2450 2190 2600 1890 1970 2670 2740 3160 2860 1727 1540 2653 2695 2835 2525 2680 2663 2752 3.1 19.707 3.6 VP m/s 3808 3075 2850 Frequency loss.

29 2.3 39.723 References 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 106 OmAm or61 Dk9 Rb$SizOs SrSi205 Tholeitic Basalt Basalt-Andesite Andesite Ryolite Abbreviations: An.9 19.833 3.88 3.33 2.2 41.8 14.35 2.5 78.1 33.44 2.2 41.7 -0.889 3.6 2.6 13.673 3. Ab.1 17. CaMgSi2Os. CaAlzSinOs.1 69.6 19.9 G GPa 31.836 3.8 9.0 30 37.790 3.4 6K/6T MPa K-’ 16 6G/6T MPa K-l 4 References 38.31 1783 1598 1768 1578 1693 1408 1758 1653 1708 1505 1803 1503 1783 1553 1803 1553 I&X2 GPa 13. GPa 36.1 16.839 3.0 29.909 3.8 0. Di.2 30.2 76.0 16. NaAlSisOs.8 52.9 18.777 of Glasses I(.1 -3.847 2.490 2.4 -10.8 69. 79 129 129 129 113 129 129 75 129 44 74 75.693 2. Elastic Moduli Composition kg/qn3 SiO2 MgSiOs CaSiO3 caMgsizo6 CaAlaSizOs Na2Si20s (Nazo)3s(SiOz)ss” NaAlSisOs Na2AlzSizOs (Naz0)30(Ti0z)zo(Si0z)soa 2.5 -1 -1.5 VP m/s 4300 5200 2795 3470 1678 2130 2550 2570 2600 2610 2700 2980 2775 3850 4350 5280 Frequency loss-’ 3.1 50.974 3.1 23.4 (Kz0)z5(Si0z)75a Obsidian Andesite Basalt ’ Composition given as mole percentages of oxide components.1 45. 36 79 79 79 4.8 38.7 -9 -7.0 39.7 24.9 -4to+4 -1.1 16.65 2. ’ From shock wave experiments.8 -0.35 0.369 2.495 2.0 13.6 2.880 2. Table 10.46 2.3 18.38 2.9 41. .6 20.4 4.690 3.40 2.9 74.5 7.204 2.863 2.4 16.6 36.923 3.2 21 30.2 30.749 2. Or.3 .827 3.04 2. KAlSisOs.12.656 3.664 3.02 3.494 2.78 2.8 36.7 -0.1 0.5 62.68 2.2 -7 -8.55 2.761 2.571 2.56 ELASTICITY Table 9.59 2.42 2.1 -2.863 3. (continued) Composition T K kgTm3 2.5 6K/6P -6 6G/6P -3.7 38.945 3.331 2.

114 22 78.5 -48.5 2. Spine1 %Wh Mg0.7 -27 -33 -47 -43 -14 -17 -30 -27 -24 -24 -12.1 -12.7 Structured Oxides -11 14.1 4. 114 81 26 120 120 56 69 131 138 89 120 115 4 52.2 5.2 -14.83 1.303 195 . Gold C. 52 52 26 8.920.13 4.5 -31.373 @293 298 . Wadsleyite MgA1204.3 1. 40 40 40 2G 127 112 8.9430.2 -36 -12 293 .27 5.27 2.89 4. 102 29.55 1.78 coo Feo.97 5.78 1. 73.293 300 .0 P-Mg2Si04.118 34.7 -14.800 @30011 @1200K @180011’ 281. (bee) 6.0 4. Periclase 3.18 6.16 3. 49 71 103 103 39. Lime 5.583 2.8 20 -20 @296 @lOOO @1825 281. Hematite G&t.5 1. (rutile structure) MnO.61 0.5 6.1 -19 -8.23 6.3 -17. 76 35 43 70.12 1.BASS 51 Table 11.3 1. 128 29.473 @298 300 .09 6. SiO2.0 -13.4 -21.7 -9. Wiistite Feo.7 0.152 Simple A1203.52 5.5 4.82 1.7 -15.8 -15.373 MgO.91 2.7 -8.13 4.0 -8.6A1203 1.76 4.8 -7. Manganosite -15 -23 -19 -23.50 6.3 -14.4 AT K 79 .5 2.303 @I298 5.9 -7 -14.298 79 .66 4.18 -20.0 5. TiO2.61 0. 57 23.293 283 .64 1.6 -11.7 -0.42 Spine1 SrO Sn02.298 195 .9 -6.298 References Ag.46 0. 42 29.7 -31 -43 -51 -43 -18 -19 -33 Oxides 223 25 300 500 800 77 80 298 - 323 300 500 700 900 300 298 900 17 17 77 29.85 4. Corundum 4.5 -22.8 -21.4 6. 110.2 1.4 293 .7 1.9 112 12. UO2.71 0.0 5.4 -5. Diamond a-Fe. Silver Au.3 -21 -15. P and T derivatives of Isotropic Elastic Moduli Material 6&/&P 6G/6P GKs/ST &G/ST MPa/K Elements.3 -19. Wiistite FezOs.298 293 .2.0 -14.8 5.1200 281 .73 1.29 5.5 -21.68 1.28 4.298 195 . Cassiterite Quartz Rutile Uraninite -24 -26 -21 -12.293 298 .3 BaO CaO.423 24 106 . Metallic Compounds MPa/K -12.6 273 .13 4.69 4.

Spessartite Mn3A12Si3012.06 2. NasKAl&Ors Zircon.8 1.2 865 -19.0 2. CaCOs Nepheline.13 4.5 -17. FesSi Orthopyroxene (Mg.6 -13.00 77 .37 1.353 298 . Berlinite Beryl.2 -5.9 -2 298 .9 -14. Alm.74 4.5 -13.0 -15. Almandite Mg3A12Si3012.80 -17.1250 300 298 293 300 700 306 673 1700 Other Forsterite (Fo).300 298 . Fo.05 4.5 -1.8 9.6 -15.56 Halides 0. FeaSiO4.13 -10.75Feo.8 -13 288 .5 -3. .27 5.71 1.6 -18.7 -15. Pleonaste PbS.2 -7.2)SiO3 AlPOd.9 -24 Olivine.9 KCl. Andradite Ca3Fe2Si3012. BesAl2SisCrs Calcite”.83 2.373 195 .9004.14 -9.0 -9.0 -16.44 1.4 298 .1350 300 .40 -20.313 300 .1500 300 .500 10.92 5.573 Abbreviations: Py.38 -26.97 5.7 6.79 1. MgsSiOa 4.1000 298 .6 -9. Sylvite 5.256 0.5 4.78 -21 1.8 -7 -11. Fogs Fo9&7 Fog1Fag Fodalo FogzFaa Fayalite (Fa). Ca3Cr2Si3012.1 -14.d%.9 298 .7 Garnets 2.56 5. 30 146 121 137 20 132 111 54 54 41 65 119 53 154 65 136 51 51 55 137 33 25 153 58 19 88 Uv.2 -8. Pyrope Mg3AlZSi3012.5 -15.5 0. ZrSi04 4.6 1.90 4.93 4.0 -8.623 180 .298 -3.5 -13.92 0.0 -16.00 Binary -39. And.95 5. Fayalite BaF2. Forsterite MgzSi04.82 1.56 -18.5 -12.6 -10. Halite -14.30 -13.94 21 145 145 7 116 147 147 7. Uvarovite Fa.8 -11. Galena ZnS. 28. Fluorite NaCI. Frankdicksonite CaF2.28 4.58 ELASTICITY Table 11.298 195 195 300 294 745 300 294 298 295 800 338 766 1000 91.5 -10.1500 300 .6 3.7 Minerals 298 .6 -13.36A11.6 -12.338 -10. Sp. Grossular Ca3A12Si3012. (continued) Material iX’s/bP GGISP 6Ks/6T &G/&T MPa/K MPa/K AT K References 130 Mgo. Gr.29 Svlphides 6.2 -9.43 1.37 5.0 -13.306 300 . a Pressure derivative of KT is given. Wurtzite 4.

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a. Los Angeles. coupled with the elasticity data. Poisson’s ratio. Using the techniques of resonant ultrasound spectroscopy (RUS) [6. determined from sound velocities. Institute of Geophysics Planetary Physics. In Tables 15-28. v. allow the computation of the Griineisen ratio y and then values for the isothermal bulk modulus KT (computed from KS) and the specific heat at constant V Cv (computed from Cp). Isaak 1. we present isotropic thermoelastic properties. 0. UCLA. From the values of properties in Tables 15-28 the temperature derivatives are calculated. they are restricted to temperatures at or near room temperature. which allows the respective isotropic longitudinal and shear sound velocities. [60] (see Shankland and Bass [49] for a review of techniques). to be computed from KS and G. and (YKT and its integrated value APT. where 0 is the Debye temperature [13]. INTRODUCTION Though compendiums of elastic constant data for minerals exist [ll. We present the elastic constants. G. at high T for fourteen solids listed in Tables 1-14. . We note that of the several RUS techniques. Cij versus T. We also list the Debye temperature. including the adiabatic bulk modulus KS and the shear modulus G obtained by appropriate averaging schemes (See Section 4). Center for Chemistry Physics of Earth and Planets. Anderson and Donald G. the predominant technique used to obtain the data here is the rectangular parallelepiped technique (RPR) pioneered by Ohno [44] and Sumino et al... the dimensionless ratio of change of G with T. up and v. 591. 64 and and The techniques of RUS do not lend themselves to pressure measurement. elastic constant data have been taken above the Debye temperature of mantle minerals. Isaak. We list the Anderson-Griineisen parameters. oxides. 6s and 6~. which is the change of thermal pressure relative to the pressure at 300 K. often as high as 1825 K. L. and two alkali halides. 71. thus defining several important dimensionless thermoelastic parameters that are presented in Tables 2942. and the measure of the rate of change of shear sound velocity with the longitudinal velocity. A synopsis of quasiharmonic theory in the high temperature limit shows that anharmonic corrections to the quasiharmonic determination of thermal pressure are not needed in the equation of state throughout conditions of the lower mantle. Values of thermal expansivity CYand specific heat (at constant P) Cp. 50. 2. included are silicates. Equations for extrapolating the bulk and shear moduli to temperatures beyond the limit of experimental measurement are given and evaluated.Elastic Constants of Mantle Minerals at High Temperature Orson L. The density p is computed from (Y. which is of the order of T = 20. I?. ABSTRACT Data on elastic constants and associated thermoelastic constants at high temperatures for 14 solids of significance to geophysics are presented and discussed. CA 90024 Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union. 0. Anderson and D. Current problems in mantle geophysics and geochemistry often require values of elastic constants at temperatures found in the lower crust and mantle (1000 to 1900 K).

7 98.3 57.6 88.2 88.3 155.66 58.6 292.4 98.7 307.5 92.6 96.0 224.0 f0.1 97.7 91.1 88.23 58.8 282.62) Cl1 Cl2 c44 c.5 f1.6 98.l 215.9 86.0 108.5 90.0 f0.72 74.3 139. cs 318.6 66.9 f0.0 85.0 84.0 95.7 274.4 107.2 101.5 75.7 103.52 64.0 Al.2 196.6 98.48 f0.5 Al. modulit (GPa) from 300 to measured value of T/O: 1.2 231.8 87.5 101.09 81.4 = (1/2)(Gl-- tAfter Isaak et al.0 91.3 152.8 154.2 134.25 73.3 94.2 94.7 289.89) Cl1 Cl2 c44 c.2 261.7 63.6 106.2 287.3 113.44 58.67 f0. 157.9 89.5 268.4 86.17 73.1 108.9 105. Table elastic (max.7 91.7 249.94 77.0 89.4 99.5 137.8 303.2 102.6 f1.3 f1.9 f0. modulit (GPa) from 300 to measured value of T/O: 1.6 97.8 300.2 296.2 98.7 148.8 315.6 89.7 95.3 86.2 182.8 273.8 89.2 296.8 96.96 58.2 G2).5 283.1 85. MgO: modulit measured Cl1 AND ISAAK single- 65 Measured single-crystal Table 3.9 106.8 f1.1 284.ANDERSON Table elastic (max.8 91.7 292.7 86.99 ho.04 78.3 237.1 f0.28 68.2 f0.3 149. .2 101.4 f0.5 f0. 1.5 98.7 205.1 271.5 fO.7 97.02 79.0 187.7 f1.18 76.6 104.9 61.8 143.4 100.5 T W) 300 400 500 600 700 800 900 1000 1100 1200 cs Tw 300 400 500 600 700 800 900 1000 1100 1200 1300 1350 220.2 89.4 106. [34].2 104.6 274.5 72.2 Gz).1 146.88 66.72 71.92 74.9 103.5 276.8 151.1 f0.81 58.98 58.3 285.3 278.1 88.8 90.9 296.5 294.5 91.03 f0.6 88.5 89.70 77. 2.2 f0.9 C12).6 104.8 89.4 98.1 101. [43].2 103.7 210.5 292.9 136.56 f0.2 96.6 f0.3 111.7 178.6 102.6 91.89 59.5 86.6 98.7 133. [36].6 192.9 255.5 278.35 78.85 76.5 101.0 213.1 96.1 280.4 99.09 = (l/q(cll- tFrom Oda et al.2 311.08 57. Grossular garnet: Measured single- from 300 to 1200 K of T/O: 1.43 f0.0 97.7 291.4 cs = (W)(C11- cs = (1/2)(G1- tAfter Suzuki & Anderson [65].4 92.3 f0.5 144.1 141.24 Cl2).7 97.96 58.5 69.5 T (K) 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 T (K) 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 299.6 f0.2 f1.9 56.2 91.4 90.0 87.9 280.9 92.1 90.2 f2.8 98.98 58.22) Cl2 c44 c.7 78.4 f0.0 289.O 93.3 91.61) Cl2 c44 CS crystal elastic 1350 K (max.2 90. t From Isaak et al.9 201.5 95.3 58.7 110.4 95.46 75. 91. 102.5 105. Pyrope-rich garnet: Measured (GPa) from 300 to 1800 K value of T/O: 2.4 208.0 100.0 fl.0 94.9 219.5 243.8 91.8 280.7 88.9 crystal elastic 1000 K (max.2 93.8 _ 81. CaO: modulit measured Cl1 Measured (GPa) value single-crystal Table 4.13 61.4 90.6 97.1 f0.3 88. 80.0 98.3 87.1 90.

1 297.28 6.5 7.4 154.2 151.3 164.7 7.3 = (1/2)(C11- tAfter Yamamoto et al.4 Cl2).1 f0. measured value of T/O: 0.8 157.7 7.21 6.8 111.8 111.79 f0.8 163.5 147. f0.5 154.2 23.84) T (K) 300 350 400 450 500 cs Cl1 Cl2 c 44 CS Tw 300 350 400 450 500 550 600 650 700 750 cs Cl1 Cl2 G4 cs 223.7 28.1 60.9 149.8 44.5 13.7 146.3 61.3 273.2 55.1 42. measured value of T/O: 4.9 55. 6.5 38.4 13.9 f0.4 47.9 160.96) Table 8.8 158.52 11.2 49.8 57.6 f2.87 5.1 7.3 76.11 6.8 f0.2 214.2 f0.9 152. 12.3 7.4 38.1 f1.5 8.1 29.7 162. [77].5 fl.5 f0.43 12.7 11.7 7.2 9.42) Measured single-crystal elastic modulit (GPa) from 300 to 1000 K (max.0 f6.2 7.3 56.7 156.5 6.5 292.02 18.2 10.1 210.8 159. NaCl: Measured single-crystal elastic modulit (GPa) from 300 to 750 K (max.3 266.1 12.7 49.1 288.8 77.79 5.7 58.3 17.3 31.7 f5. = (1/2)(G1-G2).7 111.4 40.7 f0.5 12.4 33.20) T (K) 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 cs Cl1 Cl2 c44 G Tw 300 350 400 450 500 550 600 650 700 750 800 850 cs Cl1 Cl2 G4 c.02 12. KCl: Measured single-crystal elastic modulit (GPa) from 300 to 850 K (max.1 77. 78. t After Cynn [19].3 13.5 111.8 32.5 = (W)(Gl t After Pa&o & Graham [47].31 11.1 f0.7 f0.57 5. MnO: Measured single-crystal elastic modulit (GPa) from 300 to 500 K (max.2 275.8 161.3 52.3 154.4 f0.3 14.0 14.69 5.2 267.9 146.5 13.2 167.7 60.2 26.7 37.1 13.9 56.7 7.26 12.1 111.6 59.1 58.5 f0.02 6.3 15.5 150.4 13.9 f2.9 35.15 6.4 36.5 f4.5 11.8 f3. measured value of T/O: 1.6 13.62 12.9 f4.1 13.9 11.5 156. Table 6.1 .2 57.4 153.71 11.2 13.3 12.66 HIGH Table T ELASTICITY 5.2 290.3 61.57 f0.7 f0.5 6.5 168.4 56.3 60.4 282.9 f0.0 155.9 78.35 f0.5 155.8 7.4 = (W)(G1- t After Yamamoto & Anderson [76].96 5.0 59.5 220.6 152.1 269.8 281.09 11.5 Gz).0 f6.1 f0.0 10.4 217. .O 155.10 f0.4 40.0 f0.7 f3.7 149.0 35.6 25.7 51.6 f0.8 7.4 13.8 15.05 5.1 277.4 13.7 54.6 286.4 33.02 16.1 16.2 148.8 11.Gz).90 11.6 45.2 166.2 284. measured value of T/Cl: 2.3 271.2 15. MgAlz04: OF MANTLE MINERALS Table 7.0 7.5 61.

3 306.1 58.0 64.61 74.2 f0.0 293.4 292.3 63.1 65.5 272.2 194.37 61.6 64.0 72.5 63.1 f0.72 f0.3 56.2 f0.0 f0.6 202.5 f0.5 59.9 66.0 300.7 199.5 65.7 59.0 309.4 56.3 302.4 66.3 69.7 53.6 71.7 63.6 67.4 269.8 61.8 168.8 60.2 f0.2 195.29 f0.4 58.4 69.2 f0.0 285. Olivine FogoFalo: Measured measured value of T/O: 2.2 81.4 63.3 283.2 f0.26) Cl1 c22 c33 elastic modulit (GPa) from 300 to 1500 K T (K) 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 c44 cs5 C66 c23 c31 Cl2 320.3 169.2 159.3 195.9 199.7 326.3 74.0 184.9 187.3 62.28 51.6 67.05 62.1 70.57 77.0 f0.97 73.6 f0.1 289.6 f0.5 209.1 274.9 66.0 297.3 54.6 62.6 73.1 220.1 280.4 62.08 76.5 f0.4 71.47 52.01 62.8 67.4 61.6 220.5 61.0 f0.33 71.7 77.2 166.0 zto.1) c 33 (744 elastic modulit (GPa) from 300 to 1700 K T (K) 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 css C66 c23 c31 Cl2 330.3 175.l 65.5 67.9 73.3 69.1 68.9 58.8 f From Isaak et al.17 68.2 t From Isaak .3 71.0 f0.2 214.l 76. Table (max. 10.6 217.0 63.4 f0.3 71.53 64.5 59.4 70.0 62.2 fO.52 74.6 67.9 61.0 f0.0 f0.6 314.0 305.0 67.8 279.5 66.3 210.83 f0.91 54.9 50.9 61.4 71.8 67.6 f0.3 74.0 63.1 64.1 65.5 178.1 66.0 f0.8 60.4 318.9 f0.06 49.4 68.1 226.0 227.0 [32].4 316.7 297.1 78.2 75.59 67.5 61.7 73.0 66.68 53.1 162.1 190.51 61.2 80.0 188.6 60.1 171. 197.2 66.3 216.3 66.4 60.0 61.1 202.5 192. 9.8 69.4 159. MgzSi04: Measured measured value of T/O: Cl1 c22 AND ISAAK 67 single-crystal 2.4 58.8 f0.6 49.6 71.3 72.0 65.5 67.1 163.2 79.3 69.7 165.0 f0.5 57.8 54.9 64.8 64.3 322.3 55.3 74.8 71.2 57.8 181.9 276.3 51.7 68.0 69.ANDERSON Table (max.6 56.4 64.9 213.6 f0.2 65.6 62.8 57.8 206.8 313.ll 59.4 59.9 65.2 Al.3 175.2 188.2 62.7 184.6 66.2 191.2 66. [35].1 51.5 59.8 f0.1 f0.3 68.6 181.8 288.1 200.7 192.2 52.07 48.1 54.02 fO.0 71.5 178.23 55.1 230.6 72.2 68.07 65.8 223.3 172.4 56.9 68.3 67.2 81.0 76.4 73.2 zto.2 64.3 f0.9 68.0 155.5 231.4 197.5 310.6 78.0 62.7 69.05 59.2 78.2 64.6 224.6 233.4 57.7 55.2 64.5 60.1 63.45 57.8 fl.3 67.8 236.3 69.73 58.2 70.8 74.4 58.6 fO.4 206.73 70.3 72.2 53.3 194.8 234.3 48.

4 224.4 f0.5 41.3 fO.5 225.4 92.7 50.8 244.7 31.4 31.8 f0.9 87.8 251.1 46.2 c22 c33 c44 c55 (766 c23 (731 Cl2 173.8 100.2 80.9 230.1 222.7 Al.0 95.3 51.8 f0. Fe#iOa: Measured single-crystal 700 K (max.3 87.7 97.25) elastic modulit (GPa) from 300 to Tw 300 400 500 600 700 Cl1 c22 c33 (7-44 c5s C66 c23 c31 Cl2 307.5 f0.7 220.0 220.5 31.9 f1.3 100.3 93.7 97.68 HIGH T ELASTICITY OF MANTLE MINERALS Table 11.2 54.9 87.9 f0.0 198.2 f1.4 83.9 264.8 160.1 94.7 t After Sumino [58].4 166.0 154.8 95.5 96.9 227.7 45.4 97.8 f1.7 232.3 85.7 f0.2 260.6 f0.7 101.6 51.9 99.6 43.6 f0.3 f1.0 51.3 206.8 186.2 57.4 229.4 89.9 162.l 56. Table 13.1 105.2 90.5 55.4 237.3 tAfter Sumino [58].2 97.3 203.0 90.3 f2.3 239.4 fO.3 52.5 f1.8 45.5 94.0 255.2 46.0 162.1 Al.3 95. measured value of T/O: 1.6 51.2 45.9 31.2 304.0 f0.l 46. Table 12.2 44.3 f1.6 t After Sumino [58].1 63.8 91.5 42.7 f1.2 f1.1 82.4 46.9 201.7 45.1 63.9 f1.1 297.0 f2.2 103.4 f1. Co2SiO4: Measured single-crystal 700 K (max.5 262.2 f1.2 91.5 31.7 194. measured value of T/O: 1.5 97. .9 60.8 45.8 f0.5 94.3 98.9 254.l 44.4 165.7 f1.9 159.4 94.5 93.7 52.2 96.6 f0.9 96.9 89.0 96.8 fl.8 257.0 234. measured value of T/O: 1.2 56.7 159.1 168.7 45.8 97.9 91.7 fl.3 fO.6 f1.3 55.0 fl.5 f1.1 95.7 fO.7 227.5 fO.3 247.7 192.6 96.4 31.2 97.6 190.8 60.1 f0.8 170.1 f1.6 32.2 195.2 f1.5 188.1 97.5 fl.3 54.7 258.l 57.6 51.0 252.0 88.2 f0.3 101.6 98.8 fO.7 f1.5 f1.8 99.41) elastic modulit (GPa) from 300 to Tw 300 350 400 450 500 550 600 650 700 Cl1 266.0 f1.8 62.1 171.6 164.4 92.3 f1.2 97.O 90.4 31.2 234.8 59.l 64.9 52.l 31.8 53.9 f1.1 55. MnzSi04: Measured single-crystal 700 K (max.6 45.8 53.1 46.8 294.0 301.8 157.5 53.6 102.28) elastic modulit (GPa) from 300 to T m 300 400 500 600 700 Cl1 c22 c33 (744 C55 (766 c23 c31 Cl2 258.8 251.6 45.1 f1.9 61.8 96.1 62.4 88.8 f0.0 45.5 99.7 f0.7 52.O 103.8 61.

01 9.85 8.4 99.67 5.4 104.68 9.7 442.7 115.6 -24.8 446.24 3.02 4.33 9.1 100. Table 15.80 4.2 432.3 -23.52 1.9 132.3 427.2 493.3 451.7 490.06 3.6 116.92 8.5 476.62 5.2 120.0 96.3 114.10 expansivity.4 117.26 4.1 148.5 494.1 -24.2 -24. [25].9 162.2 -22.1 128.246 1. MgO: Thermal at 10-‘/K 0.54 1.1 132.7 -23.78 kr$s 6.9 437.262 1.0 130.7 94.454 3.9 124.6 f0.59 1.7 fl.191 1.6 486.3 134.2 500.2 144.2 112.2 484.501 3.1 -21.191 1.2 450.3 160. isotropic elastic constantst ciJ* Y 1.5 159.9 -24.9 446.597 3.405 3.ANDERSON Table 14.03 cv J/(gK) 0.9 110.54 1.166 1.5 99.12 f0.6 109.53 1.098 1.185 1. tS uzuki [64].9 156.31 f0.1 162.4 f2.289 1.53 1.4 142.8 f1.7 114.84 4.4 -23.8 161.8 51.5 110.4 -24.8 497.7 164.5 f1.05 9.6 489.47 4.4 101.0 107.354 f0.4 113.04 5.0 106.3 -24.1 153.0 159.73 f0.51 9.53 1.662 0.4 161.5 133.194 0.227 1.153 1.19 9.928 1.4 476.131 1.1 125.1 lcr$s 9.82 5.5 -24.26 9.0 -23.54 f0.1 105.301 1.0 481.72 5.8 123.1 456.2 150.1 102.130 1.4 144.602 3.3 436.41 5.4 147.0 471.181 1.358 GPa 165.95) AND ISAAK 69 (GPa) T WI 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 Cl1 G4.9 480.3 141.346 1.191 1.80 9.7 158.5 f 0.14 4.50 1.323 1.4 158.7 f0.6 163.63 0.1 111.9 157.0 158.4 f2.371 3.1 151.8 163.01 6.5 432.194 0.10 6.173 1.061 1.7 122.3 99.658 0.50 f0.78 f0.334 1.89 4.2 128.7 163.0 fl.5 457.0 116.53 1.6 163.8 139.9 146.13 9.8 472.204 1.7 163.52 1.6 158.2 f1.2 466.6 J/W) 0.04 $Computed from Table 1.6 f2.57 9.54 1.5 146.36 5. AlsOs: Measured single-crystal elastic modulit from 300 to 1800 K ( max.53 1.007 [ia 165.3 467.4 160.03 1.188 1.4 141.0 139. [26].97 5.573 3.53 1.13 fO.1 153.2 159.56 4.4 138.193 IcT and velocitiesf T K 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 g/A 3.276 1.6 125.005 3. ‘Garvin et al.5 -24.585 f0.422 3.312 1.1 155.8 f0.05 8.56 5.6 162.9 131. .4 461.7 137.516 3.438 3.0 111.52 1.2 136.87 5.2 116.5 109.39 9.388 3.559 3.5 -23.190 1.98 5.4 121.3 c44 Cl2 Cl3 Cl4 497.02 5.4 103.57 3.175 1.3 135.38 4.1 441.63 2.486 3.8 119.4 162.1 Gta 132.7 144.5 129.51 1.77 5.6 fl.65 4.9 f0.8 101.51 5. specific heat.1 f0.4 126.915 1.45 9.470 3.06 dLo.7 160.55 1.6 108.048 1.4 462.2 107.5 161. measured value of T/O: 1.5 tFrom Goto et al.71 4.92 5.2 f1.5 119.193 1.13 6.3 131.9 f 0.46 5.98 8.531 3.4 162.O 115.2 -24.545 3.

1 225.45 5.11 f0.36 5.005 from Table f5.17 6.2 139.42 5.04 6.32 f0.2 224.6 142.6 106.28 10.37 6.84 10.32 1.7 249.9 149.09 6.09 9.933 1.9 up v.51 2.190 1.094 1.6 230.523 3.0 210.12 f0.811 0.916 3.2 127.848 3.37 1.30 1.42 1.41 1.09 3.28 1.5 184.59 2.201 1. [48].74 2.7 234.40 f0.568 3.209 1.906 3.32 2.39 10.982 f0.2 232. 6.87 9.06 KS 209.5 200.2 207.0 f1.194 1.18 2.223 1.213 1.51 f0. [24].43 f0.564 3.40 5.7 193.36 1.952 KT 207.ll 5.15 3. MgA1204: P Thermal expansivity.5 1.3 9.8 161.2 f2.05 Cv 0.512 f0.13 6.0 102.4 240.80 2.6 103.121 1.7 137. KS specific heat.9 247.8 199.70 10.88 f0.208 f5.9 G 108.45 5.27 1.06 5.014 1.160 1.61 fO.8 201.73 2.2 106.872 3. Dimensions as in Table 15.2 208.5 131.975 3.2 vp 10.41 5. [69].178 1.0 228.229 1.3 199.5 99.1 205.28 1.318 7 1.27 1.819 0.0 105.50 f0.277 1.5 220.40 1.927 3.088 1.823 f0.1 243.9 224.009 3.6 250.835 3.3 185.179 1.37 1.860 3.55 10.47 5.95 5.29 6.0 191.966 3.82 5.83 9.4 f6.883 3.8 235.069 1.4 228.80 2.103 1.45 2.943 1.779 0.65 9.286 1.167 1.7 190.8 196.4 242.61 10.009 from Table 253.95 f0.1 144.0 197.7 252.8 101.ll $Computed 14.43 1.34 1.6 244.2 151.2 194.17 10.33 6.518 3.06 6.8 231..894 Thermal fft 1.774 0.05 1.78 9.91 9.4 192.00 5.947 3.551 3.65 10.7 107.63 2.3 103.0 f2.96 3.06 expansivity.71 9.296 1.04 2.8 133.547 3. Dimensions as in Table Table 17.5 107.23 2.0 237. .38 5.7 196.055 1.133 1.92 9.27 1.28 f0.257 1.199 1.963 1.532 3.148 1. T 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 3.937 3.50 10.88 2.70 HIGH T ELASTICITY OF MANTLE MINERALS Table 16. 3.85 9.205 1.2 134.21 6.009 15.73 9.33 f0.3 t 0.03 1.528 3.27 1.85 2.90 2.94 f0. +Touloukian al.28 1.03 1.76 9.07 $Computed 5.34 5.164 1.33 10.8 217.40 2.899 0.25 6.5 147.03 3.03 Cv and velocities1 KT 252.4 192.1 214.25 f0.8 f2.9 204.4 197.572 3.179 1.205 1.1 100.9 202.75 10.6 200.27 1.267 1.8 156.78 fO.62 f0.253 7 1. t White Roberts [75].20 3.36 1.2 205. AlsOs: P 3.91 5.082 1.43 1.8 240.024 1.6 f1.48 5.23 10.180 1.1 158. isotropic mod& G 163.306 1. *Robie et al.86 5.5 204.81 9.139 1.05 10.36 1.5 f4.3 203.37 5.7 f2.203 1. specific heat.66 2.46 5.41 1.244 1.68 9.49 5.555 3.542 3.149 1.148 1.4 101.0 187.6 202. isotropic modulit and velocities* T 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 at 2.1 194.25 2.560 3.957 3.9 104.99 2.36 1.51 2.8 237.537 3.5 104.8 Cp* 0.38 2.576 f0.889 0.9 248.69 2. *F urukawa et al.8 f2.212 1.001 1.63 9.36 1.7 207.180 1.37 1.207 1.38 1.005 3.44 10.8 221.243 1.6 246.216 u.7 et C$ 0.6 154.9 189.115 1.040 1.039 1.80 10.3 f6.57 2.115 1.27 1.

008 81.9 111.34 fO.17 1.4 123.03 3.91 7.8 68.14 1.236 1.2 116.2 107.6 116.13 8.013 KT 128.7 121.263 3.15 1.6 103.6 f0.055 1.6 95.06 f0.14 1.816 0.808 0.0 74. isotropic mod& and velocities 3 up V.840 0.18 1.14 1.343 3.02 [15].5 71.46 3.333 3.15 1.2 118.235 1.48 f0.8 f0.145 1.192 3.9 117.7 109.09 1.3 116.4 63.1 122.048 1.4 125.72 4.370 1.03 Ito.2 123.99 3.083 3.352 1.27 8.216 8.2 120.294 & Knacke 7 1.O1 4.8 64.38 8.02 1.12 1.6 121.O1 5.65 4.2 69.35 3.5 73.9 77.27 4.944 1.5 67.70 3.2 f0.02 5.55 3.147 1.08 128.92 7.240 1.97 7.25 f0.6 102.0 115.15 1.238 3.61 4.60 4.275 1.3 f0.9 104.6 103. Dimensions as in Table Table 19.171 1.69 fO.02 1.15 8.22 4.t and velocities 3 G CP* T KS 2.16 4.191 109.007 3.2 99.8 75.24 8.1 68.38 f0.990 1.1 109.203 3.75 4.1 110.96 4.56 4.1 113.81 3.287 3.85 4.7 61.17 1.7 112.222 f0.29 f0.831 0.256 1.170 3.122 3.O1 4.60 4.976 KT ‘UP V.8 105.203 1.93 4.08 KS 129.0 f0.00 4.3 125.15 1.43 8.135 3.48 3.0 107.15 1.29 4.186 1.096 3.112 1.6 f0.353 f0.03 7.3 114. specific heat.167 1.77 4.1 71.4 101.2 f0.4 106.9 120.75 7.69 4.156 1.3 0.83 fO.22 3.334 1.3 78. t K ajiyoshi [38].93 4.15 1.9 97.4 76.50 4.8 112.03 7.277 1.3 f0.2 118.21 1.068 1.19 8.1 125.251 3.89 4.212 f0.9 72.19 1.9 123.1 65. MgzSiOa: P Thermal expansivity.15 1.02 cv 0.92 4.0 111.39 4.14 f0.65 4.68 4.36 3. specific heat.322 3.109 1.220 1.59 3.213 3.16 1.05 3.211 1.1 120.256 1.07 8.05 2.194 1.62 f0.3 Cp' 0.07 f0.6 64.177 1.01 10.85 7.315 1.00 4.216 1.6 114.79 1.71 3.48 8.58 fO.6 107.069 3.055 f0.181 3.64 3.3 127.5 15.2 111.004 3.86 7.52 4.01 $Computed from Table 9. *Barin as in Table .119 1.163 1.093 1.5 105.05 4.129 1.225 3.8 118.ANDERSON AND ISAAK 71 Table 18.1 62.50 4.81 4.16 1.5 1.6 114.O1 8.080 1.9 124.73 4.311 3.54 4.08 1.1 f0.7 f0.109 3.13 1. tS uzuki [64].3 80.124 1.21 8.97 7. *Barin & Knacke [15].6 67.2 76.197 1.86 3.1 65.6 70. 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 3.148 1. T 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 $Computed P 3.957 1.299 3.159 3.249 1.72 f0.257 127. 8.5 15.54 8.07 1.147 3.79 3.57 4.004 from Table CN~ 2.10 1.32 8.66 f0.3 73. 8.032 1. 8.3 118.81 7.4 G 78.296 1.5 Y 1.79 f0.09 8.3 f0. Dimensions Cv 0.7 125.1 61. isotropic moduh .7 f0.21 3.4 127. Olivine FoseFals: Thermal expansivity.086 1.11 1.275 3.183 1.231 1.210 1.

O1 6.05 f0.5 f0.5 49.91 3.74 3.6 148.84 f0.1 120.011 $Computed from 12.3 142.831 and velocitiest 1-T 128.6 66.8 137.9 134.02 15.57 f0.6 127. 3.8 as in Table 15.623 0.99 fO.55 3.89 6.97 6.03 f0.6 125.84 6.8 118. [66].77 2.51 1.37 3.03 [72].779 0.0 123.21 f0.79 6. FezSi04: Thermal expansivity.51 f0.009 fft 2.0 f0.86 50.7 f2.0 f0.8 G 54.6 64.1 f0.04 3.57 2.840 0.03 modulil cv 0.51 1. up 6.89 6.781 0.8 up V.665 0.8 48.+ 0.53 3.0 f2.O1O IComputed Table 23.00 fO.5 145.813 0.11 f0.0 47.512 f0.06 Table KS 138.119 4.2 139.5 144.0 125.06 1.388 4.02 3.850 6.6 123. 3.94 6.05 2. isotropic 7 1.03 1.7 142.27 f0.3 cp* 0. specific *Watanabe heat.13 1.653 0.07 1.91 3.40 f0.46 f0.009 3.8 129.9 G 51..096 4.77 3.747 0.8 f2.2 f0.04 1.575 3.85 ho.O1 6. t Ok ajima et al.634 f0. t ( assume MnsSiOa).611 3.868 cv 0.4 60. *Barin & Knacke [15].68 f0.08 1.02 6.47 f0.359 5.05 15.349 5.4 f0.50 3.2 140.825 0. $ 3.3 f1.682 0.60 6.63 6.375 4.0 121. V.12 3. specific heat. tS uzuki et al.03 1tO.61 f0.7 48.400 f0. 13.7 G 62. CosSiOa: Thermal expansivity.369 5. 0.362 4.9 59.77 2.51 1.6 as in Table and velocitiesz VP 7.57 2.05 6.108 4.009 4.791 0.669 0.02 3.OO1 5.02 $Computed from 11.640 0.06 f0.6 142.348 f0.8 135.803 0.4 f0.5 as in Table I+ V.7 129.661 0.543 3.06 Table I& 128.93 6.736 0.7 f0.793 0.04 SComputed from et al. tSuzuki KS 149.t and velocities T 300 400 500 600 700 P 4.0 126.641 0.682 4. [46].4 f0.378 fO.01 15.08 1.4 C.1 f0.692 7 1.7 59.0 f0.849 I-T 147.05 2.667 0.636 0. isotropic 7 1.009 3.9 145.65 f0.04 Cv 0.557 fO.005 at 2.07 3.3 c.8 134.4 f0.4 50.339 fO.7 65.706 f0. [72]. MnsSiOe: Thermal expansivity.3 53.70 6.621 zto. expansivity.5 52.16 1.03 1. isotropic modulit and velocities4 T 300 400 500 600 700 P 4.9 f0.12 f0. [67].3 f0.02 moduh .009 from MnO: P 5.5 67.68 3.34 3.728 0.673 KT 146.03 1.2 144.7 f2.770 0.739 0.00 3.06 f0.57 f0.632 0.07 1.30 f0.5 51.3 140.666 0. T 300 400 500 600 700 P 4. specific heat.695 4.084 f0.005 4.669 4.74 6.51 f0.0 f0. Dimensions as in Table Table 22.58 3.27 f0. specific heat.1 f0.842 KT 136.6 G 68.1 f0.818 0.655 f0. Dimensions .5 146.673 0.594 3.655 0.863 y 1.4 f1.803 0.604 3.0 131.08 Table 6.830 0.06 Table I& 148.OO1 at 2.573 3.0 146.3 f0.Table 20. Dimensions Cv 0.05 2.66 6.1 131.32 3.746 0. 6.79 f0.009 4.3 61. *B arin & Knacke [15].736 0.129 f0. Dimensions isotropic modulit Thermal T 300 350 400 450 500 CY~ 3. *Watanabe Table 21.2 143.06 1.22 f0.18 1.8 144.6 Cp* 0.

095 1. 5.5 103.4 f0.6 50.512 3.99 67.198 5.64 40.03 1.19 1.35 f0.97 3. Grossular garnet: Thermal expansivity.3 f0.6 Cp* 0. 24.98 4. tb uzuki KS 171.301 3.94 4.6 160.003 IComputed Table 2.964 1. isotropic modulit and velocitiest 300 400 500 600 700 800 900 1000 1100 1200 3. Dimensions as in Table Table 26.7 164. isotropic modulij and velocities1 T 300 400 500 600 700 800 900 1000 P 3.8 f0.03 Cv 0. specific heat.259 5.028 1.2 104.2 15.92 4.032 1.59 f0.532 3.5 109.28 2.318 5.20 1.1 101.87 4.730 0.248 3.7 104.24 1.37 1.889 0.705 zto.0 161.041 1.088 1. t1 saak et al.6 106.880 0.1 97.933 0.170 y 1.1 15.640 f0.56 f0.83 2. Dimensions as in Table 15.18 1.2 154.5 106.113 1.2 98.008 $Computed Table 4.858 0.7 100. t Oda et al.0.094 *to.9 157.848 7.22 1. [25].834 0.47 3.02 8.759 4. Table 25.71 76.6 90.23 1.121 KT 166.905 fO.3 94.49 2.6 86.052 1.946 7.005 from Table at 2.743 0. * idem. vp v.726 y 1.796 4.4 f0.675 3.6 Al.3 fl.686 3.35 zto.1 156.2 f1.16 1.3 158.34 1.903 110.646 4.653 3.22 f0.2 164.03 1.35 1.90 4.327 3.006 4.68 8.4 94.07 3.068 1.262 3.64 2.02 79.1 151.3 157.072 1.29 fO.631 AO.96 4.3 150.4 104.943 0.9 163.76 73.945 0.00 f0.06 9.076 8.72 8.4 159.314 3.006 5.005 3.6 f1.959 0.5 85.289 5.897 7.073 1. Pyrope-rich garnet: Thermal expansivity.2 105. specific heat.36 50.5 156.99 8.OO1 3.19 1.562 3.22 9.37 1.94 8. ‘G arvin et al.36 1.03 3.6 148.4 152.965 1.3 8.03 0.718 KT 169.686 4.3 101.36 1.752 0.00 zto.865 0.7 f0. 5.002 8.8 100.002 from 3. [36].0 fO.14 9.33 71.3 102.1 156.571 3.453 f0.6 89.04 2.981 1.OO1 4.87 8.996 7.7 88.01 4.9 163.8 166.O1 9.010 1.84 8.7 103.693 7.696 3. specific heat.02 CV 0. vp 9.80 2.97 3.81 3.11 f0.92 &to.12 *0.03 8.14 4.25 9.952 0.609 4.373 5.6 f0.855 0.139 1.3 92.4 162.3 100.903 0.01 4.14 1.542 3.3 98.2 161.02 v.2 G 106.597 zlzO.869 4.4 96.898 0.427 5.26 f0.581 3.5 160.338 3.2 80.6 f0.03 $Computed & Anderson [65].116 0.8 168.006 3.80 8.76 8.l 110.2 f0.61 2.21 1.02 0.18 9.346 5.401 5.90 2.85 f0.045 7.20 4.2 154.90 f0.9 167.9 93.894 0.1 108.1 107. Dimensions as in Table .78 2.37 1.901 0.006 from cryi 1.08 4.888 0.3 158.26 1.05 2.589 3.977 1.3 152.902 0.1 G 92.9 f0.15 77.522 3.3 146.006 1.09 112.5 99.07 KS 167.50 f0. [43].03 1.067 1.67 3.664 3.36 1.642 3.834 4.04 *to.092 1.288 3. CaO: Thermal expansivity.877 0.025 1.4 91. *Krupka et al.06 3.21 f0.0 164.040 1.88 2.37 1.501 f0.92 f0.5 f0.3 159.2 Cp* 0.995 1.056 1.275 3.40 68.349 fO.234 f0.057 1.29 1.92 4.723 4.22 1.6 154.7 166.745 7.08 0.06 3.799 7.7 87.22 74.921 0.230 5.904 0.931 0.Table. [39].10 9.92 2.552 3.71 2.571 f0.819 0.3 161. isotropic modulit and velocitiesf T 300 400 500 600 700 800 900 1000 1100 1200 1300 P 3.104 1.165 f0.736 .90 70.5 164.19 1.7 96.

44 1.059 2.6 12.7 15.5 f0.2 23. isotropic elastic modulit G Cg and velocities3 T 300 350 400 450 500 550 600 650 700 750 800 850 $Computed 7 1.42 1.7 15.830 0.0 f0.0 18.12 2.5 10.3 16.701 0.88 3.883 0.04 1.830 0.67 6.71 3.449 2.074 2. 2.3 24.63 1.104 2.791 0.52 4.8 f0.745 0.53 3.006 from 4.0 16.6 16.829 0.4 15. et al.4 14.45 1.93 1.7 23.46 1.80 3.8 f0.5 21.9 19.85 7.672 0.2 12.545 2.25 10.39 12.823 & Prophet 3. Dimensions .7 16.012 & Dommel [22].2 14.514 2.869 1.1 17.3 17.7 13.822 0. *St&l [57].60 1.6 12.910 0.74 HIGH T ELA!JTICITY OF MANTLE MINERALS Table 27.3 as in Table up v.923 0.47 f1.33 4.16 2.22 4.91 8.008 2.132 2.6 f0.767 0.42 1.826 0.8 19.855 1.41 f0.03 2. NaCl: Thermal P expansivity.19 f0.06 2.7 14.829 KT 24.159 f0.982 f0.868 0.02 15.39 f0.48 3.80 fO.2 13.75 3.971 1.64 1. KS specific heat.674 0. isotropic elastic modulit and velocitiesl I+.416 2.830 0.610 &0.1 15.830 0.27 13.937 0.3 Table 8.669 0.68 3.96 12.03 15.676 0.683 0.ll Cp* 0.62 1.59 3.53 12.735 0.005 2.713 0.7 21. tEnck KS 25.897 0.08 14.63 f0.56 f0.39 8.17 4.00 1.64 8.840 f0.0 f0.4 21.29 6.09 3.677 0.9 15.724 0.4 15.0 13. T 300 350 400 450 500 550 600 650 700 750 $Computed CX~ 11. V. Dimensions as in Table Table 28.756 0.3 14.8 15.3 2.8 f0.806 0.043 2.146 2.81 13.04 AZ Prophet Cv 0.0 11.03 9.04 1.63 1.2 15.6 20.0 f0.691 KT 17.3 11.0 f0.64 1.13 2.39 4.883 1.43 1.675 0.309 f0.97 1.959 1.84 3.3 16.02 1.43 1. *Stull [57].3 G 14.897 1.18 8.42 f0.2 13.7 14.6 13.2 22.828 0.2 f0.61 1.2 12.4 16.4 9.997 7 1. KCI: Thermal P at expansivity.11 11.950 0.27 4.7 12.948 1.7 13.90 1.44 f0. tEnck 17. specific heat.689 0.346 2.2 Table 7.11 2.910 1. 2.42 1.829 0.1 20.0 16.2 22.2 12.5 19.664 0.4 17.43 4.923 1.44 1.87 f0.13 0.08 2.9 f0.1 12.64 3.2 13.382 2.979 0.71 50.778 0.57 7.482 2.47 4.935 1.63 1.3 f0.005 from 11.089 2. [23].5 14.13 7.579 2.98 6.46 1.657 0.026 f0.2 11.118 2.04 Cv 0.0 14.8 24.7 14.02 4.59 f0.676 0.964 0.11 f0.005 1.68 11.92 f0.679 0.3 23.

251 0.24 6.09 1.52 1.82 1.35 1.37 5.98 4.247 0.03 5.67 6.235 0.12 885 0.04 1500 838 0.46 1.35 2.09 6.37 5.00 6.08 6.S 6T r lb -6.08 4.04 5.30 1.36 1.26 1.24 6.239 0.73 1.05 6.40 1.61 4.85 6.15 6.62 6.03 1.66 0.47 5.92 1600 828 0.02 3.22 6.244 0.09 6.192 2.12 1. pressure MgO: Dimensionless parameters.92 5.98 3.34 Calculated from Tables 1 dc 15.183 0.43 3.06 1.60 1.08 5.95 4.64 5.60 6T r (bT--6s) 7 Y ~KT APTH MPa/K GPa 300 400 500 600 700 800 900 1000 1034 1029 1022 1015 1008 1001 994 986 1100 1200 1300 1400 1500 1600 1700 1800 979 971 963 955 947 939 932 924 5.87 5.60 3.28 6.78 5.198 4.32 5.92 4.16 5.248 0.20 1.32 6.08 4.59 7.208 3.212 811 3.00 2.17 0.15 2.16 3.93 6.ANDERSON Table 29.12 5.65 3.64 6.99 5.24 3.43 1.12 1.06 2.20 3.29 1.42 1.36 4.16 1.42 5.73 4.23 1.04 4.40 1.37 1. Table 30.57 9.28 1.66 1.67 5.03 894 0.03 6.26 5.74 5.29 5.32 1.56 1800 0.69 5.08 1200 806 0.11 1.40 1.32 1.17 5.52 6.211 3.39 3.58 9.05 1100 875 0.29 1.55 3.08 5.36 1.24 7.237 0.32 1.) 7 v QKT APTH 5.196 3.03 6.32 6.241 0.35 1.12 6.246 0.253 0.250 0.76 1.38 1.91 8.50 5.83 2.257 0.70 5.40 6. pressure A120s: Dimensionless parameters.28 1.206 3.12 1.57 1.209 3.43 4.93 5.30 6.30 4.06 6. Dimensions as in Table 29.24 Calculated from Tables 14 & 16.85 2.10 1.243 0.84 5.46 5.12 4.64 6.23 6.97 8.98 1.34 1.36 1.80 5.19 1.54 1.10 1400 847 0.79 2.255 0.259 6s 3.52 4.66 3.71 5.204 5.200 3.188 6.194 2.66 4.21 1.240 0.92 4.47 1.36 7.13 6.49 1.98 1.31 3.75 1700 820 0.39 5. Debye temperature and thermal T 300 400 500 600 700 800 900 1000 0 945 937 928 920 Is 0.20 .07 6. Debye temperature and thermal AND ISAAK 75 T K 0 K u 0.28 1.73 4.38 1.30 1.15 1.51 3.30 1.58 5.41 857 0.08 911 0.28 1.03 5.24 4.22 1.81 2.00 0.74 5.16 0.53 5.86 1.202 3.50 5.98 5.87 5.16 6.93 5.38 1. 2.74 7.27 6.13 4.185 0.30 1.07 1.28 6.190 4.07 4.00 0.34 4.42 5.45 6.29 1.09 1300 3.07 1.57 6.71 5.23 6.40 1.62 3.83 5.18 1.31 1.33 1.13 1.22 5.01 4.16 6.55 2.31 6.30 3.30 1.21 4.29 1.50 6.45 0.05 902 0.

36 4.29 3.93 4.73 4.01 1.38 0.36 4.60 4.72 4.25 4.64 4.10 1.28 4.98 1.07 3.75 2.54 5.25 6.09 5.13 3.87 1.97 6.Table 31.23 1.64 4.237 0.239 0.53 from Tables 2 & 24.04 1.52 4.53 2. Debye temperatures and 0 779 777 775 773 771 769 767 765 764 761 759 757 755 753 751 t7 0.98 4.41 3.216 0.75 3.270 0.29 5.00 1.270 0.26 1.97 1.42 0.98 3.36 0.270 0.244 0.06 1.94 0.26 3.04 2.84 4.11 1.05 1.14 5.92 0.57 4.32 3.55 5.99 4.97 4.25 1.95 4.270 0.08 1.30 5.242 0.38 4.22 1. .99 3.64 3.22 1.270 0.04 1.24 4. Table 32.57 4.08 1.74 4. Dimensions as in Table 29.221 4.54 3.06 4.03 5.58 6.86 3.11 Y 0.73 3.40 2.270 0.36 3.07 1.88 0.90 3.08 1.69 5.00 0.01 1.10 (b-i-k.27 5.90 5.70 5.81 2.86 3.30 5.98 3.09 1.93 0.01 4.05 1.01 6.70 4.86 4.74 4.215 0.00 3.07 5.17 1.28 2.24 1.40 4.02 1.01 4.97 0.96 3.13 5.58 3.57 1.98 4.17 1.11 5.30 1.02 1.00 1.74 4.99 1.22 3.210 0.16 1.00 4.36 4.24 1.02 4.09 1.270 0.270 6s 6.22 1.96 5.00 5.25 3.10 1.36 0.271 0.93 0.81 4.02 4.35 5. Dimensions as in Table 29.00 1.90 0.92 3.04 1.90 3.93 3.240 0.243 0.270 0.41 4.89 3.212 0.97 3.86 3.00 5.28 5.88 3.24 1.35 3.34 4.51 4.23 1.16 4.05 1.55 3.01 3.27 3.52 3.04 1.49 3. Table 33.41 5.23 1.19 5.00 1.07 4.15 1.10 1.22 1.60 3.27 1.27 5.18 4.211 0.245 0.218 0.52 2.69 4.241 0.36 1.270 0.94 4.05 4.29 4.58 4. Dimensions as in Table 29.03 1.30 5. Pyrope-rich thermal pressure T 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 Calculated garnet: Dimensionless parameters.270 0.65 0.96 4.07 1.23 1.53 3.83 3.21 0.270 0.21 3.74 1.94 3.239 0.98 3.18 1.90 4.51 1.34 2.271 0.31 3.219 0.80 4. CaO: Dimensionless parameters.64 3.238 0.23 from Tables 3 & 26.00 1. Debye temperatures and 300 400 500 600 700 800 900 1000 1100 1200 1300 Calculated 824 820 816 811 806 801 796 791 786 780 715 0.96 3. 4.98 4.22 1.40 4.23 1. Debye temperatures and thermal pressure 300 400 500 600 700 800 900 1000 1100 1200 Calculated 671 666 660 654 649 643 637 631 625 619 0.65 6.31 1.62 3.08 1.74 4.71 0.15 3.99 3.01 5.00 0.01 4.59 4.01 5.00 0.27 4.31 1.11 4.13 1.28 1.13 1.40 from Tables 4 & 25.32 4.68 4.34 1.20 1.96 0.11 1.06 ~KT APT.246 4.34 2.03 5.54 3.29 1.03 4.87 4.38 5.29 5.75 1.270 0.30 5.46 5. Grossular thermal pressure garnet: Dimensionless parameters.57 1.220 0.34 5. r 4.98 2.73 4.89 0.213 0.) -i 0.

57 3.87 4.13 10 & 19.18 1.36 5.28 1.252 0.63 5.18 1.14 4.00 0.18 1.14 4.49 5.96 6.05 4.15 4.36 0.ANDERSON Table AND ISAAK 77 34.28 1.83 3.46 5.21 1.70 4.26 4.44 5.15 1.46 4.19 4.37 1.05 4.36 4.48 5.16 1.56 1.240 0.54 5.21 1.25 4.25 3.45 5.39 5.42 5.97 3.20 3.95 5.37 5.10 4.17 1.19 1.38 5.41 5.05 4.252 0.35 5.07 5.28 1.18 1.16 1.13 4.43 6.18 1.44 5.40 5.20 1.02 ST r (6T-6s) 7 u ~KT APT.33 4.20 1.18 3.33 4.19 1.38 2.02 1.92 3.17 4.40 5.249 0.10 6T r (6T-6S) -7 u Cd--T APTH 6.02 1.46 5.07 4.46 3.14 1.24 5.246 0.69 4.22 1.08 4.28 1.50 5.49 5.27 1.10 1. Table 35.97 4.00 0. Olivine FosoFalo: Dimensionless parameters.22 5.20 1.43 5.21 4.45 4.45 5.98 2.15 1.20 1.16 4. Debye temperatures and thermal pressure T 300 400 500 600 700 800 900 1000 0 731 725 719 713 706 700 699 688 u 0.238 6s 4.35 5.75 1.07 1.65 5.23 1.32 1100 1200 1300 1400 1500 Calculated 681 675 669 662 665 from 0.88 3.97 2.18 1. Mg2Si04: pressure T 300 400 500 600 700 800 Dimensionless parameters.49 5.39 9 & 18.03 1.59 5.76 0.40 2.17 1.47 5.15 4.242 0.11 4.90 3.18 4.56 5.20 1.251 0.23 1.248 5.41 as in Table 29.20 1.260 Tables 5.80 3.75 1. Dimensions . Dimensions as in Table 29.258 6s 5.35 5.241 0.37 3.16 1.253 0.37 5.92 5.94 5.38 5.22 3.44 5.28 1.252 0.50 5.46 4.16 1.38 5.255 0.17 4.14 1.13 4.18 1.07 5.80 0.97 4. 5.18 1.93 3.32 5.42 697 689 682 674 668 from 0.250 0.51 5.47 5.16 4.31 4.50 5.38 5.249 0.256 0.21 1.46 900 1000 1100 1200 1300 1400 1500 1600 1700 Calculated 5.239 0.06 1.19 5.07 1.17 1.16 4.22 4.66 5.04 1.36 0. Debye temperature and thermal 0 763 757 751 744 738 731 724 718 711 704 u 0.255 0.36 5.28 1. 1.07 4.14 1.15 1.243 0.58 0.20 1.00 4.245 0.63 4.17 1.25 1.254 Tables 3.26 1.13 4.13 4.18 4.12 4.20 4.13 1.36 5.259 0.36 5.251 0.39 4.24 4.244 0.43 5.257 0.20 1.18 1.40 4.14 4.250 0.

95 4.34 7.00 0.303 0.50 6.51 4.57 1. Debye temperatures (h-b) 7 v and thermal 0 511 506 501 497 494 u 0.17 1.337 0.11 1.91 4.79 1.99 1. Debye temperatures and thermal pressure 300 400 500 600 700 Calculated 535 530 525 520 515 from 0.20 1.69 3.20 2.60 3.52 3.338 6s 5.07 5.82 3.21 0.317 0.95 5.84 1.19 6.30 1. Dimensions TabIe 37.316 5.24 5.338 0.14 4. Dimensions as in Table 29. MnO: Dimensionless parameters.302 0.18 1.52 0.34 3.305 0.71 5.22 1.94 as in Table 29.71 4. Table 38.09 1.62 4.96 0.94 3.88 3.25 1.56 from Tables 11 & 20.57 1.88 4.61 5.00 0.46 4.57 7.90 3.317 0.96 3.12 1.96 5.59 0.64 0.66 5.27 1.301 0.35 1.19 1.14 29.62 6.56 5. 1. CogSiOd: Dimensionless pressure parameters.96 0.05 6 & 23.307 Tables 4.17 6. Dimensions .316 0.41 0.19 1.35 0.57 1.64 5.00 0. MnsSiOa: Dimensionless parameters.49 6.01 7.26 0.02 4.56 3.95 7.00 0.06 0.43 5.44 1.20 5.316 0. Table 39.09 1.37 0.19 7.35 1.14 8.72 3.58 8.29 5.18 ST r QKT APTH 7.58 5.02 4.317 Tables 6.23 3.16 1.33 8. Debye temperatures and thermal 300 400 500 600 700 Calculated 551 548 545 541 538 0.82 5.76 1.55 from Tables 13 dc 22.83 5.99 5.43 as in Table 1.85 6.33 1.31 8.316 0.14 1.23 1.32 6.316 0.34 6.31 0.56 1.24 1.88 5.96 0.19 1.45 9.16 1.315 0.25 1.315 0.19 1.07 4.34 12 & 21.41 3.56 6.336 0.16 0.85 0. Dimensions as in Table 29.36 5.76 6.96 6.97 6.94 4.43 7.35 6.54 1.63 8.60 7.03 3.96 0.81 5.01 5.338 0.74 1.19 4. Debye temperatures and thermal pressure 300 350 400 450 500 Calculated 534 531 527 523 519 from 0.78 HIGH T ELASTICITY OF MANTLE MINERALS Table 36.09 0.35 5. 1.16 1. FezSiOd: Dimensionless pressure T 300 400 500 600 700 Calculated parameters.

95 6. Dimensions as in Table 29.00 0.86 1.96 3.97 4.27 4.18 1.29 1.274 0.34 1.43 0. 1.09 4.08 2.88 5.91 4.37 0.ANDERSON AND ISAAK 79 Table pressure 40.26 1.280 6s 6.91 2.56 5.20 4.90 2.43 0.24 5.29 1.76 5.96 4.278 5.84 0.19 1.38 4.278 3.88 1.80 3.02 7 & 28.278 0.56 3.86 1.93 4.268 0.90 0.49 from Tables 5 & 17.26 1.10 6. Debye temperature and thermal pressure 300 350 400 450 500 550 600 650 700 750 800 850 Calculated 230 227 224 221 218 214 211 208 204 200 196 192 from 0.265 0.74 900 1000 Calculated 7.93 1.23 1.13 1.18 1.00 296 291 287 283 278 274 5.30 5.86 1.88 5.34 1.266 0.77 4.30 4.20 1. NaCl: 0 304 300 Dimensionless parameters.34 6T 5.17 0.88 5.23 1.19 1. Dimensions Table 42.47 3.29 1.92 1.85 0.13 1.284 0.264 0.78 2.75 0.77 0.278 0.77 2.00 0.87 5.22 1.32 1.90 0.04 6.277 0. Dimensions Table T 300 350 400 450 500 550 600 650 700 750 41.69 5.279 0. 269 264 from 1.27 1.18 1.86 2.65 3.35 6.27 1.270 Tables 6s 3.95 4.10 1. Debye temperature and thermal T 300 400 500 600 700 800 0 862 858 854 850 845 840 835 830 tT 0.83 4.286 0.79 4.17 1.88 1.90 4.82 5.85 4.18 4.17 1.28 0.279 0.82 6.47 0.14 4.27 1.19 1.88 5.83 1.19 5.07 6.72 ST r (6.01 4.24 6.43 4.86 1.92 3.27 Calculated 8 & 27.33 5.285 0.02 4.02 5.56 0.17 1.21 1.265 0.83 4.36 7.73 7.76 as in Table 29.97 5.77 3.83 2.11 as in Table 29.20 1.74 5.41 1.87 1.23 1.24 5.32 1.258 0.278 0.19 1.05 4.84 2.288 Tables 4.90 4.17 1.20 1.84 5.17 1.76 4.18 1.49 5.277 0.79 4.19 0.78 4.50 5.34 4.282 0.86 2.90 0.35 1.03 4.62 5.84 2.86 1. .71 0.18 1.03 5.27 5.98 6.260 0.28 1.44 5.57 0.87 1.33 1.66 4.28 0.81 1.47 6.53 4.16 1.25 1.275 0.06 0.11 5.97 5.25 1.65 0.31 1.43 0. MgA1204: Dimensionless parameters.99 1. KCl: Dimensionless parameters.12 1.-b) 7 v ~KT A~TH 0.00 0.18 1.37 6.21 1.73 0.25 1.62 6.05 5.59 4.30 1.86 4.77 4.256 0.86 3.84 5.61 5.45 4. Debye r temperature (6T-b) 7 and thermal v ~KT pressure APTH I7 0.262 0.82 2.90 0.24 1.90 5.09 0.90 0.289 0.86 4.90 0.14 0.60 0.278 0.17 1.30 5.10 4.72 3.279 0.81 2.23 4.10 5.11 1.

which are in the neighborhood of T/O = 2. A well-known thermodynamic identity is that the V is temperature derivative of the pressure at constant exactly equal to CYKT by means of calculus definitions. Thus (YI<T is the V. EQUATIONS OF PHYSICAL USED IN TABLED PROPERTIES VALUES where l+~ is the thermal pressure. Theory appropriate to the high temperature trends of the data is presented in Section 5.3)-1/3. slope for the PTH versus T curve at constant Using (6) for an isochore. Mie-Griineisen equation of state). The various correlations between the thermoelsstic constants are presented in Anderson et al. so that 3. the four dimensionless thermoelastic parameters at each T are computed [7] using the following nomenclature: -/x-zCXKS PCP (YIiT PCV PTH = J (YKT dT. [13] and reviewed in Section 3.= (g$f). (g)p = (a. and we usually find satisfy A&H The = CYKT(T . measured Cp data can be used to find 6-Q CV from (lOa) once y has been e= (k) (z!F)1’3(v.. Extrapolation equations are reviewed in Section 6.. MgzSiOa. For example. The definition of 0 used is As an empirical finding. (8) The parameter y is known as the Griineisen ratio. Such high T data permit the verification of classical equations. and v. The measurements must be done at sufficiently high temperature so that one is justified in speaking of observations in the hightemperature region. We list our experimental values for the dimensionless parameter v defined by Since vr. ( lob) In isobaric high-temperature calculations the thermoelastic parameters given by (2) and (3) are useful for many thermodynamic applications relating sound speed or bulk modulus to temperature.T)p (2) c3) PTH = If CYKT is independent of T at constant V and also independent of volume. then (YKT comes out of the integral shown by (7). Once the elastic constants have been determined over a wide range in T. measurements have to be taken up to the 1300 to 1800 K range so that the high-temperature trends are clearly discernible.0). The parameters 6~ and 6s are often called the AndersonGriineisen parameters [17]. is equivalent to the statement that (7) which (1) 6+&-) 61 = (&) (Z). the adiabatic case arising from adiabatic elastic constants and the isothermal case arising from isothermal elastic constants. KCl. 8 also decreases with increasing T.3 [4]. determined. much lower temperatures empirically that the data APTH is linear in T down to than 0.3+2v. AlzOs. NaCl) either exceed or are close to those of the lower mantle. Since the value of 0 for most mantle minerals is 600900 K.300). decrease with increasing T. Similarly.PTN(O) = CXKT(T . The dimensionless temperatures reached by some of these data (MgO. giving PTH(T) r=-(h) (sgp=(3EJp* . one can test whether CV is independent of T (as in the Dulong-Petit limit) and whether 7 at constant V is independent of T (as required in the derivation of the .80 HIGH T ELASTICITY OF MANTLE MINERALS The appropriate equations used in preparing the tables are presented in Section 2. The mineral data are set forth in Section 4.

For some solids. the sure.2G IY= 6Ks+2G’ 4. at high T is close to zero for many minerals. We know that when the average mass is constant from material to material. Thus an empirically determined approximation where actual high-temperature data are lacking is 6. The variation of 7 with T for all fourteen minerals is listed in Tables 29-42. is shown in Figure 1. and pc suggests that the measured thermal pressure of corundum could be used as a guide for that of perovskite at mantle temperatures and pressures. the value of (dy/dT). where O.6s = 7.6s is close in value to 7. = 6. integrand are positive). especially for AlsOs.ANDERSON AND ISAAK 81 v= ( > 8 Cn 21. the approximation 6T-6s = 7 is useful. for corundum is 1033 K. of 0 1900 (K) 1. the value of 8... (14) is in error. p’ (11) ues in the (87/8T).981. then we may expect that 6~ . 30. show data ature. is close to zero at high T. we see that ST -6s = 7 may be an approximation valid only over a limited range of temperatures. The value of O. and 34.. however. for perovskite at ambient conditions calculated by (5) is 1094 K. 20. shows that minerals with higher density have higher values of 0. but for CaO. Since the rate of change of 7 with T is seldom the same as the rate of change of (Y with T. Plots of 0 (acoustic) versus T. Solid lines data on 8 from Tables 29. O.6s and 7 is [lo]: sT-a s =7{l+K%L+G%]) (1+ a7TbT) . Equation (14 Debye 1200 1 Temperature (four minerals) I 1100 ~ perovskite ---- El P=O 1 (14) is seldom a good approximation below We note. While the value of (87/aT). with T for perovskite of perovskite is compared to that of forsterite and periclase.. = 10. and pc = 3. . that even in some hightemperature regions.. In some thermodynamics manipulations... it appears that (87/aT). is less and is always a negative number not close to zero (because the correction involves . rises as the 4/3 power of the density [2]. This behavior of has an important effect on the validity of Mie-Griineisen formulation of the thermal pres- which is of interest in seismic tomography calculations [l. We would therefore expect that O.JTO cryq dT. The expected variation of O. between the thermoelastic dimensionless parameters. usually near and above 0. This similarity in values of 8. yielding a value near 900 at K. 8. v..69 km/s.. [78]. afhv. 371. 600 200 ' 600 1000 1400 1800 Temperature Fig. AlsOs. The A is for 0 (acoustic) for perovskite at room temperThe dashed line shows the expected variation (acoustic) with T.94 km/s. and all val- T = 8. and MgzSiOd. The values vr. SOME CORRELATIONS PROPERTIES IN THE This section deals with FOUND TABLES relationships FOR (12) The acoustic version of 0.. In Tables 29-42. (13) If the relative increase in (Y with T nearly compensates for the relative decrease of 7 with T taking into account the change in the denominator of (13). 7 decreases with T at high T. for perovskite will be high.108 g/cm3 used in the calculation are given by Yeganeh-Haeri et al. and ps = 4. we show the variation of (6~ . . in the neighborhood of that found for AlzOs. We also list values of the adiabatic Poisson’s ratio u given by 3Ks .6s) /7 with T/O for our fourteen minerals. The equation showing the relationship between ST .

82 HIGH T ELA!XICITY Another significant erals is r=bT,

OF MANTLE

MINERALS

correlation

found for most min-

(15)

which allows one to calculate G for KT in high temperature ranges where G is not known. It immediately follows from (15) that, because G is less than p 1 must be smaller than I(dKs/aT)pI. KS, I@WT) 5. PRESENTATION OF MINERAL DATA

We tabulate the adiabatic single-crystal elastic moduli (Cij) for 14 minerals in Tables 1 to 14 starting at 300 K and proceeding in intervals of either 50’ or lOOoK. The errors indicated at selected temperatures in Tables l-14 are those listed in the original references. The Cij data for thirteen of the fourteen minerals in Tables 1-14 were retrieved by the already defined RUS method (either rectangular parallelepipeds or resonant spheres). The tabulated errors in the Cij from these thirteen minerals are the standard deviations determined from the difference of each measured modal frequency with that modal frequency value calculated from the final set of Cij. Thus the listed uncertainties reflect how consistent the frequency data are in providing Cij values for a particular specimen. The MnO Cij data and their uncertainties are not from RUS measurements, but are those recommended by Pacalo and Graham [47] from a weighted linear regression analyses together with the Pacalo and Graham [47] temperature derivatives. The isotropic adiabatic bulk KS and shear G moduli computed from the Cij in Tables l-14 are included in Tables 15-28. For minerals with cubic crystal symmetry, I<s is given by (1/3)(Cii + 2Crz). We use the Hashin-Shtrikman (HS) [29,30,73] scheme to compute G for cubic minerals (MgO, MgAlzOd, MnO, CaO, garnet, and NaCl) and both KS and G for minerals with orthorhombic symmetry ([Mg, Fe, Mn, Co]zSiO.+). Very small variations (typically 5 0.1 GPa) between our tabulated values of I<s and G for the orthorhombit minerals and the values found in the original references are due to the differences in KS (or G) that result when using the HS and Voigt-Reuss-Hill (VRH) schemes. However, the HS scheme usually provides significantly narrower bounds and is preferred. The values in the tables are the averages of the upper and lower bounds found with the HS scheme. We use the VRH scheme to determine the isotropic G for KC1 because of difficulties in interpreting the HS upper and lower bounds (see Section g. below). For corundum (AlzOs) we use the KS and G values tabulated by

Goto et al. [26], which are based on the VRH scheme. The errors indicated in Tables 15-28 for KS and G are propagated by standard error techniques in which two sources of error are considered. These errors include both the uncertainty with which the midpoints of the upper and lower bounds of KS and G are known and the difference between the midpoints and the upper bounds. We couple thermal expansion CYand heat capacity Cp (at constant P) data with KS and G and calculate the values for several other thermoelsstic quantities given in Tables 15-42. We assume LY is accurate to 2% (unless specified otherwise in the original reference from which the a! data are obtained) and rigorously propagate errors to p, Cv, KT, up, and vI at high and low temperatures in Tables 15-28. The uncertainty in the dimensionless quantities 6s) 6T, I?, and v should be taken as 5% or more, since the values of these parameters can depend somewhat on the order of polynomial fit used when determining the T derivatives. 5a. MgO Prior to the work of Isaak et al. [34], high T data on the elastic moduli of single-crystal MgO were available up to 1300 K. Spetzler [55] used an ultrasonic pulseecho method to obtain ambient P data at 300 and 800 K and provides a table listing T derivatives of elasticity at these two temperatures. Sumino et al. [63], using the rectangular parallelepiped resonance (RPR) method, extended the T range for which data were available up to 1300 K. Isaak et al. [34] (RPR) and Zouboulis and Grimsditch [80] (Brillouin scattering) report Cij data for MgO UP to 1800 and 1900 K, respectively. We list the Cij values as reported by Isaak et al. [34] in Table 1 and note that an alternative source for high T data can be found in Zouboulis and Grimsditch [80]. In their Table 2, Zouboulis and Grimsditch [80] report (711(T), &(T), and the combined moduli (Crr + Crz + 2644)/2 and (Cir - &)/2 versus T. However, there is more scatter (especially in the Cd4 modulus) in the data of Zouboulis and Grimsditch [80] than in the data of Isaak et al. [34]. We find excellent agreement in (dC~/dT)p values when comparing the results of Spetzler [55], Sumino et al. [63], and Isaak et al. [34] in their T range of overlap. The high T (i.e., T > 1400 K) Zouboulis and Grimsditch [80] data have T dependence nearly identical to that of the Isaak et al. [34] data up to 1800 K. The values of the dimensionless parameters, 6s, ST, I’, and Y, in Table 30 are found using sixth order poly-

ANDERSON

AND

ISAAK

83

nomial fits to the KS, KT, G, up, and v# results as done by Isaak et al. [34]. We find very little difference in the value of these dimensionless parameters, other than a slightly less rapid decrease when T > 1500 K, when a lower order of fit, such as 3, is used.
5b. CaO

The appropriate thermoelastic quantities for CaO [43] are listed in Tables 2, 24, and 31. Oda et al. [43] used the resonant sphere technique (RST) to reach 1200 K. We include the o data of Okajima [45] as tabulated by Oda et al. [43] in our Table 24. The dimensionless parameters in Table 31 are obtained from a second order polynomial fit of the I<s, KT, G, up, and v, [43].
5c. Pyrope-Rich Garnet

pyrope, 1.2%; less than 0.5% almandine or spessartine) to 1350 K. Table 4 is constructed using the KS, Cs, and Cd4 of Isaak et al. [36] as primary data. Cir and Crz and their errors are calculated from these primary data. The Cij values in Table 4 are plotted by Isaak et al. [36], but not explicitly tabulated in their presentation. We follow Isaak et al. [36] in the order of fit used to calculate the T derivatives for the dimensionless parameters. The parameters bs and & are found using first order fits to the KS and KT data. Second order fits were applied to the G data to obtain I’ and to the I+, and v, values to obtain V. Isaak et al. [36] also provide new cx data for grossular-rich garnet and point out the possibility that the Skinner [51] thermal expansion values for garnets may be low.
Spine1 (MgAl~O4) Cynn [19] provides Cij for single-crystal MgAlz04 over the range 298-999 K at irregular intervals of T. There are data [19] up to 1060 K, but a sudden change in the slope of the data near 1000 K is attributed to the effect of cation disordering. We use the KS, Cs, and C44 values from 298-999 K given by Cynn [19] as the primary data source and interpolate to obtain the Cij in Table 5 at regular 50°K increments of T. Errors in Table 5 are either those given by Cynn [19] or are propagated from the errors in KS, C’s, and C44. The uncertainty in p at 300 K (Table 17) is assumed since it is not reported by Cynn [19]. The uncertainties in the Cij for MgA1204 are large relative to most other resonance data; thus we present the dimensionless parameters in Table 40 based on linear fits of KS, KT, G, vr,, and v6 with T. 5e.

Suzuki and Anderson [65] provide Cij for pyroperich garnet over the temperature range 298-993 K at irregular intervals of T. The specimen used by Suzuki and Anderson [65] is a single-crystal natural garnet with composition: pyrope, 72.6%; almandine, 15.7%; uvarovite, 6.1; androdite, 4.3%; spessartine, 0.7%; and grossular, 0.6%. We use the KS, Crr, and CJ~ values given by Suzuki and Anderson [65] (see their Table 1) as the primary data source and interpolate to obtain these moduli given in Table 3 at 100°K increments of T. The C’44 value at 638 K given by Suzuki and Anderson [65] seems unusually low and is excluded in our fit for interpolating. All errors in Table 3 are either those given by Suzuki and Anderson [65] (i.e., errors for KS, Cir, C,,) or are propagated from the errors in KS, Cr1, and Cd4 (i.e:, errors in Ciz and Cs). We extrapolate (linear in ii’s and Cir; quadratic in C&a) the Suzuki and Anderson [65] Cij data over seven degrees to include the 1000 K values in Table 3. The dimensionless parameters 6s and ST (Table 33) are found by a linear fit of the KS and KT values in Table 26. We find that G and v, have noticeable curvature, so that second order fits are preferred when calculating F and V. It is worth noting that v tends to increase gradually from about 0.88 to 1.06 over the 300-1000 K range when second order fits to v, and vr versus T are used. If first order fits are assumed, v is constant with a value of 0.97 over the 300-1000 K range in T. Thermal expansion cx data on pyrope-rich garnet are also provided in the Suzuki and Anderson [65] paper.
5d. Grossular Garnet

Isaak et al. [36] provide elasticity data for near endmember grossular (grossular, 96.5%; andradite, 1.6%;

MnO Pacalo and Graham [47] present new data on MnO from 273-473 K. We construct Table 6 using the Cij and (X’ij/dT)p values recommended by Pacalo and Graham [47] (see their Table 10) for MnO. For C44 we use a second order polynomial to interpolate at intervals of 50°K where the nonzero value of (8”Cij/dT2)p is found in Table 6 of Pacalo and Graham [47]. The recommended first temperature derivatives are based on both ultrasonic pulse-echo [47] and resonant [62] measurements. For minerals of cubic symmetry there are only two independent moduli among KS, &I, and Ciz. The recommended values for KS, Cir, and Ciz in Table 10 of Pacalo and Graham [47] are not selfconsistent. We take Cl1 and Cl2 from Pacalo and Graham [47] as the primary data and use these to compute KS for Table 23. Thus a small difference appears between the 300 K value for KS in our Table 23
5f.

84

HIGH

T ELASTICITY

OF MANTLE

MINERALS

(149.0 f 2.6 GPa) and that given by Pacalo and Graham [47] (150.6f 2.5 GPa). The values at 500 K in our Table 6 require an extrapolation of 27°K beyond the maximum T measured, but are below the Nkel temperature (522 K for MnO). Temperature derivatives of KS, KT, C, up, and v, are done with a linear fit in T when calculating the dimensionless parameters in Table 39. 5g. KC1 Table 7 shows Cij for KC1 where we use the Yamamoto and Anderson [76] data to interpolate at even intervals of 100°K. The Crr, Ciz, and Cd4 [76] are taken as the primary data from which C’s and KS (Table 28) and their errors are derived. In determining the isotropic shear modulus G we used the VRH rather than the HS scheme. When attempting to use the HS scheme [30], we found that the resulting upper bound 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 seemingly contradictory result is likely related to the fact that the shear modulus C’s is very near to the value of the bulk modulus KS at the lower temperatures. In any case we must defer to the VRH scheme for this material and note that there are relatively wide bounds on G (thus also on up and v,), especially so at lower temperatures. Statistical analysis indicates that a second order polynomial fit of KS, G, up, and v, is warranted when determining the T derivatives, whereas a linear fit of KT with T is adequate.
5h. NaCl

al. [77] is -0.012 GPa/K. The Yamamoto et al. [77] results tend to favor those of Spetzler et al. [56], who obtained elasticity data to 800 K for NaCl. Spetzler et al. [56] find (i?Ks/aT)p to be -0.011 GPa/K from 300-800 K. The Yamamoto et al. [77] data are out to a slightly lower maximum temperature than Spetzler et al. [56], but contain a much denser set of tabulated Cij values. We interpolate the Crr, Clz, and C’44 found in Table 2 of Yamamoto et al. [77] to regular intervals of 50°K for our primary elasticity data source in Table 8. The uncertainty in the density of the specimen used by Yamamoto et al. [77] is assumed to be 0.005 gm/cm3 at 300 K (Table 27), since this is not provided by Yamamoto et al. We calculate the dimensionless parameters in Table 41 using a second order fit in T to the KS, I<T, G, up, and v, values in Table 27, and note that this results in 6T at 300 K having a value near 5.6 rather than 5.3 as indicated by Yamamoto et al. [77]. We also find that above 600 K, ST increases gradually 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; Yamamoto et al. [77] find T derivatives by taking a finite difference between two adjacent data points.
5i.

MgaSiO4

Yamamoto et al. [77] report elasticity data from 294766 K for NaCl. Elasticity data up to the melting temperature of 1077 K for NaCl [31] were obtained with the composite oscillator method. To find accurate Cij results with the composite oscillator requires that the resonant frequencies of quartz and silica rods that are coupled to the NaCl specimen be known in order to reduce the NaCl data. We also note that the experimental arrangement of Hunter and Siegel [31] requires a large volume to be heated when increasing temperature. For these reasons we prefer the data of Yamamoto et al. [77], but emphasize that Hunter and Siegel [31] report data 300’K higher in T than do Yamamoto et al. [77]. There are relatively small but measurable differences in the T dependence of the elastic moduli between these two data sets where they overlap. For instance, from 300-700 K the average value of (aKs/BT)p from Hunter and Siegel [31] is -0.015 GPa/K, whereas that found by Yamamoto et

Following the work of Sumino et al. [61] to 670 K and Suzuki et al. [68] to 1200 K, the MgzSiOd (forsterite) data of Isaak et al. [35] to 1700 K extend the T limit for which elasticity data are available. Prior to bhese studies the available data were limited to T near ambient [27, 401. There is general agreement between the data where they overlap. Sumino et al. [61] provide schemes for extrapolating that are generally confirmed by the higher temperature measurements of Suzuki et al. [68] and Isaak et al. [35] (See Figures 3 and 5). We construct Table 9 from the Cij reported by Isaak et al. [35]. The thermal expansion results of Kajiyoshi [38] are used (see our Table 18) to calculate the thermoelastic properties of MgsSiOd (see Isaak et al. [35] for a comparison of the Kajiyoshi [38] values of a with other values in the literature). Isaak et al. [35] used the VRH scheme to calculate isotropic KS and G moduli, whereas Table 18 lists KS and G obtained from the HS averaging scheme. There is only a small difference (5 0.1 GPa) between the two approaches. Isaak et al. [35] show that fits of the KS, KT, G, v~, and us data with T imply that third order polynomials are appropriate to describe the data. Thus we use third

ANDERSON required to determine order fits for all T derivatives dimensionless parameters in Table 34. There are some small differences in the 6s, 6~, and I between our Table 34 and Table 5 of Isaak et al. [35] due to different methods used in calculating the T derivatives. Isaak et al. [35] used the interval between the two neighboring points to calculate the derivative at a particular T; here we apply polynomial fits over the whole temperature range from which the derivatives are obtained. The present approach produces smoother variations in 6s, 6~, I, and v with T. Olivine (F~Fa~o) Isaak [32] reports data to 1400 and 1500 K, respectively, on two natural olivine samples with compositions of Fos2.iFar.r and Fos0.sFas.a. Previously available T data on the elasticity of iron-bearing minerals were limited to temperatures near ambient [40]. We include the Cij for Foss.sFas,s (referred to here as olivine FoaeFais) in Table 10. There are some differences between the Cij of the two olivines reported by Isaak [32] that do not appear to be due to fayalite content. The differences are small, but caution should be used when interpolating between specimens with small differences in chemistry. The uncertainties in KS and G (and in all properties that depend on KS and G) are somewhat smaller in Table 19 than found in Isaak [32] for these quantities. Isaak [32] estimated the uncertainty by simply adding the uncertainty with which the HS average value is known to the distance between the average value and the HS high value. Here we square both the uncertainty of the HS average and the distance from the HS average to the HS high value, add the squares, and take the root. We use linear fits in T to the KS, KT, G, up, and v, data when obtaining the dimensionless parameters 6s, 6~, I’, and v. We start our olivine tables by interpolating the T = 296 and 350 K data of Isaak [32] to 300 K. This shift in starting T causes minor differences in the T derivatives; hence the slight differences between 65, 6~, and I in Table 35 and in Table 6b of Isaak [32]. 5j. 5k. Fe#iO,, Mn#iO~, CosSiOd Sumino [58] presents T data from 25’-4OO’C (398673 K) on the elasticity of single-crystal FezSiOa (fayalite). We interpolate the Sumino [58] fayalite data (see his Table 3, specimen TA) so as to provide C;j from 300-700 K in regular 50’K intervals in Table 11. A small extrapolation over 27’K is required to extend the values represented in Table 3 to 700 K. It should be noted that there are questions regarding the values of some of the Cij and some of the T derivatives of fay-

AND ISAAK

85

alite (see Graham et al. [28], Isaak and Anderson [33], and Wang et al. [71]). As an example of the effect of uncertainties in the derivative values, Graham et al. [28] report (llKs/dT)p = -0.030 GPa/K, whereas Sumino [58] reports -0.0205 GPa/K. The reasons for these types of discrepancies are under investigation. At present, we defer to the data of Sumino [58] since they involve a significantly wider range in T (up to 673 K) than the maximum temperature of 313 K used by Graham et al. [28]. However, no compelling reasons exist to suggest that the Sumino [58] fayalite data should be preferred over those of Graham et al. [28]. From Figure 2 of Sumino [58] it is clear that KS is linear in T, whereas G requires a higher order T dependence (at least a fourth order polynomial). In calculating the dimensionless parameters for fayalite in Table 36 we use linear fits in T for KS and KT and fourth order fits for G, vr, , and v,. Sumino [58] attributes the strong nonlinear behavior of the shear modulus to influences of the antiferromagnetic to paramagnetic transition, even though this transition occurs at a much lower temperature (65 K). elasticity data on singleSumino [58] a 1so reports crystal Mn$SiOa and CosSiO4 at 300 and 673 K. Sumino [58] indicates that all the Cij of Mn#iOr and Co2SiO4 are linearly dependent on T with the exception of Cad for Co$jiO4. We construct Tables 12 and 13, which show values of Cij at incremental temperatures of lOOoK for MnzSi04 and CozSi04, using the Cij and the (dCij/aT)p given by Sumino [58] in his Tables 4a,b. We assume a linear T dependence of the Co$SiOh Cd4 modulus in constructing Table 13 since the presence of nonlinearity in this modulus is asserted by Sumino [58] but no quantitative result is provided. As with FesSiOh, we must perform a small extrapolation outside of the maximum T measured in order to include the T = 700 K values in the tables for Mn$SiOa and Co$SiO4. When calculating the dimensionless parameters all T derivatives are assumed linear in T (see Figure 2 in Sumino [58]). 51. Corundum (AlaOs) The C, (Table 14), I<s, and G (Table 16) for AlaOs are those found in Goto et al. [26]. The KS and G given by Goto et al. [26] are found by the the VoigtReuss-Hill averaging scheme. Full account is made of the difference between the Hill (averaged VRH) values for KS and G and the Voigt (upper bound) values when assigning errors to KS, G, and other isotropic quantities derived from them. This accounts for larger errors being assigned to the G values in our Table 14 than are found in Table 2 of Goto et al. [26]. Appar-

86

HIGH

T ELASTICITY

OF MANTLE

MINERALS

ently Goto et al. [26] assigned errors in G that include only the uncertainty in the Hill average itself, but do not consider the difference from the Hill average to the upper (or lower) bound. We interpolate the Cij, KS, G, and p provided at 296 and 350 K to start our Tables 14 and 16 at 300 K. We use (Y from White and Roberts [75] rather than the cu preferred by Goto et al. [26], i.e., those from Wachtman et al. [70]. We use a third order polynomial fit to determine the T derivatives for each of KS, KT, G, vP, and v, required for the dimensionless parameters shown in Table 29. This order of fit seems appropriate from a statistical consideration, i.e., an F, test [18]. Thus, the SS, ST, and u found in our Table 29 for AlsOs may differ somewhat at a particular T from those given by Goto et al. [26] in their Tables 4 and 5. The Goto et al. [26] 6s, 6T, and v values are calculated from derivatives found by using a finite interval from the two nearest data points. Thus, we find considerably more scatter in the Goto et al. [26] 6s and ST values than in Table 29. 6. THEORETICAL BASIS FOR OBSERVED PROPERTIES AT HIGH TEMPERATURE 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 approximation of the statistical formulation of the free energy. 6a. The Helmholtz Free Energy The expression for the Helmboltz energy for an insulator is [41] A =
EST +-km,

number; and p is the number of atoms in each cell (or molecule). The first term on the right is the zero point vibrational energy EZV given by E zv =

:EhWj.

(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 levels to find the energy of each normal mode, according to the Hamiltonian [42]. We replace w with y, the dimensionless frequency, so that (18) Thus (16) can be given in terms of the thermal energy dvzB where
3pN 3pN

= Ezv + dmz,

W-9

dTH = kT c
j=l

en (1 - emyj) = kT c
j=l

dTHj,

(20)

dTH is the energy arising from temperature excitation, called the thermal energy. Ezv is not affected by T, as shown in (17). Thus dTH --$ 0 as T --+ 0. However, dvzs -+ EZV as T + 0, 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 dvrB for algebraic manipulations done lat>:r on. The expression for the Helmholtz energy for an insulator is thus A =
EST +

Ezv + dTH.

(21)

where electronic and magnetic effects are ignored. EST is the potential of a static lattice at absolute zero, and dvrB is the vibrational energy due to motion of the atoms as each is constrained to vibrate around a lattice point. The statistical mechanical definition of the vibrational contribution to the Helmholtz energy arising from 3pN independent oscillators is dvrB = i3EhWj
j=l

We need to divide (21) into temperature-dependent and nontemperature-dependent parts, so we use A =
ET=O +

dTH,

(22)

where
ET=o=EsT+Ezv.

(23) and nonvibrational

+kT3E!n(l-e-‘ui”T),
j=l

(16)

Dividing (21) into its vibrational parts, we define
A = EST +dvzB,

where wj is the jth modal frequency; N is Avogadro’s

ANDERSON

AND

ISAAK

87

where AVrB
6b. The

is given by (16).
Approximation

Cv= kcj
A, obtaining
S=kCYi(&)

(eyj - 1)2

‘jeyj = c C,,.
j

(31)

Quasiharmonic

Before we can find thermodynamic properties such as P and CV from (20), we must make decisions on the volume and temperature behavior of 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 dependent upon T, the sum C en (1 - e-y”) depends upon T. When wj are different, then yi are also different, and the sum above becomes T-dependent, especially at low T. The internal energy 24 is found by applying the formula U = -T2 ((ad/T)/aT) [41], yielding

Entropy is found by applying the operator (h’/c?T),

to

-kx

en(l-e-y;)

(32)

The expression for (YKT is found by applying a2/8T8V to (22), yielding

(YI(T = zCY,Z

"/j

(33)

=

ET=o

+kT

c
j=l

-&

=

ET=O

+

kTx j=l - (d/W),

ETHje

(25)
The pressure P is found by applying (21), yielding to

To get cu we divide [YKT (given by (33)) by KT, definT , and using P given by (26). ing KT = -V(aP/cW) Using (30), we find that (YI<T = yCv/V, and equating this to (33), we find that [16]

(34)

(26) where d en Wj ^lj = 8 en V and where yj are called the mode gammas. Thus
P=Po+fiH,

(27)

The bar over y indicates that this result is an approximation of y = (YKTV/CV resulting from invoking the quasiharmonic approximation to the Helmholtz energy.
6c. The harmonic High-Temperature Approximation Limit of the Quasi-

(28)

where the thermal energy (20) effect on the pressure, called the thermal pressure, is

At sufficiently high temperatures, the expression for &H can be simplified due to the convergence of certain series expansions. The argument in (16) becomes small since tiwj << kT, that is, yi is small. At high temperatures, we take advantage of the expansion [79], en (1 - eeyj) = en
Yj

-

(29)
= &nyj+

(

iy,” + . . .) (35)

en (1-kyj).

Comparing

(29) with (20), we see that

PTH=

$cYjdTHj. 3

(30)
to

By replacing the last logarithmic term above with its argument, which is valid for low values of yj, we find that en (1 - eWyj) 2: en
yj

- f

yj.

(36) of (20) is

The specific heat is formed by applying - (a/aT), (25), yielding

Thus the high-temperature

representation

88

HIGH

T ELASTICITY
3pN

OF MANTLE

MINERALS clude that insofar as specific heat is concerned, the quasiharmonic approximation is not adequate for some for other solids solids up to T = 20, but is adequate up to T z 20. The high temperature Griineisen parameter is found from (34), and considering that as T -+ 00, Ci + k,

A&

= kT

CC j T Helmholtz
energy

By using (21) and (34)) the high for insulators at high T is

Aht=Es~+Ezv+kT(Cenyj-~Cyj). j
We see that temperature the last term energy given
3pN

(38) j
the zero which is independent of T. The data on y is found in Tables 15-28. We see that there is an approximate trend for y to be independent of T at high T. For these solids when dy/dT is not zero, it is also true that CV does not obey the Dulong and Petit limit. Thus departures from quasiharmonic theory in CV create a departure from the quasiharmonic theory of 7. Above T = 8, the departure from (dy/dT), = 0 is slight, however. Applying the operator -(a/W), to (38), we find the high T pressure, Pht , which by using (44) becomes
‘?‘ht = Y(T+m) = -

(44

above just cancels by (17), so that

Aht = EST + kT c
j=l

(en hwj - en kT).
by defining an average

(39)
frequency

This can be simplified a, given by

en v =
in which

-J-C

hwj,

3pN
case (20) becomes

ATH = 3pNT ( en IiiZ - en kT) .

(41) Pht(T, V) = P(0, V) + y7ht
Thus the thermal pressure is

6d. Thermodynamic Properties in the High T Limit of the Quasiharmonic Approximation At high T, .4 includes only the static potential and the thermal energy in the quasiharmonic approximation. Using the equation U = -l/T’ ((BA/T)/aT),, we find the high temperature internal energy to be

T.

(45)

3pR PTH = - v

-f’ht T.

Uht = EST -I- SpRT,

(42) V is a function of T, and it is also equal to M/p where it4 is the molecular weight, so that the above is P TH
We

where R is the gas constant, kN. Equations (41) and (42) are important results for the high temperature limit in the quasiharmonic approximation. Taking the temperature derivative of U to find specific heat.

3R-m
= m~o(laT)T.

see that

the

Cc” = 3pR.

(43)

Equation (43) is known as the Dulong and Petit limit. Thus the high temperature quasiharmonic approximation leads to the classical limit in specific heats. If at high T the experimentally determined CV is not parallel to the T axis, we must conclude that the quasiharmanic approximation is not adequate for this property, and anharmonic terms must be added to A. From Figures 14-26, where the data for specific heat versus T are listed, we see that for several solids of interest to geophysicists (dCv/8T)~ = 0 at high T. This is true for MgO, CaO, and A1203 and NaCl, but not for olivine, garnets, spinel, or KCl. We must con-

PTH to be virtually linear in T: at the sured T, aT II 0.05. But 7ht is not, as exactly independent of T, though close there are counter effects in T, and the
is often obscured. PTH is proportional proximation. The thermal pressure is given by
APTH = PTH (T, fi)

allows for highest meawe shall see, to it. Thus 1 - aT term Thus to a very good approximation to T under the quasiharmonic aprelative to T = 8 for T > 0

quasiharmonic

theory

-

PTH

(6

b)

.

(47)

As shown in Tables linear with T (for

15-28,

T/O0

we see that APTH is indeed > 1). (See also Figure 2).

we have (qth 1) . and qht = 1. and 0. (aK~/tlT)v nation of (50) ordinarily yields a small quantity.$-$pt (1 . KTH.T curve from (47) is empirically a constant. we see that (aP~~/llT)p should increase as 03i4: In general.5 [8]. V) . . CYKT. contributes a minor amount to (aK/dT)p. (49) where qh’ = (a en 7ht/a en V).Qhl). (51) This means that for the thermal pressure property. 0. according to (48).031 GPa/K. 0. 0. bulk = (yI(T= f$$ po (l-oT) = const. [12]). To obtain the isobaric derivative.= ar-4 - = -$$7& . V) = KT(O. is linear in T/00. 0. = -3 -f.073. the qua&harmonic approximation appears quite adequate up to relative temperatures of T/C& x 2. such that Thus at high T. we find that the bulk modulus IcT along an isochore is Kp(T. it is also found for gold (see Figure 10 of Anderson et al. We evaluate (53) for the case of MgO from the data as an example.151. = -CYKT (Ii’ + qih . 0. The linearity of PTH with T is not unique to silicates and alkali halides. for nine minerals showFig. and 2) the slope deof the APTH . Thus from (48) for M/p = constant the slope increases from mineral to mineral as the ambient density increases. on (45). Using (48) in (52). Since PTH = s CYKT dT. 0. and that is borne out by the experimental results shown in Figure 2.053.4 [8]. In this table CYKT is shown to be c 1ose to actual measured values of ~KT 0.qh’) T..160. to be 0. The data in Tables 27-30 bear this out. Thus at high T.T/O0 line decreases as pc/(M/p) creases.0. (53) We thus see that the thermal bulk modulus.119. APT. good for T above 0.ANDERSON AND ISAAK 89 T 6e.. This range covers values of T/O0 for the mantle of the earth. For non iron-bearing silicate minerals. The Bulk Modulus at High Using the operator -V(a/aV). along an isobar.178. Values of pc/(M/p) in ascending order (l-9) are: 0. The high T value of K’ = 4. KTH. (aK~/aT)p. Letting ffI(T = (YIcT in the above (48) where M/p is the mean atomic weight (per atom). Thus we find from (53) that a predicted value of (dl(~/aT). Since to a good approximation for silicates of constant M/p. at high T. (fi!$).195. This result agrees well with the measurements found in Table 16 showing (c?Ks/dT). The average value of QKT is found from the values of APTH between 1000 K and 1800 K listed in Table 30.160. so the determiFor q ht = 1. = 0. M/p varies little from mineral to mineral and is near the value 21 [74].T (52) The term on the far right of (49) is the thermal modulus.1).d(T T . ing: 1) APT. 00 is the acoustic 0 at T = 300 K. 2. v (50) vanishes. we use the calculus expression: (s)v-&-T(=$)T.0064 GPa/K. 0. Also 7hi does not vary greatly from mineral to mineral.03 GPa/K in the high T range. as shown in Figure 2. then we can define an average value of CXKT.t(l-qht)-(Yli.176. 0 = const p413 [2]. the mineral with the highest value of po/(M/p) will have the highest slope. the isochoric bulk modulus creasing with T according to the slope is de- ( ) fw versus T/O. The slope of the APTH .

(59) reduces to (58) because is independent of V above the Debye temperature. then (t3P/BT)v is independent of T. 6h. and (BKTI ~P)T = Kh is virtually the experimental evidence is in favor of this. The above equation can be expressed as Qht =6T-I<. (54) The entropy increases with en T in the quasiharmonic approximation at high T. We note that (57) results from the quasiharmonic approximation. For an explana- . providing q > 1. LY Versus T at High T Along Using the expression for Kp expression for crI<~ given by (48). for the P = 0 isobar given by (53). aa shown by (43). (58) 6g. arising as it does from the high temperature limit of the quasiharmonic approximation. and using Theory (51). (59) Cv ff = KT. We note that if P is linear in T. CV is independent of T in this approximation at high T. & and q From From the definition and (53). We derived a relationship between three important dimensionless thermoelastic constants at high T. (52) ST = (qht . however. but even so.90 HIGH T ELASTICITY OF MANTLE MINERALS in Cv erties A as there cause .cm (55) The actual than (YKT fair approx- Equation (55) is to be compared to (48). = -3PR-h = -@Yht (M. (49).QT (57) and where a = (13Kp/dT). . Entropy Applying is found and CV& the operator (a/X!‘). They also suggest that the quasiharmanic approximation may or may not be valid for Cv and entropy for temperatures up to T = 28. This steady increase of (Y with T at high T does not necessarily require the assumption of additional anharmonic terms in A beyond the quasiharmonic high T approximation. Nevertheless to a imation CYKT is parallel to the T axis for Tables 29-42 show. It arises because the denominator in (57) has a term that decreases with T even in the qua&harmonic approximation. (41). we find that CYKT is independent of T (or approximately form of (YKT so) only at T above 0. and all the respective volume derivatives of these four properties. T (+7)h’ V PO(1 . (Y. This means that equations of state should not be corrected for anharmonic effects for pressures and temperatures corresponding to mantle conditions. We saw some evidence of anharmonicity 6i. T > 8.. This is demonstrated in Tables 29-43. Summary of the Quasiharmonic Approximation Effects Upon Physical Properties The data presented here strongly suggest that the quasiharmonic approximation is valid for the following properties at least up to T = 20: P. is parallel to the T axis. to the pressure given by (45). Thus (aP/aT)v should be esa 6f. we have for isochores. the entropy Sht = -3pR( Cn kT - en Foss+ 1). We also note that if independent of T.1) + . we take the logarithmic derivative of 7. which show that roughly speaking. strictly quasiharmonic equation. (3). KT. Examination of (57) shows that at high T we may expect IY to increase with T at high T even under the quasiharmonic approximation.+l. measured (YKT will have more structure determined from PTH. 6. 6~ at high T should be slightly higher than Kh. we also showed that is no evidence of anharmonic effects in PTH beit is linear in T. we find the Quasiharmonic of 6T. to (38). CYKT. this effect does not appear in propthat are controlled by the volume derivatives of described above. The functional resembles a Cv curve. as The above equation tells us that 6T should be virtually independent of T at high T. and for some solids const exactly equal to. and the we have (56) Equation (58) is appropriate for high T only. Further. In contrast. Applying the operator (d/aT). which is close to. From experiments. Isobars versus T. For the low temperature equation corresponding to (59).p) sentially independent of anharmonicity. is independent of T. then (Y is controlled by (57). If (BP/BT). as defined by (1)) yielding =bT-K’+lAt high T and P = 0.

Anderson’s equation for G(T) in terms of the nomenclature used in this paper is 7a. respectively. [63]. Sumino et al. However there is another method that minimizes the dependence of KS upon a(T) and p(T). Sumino et al./ F dT. Using (1) G(T)= Go[dT)l~o]‘a (63) Knowledge of Cp(T) is not required for (62) and (63). Combining (1) and (2). 7 and 6s are virtually independent of T for some minerals. KS0 CP(T) (60) For some solids. p(T) at high T may not be known.Ks(To) = -e [H(T) . and nearly so for others. Anderson [3] used (61) in a more convenient form. Extrapolations for KS Using 6s Constant With T Anderson and Nafe [9] pointed out that if bs is independent of T along isobars. 7c. (62) Using (62) he estimated I<s for MgO up to 2OOO’C (see Figure 1 and Equation (21) of Anderson [3]). while at the same time Cv and S may require anharmonic correction. Anderson [21] present a general formula for extrapolating elastic constants. Extrapolations for KS Using 7 Constant With T If 7 is independent of T. in which (62) is a special case. Duffy and D. (64 Ks(T)[ 1 =yq-$rq . We have seen that at high temperature (above O). Duffy and D. Along isobars. [61] used (62) to extrapolate values of KS for forsterite from 700 K to 2000 K. we find to a very good approximation [54] KS(T) . (65) Integrating .H(To)] . 7b. (YKT and Q do not require anharmanic correction. which follows when 6s is independent of T. We emphasize that reliable extrapolations using (60) require that CYbe known at high T and the assumption that 7 is constant. Cp. and MgzSiOd at high T. determined from (l). Since the values of bs and 7 are often not steady for T < 0. it is not safe to use the extrapolation formulas described below when only low T data for 6s and 7 are available. [61] and Sumino et al. HIGH TEMPERATURE TION FORMULAS EXTRAPOLA- 91 could be used to find KS vs. is useful. we have where Ksc. The appropriate equation relating p and (Y is p(T) = PO exp [ . KT. and Vo all refer to values of these quantities at some reference T beyond which 7 is approximately constant. Introductory Comments Knowledge of the high temperature thermoelastic properties permits one to generate extrapolation formulas for estimating KS and G at temperatures higher than measured. [13].ANDERSON AND ISAAK tion of why P. p (65) with respect to T = . T. used (60) to extrapolate KS from 700 to 2100 K (forsterite) and 1300 to 3100 K (MgO). and taking V = Vc(l+ aT). 7. as in the case of MgO. good estimates of KS are found using the definitions of 7 and 8~. for in this case ambient values of 6s and 7 are measured at temperatures much lower than 8.Ks(To) Assuming now that the product 6~7 is independent of T at high T. and if cr(T) and Cp(T) data are available at high T. This is true especially for minerals. see Anderson et al. then the following formula. but some knowledge of a(T) at high T is required to get p(T) at high T.. because V is a function of T.L. CaO.L.~+w]. (~0. By assuming that 7 and 6s are exactly independent of T. then en KS = -SS en V + constant (61) c-1 aKs aT KS(T) = -6s aKs = !p.

Both extrapolation (6% equations give reasonably good re- Sumno -. and (c) using Equation (67). and (67) assuming y and 6s constant in the high temperature regime. They then extrapolated the values of KS up to 2200 K using (60). It is clear that the extrapolation formula given by (60) is reasonably successful in the case of MgO. and there is much enthalpy data published listing H to temperatures about or greater than 2500 K. Extrapolations by Sumino et al. However. and their values are also plotted in Figure 3. (62). Experimental (plotted symbols): Isaak et al. [61] used for one extrapolation and an equation involving linearity in Poisson’s ratio is also used (T . and for the same three minerals for 300 < T < 1800 K by Anderson [5]. 170.To) P To ‘:::: _\__I MgO 100' 0 ' 500 ' 1000 ' 1500 ' 2000 ' 2500 ' 3000 T (K) Fig. They used equation (60) to extrapolate values of KS above the maximum measurement (1300 K) up to 3000 K. [35] measured G up to 1700 K. Figure 3 illustrates the point that (60) is not a good extrapolation formula. Observed and extrapolated values of I<s versus T for forsterite.92 HIGH T ELASTICITY OF MANTLE MINERALS where H(T) = s Cp dT is the enthalpy. 119771 (Eq 60) (Eq fiZj Exlrapolauon Exlraplation Sumino et al. 7d. [34]. Equation (67) is very useful because a(T) is not needed to find KS(T). Sumino et al. Extrapolation of G to High I loo\ 0 Mg2Si04 400 800 1200 -r (K) 1600 2000 Fig. [35] reported measured values of KS up to 1700 K. The term a(T . Sumino et al. Isaak et al. The extrapolation to 2000 K is shown in Figure 3. Equations (62) and (63) gave good results for extrapolations. [61] measured G for forsterite up to 400°C and reported extrapolated values from 700 K to 2200 K. [61] are confirmed to within 2% out to 1700 K by the measurements of Isaak et al.To)/2 is of little consequence in the calculation and can be ignored. Sumino et al. in which the measured values of KS [35] up to 1800 K are also plotted. since the actual measured values are quite close to the extrapolated ones. Extrapolations of KS by Sumino et al. Isaak et al. [61] measured the elastic constants of forsterite between -190°C and 4OO’C. Experimental (plotted symbols): Isaak et al. [35]. [63] measured the elastic constants of MgO from 80 to 1300 K. They [53] later measured G and KS up to 1100 K for MgaSiO4 and MgSiOs and also found linearity for G and I(s. [54]. 60 1 50 I dG G(T) = Go dT (>I (T .To). Sumino et al. [35]. Equation (67) sh ows that KS(T) should be linear in H(T). They used the empirical formula 7e. [63] using Equation (60). Extrapolation by Sumino et al. [61]. __ et al. 3. This is shown in Figure 4. Equation (68) is . Observed and extrapolated values of ICs versus T for MgO. Anderson [5] used (67) t o extrapolate the velocities of sound from 0 to the melting point. These results are plotted in Figure 5. [63]. This was proven experimentally for three minerals for 300 < T < 1200 K by Soga et al. Two extrapolations made by Sumino et al. 21 (3 -1 40 30 (68) to estimate shear velocities up to 2500 K. T Soga and Anderson [52] measured Ii’ and G for MgO and Alz03 up to 1200 K and found that G was linear in T above 800 K. [61]: (s) using Equation (60) where 600 K is the reference T. 4. at least for forsterite. (b) using Equation (62).

. short dashed line using Equation (62) with high temperature values of 6~. [35]. 6. Experimental (plotted symbols): Sumino et al."". If I( and G are successfully extrapolated.. [35] The equation of G is G(T)= 3 Cl. It is clear that the extrapolations by Sumino et al. Observed and extrapolated values of G versus T for forsterite. long dashed line using Equation (62) with low temperature value of 6s. 5. Extrapolations by’ Sumino et al.. .". These are shown in Figure 6. Experimental points shown with symbols [36]. and vr for forsterite up to 2200 K using their 100 K to 200 K measurements. [35]. Observed and extrapolated values of vP and v. and vr. Extrapolations: TSl refers to first order Taylor expansion using lower temperature data.'.c3_ xm 150 Extrapolated (Sumino et al. [61] up to 700 K. Experimental (plotted symbols): Isaak et al. at low T \ \ \ \ 4.ANDERSON AND ISAAK 93 sults when compared with the later measurements of Isaak et al.2 4-. Fig.5% out to 1700 K by the measurements of Isaak et al. [1977]) 140 6. Comparison with the actual measurements of v. Observed and extrapolated values of I<s vs. [61] gave values for the extrapolated values of v. then v.2a(T))I&(T) 2 (l+u(T)) ’ 7f. [35] up to 1700 K. 7.:oy 2 . [61]. Sumino et al."" 0 500 1000 T (K) 1500 2000 130 200 600 1000 1400 1800 Temperature (K) Fig. are extrapolated.5% at 1700 K by the measurements of Isaak et al.'. Extrapolations for u. T for grossular garnet. [61] were quite successful. 170 160 pzisjiq $:‘. Sumino et al. and up (70) to High T 60- _ 50 ” 0 Mg2Si04 ” 400 ” ” 800 ” T (K) ” 1200 ” ” 1600 ” 1 2000 Fig. and vP by Isaak et al. [61] are confirmed to within 1. [35] and presented in Table 15 are also plotted. [35].. [61] are from 700 to 2200 K and are confirmed to within 1. Isaak et al. Extrapolations by Sumino et al. The extrapolations made by Sumino et al. versus T for forsterite. (b) using Equation (70). [61]: (a) using Equation (68).

pp. are the average high temperature values.. L. The salary of one of us was provided by grants from the LLNL-IGPP branch under the auspices of the Department of Energy under contract W7405-ENG 48. Geophys. Shear properties and thermodynamics of the lower mantle. 0. Suzuki. vol.. J. L. Support for Mr. 90 a5 a0 75 200 600 1000 1400 1800 Temperature (K) Fig. Miner. and M. 22452253. 4963-4971.. Yamamoto. K. Sung Kim of Azusa Pacific University provided much help in the statistical analysis required to arrive at values for the various dimensionless parameters. . N90014-9310544. and not the low temperature values of I’ (T < 0). Observed and extrapolated values of G (GPa) versus T for grossular garnet. as shown in Figures 7 and 8. P. 559-562. Oda. S. 0. 0. The authors thank former members of the mineral physics laboratory who contributed to the data bank published here. provided that Equation (63) f or extrapolations values of 6s and F measured above 8 are used in the equations. Therefore we recommend Equation (62) for extrapolations of KS and of G. 1966. L. N. If enthalpy data are available.. Cynn. T. Anderson. Goto. Determination and some uses of isotropic elastic constants of polycrystalline aggregates using single-crystal data. Phys. Academic Press. Saga. J. H. Geophys. J. Experimental points shown with symbols [36]. and H. 1992. 4. SOL. New York. They also found Equations (62) and (63) t o b e a much better representation of G(T) provided that the exponents. short dashed lines using Equation (63) with high temperature value of I’. I.. long dashed lines using Equation (63) with low T values of F. Anderson. 1979. Res. Kim was provided by the Office of Naval Research through Grant no.94 HIGH T ELASTICITY 110 OF MANTLE MINERALS Gfossular (GGD) 7g. 1987. 3849. Res. Acoust. L. 6. 6~ and I?. II. L. I. Sumino.. Mason. 5.. 84. L. They tried both a first order polynomial and a second order polynomial. Acknowledgements. The relationship between adiabatic bulk modulus and enthalpy for mantle minerals. D. Phys. in Physical Acoustics. Rectangular parallelepiped resonance-a technique of resonant ultrasound and its applications to the determination of elasticity at high pressures. 1965. 0. IGPP contribution no. The fits were marginally successful. Spetzler. Y. Inter. Evidence supporting the approximation yp for the Griineisen constant of the earth’s lower mantle. A proposed law of corresponding state for oxide compounds. Graham. R. we recommend (67) for extrapolations of KS. J. Kumazawa. 4395. The Importance 6sandI’ of Using High T Values of 105 100 2 4% u 95 Isaak et al.. 0. D.. Anderson. I. Jackson. REFERENCES 1. Ohno. edited by W. including M. 307-327. A seismic equation of state. 1989. Extrapolations: TSl and TS2 refer to first and second order Taylor expansions using low T data.. H. measuring 6s and F over a wide T range. Ota. Anderson. 71. Earth Planet. Figures 7 and 8 show the extrapolations presented by them up to 2000 K. Bass. 45. 3. Liebermann. Anderson. 2. Anderson. 91. Weidner. L. [36] reported ICS and G for grossular garnet up to 1350 K. Manghnani that affected our research programs. 3. with 4 methods. We acknowledge with thanks the works of E. 3537-3542. 8. Chem. 16. S.

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i981. 1658 pp. and E. Watanabe. 1983. and K..7.. .1983. .. Mao.. B. 23. Anderson. Elastic properties of Fe-bearing pyroxenes and olivines (abstract). Minerals. Miner. G. Shankland. H. edited by S. Earth. Chem. Yamamoto. 1987. Monogr. New York.. Weidner. Scuderi. and G. Wachtman. 3. 1989. vol. and M. I.. 319-323. Geophys. 0. J. Taylor. Earth. 12.. 67. in Perouskite. C. 321-328. Thermochemical properties of synthetic highpressure compounds relevant to earth’s mantle. Sumino. 13-26. S. R. and 0. Chem. 38-46. I. 10. L. 9.. Ser. Refractive index and elastic properties of MgO up to 1900 K. 143-151. Watt. L. edited by A. 257 pp.. 71.. Sot. Lee. Phys. J. 0. 1975.. 73. J. Temperature coefficients of single crystal MgO between 80 and 1300 K. 13... J.ANDERSON magnesiowiistite. H. 1977. . K. Navrotsky and D.. 1975. 69. and N. Phys. 145-159. pp. Ohno.. Hashin-Shtrikman bounds on the effective elastic moduli of polycrystals with orthorhombic symmetry. Zouboulis. Zharkov. Phys.200 K. Tybulewicz. 1991. Phys. White. Elasticity and anharmonicity of potassium chloride at high temperature. Uniformity of mantle composition. Y. 1982. A. 1989. B. Earth. 45. 50. P. Suzuki. Earth. 63. 125-138. 48.. 78. Miner. Grimsditch. 60-63. 474... Suzuki. 76. I. H. Am. D. Sumino. and 0. KaIinin. Roberts. AGU. S. Anderson.I.. Res. Nonmetallic Solids: Thermophysical Properties of Matter. 63-69. Geophys. Miner. L. Suzuki. J. Phys. 14. and T. Thermal Expansion. Weidner. Y. I. 4167-4170. 1983. Single crystal elastic moduli of magnesium metasilicate perovskite. 74. Elastic properties of a single-crystal forsterite Mg#Oa up to 1.. 96. 72. 64.. Appl. Y. D.. Thermal expansion of single-crystal manganosite. Chem. 441464. lOOoK. G. J. Eos Trans. Ito. Okajima. AND ISAAK 97 Thermal expansion of reference Tungsten and CYmaterials: AlzOg. Seya. J. Takai. 79. R. Kirby. Phys. L. Center for Academic PubIications. 1983. A. S. J. E. D. Sumino. Suzuki. Akimoto and M. Anderson. Rossman. S. Tokyo. 1987. T. E. 1979. L. I. Thermal expansion of fayalite. J. 66. Thermal expansion of periclase and olivine. High Pressures. 15.. 27. Advances in Earth and Planetary Sciences. and their anharmonic properties. 31. K. New York-Washington. P. J.. H. High Temp. Touloukian. 475-495.. and Y. Suzuki. Manghnani. High temperature elasticity of sodium chloride. Consultants Bureau. 68. S. Seya. 1980. 1.. 91-99. Chem. R. 65. 77. in High Pressure Research in Geophysics.. Cleek. 332-340. 1979. 70. and G. Elasticity and thermal expansion of a natural garnet up to 1000 K. K. Wang. I. Watt. 38-47. and V. Plenum. N. Geology. translated from Russian by A. Anderson.. Anderson. R. Washington. Solids. Yeganeh-Haeri. Suzuki. 70. Yamamoto. Equations of state for solids at high pressures and temperatures. AGU. 80. 45. Phys. J. W.. and 0. pp. 6290-6295. Linear thermal expansion of aluminum oxide and thorium oxide from 100’ to 1. and R. 75. vol. Bass. T. Chem. and Y. 1962. 1971. and Y. Ceram. J. Phys. Jr. 28. Phys. Phys. vol. V.

Here.l/v(dp/dv)T) and its pressurederivative (dKoT/dP = KOT’) as well as characterizing the pressure conditions of structural phase transitions. 2. in order to determine the isothermal bulk modulus (Km = . 98 The most widely used high-pressure apparatus for measuringstatic equationsof state is the diamond-anvilcell coupled with x-ray diffraction. INTRODUCTION Generation of high pressures and temperatures in the laboratory is essential in exploring the behavior of solids and liquids at the pressureand temperatureconditionsof the Earth’s interior. for single-crystal measurements. There are severalexcellent recent reviews on the use of the diamond cell [88. thesediamond cells are used for pressures below about 10 GPa. CA 95064 Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union. With the bulk modulus and its pressure derivative. University of California. I tabulate bulk moduli data for a variety of mineralsand relatedmaterials. a Mao-Bell or “megabar”-type diamondcell. For equation-of-state measurements. To date. is necessaryto maintain the it samplein a hydrostatic environment. is optimal for obtaining x-ray diffraction data to pressures up to 300 GPa.In this chapter. Sinceliquid pressure media (such as 4:l methanol:ethanol mixtures) are only hydrostatic to -12 GPa. the sampleis a powder and the xray diffraction data collected is directly analogous to a Debye-Scherrer powder pattern. as well as the geochemicalbehavior of materials at depth in the planet have been derived from experiments involving static compression. . However.1. elements and related materials. or for E. it is possible to extrapolate the density of a material to any pressure condition. Institute of Tectonics.2151. The Merrill-Bassett-type diamond cells are commonly used for single-crystal x-ray diffraction measurements. two basic diamond cell designsare used (see Figure 1).Static Compression Measurements of Equations of State Elise Knittle 1. Diamond-Anvil Cell There are a number of different experimental techniques and apparatuses achieving high pressuresstatically. or 2) maintaining large sample volumes(large-volumepresses). EXPERIMENTAL TECHNIQUES pressuresmaintainable for long periods of time. A typical sample configuration in the diamond-cell is shown in Figure 2. 2. The bulk moduli data havebeencollectedusingprimarily either x-ray diffraction or piston displacement in conjunction with a high-pressureapparatusto measurethe changein volume of a material as a function of pressure. the primary insights into magma genesis. the emphasisis on static-compressionmeasurements the of equations of state of minerals. Knittle. Usually. the vast majority of static compression experiments have focused on measuring isothermal equations of state (P-V measurements at constant temperature). and thus no details of its operation are presentedhere. in this type of diamond cell.97. Santa CNZ. high pressureapparatusesare optimized for either: 1) allowing optical accessto the sample while held at high pressures (diamond-anvil cells). In general. The second type of diamond cell.phasetransitions and the equationsof stateof deep Earth constituents. Mineral Physics Laboratory. the pressure limitation of the diamond cell is not a limiting factor for the experiment.as their small size makes them convenient for mounting on a goniometer to obtain singlecrystal x-ray patterns. Indeed. Santa CNZ. In general.

are excited with blue or green laser light (typically He:Cd or Ar-ion lasers are used). either Laue spots for single crystal samples or diffracted cones of radiation for powdered samples. la. 1291. The relationship between dspacings and lattice parameters for the various lattice symmetries are given in most standard texts on x-ray diffraction [e.g.KN1l’TL. 128. are detectedby a solid state detector or on film. Additionally. These fluorescence bands have a strong wavelength shift as a function of pressure. accurate adiabatic moduli and their derivatives may be obtainedusing Brillouin spectroscopyin conjunction with the diamond cell (see the chapter on Elasticity).E 99 Optic Access A schematic diagram of the geometry of an x-ray diffraction experiment in shown in Figure 3. ruby can be finely dispersedin the sample (fluorescencemeasurements be can obtained for ruby grains less than 1 pm in diameter). Usually. the changesin the volume of the sample chamber as a function of pressure can be directly measured [cf. . Because diamondsare transparentand allow optical access to the sample. This shift has been calibrated using simultaneous x-ray diffraction measurements metals whoseequationsof state(pressureon volume relation) are independentlyknown from shock-wave measurements Chapter on Shock-waveMeasurements). the RI and R2 fluorescence bands of ruby.92 nm. For example. and exert a minimum amount of torque on the piston. 1431. 361. 28 is the anglebetweenthe diffracted x-ray beamand the transmitted beam. The diamonds are glued onto half-cylinders of tungsten carbide which are mountedin a piston and cylinder madeof hardened steel tool (shown here in a cutaway view at the top). The set of dspacings for a crystal is used to determine the lattice parametersand thus the volume of the crystallographicunit cell as a function of pressure. other methods for measuring equations of state are possible.24 nm and 692. thus enabling pressure gradients to be accurately determined within diamondcell samples.. In addition of to average pressure measurements. The piston and cylinder are placedin a lever arm assembly (bottom) designed to advance the piston within the cylinder.. apply force uniformly to the sample held between the diamonds. where A is the wavelength of the incoming x-ray.. The diamonds can be translationally aligned by means of set screws and tilted with respect to each other by rocking the WC halfcylinders. The Mao-Bell-type diamond cell capable of generating pressures up to 550 GPa. The diffracted x-rays. (see Therefore. the accuracy of the pressure measured in the diamond cell is ultimately determined by the accuracy of measurements shock-waveequationsof state. Pressurein the diamondcell is usually measuredusing the ruby fluorescence technique [20. X-ray diffraction from a crystal occurs when the Bragg equationis Satisfied: A= 2dsintI (1) Sample zl Cylinder L Sample fl Lever Arm 2cm - 0 Fig. MoKa x-rays are passedthrough the diamondsand sample along the axis of force of the diamond cell. Here. and d is the d-spacing or the distance between the diffracting set of atomic planesin the crystal. 1393. at zero-pressure wavelengthsof 694. or changes in the sample dimensions with pressure may be directly measured [cf.

In these devices. and by careful measurement of the resulting piston displacement as a function of pressure. and also allow the diamonds to be translationally aligned relative to one another. the samplesare typically contained within either a tetrahedronor a cube composedof oxides. the P-V equation of state can be determined.as their names imply. A second family of large-volume apparatuses is the multi-anvil press. As illustrated in Figure 4c for a cubic-anvil press. high-pressureapparatuses: piston-cylinder devices. Holes or slits in the backing plates provide optical accessto the sample. Large-Volume Presses Equationof statemeasurements havealso beencarried out using a variety of large-volume. This device can be usedto generatepressuresof . The routine pressure limit of the pistoncylinder at room temperatureis betweenabout 3 and 5 GPa.30 GPa. large-volume devices utilizing opposedanvils for equationof state measurements are Bridgman anvils and the Drickamer press. Rather than uniaxially compressingthe sample. diffraction measurements be madeon can a sample held at high pressures. One of the most widely used high-pressure. or six hydraulic rams for the cubic press. circular backing plates typically made of hardenedsteel. In tetrahedral and cubic-anvil presses. 2. where the pressure is applied uniaxially by a piston on a sampleembeddedin a pressure medium and contained by the cylinder. however.100 STATIC COMPRESSION FWD Plate f f 1 cm Holeto Diamond Back Boltsfor pressure andOpticAccess Application Fig. Pressureis applied by sequentiallyturning the three bolts which compressthe top and bottom plates together. in-situ x-ray diffraction . tungsten carbide or copper-beryllium alloy. Merrill-Bassett-type diamond-anvil cell shown in schematic from both side (top) and top views (bottom). If all or a portion of the retaining ring is madeof a material transparentto x-rays (suchas B or Be). as the anvils must be carefully alignedand synchronizedto compressthe sampleuniformly and thus prevent failure of the anvils.Drickamer presses. and the limit of the Drickamer press is about 30-35 GPa. Alignment pins ensurethat the the top and bottom halvesof the cell are correctly oriented. these devices compress simultaneously from several directions. For recent reviews of the designand use of large-volumepressesseeGraham [59] and Holloway and Wood [85]. As the sample is compressed its volume decreases. Such instruments are more difficult to use than a piston-cylinder.2. A number of designs exist for multi-anvil pressesof which the ones most commonly used for equation of state measurements are the tetrahedral-anvil and cubic-anvil presses(Figure 4b). lb. The backing platesare held in place in recesses larger steelor in inconel plates by means of set screws. is compressed by four hydraulic rams in the caseof the tetrahedral press. with the sample occupying a cylindrical cavity inside the cube or tetrahedron. Other types of high-pressure. The pressurelimit of the Bridgman-anvil press is about lo-12 GPa at room temperature.large-volume devices for equation of state measurementsis the pistoncylinder (Figure 4a). two tungsten carbide anvils are driven together to uniaxially compress a sample contained within a large retaining ring which acts as a gasket. and multiple-stagesystems. which varies in complexity dependingon the experiment. The sample assembly.cubic and tetrahedral-anvil pressesand multianvil presses(Figure 4).Bridgman-anvil presses. The single-crystal diamonds are glued on flat. much higher pressurescan be attained in multi-anvil devices. which is contained between the diamondsin a metal gasket.

the diffraction angles available through the apparatusmay be limited. and the gasket is centeredbetween the diamond anvils (shown with a typical culet diameter of 0. V is the volume and P is the pressure. this .30 mm). which represents the most common method for estimating the pressure in all largevolume devices.7 GPa). Schematicview of the sample configuration in the diamond cell. For equation of state measurements. (From [2151). Furthermore. Such a multi-anvil design can reach typical pressuresof about 25 GPa.such as thoseoccuring in Bi (the I-II transition at 2. which necessitatesboth careful experimental design and a high intensity x-ray source. An equationof state formalism usedextensivelyprior to 1980 and sporadically since is the Mumaghan equation [ 1533. where KOTis the isothermal bulk modulus. A hole is drilled in a metal gasket (here a typical diameter of 0.the sampleassembly in a cubicanvil press can be replaced by a second. A linear fit to pressure-volume data is often used for static compressiondata limited to low pressures(small compressions). The bulk modulus is calculated from the thermodynamic definition: KOT = -l/V(dP/dV)T. I summarize the most common methods for data reduction. this analysismethod will tend to overestimateKm. and thus is at best approximate. ANALYSIS OF THE DATA I c / Ruby Grains y Pressure Medium ( Lower Diamond) Fig. At modest compressions.5 GPa and V-VI transition at 7. or a noble gas suchas argon) and small ruby chips for pressurecalibration. producing few redundancies the measurement lattice parameters. and is most appropriate for rigid materials over narmw pressureranges(preferably less than 5 GPa). an equationof state formalism must be used. 2. Equationof statemeasurements have typically beenmadeto pressures of about 12 GPa in the cubic-anvil press. the oil pressureof the press is calibrated against a series of materials or fixed points.10 mm is shown). or by calibration of the external load on the sample. x-ray diffraction patterns can be obtained at high pressure along the axis of force of the diamond cell for either single-crystals or powders. The pressureinside a large-volume device is determined either by including an internal stress monitor within the sample. Specific disadvantages of x-ray diffraction measurements large volume pressesinclude: 1) indirect in pressure calibration.and 3) the small volume of the sample relative to the containing material. Here. 2) an inability to accurately characterizepressuregradients.in which: p = KoT/&$((VO/~~OT’ -1 j (2) The Mumaghan equationis derived from finite strain theory with the assumption that the bulk modulus is a linear function of pressure. To determine the values of Km and Km from pressurevolume data. pressureintensifying stage. The transparent diamonds allow for a wide range of different in situ experimentsto be performed on the samples. with wellcharacterizedphasetransformations.KNITTLE 101 measurementscan be made through these presses if the sample is contained in an x-ray-transparent material. This analysisimplies that KOT' = 0. In the latter case. To achieve higher pressures. in of 3. In general. The sample is placed in the hole in the gasket along with a pressuremedium (generally either an alcohol mixture. becauseKOT' is usually positive.

KOT’ is close to 4 for many materials.e.! = 312 [KmKm” + Kof(Kof-7) P Direct X-ray Beam Note that Km = 4 reducesequation (3) to a secondorder equation in strain. as are the specific structure for solids with more than one polymorph at ambient conditions. This equation has been empirically shown to describethe behaviorof a wide variety of materialsover a large rangeof compressions. which is used in the Bragg equation to determine the set of d-spacings of the crystal at each pressure. the structures of the high pressure phasesare explicitly given. sulfides. halides and hydrides were included which are useful as mineral analogues.) whemfis the Eulerian strain variabledefinedas (3) State Detector Sample f = 1/2[(V/V&‘3 -11 and the coefficients in (3) are: xl = 3/2(K()f ..either due to structural similarities to minerals. It should be noted that entries with no errors simply reflect that error bars were not reportedin the original references. 3. Schematic of an x-ray diffraction experiment through the diamondcell. except where noted. another equation of state formalism has been proposed by Vinet et al. Recently. Here the schematic x-ray pattern is that of a powder diffraction experiment. piston displacementmeasurements direct volume measurements or at high pressures). is often assumedto equal4. Indeed. Howie and Zussman’s An Introduction to the Rock- This equation is successful in describing the equation of state of a material at extremely high compressionsand is being used with increasingfrequency in static compression studies. One of the most widely used equations of state in reducingstatic compressiondata is the Eulerian finite-strain formalism proposedby Birch. mineralsare seldom compressibleenough for KOT” to be significant. x-ray diffraction. The maximum distance between the correspondingx-ray line on either side of the transmitted xray beam is 40. (4) mineral or native element. All the KOTand KOT’ data listed are for the structure of the common room-temperature. Here: P = 3 Fig. mineral analogues and chemical elements studied using static compression techniques (i. KOT (VO/V)~~[~-(VIV~)~/~ exp(3/2(KoT’-1) [~-(V/VO)~‘~I). In addition. or to provide the systematics of the behavior of a given structural type. where the film intersects diffracted cones of radiation. x. [205] and is known as the Universal equationof state. Not every entry in the Table is a . atmospheric-pressure phase.102 STATlC COMPRESSION assumption is sufficiently accurate that the Murnaghan equationaccuratelyfits static compressiondata. Oxides. 4. The silicate minerals are categorized following Deer. EXPLANATION OF THE TABLE The Table lists the isothermal bulk moduli (KoT) and pressurederivatives (dKo~/dl’=K& for minerals.. All the data reported is from the literature from 1966 to the present: static compressiondata from before 1966can be found in the previousHandbookof Physical Constants.Pressure is expressed a Taylor seriesin strain: as P = 3f(1+2j)5/2Ko~(1 + xrf + x2f2 + .4) + 143191. MOK~ x-rays are passedthrough the sample and the diffracted x-rays are recordedeither on film (shown here) or by a solid-state detector. the x2 term is usually droppedfrom the equation. In particular. therefore. Specifically not included are data for nonmineral III-V compoundsand other non-naturally occurring semiconductors. and in the reduction of pressure-volumedata. and referred to as the BirchMurnaghan equation 1251.

The data for high-pressurephases are given in the same category as for the low-pressure phase. 12151). Such studies often do not report either bulk moduli or the numerical static compressiondata. For example. . The sample geometries can vary from relatively simple. iron-nickel and iron-cobalt alloys are found in this portion of the Table. iron hydride.monitor temperatureand pressure. which have the same stoichiometry. to a sample contained in a second. and iron-silicon. 46 A cubic-anvil press in which six. Finally. under the “Chain Silicates” category. measurementsare not given which clearly seemed to be incorrect. x-ray diffraction measurements can be obtained on samples held at high pressures. Equation of state measurementscan be made in this device by determining the piston displacement as a function of pressure. Also. while more oxidized iron minerals such as hematite (Fez@) and magnetite(Fe304) are listed with the oxides. A piston-cylinder apparatus shown in crosssection. The piston and cylinder are usually made of tungsten carbide and the maximum routine pressurelimit of this device is 5 GPa at room temperature. a uniaxial force is used to advancea piston into a cylinder. 4a. and measure pressure-induced changes in electrical conductivity. Electrical leadscan be brought in between the rams of the pressto heat the sample. with the sample assemblyembeddedin a cube of pressuremedium which is directly compressedby the rams. (From Assembly V 2% Fig.KNll-TLE 103 Feedthrough l-l I l-l edium X-Rays 5cm Fig. (From [215]). The data for the iron polymorphs and iron alloys which are important as possible core constituents are listed in a separatecategory (“Iron and Iron Alloys”). electricalleadscan be introducedinto the sampleto measure temperature or as a pressure gauge. the bulk moduli for perovskitestructured silicates are given with the data for the pyroxenes. by using a low-atomic weight pressure medium such as B or Be. compressing a pressure medium and thus applying hydrostatic or quasi-hydrostatic pressure to a sample contained within the medium. iron sulfides.O. The rams are usually made of steel with tungsten carbide or sintered diamond tips. Therefore. I note that a range of materials have been statically compressedwith the primary motivation being to characterizethe pressureat which phase transitions occur. ultrasonic data or Brillouin spectroscopic results. cubic. Here. based on comparison with other static compression measurements. Another use of the feedthrough is to provide current to a resistance heater surrounding the sample (not shown). pressure-intensifying set of anvils (a multi-anvil press). In addition. Forming Minerals [38]. and are accordingly not included in the Table (an example of this type of study are several static compressionrest&s for Ge). Fet-. The feedthroughinto the cylinder gives a way of monitoring the sampleenvironment. For example. synchronized rams are used to compress a cubic sample.

4.65 6. scXRD. B-M EOS DAC.12 159 f 3 4 (assumed) DAC.76 67 94 -_- 14 14 2. XRD. P I 5 GPa. scXRD. scXRD.5 63 . P 2 12 GPa.5 GPa.56 2. P I 5. 1inPVfit DAC.4 8. XRD.2 GPa.92 4. P 5 2.29 38.4 98 2. O-H method CAP.4 f 1. M EOS BA. Framework SiO2 QUUHZ Si02 Quartz Si02 Quartz Si02 Coesite Si02 Stishovite Silicates: 2.8 + 0. 1inPVfit DAC.76 106 _- 14 3.2 AZ1 DAC. P 5 5 GPa.XRD. Bulk Moduli from Static Compression Data Chemical Formula1 Density @kh3) Isothermal Bulk Modulus (GPa)2 dKoTldP3 Technique and Notes4 Ref. ND. XRD. scXRD.4 AZ0. scXRD. B-M EOS DAC. 1inPVfit DAC.P112 GPa. P I 12 GPa.65 2.61 70 r/I 3 5.2 _- 157 113 176 Si02 Stishovite Si02 Stishovite Si02 Stishovite NaAlSi3Og Low Albite KAlSi30g IIigh Sania!zke caA12si2og Anorthite (low-pressure phase) caA12si2og Anorthite (high-pressure phase) BeAlSi040H Euclase BeqSi2WW2 . 1inPVfit 21 6 5 -- 158 179 14 2.5 6.29 4.9 1. scXRD.7 + 0. O-H method DAC.5 GPa. B-M EOS 77 2. B-M EOS 115 2.3 l!Y 1.0 96 + 3 313 f 4 306 (fixed from Brillouin data) 5. P I 5 GPa.29 2.1 f 0.65 37. P < 16 GPa. scXRD.2 (fixed from ultrasonic data) 36. P 2 5 GPa. P < 5 GPa.3 rk 0. scXRD.29 4. P 5 5 GPa. B-M EOS DAC. scXRD. 1inPVfit BA. P I 8.. P I 5 GPa.6 2. B-M EOS PC.62 3ooIt30 288 rk 13 281 70 TAP.104 STATIC COMPRESSION Table 1.

scXRD. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density @Wm3) Isothermal Bulk Modulus (Gl?i~2 21. P I 5 GPa.H20 Analcite Na4A13Si30l2Cl Sodalite o.8 4.7 4 (assumed) 4 (assumed) 4 (assumed) DAC. P I 6 GPa. 1inPVfit 33 2.30 2. P 5 5. B-M EOS DAC. B-M EOS 73 2.Fe. scXRD.4WI.42 82. P I 5 GPa.8 f 0. P c 3 GPa. scXRD.l2(NaqA13 Si9024Cl) Scapolite 2.22 3. 1inPVfit 69 cwYrl@3 Technique and Notes4 Ref.3 GPa. scXRD. P < 3 GPa.24 40 I!I 1 -DAC. scXRD.54 52 f 8 4 (assumed) 76 60 -- 33 2. scXRD.17(c&jAl(jsi&‘4 C03) . B-M EOS DAC. scXRD.68(CaqAlgSi6024 C03) * 0.0.88(CaqAlgSQjO24 C03) .71 90 f 12 4 (assumed) DAC.6) Si206 Heafenbergite ~Ca.~) Si206 Omphacite (vacancy-rich) 3.7 f 1 228 3. P I 5. B-M EOS 112 1131k2 122 f 2 119f2 116 142 228 3. 12NaAlSiO4 -27H20 Zeolite 4A NaAlSi206.22 3. P I 10 GPa. P I 10 GPa. scXRD. B-M EOS DAC.O.56 114f4 4.66 86 DAC. P I 6 GPa. P I 4 GPa.7 (in glycerol) 142. B-M EOS DAC. B-M EOS 76 Chain silicates: CaMgSi206 Diopside caMgsi206 Diopside CaMgSi206 Diopside CaFeSi Heaknbergite Ca(MgO. B-M EOS DAC. scXRD. scXRD.32(NaqA13 SigO24Cl) Scapolite O.8 (in water) 2.44 4 (assumed) DAC.83(NaqAl3 Si9024Cl) Scapolite O. B-M EOS DAC. pXRD. P I 4 GPa.KNI'lTLE 105 Table 1. pXRD.5 + 1.Na)Wg.22 3.26 129 k 3 4 (assumd) 142 . 1inPVfit DAC.3 GPa.

3 (k0.WwaSiO3 Majorite 3.4 + 4.25 281 f4 4 (assumed) DAC. B-M EOS 224 4.41 164. P < ?. B-M EOS 142 MgSi03 Enstatite 3.nSi03 (high-pressure perovskitestructure) 4.XRD. P < 30 GPa. B-M EOS DAC.52 125 161 5 (assumed) 4 (assumed) BA.6 4 (assumed) WgW2Si3On)o. B-M EOS DAC.6 3. scXRD.10 221 + 15 247 4.5) x 1O-2GPa/K 138 Mgl.88Feo.1 4 (assumed) 224 Mgo.8 + 0.4 DAC.22 3. P I 7 GPa. P I 134 133 GPa.10 254 zk4 4 (assumed) 173 4. XRD. pXRD.sFeo-0. P I 112 102 GPa. P I8 GPa. scXRD. O-H method DAC.55 159.29 139f4 4 (assumed) DAC.2 O. B-M EOS . B-M EOS dKm/dT = -6. P I 6 GPa.A~) Si206 Omphacite (va=y-poor) 3. P < 6 GPa.9 ?I 0. B-M EOS 159 223 MgSi03 (high-pressure tetragonal-garnet structure) (Mf%Si4012)0.6 + 1. P I 6. pXRD.2 GPa. scXRD. P I 13 GPa.74 4. pXRD. B-M EOS DAC. pXRD.33 261+4 4 (assumed) 4.4 Majorite (Fe4SWi2h. P I 10 GPa.10 258 + 20 4 (assumed) 220 Mgo. XRD.8 Majorite CAP.2 SiO3 (high-pressure perovskitestructure) CaSiOg (high-pressure perovskitestructure) 4. pXRD. B-M EOS DAC.P16 GPa.26 266+6 3. B-M EOS CAP.106 STATIC COMPRESSION Table 1.e3&?si3012)0.Fe.o-o.8 4 (assumed) 90 106 MgSiO3 (high-pressure perovskitestructure) MgSi03 (high-pressure perovskitestructure) MgSiOg (high-pressure perovskitestructure) 4. Bulk Moduli from Static CompressionData (continued) IsothermalBulk Chemical Formula1 Density dKoT/dp3 Modulus oMg/m3) Technique Notes4 Refand VXWMg.10 4. XRD. B-M EOS DAC.

1inPVfit 35 Glaucophane NaCa2MgqAlSigA12 022WU2 3. P I 4 GPa. pXRD.22 120 5.22 135.0 3. scXRD. B-M EOS 199 4.1 DAC.10 97 -- DAC.9 + 4.7 + 1. B-M EOS DAC. P I 30 GPa. XRD.98 r!z0.39 123. P I 85 GPa.6 119 * 10 124 f 2 5.6 4. CaSiO3 (high-pressure perovskite structure) CaSiO3 (high-pressure perovskite structure) ZnSiOg (ilmenite structure) ca2mssi8022 O-02 Tremolite Na2MgsA12Si8022 w-02 325 + 10 4 (assumed) DAC.99 85 35 3.C1)2 Grunerite 3. scXRD.3 105 4.96 216 f 2 4 (assumed) -- CAP. 1inPVfit 35 Pargasite (Na. B-M EOS CAP. P I 10 GPa. P I 4 GPa. P < 7 GPa.WwW (Si. M EOS BA.F.0 5 0.8 7+4 5 (assumed) 216 222 . pXRD.KNI’ITLE 107 Table 1. P < 15 GPa. pXRD. B-M EOS 229 Ortho- and Ring micates: 3. P I 31. XRD.1 GPa.6 159 3. B-M EOS DAC. P I 5.50 50 + 1 13 f 1 DAC. scXRD. B-M EOS 214 Mg2SiO4 Forsterite Mg2SiO4 Forsterite Mg2SiO4 Forsterite Fe2SiO4 Fayalite Fe2S i04 Fayalite 3. P I 10 GPa.22 122. XRD. P c 38 GPa.5 GPa. P I 4 GPa.39 4.A1)8022 (OH.25 275 f 15 4 (assumed) DAC. scXRD. pXRD. O-H method DAC.KFe.25 fsothe~~~u~ dKoT/dp3 Technique and Notes4 Ref. B-M EOS 200 2. scXRD.10 % -- DAC. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density @Wm3) 4. 1inPVfit 184 2.

38 f 0. dK/dT= -5. P < 27 GPa. P I 10 GPa. scXRD.78 171 + 0. 1inPVfit 151 (Mgo. scXRD. P d 5 GPa. B-M EOS DAC. B-M EOS DAC. P < 6.wFeo. scXRD.39 134 4 (assumed) 104 4. i 612 Si04 Wadsleyite or PPhase (Mgo.2 GPa.47 166*40 -- MAP. 1inPVfit 151 3.0 GPa at 400 “C. P < 14 GPa.7 (fixed from ultrasonic data) 4 (assumed) 52 3.47 3. XRD.8 (at 400 “C) 168 (at 4% “C) 3. dK0T/dT = -2. P I 50 GPa. DAC.108 STATIC COMPRESSION Table 1. 1inPVfit 56 .6Feo&SiO4 Ringwoodite or YPhase (spine1 structure) Fe2SiO4 (spine1 structure) 4.55 213 + 10 _- MAP. scXRD.6 4 (assumed) Re-analysis of [78] 92 3. P I 10 GPa. 16)2 Si04 Wadsleyite or PPhase (MgW2siQ 1002Mg/(Mg+Fe)2 0.4 x 1O-2 GPa/K DAC.09 183 f 2 5. B-M EOS.05 113 rf: 3 4 (assumed) -- 186 4. pXRD.3 x 1O-2 GPa/K DAC. pXRD. pXRD. B-M EOS 227 4.39 124 + 2 4 (assumed) Technique and Notes4 Ref. P I 5 GPa. B-M EOS DAC.7 * 0. pXRD.sd+o.65 227 ?z2 67 3. P < 8. P I30 GPa. XRD.75 Wadsleyite or PPhase Mg2SiO4 Wadsleyite or /I-P/use Mg2SiO4 Ringwoodite or FPhase (spine1 structure) 4. B-M EOS 131 4. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density Isothe~~u~u~ dKoT/dp3 @Wm3) (GPa)2 Fe2S i04 Fayalite Fe2SiO4 Fayalite Fe2S i04 Fayalite CaMgSiO4 Monticellite ZrSiO4 Zircon (Mgo. 3 168 f 4 4 (assumed) 4. scXRD.39 103.24 DAC.53 164*2 78 3. P 5 4 GPa.53 174 f.85 196 Ifr 6 _- DAC. 1inPVfit DAC.

58 3. 1inPVfit CAP.59 168 f 25 168. pXRD. pXRD.1 f 1. P < 30 GPa. P I 30 GPa. B-M EOS DAC. P I 19 GPa.4 f 1 7.5 CAP. pXRD.5 2 0.6 156 Ca3Al2Si3012 Grossular Mn3A12Si3012 Spessartine 3.P<S GPa. pXRD.8 174. B-M EOS DAC. B-M EOS DAC.5 + 0.KNI’ITLE 109 Table 1. B-M EOS DAC. P 5 43 GPa. B-M EOS DAC.35 5. XRD. B-M EOS 66 108 WwWWOn Pyrope 3.6 4 (assumed) 4. P I 26 GPa.5 -7.XRD.8 zk0.59 4. P I 30 GPa.17 5.2(fixed from ultrasonicdata) DAC. B-M EOS 114 183 195 MS3Al2Si3012 Pyrope WwWSi3012 Pyrope . scXRD. scXRD. B-M EOS 178 131 56 178 127 123 178 156 Ca3A12Si3012 Gross&r 3.58 3.0 f 0. P I 25 GPa.0 5 1. P I 6 GPa.35 5.35 5. pXRD.P58 GPa. B-M EOS DAC. 4. 1inPVfit DAC.17 2.85 5. scXRD. P I 4 GPa.4(fixed from Brillouin data) 6.58 175 f 1 171 f 3 212 + 8 DAC.7 3. Bulk Moduli from Static Compression Data (continued) Isothermal Bulk Chemical Formula1 Density dKoT/dp3 Modulus (Mg/m3) (GPa)* Fe2SiO4 (spine1 structure) Fe2SiO4 (spine1 structure) Ni2SiO4 (spine1 structure) Ni2SiO4 (spine1 structure) Ni2SiO4 (spine1 structure) Co*SiO4 (spine1 structure) Co*SiO4 (spine1 structure) Ca3A2(04Hq)3 Katoite or Hydrogrossular TechniqueandNotes4 Ref.1 f 0.5 1.0 4.52 197 f 2 212 227 f 4 227 f 4 214 210 f 6 206+2 66 f 4 4 (assumed) 4 (assumed) -4 (assumed) 4 (assumed) 4. B-M EOS CAP. B-M EOS DAC.19 139 Ifr 5 171. P I 5 GPa.XRD. pXRD.2 + 4 6.P18 GPa.XRD. B-M EOS CAP.xRD.P18 GPa.85 4.

B-M EOS DAC.75 58.110 STATIC COMPRESSION Table 1.3 f 1 3. B-M EOS 183 4. B-M EOS DAC. IinPVfit 65 . B-M EOS DAC and PC. pXRD. P I 5 GPa.5 195 3. scXRD.86 159 + 2 4 (assumed) 75 3. P I 4.83 162 4.58 175 f 0.3Feo.8 + 1 DAC. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density @kh3) 3.7 108 3. P I 25 GPa.5 f 1.2 GPa.7 GPa.7 * 0. XRD and PD. Na+.5 f 2 -DAC.32 175 + 7 1.15 135+ 10 4 (assumed) --- 169 Mg1. scXRD. B-M EOS DAC.66 2. P I 25 GPa. P I 30 GPa. B-M EOS DAC. P I 3. P I 5 GPa. scXRD.P18 GPa. scXRD.32 190 rt 5 3 f 0.8 (fixed from Brillouin data) Fe3A12Si3012 Almandine Fe3A12Si3012 Almandine Ca3Cr2Si3012 Uvarovite Ca3Fe2Si3012 Andradire A12Si05 Andalusite 4. B-M EOS 63 Sheet silicates: KMg3AlSi3010 (FDW Phlogopite 2.6 CAP.63 170 + 5 110 4 (assume4I) - DAC. P I 3 GPa. scXRD. pXRD. P I 6 GPa.58 Isothermal Bulk Modulus (GPa)* 179 f 3 dKoT/dp3 Technique and Notes4 Ref.XRD. K+) Cordietite Be2SiO4 Phenakite 2.96 201 + 8 2+4 DAC. pXRD. scXRD.7 GPa. B-M EOS DAC. P I 4. scXRD. 1inPVfit 77 150 WgJW2A4Si5018 n(H20. 4 (assumed) 3.68 148 + 5 GPa 34 2.3 172. B-M EOS DAC. C02. B-M EOS 75 108 3.7A@i2 Olo(OH)4 Magnesiochloritoid Be3Al2Si6018 Beryl 3. P < 5 GPa.

M EOS DP. scXRD. 1.2 3. scXRD.56 3.0 f 10 -- DAC.54 156 f 9 178 157 4. pXRD.0 4 (assumed) 126 41 51 MgO Wgo. 55<P<135 GPa. pXRD. P I 4.7 * 2 4. B-M EOS 74 MgO Pericke Per&se 3.A1k(Si. P I 30 GPa.72 62 + 3 4 (assumed) 71 BaFeSi4010 Gillespite II (high-pressure ortborhombic stlucture) 3. B-M EOS DAC. M EOS DAC.79 111* 112 1 4.4 DAC.5 f 0.6Fe0. pXRD. M EOS DAC.38 3.5 170 41 170 130 + 20 4. B-M EOS.01 Bromellite 212 f 3 4 (assumed) DAC. PkFe.3 120 .4 f 4. P I 34 GPa. B-M EOS DP.6 It 2. B-M EOS 49 3.56 4.6 GPa. P I 55 GPa. 0 < Pc1.7 f 3 x 1O-2 GPa/K DAC. 1inPVfit 65 Chlorite KAWi3OloO-02 Muscovite BaFeSi4010 Gillespite I (low-pressure tetragonal structure) 2. P I 95 GPa.65 55.9cPc4.Ah 010 (Fm-02 2.80 61. scXRD. B-M EOS DAC.2 + 0.KNITTLE 111 Table 1. scXRD.70 90. P I 30 GPa. dKT/dT)p = 2. Bulk Moduli from Static Compression Data (continued) Density Isothermal Bulk Chemical Formula1 dKOTfdP3 Modulus (Mg/m3) Technique and Notes4 Ref. pXRD. T I 800 K. M EOS 71 B- Oxides and Hydroxides: 3.9 I!I 1. pXRD.4 f 0. P < 18 GPa.7 GPa.40 Magnesiowiistite CaO Lime CaO Lime CaO (high-pressure B2 structure) SIO 3. XRD.38 3. XRD.0 6.76 66f3 4 (assumed) DAC.4 4.9 GPa. B-M EOS DAC. P I 5 GPa. P < 30 GPa.9 3. pXRD.

P 5 30 GPa.0 DP.23 63.6 2 8.9 9.46 6.? (quartz structure) GeO. XRD. B-M EOS PC. P I 5.1 f 0.0 41 32 199 190 (fixed from ultrasonics) coo Cd0 Monteponite PbO Massicot EuO cu20 Cuprite GeO.8 + 1. fit to Hooke’s Law 41 41 9. M EOS BCAC.8 + 1. M EOS DAC. Bulk Moduli from Static Compression Data (continued) Density Isothermal Bulk Chemical Formula1 WTldP3 Modulus (M8fm3) (GPa)2 SKI (high-pressure B2 structure) 6. B-M EOS DP.63 22.67 66. XRD. ND.? (quartz structure) 6.25 5.3 16. M EOS DP.9 5.7 GPa. P I 13 GPa. pXRD. M EOS 182 5. B-M EOS DAC.9 f 0.3 4.14 160 f 19 4 (assumed) Technique and Notes4 Ref.15 190. P I 5 GPa. B-M EOS DAC. P I 30 GPa.23 4.1 5.3 211 211 162 3117 4. M EOS 231 208 4.7 4 (assumed) 225 39.8 33. P I 10 GPa. P $30 GPa.0 3. scXRD. DAC.2 17. pXRD.5 108. pXRD. P I 2.09 (high-pm%e PlQI structure) MnO Manganosite MnO Manganosite NiO Bunsem’te 5. M EOS DAC.7 + 6. XRD. XRD.7 DAC. P I60 GPa. B-M EOS DAC. pXRD.1 93 144 3.5 98 4.2 f 0.91 97. pXRD. 36<P<59 GPa.? (quartz structure) Gee.5 GPa. P I 10 GPa.2 AI 1.2 AI 0.112 STATIC COMPRESSION Table 1.23 26.46 5. M EOS DP.8 86 .7 (fixed from ultrasonics) 6. pXRD.5 34.0 131 4 (assumed) 5. P 2 30 GPa.02 zk 0. pXRD. 18<pc60.4 2. P I 6 GPa.45 8. EXAFS. B-M EOS DAC.72 6.5 GPa.

17 270 If: 6 95 f 8 220 4 (assumed) Ceo2 70 zfl2 Baahkleyite zfi2 4-5 (assumed) DAC. pXRD. P I 9. P I 31 GPa. B-M EOS 225 (rutile structure) GeO. B-M EOS 5 (assumed) DAC. pXRD. scXRD. B-M EOS DAC. 3 lcPc70 GPa.8 f 0. P I 5 GPa.96 7. P c 9 GPa.2 4 (assumed) 4 (assumed) 24 45 45 (high-pressure a-PbC12-type structure) Ru02 6. P I 5 GPa. B-M EOS 104 70 178 70 4. XRD.13 7. B-M EOS DAC. P I 12 GPa.KNITTLE 113 Table 1. B-M EOS DAC. B-M EOS DAC. pXRD.lfkP<25 GPa. scXRD.M .6 GPa. B-M EOS DAC.97 5. P I 25 GPa.84 207 230 f 10 304 f 25 GPa 7.8 (fixed from ultrasonics) 4 (assumed) 7 (assumed) 4 (assumed) 5.24 IsothermalBulk Modulus (GWG myrm3 Technique Notes4 Ref. Paratellw-ite 6.24 258 f 5 265 f 5 7 (assumed) 70 (rutile structure) Ti02 Ruble 4 (assumed) 7 (assumed) 4 (assumed) 4 (assumed) 6.24 7.! Argutite 6.9 f 0.2 4 (assumed) DAC. B-M EOS 110 (high-pressure orthorhombic-I pha.4 f 1. B-M EOS CAP. scXRD.00 187 218 f 2 224 f 2 Sn02 Cassiterite TeoZ.24 216 IL 5 222 k 5 Ti02 Rutile 4. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density (Mg/m3) 6. XRD. scXRD. P I 5 GPa.81 6. pXRD.6 (tetragonalstructure) WI Uranhite CeQ2 Cerianite 10. scXRD.5 DAC. B-M EOS DAC. pXRD. P I ? GPa. B-M EOS DAC. pXRD.24 203 197 Ti02 Rutile 4.26 44. and GeQz Argutite 394. P I 5 GPa. O<P<lO 110 GPa. B-M EOS 119 DAC.

pXRD. scXRD.6 + 2. scXRD. B-M EOS 16 16 2. pXRD.OcP<lO GPa.6 (from ultrasonics) 5. pXRD.20 181 zk2 DAC.3 183 -+ 5 4 (assumed) 5.57 36 4 (assumed) 190 3.0 + 3.6.5 GPa.39 269 + 3 I75 + 11 --- DAC. pXRD.5 * 15 55 Fe304 Magnetite Fe304 Magnetite Fe304 Magnetite Mn304 Hausmannite Mn3O. B-M EOS DAC. pXRD. lO<P ~39 GPa. O<P<lO GPa. B-M EOS 109 4.20 4. scXRD. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density (Mdm3) 9.! (high-pressure orthorhombic-II ph=) HfoZ (high-pressure orthorhombic-III Phase) HfO.d (high-pressure marokite-type structure) 5.68 Isothermal Bulk Modulus (GPa)2 145 dQT/c+ Technique and Notes4 Ref.88 550 5 (assumed) DAC. B-M EOS DAC. P I 4 GPa. P 5 ? GPa.3<P< 7.98 475 5 (assumed) DAC. P I 8.55 194 III 6 4 (assumed) 55 5.? (high-pressure tetragonal phase) v305 v305 (high pressure phase) AlPG4 Berlinite WAW4 Spine1 Fe304 Magnetite 5 (assumed) DAC. B-M EOS DAC. B-M EOS 154 5.83 183 31 10 137.14 210 5 (assumed) 309 10. scXRD.7 4 (assumed) 163 .73 5. 1inPVfit DAC.114 STATIC COMPRESSION Table 1.20 186. B-M EOS DAC. pXRD. 1inPVfit DAC. Hf% HfO. B-M EOS DAC. B-M EOS DAC.5 GPa. P 5 4.5 GPa.5 GPa.20 155 f 12 4 (assumed) 212 5.26cP<42 GPa.42<P<50 GPa.8 4 (assumed) 4 (assumed) 130 163 5.33 166. 1OcP<26 GPa. pXRD. P < 32 GPa. B-M EOS 109 11. scXRD. B-M EOS DAC. P 5 4 GPa. pXRD. B-M EOS 109 10. scXRD.O<P< 5.

Al2Be04 Chrysoberyl Re03 4 (assumed) -- DAC. P 5 5 GPa. B-M EOS DAC.Pl8 GPa. P I 20 GPa.. XRD.72 170+ 7 177 + 3 8f4 4 (assumed) 5fl 207 OWQ9TiO3 Ilmenite MnTi03-I Pyrophanite MnTi03-II (LiNbo3 structure) MnTiOg-III (perovskite structure) MnSn03 (perovskite structure) MgGe03 (ilmenite structure) MgGe03 (ilmenite structure) CuGe03 4.12 4.4 <Pc5 GPa.3 GPa. B-M EOS DAC. pXRD. P I 22. P 4 20 GPa. pXRD. 1inPVfit DAC.88 6.4 GPa. B-M EOS see ref.5 GPa. B-M EOS DAC. pXRD.44 168 * 13 DAC. P I 6. scXRD.3 57 5. pXRD. B-M EOS DAC.97 195 3. B-M EOS 175 4.2 (fuced from ultrasonic value) 176 2. B-M EOS DAC.6 (assumed) 37 218 5.63 3. B-M EOS 47 4.12 5. 2. P I 13 GPa. P c 28 GPa.12 227 + 4 4 (assumed) 175 111 196 f 20 4 (assumed) 4.9 I!I 0.9 2OOf4 23 LiNbOg CaTiO3 Perovskite SrTi03 Tausonite SrTi03 Tausonite FeTi03 Iimenite 4.5 GPa. B-M EOS DAC. B-M EOS 123 4.54 70 I!I 9 4 (assumed) DAC. 1inPVfit 175 4. B-M EOS CAP. scXRD. M EOS DAC. P c 0.11 67. scXRD.6 -- 17 1 5. P I 7.8 .XRD.4 DAC. pXRD.68 158 f 9 4 (assumed) DAC. P 5 3 GPa.3 GPa. scXRD. pXRD. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density @Wm3) 3.97 187 f 2 4 (assumed) 184 4.5 5.98 134 IfI 3 210 r!z7 174.KNITI’LE 115 Table 1. 7<P<20 GPa. P I 10.70 Isothermal Bulk Modulus (GPzI)~ 242 f 5 dQlTldP3 Technique and Notes4 Ref. scXRD. pXRD. B-M EOS 62 6. P I 5 GPa.

23 fsotheziufulk (GPa)2 dKoT/dp3 Technique and Notes4 Ref.006 DAC. P I 10 GPa. B-M EOS CAP. B-M EOS DAC.3 GPa. P I 65 GPa.61 91 -- 72 5.44 119 _- 72 Nao.0 f 1. scXRD.3 GPa. P < 5. B-M EOS CAP. XRD. P < 12 GPa. scXRD. P 5 5 GPa. scXRD.21 222 f 2 231+5 4 (assumed) 2.25 228 + 15 4 (assumed) 22 5.275 IL 0.4 + 2. pXRD. B-M EOS CAP.3 GPa. B-M EOS DAC.7 4 (assumed) 4. B-M EOS DAC.25 178+4 4 (assumed) 181 3.9 f 0.98 4. 1inPVfit DAC. B-M EOS 72 Nao. P 2 5 GPa.62W03 (perovskite structure) 7. B-M EOS 40 181 4 (assumed) 3. P I 12 GPa.4 171 3.25 225 199 f 6 4 (assumed) 4 (assumed) 54 212 Hematite Fe203 Hematite Fe203 Hematite Fe203 Hematite A1203 Ruby A1203 Corundum A1203 Ruby A1203 Corundum v203 Karelianite v203 Karelianite Cr203 Eskolaite Cr203 Eskolaite 5.98 257 f 6 DAC. pXRD. XRD. scXRD.116 STATIC COMPRESSION Table 1. 1inPVfit DAC. scXRD. B-M EOS 53 3.25 5.21 238 f 4 54 . P 5 5 GPa.87 195 f 6 DAC. B-M EOS 54 5. XRD. B-M EOS CAP.s#‘% (perovskite structure) 105 _- DAC.87 254. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density @Wm3> 7. XRD.98 253 ck 1 5. B-M EOS DAC. Nao. P 5 5 GPa.1 f 0. P < 5. P < 5.98 226 f 2 239 f 4 4 (assumed) 0.7oWO3 (perovskite structure) Fe203 7.0 171 + 1 175 f 3 4. P I 30 GPa. scXRD. P I 30 GPa. XRD.8 4 (assumed) 181 3. P I 12 GPa. scXRD.1 4 (assumed) 181 5. scXRD. P I 12 GPa. 1inPVfit DAC.0 f 0.

P I 5 GPa. DAC. P I 11 GPa.5 GPa.6 GPa. DVM. XRD.2 310. pXRD.9 AI 0.1 4 (assumed) 4 (assumed) DAC. scXRD. l<P 6.17 21. PD.7 144 Minerals: Sic Moissonite C~~(CO3)2 Dolomite 3. 1inPVfit DAC.5 GPa. 2.5 GPa.7 f 0. l<P 6. B-M EOS DAC.5 4. pXRD.6 6. P 5 5 GPa.67 58 f 5 95 lk 9 4 (assumed) 4 (assumed) 139 139 2.5<P 4.018~0003 GPa/K DAC.0 GPa. P I 1. P < 35 GPa.15 189 .5 68 2. scXRD. B-M EOS 5 174 CaMgo. scXRD.2 4. DVM.3 f 1.8 f 0. P I 5 GPa.3 k 0. P I43 GPa DAC.6 GPa. B-M EOS DAC. scXRD.22 2. P 24.7 (CO312 Ankerite BaC03 Witherite srco3 Strontianite M&03 Rhodocrosite CaC03 Calcite 174 4. scXRD. B-M EOS PC.1 4.26 25.39 54. B-M EOS 3 RbV03 ? 42.KNITTLE 117 Table 1. B-M EOS DAC.6 Ik 1.71 71.86 3. polyPVfit 139 3. P I4. B-M EOS DAC.1 f 0. P I 2.8 + 1.9 -- 3 2.5 GPa.8 68 NaN03 Nitratine MgKW2 Brucite 2. 1inPVfit DAC. Bulk Moduli from Static Compression Data (continued) Isothermal Bulk Chemical Formula1 Density dK0TldP3 Modulus Wdm3) (GPa)” KV03 ? 84. B-M EOS dKT/dP= -0.7 GPa.30 50 * 3 4 (assumed) DAC. B-M EOS DAC.8 5.24 37.73 3. P < 2.9 -- 3 csvo3 ? 62.7 -- Technique and Notes4 Ref. 1inPVfit DAC. scXRD.05 227 f 3 94 91 4.2 50 CaWO2 Portlandiie Carbon-Bearing 2. scXRD. DVM.Feo.

7 4.1 192 41 41 140 27 211 211 5. P I 24 GPa. B-M EOS DP.5 (assumed) 7. 6.9 4.7<P<4 GPa.82 4. B-M EOS DP.6 3.0 f 0. 1.71 Isothermal Bulk Modulus wTm3 Technique and Notes4 Ref. B-M EOS ---- 210 210 41 56. pXRD.2 (at 1. PD. DVM.67 86. B-M EOS 230 . pXRD.49 4 (assumed) DAC.5 7. P I 30 GPa. XRD. P I 30 GPa.1 + 1. P c 45 GPa. P I 55 GPa. M EOS DAC.2 + 1.13 19.50 16.99 5. PD.8 4.99 3. B-M EOS DAC. M EOS DAC. 3cP< 5 GPa.72 76. polyPVfit DAC.25 4. P I 24 GPa.4 GPa) 75.09 2. B-M EOS DAC.02 4.3 4. pXRD.5 11. B-M EOS DAC.4 + 0.118 STATIC COMPRESSION Table 1. B-M EOS 189 2.3 4.4 f 0. pXRD.5 GPa.1 DAC. P I21 GPa.0 72 f 2 156 2~10 55. P I 6. CaC03 Calcite II CaC03 Calcite III CaC03 Cal&e III 32. pXRD.8 f 0. pXRD.5 85.36 7. M EOS DP.0 IL 3.5<Pc89 GPa.7 94.3 4.85 4 (assumed) 139 Sulfides and Tellurides: Cinnabar HgTe Coloraabite CaS Oldhamite CdS Greenockite CdS Greenockite MnS Alabandite MnS Alabandite NiS (NiAs-type structure) BaS 8. pXRD.50 4. 1.l lcPc45 GPa. pXRD. XRD. B-M EOS DAC. XRD.7 GPa. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density (Mg/m3) 2.0 81.7 GPa) 84.3 HgS 8.4<P< 1. P I 30 GPa.82 3.4 f 0. polyPVfit PC.7 (at 1.0 + 8 (at l?GPa) ? PC.1 (high pz%re B2smlcture) ZnS Sphalerite ZnS (high-pressure phase) 4.85 189 2.4 21.

pXRD.91 141 f 11 -- 48 3. P < 12 GPa. P I 8 GPa. P I 5 GPa.0 5.. XRD.38 82 101.6 GPa. 1sqPV fit DAC.5 + 1.0 30 4.58 4. B-M EOS DAC.50 29 -- 64 3.46 76. 4<P<ll GPa.1 204 89 ThS 9.7 GPa. XRD. 1inPVfit 194 CeS ErS 5. M EOS DAC.4 + 0. scXRD. scXRD. P I 4 GPa.3 -- DAC. XRD. 1inPVfit BA. IinPVtit DAC. P < 3 GPa.1 f 0.5 31 55. M EOS 58 4.70 60 IL 8 6 209 . B-M EOS 30 4.4 * 0.0 5.7 96+ 10 4 (assumed) 6.45 109 3~6 48 4.38 6Of3 4 (assumed) Technique and Notes4 Ref. P < 5 GPa.8 5. XRD. pXRD.2 -- 160 NiS2 Vaesite NiS2 (high-pressure metallic phase) MnS2 Hal&d? MnS2 (high-pressure orthorhombic marcasite-type structure) cos* ‘Cattierite SnS* Berrdtite As4S3 Dimorphite CuFe2S3 Cubanite CuGaS:! Gallite AgGaS2 4.0 145 & 6 2. XRD.02 213. PI 3. P I45 GPa.93 8. P I 3.11 17. pXRD. P I45 GPa. 1inPVfit BA. 10 cPc35 GPa. M EOS DAC. B-M EOS DAC.4 DAC. M EOS BA.87 92 ck 9 9.3 + 1. DAC.56 160 us 10.36 209 4. pXRD. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density Isothehed$dk c-uQTl@3 @Wm3) (GPa)* YbS 7. B-M EOS see ref. pXRD.2 5. P < 16 GPa. scXRD. M EOS DAC. B-M eqn DAC. o<P<lO GPa.27 118.2 5. pXRD. P I25 GPa.KNI’ITLE 119 Table 1.5 141 4.

64 66. XRD. PD.9 46. B-M EOS DAC. M EOS DP.9 180 .2 3.9 41 202 2. B2 structure) NaCl Halite NaCl Halite NaCl Halite 4.9 f 1. B-M EOS PC.5 GPa.46 65. P I 23 GPa. P 5 30 GPa. 1inPVfit 145 La6NiSi2S 14 4. P I 9 GPa.5 3.5 GPa.9 24. P I 4.37 75. B-M EOS PC. M EOS PC.5 GPa. pXRD.3 4. P I 4. PD. B-M EOS DP.7 6. XRD.3 4.56 16. PD. P I 30 GPa. XRD. XRD.5 41 202 202 LiI NaF Villiaumite NZIF Villiaumite NaF Villiaumite NFIF Villiaumite (high-pz%rre. M EOS PC.56 2.7 4.0 31.8 202 LiF LiCl LiBr 2. P I 29 GPa. M EOS DAC.0 Ik 3.64 2. Bulk Moduli from Static Compression Data (continued) Density Isothermal Bulk Chemical Formula1 dKoT/dp3 Modulus (Wm3) (GPa)2 LagCoSi2S 14 4. 1inPVfit DAC. P < 5 GPa.56 2.5 4.56 2.4 4. P 5 4.2 46. pXRD.08 2.5 CAP.17 26. P 2 30 GPa. DAC. B-M EOS 219 LiF 2.4 -- Technique and Notes4 Ref. P I 4.4 + 6.4 23.9 4.2 5.7 3. M EOS PC. XRD. M EOS DAC.37 79.120 STATIC COMPRESSION Table 1. P 5 4.7 202 219 180 202 41 45. M EOS CAP.5 GPa.5 GPa. P I 5 GPa. PD.5 GPa.5 _- 145 Halides: LiF 2. P I 4.5 f 0. PD. scXRD. pXRD.8 45. 23<P<60 GPa.07 3. scXRD.64 62.16 4 (assumed) 180 2.8 f 7. PD.2 AZ0. P I 9 GPa.2 5.17 2. M EOS DP.4 3.6 103 f 19 3. M EOS PC.17 23.

1 5. B-M EOS DP. pXRD.34 36. M EOS CAP.5 4. pXRD. pXRD.3 2. P I 30 GPa.2 f 4. P I 4.5 GPa.5 GPa. XRD. M EOS CAP.0 5. M EOS DAC.20 3.XRD. P I 4.0 4 (assumed) 41 26 3.1 103 CSI 4.4 4.67 3.2 4 (assumed) Technique and Notes4 Ref.1 202 180 Nd 3.2 5. PD. P I 4. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density lsothe.44 18. DAC.1 4.99 3.1 14.4 219 37. pXRD. B-M EOS 41 219 202 202 19. P I 39 GPa.9 ?I 0. B-M EOS PC.8 5. M EOS DAC.4 41 NaI Nd KF Carobbiite 3.0 18.2 5.51 5.XRD. B-M EOS FC. XRD. PD.4 4.48 180 202 219 29. B-M EOS DP.9 13.7 f 1. pXRD. B2 structure) KC1 Sylvite KC1 (high-pressure B2 structure) CsCl CsCl CsCl CsBr CsBr 1.0 14. XRD. PD.87 (high-prl:urc.ilIlulk dqrrm3 @Wm3) NaCl (high-pressure B2 structure) NaBr NaBr 2.9 101 .0 28. P I 30 GPa. P I 4. pXRD.1 5.67 2. P < 53 GPa.3 5. B-M EOS 80 3. M EOS DAC.8 + 1.67 15.P< 9 GPa.1 5.3 18.44 4.7 310.7 f 0. B-M EOS CAP. M EOS PC.5 GPa.0 f 0.20 20.5 f 3.98 2.3 DP.KNI’ITLE 121 Table 1.99 3. P < 61 GPa. M EOS DAC.99 4.34 37.1 * 0. PD. B-M EOS DAC.5 GPa.P19 GPa.6 5.XRD. P I 56 GPa.1 15. B-M EOS PC.3 f 2. 25cP<70 GPa.2 17.Pl 9 GPa. P I 36 GPa. P I 30 GPa.

06 137 AgCl Cerargyrite AgBr Bromyrite CuBr 5. pXRD. P 5 4.22 I! 0.166 (4 K> (4’2) PC. B-M EOS DAC. P I 4. M EOS DAC.98 41. M EOS PC.004 (4 K) 4.088 (4 W 0.5 Technique and Notes4 Ref.003 (4 K) 0. P I 2 GPa.47 4.73 69. Bulk Moduli from Static Compression Data (continued) Density Isothermal BuIk Chemical Formula1 dKoT/dp3 Modulus @Wm3) (GPa)2 CSI 4. 6.18 4.87 69.5 1. P I 4 GPa. P I 4. PD.088 0.05 DAC.2 149 BaC12 3.8 IL 0. scXRD.03 (4 K) 7.9 202 202 202 MnF2 3.24 81.46 + 0.19 f 0.3 f 2 8.0 f 1.5 GPa.172 f 0. XRD. PD. 5. M EOS 202 Cd 4. P I 4.2 + 0.05 5.20 0.122 STATIC COMPRESSION Table 1. PD.51 12.5 GPa.5 GPa.9 2.56 6.5 Ik 0. B-M EOS 83 .4cPc26. PC.5 GPa.04 (4 K) DAC. PD.5 4.98 94 f 3 4 (assumed) 70 (32 Fluorite SrF2 3. B-M EOS PC. B-M EOS 107 BaC12 (high pressure hexagonal phase) Group I Elements: 4. P I 5 GPa.1 5.35 13 69. P < 9 GPa. scXRD. 1sqPVfit 8 D2 0. P _< 100 GPa.362 AZ0. XRD.40 I!I 0. scXRD.6 f 0.1 107 H2 0. PD. V EOS PC. B-M EOS V EOS 83 136 H2 0.0 5. scXRD.2 36.2 5.2 DAC. B-M EOS DAC.71 f 0.2 5.2 GPa.5 GPa. O<P<lO GPa. PD. M EOS PC.5cPc14.2 6. M EOS DAC.5 38.51 13.45 _+0. lO<P<50 GPa.

8 2. 1sqPVfit 11 Na 0.97 6.04 10 K K 0. 1sqPVfit see ref. P < 0. B-M EOS PC.62 3. 1sqPVfit 203 201 12 Sr Sr Ba Ba 2. 1sqPVfit PC.83 If: 0. 1sqPVfit DAC. P I 2 GPa.15 x!z0.7 17. P I 4. P I 2 GPa. P I 12 GPa.006 3.5 GPa.35 Lb0.90 2. PD.54 33.033 3. pXRD.06 PC.301 * 0.03 6. M EOS PC. M EOS PC. PD.02 4. PD. PD.13 f 0.50 3.53 1. PD.07 9.86 3.79 * 0. PD.4 k 0.01 118 10 K 0.47 + 0.60 2. P I 2 GPa.003 3.61 1. P I 2 GPa.01 99 Rb 1.10 4.5 GPa. PD. Bulk Moduli from Static Compression Data (continued) Density Isothermal Bulk Chemical Formula1 dQT/cP3 Modulus (Mg/m3) (GPa)2 0. 1sqPVfit PC.6 i 0.1 10 Rb cs 1. V EOS Li 0.74 1.10 f 0. PD. PD.15 f 0.1 4.50 12.1 11.963 f 0. M EOS PC.99 + 0.91 f 0. M EOS PC.02 2.698 ? 0. PD.02 197 11 Group II Elements: Mg Ca Ca 1.51 f 0. P 5 4. P 5 11 GPa.53 2. 1sqPVfit PC.KNI'ITLE 123 Table 1.556 + 0. P I 2 GPa.6 18. B-M EOS PC.86 0. P I 4.60 3.6 2.4 8.5 3.5 GPa.76 IL 0.7 GPa. 1sqPVfit DAC. P I 2 GPa.5 2.2 Technique and Notes4 Ref..208 f 0.86 2.5 GPa.05 203 12 201 12 .93 f 0.1 2. P I 4.53 11. P 5 2 GPa.07 2.001 4. PD.54 1.06 + 0.003 4. M EOS PC. P I 2 GPa. PD. XRD.1 PC.7 f 0.

M EOS DAC.0 139. XRD. B-M EOS DAC. PD.5 GPa. M EOS DAC.8 .49 44.1 203 217 203 102.52 4.89 (fixed from ultrasonics) 6.0 8.0 + 11. P I 4. B-M EOS DAC.2 147 V V 6.9 104 2.19 253. B-M EOS PC.96 7. P I 4.5 162. B-M EOS 203 V 6. M EOS PC. M EOS DAC.14 190.5 GPa.5 GPa. PD. M EOS DAC. PD. XRD.92 8.27 (fixed from ultrasonics) 4 18.4 If: 3.5 GPa. P I 10 GPa. PD. PD. P I 4.4 Technique and Notes4 Ref. P I 4.0 4. XRD.90 131+ 6 167. P < 4.43 8.4 201 201 124 201 Y zr zr 4. P I 4.5 137. XRD. PD. P I 10 GPa.3 19 147 7. M EOS pPC.24 5.124 STATIC COMPRESSION Table 1.4 DAC.46 6.8 4.51 109. B-M EOS PC. Ti PC.2 2. M EOS 19 203 Cr Cr 7.10 154 AZ5 4. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density fsotheretllfulk dKoTldP3 @Wm3) (GPa>2 Transition Metals: 4. XRD. P I 40 GPa. XRD.05 3. P < 42 GPa.5 GPa. P 2 4. XRD. P I 10 GPa. PD.10 6.10 176 .1 198 203 Ni cu cu Zn 8. B-M EOS PC.46 4.4 59. P 5 60 GPa.4 3.6 + 7 17. PD. B-M EOS PC. P I 4.5 GPa.9 4. M EOS PC.96 8. P I 30 GPa.5 GPa.19 193 rt 6 Mn co 7.5 GPa.

9 1. XRD. XRD. XRD.50 10.6 f 0.50 8. P I 4. M EOS DAC.2 Nh 8.1 193 201 201 201 La Ta Ta 16.5 GPa. XRD.65 6.60 4. B-M EOS 19 Ag & 10. P 5 4. P I 10 GPa. B-M EOS DAC. P I 4.5 GPa.41 14.7 266.5 GPa.7 f 0.5 GPa.00 128.KNITTLE 125 Table 1. B-M EOS PC. M EOS DAC.1 203 W 19. B-M EOS DAC.32 (fixed from ultrasonics) 147 .80 (fixed from ultrasonics) 19. PD.7 4.50 120. XRD. XRD.5 GPa.4 60 124 As Ag cd 10. P I25 GPa. P I 10 GPa. P I 60 GPa. B-M EOS PC. B-M EOS 203 Nb 8. XRD.0 f 5. P I60 GPa. (GPa jL 144. XRD. M EOS DAC. M EOS DAC.9 106.20 175.5 GPa. PD. M EOS TCOA.8 24.7 3. PD.2 201 10. M EOS PC.50 103 f 5 116. PD.30 300. Bulk Moduli from Static Compression Data (continued) Isothermal Bulk Chemical Formula1 Density dQTidP3 Modulus @Wm3) Technique and Notes4 Ref. P I 10 GPa.46 (fixed from ultrasonics) 5 147 19 201 Nb MO MO 8.7 194 + 7 5.40 10.7 5. PD. M EOS PC. P I 4. PD. P I 10 GPa.0 DAC. B-M EOS PC.7 f 2. B-M EOS DAC.5 GPa.20 10.5 PC.1 44.5 205.60 147 w 19. XRD. P 14.6 3. P I 12 GPa.8 3.0 267 f 11 147 Pd 12. P I 4.40 171 f 7 4.30 307 f 11 4. P < 4. PD.03 4 3. P I 10 GPa.17 16.5 4. B-M EOS PC.

8 DAC. B-M EOS 81 Group III Al Elements: 2.6 163. 201 193 201 Al In 2. XRD. XRD. P I 20 148 GPa. B-M EOS PC. XRD.7 39.1 I!C1. P I 14 GPa.8 18.8 f 3 1. PD.30 166.8 DAC. M EOS TCOA. P I 20 C 6 Diamona’ C Graphite C Graphite C60 Fullerite 2.3 8. 185 Tl 11.30 19. P c 67 GPa.30 Isothe. B-M EOS DAC.9 PC.0 4 (assumed) 5.5 zk 0. P 5 4.tllulk (GPa)2 Au Au 166.5 GPa. V EOS DAC.4 + 2.25 2. XRD.8 1.7 f 0. scXRD.2 5. XRD.31 DAC.16 (fixed from ultrasonics) 5.51 444 f 3 33. P I 20 GPa.31-6. B-M EOS 124 148 dQT/m3 Technique and Notes4 Ref.6 DAC. B-M EOS .5 + 8. P I 4.6 f 10. P I 12 GPa. B-M EOS Al 2.0 201 M EOS Group IV Elements: 3.70 7.6 3.3 M EOS In 7. M EOS DAC.1 38 f 2 4. XRD. XRD.3 7.5 GPa. P I 4. XRD.126 STATIC COMPRESSION Table 1.5 rf: 0. XRD. B-M EOS C. Au 19. PD.3 5. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density @Wm3) 19.67 GPa.70 77.85 36. PD. P I 10 GPa. P I42 GPa.42-5.6 DAC.9 + 1. P I 70 GPa.43 (fixed from ultrasonics) 4.3 4. M EOS DAC. P I 11 GPa.5 GPa.25 61 226 44 30.7 f 3.6 5.31 72.9 f 0.70 71.

XRD.19 2. P I 4. B-M EOS PC. P I 4.53 310. XRD.16 3.38 (k 0.0 f 1.3 GPa.3 f 0. XRD.81 DAC.40 11. 45cP<120 GPa. XRD.2 206 . M EOS DAC.5 GPa.91 f 0.04 39 40.40 56. B-M EOS dK/dT = -1.07 Technique and Notes4 Ref. B-M EOS DAC.25 (high-~&sure fee phase) Sn Sn 7.09 100.KNITI-LE 127 Table 1. XRD.5<P< 53. M EOS DAC. PC. P 5 10.8 97. XRD.30 7. PD.87 201 43.24) x 1O-2 GPa/K DAC. Bulk Moduli from Static Compression Data (continued) Isothermal Bulk Chemical Formula1 Density dQ-rm3 Modulus @Wm3> Si Si Si (high-pressure hcp phase) 2.22 & 0. B-M EOS PC. P I 15 GPa.9 50.5 GPa. M EOS DAC.7 4. bOdj-Zltered tetragonal structure) 7.33 3.49 82. B-M EOS 203 191 43 3. B-M EOS 167 76.5 GPa.5 GPa) 121 (at 9?GPa) 7. XRD.8 4.13) x 1O-2 GPa/K DAC.30 82 f 2 4. 42<P<79 GPa. B-M EOS DAC.5 GPa. XRD. PD. 9<P<17 GPa. B-M EOS 43 54.49 (high-~&sure body-centered cubic strllcture) Pb Pb 11.04 4.30 56.63 (& 1.49 (high-~&wrc.33 2.05 DAC.65 f 9.0 5. XRD.4 GPa.2 (at 9.2 f 0.8 4.4 4.82 f 2. P I 4. body-centered tetragonal structure) 7.8 28 Sn (high-pressure. 79<P<248 GPa. PD.5 4. P I 9. P I 10 GPa. B-M EOS dK/dT = -4.9 72 312 4.9 201 121 Sn 7. 9.

XRD. M EOS 98a 98a 95 f 5 2.8 DAC.4 114 -- Technique Notes4 Ref.5 3. M EOS DAC. XRD. pXRD. P I 4. XRD. and 11. pXRD. lO<P< 100 GPa. XRD.16 DAC.4 29. pXRD. lO<P<62 GPa.9+ 0.5 3. V EOS 134 11. PD. XRD.21 2.5 lk 0.98 36 f 2 46 + 4 3. 201 M EOS DAC.5 GPa.2 6. llcP<60 GPa.93 DAC.23 DAC. B-M EOS 177 .0 f 0. O-H method 155 1. P I 4.128 STATIC COMPRESSION Table 1.03 2. 5<P<16 GPa.62 39.3 2.32 37. 5.66 29. B-M EOS 206 11.63 5.13 2~0.78 4.7 4.1 f 0.6 DAC. lOO<P< 206 272 GPa. PD.69 3. XRD.5 GPa. 16<P<44 155 GPa. O<P<5. 15<P< 238 GPa.80 40.02 7. 10 <P<32 GPa.57 46.31 6. M EOS DAC.10 DAC. B-M EOS 1.5 GPa. XRD.08 (high-pres:uresimple cubic structure) 3.5 <P<lO GPa.70 2. O-H method DAC. B-M EOS 98a 187 PC. Bulk Moduli from Static CompressionData (continued) Chemical Formula1 Density IsotheGiufulk dKoT/dp3 OWm3) (GPa)2 Pb (combinedhcp and beehigh pressure ph=s) Pb (high-pressure hcp ph=J Pb (high-pressure bee phase) Group V Elements: N2 (cubic &phase) N2 (hexagonal E-phase) P (orthorhombic) (high-Lessme rhombohcdml structure) 3. 203 M EOS PC.97 2.62 9.08 (high-presfure simple cubic structure) Sb Bi Group VI Elements: 02 (high-pressure Ephaseindexedas monoclinic) 1.

10 13.72 14.7 5. lOcPc62 GPa. 5<P<24 GPa.94 13.2 (at 2 GPa) 203 164 Group VII Elements: Cl2 2.5 GPa.04 (at 7. M EOS PC.3 310.09 Technique and Notes4 Ref.07 2. PD.21 0.1 k 0. XRD.4 2.33 * 0.KNITTLE 129 Table 1. DAC. P I 4. XRD.6 f 0.94 8. XRD. Bulk Moduli from Static Compression Data (continued) Density Isothermal Bulk Chemical Formula1 dKoTldP3 Modulus (Mg/m3) (GPa)2 02 (high-pressure Ephase indexed as orthorhombic) S 1. XRD. OcPc5 GPa.7 GPa) 5.085 -seereference 42 0. PD.9 18.79 203 Te Te 6. XRD.2 5.7 GPa) 7. B-M EOS DAC.32 16.3 48. B-M EOS 46 Br.5 17.2 (assumed) 46 Noble Gases: He (solid) o-o.8 (high-preszure phase) Se 4. B-M EOS 177 2.18 GPa: 0.24 6.8 6. P I 45 GPa.23 >0.2 (assumed) 46 I2 4.7 f 0. B-M EOS DAC. PD. M EOS DAC.24 8. P < 45 GPa.9 5. PD. P I 4. P I 4. B-M EOS DAC.2 (at 7.5 GPa. P I 4.5 GPa. M EOS PC.79 125 165 Se 4.2 (assumed) DAC. O<P<12 GPa.5 GPa. XRD.43 GPa: 0.082 . XRD.? 4.7 4. B-M EOS PC. M EOS 203 S 2. P I 45 GPa.0 203 I2 4. XRD.2 24 + 2 (at 2 GPa) 7 125 5 4.3 f 0.4 6. O<P<4 GPa. M EOS DAC.07 8. M EOS DAC.09 11.5 PC.

03 DAC. M EOS 203 203 203 7 Nl Gd Gd DY 8.58 (at 110 K) 5.78 (4 K) 3.73 (4 K) 1. PD. 1sqPVfit 135 84 2.32 GPa (0 K) 3.78 (0 K) 3. (at 8. PD.3 5. XRD. M EOS PC. P I 2 GPa. P I 106 GPa.5 GPa. PD. B-M EOS PC.09 (4 K) 2. 51 (4 K) 1.4. M EOS PC.8 4.23 (0 K) 1.00 8.: K) 9 (159 K) (at 159 K) Lantbanides: Pr 6. P I 4. M EOS DAC. PD.86 (at 4 K) 1.5 GPa. P < 24 GPa DAC. 1sqPVfit 15 Xe (solid) Xe (solid) 3. P I 4. PD.XRD.23 8. P I 2 GPa. PD.48 f 0.317 DAC.73 (0 K) 2.34 (at 4 K) 1. XRD.71 + 2. P I 32 GPa.0 4.29 PC.77 7. M EOS PC. P I 4. P < 80 GPa 4. XRD. B-M EOS PC.18 + 0.78 40. P I 32 GPa.5 22. P I 2 GPa.7<P< 110 GPa.23 30.63 (at 4 K) 1.41 5. P 5 4.65 (77 W P-V data tabulated only 1.41 (at 77 K) P-V data tabulated only 1.130 STATIC COMPRESSION Table 1.23 + 0.2 32.3 IfI 0. XRD.41 9 (at74K.6 35. Bulk Moduli from Static Compression Data (continued) Isothermal Bulk Chemical Formula1 Density dKOT/dP3 Modulus (M8Jm3) (GPa)2 Technique and Notes4 Ref. He (solid) Ne (solid) Ar (solid) 0.07 1.82 (110 K) 3. XRD.48 (at742K) (at :i”oK) DAC.1 203 .1 DAC.5 GPa..5 GPa. PD.24 (0 K) (at7i2K) (at 1”.6 3.31 zk 0. 1sqPVfit 172 166 9 3.097 9. B-M EOS PC.K) Ar (solid) Kr (solid) Kr (solid) 1.

XRD.7 f 0.8 f 3. Er 3.40 54. XRD. P I 78 GPa.86 196 7. % Ni a (bee) phase Fe-lo. B-M EOS PC.KNITTLE 131 Table 1.30 8. M EOS DAC. P I 23 GPa.0 4.0 3. PD.9 dKoT/dp3 Technique and Notes4 Ref. XRD. M EOS DAC.3 + 1. B-M EOS DAC.29 + 0.86 164f7 175.6 5.58 8.9 1.7 5.0 208 + 10 192. P I 30 GPa. P I 30 GPa.88 7. B-M EOS 203 24 157 Iron and Iron Alloys: Fe a (lxx) phase Fe a @cc) phase Fe a @cc) phase Fe-5.30 4 (assumed) 4. P I 16 GPa.8 4. XRD.70 15.8 162. M EOS DAC.37 Isothermal Bulk Modulus (GPaj2 44. % Si a (bed ph= Fe3Si Suessite Fe E (hcp) ph= Fe E (hcp) phase Fe ph= 7.8 DAC.5 GPa.5 f 0. XRD. P < 300 GPa. P < 4. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density (M8h3) 9. B-M EOS DP.8 -2. P 5 30 GPa.86 7.77 214 +9 250. P I 23 GPa. PD.5 PC.2 wt. P I 30 GPa.36 196 96 8. P I 38 GPa. P I 30 GPa. XRD.5 PC.30 164.7 + 9. % Si a (bed ph= Fe-8 wt. P I 4. B-M EOS DAC. M EOS DAC.0 4. XRD.5 + 5 4 (assumed) 3. PD.33 f 0.09 132 E VW .2 Y!Z 0.0 188 41 6.2 wt.39 7.0 4. B-M EOS DAC. B-M EOS DAC. B-M EOS 212 201 7.88 7.6 196 196 188 41 6.35 156 f7 153 f 7 175 f 8 174.5 GPa.8 5. XRD.5 GPa. B-M EOS DP. B-M EOS DAC. P I 4.3 wt. XRD. % Ni a (bed ph= Fe-7. XRD. M EOS 203 Actinides: Th Pa 11. % Si a @cc) phase Fe-25 wt.5 f 0. P I 30 GPa. XRD. XRD.

19 154.95 + 0. P I 30 GPa.9450 Wiistite Fe0 Wiistite Fe0 Wiistite FelmxO x = 0.3 GPa.2 wt. P I 45 GPa.980 Wiistite Feo. P < 30 GPa. Feo. B-M EOS DAC. P < 260 GPa. pXRD. 0.37 171.8 zk 2.10 Wiistite Fe0 Wiistite 157 f 10 4 (assumed) 94 142 f 10 4 (assumed) 131 150 * 3 155 + 5 3. Bulk Moduli Chemical Formula1 from Static Compression Data (continued) Density Isothermal Bulk dKoTldP3 Modulus (Wm3> (GPa)2 8.2 wt.4 GPa. B-M EOS DAC. B-M EOS DAC.4 DP. XRD. XRD. P I 23 GPa.0 154 + 5 239 3. XRD.93 215 k 25 188 + 14 171 + 6 4 (assumed) 196 4 (assumed) 4 (assumed) 188 162 Fe-20 wt.132 STATIC COMPRESSION Table 1.76 7. XRD. B-M EOS DAC. XRD. XRD. P I 30 GPa. XRD. B-M EOS DAC. % Co DAC. XRD. B-M EOS 41 Feo. XRD. P I 12 GPa.87 (ideal) 5. B-M EOS DAC. XRD. B-M EOS DAC. B-M EOS DAC. B-M EOS DAC. % Si E (hcp) phase Fe-10 wt. scXRD. % Ni E (hcp) phase Fe-7. % Co 7.2 4.87 (ideal) 166 f 6 169 f 10 4 (assumed) 4 (assumed) 162 221 Fe0. P I 14 GPa. B-M EOS DAC.08 5. P I 5 GPa.98 169+ 6 4 (assumed) 162 Fe-40 wt.41 212 f 15 4 (assumed) 196 8.055.3 wt.87 (ideal) 5. P 5 30 GPa. 1inPVfit 132 8. XRD.07. XRD.09 Technique and Notes4 Ref. P < 30 GPa. 0.87 (ideal) 5. P I 26 GPa. scXRD. M EOS DAC. P I 20 GPa. % Co 8.8 _- 122 91 5.42 7.8Nio. M EOS DAC. P 5 3.87 (ideal) 13.87 (ideal) 5. B-M EOS DAC. B-M EOS DAC.87 (ideal) 5. XRD. P I 8. % Ni E (hcp) phase Fe-IO.2 E (hcp) phase Fe-5.74 82 f 7 -5 f 4 100 .9410 Wiistite Fe2U 4 (assumed) 3 213 87 FeS Troilite 4. P 5 30 GPa.

IinPVfit DAC.46 82 Hydrides: VHo.6 4.56 + 0.9 5.3 GPa) 4.95 215. P <50 GPa.KNI’ITLE 133 Table 1. V EOS 100 FeS (high-pressure MnPtype structure) FeS2 Pyrite FeS2 Pyrite FeS2 Pyrite FeS2 Pyrite FeS2 Marcarite FeH 4.31 f 0.9 18 Ices: CO2 1.15 f 0.93 + 0. 3. Avg.75 -5.4 GPa. 2.0 4 DAC.73 193. XRD. B-M EOS 117 NH3 H2G (cubic phase VII) D2G (cubic phase VII) 0.40 2.5 -- 41 58 4. B-M EOS 19 6. (GPajL 35 f 4 5+2 DAC.95 143 4 (assumed) 95 4.0 f 1. P I 34 GPa.87 146.95 4. XRD.48 152 H2G (cubic phase VII) 1.3 -t 3.77 IsothehetuIUlk dQT/dP~ Technique and Notes4 Ref.29 + 0.9 29 3. of several EOS DAC.3 GPa) 30. scXRD.PI30 GPa.0 4 19 . B-M EOS DAC.9 GPa) 23.3<Pc36 GPa.1kO.86 1. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density Wtim3) 4.7 f 0. XRD. XRD.06 22. XRD.9f0.3<P<128.0 (PO = 2. B-M EOS DAC.6ec6. B-M EOS DP.2 5. P I 4. of several EOS DAC. XRD 2. XRD.5 * 4.5 (PO = 2.9 GPa) 4. 2. P I 35 GPa. XRD. P I 34 GPa.2 GPa.07 161 152 1.03 4. XRD. M EOS DAC. XRD. B-M EOS DAC.46 7.21 121 f 19 5. P I 70 GPa.XRD.7 (PO = 2. B-M EOS DAC.5 (PO = 2. XRD. B-M EOS DAC.1 7. P < 35 GPa.8 DAC.60 202.3cP<36 GPa.3 f 1.4 + 0. P < 62 GPa. B-M EOS DAC. scXRD.5 NbH0. 3<P<56 GPa.5 29 4.95 148 157 5. Avg.5 + 0.

XRD. V EOS = Vinet et al.1 143 1 2 3 4 Mineral names are given in italics where applicable. B-M EOS DAC. l. B-M EOS DAC. A dash implies a linear tit to the pressure-volume data (implies that Km’ = 0) or an unstated Kor’.2 -10. B-M EOS DAC. AlH3 -1. MAP = mulianvil press.5 GPa. P I 35 GPa. XRD. P I 35 GPa.5 -5.0 f 5.4 (1773 K) 10. Bulk Moduli from Static Compression Data (continued) Chemical Formula1 Density @Wm3) -10.7 11. 4. XRD = x-ray diifraction. 1inPVfit = linear fit to the pressure volume data. P I 35 GPa. B-M EOS DAC. B-M EOS DAC.0 248. XRD. length-change measurements. The temperature derivative of the bulk modulus (dKor/dT) is given where available. XRD.3 19 19 HOW -5. BA = Bridgman anvil press. CAP = cubic-anvil press.8 4. P 5 35 GPa. XRD.38 30.0 + 9. 1sqPVfit = least sqares fit to the pressure volume data.0 f 5.0 lk 5. Key: DAC = diamond-anvil cell.747 (1773 K) 24. P 110 GPa.0 DAC. P I 35 GPa. XRD.50 47.2 143 Ca-Mg-Na glass ? 35.42 22.2 f 0.3 4.3 f 0. DV = direct volume measurement. O-H method = Olinger-Halleck method of reducing P-V data (see reference).2 f 2 3. (“universal”) equation of state.21 37.6 + 6.1 (1773 K) PC.2 19 WAW CuH -1. length-change measurements. All values are at ambient pressure and room temperature except where noted.5 f 3. PD = piston displacement.23 Isothe~~~u~ (GPa)2 PdH PdD CrH 130. B-M EOS DAC. P 110 GPa. sink/float measurements. XRD. B-M EOS 19 19 19 wJIw3 Technique and Notes4 Ref.O<Pc5.5 + 2 3. EXAFS = extended x-ray absorption fine structure.7 f 0.9 + 2 72. P I 35 GPa. BCAC = boron carbide anvil cell.6 f 0. scXRD = single-crystal XRD. TAP = tetrahedral-anvil press. B-M EOS DAC.3 19 Amorphous Fe2SiO4 liquid Materials: 3.7 -2.9 It 1 3. ND = neutron diffraction. P I 35 GPa. P = pressure in GPa.28 6. TCOA = tungsten carbide opposed anvils.4 2. . B-M EOS 4 Si02 glass 2.0 135. M EOS = Mumgahan equation of state. B-M EOS = Birch-Mumgahan equation of state (includes a variety of Birch equations). DP = Drickamer press.9 f. pXRD = powder XRD. B-M EOS DAC.2 -6.134 STATIC COMPRESSION Table 1.

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[24] and Trunin [203]. result via . L.g. Earlier summariesproviding fits to data are given by Al’tshuler et al. in some cases. 252-21. usually describedas a mixture of minerals are given in Chapter 34. and (2) the production of a shock-melted “magma ocean” and concurrent impact volatilization versusretention of volatiles during accretion [l]. the present summary provides fits to shock wave data. Santa Monica.185]. L. 109. or 108. Gemological Institute of America. Three pressure units are commonly in use in the shock wave literature: kilobar (kbar). Johnson 1. INTRODUCTION Shock compression of the materials of planetary interiors yields data.. and lo1 1 pascalsin SI uniis. Ahrens and M. provided physical data on the nature of either shock-inducedphase changesor phasechangeswhich occur upon isentropic releasefrom the high-pressureshock state (e. Seismological Laboratory. Pasadena. A related application of both shock compression and isentropic release data for minerals T. The formation of primitive atmospheres. which upon comparison with density-pressureand density-sound velocity profiles of both terrestrial planetary mantles and cores [4. CA 91125 Present Address: M.5. as well as density profiles for the interior of the major planets [ 1481. SHOCK WAVE EQUATION OF STATE The propagationof a shock wave from a detonating explosive or the shock wave induced upon impact of a flyer plate accelerated.g. and 1012 dyne/cm2 respectively. Hugoniot data specify the locus of pressure-density (or specific volume) states which can be achieved by a mineral from some initial state with a specified initial density.112]).as well as the effects of giant impacts on the Earth [183.192]. Johnson.containing a large fraction of H20 and CO2 is also addressable using shock wave and other thermodynamic data for volatile-bearing minerals (e. or have been. Finally.g. constrain internal composition and temperature. 143 [ 13. Whereassome earlier summarieshave provided raw shock data [47. lOlo. Also of interest are the shock-induced chemical reactions between meteoritic components(e. a very large data set exists describing the Hugoniot equation of state of minerals. gigapascal(GPa). 1639 Stewart Street. and megabar(Mbar). Johnson.94].Shock Wave Data for Minerals Thomas J. 2. H20 and Fe: [ 1111). [110.141 is in the mechanics of both the continued bombardment and hence cratering on planetary objects through geologictime [ 1701. for example. Theseare equal to 109. studied using shock wave data include: (1) the formation of planetary metallic cores during accretion [ 169. CA 90404 Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union. explosivesor with a gun. California Institute of Technology. Significant processes which can. Ahrens and Mary L.121. recovery and characterization of shock-compressed materials have provided important insights into the nature of shock deformation mechanismsand. As indicatedfor the data summary of Table 1. melting) [193. J. Other important applicationsof shock wave data and related properties are found in the impact mechanicsof terrestrial planets and the solid satellitesof the terrestrial and major planets. An analogous summary for rocks.194].213].

04 1.73 1.88 1.01 0.04 0.3 2.10 0.807 1.146.11 0.245 7.56 1.19 0.715 3.03 2.84] [2141 [2131 Argon k Argonf Argon’ ArgonC 0.34 1.79 2.451 2 2 [I791 [83.46 1.04 4.10 0.3 1.018 0.85 3.44 1.TABLE 1. 2141 / [80.28 4.59 1.02 0.85 3.01 1. of Data E 8 x s Mineral Formula Co (kmhec) Gases: AirC (mixture) 1:1 N2+02 0.45 0. E Phase* NO. Refs.02 0.04 2 2 2 2 3 4 2 3 4 2 4 25 6 7 9 24 10 [80.68 4.65 3.60 3.03 3.08 -_ 1.54 2.08 0.010 0.06 0.01 1.788 2.54 3.221] ArgonC Ar 1.68 3.549 1.3 1.00 1.692 2.07 0.401 0.026 1.263 0.919 1.10 0.04 0.21 1.15 0.140]/ u591 [58. 1891 Carbon Dioxide’ co2 1.01 1.788 7.9 2.07 0.06 0.10 1.40 0.06 0.07 0.25 1.178] Carbon Dioxideh Carbon MonoxideC CO? 1.541 0.945 2 NO NH3 Ar Ar Ar Ar 1.99 3.42 0.71.03 __ [147.26 __ -_ 0.09 0.60 4.36 1.608 7.379 3.32 3.566 7.02 0.0013 0.301 1.56 1.173 1.5 0.83 1.11 lower S error AS VP (kndsec) upper UP (kmhec) References / Temp.76 2.1 1.35 3.09 0.4 1.180.03 0.765 6.235 5.264 8 7 3 16 3 [64.471 5.121.884 2.03 4.28 3.92 2 4 2 3 4 [233] co 0.785 2 4 [1471 Cl791 7 12 Nitrogen plus OxygenC Nitric Oxidee Ammonia’ 0.109.317 5.29 0.85 1.59 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System Sample Density (Mg/m3) error ACo (kmhec) __ __ 0.974 1.758 6.585 4.14 0.79 1.608 t1501 .3 __ 0.121.471 5.71 1.04 1.45 1.20 0.3 0.041 1.2 0.60 1.27 0.65 0.21 __ 0.58 1.98 1.121.81 4.

03 0.568 8.04 1.26 5.014 9.45 1.TABLE 1.18 0.21 1.83 1.81.49 1.7 2.525 3.06 0.57 3.179.366 1.216] Xenong Xe 3.80 2.38 1.011 0.071 H2 [63.99 1.08 0.10 0.63 2 3 2 1 2 4 2 2 4 2 1 2 3 4 8 4 3 5 3 10 4 2 4 10 9 15 24 12 [63.03 0.121.1 2.26 5.08 0. Mineral Formula Sample Density (Mglm3) Co (km/set) ACo S Udsec) 0.004 0.51 1.0013 0.4 0.185 2.13 0.15 0.05 0.233] I [ 149.014 0.5 0.13 0.15 0.221] OxygenC 1.17 1.149.02 0.12 -0.263 9.39 1.213] /[161.423 W u501 [571 Nitrogen Nitrogen k c N2 N2 0.12 0.98 6.69 11.11 7.160.22 1.212.3 0.82 2.62.49 2.14 2.82 5.006 [151.502 2 4 1 3 2 4 1 3 2 4 9 16 [121.26 0.11 7.144.568 3.829 1.105 3.23 1.674 1.1 4.13 4.87 0.6 0.10 0.811 [60.341 8.0 0.080 0.35 0.09 __ 0. 0.105 3.06 0.19 0.2231 Xenonk Xe 0.002 0.03 0.146.35 1.212] .167 1.51 2.58 3.88 error AS UP (kmhec) upper UP (kmhec) Phase* NO.7 3.05 0.47 0 1. Refs.91 1.14 0.29 1.09 d.94 1.23 8.222 3.02 0. 146.013 0.1 1.06 2.04 3.215] [lo91 Hydrogena Methaned H2 0.89 1.05 0. 213.4 0.089 0.8 1.51 2.006 0.03 2.678 6.16 0.09 0.14 1.59 1.2 1.962 1. of Data Deuteriumb D2 He 0.1W [ 1451 Heliuma Hydrogenb 0.7 1.123 0.16 0.202 1.166 1.801 2.33 4.263 2.5 i:.33 1.74 1.80 0 1.94 0.69 1.038 1.33 1.012 [71.2 6.3 0.60 2.19 2.080 9.93 1.09 0.61.128 1.766 3.09 0.7 3.2 1.51 3.38 0. Shock Wave Equation of State of Minerals and Related error Materials of the Solar System lower (continued) References / Temp.

5 5.42 0.14 1.06 1.ooo 1.069 0.121.05 0. 2171 u531 Diamond Diamond DiamondCl Glassy Carbon 1.68.03 0105 2.2 1.331 0.316 28.02 0.126.04 0.2 2.71 1.019 _0.79 1.30 I .08 5.131.4665 1.162.358 0. 2171 Graphite C 2.617 4.008 [58.83 0.213.213.07 0.09 1.114 0.5 0.205 3.4 0.8 0.04 4.89 3.817 1 2 4 [30. 126.311 0.75 0.08 0.04 -0.133 8.18 0.08 2.72 0.11 0.42 0.695 error ACo (krrdsec) lower UP (krdsec) 0 0.51 1.794 2.89.226] Carbon: Graphite Graphite Graphite 0.22 2 2 2 6 36 60 [I211 [121] [82. 217.21 1.2 7.41 1.121.3 0.19 7.699 0.217.372 3.133.66 0.03 2 1.11 4.7 1.012 0.456 1 1.5 0.147 5.119 2.32 1.06 0.121.45 References / Temp.133.03 0.183 upper UP (kndsec) 0.11 1.38 2 3 4 1 2 3 4 30 19 41 12 77 24 22 [82.166.404 1.73 1.95 1.311 0.06 0. 217) Graphite 1.62 2.65.911 6.611 0. E 2 is ?? e Mineral Formula Co (kmhec) S error AS Phase* NO.997 2. of Data Elements: Antimony Sb 3.2 0.74 12.5 3.07 0.772 0.20 1.364 2 0 6.TABLE 1.113.507 1.563 3. 121.2 0.183 4.05 _0.019 1 2 4 2 6 13 17 30 21 [121.133.06 0.04 0.9 0.16 2.9 3.14 0.121. 2271 Bismuth Bi 9.989 0 0.01 0. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density @Q/m3) 6. Refs.0 2.8 2 2 2 2 5 3 -45 w11 11531 [82.03 2.92 4.3 0.90 3.3 0.17 1.12 0.07 0 2.61 -1.1811 .32 1.12 0.05 0.82.191 3.49 0.07 0.5 3.

38 4.56 0.734 2.03 0.10 0.361 5.12 0.3 lower VP (kmhec) 0.134. 209.09 0.126.04 0.03 0.121.37 0.39 3.8 0.04 0 0.131.217] Copper cu 7.27 0.209] Copper Copper Copper Copper cu cu cu cu 1.18 2.327 1 2 4 [56.05 0.07 -0.04 0.76 1.89 5.121.2 0.73 0.03 0.4 -1.1 17.863 2.15 0.534 3.33 0.136.209] Copper cu 6.88 1.651 0.144 2.9 1.482 2.209] [24.063 1 2 3 18 [56.924 2.85 -0.014 0.017 0.121. 136. 204.128.406 1.13 0.594 4.15 1.53 4.315 2.52 -0. of Data Carbon Foam C C 0.534 3.08 -0.172.07 0 0.11 1.315 3.435 1.09 0.293 2. Mineral Formula Co (kmhec) 0.98 S error AS 0.119 0.482 2.06 0. 134.121.7 1.07 0.015 0.014 0.25 3.2 0.126.887 3.35 0.944 26.301 6.11 0.63 0 0.815 2.94 0.14 0.73 0.TABLE 1.14 1.297 4.03 0.82 [24.675 -2.63 2.34 1.87 1.361 0.73 1.365 8.02 0.217.05 0.57 4.15 0.35 1.08 0.66 2 4 2 4 2 2 2 4 1 2 4 2 2 2 1 2 4 ii 5 15 11 8 10 4 2 17 4 11211 WI W-Y PO93 Carbon Fibers Cobalt Cobalt Cobalt co co co 2.289 upper VP (kmhec) 2.615 0.315 2.08 0.128.77 1.519 error ACo (kmhec) 0.2 0.009 0.15 1.661 1.02 0.285 1.02 __ 0.32 References / Temp.121.041 6.4 1.226] [24.008 6.02 -_ 0.533 PO91 Cobalt co 8.89 0 0.669 0.96 0. 166.361 1.87 3.134.602 1.475 0.06 0.909 2. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 0.42 1.77 3.02 0.05 0.97 1.77 27 28 6 2 14 8 14 39 5 [2091 [56.03 1.05 0.02 1.701 3.15 5.136l .04 Phase* NO. Refs.204.944 9.

07 0.66 4.2261 Indium In 7.1 2 315 K z F v1 Germanium Ge 5.633 [204.121.019 0 0.3 0.127.03 UP (kmhec) 0 0.328 5.172.07 0.902 1.006 0 12.65 0.141.08 0.52 1 2 5 11 [24. 2261 s z Mineral Formula Sample Density (Mg/m3) 7.02 0.36 -0.90 1 2 Copper cu 8.136.014 1.06 1.54 i.03 0.932 2.143.62 1.28 1.460 0.73 0.29 ACo (kmhec) 0.04 0.08 0. 2261 Iodine I2 4.25.982 0.121.134. ii NO.76 1.646 2.8 1. 166.121.24.136] Iron Fe 2.09 1. 2131 Gold Au 19.209] [121. 1361 [22.10 0.8 0.04 0.08 0.28.71 3.184.03 -- 0.217.23 0. Shock Wave Equation of State of Minerals and Related error Materials of the Solar System lower (continued) upper References / Temp.48 0.04 1.04 0.932 4.29.05 0.67 0.39 2.226 3.121.933 1.90 Cc (kmhec) 3.969 Phase* Copper cu -0.54 5. 166.63 1.49 0.933 1.27 0. 131.121.03 0.06 S error AS 0. of Data 3 18 !z 8 $ [56.4 3.629 0.81 4.17 1.627 UP (kndsec) 0.126.213.546 0.04 0.126.188 1 2 17 46 [79.52 1 2 4 1 3 4 2 4 2 5 38 13 6 4 3 6 8 24 [ 125.08 0.04 1.49 0.226 1.81 1.2 0.95 3. 30.121.166.05 0.54 5.9 2.56 2. Refs.76 1.03 0.93 1.0775 1.100.25 1.359 2041 .37 3. 205.19 0.04 0.213] Iridium Ir 22.217.90. 139.15 1.09 3.27 21.281 2.71 0.34 2.98 0.47 0.646 3.217.3 0.04 0.931 3.644 [24.629 3.04 0.134.136.263 2. Iron Fe 3.10 -1.TABLE 1.9 2.05 -- 1.63 0.59 1.134.87 2 4 15 2 [24.131.136.09 0.

941 1.05 0.05 0.48 3.202.7 1. of Data 33 6 12 4 3 IO 2 5 4 15 16 42 97 18 Iron Fe 1.134.565 0.134.61 0.77 5. 4. 131. 33.4 Phase* NO.121.1 2.30.04 0.5 1.121] Wll .25 0.36 -1.85 3.49 3.249 4.71 0.853 [24. 172.01 2.136.972 4.591 3.584 1.85 1.95 1 2 3 4 [31.134.132.641 7.06 1.31.108.3 0.975 3.569 0.2 2.121.22 1.427 0 0.217.6 0.TABLE 1.41 Iron-Nickel (see Taenite) Iron-Silicon Iron-Silicon Iron-Silicon (see Suessite) (Fe.29.94 5.08 0.3 0.7 1.04 0.8 0.91 1.55 21.209] Iron Fe 5.09 0.98 3.03 0.10 0.09 0. 206.213.136.03 0 0.763 1.50 0.57 2.85 1.537 0.67 1.01 0.87 4.569 0.04 0.3 lower S error AS 0.03 0.131 0.783 3.12 0.59 9.136] Iron Fe 7.15 1.05 UP (kmhec) 0.008 0 0.291 2 2 37 3 [42.58 upper DP (kmhec) 3.126.568 2.1 References I Temp. Mineral Formula Co (kmhec) 0.138.71 -1.162.302 0.413 4.20.172. Refs. 136.547 error ACo (kmlsec) 0.013 0.08 0. W FelTSi Fe7Si Fe3Si 7.8 1.02 0.88 1.433 4.04 0.17 0.3 2.453 3.537 0. 226]/[6.984 0.04 0.73 1 2 3 4 1 2 4a 4b [121. 166.2 0. 204.38 2 4 [121.2 0.09 -0.25.134.07 -1.941 1.213] Iron Fe 6.573 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 4.43.4 1.

217.141.03 0. of Data 2 3 4 2 3 4 2 3 4 2 3 2 4 2 5 3 4 3 2 3 6 5 3 3 93 42 Lead Pb 1.9 1.46 1.009 0.44 3.54 1.98 8.71 1.71 1.23 1.992 2.275 [209] .64 -0.28 0.94 1.05 0.206.09 0.59 1.56 0.198 5.87 1.40 m91 [2091 [25.77 1.016 2.86 1.07 0.59 1.33.91 0.55 1.17 0.07 0.15 LW [209] Nickel Ni 6.607 1.131.14 0.16 2.56 0.24 0.45 1.13 __ 0.991 3.016 2.06 0.08 0.54 0.166.10 1.70 Phase* NO.18 4.05 0.05 0.53 4. 213. Refs.26 1.73 2.78 0.045 10.51 11.09 0.511 1.85 0.79 ~2091 Lead Pb 8.15 __ 0.04 -0.213 [209] Lead Pb 6.62 2 4 1 2 2 4 2 2 4 1 2 4 2 3 16 19 6 3 15 2 7 3 9 2 [121. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 4.73 4.02 0.51 1.306 1.32 1.42 1.17 0.006 UP (ludsec) 0.15 1.04 lower S error AS __ 0.12 References I Temp.67 2.TABLE 1.226] Lead Lead Pb 9.84 1.016 0.019 0.61 1.79 2.23 1.03 0.80 3.31 3.02 0.16 0 2.73 2.09 0.36 19.555 0.26 0.40 0.05 __ 0 0.7 1.02 0.644 3.73 2.05 -0.98 0.02 2.80 3.335 upper UP (kmkec) 1.71 error ACo (km/set) __ 0.12 0.012 0.88 1.36 0.20 1.726 1.47 1.014 0.31 0.91 1.02 0.33 2.83 0.87 0.018 __ 0.016 0.28.13 0. 121.345 Pb Mercury Nickel Hg Ni 13.015 0.752 -0.58 1. 163.462 1.37 1.18 0.10 __ 2.045 0.4 -0.83 5.24 4.225] 1.28 4.3 0.30.07 0.007 0.05 0.03 1.08 0.02 0.86 1. Mineral Formula Co (km/set) 0.06 0.15 5.606 2.05 -0.44 3.202 G'W PO91 Nickel Ni Nickel Nickel Ni Ni 4.46 1.724 1.

40 2.825 2.3 2.02 0.444 2 4 7 13 29 [56.30.00 2.984 12.83 4.166.03 0.556 0.713 0.136.04 0.00 0.79 4. 131.04 0.149 4.00 0.17 1.23 3. 2261 [42. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 8.317 3.49 3.18 -_ 0.004 0.635 2. Mineral Formula Co (kmlsec) 4.121.04 0.04 0.004 3.217.83 1. 217.02 Wll Taenite (also Kamacite) (Fe.08 0.217.49 0.00 0.226] Platinum Pt 21.05 0.166. 2171 .28 4.121. Refs.010 0.05 1.03 0.41 3.803 0.5 References / Temp.08 lower S error AS 0.04 0.633 2.300 [24.00 0.043 0.8 3 7 6 7 4 14 3 [121.00 2 1 2 4 2 1 2 4 Rhenium Re 20.018 -0.349 0.03 0.05 0.121.63 1.63 upper UP (kmhec) 0.08 0.006 0.136.5 I .4 0.03 0.166.23 0.3 0.53 3.132.426 2.13 1.8 -0.369 2.12 0. 217.18 0.01 1.12 3.896 error ACo (kmlsec) 0.32 1.422 [24.46 0.31 5.21 5.014 1.32 2 4 16 9 [24.05 0.65 1.019 2.121.59 [36.0 4.166.16 4.445 3.013 0.015 UP (kmhec) 0 0.372 1.09 2. of Data 1 2 4a 4b 4 28 52 18 Nickel Ni 0.41 Phase” NO.2 0.17 0.25.933 4.15 0.TABLE 1.209.635 2.372 1.136] [121.495 3.06 0.04 0.56 4.29 2.76 4.83 4.226] [86.723 1.431 0.587 0.59 1.008 0.495 0.627 1.996 3.354 0.121] Suessite (Fe.166.09 0.25 1.897 1.57 3. 213.05 0.127 0.00 0.06 0.028 1.121.12 0.00 1.04 0.441 2.56 0.346 0.121.7 1.17 0.63 1.226] Palladium Pd 11.Ni) 7.Ni)$i 6.046 1 2 2 4 1 2 4 2 32 3 6 11 41 11 Sulfur S 2.90.606 1.136.41 1.53 4. 131.05 0.05 1 0.1361 Rhenium Rhodium Re Rb 20.04 1. 2261 Silver Ag 10.63 7.470 2.56.20 0.777 4.870 5.48 0.12 2.136.02 0.

29 7.33 2.08 5.49 1.64 5.14 1.205 [24.136] Tantalum Carbide Tantalum Carbide TaC 12.35 1.43 error ACo (kmhec) 0.0 -0.048 1.131. i R s Mineral Formula S error AS 0.48 3.674 1.5 2.03 0.62 6.69 3.85 8 2 3 4 2 4 2 3 4 12 5 10 3 4 39 10 9 Wll PI Zinc Zn Zn 6.04 3.10 1.57 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density Co CJv&/m3) (kndsec) 7.333 3.02 1.12 0.10 0.112 0.842 0.5 2.2 -0.25.008 Phase* NO.04 0.05 0.34 0.32 4.05 [ 121.127.3 0.3 8.25.36 0. 2261 Wairauite CoFe 8.647 1.00 0.15 0.15 0.69 3.299 2.11 0.00 0.464 1.30.98 1.003 0.3 0.TABLE 1.54 2. 126.121.63 -0.14 0.03 1.04 3.127.801 2.626 14.00 3.02 0.15 0.029 2.00 0.678 2.60 3.4 5.51 Zinc 7.586 1.02 0.6 0.38 1.304 0.304 0.887 0.76 4 3 4 1 3 4 2 10 3 4 2 9 10 20 21 [121.04 0.444 2.62 0.535 2.37 1.435 3.04 0.03 2.3 1. 126.09 0. 217.05 0.07 0.84 0.110 Cl211 [121. of Data 1 3 2 4 3 6 66 33 Tin Sn 2.121.152] TaC 2 .138 [24.78 3.08 0.013 0.13 0.30. 2261 Carbides: Moissanite Moissanite Sic Sic 2.00 2. 213.08 0.3 1.166.122 i.9 0.01 4.0 10.166.98 4.136] Cl211 Moissanite SIC 3.037 2.05 0.038 0.12 0.70 4.663 1.131.6 8.02 0.08 0.05 0.112 2.912 2.03 lower UP (kndsec) 0.17 0.15 upper UP (kmhec) 0.217.84 3.15 0.15 8 References / Temp.224.678 0.303 0.619 3. Refs.091 4.85 0.03 0.

49 -1.7 2.03 2.819 3.03 0.0 -0.70 0.10 -0.235 0.223 2.59 10.5 0.79 1.1 1.9 5.4 0.181 1.08 3.00 0.127.52 2.54 2.013 4.66 Phase* No Of Data 4 12 4 References / Temp.45 upper Utl (kmLec) 0.4 0.186] Potassium Iron Sulfide KFeS2 2. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density error ACo lower S error uD Mineral (Mglmj) Tungsten Carbidep Tungsten Carbide Sulfides: Sphalerite Formula Co (kmiiec) WC 15.792 0.74 5.369 0.933 [10.3 0.03 0.013 0.2131 i u 3 z P 5 Villiaumite NaF 4.83 -0.10 0.03 0.195.868 I1211 .27 2.14 0.3 __ 1.03 1.56 0.225 1.06 0.0 -4.017 0.17 0.54 2.547 1.S 4.952 5.599 5.5 1.04 0.163 0.28 1.16 0.10 -0.79 4.13 0.361 1.0 0.912 0. 1 2 2 [121.5 0.05 2.635 1.2301 Halides: Griceite Griceite LiF LiF 1.121.2 1.027 3.10 0.04 __ 0.496 0.63 1.2 0.72 2 3 4 1 2 4 1 2 2 3 4 3 3 2 3 10 14 7 11 11 2 3 w361 Pyrrhotite Fel-.7 2.452 6.11 0.1361 WC 15.22 2.01 2 2 2 68 8 4 8 4 3 2 [lo61 [38.25 0.04 0.0 1.027 1.3 __ 0.97 -1.54.05 __ 0.4 1.72 -0.14 1.08 6.05 2.39 5 2.638 2.19 1. 2131 /[ 1771 tz B [54.494 1.181 5.35 -0.21 4.66 [1521 ZnS 3.605 [3.10 1. Refs.47 1.32 8.942 3.007 0.02 0.926 0.70 3.09 1.58 1.15 0.09 1.3 2.15 7.31 3.TABLE 1.552 2 3 4 2a 3 2b Halite NaCl 0.52 2.23 8.4 0.0 0.62 4.2 0.42 -0.08 1.07 -0.8 5.59 [191.62 4.369 1.97 5.014 2.06 0.133 0.531 Pyrite FeS2 4.982 3.8 2.

Refs.73 4.106.02 0.5 3.88 1.12 1.66 6 0.23 0.88 2.3 i.57 2.09 0.85.61 2.9 1.9 -17.24 1.03 0.5 1.3 0.02 DP (kmkec) 2.09 -0.2 6.4 3.71 7.16 0.27 0.9 5.49 0.23 4.03 _-0.106.52 6.249 2.02 6.25 ___ 0.11 1.02 6.1 7.6 2.41 1.8 Phase* Halite NaCl 1.427 [lo61 Halite NaCl 2.33 -1 1.3 0.66 6 6.6 1 2 4a 4b 2 4 4 13 12 6 [38.63 3. 213]/[48] Cesium Iodide CSI 2.19 6.7 2.324 6.2 lower S error AS 0.05 -0.00 0.1 1.3 0.5 3. E E B L NO.TABLE 1.09 0. 213]/[48.04 0.09 0.60 3.8 11.09 --0.53 6.66 1.3 1.356 6.986 0.19 -0.0 14 2. 107.03 0.52 6.03 0.2 6.04 2.75 6 4 u541 .862 5.12 --0.647 1. 1771 Sylvite Sylvite Sylvite KC1 KC1 KC1 0.11 0. 1771 Potassium Bromide KBr 2.42 1.0 1.2 -0.56 5.8 2.470 0.18 0.43 4.84.5 --0.38.73.38 2 2 1 2 3 4 2 2 33 9 2 3 [lo61 ma [34.04 0.9 4.05 0.213] /[48.05 __ 0.23 6.1 1.159 [32.09 10.3 1.41 4. of Data 5 2 2 5 2 2 28 113 109 95 43 8 2 3 Mineral Formula Co (kmhec) 0.66 1.51 0. 103.74 3.86 4.79 1.9 2.04 4.71 7.7 5.02 1.646 1.09 0.747 2.18 2 3 4 [lo61 Halite NaCl 1.75 4. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 0.018 -__ 0.35 2.1 11.09 0.56 2.08 0.107.29 5.121.02 0.03 0.1 3.5 19 3.12 0.17 1.50 1.37 0.22 0.989 error ACo (kmhec) 0.4 1.66 2.42 0.26 1.6 -5.6 6.7 2.106.8 upper UP (kndsec) 6. 176.4 1.83 1.11 0.09 0.05 1 2a 3a 4a 3b 4b 3c 4c References I Temp.07 0. 121.

157.03 0.11 1.915 0.38 1.53 32.1 1.8 References I Temp.3 0.76 Phase* NO.22 3.31 1. of Data 2 3 4a 4b 1 2 3 4 2 4 7 2 13 3 Cesium Iodide CSI 1. 2131 /[199.67 0.577 1.019 0.76 2.42 2 2 1 2 1 2 4 5 5 7 9 14 58 25 [411 [411 [41.56 4.47 1.16 1.57 3.22 3.07 0.70 2.999 [19.16 __ 0.03 0. Icei Hz0 H20 H20 0.25 3.5 5.18 0.93 1.16 0.35 0.70 3.07 1.09 0.3 1.07 3.38 3.121] Bromellite Bromellite Be0 Be0 2.799 0.40 1.154.09 0.66 5.46 2 4 2 1 2 3 4 6 2 3 [2101 [120.14 2.67 5.04 VP (krnhec) 0.76 3.29.75 6.32 1.92 -1.4 0.66 0.96 U861 Oxides: Water.95 2.12 lower S error AS 0.121.858 0.16 0.05 0.04 0. 2131217.858 5.43 1.17 __ 0.00 0.25 1.11 0.28 2.57 upper UP (kmhec) 1.03 0.83 4.479 6. Icei Water.2 1.06 __ 0.73 1.4 4.3 -0.1 2. Icei Water.5 4. Refs.8 1.64 0.5 8.64 8.045 0.1141 Water.3 9.121.06 0.661 [120.019 __ 0.209] Fluorite c*2 3.2 0.56 1.8 1.03 1. Ice” H20 0. 2251 / [87.119] & H Seawater (mixture) 1.302 1.11 4.10 0.8 1.6 0.89 1.167.38 3.40 -1.89 1.270 0.71 1. Mineral Formula Co (kmhec) 1.51 error ACo (kmhec) 0.9 2.12 -0.4 0.2 0.008 2.05 1.67 0.60 0.10 0.08 0. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 4.57 3.03 0.71 1.05 0.97 2.57 0.116.18 0.03 0.356 1.13 __ 0.48 1.27 0.32 1.454 2.213] .69 2.44 [351 Cryolite Na3 AlFg 2.19 0.121.17 __ 0. 140.141 [38.080 0.75.TABLE 1.06 0.56 4.

121.50 4.083 3.842 3.44 1 2 4 2 2 2a 2b 4 2 4 4 4 4 6 13 8 9 11 25 16 [120.939 1.558 2 3b 4 1 3a 2 3b 4 2 3 4 3 4 4 2 3 3 4 3 6 3 5 P191 Magnesiowiistite Mm.76 3.705 1.12 -0.10 6.83 0.218] /[197] Magnesiowiistite Mgo.33 0.04 0.368 1.127] Periclase Periclase Periclase MU MgO MgO 2.84 9.11 0.721 2.626 1.29 0.81 6.1271 [56.121] [56.06 0:03 0.47.00 3.78 5.00 0.75 1.094 0.1 2.07 0.74 5.13 0.07 0.79 0.84 1.49 1.317 0.78 0.980 [1211 .02 0.74 DP (kmkec) 1.7 7.63 0.121.3 0.36 1.127] Periclase W@ 3.07 0.06 S error AS 0.3 0.56 6.56 1.083 3.797 Co (km/se4 9.619 0.191 [121] Lime CaO 2.13 0.90 5.56.88 2.042 1 2 2 4 [120.989 10.6 4.16 8.05 0. of Data 4 5 12 3 Bromellite Be0 -1.094 3.06 0.3 3.65 7.397 4.825 2.2 0.33 4.29 0.10 3.557 2.05 0.967 4.6 0.78 Phase* NO.2 0.40 4.629 1.11 0. Refs.749 1.08 0.01 2.332 0.939 1.5 4.96 5.886 [120.27 4.121.528 3.53 4.217.5 0.332 0.583 [2.169 0.42 ACo (km/=) 0.11 0.08 0.22 1.17 __ 0.825 1.7 1.91 1.04 0.3 0.53 1.169 2.14 1.121.10 0.01 3.77 1.705 1.3 1.06 0.2 0.882 2.8 3.56.16 0.62 1.71 2. 2131 Bromellite Be0 2.08 0.6Fe0.7 __ 0.259 0.32 1.12 0.77 2.18 0.509 2.67 0.61 0.7 -0.355 [37.3 3.92 0.16 1.362 1.213] Bromellite Be0 2.3 1.013 UP (kn-dsec) 0.55 2.0 1.Peo.07 0.76.18 0.28 2.07 0.12 0.28 2.10 0.7 2.121. Shock Wave Equation of State of Minerals and Related error Materials of the Solar System lower (continued) upper References / Temp.14 0.14 0.05 1.152. 127.2 0.822 3.09 6.121.10 0.49 1.51 5.3 6. 5 2 8 75 s Mineral Formula Sample Density (Mg/m3) 2.TABLE 1.652 5.13 6.

00 1.435 4.9 1.33 6.03 2.055 1.007 0. 122.979 8.662 -_ 0.59 2.621 3.12 0.35 -1.3 11.85 7.955 1.766 2. Refs.17 0.51 0.5 S error AS 0. 2171 Ihnenite Fe+2Ti03 4.09 0.16 0.8 1.07 0.801 3.52 6.28 0.3 0.11 0.2 1.15 1.18 0.54 0.84 3.18 7.92 0.787 6.294 3.097 2.08 1.8 8.11 -0.011 __ 0.73 2.3 3 0.716 1.10 -0.127] w361 __ 0.93 0.217] [I521 Corundum Hematite A1203 4.75 5.898 2.011 0.127] Corundum A1203 3.78.08 ACo (kmlsec) 0.009 3.20 7.766 2.02 0.4 4.06 0.285 4.652 2.122.O 5.761 [9.43 5. Shock Wave Equation of State of Minerals and Related error Materials of the Solar System lower (continued) upper References / Temp.03 0.3 0.200.07 Ilmenite Fe+2Ti03 4.07 -- 0.121.285 1.127.548 1.555 5.28 1.9 3.73 2.71 11.5 0.035 1.80 6.125 0.5 0.898 UP tkmlsec) 3.04 UP (kmlsec) 1.706 0.4 6.39 0. 127.33 0.04 17.033 0.38 1.414 1.18 0.36 [971 Wiistite FetmxO 5.02 -0.07 0.18 2 2 3 4 4 6 4 10 a-Fe203 [47.12 0.46 0.04 0.034 4.017 0.72 3.706 3.37 0.008 0.2 0.8 -4.18 __ 0.00 5.626 2.46 0.05 0.6 0.07 . 2171 [I521 Corundum Corundum A1203 A1203 3.17 1. of Data 3 4 2 3 4 2 3 4 1 2 1 2 5 9 3 2 4 2 3 2 7 15 5 10 [2321 Lime CaO 3.5 1.979 Phase* NO.00 0.47.121.TABLE 1.05 Corundum A1203 3.04 1.4 0.127.04 6.1 -14 0.51 2.324 [971 I[501 Wiistite Fet-.56 1.13 1.009 1.06 0.628 1.2 4.83 0.3 0.3 1.18 0.2 0.047 9.22 1.62 0.843 [47.46 0.05 0.07 1.40 0.86 4. Mineral Formula Sample Density @Q/m+ Co (kmlsec) 7.282 0.85 1.92 3.121.37 0.92 3.38 1.408 1.121.0 0.082 2 3 4 2 3 4 3 2 2 3 5 12 [121.294 8.064 2 0 1 2 6 41 6 52 [9.61 10.15 0.

21 6.348 References I Temp.42 0.987 2.07 0.3 0.0 2.14 0.05 0.TABLE 1.03 0.05 7. 2171 Ru tile TiO2 4.60 1.217] Pyrolusite Mnf402 4.63 1.07 Phase* NO.06 0.1 7.8 0.44 5.24 0.121.42 [WI Barium Titanate Spine1 Spine1 BaTi 5.08 0.09 0.127] r z 2.43 1.61 1.48 0.36 0.4 -0.00 0.26 8.245 [11.1 10.1 8.468 2.676 2.514 7.16 lower S error AS 0.507 1.07 0.12 0.06 DP (kmhec) 0.3 0. of Data 2 3 4 1 2 4 4 2 3 4 5 3 2 23 55 9 9 2 10 13 Perovskite CaTi 1.757 1.213] [ 121.05 1.127. 2171 Spine1 Mg&Q 3.134 upper DP (kmhec) 2.59 2.2 2.06 0.06 0.2 0.17 0.19 _0.10 0.10 -0.8 1.0 3.2 3.07 -_ 0.24 5.14 2. Refs.07 0.121.479 3.11 0.11 1.191 3 4 1 3 4 3 5 11 8 8 16 [351 Rutile TiO2 4.655 1.35 3.25 6.26 2.688 2.2 1.117 [47.991 3.858 3.1 4.07 0.07 0.52 0.5 4.46 0. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 3.447 [66.04 5.334 2.417 [47.3 0.63 0.68 3.08 1.5 __ 1.11 0.0 6.15 -4.03 1.0 5.318 0.263 2 .217] [47.130.6 0.533 1.86 error ACo Ndsec) 0.321 1.35 -0.14 2.016 0.3 0.23 2.3 _0.3 0.146 3.96 2.77 0.47.121. 00 is H a Mineral Formula Co Odsec) 5.27 1.127.48 0.23 5.21 1.9 6.04 0.10 0.93 1. t.987 2.975 2 3 4 3 4 2 3 4 3 5 8 2 3 2 10 15 [121.5 4.769 3.127] Magnetite Fe+2Fe+3204 5.33 3.311 3.121.688 2.61 1.5 0. 127.56 4.44 0.13 -0.16 -_ 0.786 2.24 0.35 3.4 _0.07 [ml Magnetite Fe+2Fe+3204 5.00 0.7 -4.14 1.00 0.72 0.3 7.121.858 0.311 1.727 0.123.03 0.2 0.

03 0.337 w11 w11 11211 Wll WI Uraninite Uraninite Uraninite Hydroxides: Brucite uo2 uo2 uo2 6.286 3.TABLE 1.04 0.0 4.925 0.51 2 4 2 2 3 4 6 2 13 2 3 2 w361 [@I Brucite Goethite Mg@Hh a-Fe+30(0H) 2.59 1.03 0.2 -0.133 10.983 1.06 -0.41 3.11 0.13 0.4 0.355 upper UP (kmlsec) 1.51 1.17 2.6 9.02 1.11 -- 1.4 5.20 0.7 0.4 1.00 0.82 5.75 0.12 -0.3 0.306 3.17 1.41 0.08 0.02 -0.03 0.41 2.493 3.12 -0.17 4.70 1.0 WI .05 0.47 [47.37 4.25 3.05 0.025 0.29 0.7 0.866 2.15 0.57 1.571 1.16 0.68 1.383 4.88 1.34 2.10 lower S error AS 0.06 0.256 References I Temp.34 2.079 1.35 1.88 1.15 2.99 3.26 2.855 4.07 0.43 0.6 0.99 5.03 0.512 w11 ~241 Baddeleyite m2 5.03 UP (kn-dsec) 0.9 5.Th)02 uo2 1.4 0. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 6.07 0.? 302 6. of Data 1 2 4 2 2 4 2 4 2 1 2 4 4 4 4 7 4 3 6 2 8 4 4 7 3 12 6 18 15 15 Cassiterite SnO2 -0.61 1.52 3.277 4.11 __ 0.8 0.52 3.04 0.568 1.51 4.91 1.77 2.42 0.22 1.22 Phase* NO.20 0. Mineral Formula Co (kmhec) 6.814 Cerianite Uraninite (Ce+4.501 2.347 4.27 1.9 0.8 1.437 0.9 5.509 1.07 0.6 0.4 1.96 3.694 error ACo (kmhec) 0.111 W&W2 2.17 0.22 0.833 2.121.11 -_ 0.05 0.622 2.983 2.866 2.06 0.06 -- 1.217] W’l Argutite Baddeleyite GeO.501 0.622 0.2 3. Refs.02 1.2 0.994 2.886 1.00 1.

77 1.2 0.2 0.54 2.10 0. 2 $ s Data Carbonates: Calcite CaCO3 2.081 0.5 1.928 WOI (w4)2so4 1.28 0.08 6.2 2.72 2.4 0.1 1.71 1.61 1.7 2.85 0.471 2.04 0.3 0.6 0.86 1.11 Aragonite Sulfates: Mascagnite CaCO3 2.69 3.375 [W GYPSY CaSO4 l 2H20 2.14 0.0 0.701 6.13 __ 0.10 0.06 __ 0. of lower S error Mineral Formula Co kdsec) AS (kndsec) UP (kmhec) upper VP Phase* References I Temp.828 6.15 5.09 1.82 0.73 1.21.05 ii.28 1.12 0.184.28 [1861 / [1031 Borates: Sassolite HNh 1.27 1.16 0.80 5.9 3.30 5.213] 0.55 1.81 3.03 -2.03 1.5 1.71 0.09 1.79 0.8 1.435 1.495 1.10 0.69 0.2 0. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) error ACo (kmhec) E NO.54 1.87 1.78 0.06 2 4 2 2 2 3 4 2 3 4 2 3 4 8 11 8 5 3 2 4 2 3 5 3 2 5 [991 [991 [991 Mascagnite Mascagnite Anhydrite (NHdSh WLh‘Q 1.11 _1.83 2 2 4 2 6 5 19 12 uo21 [102.81 0.04 0.21 2.12 0.15 4.9 0.845 1 2 24 6 [11.14 0.5 1.75 1.975 2.36 1.72 2.03 1.29 1.95 0.15 0.639 2.08 __ 1.72 1.15 0.102] / HO31 Magnesite Dolomite MgCOs C~g(CO3)2 2.12 0.12 0.32 1.3 4.03 __ 0.97 1.3 2.16 0.85 3.11 3.96 3.64 1.6 3.71 3.5 0.17 -0.167 0.15 1.12 CaS04 11861 Barite BaS04 4.24 3.09 0.49 0.114 2 4 3 2 Wll .8 0.013 0.254 1.639 1.85 1.15 0.55 2.26 0.03 0.4 1.2 2.2 5. Refs.6 1.42 0.11 _0.34 1.60 4.73 2.83 1.TABLE 1.

65 0.32 -0.43 0.08 0.05 0.2071 SiO2 1.07 0.2 0.374 4.55 9.11 0.84 1.508 0.61 5.67 1.009 1.15 1.207] Porous Quartz Porous Quartz Porous Quartz Porous Quartz Porous Quartz Silicic Acid Silicic Acid Silicic Acid SiO2 SiO2 SiO2 1.17.04 0.52 0.2 4.589 0.121.06 0. 208.40 1.03 0.93 1.27 1.13 2.59 5.94 0.47.98 5.011 0.155.05 1.52 6.20 1.19 0.799 3.0 0.51 4.815 1.09 0.11 0.018 0.02 0.55 4.13 0.7 -0. 2221 / [118.38 1.285 0.165] [188.151 H4Si04 HaSi H4Si04 0.13 2.34 1.48 8.199 6.877 Wll [121.217.14 6.51 2.03 0.TABLE 1.75 -0.03 0.356 0.03 0. Refs.651 6.815 2.08 2.374 0.4 0.10 0.84 26.27.275 I.44 5.81 0.28 5.12 0.207] SiO2 2.42 0. 72.2071 [ 188.87 1.127.68 1. of Data Silica Polymorphs: Quartz SiO2 2. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) error ACo (kmlsec) lower S error AS UP (kmhec) upper UP (kndsec) References / Temp.12 0.02 0.25 2.162.6 0.9 -1.65 0.118. 129.5 3.0 3.55 0.80 w31 Cl881 [1881 .71 2 2 2 3 4 2 4 2 4 4 4 2 4 15 30 4 3 9 11 15 11 16 5 6 3 7 [188.48 4.2 0.41 0.12 0.16 0. Mineral Formula Co (kndsec) Phase* NO.80 0.86 0.29 1.199 3.863 3.09 -0.295 0.27 3.82 1.006 0.48 1.98 5.09 0.09 0.283 0.261 0.10 0.33 0.07 0.46 4.849 3.66 1.02 0.33 1.03 0.76 Oa Ob la lb 3a 2 3b 4 16 29 16 12 6 24 3 10 [11.08 0.78 0.01 0.803 2.04 1.55 0.08 0.2 1.02 0.03 0.37.766 0.65 8.43 1.62 2.03 0.05 0.019 0.84 0.

01 1.05 0.65 -3.18 0.99 4.749 2.018 0.03 0.86 upper UP (km/set) 4.10 0.3 5.771 3.219 1.44 3.51 0.214 0.6 0.55 CristobaLite SiO2 2.6 Pha.401 0.68 * is u 5 Aerogel Aerogel SiO2’ SiO2’ 0.06 0.164 1.01 1.44 1.5 6. 229]/ [ 1651 .433 2.05 References I Temp.765 3.006 0.05 0.2 1.86 4.07 0.3 0.07 0.010 0.4 4.44 0.00 0.006 0.6 0.99 1.212 [91.302 1.3 0.48 2.29 -0.03 0.92 2.97 0.127.40 Coesite SiO2 2.8 1.48 2.494 4.55 1.64 1.11 1.19 _0.771 0.29 1.626 0.43 6.168 1.795 2.TABLE 1.011 0.21 -0.12 UP (kmhec) 1.05 4.43 0.089 1.127.009 0.63 0. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 0.66 1. of Data 2 4 2 2 4 2 4 2 4 2 2 3 2 3 4 6 8 3 4 4 3 7 3 6 5 3 2 3 3 3 Aerogel SiO2’ 1.37 1.4 lower S error AS 0.02 0.23 0.833 6.172 error ACo (km/set) 0.21 4. 5 E i * [88.42 0.92 W61 Silicates: Forsterite MgzSiO4 3.10 0.121.15 2.825 2.003 0.se* NO.008 0.15 2.0 10.66 4.3 _0.02 0.07 0.06 0.05 0.59 2.797 0.014 0.059 5.96 1.545 1.4 0. Refs.335 1.3 0.40 [1581 mm [1881 W61 WI W61 B 3 z F v) Aerogel SiO2’ 0.2 0.1 1.013 0.01 0.16 1.201.188] Mineral Formula Co (krnhec) 0.456 3.10 0.09 0.121.02 0.71 3.13 Coesite Coesite SiO2 SiO2 1.63 6. 2171 Forsterite Mg2SiO4 3.449 4.33 2.224 0.902 0.4 0.590 0.03 0.8 7.61 2 4 la lb 2 4 6 6 16 12 20 20 [47.08 0.295 0.01 7.945 1.010 0.21 0.04 0.

TABLE 1.967 3.479 2.14 1.016 0.745 3.157 2. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m+ 3.3 2.717 1.549 8.02 -_ 0.1 6.9 -0.3 0.015 0.19 2. Refs.19 1.15 0.09 0.65 -0.6 -0.3 -1.58 -0.07 0.817 3.43 2.1 2.45 7.359 1.003 0.383 2.0 1.077 1.14 @x04Mwod3 M2Si3012 4.272 1.13 0.11 1.121.05 0.19 2.479 2. 2171 Zircon ZrSiO4 4.22 1.29 0.99 1.13 0.14 -1.88 0.o8hsio4 Fayalite FezSiO4 4.074 [47.80 0.78 S error AS 0.4 0.07 2.2 7.42 [15.181 1771 Grossular Mullite Mullite Ca3A12Si3012 A6Si2013 M6Si2013 3.3 -0.32 1.58 7.08 _0.121.03 0.732 8.3 -1.07 2.13 lower UP (kmhec) 0.967 0.7 __ 0.84 5.17 3.5 7.16 Phase* NO.6 -10 5.47 1.745 0.92 2.46 1.3 6.13 _-0.8 4.85 0.06 0.1 2.817 3.702 1.06 0.09 0.92 3.935 0.45 1.3 0.05 0.6 1.483 1.121] [47.17 0.6 8.8 References / Temp.359 3.00 1.46 upper DP (kndsec) 1.04 -0.264 error ACo (kmhec) 0.02 3.10 _0.52 2.608 1.9 0.127] r1211 Kyanite A12SiOs 2.02 2.4 0.537 2.31 1.154 8.921 WI Kyanite A12Si05 3.245 -0.39 3.81 1.311 1.04 4.3 0.668 3.73 2 2 1 3 4 1 3 4 2 4 2 3 4 16 13 3 3 2 3 5 5 2 3 2 12 8 WI [121.29 1.003 3. Mineral Formula Co (kmkec) 8.79Mgo.394 -0.9 5.78 -0.8 3.08 0.10 0.07 -0.6 2.4 0.0 6.157 2.45 2.33 1 3 2 1 2 3 4 7 4 4 w41 Almandine (Feo.09 0.84 0.05 0.18 -_ _0.04 0. (Wow FeO. of Data 1 2 3 4 2 4 10 10 Olivine (MgFehSiO4.5 50 1.23 1.43 2.645 WI Andalusite A12Si05 3.29 6.15 0.52 0.30 8.18 1.18 0.8 0.9 0.217] .127.07 0.0 6.

16 0.956 2.60 2.4 0.8 8.18 4.11 4.68 -0.43 -1.1 1.3 6.11 0.217] ? 2 Mineral Formula Sample Density (Mg/m3> 3.10 5.658 upper UP (kmisec) 1.722 1.3 2.555 2.30 6.11 0.74 6.052 1.08 0.2 0.2 0.121.1 3.054 1.427 Phase* NO.09 0.258 2 5 [47.128 0.4 3.OHh 3.2 0.3 6.11 1.719 2.29 0.98 7.128 3.746 1.179 F.13 0.44 3.349 4.121.2 0.8 3.817 2.3 _0.127.53 M51 Tourmaline Ca(Al.16 __ 0.561 5.05 0.946 0.00 1.59 1.5 5.127] Enstatite Ma&06 3.15 0.121. of Data 3 8 10 4 6 2 7 Sillimanite A12Si05 0.07 0.18 0.461 0.067 [8.2 0.211.09 0. 2171 Pyroxenes: Enstatite Ma&06 Mgzsi206 2.888 1.4 -0.57 0. Shock Wave Equation of State of Minerals and Related error Materials of the Solar System lower (continued) References I Temp.10 1.8 Serpentine MggSi205 (OH)4 2.4 0.835 3.64 8.127 Co (kmlsec) 6.555 2.43 1 1.121.15 0.2 4.714 2.27 2.621 10 10 16 [47.8 3.31 0.7 0.695 2.75 0.025 2.1 1.TABLE 1.349 1.16 0.04 1.44 3.54 2 3 4 1 2 3 4 5 2 9 6 19 6 22 [121.12 8 r1211 Muscovite KAlz(Si+l)010 @KF)2 2.54 0.461 3.4 0.956 2.165] .09 -0.18 -0. Refs.74 2.4 0.6 ACo (km/s@ 0.5 S error AS 0.901 3.126 2.888 3.5 3.97 7.5 0.15 0.08 0.16 0.7 1.231] I [117.814 2.18 0.456 1.224 0.2 8.262 2.15 UP (kmhec) 0.06 0. !i z 8 s 5 is [47.14 __ 0.18 0.75 3.05 1.Mg)s& (B%hSi6018 WV94 3.20 1.217] Enstatite 2.34 1 3 4 1 2 1 3 4 2 3 4 2 3 4 Topaz Al2SiO4(F.824 1.611 1.70 0.95 0.90 0.04 -0.5 1.068 2.Fe.62 1.

196.57 7.03 0.15 1.005 1.3 0. Refs.06 0.156 1.933 1.018 0.41 2.11 0.935 1.1 3.6 1.14 -0.15 0.08 0.14 0.003 0.8 1.933 3.44 7.85 0.434 2a 2b 4 3 8 8 [47.44 1.799 2.1 3.15 1. of Data 1 2 4 2 2 4 4 Diopside caMgsi206 8.85 4.41 6.123 6.09 0.3 6.ZOsil.018 6. 2171 Spodumene LiAlSiz@j 3.8 0.289 1.195 1.4 1.03 0.10 0.82%.94 3.1 1.08 0.65 -0.4 0.29 Tio.2 0.6 __ __ 0.0 2.24 5 w331 CaFe+2Si206 3.51 1.6 4.12 lower UP (kndsec) 0.07 0.08 __ __ 0.85)06 cmgO.2 -0.4 6.56 1.34 0.135.25 6.2 0.08 0.626 1.45 2.16 [18.3 0.37 1.TABLE 1.4 4.94 1.06 Phase* No.52 0.8 6.73 2.264 error ACo (kmhec) -0.82 2.12 0.43 1.47 1.121.195 1.44 0.196.019 u.05 0.018 0.42 2.826 4.335 6.3 0. also Salite 00.201 0.62 1.00 1.80Nwd(M&m%.14 6.007 0.986 1.00 0.778 1.09 _0.09 0.282 2 3 4 4 3 4 2 3 4 3 2 3 6 5 4 2 3 5 W'l W'l Wll Wollastonite Wollastonite CaSiOg CaSiO3 2.620 0.07 1.213] / U981 Molten Diopside” Hedenbergite cmgsi206 2.1 5.06 0.42 3.004 0.41 2.9 7.213] Jadeite Na(A1 Fe+3)f&6 3.87 2.06 1.89 [I211 . 18si206 .289 1. Mineral Formula Co (kmkec) 4.45 2. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 3.42 0. 3.82 2 3 4 2 3 4 2 2 3 5 8 5 w51 Augite.48 3.0 2.04 0.435 [18.799 0.4 0.30 S error AS _0.3 4.822 Wollastonite CaSiO3 2.76 4.64 0.94 1.dWO.7 References I Temp.61 1.37 3.30 1.87 2.30 6.85 upper UP (kmhec) 0.

Shock Wave Equation of State of Minerals and Related Materials of me Solar System (continued) Sample Density @Q/m3) 2.04 .901 error ACo (krdsec) 0.36 1.16 0.911 0.7 2.10 __ 0.6 0.06 0.06 -0.8 lower S error AS 0.309 3.174] WI CaAl2Si208 (Na.63 4.70 6.14 3.46 2.15 .3 1.21 2.769 2.88 0.6 [1871 Beryl Be3Al&G18 2.338 2.21 1.78 upper VP (kmhec) 2.22 0.35 4.- 1.32 1.21 2.91 4.11 0.TABLE 1.2 UP (kmhec) 1.83 2.7 0.20 3.2 Phase* NO.5 0.07 0.62 3.3 0.309 6.67 0.35 1.45 1.17 2.27 0.2 0.52 1.05 1.789 2.37 2 2 3 6 [96] / [173.05 1.12 6.15 2.561 7.188 1.67 1.14 1.16.11 0.91 1.08 iO8 0.14 0.57 1.39 -1.02 0.145 Wll UW SiO2 1.85 0.507 5.2 -0.1 2 4 4 2 [I871 Feldspars: Orthoclase. Refs.94 References I Temp.655 3.02 -0. Mineral Formula Co (kmlsec) 5.09 2.21 1 2 2 4 4 2 7 2 10 4 WI SiO2 0.79 0.5 - 2.09 -0.41 6.25 2.1 7.80 1.2 0.6 0. Microcline KAlSi308 2.05 0.1 0.1 1.25 1.76 5.82 3.8 -1.6 0.09 -0.12 4.55 3.07 1.51 -0.3 -1.27 0.5 Anorthite Molten AnorthiteO Nepheline h&%208 2.04 0.2 0. of Data 2 4 9 5 Tremolite Cad%Fe+2)5%022(OHh 0.K)AlSi04 2.41 0.195 1.4 4.186] Oligoclase (NaAlSi308)75(c~12Si208h9.3 1 2 4 1 14 4 4 13 [12.19 0.68 8.2 0.635 Cl61 (KAlSi308h.94 2 3 4 3 2 4 11871 Glasses: Argutite Glass Quartz Glass (fused quartz) Quartz Glass Ge02 3.

264 3.57 2 3 4 3 3 5 [671 (A1203)0.121. Quartz Glass Quartz Glass SiO2 SiO2 1.307 0.84 0.5W3)0.009 0.14 0.71 1.08 0.73 -2.51 0.397 4.14 0.45 1.TABLE 1.4FW3 2.019 0.306 2.07 0.106 2.48 14- 3.2 lower S error AS 0.5 0.731 1.00 0.06 0. of Data 4 1 3 2 4a 4b 6 7 32 20 61 3 References / Temp.55 2. 127.26 3.80 3.04 0.l(Fe203)0.57 0.61 0.118.531 1.014 0.306 2.118.4 1.063 2.08S .43 1 3 4 5 3 15 5 4 WI 1 [511 Pyrex (and soda-lime glass) (SiO2h@203)12(A1203)2.09 0.2 2.03 0.08 0.703 5.4 5.129.2(cuoh2.3(Na20)4&20)1(As203)0.17 0.3 0.5KW0.121.43 1.117.3 0.15 0.77 -0.02 0.204 error ACo (kmhec) 0. 175.1 6.11 0. 1771 Anorthite Glass CaA12Si2Og 2. 217.45@W)o.623 1.6 0.014 UP (kn-hec) 3. 1361 Soda-Copper Silicate Glass WO2)72.12 0.1 upper DP (kndsec) 4.4 (WDo.83 5.92 11 [95.731 4.10 3.33 -0.444 2.78 1.37 0.07 0.5 0.222] / [104.03 0.114 0.64 Phase* NO.6' 2.698 1.08 0.12 0.96 0.95 0.175 Mineral Formula Co (kmhec) 0. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density C&@/n& 2.8 5.444 2.012 0.70 1.196 [911 [101.3 -0.37 0.2 1.28 0. Refs.179 2.179 2.71 1.40 0.397 1 2 4 1.4 0.742 5.163.175 23.122.01 1.692 6.2 0.

361 1 2 4 3 9 15 [56. 139.77 6.12 0.115.51 0.921 2. 163.11 0.213.707 6. Russian alloys Aluminum: 1100.03 1.39 error AS UP (kdsec) 0.4 0.121.1 1.3 -0.4 0.6 3.19 2. Russian alloys Al’ 1.197 2.6 6.24 2.00 0.10 -1.00 2.2 1.012 0.19 0.2131 Al’ 1.06 0.70 2.94 0.8 llols S (2ec) 0.3 2.983 2. 2131 Al’ 2.345 K 3 F c 0.03 0.15 0. 2281 Aluminum 2024 Al’ 1.08 0.04 1.15 0. 105.07 0.142.07 0.134.20 1.428 5.324 1.38 0.885 0.142.01 0.155.13 1.739 1.00 0.01 (ki2C) 0.30 1.02 1. of Data Lunar Glass s GiO2)40(TQh(A1203)l (FeOhOW) (CaO>l 0.09 0.28.566 4.2 0.121.567 1 2 4 3 9 15 [56.181 0.825 Phase* No.76 2 4 10 4 [105.06 0.20 0.44 6.54 0.26. Shock Wave Equation of State of Minerals and Related error Materials of the Solar System lower (continued) References I Temp.105.71 2.27 2 4 12 6 [39.134.19 1.0 0.0 1 2 4 10 59 27 [24.2 0.0 30.2 0.14 0.09 2 4 4 6 s [71 : 2 3 .926 2.162.323 3.019 0.10 0.04 0.566 0.012 0.121.09 5.0 0. i 3 g 7z Q Mineral Formula Sample Density (Mg/m3) 1.11 2. Russian alloys Aluminum: 1100.8 0. Refs.d Other Standards: Aluminum: 1100.2 0. 1361 Aluminum 2024 Al’ 1.18 2.39 0.526 6.988 1.62 0.682 0.TABLE 1.11 0.739 4. 1361 .27.661 2.8 3.955 2.190.012 2.45.985 upper UP (kndsec) 1.

678 3.45 0.356 0.166.6 0.849 2.3 5.1 3.121.03 0.18 0.208 Molybdenum* MO 10.121.16 0.559 4.51 6.03 1.05 0.435 5.914 4.849 1.30 0.008 0.00 5.54 __ 0.012 0.146 -0. 121. 136.538 1.247 0.25 1.724 1.788 5.59 8.166.817 1 2 4 2 5 17 [56.65 0.3 0.8 5.07 -0.55 2.226] Aluminum 2024 Al’ 2.12 -0.72 2.79 1.01 6.06 0.3 0.208 4.124 4.305 0.04 1. Refs.981 0.013 0.99 20.18 1.277 1.14 0.217. 1361 Aluminum 2024 Al’ 2.90.761 3.58 __ 0.131.09 0.162.66 5.73 0. 136.654 0.13 2.538 1.224 3.06 0.15 0.00 0.108.03 0.02 0.3 3.04 0.06 0.22 -0.141.90 2.9 2.011 1.005 0.98 1.74.07 1.00 0.56. 1361 [56.47 1.04 0.224.724 1.6 19.962 2 325 I [1651 Molybdenum Molybdenum Molybdenum Molybdenum Molybdenum Molybdenum Molybdenum MO MO MO MO MO MO MO 1.13 2.10 0.761 0.03 0.209] [24.134.5 2.005 0.064 1 2 4 2 7 17 [56. Mineral Formula Sample Density (Mg/m3) Co (km/set) ACo (km/set) S error AS UP (kmlsec) UP (kmlsec) Phase* NO.126.414 2 5 .163.62 0.05 0.134. 217.TABLE 1.121.47 1.16 0.24 4.02 0.02 0.00 4.18 1.03 -0.05 5. 2261 [I371 Molybdenum MO 10.39 -0.735 1. of Data Aluminum 2024 Al’ 2.134.213.40 1. Shock Wave Equation of State of Minerals and Related error Materials of the Solar System lower (continued) upper References I Temp.04 0.04 0.91 2 2 2 2 2 2 2 4a 4b 2 5 4 10 10 8 13 4 6 3 61 I2091 GO91 PO91 12091 PO91 [2091 [ 162.94 1.25 1.10 0.10 0.19 0.473 1.0 1. 163.6 0.91 3.

01 0.010 0.121.76 3.97 2.7 0.41 6.06 4. 136.685 0.36 18.43 3.TABLE 1.35 2.13 0.295 2.5 -0.685 16.6 5.21 1.011 1.76 3.02 0.584 1.06 0.166.35 2.217] Tungsten Tungsten Tungsten Tungsten W W W W 8.82 error ACo (km/set) 0.07 0.61 2. Mineral Formula Co (krn/sec) 0.451 1.86 4.23 2.08 0.49 2.04 0.52 1. 136.91 1.04 0.05 0.00 upper UP (kmhec) 2.20 8.03 _0.54 1.891 1.56 0.06 2.095 2.05 0.04 0.14 0. of Data 2 4 4 3 3 5 3 6 3 5 31 Tantalum Ta 1.013 -0.08 0.721 15.54 0.649 1.17 0.17 2.885 2.04 0.67 19.139.54 0.10 0.108.04 0.4 2.8 3.1 2 2 3 4 2 3 4a 4b 2 2 2 2 8 4 2 3 3 2 4 3 6 6 4 40 PO91 Tungsten W 6. 217.84 0.49 0.45 1.028 0.31 Phase* NO.38 2.09 0.37 1.15 1.92 m91 PO91 [24.240 .306 [209] PO91 PO91 Tantalum Tantalum Tantalum Tantalum Ta Ta Ta Ta 5.04 0.94 -0.03 lower S error AS 0.003 1.12 1.010 1.75 1.09 0.53 1.68 3.02 0.00 4.17 -0.66 1.10 0.04 0.012 0.209] ~091 G'O91 [Qll [100.86 References / Temp. 163.63 3.57 [204.012 0.03 1.121.07 -1.8 0.05 1.68 3.23 1.43 3. Refs.93 2.51 3.87 13.018 0.064 0. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) Sample Density (Mg/m3) 2.03 0.08 1.07 6.302 0.7 1.64 5.4 -3.010 DP (kndsec) 0.57 1.226] PO91 Tantalum Ta 16.601 1.37 1.63 1.33 -0.204 0.25 -0.03 0.05 -0.19 10.5 0.007 -ii04 0.19 0.04 0.131.26 1.649 Tungsten Tungsten W W 4.654 2.14 0.86.

4 1. compressed gas g Starting temperature 165K h Starting temperature 196K i Starting temperature 203-230K j Starting temperature 258-263K k Starting temperature 273-298K t Starting temperature 3OOK.53 3.2 S 2.121] Notes: *Phases: 1) Elasticshock.03 0.421 2. [55.00 0.651 6.92 1 2 3 4 2 32 21 19 References / Temp. ShockWaveEquationof Stateof Minerals andRelatedMaterials of the Solar System (continued) Mineral Lexan Formula (polycarbona@ Sample Density Co (Mg/m3) (km/set) 1.38 4.3) Mixed region. Refs.TABLE 1.05 lower DP (kndsec) 0.2) Low pressurephase.101.379 3. of UP Data (krdsec) 0.27 error AS -0.193 1.04 0. compressed gas m Starting temperature 1673K n Starting temperature 1773K O Starting temperature 1923K P 5% cobalt q raw data not provided r with impurities s compositionin weight percentoxides .421 2.9 2.12 0.64 upper Phase* NO.70 1.47 2.551 0.6 error ACo (km/set) -0.019 0. a Starting temperature 5K b Starting temperature 20K c Starting temperature 75-86K d Starting temperature 1llK e Starting temperature 122K f Starting temperature148K. 4) High pressure phase.

172

SHOCK

WAVE

DATA

FOR MINERALS

FIG. 1. Profile of a steady shock wave, rise time Q, imparting a particle velocity uI pressure Pl, and internal energy density EI, propagating with velocity IJ, into material that is at rest at density p. and internal energy density E,. in nearly steady waves in materials. For steady waves a shock velocity Us with respect to the laboratory frame can be defined. Conservation of mass, momentum, and energy across a shock front can then be expressed as P 1 = PO (Us-uo)/(Us-u1) Pl - PO = Po(Ul-uo)Q-Js-uo)
El - Eo = 0’1 + Po>(l/po-l/p 1)/2 = l/2 (ul - ud2

The key assumption underpinning the validity of Eqs. (I)(3) is that the shock wave is steady, so that the rise time zs, is short compared to the characteristic time for which the high pressure, density, etc. are constant (see Fig. 1). Upon driving a shock of pressure Pl into a material, a final shock state is achieved which is described by Eqs. (l)-(3). This shock state is shown in Fig. 2, in relation to other thermodynamic paths, in the pressure-volume plant. Here V. = l/p0 and V = l/p. In the case of the isotherm and isentrope, it is possible to follow, as a thermodynamic path, the actual isothermal or isentropic curve to achieve a state on the isotherm or isentrope. A shock, or Hugoniot, state is different, however. The Hugoniot state (Pl ,V 1) is achieved via a a shock front. The initial and final states are connected by a straight line called a Rayleigh line (Fig. 2). Thus successive states along the Hugoniot curve cannot be achieved, one from another, by a shock process. The Hugoniot curve itself then just represents the locus of final shock states corresponding to a given initial state. It has long been recognized that the kinematic parameters measured in shock wave experiments Us and Up can empirically be described in regions where a substantial phase change in the material does not occur as: us=co+sup As further discussed in several review articles on shock compression [22,.59,136], and a recent book [40],

(1) (2)
(3)

where p, u, P, and E are density, particle velocity, shock pressure, and internal energy per unit mass and, as indicated in Fig. 1, the subscripts o and 1 refer to the state in front of and behind the shock front, respectively. In Table 1, shock velocity and particle velocity are designated as Us and ul. Thus for a single shock UP = u 1. In the case of multiple shocks, the values of U, and us given in the Table are for the final (highest pressure) shock state. Equations (l)-(3) are often called the Rankine-Hugoniot equations. It should be understood that in this section pressure is used in place of stress in the indicated wave propagation direction. In actuality, stress in the wave propagation direction is specified by Eq. (2). A detailed derivation of Eqs. (l), (2), and (3) is given in Duvall and Fowles [70]. Equation (3) also indicates that the material achieves an increase in internal energy (per unit mass) which is exactly equal to the kinetic energy per unit mass. In the simplest case, when a single shock state is achieved via a shock front, the Rankine-Hugoniot equations involve six variables (Us, ul, po, ~1, El - Eo, and Pl); thus, measuring three, usually Us, uI, and po, determines the shock state variables p 1, El-E, and Pl.

FIG. 2. Pressure-volume compression curves. For isentrope and isotherm, the thermodynamic path coincides shock, the with the locus of states, whereas for thermodynamic path is a straight line to point PI,Vl, on the Hugoniot curve, which is the locus of shock states.

AHRENS

AND JOHNSON

173

Hugoniot data for minerals and other condensed media may be described over varying ranges of pressure and density in terms of a linear relation of shock and particle velocity in Table 1. This table was assembled using the Microsoft Excel, version 3.0, (Redmond, WA 1993) program and the least-square fits to the shock wave data with standard errors were derived by using the LINEST function. The equations employed for line slopes and intercepts are identical to those given in Bevington [46] (Eq. 6-9, p. 104; Eq. 6-21, p. 114 for errors in slopes; and Eq. 6-22, p. 114 for errors in intercepts). The Us-Up data for a wide range of minerals are given in Table 1. Here Co is the shock velocity at infinitesimally small particle velocity, or the ambient pressure bulk sound velocity which is given by co=dGG (5)

The analogous bulk modulus along the Hugoniot is: KH = -V @P/?lv)~. The isentrope and the Hugoniot modulus arc related via: and isentropic (11) bulk

KS

=

KH +

KH

77 / (I-

q,]

W)

- [PH-ps] [Y+l-q, o-Gl+-*)I
Here we assume a volume dependence of the Gruneisen parameter Y= V (JPlJE)v where = yo (V/Vo)q, (13)

where KS is the isentropic bulk modulus, KS = -V (dP/dV)s in the absence of strength effect (see Sect. 3).. Upon substituting Eq. 4 into Eq. 2, and denoting the shock pressure as PH, this is given by: PH = PoUp (Co + S Up) (6)

q=dLnyld!nVandq’=denqJtin

V

(14)

y. is the Griineisen parameter under standard pressure and temperatures and is given by Yo = a KT V&v = a KsVo/Cp, (15)

Thus, from the form of Eq. 6, shock pressure is given as the sum of a linear and quadratic term in particle velocity, based on the data of Table 1. A pressure-volume relation can be obtained by combining Eq. 6 with Eq. 1 to yield: PH = PO co2 “‘1/(1-sqj2 where (7)

where a is the the thermal expansion coefficient, KT is the isothermal bulk modulus and Cp and Cv are the specific heat at constant pressure and volume. We note that the Ps and PH can be related by assuming the MieGriineisen relation PH - PS = + @H-E& (16)

Tl=l

-v/vo=up/LJs.

(8) if y is independent of temperature, where EH = El-E0 is given by Eq. 3 and Es is given by V jP,dV. (17) vo Because the Grtineisen ratio relates the isentropic pressure, Ps, and bulk modulus, KS, to the Hugoniot pressure, PH, and Hugoniot bulk modulus, KH, it is a key equation of state parameter. The shock-velocity particle relation of Table 1 can be used to calculate the shock pressure when two objects impact. If (A) the flyer plate and (B) the target are known and expressed in the form of Eq. (7), the particle velocity Es = -

Eq. 7 is often called the “shock wave equation of state” since it defines a curve in the pressure-volume plane. The isentropic pressure can be written (e.g. [93,98,17l])by an expression analogous to Eq. 7 as a series Ps = po co2 (11+ 2sTl2 + .*.), which upon differentiation modulus yield the isentropic (9) bulk

KS = p. Co2 (1 + (4S-1) 17+ ...)

(10)

174

SHOCK

WAVE

DATA

FOR MINERALS

ul and pressure Pl of the shock state produced upon impact of a flyer plate at velocity ufp on a stationary target may be calculatedfrom the solution of the equation equatingthe shock pressures the flyer and driver plate: in PoA (“fp - “l)(CoA + SA (qp - ul)) = PoB ul (COB + SB ul). That is; ul = (-b - o-- - 4ac)/2a, b where a = s A PoA - PoB SB, b = CoA PoA - 2SA PoA “fp - PoB COB> and C= “fp (GoA PoA + SA PoA “fp).
3. SHOCK-INDUCED DYNAMIC PHASE TRANSITIONS YIELDING’

(la

(19

Particle Velocity
(20) (21)

(22)

AND

Both dynamic yielding and phasetransitionsgive rise to multiple shock wave profiles when pressureor particle velocity versus time is recorded. Virtually all nonporous minerals and rocks in which dynamic compression has beenstudieddemonstratephenomenon related to dynamic yielding, in which materials transform from finite elastic strain statesto statesin which irreversibledeformation has occurred. Moreover, most mineralsand a large numberof compounds,elements,and organic materials demonstrate shock-induced phasechanges. The dynamic yield point under shock compression, the Hugoniot elastic limit, or HEL, is defined as the maximum shock pressurea material may be subjectedto without permanent, massive, microscopic rearrangement taking place at the shock front. As shown in Fig. 3a, the shock velocity of the HEL state remains nearly constant and for non-porous media is usually equal to the longitudinalelastic wave velocity. Viscoelasticpolymeric media generally do not display the HEL phenomenon. We denotefive regimes in Fig. 3 for the caseof dynamic yielding and phase transition and the available shock wave data are separately fit to linear relations in these regimes in Table 1. For some minerals there are more than four regimes indicated, for reasons such as crystallographic control of compressionat low pressures

Volume
FIG. 3. Sketch of shock velocity-particle relation (a) and correspondingpressure-volumeHugoniot curves (b) for a mineral which undergoesdynamic yielding and a phase change. 0: compressionup to the Hugoniot Elastic Limit mm 1: transition via dynamic yielding to a quasihydrostatic state 2: low pressurestate 3: mixed region 4: high pressurestate (such as Oa,Ob for quartz), and for more than one highpressurestate (such as4a, 4b, and 4c for halite). The crystallographic or atomistic level nature of shock-inducedphasechangesvaries from simple average coordination changes observed in various liquids, ionization and debonding in non-metallic Pluids, electronic transitions in metal and non-metals, changesin crystal structure in solid materials, and transition from the solid to the fluid state.

AHRENS

AND JOHNSON

175

In the caseof a phasechange, the pressurealong the isentrope P, at the volume Vl corresponding to a Hugoniot state(Pl,V 1) is given by Vl ?(Voo-V1)=-v\PdV++?P1-Ps)+QR

(23)

where the left-hand side is the Rankine-Hugoniot energy, and the first and secondterms on the right representthe gain in the internal energy along the paths 1 and 2 of Fig. 2 Here Voo is the specific volume of the initial material and V. the specific volume of the shock-induced highpressurephase,or the intrinsic volume of the sampleif the initial state is distended. Also ETR is the energy of transition to the high-pressurephaseat STP. In the case of no phasechange,ETR = 0. For zero initial porosity V 00 = vo* The unknown parameter in Eq. 23 is P,, which is implicit in the first integral term on the righthand side and explicit in the second term. The second term is obtainedby using the definition of the Gruneisen parameter (Eq. 13) to calculate the change in energy associated with the pressuredifference (Pl-Ps) at constant volume.
4. SHOCK TEMPERATURES

initial volume, and Vb = V, compressedvolume. For the calculation of postshock temperatures Ti = TH , the Hugoniot temperature,Va = VH, the volume of the shock state, and Vb = Voof, the postshock volume corresponding to the postshock temperature. For shock compressionto a volume V, P, is first obtained by using Eq. 23; then T,, the isentropiccompressiontemperatureat volume V, may be calculated by using Eq. 24. Finally, usingEq. 16, the shocktemperatureTH is given by
(25)

For many condensed media, the Mie-Gruneisen equation of state,basedon a finite-difference formulation of the Gruneisen parameter (Eq. 16), can be used to describe shock and postshock temperatures. The temperaturealong the isentrope [224] is given by

It is useful to carry out both postshock and shock temperature measurements as they provide complementary information for the thermal equation of state, that is, y, as well as Cv. Minerals for which shock temperatureshave been measured(usually via radiative techniques)are so indicatedin Table 1. In the case of molecular fluids such as water, a formulation basedon the nearconstancyof Cp at constant pressureis used[4 1,167]. Although there have been few data collected, postshock temperaturesare very sensitive to the models which specify y and its volume dependence, the caseof in the Gruneisenequationof state [49,164,1651. In contrast, the absolutevaluesof shock temperaturesare sensitiveto the phase transition energy ETR of Eq. 23, whereas the slope of the TH vs. pressure curve is sensitive to the specific heat.

(24) where Ti is the initial temperature. For the principal isentropecenteredat room temperature,Ti = To, Va = Vo,

Acknowledgments. Research supported under NSF, NASA, and DOD. We appreciate comments on this manuscript from William W. Anderson, Kathleen Gallagher, Wenbo Yang, and J. Michael Brown. Contribution number 5332, Division of Geological and Planetary Sciences.

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The electrical conductivity cr and the dielectric permittivity E relate an electrical stimulus and response through Maxwell’s relations. 185 (4) e” is also called the loss factor. exp (iot) equation (1) becomes JT = (a + ime) E. Recent previous compilations of data on electrical properties of rocks are given in references [17-19. and other mineral physical properties. Fisler Electrical properties of minerals and melts aid in the interpretation of geophysical probes of the Earth’s internal electrical structure (see Hermance.i&” (2) A total (3) may also be defined as a complex J. and the loss tangent 6 is defined as . and at elevated temperature and elevated pressure. and of aqueous fluids are treated by Olhoeft in Section 3-8 of this series and in [42]. AZ 85287-1404 Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union. Department of Geology. Electrical properties of elements. For a time varying electrical field of the form E = E.xz and the permittivity value & = &’ . Section 1-12). electrical conductivities and dielectric constants of minerals are used in studies of mineral structure. etc. Because minor element content and experimental conditions are known to strongly affect electrical properties. and t is time.Electrical Properties of Minerals and Melts James A. Certain previous compendia of mineral electrical properties have preferred to give only ranges of values for a given mineral [ 17-191. inclusions. We have striven to provide reliable data for each material listed. Arizona State University. for a given electrical property of a mineral. sometimes differing by as much as several orders of magnitude. K. complex conductivity may be defined as 1 crT=oT+i<=o+i6. to tabulate both chemical composition and experimental conditions for each measurement. The data and tables presented here may best be used as a guide to the literature or as a source of references from which to start a search. E is the electric field gradient. 421. Tyburczy and D. electronic and ionic transport processes. and rocks at room temperature and 1 bar pressure. This article contains data and references to electrical properties of minerals and related materials at elevated temperature and 1 bar pressure. we have attempted. defect chemistry. Fisler. In addition. Electrical parameters. rather than as a source of absolute values. and microscopic defects such as voids. minerals. A. Electrical properties of materials can be very sensitive to minor chemical impurities and variations. The first term on the right hand side of equation (1) is called the conduction current and the second term is the displacement current. Tempe. where possible. Cracks and other macroscopic defects. twins. in specimens can complicate the achievement of reliable measurements. Tyburczy and Diana K. As a result. there are often a wide range of reported values. exp (icut) in which i = J-1 and o = angular frequency. In linear systems it can be shown that JT = GE + r&L’& (1) where JT is the total current density.

Above the Debye temperature.186 ELECTRICAL PROPERTIES OF MINERALS tan 6 = E”/E’ (5) The complex resistivity is defined as the reciprocal of the complex total conductivity p’ . metallic conductors have conductivities of lo6 S/m or more. n is the concentration of the conducting species. Effects of temperature and pressure.ip” = (0.854185 x lo-l2 F/m. Materials are classified on the basis of whether they are metallic conductors.. Impurity atoms in low concentrationsmay have large effects on the magnitude and mechanismsof conductivity in insulators.and expressionsof the form 0 = b. Some solid-solution impurity atoms can donate electrons to the conduction band. the l/T factor in the pre exponential term on the right hand side of equation (9a) is not always used. semiconductors. For general references see references[ZO.e is the chargeof the electron.the band gap is large (often 5 eV or more) and prevents thermal elevation of electrons into the valence band. Many earth materials. In addition to metals. E is often expressedin electron volts eV.22. Metallic conductors. k is Boltzmann’sconstant. Even at temperatures approaching 0 K metallic conductivity is very high. halides. The variations in slope can be causedby transition from one dominant conducting species to another or by a . exp(-E&T) (10) are employedinstead.are insulators. and the conduction electrons are not localized or bound to any particular atom. The NernstEinstein relation links the electrical conductivity to the diffusion coefficient of the charge-carryingspecies cr = Dz2e2n/(kT) (8) in which D is the diffusion coefficient. and T is temperature. leaving positively charged holes in the valence band. the Fermi level (the highest filled energylevel) lies within the conduction band. In an impurity-containing insulator. At high temperaturesthe conductivity may become dominated by the fundamental ionic conductivity of the pure crystal. 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 conduction).or insulators.g. materials such as graphite exhibit metallic conduction. both types of expressionsare used. Conductivity values for insulators are generally lower than about lo-l3 S/m at room temperature. Insulators. others can accept electronscausing electron holes in the valence band. 441. Boltzmann’sconstant k is equal to 8. At elevated temperatures. In the tablesthat follow.66]. Thermal promotion of electrons from the valence to the conduction band can occur. low temperature conductivity is often dominated by the impurity-controlled mechanismsand is termed extrinsic conductivity. resulting in p-type semiconduction. In insulators. z is the valenceof the conducting species. therefore the temperature dependence the conductivity of will be of the form CT ?f exp(-E&T) = or CTT A exp(-E/kT) = (9b) (94 in which bo and A are pre-exponentialconstantsand E is the activation energy.618 x 10m5 eV/deg. At room temperature. + i&)-l (6) The SI unit of electrical conductivity is Siemens/meter(S equivalent to l/n). e. Types of conductors. The SI unit of dielectric permittivity is Farad/meter(F/m) and is often expressedas the relative dielectric permittivity K K=E/k (7) where &o is the dielectric permittivity of a vacuum = 8. many silicatesand oxides fall into this category. Plots of the logarithm of electrical conductivity versus l/T that cover an extendedrange of temperature frequently show two or more linear regions. In metallic conductors. In geological materials the distinction between‘pure’materials and ‘impure’or minorelement containing materials is not always clear-cut or useful. which is termed intrinsic conduction.42. Semiconductors. Typical energy gaps for semiconductorsare on the order of 1 eV. Semiconductorsare materialswith a relatively small difference in energy Eg between the bottom of the empty conduction band and the top of the filled valenceband (the band gap). and the reader should be careful to employ the proper form of the equation for the constants given. the conductivity decreases with increasing T. generally decreasing as l/T [37. Diffusion is a thermally activated processso that D = Do exp(-E/kT). resulting in ntype semiconduction. In practice. Semiconductorshave conductivities in the range 10v3to lo5 S/m.

the reaction 02. Incthis notation. The values in Table 5 and 6 are the best currently available.and mechanisticallymore meaningful parameters are derived if the entire data set is simultaneouslyfit to a single expressionof the form d = bol exp(-El/kT) + cro2exp(-E2/kT) (11) The electrical conductivity of a material is the sum of the conduction of each charge carrier (or defect) type acting in parallel 0 = Z Oi = Z Ciqjpi (13) In the data tables that follow. qi is its effective charge. the magnesiumvacancyconcentration . the reaction which incorporates oxygen from the surroundings and forms a magnesium vacancyis written l/2 02 = v. but more commonly measurements at elevated pressures are parameterized isobarically as functions of temperature using equation (10) or (11). the removal of a positively-charged ion from its normal site resulting in the formation of a vacancyplus an interstitial ion (formation of a Frenkel defect) can be written as A. The activation volume is often interpreted as indicating the volume of the mobile species. Each region is then described by an expressionof the form of equation (10).g + 2h’ + 0. Thus. Kroger-Vink notation [23. In MgO.Fe)O. Tables 1 and 2 give thesedefinitions and show as an example the defect species in nonstoichiometric (Mg. in which the main symbol A indicates the species oB the defect (atom. When available. leaving an oxygen vacancy and two electrons behind. the subscript B indicatesthe type of site (normal lattice site of a particular atom type or an interstitial site). slashes indicate negative charges). we can write equationsfor chemical equilibrium constantsin the usualmanner K= rvk I rqi [A. Point defects are imperfections in the crystal lattice and the types of point defects possible are substitutions. The effect of pressure on conductivity can be characterized by the inclusion of an activation volume term Vo so that u+ PVo d = b. exp(-F) in which U is the activation internal energy. and pi is its mobility (in m2 V-l see-l). For example. interstitial ions. in principle.TYBURCZY AND FISLER 187 transition from extrinsic (impurity dominated) to intrinsic conductivity. In general. vacancies. hole. electrons. experimentaldata that have been fit simultaneously to multiple linear segments are indicated by braces. all defects are presentin some amount in every crystal and each contributes to the total conductivity. Thus the mineral stoichiometry dependson the chemical potential of oxygen (or the oxygen fugacity fo2) in the surrounding atmosphere. The concentrationsof the defect speciesare governed by chemical reactions that lead to the production or consumption of each defect type. Reactions involving oxygen from the surroundings are of particular importance in oxide materials.1 (15) in which K is the equilibrium constant and square brackets indicate site fractions. For example. Point Defects and Conductivity. Usually only one or two types of defects dominate under a given set of thermodynamicconditions. = l/2 02(g) + VG + 2e’ describesthe reaction of oxygen on a normal lattice site to release an oxygen molecule to the environment. In experiments at high pressure it is difficult to control all thermodynamic parameters. The electrical conductivity of materialsis determinedby the point defect chemistry. Note how defects causedby aliovalent ions in different valencestatesare written using this notation. activation volumes are given in the tables. However. electron.=V.+A.but care should be taken when making this interpretation. eachdefect is given a symbol of the form A . and the superscript c indicates the net effective charge of the defect relative to the normally occupancy of that lattice (dots indicate positive relative charge.24] was developed to describe the type of defect and its effective charge relative to a normal lattice site. We expect that many of these values will be revised as experimentalmethodsimprove. and electron holes (electron deficiencies in the valence band commonly termed ‘holes’). (14) For such a reaction. more precise. or vacancy). in which ci is the concentration of the ith type of charge carrier. the Gibbs free energy AGOfor this reaction is given by AGo = -RT ln K (16) in which R is the gas constantand T is temperature.

Examples of defect species for (Mg.11. the exponents n for the dependence of conductivity on oxygen fugacity have been included in the tables that follow. Thus. and the Mg:Fe ratio in the solid must all be specified.Fe)O. (20) in even pure MgO depends on f02 (at constant temperature). the pressure.. Table 2. References such as [23-251 describe this process for many materials. and trace element concentration (or some subset of these conditions). in olivine the most frequently specified constraint is the silica activity aSlo2 (or equivalently the enstatite activity aEn).59. especially at low temperatures.188 ELECTRICAL PROPERTIES OF MINERALS Table 1 . Definitions of defect species (Kroger-Vink) notation. Symbol Main symbol Meaning Element or species of defect constraint means that the temperature. the concentrations of defects (and hence the conductivity) may vary widely. Mg Symbols ... The results are then combined with defect reactions such as (17) and (18) above and defect conservation laws such as conservation of mass. For a three-component system such as (Mg. so that the most general conductivity relation would have the form Oi = 00 exp(-E/kT) (F&g)m fGzn aSi& . Species Normal Lattice Sites Substitutional Defects Lattice Vacancies Interstitial Ions Electronic Defects Defect Dimers Defect Trimers. the conductivity will have the general form Oi = (To exp(-E/kT) (F&g)m fG2n (19) Atomic symbol e (electron) h (hole) V (vacancy) Normal Lattice Site (Atomic symbol) I (Interstitial) x (zero) ’ (negative) . this in which p is also a constant. and conservation of lattice sites to determine the particular defect reaction that controls the concentration of the dominant defect and predicts the correct dependence on other environmental conditions (fez in particular). and more recent references such as [9. -F& )’ e’ h’ V” V. In the presence of even relatively small amounts of impurity ions.. Where available. etc. oxygen fugacity. The general practice has been to try to determine which defect dominates conduction under a given set of conditions by determining conductivity under varying conditions of temperature. This extreme sensitivity of defect concentration to minor and trace element concentrations makes it very difficult to establish absolute values for the conductivities of ‘pure’ minerals. For a four-component system such as olivine (Mg.11. but the parameters in full expressions of the form of equation (20) are still not commonly determined. (F& -V.Fe)O. the oxygen fugacity. (positive) Subscript Site Superscript Charge relative to normal lattice site in which F& is the fraction of Fe on Mg sites and n and m are cons Pants arising from the defect reaction stoichiometries. charge neutrality. the Gibbs phase rule must be satisfied. See [23-251 for general discussions of defect equilibria and [8. .60] describe defect equilibria in some important Earth materials. Note that Fe can be in +2 or +3 valence state.Fe)$iOq an additional constraint must be specified. To properly and completely specify the thermodynamic state of a defectcontaining crystal.58-601 for discussions applied to Earth materials.

Material Form of equation Temperature range K 1% Ai 0 in S/m.30 9.54 10.02 10.40 0. Values surrounded by braces are tits to the 2-term expression (3 = A1 exp (-El/kT) fmnl + A2 exp (-E2/kT) f&! where the top line is Al.68 2. and pressure dependences are referenced to 1 atmosphere.90 0. nl and the bottom line is A2.89 2.03 0.78 0.80 P81 [331 WI 0 tJT RbCl TIC1 373-728 823-1041 793-879 723-1073 625-823 823-1000 823-990 293-700 7.0 0.90 2.91 .1 0.48 5. synthetic AgCl KC1 LiCl NaCl 248-695 773-1001 823-1008 600-723 723-973 873-954 323-730 5.18 8.0 4. Oxygen activity buffer QFM refers to the quartz-fayalite-magnetite assemblage.22 1. single crystal.00 3.12 0.23 0.4 x lOlo Hz AC [461 Halides: Bromides.06 1.15 -1.32 8. T in K -6. El.65 1. WM refers to the wustite-magnetite assemblage. single crystal.70 8.2 1.05 > DC.5 2.2.7 1 1.9 1 1.97 1.9 0. High temperature electrical conductivities of minerals given in the format (T = Al exp (-El/kT) f&l or crT = A1 exp (-El/kT) fozni.48 -7.04 EI eV nl fo2 in atm Comments References Calcite. Pressures are 1 bar total unless otherwise stated.25 5. PC-J* = 4 MPa [361 CJ 120-723 120-723 1 100 .04 7.Oll 1.76 8. E2 and n2. CaC03 773-998 998-1073 1073-1258 1258-1473 II c IC 0.83 1.Table 3. synthetic AgBr KBr NaBr RbBr TlBr Chlorides.15 0.80 8.66 1.84 1.0 8.0 4.79 [281 [331 LW .15 -4.

68 1 6. synthetic KF LiF NaF NaMgFg .71 5.97 2.94 2.68 7.8 3.87 3.551 1473. synthetic KI Nd Oxides: Aluminum oxide.14 1.77 1.08 fmfez- 1W3.48 2.lo4 Pa fo.25 1.81 DC fez . DC fez= 16 Pa fo2= 1 Pa fa=lPa fm = 10m5Pa fo2 = 10m5Pa DC.68 2.26 2.23 7.10-4Pa lo.1 MPa 320 ppm Fe u 1473-1773 1473-1773 2.01 10.83 2.11 3.35 2. CaO single crystal Magnesium oxide. Al203 single crystal (sapphire) (3 973-l 119 993-1115 1123-1265 833-l 173 9.62 5.68 5.11 3.1 Pa { 6.92 I 5. perovskite structure Iodides single crystal.23 1.92 3.51 1 1.60 3.92 fo2 .18 1. 40 ppm Al [611 r54. 1.66 1.01 13. MgO single crystal.42 DC WI u 1573-1998 1573-1873 1898-1998 1573-1873 1898-1998 1000-1400 5.5 10 kHz AC.51 DC P81 u DC [411 u 773-953 573-934 7. continued: Fluorides single crystal.48 7. T in K EI eV “1 fo2 in atm Comments References Halides.10S3.Table 3.1 Pa fo2 . (continued) Material Form of equation Temperature range K log A1 u in S/m.1773 1473-1773 1473-1773 1.23 1.60 8.57 2.84 5.20 2.49 1 2.1 MPa .48 9.51 6.10 .18 6.11 3.96 11.5 2.59 kHz AC [431 Calcium oxide.

Fe-Mg-Al Fe2+Feg 53+Al 1504 Fe2+Fe 1’03+Al 1’04 Fe2+Fe1’53+A1204 Feo.s3+A11504 Feo.00 0.752+Mgo.82 7. CaWO4.1 MPa Magnesiowustite.52 7.Table 3.59 9.74 7.1673 873-1673 873-1673 873.20 0.25 0.74 7.23 0. T in K 8.05 0.1773 4.97 2.28 0.003 [381 .19 co:co.75 0.53+A10.86 6.15 2.16 > 2.48 0.47 4.68 7.52 7.47 0. Mgog3Feg.1673 873.26 0. single crystal 873-1673 973-1273 973-1273 973-1273 8.5 +Mgo.DC fm=QFM fez = ‘QFM.94 3.2g2%xx7sFtz3% Feg 5 +Mgg 5Fez3+04 Feo’7s2+Mgo 25Fez3+04 Feo:2a2+Mgo:7sPeo.1O-3.1673 7.15 0.24 fm .003 [391 873.07 2.39 0.00 Spinel.97 7.18 0.48 0.68 1.40 2.104 Pa fez .84 co:coz = 0.1673 873.0 pH2dpH2=0.! = 0.97 5.1 1173-1573 1173-1573 8.22 0.25 2.36 0.77 5.79 3.30 0. single crystal polycrystalline Scheelite. High temperature electrical conductivities of minerals (continued) Material Form of equation Temperature range K 1% Ai 0 in S/m.003 1391 [631 fo2 = NiINiO in air fm = Ni/NiO DC [471 PHzdpH2 = 1.504 OT 873-1673 873.52 7.16 El eV ni fo2 in atm Comments References Oxides.42 3OO-5x104HzAC.21 7.1673 873-1673 873-1673 6.44 7.25Fe1.30 6.78 co:co2 = 0. continued: 400 ppm Al 1473-1773 1473.41 7.t 70 1273-1773 1273-1773 2.1673 873-1673 873-1673 873-1673 873-1673 873. Fe304 Nickel oxide.39 0. NiO.&+AQ Fe0.16 3.18 0.84 7.1’ to ‘QFM-2 [701 Magnetite.

continued: 873-1673 873-1673 873-1673 873-1673 873-1673 873-1673 873-1673 860.1039 . d DC Fell tST 1173-1573 1173-1573 1173-1573 1173-1573 1173-1573 1000-2025 8.003 [381 0 Strontium oxide.08840.77 7.70 0. (continued) Material Form of equation Temperature range K logA1 0 in S/m. Mewry. polycrystalline. T in K El eV nl fo2 in atm Comments References z F $: ii! F 0 Oxides.967 7.86 0.oi 0 1 VW Feldspar.79 7.168 0.35 0. Albite. fluorite structure Silicates: Cordierite.1173 673-l 173 673-1173 3.59 7.j Albite. Grisons.20 0.Table 3.85.25 2.10kHzACinair 1491 134. ko2Nao 98AlSi308.38 0.18 0.26 0 Constant thermoelectric potential 161 CJ fo2 = 10m5to 16 Pa WI Mgi.85 0.161 0. CaAl&Og. synthetic Wustite.0. polycrystalline Albite.87 Impedance spectroscopy 1. Spinel.48 0.869 5.o8Mno. synthetic (disordered) NaAlSi3 Og Anorthite.1173 473-l 173 673.182 1.025 7.77 7.167 0.23 0.41 0.899 7.69 7.0 co:co2 = 0.86 0.19 0. Fe-Mg-G-Al.1 -0.163 0.1095 x=0.85%1501. France Ndlsi$$.75 0.0706 x=0. France.15 0.04940.351 0 673-l 173 .08 -0.0967 x=0.0706 .0.84 7.0566 .062 8. polycrytalline.0.0817 x=0. synthetic.1050 7.25 0.oiA13. SrG.95Si5.72 0.71 5.0593 fiO.giFe0. Fel-x0 x = 0. 0 473.26 0.

TYBURCZY AND FISLER 193 0 3 .

36 5.87 [481 998-1773 2. 1473-1523 1473-1523 1473-1523 1323-1498 1523-2083 1573-2083 1063-1673 ----- [511 1.od2Si049 [ 1001 orientation [OlO] orientation [OOl] orientation 1373-1773 1373-1773 1373-1773 0.97 2. singlecrystal SanCarlos.77 1 0.40 1. Pyroxene-buffered.18 0.5.18 -0.34 1.45 12.whSi04.Table 3. (continued) Material Form Temperature of range equation K log Ai 0 in S/m. AZ (Fogg) [ 1001orientation SanCarlos.gFeg.31 6.10m6 Pa.10kHzAC co2:co = 10:1.08 > 1.~d%.1 .0 1. (Fogl) 1.30 2.2 0.9Fe0. synthetic(Fol& WSQ. synthetic Co2SiO4 Olivine. polycrystalline. T in K 0.10-“.41 10 kHz AC co2:co =157.55 2.7/l co2:co =157. natural.olivine. SanCarlos olivine O.18 1.75 0.65 4.l.75 1. 1681 [681 -0.77 Forsterite.18 (Mgo.10kHzAC fo2 .10kHzAC fo2 .86 1.37 4.60 9.10kHzAC co2:co = 30:1.66 6.l.63 1.10 kHz AC co2:co = 10:1 181 -0. hSi% 1 [ 1001orientation SanCarlos.Mi041 1373-1473 1373-1473 0. AZ (Fo9()) (Mgo.9@o. AZ (Fo91) (Mgo. O.11 3. W-M buffer Isotropic parametricmodel for self-buffered case.63 0.17 0 O. O.77 2.03 1 22.25 PI .99 1.5.10-“. continued: Olivine.17 4.lC@Pa. [ lOO] orientation [OlO] orientation [OOl] orientation Co.52 2.36 2.l.7/l (332 iP Orientationally-averaged grain interior conductivity from impedance spectroscopyon polycrystalline olivine.49 El eV “1 fo2 in atm Comments References Silicates.l.30 1561 (Mgo.25 0. 0.

I mineral fabric Synthetic II mineralfabric I mineralfabric cfr 473-773 473-773 473-773 4.l.30 5. amorphousSiO2 Natural.02 1.64 1.17 1.05 -0.89 0.0733:1 CO2:H2 = 0. UK 1273-1473 1273-1473 1273-1473 1.Table 3.72:1 CO2:H2 = 29.38 8.5691 CO2:H2 = 0.20 -0.94 5.67 0. Impedance spectroscopy 1711 Measurements madeparallel and perpendicular mineral to fabric fo2 = 104 tolOmg Pa at 1273K.84 1.43 0.11 0.67 1.NY NagCaggMggd.72:1 [41 [OlO] orientation . and 10e3 1(r7 to Pa at 1473K 1151 Pyroxene.8gfeO.88 1.00:1 C02:H2 = 29.643:1 CO2:H2 = 3. Australia.0420:1 CO2:H2 = 29.15 2. and lOa to 1e7 Pa at 1473K Cl51 Mgo.15 0 1273-1473 1273-1473 -0.0733:1 C02:H2 = 0.92 0.70 3.36 2.26 1.30 1.36 1.03 Air.10kHzAC co2:co = lO:l.North Wales.25 0.13 1592Hz AC CO2:H2 = 99.90 Isotropic parametricmodel for self-bufferedcase.42 1.01 1. T in K El eV nl fo2 in atm Comments References Silicates.15 1.643:1 C02:H2 = 0.12 -0.32 0.43 1.64 2.569:1 CO2:H2 = 0.03 -0.54 1.02 fo2 = 104 to ltJg Pa at 1273K.Brazil Na3Cag~g8sFe12~2sizooO6oo [ 1001 orientation [OlO] orientation Ortbopyroxene.58 2.72:1 CO2:H2 = 3. continued: (T 1373-1773 1.19 1.02 2.20 0. O.91 1. singlecrystal Diopside.60 1.92 1.iisi% (En891 [ 1001 orientation 0 1190-1282 1136-1298 1163-1282 1031-1099 1190-1282 1020-1163 1111-1235 1010-1099 12351316 1190-1282 1020-l 163 0.25 1.23 0.e3A12Si2000600 [ lOO]orientation cf [OIO] orientation [OOl] orientation Diopside. (continued) Material Form Temperature of range equation K logA1 0 in S/m. 1561 Opal.18 -0.

5Ai7.57 3.569: 1 0.87 1.4Sii95.4 8.643: 1 CO2:H2 = 0. continued: WI orientation Orthopyroxene.4 Cro.39 0.82 1.71 1.6Mgi72.25 1.oWh (Ew) [OlO] orientation 0 1176-1282 1176-1282 1149-1282 1136-1282 1190-1282 1111-1282 2.9Fe34.7Mg160. T in K 0.1473 1098-1449 1111-1449 0.67 1. z-cut Synthetic.569: 1 0.36 2. z-cut 0 973.73 EI eV nl fo2 in atm Comments References s 9 $: ii! F 1087-1282 1149-1282 1042-l 124 1136-1282 1136-1282 1020-l 136 1.8Mg16l. z-cut Synthetic.2Mno. Papua. Cag.50 1.62 Orthopyroxene.3 8.0 0.36 1. Grade EG.8 8.99 1.72 3.0733: 1 CO2 Air 1kHzAC co2:co = 1999: 1 Mean of 3 orientations: [41 1141 WI.2 Cr0sh9.12 1.40 1.76 1.qFe31.24 1.15 CO2:H2 CO2:H2 C02:H2 CO2:H2 Air Air = = = = 29.80 1.Table 3. Grade S4.569: 1 CO2:H2 = 0. z-cut Synthetic.20 1. WOI.28 1.93Fe0. SiO2.5~5.72: 1 0.0%0 Quartz.6%00 Ca0.76 1. single crystal Natural. New Guinea Mgo.07 2.03 1.4A12.8 Cri.75 1. impedance spectroscopy 200-300 x 10s6Al/Si 200 x 10q6Al&i 15 x 10e6Al&i 1 x low6 Al/Si [ 161 .0733: 1 Silicates.11 3.8Mno. Arkansas. (continued) Material Form of equation Temperature range K 1% Ai 0 in S/m.13 1.33 Air.72: 1 C02:H2 = 3.4Fe2A.20 1592 Hz AC CO2:H2 = 29. [loo1 0T 370-454 450-700 450-700 450-700 6. Grade PQ.18 1.31 2.4%00 Ca0.66 1.21 2.2Mno.2Sii97.

33 1.Fe)O Mgo.Table 4.92160 90-250 Piston-cylinder [621 Fe0.0955 0.45 0. external heating Diamond cell.58 0 0.66 I x IO. exp (-E/kT).g9gsG go-250 Piston-cylinder [621 .0925 0.0960 0.0945 0.Mg)2SiO4 olivine.oQ Mgo.220 Mgo. High pressureelectrical conductivity of minerals given in the form o = o. Valid in the composition range 0.45 0.0945 0.37 0.75 1. Values given for the constants in the expression cYT= A 1 xn exp(-EikT) in which x is mole fraction Fe.0918 0.098 1 0. Material Temperature range K 400-700 333-2000 90-250 Pressure cro GPa 15 30 32 0 0.0980 0.00 1.29 0.94220 1621 FeO.27 0.1573 K at 1 bar total pressure.0905 0. Iron content dependence of the electrical conductivity of single crystal (Fe.0993 0. laser heating 1 kHz AC Piston-cylinder 1321 [29] Remarks References Magnesiowustite (wustite) (Mg.92 [ 121.lS 1.33 1. E Al Fx in mole S/m fraction Fe) eV ~()6.73 1.0978 0.58 0 0.0986 0.26 0.mO FeO.36 1.0970 0.9lFe0.0897 Diamond cell.n@o.102 0. Measurements made in the [ 1001direction at temperatures between 1423 .35 f 0.54ko.38 0.0995 0.0960 0.02 1. Oxygen fugacity is that of a CO2:CO 5: 1 mixture.04 Table 5.zFo.01 1.0982 0.81 f0.79 1.55 S/m E eV 0.0980 0.02 1.

guard ring MgO buffer MgO buffer QFM buffer QFM buffer IW buffer QFM buffer IW buffer QM buffer QI buffer Piston-cylinder.0 5.85 Pistoncylinder.0 2.04 0.22 0. 2 electrode.21 0.0 1.0 1.777 0.0 5.0 1.21x 102 1.2 x 3.0 1.0 1. range GPa S/m K 293-623 623-923 973-1473 293-623 623-923 973-1473 293-623 623-923 973-1473 2.984 2. 2 electrode.0 3.0 5.64 x 106 1.43 x 101 6.polycrystalline Fo1t)oForsterite 795-1223 1223-1348 847-1331 875-1160 800-1212 823-1223 866-1212 636-1217 574-1091 1.52 0.83 DC.582 0.479 0.4) Li Temperature Pressure o.0 1.976 1. (Fo92) Sancub & (FOg1.683 0.5 3.00 0.0 2. Germany.0 2.52 . NiiNiO buffer.5 x 8.70 0. guard ring naturalparagenesis QFM buffer IW buffer 1592Hz AC. PQ38.5 5.0 5.polj&y&lline Dreiser Weiher.33 0.0 1.38 0.14 x lo1 8.6 kHz AC guard ring QFM buffer QFI buffer [@I 615-1273 1.Al203 insulator [71 [511 [311 [71 Olivine. (Fo93. synthetic.FehSiOp natural.6 kHz AC.33 6. Germany.0 1. (continued) Material Olivine.42 0.5 x 2.71 2. (Mg. Australia.92x 101 9.54 7.37 0.18x lo2 0.0 1.383 0.7 x 2. 1.96 0. guard ring [501 Remarks References P E ii cl F 3 $ E A E % 3 2 !i DreiserWeiher.5 3.75 x lo1 0.523 Fotio Fog0 Wo WI (Falt-x-11 FaWh FoeFayalite Piston-cylinder.6 x E eV 10-l 101 1O-2 103 10-2 10-l lo2 0.8) 900-1093 915-1236 945-1189 953-1429 953-1429 923-1223 1.5 3.0 x 4.622 0.0 1.8 x 1.6 kHz AC.17 1.0 1.1.77 2.0 1.953 0.69 5.Table5.0 5.04 1.6) Mt.461 0.0 1.941 0.17 7.0 1.41 2. Leura.76 1.1.

1 536842 Bamle.42 0.Impedance spectroscopy.56 2.0 2.10 1.89Fq.76 x lo7 6.0 1. Vo = -.05 0.5 2.0 1.17x 102 1. laser heating [301 1531 Pyroxene.w Diamond cell.41x 102 1.24 1.78 [51 .89FeO.42 0.natural polycrystalline Dreiser Weiher.0 2.ERGAN buffered [691 Remarks References a-Mg2GeO4 Perovskite(silicate) Mgo.5 x 101 E eV 0.0 2.80 0.0 x 100 7.79x 103 9.Table5.0 2. guard ring Quartz buffered Quartz buffered For&rite buffered Forsteritebuffered Si02/CCO-buffered SiO2/CCO buffered SiO2/CCO buffered SiO2/CCO buffered SiO2/CCO buffered QFsI buffered QFsM buffer Piston-cylinder.59 1.0 2.73 x 101 1.18 0.i SiO3 i Mg0. 1.13 x 102 1.15X lo2 1.92 x lo6 7.98 1.97 0.51 1.0 1.0 2.74x 102 1.70 2.26 cm3/mole Diamond cell.gFo Wo2.30 x lo2 1.37 0.0 x 100 2. Ni/NiO buffer Piston-cylinder.8 x lo1 5.48 eV. continued: Fog Fayalite Fog Fayalite Ni2SiO4 Temperature Pressure cr.35 x 100 6.05 2.0 0.40 1. 2 electrode.42 0.0 1.08 0. 1. 11 SiOg i4.13 1.0 2. synthetic.2 40 46 55 5.6 kHz AC guard-ring Natural paragenesis QFM buffer Argon gasmedium vessel.0 2. 1.08 5.49 1.37 Piston-cylinder.0 7.24 0.12x 102 1.94 x 108 6.78x lo3 1. polycrystalline.31 x lo2 1.95 x 102 6.55 0.Fe)SiO3 Enlm (Enstatite) 550-1000 550-1000 550-1000 550-1000 550-1050 %oWo 500-1020 EwoWo 510-1020 End%o 510-1010 En’LOFs8o Fs1~ (Ferrosilite) 520-950 Fs1~ (Ferrosilite) 500-900 Fs1~ (Ferrosilite) 500-970 Qrthopyroxene.24 buffered MgSi03 (SiO2-sat) buffered MgSiO3 (stoichiometric) buffered MgO DC.00 1. CO2:CO =ll:l 171 1. (continued) Material Olivine.5 0.6 kHz AC guard ring.51 0.6 kHz AC. synthetic.0 1. Norway En86 1070-1323 1323-1673 1.pyrophyllite insulator [II Piston-cylinder. range K GPa S/m 799-1500 9151236 940-1283 423-l 173 773-l 100 1loo-1273 1323-1518 1568-1673 293-673 293-673 295-3200 295-3200 1.0 3.25x lo2 1.08 4.o lo.10 x 101 4.82 3. Orthoyroxene. Germany 544-831 En87.843 1.48 0.0 2.05 1.1592Hz AC. polycrystalline(Mg.0 1.38 x 10-l 7.71 2. external heating 1571 U = 0.

12 x 1O-4 1.27]. + bx)P].125 0. Crystallographic Orientation lc’ 293 K l/K’ (&cXlT) K-l (loco (010) (001) olivine spine1 . natural. polycrystalline Dreiser Weiher.69 f 0. 1. in S/m m (x in mole % Fe) 0.0 6. P is pressure in GPa [26. Germany i 640847 1.24 x lo2 1. guard ring Piston-cylinder Impedance spectroscopy ERGAN buffered [71 % E z F cd Spinel.0 1.28 Piston-cylinder. continued: Clinopyroxene.2 x 10-l 6.24 f 0.6 kHz AC. Values are given for the constants in the expression axp = rso exp[mx + (B.14x lOti 1. Electrical conductivity of (Fe. where x is mole per cent Fe.20 x 104 .97 f 0.Table 5.7 1 f 0.22&0.24 x 10-l 0. 1. guard ring. Valid in the range 50 5 x 5 100.I 4.6 kHz AC.20 x 1O-4 - Table 7. Mineral log (z. (x in mole % Fe GPa.7 Clinopyroxene.Mg)zSiOq olivine and spine1 (y-form) at room temperature (295 K) and pressures to 20 GPa. synthetic.0651x lo1.21 7.43 hm7Fv.05 7.153 Bo GPa-1 b. ?I-MmGeQ 1122-1518 2.98 WI For oxygenbuffer assemblages: = ferrosilite Fs F = fayalite I=iron M = magnetite Q=qmrtz W = wtistite Table 6. CaMgSi206 746-1064 1. polycrystalline Diopside.24 x lo5 1.21 1.77 2. o. Real relative dielectric permittivity K’ (1 MHz) and temperature derivatives for for&rite Mg2SiO4 over the range 293 K to 1273 K [3].10.6Wo3o. natural paragenesis [71 $ 9 E Piston-cylinder.11 f 0. (continued) Material Temperature range K Pressure cro GPa S/m E eV Remarks References Pyroxene.42 -5.24 7.

96 0.77 0.59 0.12 1.92 0.5 12. Temperature.4.71 0. Electrical conductivity of naturally occurring silicate melts at elevated pressures over the temperature range 1200-14OO“C.15) Tholeiite (PG.8 .71 0.49 1.8 17 .65 0.1 5.5 0 .17 1.16) Quartz tholeiite (HT.05 1.85 1.36 2.95 1.19 2.95 0.23 1. ‘C 1350 1400 1.91 0.81 0.66 0.5 .83 0.30 1.36 0.53 0.25.69 0.95 0.02 0.97 0.62 0.76 0.93 0.35 1.72 0.26 1.25.96 0.53 1450 1. Melt Type P range kb 0 .48 0.5 0 .03 0.73 0.56 0.11 1.128) Rhyodacite (HR.21 1.67 0.16 0. .53 AV cm B/mol 7.87 0.75 0.71 0.1 Yellowstone Rhyolite Obsidian.82 0.41 0.02 0.62 Melt type Nephelinite (C.42 0.3kT 16%651.16 1.47 1300 1.25 1.78 0.78 1.71 1550 1.64 0.1) Hawaiite (C-42) Alkali olivine basalt (C-222) Alkali olivine basalt (C-70) Alkali olivine basalt (BCR-2) Mugearite (C-2 10) Andesite (HA) Andesite (VC-4W) Latite (V-3 1) Trachyte (C.07 0.67 1500 1.41 042 0.67].27 1.77 0.00 0.82 5.195) Basanite (C-90) Tholeiitic olivine basalt (C-50) Olivine tholeiite (C-2 14) Tholeiite (C-8) Tholeiite (70.43 1. YRO Hawaiian Rhyodacite.58 0. Data from [45.9 3.3 17.TYBURCZY AND FISLER 201 Table 8.88 1.06 0.75 0.3 4.75 3.12.77 2.06 0.92 0.15 1.48 1.07 1.48 0.57 0.59 0.25.30 0.00 3.48 0.82 0.64 0.74 0.1 Crater lake Andesite.2 11.81 0.52 0.85 0.84 0. VC-4W Hawaiin Tholeiite .48 0.20 1. Electrical conductivity of anhydrous naturally-occurring silicate melts at temperatures between 1200 and 1550°C. where Q is in S/m.81 0.17 1.05 5.20 1.73 0.79 0.1) Rhyolite obsidian (YRO) 1200 0.58 1.65. HR.50 0.46 0.88 0. in S/m 2.56 0.15 1.76 0.66 0.15 1.5 1% Qo b.27 1.3 8.46 0.22 1.25 1.5 0 .9 3.93 0.41 1250 0.36 1.40 0.64.33 Ea eV 0.65 0.27 1.59 0.49 0.8.8 .(Ea + PAVo)/2.04 0.76 0.8.04 0.60 0.45 1.39 0.00 1.60 0.58 0.16 0.5 12.55 0. parameters for tits to the equation log 0 = log o.11 1.34 0.01 1.6 -0.69 0.91 0.00 0.90 1. Expressed as log <r.74 Table 9.00 0.39 0.91 0.76 1.27 1.25.71 0.83 1.50 0.86 0.

MPa) Figure 1. in MPa Figure 2.I -4 . . for Fog0 olivine at 1473 K [l 11. Calculated point defect model. dashed lines are ionic conductivity [54. Vertical dotted lines representstability rangeof olivine. plotted as log of the defect concentration versus log of oxygen fugacity. Log conductivity versus log fm for MgO containing 40 ppm Al. MgO: 40 ppm Al 1300°C .A - I -??O I -16 -12 -8 I 1 ... I I I -I 0 Log(fO. Solid lines are total conductivity..55]. PO.- . & -1300% -7 -1 1 Log PO.

.. . ..5 -5 -5. . Figure 3.5 San Carlos Olivine T= 1473 K -3 Electrical Conductivity -3.6 6. . .“~l’~~l~‘~l~ I’_ : MgO: 400 ppm Al f 02= 1 Om3-1Ow4 Pa II I1l. for MgO containing 400 ppm Al. bar conductivity.. . . Log conductivity versus T-1 for f& . . . . . I I I I I I I I I I I. .l. .5 -4 -4. . d/ .l.5 -4 . l . . . .. . . .l. e/ .- 5. . - -2. . .. # .8 6 6. ..8 1 d/T (K-l) Solid line is total (dashed line) [54.I. . .. Log conductivity versus log fo2 for San Carlos olivine @go) illustrating that total conductivity is given by the sum of the two mechanisms (dashed lines) with differing oxygen fugacity dependences [68]. . ( l . l .-2 -2.l.2 18 ~‘l~~~l~“. . .... .. .5 -3 -3. . . / . / .4 6.5 -8 -7 -6 -5 -4 -3 -2 -1 0 Log fo2 (Pa) Figure 4. I . . . which is the sum of ionic conductivity (dashed-dot line) and the electronic conductivity 551. 1 -4.2 6. l ( .4 5. .10m3to 10m4..6 5. ( ’ >: .. .5 -6 5.

691.5 2 2. 331. Solid buffer assemblages controlling fo2 are given in parentheses.5 3 3.5 103/T (K-l) Figure 6. . Log conductivity versus T-l at 1 GPa for olivines of different compositions. Conductivities for KC1 and RbCl coincide. The low temperature conductivity of NaCl and NaBr is impurity controlled. San Carlos olivine at 1 bar (self-buffered at QFM) is shown for comparison. Data are from [7. 2 3 . Data from [28. [68]. dashed lines at IW. 8 ’ 8 -5 -6 6 8 10 12 14 16 18 104/T (K-l) Figure 5. 8 ’ ’ . Log conductivity versus T1 for some halides.5 s -4 -6 -12 0. solid lines are QFM.5 1 1.> .1 Olivine I @ 8 ‘I’ Electrical 8 1 I’ Conductivity r ’ .

Fe 0.. Lines labeled by formula only are synthetic samples. Log conductivity versus T1 for some binary oxides. 351.) : -8 6 I I I I I I I I 7 8 9 10 11 12 13 14 15 104/T (K-l) Figure 7. Data from [6.61. All lines refer to intrinsic regime.9s0 bMgo. those labeled ‘nat’ are natural samples.-’ -2 -3 -4 -5 I I : Feldspar and Feldspathoid : Electrical Conductivity : NaAlSiO I I I I : NaAISi3G8 : NaAISi308 (nat.70].’ 11 ’ 8 6 4 2 0 -2 -4 -6 -8 5 : Conductivity 1 1 of Some Binary Oxides Feo. 10 I’ 1 I ’ I ’ * @ r II 8 8 8 1. parentheses where appropriate.17 0 (QFW 6 7 8 9 10 11 12 104/T (K-l) Oxygen buffers are shown in Figure 8. Data from [34. Log conductivity versus T-l for feldspars and feldpathoids. .63.Adularia (nat.) CaAlzSiz08 : . 8 8 * II 2 I’.

377-384. The electrical conductivity of pyroxene. Electrical conduction and polaron mobility in Fe-bearing olivine.206 ELECTRICAL PROPERTIES OF MINERALS Saturation Line 1O-6 I I 0. 65.1976. Duba. 81. REFERENCES 1. 96. Shankland and A. Eifel (Germany) under defined thermodynamic activities as a function of temperature and pressure. 97. C. 4.. Hirsch. Shankland. and T. . Shankland and A. E.199O. 1993. J. The responsibility for errors rests with the authors. Mason. Journal of Geophysical Research. Shankland. N. A. Electrical conduction of Co. Physics of the Earth Interiors.5 I I I I I I I I I I I I 1. S. T. and diopside from Dreiser Weiher. Cemic.. Shankland. Journal of Geophysical Research. and T.. J. Acknowledgements. Ringwood. T. and T. M.Proceedings of the 7th Lunar Science Conference. H. L. Will and L.. Journal of Geology. J. 2. G. L. Journal of Geophysical Research. and T. Gartstein. 6.. M. 17. C. C-24 . Demonstration of the electrical conductivity jump produced by the olivine-spine1 transition. M. E. 443449. Journal of the American Ceramic Society.245254. 158-766.1973. L. 11. Geophysical Journal International. Hirsch. Hirsch. 1981. High pressure electrical conductivity of supercritical H20 versus density [13].5 Density (g cm-a) Figure 9.and Al Duba for helpful reviews. Cygan. T.36-44. Hirsch. Lasaga. 0. M. 1991. 385-403. Jeff Roberts. 10. Heard and R. 70. Akimoto. and the role of Fe impurities. A. This work was supportedby the National ScienceFoundation. and A. Duba. E. and Planetary Determination of defect equilibria in minerals. Schock. J.1992. S. The electrical conductivity of an isotropic olivine mantle. 5. American Mineralogist.SiO. Duba.21-35. 114.0 1. 187-190. 1991. J. 7. 3.. G. Boland and A. We thank Lee Hirsch. %. Geophysical Journal International. N. 9. 25. Fujisawa. 1986. R. Electrical conductivity measurements on synthetic olivines and on olivine. Reanalysis of wustite electrical properties. 3404. Hirsch. and H.C-26. G. Quantitative olivine point defect chemical model: Insights on electric1 conduction. 1965. L. 71. Constable. Equilibrium point defect concentrations in MgO: Understanding the mechanisms of conduction and diffusion and the role of Fe impurities. orthopyroxene to 1400°C and the resulting selenotherm. Duba. Electrical conductivity of 1982. 114. diffusion. 8. Dielectric and polarization behavior of forsterite at elevated temperatures.. M. enstatite. 727-735. 3397 3173-3181. L. Tom Shankland. Journal of Geophysical Research. 12. 1993. Hinze. J. Physics and Chemistry of Minerals.

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High pressure electrical conductivity in naturally occurring silicate liquids. 45. Effect of enstatiteactivity and oxygen partial pressure on the point-defect chemistry of olivine. 47596. E.. H. Journal of Geophysical Research. Dielectric dispersion and its temperature variation in calcite single crystals. OR. 98. in High Pressure Research. 94. The electrical conductivity of some samples of natural olivine at high temperatures and pressures. Physics of the Earth and Planetary Interiors. J. Smyth. Poirier. 37. Shankland. 56. Nature. Applications in Geophysics. Schober. Geophysical Journal International. Electrical conductivity of magmatic liquids: Effects of temperature. Rai. 478.. D. B. A.. M. D. A. Y. G. N. H. Journal of Geophysical Research. pp. 1980. Journal of Applied Physics. Physics.. 4.. N.1983. 16. 1975. G. American Mineralogist. Sempolinski. 74.- 61. Z. D. J. %. 1978. edited by 675.Cambridge. Journal of the American Ceramic Society. R. 1977. Oregon and Mineral Department Industries. edited by W.Journal of the American Ceramic Society. Kingery and H. R. J. Electrical conductivity of basalts to 1550°C. American Geophysical Union. V. 17. Earth and Planetary Science Letters. Schock.. Electrical conductivity measurements on synthetic pyroxenes MgSiO. E. and J.199l. Duba. V. Cemic. Zeitschrift fur Geophysik. 669.6462. W. MA. A. L. Tybumzy. Voigt. Heard and H. OH. 66. F. pp. Electronic conductivity of single crystalline magnesium oxide. G. Journal of Geophysical Research. A. Shankland. 47. Roberts. D. XII. Rigdon.283-292. Wood. 63. 344. Tyburczy. 189197. 1966. A. and J. Nell. 69. 669- 2413~2430. 64. 78-87.-P. R... 46. 821-825. L.Stuttgart. S. homogeneousolivine in the temperature range 1200-15OO”C.300-306. 1989. Academic Press..208 ELECTRICAL PROPERTIES OF MINERALS and polycrystalline alumina at high temperatures. Physics of the Earth and Planetary Interiors. L.197l. R. and H. and R. 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(qs) q1=qv+ $rls (3) A comparison of longitudinal and shear viscosities illustrates that volume and shear viscosities are subequal at very low strains [9] (see Figure 1). Figure 2 illustrates these components for a creep experiment. Deformation experiments performed in the viscoelastic region contain three distinct time-resolved components of deformation. DEFINITIONS A Newtonian fluid is one for which a linear relation exists between stress and the spatial variation of velocity. the elastic modulus of a Hookean elastic material is defined as the ratio of stress to strain (2) As is the case for elastic moduli. for an isotropic medium like a silicate melt. It can be mechanically represented as a series combination of viscous dashpot and elastic spring (a Maxwell element. This relaxation time is a convenient approximation to the timescale of deformation where the transition from purely viscous behavior to purely elastic behavior occurs.a region of viscoelasticity. Structural relaxation in silicate melts is but one example of a relaxation mode. The purely viscous response of a silicate melt is termed “liquid” behavior whereas the purely elastic response is termed “glassy” behavior. Viscous flow is the delayed non-recoverable component. Bayerisches Geoint. speak of two components of viscosity. University Postfach 101251. The combination of volume and shear viscosity yields a longitudinal viscosity. several additional mechanisms of deformation are contributed at distinct timescales of deformation via additional relaxation modes within and between the added 209 Union. Dingwell. . The viscosity of a Newtonian material is defined as the ratio of stress to strain rate viscosity to elastic modulus yields a quantity in units of time. delayed recoverable and delayed non-recoverable. the term anelasticity refers to the instantaneous plus the delayed recoverable deformation and the entire deformation behavior falls under the heading of viscoelasticity [26]. The term silicate melt is used to describe molten silicates quite generally. Germany Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Bayreuth. Donald B. For more complex materials such as crystal suspensions. see Figure 3). regardless of their rheology. Even for the simple case of a Maxwell body. is the Maxwell relaxation time [24]. The ratio of Newtonian D. foams and partial melts. Dingwell 1. B. instantaneous recoverable. a volume (qv) and a shear (qs) component. D 8580 Bayreuth.. we can. the change from liquid to glassy behavior does not occur as a sharp transition but rather describes a region of mixed liquid-like and solid-like behavior . This ratio T=rl M (4) In contrast.Viscosity and Anelasticity of Melts.

beam bending or fiber elongation).g. involving additional viscoelastic elements in the linear regime and non-linear effects as well. the delayedrecoverablestrain. Stress relaxation involves the recording of stress versus time as the stress field decays to zero after the application of a step function of strain. ultrasonic wave attenuation).g.g.g. The instantaneous recoverableelastic strain. distinguish between those in which the strain rate is controlled and the resultant stress is measured (e. The characteristic strain rate of the experiment is easily defined in most rheological experiments.. Ultrasonic measurements are performed on time scales of l-50 ns.. torsion. we can distinguish between time domain experiments where a stress is applied and the time variant relaxation of the system to the new equilibrium is measured (e.210 VISCOSITY AND ANELASTICITY OF MELTS LOG . . CLASSES OF EXPERIMENTS In principle.. concentric cylinder) from those which involve a combination of shear and volume (compressive or dilational) stress (e.g. creep experiments) and frequency domain experiments where sinusoidal variations of the stress field.g. Such measurements probe the response of the system to stresses without macroscopic rearrangements of the phases. We can. fiber elongation).01-150 s and fiber elongation 2.e. We can also separate those methods that involve only shear stresses (e. Steady-state strain experiments record the equilibrium stress sustained by the liquid due to the constant strain rate being applied to the sample. The relationship betweenlongitudinal and shear viscosities in silicate melts. for example. Redrawn from Dingwell and Webb (1989). Finally. several experimental timescales are compared with structural relaxation times of silicate melts. at lower rates of deformation). For example. As a consequence of the multiphase nature of flowing magma the accompanying mechanical models become more complex.). In contrast nonlinear measurements can deal with the redistribution of phases during macroscopic flow.O SHEAR VISCOSITY Figure 1. These relaxation modes involve chemical and textural equilibria and thus occur at increasingly longer timescales (i. etc. stress relaxation versus steady-state flow). t=O.g. is the experimental deformation rate or its inverse. Inherent in the experimental study of magma rheology then. For any given geometry that employs controlled strain we in DELAYED RECOVERABLE STRAIN INSTANTANEOUS ELASTIC STRAIN t=o TIME Figure 2. the experimental timescale.. are applied and the magnitude and phase shift of strain is measured (e. The solid line representsthe correlation predicted from the assumptionthat volume and shearviscositiesare equal. phases (e.. Implicit in considerations of rheological measurements is the ratio of deformation rate to the relaxation rate of structural components in the material.g. any experiment that records strain as a function of time and applied stress can be used to obtain viscosity. small in magnitude but up to very high frequencies (from mHz to MHz)... crystal-crystal interactions. can further distinguish between the application of a step function of strain and the continuous application of strain (e. concentric cylinder) and those in which the stress is controlled and the resultant strain rate is measured (e. in Figure 4. Viscosity experiments can be subdivided in several ways.. The dashedline is the best lit to the data and lies within la of the theoreticalline.. matrix compaction. We can distinguish between experiments performed at low total strains such that the perturbations from equilibrium are small and in the linear regime of stress-strain relations. bubble deformation. It is this experimental timescale which must most closely match the natural process in order to make secure applications of the rheological results. and the delayednon-recoverable viscous flow occurring in a linear viscoelastic material upon applicationof a step function in stressat time. forced oscillation techniques in the range of 0.

3 mm and lengths lo-18 mm are commonly used.DINGWBLL 211 . imposed on an annulus of liquid filling the gap between an inner cylinder (or spindle) and the outer cylinder (or cup) which usually takes the form of a cylindrical crucible. vtscostty. Shear viscosities in the range 109-1014 Pa s can be ‘determined using fiber elongation techniques (see Figure 5). Equation 6 is known as Trouton’s rule. Each structural or physical component of the system relaxes as a distinct relaxation mode at a distinct timescale of frequency which is a function of pressure and temperature. Frequency-dependent or nonNewtonian effects are seen in frequency domain rheological experiments when the measurement timescale approaches a relaxation mode timescale. GEOMETRIES (5) [ 11. The shear stress sustained in the liquid is usually recorded as the torque exerted by the liquid on the inner cylinder. Another form of the Couette viscometer is the cone-and-plate geometry. The subscripts“0” and “00” indicate zero frequency and infinite frequency values. A second silica glass rod holds the lower bead of the fiber in tension. . The concentric cylinder method is commonly used for viscosity measurements in the range of loo-lo5 Pa s. Viscometers based on the cone-and-plate geometry have been used in both steady state (as above) and pulse strain modes.gKo. Q.Go 0 LOG Wl 3 Figure 3. This avoids the need to pour or melt the silicate material into the cylinder and to immerse the spindle into the liquid at high temperature. The strain rate is [ 11. The strain-rate range is machine limited to 10m7-10m4s. by from lo2 to lo6 s.) and moduli (M. q. This method has also been used in the investigation of the viscoelastic behavior of silicate melts at/near the glass transition [41]. approaches an infinite value with increasing time and Equation 5 becomes The most widely used example of controlled strain rate and measured stress is the rotational (Couette) method (see Figure 5). volume and shearviscosities (rt 1. K. G) of a linear viscoelastic melt with a relaxation time r plotted as a function of ex where 61is the angular frequency of the applied sinusoidal stress. The volume viscosity of a melt.e. therefore. Ryan and Blevins [34] provide a description of the physics of Couette viscometry. a Maxwell element).. The strain rate is delivered to the liquid by rotating either the inner or outer cylinder. The cone-and-plate method finds application at lower temperatures and higher viscosities than the concentric cylinder method. The shearrelaxation time z = n/G is for the mechanical model of a spring and dash-pot in series (i. This involves determining the rate at which an . The geometry of the cone-and-plate viscometer allows the preparation of starting materials by pre-machining to the final form. Calculated frequency dependent behavior of longitudinal. volume strain must be limited in magnitude [25]. 3. 15. 171 Although infinite shear strains are possible in a melt. In a vertically mounted silica glass dilatometer the silica glass holder of the dilatometer supports the beaded glass fiber in a fork.1-0. In this geometry the observed . Glass fibers with a diameter 0. is the elongational viscosity and is related to the shear viscosity. nv. Absolute shear viscosities in the range lo9 . A tensile stress (-lo7 Pa) is applied to the melt fiber and the viscosity is determined as the ratio of the applied stress to the observed strain-rate.IO1 1Pa s can be determined using micropenetration techniques (see Figure 5). 251 for times greater than the relaxation time of the melt. ?~etcn~.

the applied force. (9) Figure 4. a(w). and time. m (kg). t (s) [12. the volume.l log10 Pa s) is obtained by using a silica glass sample holder and pushrod for temperatures under 1000°C. where the amplitude of the wave is A(w. cylindrical or spherical in shape [6]. The indenter may be conical. Riebling [30] has described a counterbalanced sphere viscometer which he subsequently used in viscosity determinations in the B203SiO2 [31] and Na20-Al203-Si02 [32] systems.lo8 Pa s [12. The liquid-glass transition as a function of temperature plotted for several silicate melts calculated from Equation 4 together with the timescales on which a range of experimental measurements are performed. of a shear or longitudinal wave travelling through the melt. the height. For the case in which the surface area between the cylinder and the plate increases with deformation and the cylinder does not bulge the viscosity is qs (Pa s) = m ’ h2 3V 6h/6t . This is the “perfect slip” condition. V (m3) of the material. g (m2/s). The shear and longitudinal viscosities of a melt can be determined from the velocity. This is the “no-slip” condition. High accuracy (+O.10” Pa s [2] can be determined. (t=O and 1 =0 upon application of the force). indenter under a fixed load moves into the melt surface. P (N). indent distance 1 (m) and time. Very high pressure measurements of viscosity have been made [19] by imaging the falling sphere in real time using a synchrotron radiation source and a MAX 80 superpress. t (s). and attenuation. h (m) of the cylinder. Falling sphere viscometry has been employed at 1 atm and at high pressures [13. c(w). Errors in density contrast can be reduced below the uncertainties inherent in the other variables affecting viscosity determination. This method extends the lower limit of measurable viscosity using the falling sphere method at high pressure to 10m3Pa s. r (m). 161 for the case in which the surface area of contact between the melt and the parallel plates remains constant and the cylinder bulges with increasing deformation.e t (7) [28. 441 for the radius of the sphere. 34.t) = A0 expQX expfw(f-x’c (10) . The falling sphere method may be used for the simultaneous determination of density and viscosity. the acceleration due to gravity. Redrawn from Dingwell ‘and Webb (1989). 361. 161 and lo7 . Maximizing the density contrast reduces errors associated with the estimation of melt density. . The relaxation times relating to the various experimental techniques are discussed in Dingwell and Webb (1989). For the case in which a spherical indenter is used [8] the absolute shear viscosity is determined from qs (Pa s) = “. Alternatively the falling sphere method may be used with input values of density provided the density contrast between melt and sphere is relativeIy Iarge. The parallel plate method involves the uniaxial deformation of a cylinder of melt at either constant strain rate [ 181or constant load [40].:zJf. Absolute viscosities in the range lo4 . The shear viscosity of large cylinders of melt or partially molten material can be determined by deforming the cylinder between parallel plates moving perpendicular to their planes.212 VISCOSITY AND ANELASTICITY OF MELTS Specimen deformation rates are measured with a linear voltage displacement transducer. The counterbalanced sphere and falling sphere viscometers (see Figure 5) are based on Stokes law. For a cylindrical specimen of any thickness the shear viscosity can be determined by qs(Pas>= 2rtmgh5 3V Fh/Gt (27r h3 + V) (8) for the applied mass.

i.oq = logloqo + 2.’ Figure 5. synthetic silicate melts [33]) where the experimental conditions were approaching the relaxation frequency of the melt. With the possible exception of SiO2 however. In studies where the frequency of the applied signal has been greater than that of the relaxation frequency of the melt shear wave propagation has been observed (BzO. :i (4 P m II^’ -. In cases (basalt melts [22]. (13) Angel1 [I] describes the concept of strong and fragile liquids based on the extent of nonArrhenian temperaturedependence of viscosity. 4. 451.303 $ for time t and distance x [27]. is a linear dependence of the logarithm of viscosity on reciprocal temperature. Na2Si205 [46]). ‘in general.. often valid for restricted temperature intervals. The shear viscosity can be calculated from the velocity and attenuation data in that 17*(o) = M *(O)/iO. This consideration is extremely Most ultrasonic studies of silicate melts are conducted at .: ~~A~ MY. q*l(w) = q*~w> + 4 q*s(o)/3 42. and 770and E are termed the frequency or pre-exponential factor and the activation energy. [43].I// i/u lb‘ (11) 0) CT) ffh\._. The real component of the modulus. The simplest form. (4 p -1 4$ Ii . x [27]. “. silicate liquids exhibit non-Ahrrenian viscosity temperature relationships. frequencydependence of the longitudinal viscosity has been observed. respectively. (12) The shear viscosity can be calculated from the velocity and attenuation of the shear wave. 15. or M*(CO) = M’(0. M’(o) = PC*.303A NT.DINGWELL 213 the temperature (1000-l 500°C) and frequency (3-22 MHz) conditions required to observe the relaxed (frequencyindependent) longitudinal viscosity of most silicate melts. Na20-B203-Si02 [23]. The degree of “curvature” of the viscosity temperature relationship plotted as log viscosity versus reciprocal absolute temperature varies greatly with chemical composition (see [29] for a summary). M “(0) = M’(w)cti~f (where the quality factor Q = M’(o)lM”(o) = 7cflca [27]. t and distance. Small strains (<10m6) are used and linear stress-strain theory is applicable. .(7-j Al T r p k) . Methods of determining viscosity: (a) falling sphere (b) restrained sphere (c) rotational viscometer (d) sink point measurement(e) free fiber elongation (f) loaded fiber elongation (g) beam bending (h) micropenetration (i) torsion of a cylinder. The temperature-dependence of non-Arrhenian data can be reproduced by adding a parameter to Equation 14 to yield logI aq =logioqa + 2.. Quite often the data obtained by a single method of investigation over a restricted temperature or viscosity interval are adequately described by Equation 14. Redrawn from Zarzicki (1991). basaltic andesite [35]. and the imaginary component of the modulus.l) + iM”(C0) q”(O)-0 + iq’(O)-0 = M”(C0) + iq’(0)4 = (1 1) (14) where q is the viscosity at temperature. Viscosities are calculated for time. This empirical description of the temperature-dependence of liquid viscosity is called the Fulcher or TVF (Tamann-Vogel-Fulcher) equation [ 14. sufficient data now exist to demonstrate that.e. TEMPERATURE VISCOSITY DEPENDENCE OF gg$fp!i a-. The data from the propagating longitudinal wave results in the determination of the longitudinal viscosity from which the volume viscosity can be calculated (15) where To is a constant. The temperature-dependence of silicate liquid viscosity has been described using a number of different equations. ~. the Arrhenius equation lbg.To) and the real component of the frequency dependent viscosity is q’(o) = T . T.

7. Redrawn from Scarfeet al. Viscosities of melts in the SySteln &.2 through pressure invariance at CaAl204 = 0. (1989).201. Kushiro [21] investigated liquids along the SiOz-CaAl204 join observing a linear pressure dependence of viscosity that changed from a negative value at mole fraction CaAl204 = 0. silicate melts are strong liquids in comparison with nonsilicate liquids.5kbar - 4r 0 $ 3- The falling sphere method has been used to study high pressure viscosities of natural and synthetic silicate liquids [ 10. In general. [5] also observed a transition from positive to negative pressure dependence of viscosity along the join CaMgSi206-NaAlSi308. more fragile. 38. Brearley et al. 5- Albite-H20-F20-. Volatile-bearing silicate liquids have also been studied at high pressure [4. Viscosity as a function of pressure for various silicatemelts.33 to a positive pressure dependence at CaAl204. Redrawn from Dingwell (1987). important where extrapolations of viscosity to lower temperatures are performed. CALCULATION SCHEMES Abyssol Ol~v~ne Tholellle (13OO’C) A number of empirical calculation schemes for the viscosity of silicate glass melts have been around for several decades [37] but calculation methods for geological melts are a more recent phenomenon.214 VISCOSITY AND ANELASTICITY OF MELTS I I I I K?O M90 5510~ (1300°C) investigated the pressure-dependence of silicate melt viscosities across compositional joins exhibiting both negative and positive pressure dependence of viscosity. Decreasing SiO2 content generally leads to less Arrhenian.15 and 0. 13. 6.41Si308H20-F20-1 with (X/X+0) = 0. Two studies have I 6 I 7 104/T (K) 8 Figure 7. Bottinga and Weill [3] produced a method for the estimation of melt viscosities L I I I I 0 10 Prt?ssi?eohbor 3o I 4( ’ 1 I I Figure 6. 491. behavior. Additionally the increase of pressure likely leads to more fragile behavior. PRESSURE DEPENDENCE OF VISCOSITY - 7. 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.2 plotted versus reciprocal temperature (X = F. The extent of nonArrhenian temperature dependence varies greatly with composition. Figure 6 illustrates the pressure dependence of silicate liquid viscosities to 2 GPa.1 and 0. The pressure-dependence of anhydrous silicate liquids has been summarized by Scarfe et al. [36]. In contrast the viscosities of some silicate liquids increase with pressure. . 5. Figure 7 summarizes the effects of Hz0 and F20-1 on the viscosity of NaAISi308 liquid.OH).

I -4 STRAIN RATE I I whereas shear thinning (a decrease in viscosity with increasing shear rate) sets in at higher strain rate. The onset of non-Newtonian rheology has been extensively investigated [47. The low-strain-rate limit of Newtonian viscosity is seen below strain rates of 10e4 t -. CLA I rheology in silicate melts. Redrawn from Webb and Dingwell (199Oa). Shaw [39] included water in his calculation model and with that allowed for the calculation of granitic melt viscosities at low pressures. calculated from the Maxwell relation for each melt. No intrinsic pressure dependence of viscosity was included. -.. These reduced plots basedon Equation 4 remove the temperature. a basalt and a nephelinite) is illustrated in Figure 8. The onset of non-Newtonian rheology for four geological melts (a rhyolite.6 . NEP I : 11. Redrawn from Webb 1 Dingwell (1990b).d 3 ‘z 11. The arrows indicate the calculated rxation strain-rate for thesemelts.0 t I I I I I1 -I Figure 9.and composition-dependence of the onset of non-Newtonian viscosity of silicate melts. .0 ‘. With increasing strain rate the viscosity of silicate melts eventually becomes strain rate dependent as the inverse of the strain rate approaches the relaxation time of the silicate melt structure. (a) A reducedplot of shearviscosity relative to Newtonian versusstrain-ratenormalizedonto the relaxation strain-rate for Na$Q09 at temperatures from 474 to 506°C. 7. The onset of non-Newtonian rheology occurs approximately 3 log10 units of time “above” the relaxation time of each silicate melt approximated from the Maxwell relation. Crater Lake andesite (CLA).DINGWELL 215 at 1 atm pressure that was based on the literature data for synthetic melt compositions. I -3 I -2 (s-0 -1 I -5 log. This is the direct consequence of the relaxation mode due to structural relaxation in silicate melts. 481. With increasingstraine the onset of non-Newtonian (strain-rate dependent) lravior is observed.2 L I . an andesite. A normalization of the data for several compositions and at several temperatures is illustrated in Figure 9 where the viscosities are normalized to the low-strain-rate limiting Figure 8.’ I 12. 12. 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 Newtonian viscosity and the shear modulus. . NON-NEWTONIAN MELT RHEOLOGY The Newtonian viscosity of silicate melts is a low strain rate limiting case. (6) A reduced plot of shear viscosity versus normalized strain-rate for a range of silicate melt compositions. Shear viscosities of Little Glass Mountain rhyolite (LGM). The composition-dependence of the onset of non-Newtonian rheology can be removed in large part through this normalization. Hawaiian ‘holeiite (HTl3) and nephelinite (NFP) composition melts a function of applied strain-rate. . All available evidence points to a single relaxation mode being responsible for the onset of non-Newtonian -1. value of Newtonian viscosity and the strain rate of the experiment is normalized to the relaxation frequency (the inverse of the relaxation time).. .

1986. J.C. C. 81. Akimoto. Carnegie Inst. G.. Dingwell. Riebling. 80. Shimomura and S. 23. J.F. Load-dependent relaxation behavior of various glassmelts with different structural configurations. Kanzaki. 15. Volt. Viscosity and configurational entropy of silicate melts. Proc. Viscosities in t B203-Si02 system. Am. 13. 1992..S. . T. in: High-pressure research in Mineral Physics edited by M. Geophy. Pocklington. 1989. and T. 339-341.. J. Kurita. 1992.. M. Briickner. I I.I. Manghnani and S. New York. 47 l-483. Viscoelastic properties qf polymers. II. Strong and fragile liquids..H.S.. Dickinson Jr and C. K. Phys.S. Philos Trans R Sot London Ser. 22. T. 5.B. Ins. Geochim. Kushiro. Chem. Wash.E. 48. Carnegie Inst. 507508. Fontana.. Riebling.. 1976. Sot. 1989. Arlington. 21. 17. and R. 467-47 1. 1977.N. E. 508516. Dingwcll. 392-401. J. 1960. and C.. Demharter.. 438-475. P. Geochim.. 1959. 195-200. Rough measurement of high viscosities. Cosmochim. Mazurin. Fujii. Measures of dissipation in viscoelastic media. 1987. and D. viscosity and compressibility of basaltic liquid at high pressures. Phys. 50. Nowick. Macedo. Sol. Anelasticity in the Earth Geodynamics Series. 1972. 18..L.V.. Ce 3. Cambridge Philos. Fulcher.H. 1989. 1867. 307-322.L. Montana. Res.H. Kushiro.. Olhoeft. M. J. 36. 1968. Rev.. Knoche . Amer. Pichavant. K. 6. Angell. 30. Ferry. Washington. Chem. Academic Press. Litovitz. Cer. 7.. Phys. Brit. Yearb. 1978. L. K.. Variation in the chemical diffusivity of oxygen and viscosity of an andesite melt with pressure at constant temperature. Geochemical Society Special Publication. 1975. Cu. . Density. Fujii. Am Mineral.. 1980. 118-122. 19. American Geophysical Union. . 49-88. 1925a. Res. Acta. 423-433. 1963. The effect of B2O3 on the viscosity of haplogranitic liquids.. 641 pp. Fulcher.Webb.B. J.. 1986.H. Katahara and G.A. Changes in viscosity and structure of melt of NaAlSi206 composition at high pressures. N. A new technique to measure the viscosity and density of silicate melts at high pressure. Glass relaxation. Herzfeld. J. Simmons and W. 49. 1984. Non-Cryst. Dingwell. Sot. John Wiley. T. Structural relaxation in silicate melts and non-Newtonian melt rheology in geological processes. 8. R.B. 1987. 85-88. 1981. 2609-2616.F. 26.W.S. 87. Y. New York. Naval Research Lab. Glastech. 156-164. Bull. 339-355. 0. Res. Washington. 12-18. Absorption and Dispersion of Ultrasonic Waves. The viscosity of magmatic silicate liquids: a model for calculation. A. 2563-2570. 9.. Cer. Cosmochim. Mineral. Rai.. Geochim.F. I. Chem.B. 789-794. and A. 277. 12. Acta.. Am.. Am.. Cosmochim. 27. Wright. 1970. R. Appl. Richet. 9.M. Briickner. 535pp. Manghnani. 5-8. and M. Systematische Untersuchung iiber die Anwendbarkeit von Penetrationsviskosimetern. Yearb. Wash. D. 1981. 1986. Gent. Maxwell. Dingwell. 568-572. E. 2. A versatile parallelplate viscosimeter for glass viscosity measurements to 1 OOO”C. 6347-6350.B. 1940. Scarfe. J. 5. Brearley .. Hailer. 1972. P. and D. 29... 5 4. An improved counterbalanced sphere viscometr for use to 175O”C. and B. 53. 16. O’Connell..R. Dunn. On the dynamical theory of gases. Glasses.Glastechn. J. A. Sci. The effect of CO2 on the viscosities of silicate liquids at high pressures. 419-424. . Weill.. 1925b. Sot. Analysis of recent measurements of the viscosity of glass. 345pp.. Anelastic relaxation in crystalline solids.F. 12. Pressure dependence of melt viscosities on the join diopside-albite.. Brearley. 34. I I. American Geophysical Union.I. 1984. and B. M. 14. 50. 20. Kato. 76. Sci. Bagdassarov. Sot. DC. H. T. and I. Melt viscosities in the system NaAlSi308-H20-F201. 1. 24 16. Webb. Lett.. 25.157. Changes in viscosity with pressure of melts in the system Si02-CaA1204. Geol. Budiansky. 3 I. and S.D.. Volume 4. Kushiro. 4. O. H. G. Ultrasonic velocity and attenuation in basalt melt. Acta. 28. D. Geotherm. 77. C. 10.. Theory of the parallel plate viscosimeter. 3-l I. S. Syono . VA.216 VISCOSITY AND ANELASTICITY OF MELTS REFERENCES 1. J. Am. Rheological investigation of vesicular rhyolite. Ber.B.C. 1-6. M. E. . ( 48. 594597. A. in Relaxations in Complex Sysrems edited by K.J. Academic Press. 203-216.S. Hessenkemper. 1. Spectrum of relaxation times and fluctuation theory: studies on alkaliultrasonic borosilicate melt. Ngai and G.M. DC.A. I. Geophy. Berry. Scarfe. 63.. 12. D. and G. Analysis of recent measurements of the viscosity of glass.S. R. Ber. Rottinga.

1966. and R. Taylor. . Simmons..5-257. Shear and volume relaxation in Na2Si205. White. G. Litovitz and P. 1921.F. 645-646. Simmons. 563pp.B. Tobolsky. Granasy. allg. Res. Int. Am. Carmichael. Rivers. basalt and nephelinite. Bull. 105. Geophys. 1972. Blcvins.. 41.. H. H. 1963. 1987.V.A. Virgo. Z.R. 34. . 9 5.S. Viscous relaxation and non-Arrhenius behavior in B2O3.. 95. Rex. .E. unorg. S. Res. Cambridge. Y. Dingwell. M.M.. Ryan. Obsidian-H20 viscosities at 1000 and 2000 bars in the temperature range 700 to 900°C. Solid. Shaw. 41. 46. Berlin. Scholze. 15695-15701. 1987. Phys. Cambridge University Press. Sot. 1988. Y. Struktur und Eigenschaften. 1985. 37.. Zarzicki. . Phys.. The onset of non-Newtonian rheology of silicate melts. J. 1990.O. Am. H. 17. Hesse. andesite. and D. 95. 38. 159-167. Glasses and the vitreous state. 45. H. 68. 313-322. The effect of H20 and CO2 on the viscosity of sanidine liquid at high pressures. 17864. 67. 1031-1038. Surv. Dingwell.. and A. and M. 2439-2442.. Non-Cryst.. Vogel. J. Geol. 22.. J. 505pp. Geophy. R. 1990a. 48. U.. 33.ssure and at higher pressures.L. Res. Tamann. Shiraishi.. Webb. 9247-9270.L. 125-l 32. 24. 272.B. J. 15683-15693. and W. Ricbling. 1963. 50. 2857-2865. 156. Webb.L.B. J. 44.L. Mysen and D. Ochoa and K. Sato. 1987. Ultrasonic studies of silicate melts. Am. Sci. Chem. Die Abhtingigkeit der Viskositgt von der Temperatur bei untergekuhlten Fliissigkeiten. Earth Planet. J.. Tauke. Wehb. J Geophys. Chem Mineral. 1968. J.I. 32. E. Ultrasonic measurements of Vp and relaxation spectrum of QP: complex modulus of basalt melt. Scarfe. 44.. and I. Phys.. I.. Springer. Manghnani. Non-Newtonian viscous flow in soda-lime-silica glass at forming and annealing temperatures. Mineral. Macedo. 1964. Pressure dependence of the viscosity of silicate melts.. 76. Non-Newtonian rheology of igneous melts at high stresses and strain-rates: experimental results for rhyolite. J.. A. Structure of sodium aluminosilicate melts containing at least 50 mole% SiO2 at 1500°C. Viscoelastic properties of a simple organic glass.K. Physik Z.H. Shaw. 1991. Chern. Chetn.. and J. 43. Solid. S. 47. 40. 9 2. 870-889. 407pp. 33. Viscosity of glassy Na20-B203Si02 system. 5 1. Viscosities of magmatic silicate liquids: an empirical method of prediction.R. Glas: Natur. 42.S. Geochetnicul Society Special Publiccrtion. 18. 1991. 1987. 6337-6343. l990b 49. M. and D.163. H. NowCryst.. 1926. l58.. J. 1988. C.P.. J. J.. 451-456. B. Waseda and E.D.Y. Geophy..B. Montana.S. 47. 35. 478-483. 36. T. Matsubara.DINGWLL 217 Sot. 39. . The viscosity of synthetic and nntural silicate melts and glasses at high temperatures and at I bar ( lOsPa) pre. Das Temperaturabhtingigkcitsgesetz der Viskosit2t von Flussigkciten. L.. Cer. Phys.H. B.

. It must be noted. Fe-O and Fe-Si alloys is found in the metallurgical literature and they are all restricted to measurements at a pressure of 1 atm. The motion associated with eddy viscosity implies the possibility of non-viscous dissipative mechanisms such as ohmic dissipation. A brief description of the method used for each estimate or measurement is also given.. is a measure of resistance to isochoric flow in a shear field whereas q” is a measure of resistance to volumetric flow in a 3-dimensional compressional field. While long period (minutes to years) geodetic phenomena. This wide range of values may be partially explained by the difference in type of viscosity. Both of these suffer from large extrapolations and from the lack of any experimental viscosity data on liquid Fe at pressures of even a few kilobars. A. and polar motion can all be accurately measured. studies of p-wave attenuation benefit from their short periods (seconds) and all 7 studies cited in Table 2 give upper bound viscosity values within a very confined range of lo*-10’ poises. inferred from the various observational and theoretical methods [24].is important for damping whole Earth torsional mode oscillation and 11. ranging from 10-l to 10” poises.Viscosity of the Outer Core R. the density. Most of the experimental data on liquid Fe and liquid Fe-N& Fe-S. The data in Tables l-4 are graphically presented in Figure 1. Secco Estimates of outer core viscosity span 14 orders of magnitude. that time independent factors that affect seismic wave amplitudes such as scattering. 218 variations. q. the outer core viscosity estimates inferred from these measurements. length of day R. molecular viscosity (a rheological property of the material) vis-a-vis a modified or eddy viscosity (a property of the motion). both TJ. suffer from long observation times which can introduce large uncertainties from additional energy sources and/or sinks affecting the observed phenomenon. 1. Canada N6A 5B7 University of Western Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union. however. Table 5 contains experimental shear viscosity data for . London. A. The majority of estimates of outer core viscosity is based on whole Earth geodetic and seismological observations. and bulk or volume viscosity. In terms of the observation times required by a particular method. Confirmation of any observation of inner core oscillation has not yet been made and therefore any so-derived viscosity estimate from geodetic observation or theory must be admitted with caution. reported in some references have been converted to dynamic viscosity. radial and lateral inhomogeneities will be embodied in derived attenuation values. Tables 3 and 4 are viscosity estimates from geomagnetic and liquid metal theory studies. and Q play significant roles but only 17. Ontario. respectively. depending on the type of strain involved [ 14. respectively. geometrical spreading.151. Tables 1 and 2 are viscosity estimates based on geodetic and seismological studies. Department of Geophysics. 7. Secco. using a value of 10 g/cm’ for p. In cases where outer core viscosity estimates are based on observations of the attenuation of longitudinal waves. Values of kinematic viscosity.for damping radial mode oscillation [4]. The data and references are presented in 9 tables. such as the radial and torsional modes of free oscillation. Molecular viscosity is separated into nearly equal components of shear viscosity. q. by v = q/p. v. Other methods of outer core viscosity estimation are from extrapolations launched from experimental data at low (relative to core) pressures and temperatures using various theories of liquid metals and from geomagnetic field observations at Earth’s surface.

35 .6 x 10-l 5 x 10’ 5 x lo2 2 lo7 I IO” 2 x 1o’O <5.4 x lo4 “Torsional free oscillations of whole Earth “Chandler wobble “Chandler wobble “Damping of free oscillation radial modes “Forced nutation of the Earth (value for MCB) “Tidal variations in the length of day ‘Chandler wobble “Retrograde annual Earth nutation measurements (value for MCB) .6 year principal MCB) core nutation (value for Stewartson and Roberts (1963) Toomre (1966) <lo’ >6 x 10’ Won and Kuo (1973) > 10-l Toomre (1974) <lo” Aldridge and Lumb (1987) 2.7 x IOX Bondi and Lyttleton (1948) <lo’* ‘Theoretically required for secular deceleration of core by viscous coupling ‘Theory of rotating fluids ‘Theoretically required for steady precession by core/mantle viscous coupling ‘Theoretical evaluation of decay time of inner core oscillation (value for ICB) ‘18.3 x lo5 “Viscous damping only for nearly diurnal free wobble (tidal measurements) “Damping of inner core translational (superconducting gravimeter data) modes Smylie (1992) 7. Dynamic Viscosity Estimates of Outer Core from Geodetic Studies Reference Dynamic Viscosity (Poises) Method”“’ Sato and Espinosa (1967) Verhoogen (1974) Yatskiv and Sasao (1975) Anderson ( 1980) Molodenskiy Molodenskiy Molodenskiy (1981) (198 1) (198 1) 0.VLBI Gwinn et al (1986) Neuberg et al (1990) <3.SECCO 219 TABLE 1.7 x 10” 2.4.9 x lo7 ‘Decay of inertial waves in outer core ’ theory ” observation .

6 x lo’* lo8 3-7 x 10” 2x lo8 4 x lo8 l-2 x IOR <<lo’ 1. Dynamic Viscosity Estimates of Outer Core From Seismological Studies Reference Dynamic Viscosity (Poises) Method Jeffreys (1959) Sato and Espinosa (1965. Attenuation of p-waves Attenuation of s-waves Attenuation of p-waves Attenuation of p-waves Attenuation of p-waves Attenuation of p-waves Attenuation of body waves and checked against radial mode Q data TABLE 3.4 x IO’ Attenuation of p-waves Multiply reflected s-waves at mantle/core boundary. Dynamic Viscosity Estimates of Outer Core from Geomagnetism Studies Reference Dynamic Viscosity (Poises) Method Bullard (1949) Hide (1971) 1O-2 lo7 Magnetic damping of core fluid motions Magnetohydrodynamic interactions between fluid motions and bumps on MCB Decay of free dynamo action during polarity transitions Value predicts correct order of magnitude of external field and westward drift Schloessin and Jacobs (1980) Officer (1986) 2x lo5 2x IOX . 1967) Sacks (1970) Suzuki and Sato (1970) Buchbinder (1971) Adams (1972) Qamar and Eisenberg (1974) Zharkhov and Trubitsyn (1978) Anderson and Hart (1978) 5 x lo8 8.220 VISCOSITY OF THE OUTER CORE TABLE 2.

5 x IO-* Leppaluoto (1972) l-5 x 10-l For a pure Fe outer core. A GEODESY GEOMAGNETISM THEoRY Method Fig. from significant structure theory of liquids (value for MCB) For a pure Fe outer core.4 x lo* Anderson (1980) lo’- lo4 Two structure state theory extrapolated to core pressures Thermodynamic scaling relation between melting temperature and viscosity and diffusivity of metals Liquid state model fitted to high pressure melting data on Fe Poirier (1988) 3 x to-* Svendsen et al (1989) 2.SECCO 221 TABLE 4. from band structure calculations From experimental values for liquid Andrade’s pressure effect on viscosity Fe and Bukowinski and Knopoff (1976) >lO’ Schloessin and Jacobs (1980) 3.7-18. as in the reference. The viscosities in Tables 6-9 are presented as either dynamic or kinematic viscosities.10-l 5 x lo* Method Bullard (1949) Miki (1952) Backus (1968) From experimental values for liquid metals at STP Quantum statistical thermodynamics of liquid metals From experimental values of liquid Hg at 10 kb and 400K Andrade formula (value for ICB) for melting point viscosity Clans (1972) 3. because of insufficient density data for many of the alloy compositions. . Dynamic Viscosity Estimates of Outer Core from Theories of Liquid Metals Reference Dynamic Viscosity (Poises) lo-2 lo-*. The common logarithm of dynamic viscosity (poises) of the outer core plotted as a function of method used for its determination. all measured by the oscillating crucible method.1.5 x lo-* OUTER CORE VISCOSITY f A A t 4 f SEISMOLOGY i : A pure liquid Fe and Tables 6-9 contain experimental shear viscosity data for liquid Fe alloys.

222

VISCOSITY

OF THE

OUTER

CORE

TABLE

5. Experimental Data of Shear Dynamic Viscosity (centipoises) of Liquid Fe at 1 atm

Reference

T(“C)

1536

1550

1600

1650

1700

1750

1800

1850

Barfield and Kitchener (1955) Thiele (1958) Hoffman (1962) Cavalier (1963) Lucas (1964) Vostryakov et al (1964) Nakanishi et al (1967) Kaplun et al (1974) Arkharov et al (1978) Steinberg et al (1981) ’ interpolated ’ extrapolated TABLE

7.60” 4.7 5.42 4.95 5.03

6.79’ 4.6 5.30 4.87 4.93 5.91

6.41 4.2 4.90 4.54 4.58

5.89’ 3.9 4.55 4.30 4.28

5.70 3.7 3.98 4.10 4.00

5.48’ 3.4

5.31

5.22

3.92 3.76

5.54”

5.44’ 5.60

5.01’ 5.01

4.69’

4.44”

5.96 5.03

6. Experimental Data of Shear Viscosity of Liquid Fe-Ni Alloys at 1 atm Viscosity

Reference

Composition wt% Ni

Temperature (“(3

Dynamic (centipoises)

Kinematic (millistokes)

Adachi et al (1973)

4.9

1516 1550 1604 1633 1665 1502 1513 1550 1596 1652 1693

6.11 5.91 5.69 5.54 5.36 6.02 5.95 5.72 5.43 5.04 4.81

9.7

SECCO

223

TABLE

6 (continued)

Viscosity Reference Composition wt% Ni Temperature CC) --___.1471 1519 1545 1581 1615 Dynamic (centipoises) -~6.15 5.62 5.37 5.11 4.91 Kinematic (millistokes)

28.6

Arkharov et al (1978)

0.52 1.04 1.49 1.99 2.46

1600

8.48 8.28 8.15 8.13 7.98

TABLE

7. Experimental Data of Shear Viscosity of Liquid Fe-S Alloys at 1 atm Viscosity

Reference

Composition wt% s

Temperature 3 (“C)

Dynamic (centipoises)

Kinematic (millistokes)

Barfield and Kitchener (1955)

1.16 (+0.02 wt%C)

1529 1600 1700 1800

7.00 6.45 5.84 5.41

Vostryakov et al (1964)

0.39 4.70 8.51 18.56

1600

6.00 6.61 6.41 3.43

224

VISCOSITY

OF THE OUTER

CORE

TABLE

8. Experimental Data of Shear Dynamic Viscosity of Liquid Fe-O Alloys at 1 atm

Reference

Composition wt% 0

Temperature (“0

Dynamic Viscosity (centipoises)

Nakanishi et al (1967)

0.012 0.046 0.071 0.072

1600

5.02 5.43 5.40 5.39

TABLE 9. Experimental Data of Shear Viscosity of Liquid Fe-Si Alloys at 1 atm Viscosity Reference Composition wt% Si Temperature (“C) Dynamic (centipoises) Kinematic (millistokes)

Romanov and Kochegarov (1964)

0.1

1540 1580 1621 1668 1743 1789 1806 1549 1605 1642 1707 1756 1508 1553 1592 1654 1712 1758 1454 1508 1575 1627 1677 1716

9.62 8.72 7.78 7.55 7.04 6.66 6.61 7.70 6.92 6.83 6.36 6.15 7.39 6.90 6.46 5.85 5.69 5.49 8.14 6.78 6.02 5.61 5.40 5.37

0.6

2.0

5.0

SECCO

225

TABLE

9 (continued) Viscosity

Reference

Composition wt% Si

Temperature (“C)

Dynamic (centipoises)

Kinematic (millistokes)

Nakanishi

et al (1967)

0.9 2.9 1 .o 2.0

1615

4.13 3.54 5.41 5.29 4.89 5.74 5.18 4.84 5.51 5.05 4.72 5.04 4.65 4.35

Kaplun

et al (1979)

1550 1550 1600 1500 1550 1600 1500 1550 1600 1500 1550 1600

3.0

4.5

6.0

Acknowledgements. I gratefully acknowledge helpful discussions with H.H. Schloessin and L. Mansinha, comments in reviews by D.L. Anderson and an anonymous reviewer, as well as financial support by the Natural Sciences and Engineering Research Council of Canada.

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pp.561-566, ed. S. Takeuchi, Taylor and
Francis, 1973. 2. Adams, R.D. Multiple Inner Core Reflections from a Novaya Zemlya Explosion, Bull.Seis.Soc.Amer. 62, 1063-1071, 1972. 3. Aldridge, K.D. and Lumb, L.1. Inertial Waves Identified in the Earth’s Fluid Outer Core, Nature325, 421-423, 1987. 4. Anderson, D.L. Bulk Attenuation in the Earth and Viscosity of the Core, Nature 285, 204-207, 1980. 5. Anderson, D.L. and Hart, R.S., Q of the Earth, J.Geophys.Res. 83, 5869-5882, 1978. 6. Arkharov, V.I., Kisun’ko, V.Z., Novokhatskii, I.A. and Khalierskii, V.P. Effect of 7.

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1989.

10.

15. Flinn, J.M., Jarzynski, J. and Litovitz, T.A., Mechanisms of Volume Viscosity in

226

VISCOSITY

OF THE OUTER

CORE

Molten Bismuth and Lead, J.Chem.Phys. 54,(10), 4331.4340, 1971. 16. Gans, R.F. Viscosity of the Earth’s Core, J.Geophys.Rrs. 77, 360-366, 1972. 17. Gwinn, C.R., Herring, T.A. and Shapiro, 1.1. Geodesy by Radio Interferometly: Studies of the Forced Nutations of the Earth 2. Interpretation. J.Geophys.Res. 91, 47554765, 1986. 18. Hide, R. Viscosity of the Earth’s Core, Narure PhysSc. 233, 100-101, 1971. 19. Hoffmann, K. These, Saarbrucken, juillet, 1962 (cited in Lucas, 1964). 20. Jeffrey& Sir H., The Earth, In Origin, Hiswry and Physical Constitution, p.255, Cambridge Univ.Press, 4th ed., 1959. 21. Kaplun, A.B. and Krut’ko, M.F. Viscosity of Fe-Si Melts with Small Silicon Contents, Russiun Metall. 3, 7 l-73, 1979. 22. Leppaluoto, D. Thesis, Univ.Califomia, Berkeley, 1972 (cited in Verhoogen, 1974). 23. Lucas, L-D. Viscosite du Fer Pur et du Systeme Fe-C Jusqu’a 4,8% C en poids. C.R.Acad.Sci.Paris 259, 3760-3767, 1964. 24. Lumb, L.I. and Aldridge, K.D. On Viscosity Estimates for the Earth’s Fluid Outer Core and Core-Mantle Coupling, J.Geomag.Geoelecrr. 43, 93-110, 1991. 25. Miki, H. Physical State of the Earth’s Core, J.Phys.Earth 1, 67, 1952. 26. Molodenskiy, S.M. Upper Viscosity Boundary of the Earth’s Core, Izv.Eurth Phys. 17, 903-909, 1981. 27. Nakanishi, K., Saito, T. and Shiraishi, Y. On the Viscosity of Molten Iron and Its Dilute Bimuy Alloys of Aluminum, Silicon and Oxygen, Jap.Inst.Meta1s.J. 37(7), 881-887, 1967, (in Japanese). 28. Neuberg, J., Hinderer, J. and Zum, W. On the Complex Eigen-frequency of the “Nearly Diurnal Free Wobble” and Its Geophysical Interpretation, in: Variarions in

29.

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Earth Rotation, eds.: D.D. McCarthy and I l-16, Geophysical W .E. Carter, Monograph 59, Amer.Geophys.Union, Washington, D.C., 1990. Officer, C.B. A Conceptual Model of Core Dynamics and the Earth’s Magnetic Field, J.Geophys. 59, 89-97, 1986. Poirier, J.P. Transport Properties of Liquid Metals and Viscosity of the Earth’s Core, GeophysJ. 92, 99-105, 1988. The Qamar, A. and Eisenberg, A. Damping of Core Waves, J.Geophys.Res. 79, 758-765, 1974. Romanov, A.A. and Kochegarov, V.G. Viscosity of Binary Iron-Silicon Melts in the Low Concentration Range of the Second Component, Fiz.Metal.Meralloved. 17(2), 300-303, 1964. Sacks, I.S. Anelasticity of the Outer Core, Carnegie Insr.Wash.Yrbk. 69, 414-416, 1970. Sato, R. and Espinosa, A.F. Dissipation in the Earth’s Mantle and Rigidity and Viscosity in the Earth’s Core Determined from Waves Multiply Reflected from the Mantle-Core Boundary, Trans. Amer. Geophys. Union, 46, 158, 1965 (also Bull. Seis. Sot. Amer. 57, 829-857, 1967). Sato, R. and Espinosa, A.F. Dissipation Factor of the Torsional Mode “T, for a Homogeneous-Mantle Earth with a SoftSolid or a Viscous-Liquid Core, J. Geophys.Res., 72, 1761-1767, 1967. Schloessin, H.H. and Jacobs, J.A. Dynamics of a Fluid Core with Inward Growing Boundaries, Can.J.Earth Sci. 17, 72-89, 1980. Smylie, D.E. The Inner Core Tnnsla-tional Triplet and the Density Near Earth’s Center, Science, 255, 1678-1682, 1992. Steinberg, J., Tyagi, S. and Lord, Jr., A.E. The Viscosity of Molten Fe,Ni,,P,, B,and Pd,lSi,,,ActuMetafl. 29,1309-1319.1981.

39. Stewartson, K. and Robetts, P.H. On the Motion of a Liquid in a Spheroidal Cavity of a Precessing Rigid Body, J.Fluid Mech. 17, l-20, 1963. Viscosity 40. Suzuki, Y. and Sato, R. Determination in the Earth’s Outer Core from ScS and SKS Phases, J.Phys.Earth, 18, 157-170, 1970. 41. Svendsen, B., Anderson, W.W., Ahrens, T.J. and Bass, J.D. Ideal Fe-FeS, Fe-Fe0 Phase Relations and Earth’s Core, Phys.Earth Planer.lnr., 55, 154-186, 1989. 42. Thiele, M. These, Berlin, juillet, 1958 (cited in Lucas, 1964). 43. Toomre, A. On the Coupling of the Earth’s 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. On the “Nearly Diurnal 44. Toomre, A. Wobble” of the Earth, Geophys.J.R.Astr. Sot., 38, 335-348, 1974. 45. Verhoogen, J. Chandler Wobble and Viscosity in the Earth’s Core, Nature, 249, 334-335, 1974. 46. Vostryakov, A.A., Vatolin, N.A. and Yesin, O.A. Viscosity and Electrical Resistivity of Molten Alloys of Iron with Phosphorus and Sulphur, Fiz.Metal. Meralloved. 18(3), 476-477, 1964. 47. Won, I.J. and Kuo, J.T. Oscillation of the Earth’s Inner Core and Its Relation to the Generation of Geomagnetic Field, J. Geophys.Res., 78, 905-911, 1973. 48. Yatskiv, YaS. and Sasao, T. Chandler Wobble and Viscosity in the Earth’s Core, Nature, 255, 655, 1975. 49. Zharkov, V.N. and Trubitsyn, V.P. Physics of Planetary Interiors, p.59, translated and edited by W.B. Hubbard, Pachart Pub.House, Tucson, 388 pp., 1978.

Models of Mantle Viscosity

Scott D. King

1. INTRODUCTION The viscosity of the mantle is one of the most important, and least understood material properties of the Elarth. Plate velocities, deep-earthquakesource mechanisms,the stress distribution in subduction zones, and estimates of geochemical mixing time scales are all strongly affected by the pattern of convective flow which. in turn, is strongly influenced by the viscosity structure of the mantle. There are two approachesto understanding the viscosity structure of the E&h: using observationssuch as the geoid and post-glacial uplift, combined with flow models; or studying the physical deformation properties of mantle minerals in the laboratory. Both approacheshave advantages drawbacks. and Laboratory measurementsof deformation indicate that the rheology of upper mantle minerals such as olivine ((Mg,Fe)$iO4) is a strong function of temperature, grain size and stress [e.g., 3, 24, 43, 45, 46, 61, 651. The deformation of minerals under mantle conditions generally follows a flow law of the form i = A(f)” P exp(-+)

constant [c.f., 3,431. Viscosity is defined as

(1)

where 6 is the deformation rate, cr is the deviatoric stress, p is the shearmodulus, d is the grain size of the rock, Q is the activation energy for the deformation mechanism,T is the temperaturein Kelvins, R is the gasconstant and A is a
S. D. King, Atmospheric Purdue University, Department of Earth Sciences, West Lafayette, IN 47907-1397 and

Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union. 227

therefore, deformation is directly related to viscosity. (Note the factor of 2 difference in equation (2) compared with the definition used by experimentalists.) For temperature changes of 100 degrees K, the viscosity changesby an order of magnitude at constant stress [c.f., 441. Changesof deviatoric stress by a factor of 2 change the viscosity by an order of magnitude [c.f.., 441. Other factors, such as partial pressureof oxygen and water may also have important effects. Two creep mechanisms are likely to dominate in the mantle; diffusional flow (correspondingto n=l in equation 1) and power-law creep (correspondingto n>l in equation 1). A rheology with a linear stress strain-rate creep mechanism, such as diffusional flow, is referred to as a Newtonian rheology. The question of which mechanism dominatesin the mantle dependson the averagegrain size of the mantle minerals [46]. In the upper mantle, with grain sizes greater than lmm, power-law creep should dominate at stresses greater than 1 MPa; otherwise diffusion creep dominates [46]. A deformation map (Figure 1) shows the predicted dominant deformation mechanisms for olivine with grain size O.lmm as a function of stress and depth. It should be noted that the strain rates achieved in the lab (typically 10m5 lo-* s-l) are much larger than those predicted in the lithosphere and mantle (- lo-l4 s-l ). While the laboratory measurements are clearly in the power-law creep field, typical mantle strain-rates lie close to the diffusional flow field at this small grain size. The deformation of the major high pressure mantle phases perovskite ((Mg,Fe)SiO3) and spine1

228

MODELS

OF MANTLE

VISCOSITY

CATA

cl\\\I\!l

NH/

11

z (lOfkml

Fig. 1. (o-z)-deformation map for polycrystalline olivine with grain size 0.1 mm. Thick lines are creep field boundaries; thin lines, constant strain rate contours (given as powers of 10). C and NH denote Coble and NabarroHerring creep, respectively [3]. ((Mg,Fe)2SiO4) can be studied only by analog minerals. Using high temperature creep experiments on a CaTi perovskite analog, Karat0 and Li [22] suggest the possibility of a weak zone at the top of the lower mantle (due to the grain size reduction from the spine1 to perovskite phase change). Karat0 [21] showed that olivine, spine1 and perovskite have similar normalized flow stresses, which suggests that, due to the effect of pressure, the lower mantle should have a higher viscosity than the upper mantle. Since creep parameters can differ greatly even for apparently-similar perovskites [44; Table 51, we should apply analog creep measurementsto the mantle with great care. Becauseof the difficulties in interpreting and applying laboratory creep measurements to mantle conditions, models of mantle viscosity based on large-scale geophysical observations continue to be important to geophysics. The post-glacial uplift problem, as described by Haskell[19], is a simple illustration. If a load is placed on the surface of a viscous fluid and allowed to deform the surface to establish hydrostatic equilibrium, the rate at which the surface deforms will dependon the viscosity of the fluid. Similarly, if the load is then removed, the rate of return is also dependenton viscosity. Viscosity models deducedfrom these observationsare not unique, however, and require knowledge of models for the surface load (i.e., ice sheet thickness and history), which are uncertain. Also, the theoretical models are often simplified to keep

them tractable; commonly, a linear rheology (i.e. n=l and T constant in equation (1)). which varies only with depth, is assumed. The classic studies of post-glacial rebound illustrate the non-uniqueness of viscosity models derived from observationsand flow models. Haskell [19, 201 proposed that the uplift of Fennoscandiawas the result of deep flow, modeled as a half space with a uniform viscosity of 1021 Pa s (pascal seconds are the MKS units of dynamic viscosity; 1 Pa s = 10 poise), while van Bemmelem and Berlage [64 - see 51 proposed that the uplift of central Fennoscandia could be attributed to flow in a 100 km thick channel, with 1.3 x 1019 Pa s viscosity, overlying an effectively rigid mantle. Haskell also showed that the viscosity did not change over the interval of time of the analysis, supporting the notation of a Newtonian, rather than stress-dependent mantle. The effects of an elastic lithosphere were first discussed by Daly [7], who appealed to the strength of the lithosphere to avoid the formation of a bulge of material squeezed of the low viscosity channelperipheral to the out ice load in his model. McConnell [28] and Cathles [4, 51 showed the strength of the elastic lithosphere as important only in considering the short wavelength harmonics. O’Connell [33] determined the viscosity of the lower mantle by looking at changesin the ice load and relating them to long wavelength rebound. He also used spherical harmonic correlation to look for the rebound signal in the geoid. The effect of phase changes in the mantle on rebound was considered by O’Connell [34]. O’Connell concluded that the effect of both the olivine-spine1and the basalt-eclogite phase change on post-glacial are rebound
negligible. Peltier [37] solved for the response of a

viscoelastic (Maxwell) spherical Earth using the correspondence principle, later adding the effects of varying sea level [42]. The correspondenceprinciple assertsthat one can construct the Laplace transform of the solution by solving a series of elastic problems over a range of complex frequenciesand then inverting to get the time domain response for the viscoelastic problem. Cathles [4, 51 presented an alternative viscoelastic formulation which avoids the complexities of the boundary conditions for long time Periods when using the correspondenceprinciple. Cathles argues for an increase in viscosity in the lower mantle, while Peltier arguesfor a uniform viscosity mantle. Because no direct comparison of the two methods has 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 sheet disintegration model, including ice massesof Laurentia. Fennoscandia,and Greenland, called

explains the longest wavelength geoid from the inferred densitiesin the lower mantle [ 11. In the case of the geoid. The resulting ODE’s can be solved for responsefunctions (kernels) which de nd only on the viscosity structure. geoid highs should correspond to mass excesses (Figure 2a). was developed by Peltier and Andrews [40]. As shown by Pekris [36] (and others since).51]. The velocities of the Earth’s plates are the surface manifestations of convective flow in the mantle. the density perturbations in equation 3 can be written as where y is the gravitational constant.KING 229 ICE-l. l&23. The geoid (SVp” can then be m. [12] used observed plate velocities to deduce the radial viscosity structure of the mantle. The models still range from the nearlyuniform viscosity (Haskallian) model PT to strongly layered models NL and HRPA (seeTable 1).3) geoid lows are associatedwith long-wavelength. Table 1 compares a number of recently published viscosity models from post-glacial rebound with geoid and plate velocity studies compiled by Hager [14]. Becauseof the limited power in the post-glacial rebound data set. Seismic velocity variations can be written in terms of elastic moduli for which the limited experimental information places reasonablebounds. The equations of motion of an incompressible selfgravitating spherical shell are presented in Richards and Hager [54] and Ricard et al. A simple. The density perturbations (6plm) are determined by seismic velocity perturbation models from seismic tomographic inversions and/or tectonic plate and slab models from boundary layer theory and deep earthquake locations in subduction zones. spherical harmonic degree 1 = 2.the final viscosity model is dependentupon another model. it has been observed that long-wavelength (i. Lambeck and co-workers have used far field absolute sealevel changes.. with an increasein viscosity of a factor of ten at 670 km depth or 1200 km depth. Thus. Plate velocities constrain the absolute value of the viscosity of the mantle. because of the difficulty in defining sources of error may have little .e. a mass anomaly will drive flow that deforms the surface and core mantle boundary (Figure 2b or 2c). the geoid doesnot. The plate velocity data does not have the depth resolution of the geoid.. 6pim is the density contrast at a depth r of spherical harmonic degree 1 and order m. c is the radius at the core.50. Forte and Peltier [lo]. In all of the studies discussed. [50]. A summary of ice sheetmodels is provided by Peltier [39]. Hager and O’Connell’smodel [15] showed that densities from the cooling of oceanplates and subducting slabsalone provide the necessary buoyancy force to drive plates at the observed velocities. it is the seismic velocity models (see equations 3 and 4). 181. Ricard et al. The differences between the models from post glacial rebound and the geoid models have led to spirited debates. and models based on Fennoscandianand Canadian Uplift could be interpreted as reflecting lateral variations in upper mantle viscosity.rather than the rebound histories at sites near formerly-glaciated regions [26.we assumethat changesin seismic velocity can be mappedinto changesin temperature and do not represent changesin composition. calculated by convolving the response functions with a distribution of density contrastsas follows surface. Most seismic tomographic inversions do not report formal uncertainties (which are difficult to perform and. 17. From early seismic tomography. a is the radius at the where 6p/6vs is a velocity to density ratio and 6vslm is the seismic velocity perturbation model. The resulting geoid is a combination of both internal (Figure 2a) and boundary mass anomalies (Figure 2b or 2c) and can be positive or negative. two-layer viscosity model. becausea low viscosity zone can effectively decouple the plates from flow in the deep interior.but until now no consensus model. [50. fast (presumably denser) regions in the lower mantle [9]. Ricard and Vigny [47].q(r)) is the geoid responsekernel. The difference between Nakada and Lambeck’s models based on relative sea level variations in the Pacific. In post-glacial rebound studies. In a static Earth. To transform seismic velocity anomaliesinto density anomalies. post-glacial rebound models. and Forte et al. Theseequationscan be solved by a separation of variables (assuming a radiallystratified viscosity). Another constraint on mantle viscosity comes from modeling the geoid and dynamic topography of the surface and core mantle boundary.which is only crudely known. They reason that relative sea level variations far from ice margins are less influenced by poorly-constrained ice models. and Gl(r. This model is different from the two end-member.49. 16. using the pattern of density anomalies inferred from seismic tomography [ 11. this is a model of the ice sheet. 321. depending on the viscosity structure (compare Figure 2a + 2b versus 2a + 2~). 511. rebound models are usually reported in very simple parameterizations. this is opposite of what one predicts.

with emphasis on near-field bMitrovica and Peltier [29] model. based on sea level variations. An additional layer. that the gravity anomaly over Hudson Bay is ‘Lambeck. gRicard and Vigny [47] model from thickness of the high viscosity lid. Johnston and Nakada [26] model 3. based on the assumption totally due to delayed rebound. the Geoid and Plate velocities. 1021 1021 3.5 x 1021 4 7 x 1021 314x 1021 7-51%!21 1. based on sea level variations variations in sites spanning the continental margin. viscosity higher by a factor of 10.5 x 1020 3. A Comparison of Recently PublishedViscosity Structures Determined by SystematicForward Modeling (from [14]) Model %m Pa s) 77lm (pa s) PTa MPb LJN2’ LJN3d LNAe NLO’ RVGPg HGPbh HS’ 120 120 100 150 75 Cl%) wm wm [41] model.230 MODELS OF MANTLE VISCOSITY TABLE 1. based on European relative variations in sites away from the ice margins. from 400 km to 670 km depth has a viscosity of 6 x 1020 Pa s. an alternative sea level variations with emphasis on to model 2. and Tnsbingham based on global sea level variations.8 x 1020 2x1020 1020 2. with emphasis on relative eLambeck and Nakada [25] model for Australia.3 x 1022 6 x 1021 6 x 102’ 2 4 15 8 40 100 50 300 30 aPeltier sites. relative variations as a function of island size. calibrated for Plate velocities and Advected heat flux [14]. fNakada and Lambeck [32] model for Oceanic response. Parentheses with emphasis on on (h) indicate the hHager and Richards [la] model for relative mantle viscosity from the Geoid. dLambeck. iA modification of model HRGP that has an asthenospheric expected for Shield regions. Johnston and Nakada [26] model 2. as might be .6 x 1020 2 x 1021 4.

surface flow driven by the internal density contrasts and Fig. The plate-like divergencepredicted by this the viscous flow formulations. one should multiply the horizontal axis scaleby 1021 Pa s. Prior to the inversion. so the absolute scale is chosen to be consistent with postglacial rebound and plate velocity studies.e. 670-2600 km and 2600 km to the CMB). 100400 km. suggesting 400-670 km. but also estimatesof the resolving power of the data and of the trade-offs between model parameters. and angular plate velocities for summarizing these results (and the post glacial uplift. 2. and Sabadini [48] discuss changesin rotation induced by Ricard and Wuming [49].. rotation poles. In this paper. Sea-Level and Mantle Rheology. produce different viscosity models [23. the best limit of the observations. There is a surprising convergence of these results and the resulting model differs from the “traditional” models. the variance reduction with an isoviscous mantle was Studiesof Earth’s rotation provide constraints on mantle 770%.KING 231 2. all of the figures will present relative viscosities. ed. 511. RECENT INVERSION RESULTS -v static only dynamic only dynamic only Several recent studies form and solve inverse problems rather than repeatedly solving the forward problem. using the lower mantle model density anomalies in the mantle. in addition.[62] as the driving force (i.e. In theory. the geoid and plate velocity studies) can be found in Glacial surface velocity boundary condition is choosen to match Isostasy. 6vslm in equation 4) and Greens functions (kernels) for viscous flow developedin Forte and Peltier [lo]. [12] used the method of Bayesian inference to invert for the radial viscosity profile which best fit the observed plate velocities. The use of different seismic models can mantle viscosity in five layers (O-100 km. Harmonic coefficients of the observedplate divergence in the degreerange 1= 1-8 were used [lo]. Ricard 3). Polar wander also has of Dziewonski [8] and the upper mantle model of recently been demonstrated to provide constraints on Woodhouse and Dziewonski [66]. that crude viscosity models may already be pushing the Their inversion produced a viscosity model (i. 2. there is a significant trade-off between viscosity. O’Connell [33] suggeststhat changing patterns the top three layers (O-100 km and 400-670 km are of convection would change the principle moments of correlated and 100-400 km is anti-correlated with the inertia of the Earth and that his viscosity model would others). The sum of (a) and (b) is a negative anomaly in a uniform viscosity medium.g. the dynamic topography of the surface is reduced and the sum of (a) plus (c) could be positive. only the poloidal part low viscosity in the transition zone and high viscosity in of the plate velocities are driven by viscous flow without the 100400 km layer with a factor of 42 jump at 670 km lateral variations in viscosity. To convert to absolute viscosities (in Pa s). Using present day plate geometries. the inverse problem provides not only a model. (a) The geoid anomaly over a positive mass anomaly (stippled) in a static earth. invert the topography. Becausethey are ignored in (seeFigure 3). Geoid models are only sensitive to relative viscosities. the stressesbetween a no-slip boundary condition at the Lambeck and Boschi [59]. (c) With an increased viscosity in the lower layer. A number of recent papers geoid. lateral variations in model explains 48% of the variance in the observedplate viscosity themselves could also introduce a major source divergence (in the range 1 = l-15). Using a tomographic shear wave model SH425. they parameterizedthe meaning). of error in the viscosity models. The resolution and trade-off analysesare not always straight-forward. (b) The dynamic flow driven by the mass anomaly causes negative mass anomalies (stripped regions) at the upper and lower boundaries. Plate velocity models also have fitting uniform viscosity in each of the five layers) with a associateduncertainties.. so a model with a low viscosity in the 100-400km permit polar wander from convection.581. . 53. mantle viscosity [e.hence negative geoid anomalies. Sabadini and layer and higher viscosities in the O-100km layer and 400Peltier [57] and Wu and Peltier [67] discussthe changesin 670 km layers tits the data nearly as well (see also Figure Earth’s rotation due to Pleistocene deglaciation. mantle viscosity..2 . Sabadini. However.1 Plate Velocity Inversion Forte et al.

Two classes of models emerged from their study. 2. and 19% for poliodal component of the plate velocities. [51] from Monte Carlo inversion using geoid and plate velocities. 421 is more appropriately interpreted as a constraint on the uppermost part of the lower mantle (i. . 2. 311. and viscosities in 100-300. and 670-2900 km layers. There is a peak changein viscosity of about two orders of magnitude from the surface to the maximum in the lower mantle. The horizontal extent of the Laurentide ice sheet suggeststhat this subset of the relative sea level (RSL) data should be sensitive to the viscosity at greater depths than other data subsets [30]. then a decrease viscosity in the lower in one-third of the lower mantle.56 [8] for the densities in the lower mantle.1000 E Y 5 1500 8 n 2000 2500 I I l l I!1111 I l l llllll I I I IllILl 670 . 300-670. The viscosities in this lot are scaled by a characteristic mantle viscosity (rl= 102P Pa s). variance reductions are 44% for geoid. [51] considereda three layer mantle. They conclude that the preference of a uniform viscosity in the lower mantle of 1021 Pa s from other studies [e. The resulting viscosity model has a continuous increase in viscosity with depth to the mid-lower mantle. the solid line is also an acceptablemodel. or uplift history. one with an increasing viscosity with depth (Figure 4 . 4. Three representative 1-D viscosity models from Ricard et al. They usedL02.232 MODELS OF MANTLE VISCOSITY 500 . It should be pointed out that Haskell [20] indicated that his result represented the averageviscosity of the mantle. The dashedline is the preferred model.-me m---m There have been several attempts to form and solve an inverse problem for the viscosity of the mantle using postglacial uplift data [35. 381. 4. they also solved for the density to velocity ratio @ipIth . [12] determined by inverting observed plate velocities for the best fitting 5 layer viscosity model. 1-D viscosity models from Forte et al. 58% for topography. 3. IO-2 lo“ loo IO’ Relative Viscosity Fig. However.e. giving them six unknowns.1800 km). and M84C [66] and a slab model for those in the upper mantle. An analysis of the relative sea level. because the geoid is sensitive only to relative viscosity change. with very weak sensitivity to changesin viscosity of up to an order of magnitude below this depth or in the upper mantle.-22 I .-_---.2 Post Glacial Uplift Inversions Ricard et al. They usedthe response kernels for Newtonian viscous flow [50].solid line) and another with the highest viscosity in the transition region and lower viscosity in the upper 100-300 0 500 z 1000 25 g 1500 p” 2000 2500 I I I111111 r .3 Geoid Inversion IO-’ IO0 IO’ 102 Relative Viscosity Fig. They performed a Monte Carlo inversion for the viscosity model which best fit both the geoid and plate velocities. 5.see equation 4) in the upper and lotier mantle.. Therefore.g. this model provides poor fits to the data. with no noticeable discontinuities or low viscosity zones. over Hudson Bay was performed by Mitrovica and Peltier [30. 2.. models with large increasesin viscosity with depth cannot be ruled out by the RSL data as long as the averageviscosity in the 670-1800 km depth range is 1021 Pa s. the density coefficient for the slab model (&lab). I . The viscosities in this are scaled by a characteristic mantle viscosity (q = 1 flow driven by the plates. and chose the viscosity value in the O-100 km layer to be 1O22 Pa s.

SH425.. Using the self. loo 10-l is quite similar to those determined by King and Masters Relative Viscosity [23] (Figure 5). The model. [13] used the recent S-wave model -t 2000 i SH8/U4L8 which they describe. the data are unable to discriminate between layered or whole 15 5 0 10 mantle models. and density models. Using Frechet kernels [Forte et al. 1-D viscosity models from King and Masters [23] constrain such a thin layer at the base of the mantle. P they inverted for radial viscosity models that best fit the observed1 = 2-8 geoid (1 = 2-6 for MDLSH) using a nonnegative.velocities.C [27]. Their results suggestthat. this could possibly represent a thicker. because layer thickness and viscosity contrast anomalies for the best fitting 11 layer viscosity model trade-off directly. basedon the inversion study. Hager et al. In addition. a low viscosity between 400 and 670 km. obtain a 65% variance viscosity in the 1284 to 1555 region. [51] are the only investigators of the recent 2500 group to consider chemically stratified mantle models. i. It is interesting Ix to note that the viscosity in the lower mantle increasesby i a factor of five below 1022 km in addition to an increase ‘i 1500 ‘I at 670 km. viscosity (lj = 102 Pa s). least-squaresscheme with smoothing to inhibit wild oscillations. As they note. The pattern of viscosity with depth for the three models is strikingly similar: a high viscosity from 0 to 400 km depth. low-viscosity zone at the base of the upper mantle and an increasein viscosity in the lower mantle (Figure 6). [13]. It may be beyond the limit of their data to Fig. determinedby inverting the seismically determined density however. 5. 1-D viscosity model from Forte et al. The more interesting result is the model that emerged when they considered both geoid and plate velocities in the inversion (Figure 4 . viscosities in this lot are scaledby a characteristic mantle following Richards and Hager [54] and Ricard et al. which contains a thin. 121.KING 233 0 km and 670-2900 km regions (Figure 4 . One of their strongest conclusions is the sensitivity of their modeling to the assumeddensity model.2 [62].heavy dashed 500 : line). All three of the seismic velocity models predict a low viscosity between 400-670 km depth (Figure 5). and increasingviscosity below 670 km.dash dot line). 6. The gravitating Green’s functions for Newtonian viscous flow. using the geoid. [18] obtained better results with the same formalism using Clayton and Comers’ [6] lower mantle and a boundary layer theory slab upper mantle. The models are normalized by the less extreme layer. This providing the driving force (6~ in equation 3): MDLSH forward model provides good fits to geoid and plate [63]. They also point out that their .heavy dashedline). The viscosities in reduction for the observedgeoid (1= 2-8). This resembles the two-layer model of Forte i 8 and Peltier [ 111. [SO]. a third model emerged (Figure 4 . The largest difference between the viscosity models is a factor of two difference z 1000 in the viscosity of the 400-670 km layer. in addition to a this lot are scaled by a characteristic mantle viscosity (11 reasonablefit to the plate velocities with these viscosity = 1B I Pa s). Forte et al. However. Ricard et al. in addition to the geoid.4 and 5. and M0DSH. they determine the viscosity profile required to fit the geoid. It compareswell with Figures 3. Forte et al. A study by King and Masters [23] considered several Relative Viscosity published models for S-wave velocity for the densities Fig. including the plate velocities.

Furthermore. J. Lmd. Large-scale R. L. Res. Dziewonski. A tomographic analysis of mantle heterogeneities from body wave travel time (abstract).. A. as discussedby Panalli [46].J.. 4. 3. Yale University Press. Res.. 29. and R.W. L. 5. Geophys. and the viscosity model from Ricard et al. B. 7. The author aeknowkdges support Erom NSF grant EAR-91 17406.H. J. seem compatible with these observations..F.. and W. Inst. 8.. Pcltier. Mapping the lower mantle: determination of lateral heterogeneity in P velocity up to degree and order 6. 10. 1747-1750. Boston.. Karato’s 1211 results on the strength of garnet are incompatible with this new model.. J. Sot. 1984. R. Geophys. AGU. Aspherical structure of the mantle.it appearsthat the results from the different observationsare compatible. R.. 89. and preprints. nonhydrostatic geoid. Forte. Plate tectonics and aspherical Earth struch~~: the importance of polidaItoroidaI coupling. Trans. REFERENCES 1.M.. O’Connell. and o’Connell.A. 3. Princeton. Anderson. 1970. 9. Thanks also to the numerous anonymous reviewers whose comments helped improve this manuscript. Andrews. Daly. if the transition zone is Ca rich. Geophys.. J. the degree 1 toroidal A number of component of plate velocities).1991. publications..P. Inferences of mantle viscosity from tectonic plate velocities. NJ. A.. EOS.131-20. Forte. and their relevance to the rheology of the upper mantle.3645-3679. however.M. neglecting lateral viscosity variations leads to errors in the magnitude of radial viscosity jumps as much as a factor of two. 1991.M. Richards and Hager [55] suggestedthis effect would be small for long-wavelength structures in the lower mantle.. Geophys. and R. and topography 6.159. and A.using a Monte Carlo inversion of geoid and plate velocity data . London. British Geographers.determined by inversion using the geoid data. [51] . [12] . 92. 59-95. Zhang and Christensen [68] also find that the effects of lateral viscosity variations are significant.M. A.A. AM. and R.M. [52] showed that a model with lateral viscosity variations between continental and oceanic asthenosphereis consistent with the observedglobal rotation of the lithosphere with respect to the hot spot reference frame (i. plate velocity and geoid predictions.. 1975.5929-5952. Ricard for providing theses. Mantle models with a hard transition zone appear compatible with observations w.R.. W..77691983. 1989. A. D.. Cathles. suggest that. 62. heterogeneities in the lower mantle. The Viscosity of the Earth’s Mantle. and R. M. 1934. Ricard et al.L. Blackwell Scientific PP. The Changing World of the Ice Age. Ashby. A.e. 57-62. 156 pp. J. New Haven. Cathles. reprints. 82.R. 18. Using perturbation theory on a 2-D Cartesian problem.M. 12.D. Viscous flow models of global geophysical observables 1. 288. 1978. the results of the post-glacial uplift inversion by Mitrovica and Peltier [30] and the experimental data. Res. Special thanks to Kathy Kincade for help in preparing this manuscript. the viscosity models from King and Masters [23] . . Geophys. An area of increasing interest is the role of lateral variations in viscosity and their effect on post-glacial Acknowledgments... 386 pp. 11. Res. because radial viscosity models underpredict the geoid compared to their lateral viscosity equivalants. A. 13. Upon considering both the uncertainty in the internal densitiesand surface loads and the uncertaintiesin the viscosity models themselves. Forte. Res. and Y. Hager. tectonic plate motions. Dziewonski.. AM. LATERAL VISCOSITY VARIATIONS rebound. Comer. 1971. Trans.239-255. 4. Woodward.are remarkably similar. Princeton University. Peltier. Thanks to R. Ph. AM. 271 pp. Micromechanisms of flow and fracture. L&t. Peltier. A Geomorphological Study of Postglacial Upliji with Particular Reference to Arctic CaMdo. The viscosity of the Earth’s mantle. forward problems. R.T. Theory of the Earth.. Forte. COMPARISON The viscosity model from Forte et al.. especially when the radial viscosity is stratified.L.determined by inversion using the plate velocity data. Dziewonski.234 MODELS OF MANTLE VISCOSITY viscosity model is consistentwith recent post-glacial uplift analysesand mineral physics.1977. thesis. However. Ritzler and Jacobi [56]. Phil. Dziewonski. investigations addressing lateral viscosity variations are currently underway.M. Clayton. Forte. 2. Rincetm University Press. Verrall. CT. as suggestedby some [1]. 96.1987.

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J. 1991. Mantle stratification and long-term polar wander. The creep strength of the Earth’s mantle. Lett. Zhang.. Sabadini. 52. J.561-571. J. 63. Vigny. 1993. 67. Versuch Einer Mathematischen Behandhmg Geoteknisher Bewegungen Unter Besondercr Berucksichtegung der Undationstheorie. J. J. Effects on post-glacial rebound from the hard rheology in the transition zone. Inferring the viscosity and 3-D density structure of the mantle from geoid. Ashby. Spada. R. Geophys..236 MODELS OF MANTLE VISCOSITY 47. R. J. Geophys.. and W. K.. J. Int. 1990. Nature. C. .M. and W.1547-1550. Ricard.W..8407-8415. 96.754..). Res.M. 708 pp. Sot. Jacobi. 61. 65. astr.. 51. Ritzler. Hager.. 64. 339. and E.H.F. R. and R. 1984. Iti.313. 17. Peltier. Dziewonski. 62. 1992.. Y.. 48.. and A. Rev. Res. 1981. Fleiotout. Long-wavelength Swave velocity structure throughout the mantle. Differential rotation between lithosphere and mantle: A consequence of lateral mantle viscosity variations. Space Phys. 89. 109. Weertman. and C. Ricard. London. 94. and U. L.1970. Pleistocene glaciation and the Earth’s rotation: A new analysis. and Mantle Rheology. Ricard. 1984.1973.1989... and R... Ricard. SOL. 100. Wu. Polar wandering of a dynamic earth. Y.1989. Geophys. 66. SeaLmel. Geophys. and C. M.. Geophys.. 50. Kluwer Academic Publishers. and D. Res.A. Res. Y. Nature. Pleistocene deglaciation and the Earths rotation: Implications for mantle viscosity.553-578. 1989.299-10. J. Richards. Geophys. 352. K.H. Geophys. Y. ht. 19-55. Spada.A. W-J... 1984. Sabadii.191. 391426. Space Phys. Sabadini. Doglioni. Stocker. G. Sabadii. Woodhouse. J. 94. Mantle Rheology... Richards.1991.753-791. Froidevaux.P. Geophys. Lambeck. in 54. Mantle dynamics with induced plate tectonics.. S.H..1935. Hager. 58. Geophys. Boschi (Eds. Geoid heights and lithospheric stresses for a dynamic Earth.L. press. Berlage. and A.R. Mantle heterogeneities. Boschi.. Geophys. 56. M. London.. 60.. Yuen. 53. Sabadini. Peltier. Glacial Isostacy. Y. Geophys. Sabadii.121-126. Res.. geoid and plate motion: A Monte Carlo inversion. Geophys. Y.145-168. II. J. and B. Rev. Res. 43. R. pp. 1992. topography. 5987-6002.. J. Ann.A. and plate velocities. 343-378. On the rheology of the upper mantle. and W. Mapping the upper mantle: Three-dimensional modeling of earth structure by inversion of seismic waveforms.373-375. Ricard.. Geoid effects in a convecting system with lateral viscosity variations. Geophys. Lambeck.R. Rotational instabilities of the earth induced by mantle density anomalies. 13.. Ricard. submitted. 10. and M.. 59. Sabadii. 55. 49. P. The effect of lateral viscosity variations on geoid topography and plate motions induced by density anomalies in the mantle.5953-5986. Geophys. 57. and H. Predominance of long-wavelength heterogeneity in the mantle. and C. J.R. 1989. R. 17. Effects of lateral viscosity variations on long-wavelength geoid anomalies and topography. astr. J. Geophys. Sabadini.A. 105. and B. 19. Geophys.R. Su. J.739-13.. Ricard.. Geoid anomalies in a dynamic earth. C. 327-336. edited by R. 68. 89. Froidevaux.. G. 1990. tnt.. 1984.. Geophys. J.. van Bemmelen. 1991. T. and R. Wuming.. D. Christensen.. Res.543-17559. Tanimoto. Yuen.. 267-286. Geophys.. R. 8. Dziewonski. L&t. 1991.. 1992. R. Vigny. 2. 76. and B. and E. Kluwer Academic Publishers. Y. M. Res. Gerlads Beitrage zur Geophsysik. 94. Ricard. and Y. 66.

at constant strain-rate: deldt = 6 .Plastic Rheology of Crystals J. if ts = GEL. if the variable time is introduced. Plastic deformation is an irreversible. but. or yield stress .Hydrostatic pressure alonedoesnot produceplastic deformation. with II n I 5. In actuality. The relevant laboratory experiments are then creep tests [45]. However. Depart. des Geomater. 75252 Paris. parallel to the strain axis (Figure la).T). the yield stressusually increaseswith &The constitutive equationcan therefore be written cr = f( i . It can therefore be seenthat a solid deforming in steadystate creep under constant stress can be considered as a perfectly plastic solid. as For perfectly plastic solids. since it flows in shearat constantrate under applied stress. the crystals are free to deform. the applied stress necessary for continuing deformation usually increases with strain (hardening ). Place Jussieu. stressremains constant and strain keeps increasingat rate i. Institut de Physique du Globe de Paris. the until eventual failure (Figurelb). France MineralPhysics Crystallography and A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union.As creep tests are usually performed at temperatures high enough to obtain a measurable creep-rate. creep-rateoften increases faster than stress and viscosity decreases with increasing stress(nonNewtonian viscosity ). P. Poirier. it can also be consideredas a viscousfluid . in single crystals. does not generally occur at constant strain-rate: at high temperatures. so that the applied stress cannot be greater than the yield stress. more interestingly.after a transientstageduring which it decreases. P.and. a sampleis put under constant stress (tensile or compressive) and strain is recorded as a function of time. and the observedcreep-rateis that for which the yield stressis equal to the applied stress. the creep rate would be continuously decreasing).. Cedex 05. Standard stress-strain curves for materials <are obtained by straining a sample in a testing J.In creep tests. the stress-sfrain curve. . PHENOMENOLOGY DEFORMATION OF PLASTIC When crystals are strained above a certain limit. In many cases. At high temperatures. 237 machine (usually in tension or compression). CT=~(E). however. strain-rate becomesapproximately constant. The creep curve is then approximately linear (quasi steady-state creep ) and the correspondingcreep-ratedependson the applied stressand on temperature: i =f(o. many crystalline materials exhibit negligible hardening and can reasonablybe considered perfectly plastic solids. Any increasein applied stresswould immediately be relaxed by strain. Poirier 1. rocks and minerals slowly flow under constant stress. viscosity is independent of CT it is said to be and Newtonian . isovolume process. is a straight line. (3= crEL. In many cases. when the yield stress is reached. Plastic deformation of materials in the Earth. it depends on the orientation of the stress axis with respect to the crystal lattice. the plastic strain can take any value. for most materials.a quasi steady-state can be reached (if not. there is very little hardening. The yield stress usually decreases with increasing grain size and increasing temperature.T). the creep-rate dependson stressby a power-law E’ocon. Time does not explicitly appear in the constitutive equation. the curve E(t) is a creep curve. 4. however. The viscosity at constant stress can be defined as: q = 01 i . If creep-rate dependslinearly on stress. they cease behaving like elastic solids and become plastic. In creep tests. A perfectly plastic solid undergoesno plastic strain if the applied stress is lower than the elastic limit oEL. which results in a permanent shear strain after the shear stressthat causedit hasbeenremoved.

whosethermodynamicstatedepends on the activity of the components.1n addition. where AHo and AV* are the activation enthalpy and volume respectively of the controlling process. Strain rate is approximatelyconstantduring quasi steadystatecreep. determinedfrom the slope of the In 6 vs l/T plot. for concurrent processes. through an apparent activation volume AV*. la Stress-straincurve of an elastic-perfectly plastic solid at constant strain rate. T is the absolutetemperature.. In many cases.). if the logarithm of the creep-rateis plotted against the logarithm of the stressto obtain the exponentn of a power law. the creep-rateof silicates is also sensitive to the amount of water present as an impurity. it becomes easier to deform an already deformed zone further than to initiate deformation elsewhere. The activation energy increases with hydrostatic pressure P. which does not correspond to any physical process.is usually expressed as: where so is a constant that often dependson the orientation of the stressaxis with respect to the crystal lattice. i. Fig.In some cases. metals) is entirely characterized by its dependenceon stress. where R is the gas constant.The resulting creep-rate can be expressedas: . The stresssensitivity of strain-rate n (or stressexponent in the creep equation) is an important parameter: if n =1 (Newtonian viscous material). [e.238 PLASTIC RHEOLOGY OF CRYSTALS i = i0 fQZm 0” exp (- AH@)+PAV* RT ) (1) Eat Fig. pressureand grain-size. The temperature dependenceof the creep-rate usually follows an Arrhenius law . AHg. If creep is controlled by only one physical mechanism. 441.exceptfor very fine-grainedpolycrystals deforming by diffusion creep (seenext section). are usually obtained by fitting a curve to the experimental valuesof i. Several T. which simultaneouslyyields best valuesof all the parameters[51. with rates E’i.then. The creep rate of pure elements(e. for sequentialprocesses. the creep rate of oxides (which constitute most of the minerals relevant to deformation in the Earth) often depends on oxygen fugacity fo2. gives only an apparent energy Q.In particular. If. P. processes. temperature.and as: 6 = [Xi ~i-l]-l. l/T. may act concurrently or sequentially. If n = 2. This. 481. AV*. m. is not the casefor ceramicsand minerals. The values of the parameters n. however. the solids still can be deformed to very 21. if creep is controlled by only one process.the activation energy can be written: Q = AHo + PAV*. Above the elastic limit oEL. stressremains constant. expressedas the ratio H+/Si.e.g. when it is possible.. and strain becomes localized in deformation bands or shear zones. The constitutive equation (rheological equation) of pure single crystal oxide minerals.and Q is the apparent activation energy .: E’ocexp (-QKI’). The creep-rate of polycrystals (and obviously of single crystals) doesnot generallydependon grain size. deformation is intrinsically stable. determinedin a range of valuesof the relevant variable (a. This situation occurs when strain-softening mechanisms predominate over strain-hardening mechanisms [27.the activation enthalpy may depend on the applied stress (decreasing as stress increases).The Arrhenius plot In 6 vs l/T is then usually curved and the fit of a single straight line.g. G= const. the stress dependenceof the activation enthalpy may appearas a spuriously high value of n (n > 5). fo2 etc.. at constant stress. fo2. more than one controlling process is active in the experimental range of CT.. More reliable results are obtainedby global inversion of the experimental results. lb Constant stresscreep curve. . plastic instability occurs.6= Ci ii . all the other variables being kept constant. for some reason.

30]. etc. that slip between localized obstaclesis easier than overcoming the obstacles. Non-Newtonian creep. overcoming of the potential hills is achieved by nucleation and sidewaysspreadingof kink pairs (K).Applied shearstressprovides the driving force for the motion of defects and the rate of motion usually increases with temperature. only the controlling processesof the strain rate differ. dislocation creepis grain sizeindependent. Glide of dislocationsis driven by the appliedshearstress. is the controlling process. the shear strain rate is given by a transport equation. resulting from the motion of defects: point defects. dislocations wait in front of the obstacle until they can circumvent it by climbing out of their slip planes and glide until they meet the next obstacle.Bo. Localized phasetransformation under non-hydrostatic stressesmay causeshearfaulting instabilities [7. If the potential hills are so low. dislocations tend to remain straight in the deep troughs along the dense rows. Creep is then said to be glidecontrolled. and v their velocity. the dependenceof the activation energy on stress can be assumedto be linear: AH (0) = AHo .Dislocationstend to lie in the potential troughs. characteristicof the slip system. and the thermally activated. where p is the density of mobile dislocations (length of dislocation line per unit volume). 6. or grainboundaries.3) is due to glide of dislocations on U/T. to move along their slip plane dislocationshave to go over the potential hills between denserows of atoms. in creep experiments. The difference between the rheological equation for glide-controlled and climbcontrolled creep essentially comes from the physics underlying the expressionof the velocity. If the potential hills are high (as they are in some minerals. stress-assisted step of passing over the hill between one row of atoms and the next (lattice friction). 2. Deformation at high temperature. to move by one Burgers vector.g. In the most frequent case of deformation by motion of dislocations. If one makes the reasonableassumptionthat. with n 2 3. the shear strain-rate i obeys Orowans equation : temperature). is potentially unstable and strain-induced structural changesor strain heatingmay causeshearlocalization. . the resultant transformation plasticity [45] appears. which balancesthe applied stress 6. crystallographicslip planesin the direction of their Burgers vector. they also have to overcome localized obstacles. the activation energy does not depend on stress. [45]. the averagedistancebetweendislocations is determined by their long-range stress field. P. climb-controlled creep is rate-limited by thermally activateddiffusion and can only occur at high temperatures.Deformation at low temperature c 0. Theoretical rheological equationssuch as (1) can be derived from Orowan’s equation by expressingthe dislocation density and the dislocation velocity in terms of the relevant physical parameters:T.it may also dependon the interaction of several kinds of defects : e. which may occur infine-grained materials.POWER 239 large strains in a stable manner by the so-called superplastic deformation . a dislocation must locally nucleatepairs of kinks over the potential hill. and is equal to the density of carriers of deformation times the strength of the carriers times their velocity. In climb-controlled creep as in glide-controlled creep. involves diffusion of point defects (usually vacancies). in most cases. In general. Orowan’s equation is valid whether shear strain is caused by slip or climb of dislocations. on the other hand. in steadystatedeformation. as an important transient enhancement the creeprate during transformation(or as a of stress drop in the case of deformation at constant strainrate). sideways migration of the kinks then brings the dislocation to the next low-energy trough.the applied stress helps in overcoming the energy barrier and the activation energy decreasesby an amount equal to the work done by the stress. plastic deformation occurs when the shear stress resolved on the slip plane in the slip direction is equal to the critical resolved shear stress (CRSS). i) In glide-controlled creep (Figure 2a). in dislocation creep controlled by vacancy diffusion or diffusion creep accommodated by grain-boundarysliding (see[45] for a review). dislocations. fo2. As climb of edge dislocations out of their slip plane is controlled by diffusion of point defects to or from the dislocations. In most cases. the dislocation density p is then proportional to cr2.due for instance to the stress field of other dislocations. the strain is still due to dislocation glide. Phase transformations strongly interact with plastic deformation. 2a Glide-controlledcreep. even at high Fig. Nucleation and migration of the kinks are thermally activated processes. PHYSICAL MECHANISMS Plastic deformation is the macroscopicresult of transport of matter on a microscopic scale. b is their Burgers vector (strength). also. In general..

Harper-Dorn creep. Creep-rate increases with decreasing waiting time. which in turn dependson the diffusion coefficient of the relevant point defects.For more complicated minerals. Diffusion creep and grain-boundary sliding are mutually accommodatingprocesses. it is equal to the coefficient of diffusion of the slower species. Constriction is thermally activated and the activation energy of cross-slip controlled creep decreases . strain results from glide of the dislocations between obstacles. at surfacesnormal to the extensive stress. to regions of low equilibrium concentration. at surfacesnormal to the compressivestress. the creep rate is proportional to the product of the climb velocity by the dislocation density (proportional to 02).g. NaCl). In the caseof crystalsof elements(e. in the case of simple ionic crystals (e. Although in many instancesthe stressexponentn of climb-controlled power-law creep is indeed n = 3.the rheologicalequationof cross-slip controlled creep is basically similar to that of glide-controlledcreep.Edge dislocations emitted by a source(S) glide on their glide plane (G) until they are stoppedin front of an obstacle (0). The diffusive flux of defects responsible for climb is driven by a chemical potential gradient. Atoms (A) diffuse in the oppositedirection..e. Since. Climb velocity dependson the diffusive flux of point defects to or from the dislocation. As the creep rate is linear in stress (Newtonian viscosity). if it is dissociated in one plane. it can usually easily glide in this plane.is characterized by a stress exponent n =l. metals) the activation energyfor creepis thereforeindependent stress of and equal to the activation energy of self-diffusion [45]. The creep rate is proportional to the applied stress and to the self-diffusion coefficient. but exhibits no grain-size Fig. with increasing climb velocity. by Orowan’s equation. which is usually assumedto be proportional to the applied shearstress. follows that the it creep-rate at constant temperature and pressure can be theoreticahy expressedby a power law: E’oc03.Vacancies diffuse from (V) regions of high equilibrium concentration.240 PLASTIC RHEOLOGY OF CRYSTALS Fig. but also causesthe creep strain: vacancies travel down the stress-induced chemicalpotential gradientbetweencrystal facesin tension and in compression.g. climb involves multicomponent diffusion and the activation energy for creep is not simply related to the activation energy of diffusion of any one species(see next sectionand [2.Deformation of the grains of a polycrystal by diffusion creep creates incompatibilities that must be relieved by grain-boundary sliding. this is by no means always the case. and since the activation energy is stress-independent.. diffusion creep can successfully compete with climbcontrolled creep only at low stresses. it is inversely proportional to the square of the grain size if diffusion occurs in the bulk (Herring-Nabarro creep ).the dislocation must be constricted. to cross-slip from on plane to another.thus deforming the crystal in response to the apphed stress. Diffusion creep is a mechanism effective only at high temperatures and in polycrystals of small grain sizes. i. like diffusion creep. diffusion of point iii) In diffusion-creep defects not only controls the creep rate. Although cross-slip helps in overcoming localized obstacles.but the strain-rate is controlled by the time the dislocations must wait behind the obstacles before circumventing them by climb and gliding further. 2b Climb-controlled creep.with increasing stress. However. (Figure 2c). they have to climb (C) to clear the obstacleand resumegliding (G).. ii) In climb-controlled creep (Figure 2b). which may be neededto avoid obstacles.23]). and inversely proportional to the cube of the grain size if diffusion occurs along the grain boundaries(Coble creep ). A screw dislocation can in principle glide on all crystallographic planeswhich contain it. 2c Diffusion creep. .and for many crystals 3165.The climb velocity is therefore proportional to the applied stress.usually the anion (oxygen for binary oxides).

221. if the correspondingstrainrate is greater than those of competing mechanisms. o/p and T/Tm) the domains where various mechanisms are dominant (e. fo2. For a review of the plasticity of crustal rocks and minerals. it has been known that the plastic behavior of quartz is very much dependent on the nature and concentration of water-related defects contained in the crystals.g. or monomineralic rocks (e. T/l m Fig. Reviews on the influence of water on the plasticity of quartz can be found in [40. Natural. 3 Deformation mechanismmap for olivine.. The creep curves correspondingly exhibit an initial incubation period during which the creep rate increasesto decreaselater during a hardening stage [ 111. except two. Thus.. which decreasesas water content increases. The role of pressure is.A mechanismis dominant over a range in the variablesdefining the experimentalconditions (T.the stress-straincurves (at constantstrain-rate) exhibit a suddenstress drop at the yield stress (yield-point ) followed by a hardening stage. or c+a. quartz crystals. 5.wet synthetic quartz is very strong and behaves much as dry natural quartz. It is only in the case of diffusion-controlled creep (climb-controlled dislocationcreepand diffusion creep) that pressurecan causea noticeable decreasein the creep rate through the activation volume for diffusion. following a power law whose parameters depend on the .Data on creepof ceramicscan be found in [81. 3. cr.g. deformation-mechanism Since the discovery of water-weakening by Griggs and Blacic [20]. Above the critical temperature. power-law climbcontrolled creep. 3. etc. one must consider a pressure dependenceof the activation volume for creep 1461.POIRIER 241 TEMPERATURE (“C) constructed (Figure 3). however. often synthetic. Dislocation glide usually occurs on the basal plane (0001) in the cl 1% direction (a).The plasticity of polycrystalline minerals. The determination of the active mechanism of deformation cannot be done entirely on the basis of the experimental rheological equation (e.g. P. The boundaries between domains are obtainedby equating the rheological equations for the mechanismsdominant in each domain.If all variablesdefining the experimentalconditions. will be treated in the “Rock Physics” section. of course.g. under an applied stress of 1GPa [ 111.. displaying in 2-dimensionalspace (e. most experimental work is conducted on “wet” (H+/lO%i > 500).27. At high enough temperatures. recent electron microscopy work identifies waterrelated defects with high-pressure clusters of molecular water [41]. This section deals only with recent investigationson the minerals most widespread in the crust and mantle of the Earth. see [29. 171. maps can be are kept constant.. important in the creep of materials in the Earth’s mantle and at the pressuresof the lower mantle. looking for diagnostic features [e. It is essential. there may exist a quasi-steady state creep. by comparing the stress exponent to that of the various models and the activation energy to thosefor diffusion of different species). PLASTICITY OF IMPORTANT MINERALS 0 02 04 06 08 10 HOMOLOGOUS TEMPERATURE. showing iso-strain rate contours (after Frost and Ashby..). Below a critical temperature. and on the prism planes (lOfi)in the a or c [OOOl] . whose plastic deformation has been experimentally investigated using single crystals. thus allowing better understanding of the physical mechanisms. dunite. The parametersof rheological equationssuch as (1) can be constrained by experiments for various possible deformation mechanisms.).). quartzite. with a stress-independent dislocationdensity. directions (the indices of planes and directions are given using Miller-Bravais notation). with grain size 1 mm. etc. to examine the deformed samplesby transmissionelectron microscopy [40] in order to characterize the dislocations and observe their configurations. Quartz dependence..1. “dry” quartz (H/106Si c 80) is almost impossible to deform plastically in the laboratory: it is still brittle at 13OO”C.wheneverpossible. 1982).. Hydrostatic pressure has little influence on plastic deformation at low temperature during glide-controlled creep.g. Water-related defects might consist of 4 protons (H+) substituted for a Si4+ ion or one OH2 group substituted for an oxygen. diffusion creep. grain-size.It is observed only at low stressesand can probably be considered as climb-controlled creep.431. Deformation-mechanism maps are useful to predict the behavior of a material only in the intervals in which the parametershavebeenconstrainedby experiments.

[18] also point out the role of microfractures in the nucleation of dislocations. and high strain rate.60 co2/H2 = 0.800 (j3) 400 . thus increasing the dislocation density.1650 1500.150 10 . ii) At higher temperatures. the elastic strain aroundthe bubblesis relievedby punchedout dislocation loops. ” I. (2iiO) c 11 (2flO) c 1. 36. Fo92 F“92 Fo92 Foloo Woo Fo90 Fo90 Fo90 Foloo Woo Foloo 1430. High-temperaturecompressioncreepof wet single-crystalquartz OH-/Si @pm) 4300 9. TABLE 2.7 3. 9.1600 1400.200 ” .3 CO2/H2 = 0.7 460 573 598 [101 WI WI 20 .1600 1550-1650 1500. 10-8.570 (a) 570 .9 .570 (a) 570 .1 = 0..162 ” 80 .7 3.4 109 33 92 92 213 117 LW 1.40 10 .5 3.5 2.6 3.43 uo11 8 . [351 I.0 5.800 (p) 40 . plastic yield occurs suddenlywith a stressdrop (yield point) for an applied stress high enoughto make massivemultiplication of dislocations possible. low water fugacity. clusters of water moleculesprecipitate into water bubbles.242 PLASTIC RHEOLOGY OF CRYSTALS TABLE 1.100 ill11 r1011 I--WA CO7JH2 = 2.1600 5 .9 525 523 523 564 667 536 536 448 1311 1131 [I31 [I41 WI [321 [321 [321 cog2 cog2 cogH2 = 0. &O (CF bars) in n Q &J/n-ml) Ref.25 f”2 = 10e6 Pa [loll UOll nm w11 [0111 H2/cO2 WC02 WC02 2. 181support the following mechanisms: i) At low temperatures.1400 1250 .1400 1250 .30 100 100 100 10 .3 3. n Q W/ml) Ref.7 3. (1OiO) a I.200 ” 80 . which expand by climb and act as sources.800 (p) 400 . Observationsof experimentally deformed crystals using transmission electron microscopy [ll. High-temperaturecompressioncreepof single-crystalolivines Crystal Orientation of stressaxis (pseudo-cubic) Various <ill> <llO> Atm. 10-9.60 3 .0 3. the dislocationsare straight and their mobility is low. deformation is controlled by lattice friction.during the incubation period. FitzGerald et al.43 = 0.100 30 100 .1400 1400-1650 1400 . the density of grown-in dislocations is very small.33 f(o) 3.1680 1250.6 2.7 3.I.:.570 (a) 570 . quartz is then very strong. 370 11 370 11 Slip System T (“Cl 400 . orientation of the samples with respect to the stress axis (Table 1).1600 1500 .

05 0.2 250 690 700 300 540 540 750 370 230 1000 290 1000 330 i1 .3 x 1o22 1. when climb-control would be expected.5 3.2 0.2 3. The results (Table 3) show wide variations in activation energy and fo2 dependence according to the experimental conditions: two or three power law equations are needed to describe . &l [Olll . e2 . according to the orientation [ 15.The common slip systems are: at low temperature (lOO)[OOl].5 3. 10-12<fo2 c lo3 atm. However.lSi03)or mw (Mg0. .65 5.2 0. .. Examination of deformed samples by transmission electron microscopy suggestthat creep can be controlled by climb and/or glide.06 0. Fe)zSiO4. [llO]opx: d = i. The thermodynamic state of olivine with fixed Fe/Mg ratio is not entirely determinedwhen T. High-temperaturecreeplaws for buffered single-crystalFog1 olivine Orientation of stressaxis (pseudo-cubic) Buffer i0 (0 inMPa) n m Q Wmol) i WI opx mw 0. 1200°C< T c 1525‘C .5 3.1 -1 -1 1 -1 -1 1 -1 1 [oll]mW: E =d.16 2..15 0. +i2 . [lOl]mw: E 1 =d. Olivine Olivine (Mg.0 x 1o14 0. High temperature creep of single crystals in various orientations obeys a power-law creep equationwith n = 3.rather than by diffusion of the slowest speciesalone [231.02 1. the dominant mineral of the upper mantle.3 0) c =e’oonfo m expC-Q$T) 2 . -1+d2 -1 . [Oil] opx: 6 = .3 x 10” 1.1 x lo4 5. 211.5 0.5 3.2.0 x 1o14 0.40 0.10 0. the activity of one component (orthopyroxene or magnesio&istite) must also be specified. opx mw .5 3.5 3.2 x lo5 1.POIRIER 243 TABLE 3. &I i2 After [2].Flow law: [loll opx: E = 6 1-1+ d 2-1 .33 0. I .0 x 1o22 25 .- 3.02 0. correspondingto slip on the basalplane of the hcp oxygen sublattice in the a direction. Bai et al [21 performed systematic experiments on olivine buffered against orthopyroxene or magnesiowiistite for various orientations as a function of temperature. e2 . and oxygen fugacity. apparently compatible with dislocation creep controlled by climb of edge dislocations. 1+i2 .5 (Table 2). One should however note that climb of dislocations should be controlled by multicomponent d. P and fo2 are fixed.23 0. El El El [1101 opx mw 1.the activation energy for creep (of the order of 500 kJ/mol) does not tally with that for diffusion of the slower species:oxygen or silicon (about 335 kJ/mol). [llO] mw: d‘ =i 1 +i.7Fe0.40 0. E2 .5 3. E2 .5 3.5 3.9Feo. buffer: opx (Mgo.5 3. and at high temperature (OlO)[lOO] (prism plane of the hcp sublattice in the c direction).36 0.5 3.+[i2‘ +t?.$%sion of all the species. has an orthorhombic lattice and a slightly distorted hexagonal close-packed oxygen sublattice. E2 .5 3.0 0. with cross-slip on other prism planes such as (001) and (011). stress. E3 .

9 4. the dislocations were pinned by tiny glassy globules (~10 nm). is equal to 3.9 x lo3 i0 (cr inMPa) 4. Samplesdeformed under wet conditions and examined in transmission electron microscopy exhibited evidence of enhanced climb of dislocations(dislocationwalls.1 x 10-23 4. In orthoenstatite.1100 4.6 742 85 442 48 526 7. and subsequently deformed in the same conditions at a constant strain rate of 10m5s1. crystals oriented in such a way that twinning is impossible deform by power-law creep (Table 4). which accountsfor the high value of the stressexponent(n = 8). with dislocation glide on the planesof the layers of chains of Si04 tetrahedra. 3.I !I P = 10 kbar 11 11 r371 [371 Ul [491 [491 [491 r491 [331 8.the flow stressis reducedby a factor of 1. with no detectable occurrence of climb. . The stress exponent. suggestingthat different mechanisms have to be considered. incidentally. Examination of deformed samples by the oxidationdecoration technique [3] shows that different dislocation structures parallel the changesin power-law equationsand confirms that several rate-controlling mechanisms may be operatingin different experimentalconditions. Examination of the deformed samplesby transmission electron microscopy [ 131showed that aboveand below the critical temperature deformation took place primarily by (1 lo] 1/2<1 IO> slip.1450 1350 . As in the case of quartz. the shear stress can favor the nucleation of very fine lamella of clinoenstatite on (100) planes. Above the critical temperature.1450 1000 .5 6.3 0 0 750 880 284 2. which might be confused with stacking faults. Fe)2Si2@ enstatite obeys a power law (Table 4). with respect to that of crystals treated in a dry environment [381. calcium present as a minor ion in enstatite can diffuse to the clinoenstatite.5 to 2. is the dominant deformation mode for clinopyroxenes at low temperatures [33]. resulting from incipient partial melting well below the currently accepted . At high temperature. Deformation is therefore probably glide-controlled.5 in all cases(which. in talc Ar 10% HZ-~% H20 II 1. Pyroxenes Although orthopyroxene Mg2Si206 (enstatite) and clinopyroxene MgCaSi& (diopside) are also important minerals of the upper mantle.and in the direction of the chains. etc.1321 900 .8 3.1 x 1015 Buffered by olivine I.1130 1130 . Ratteron and Jaoul [49] report a drastic decrease in activation energy by a factor of almost ten above a critical temperature about 200°C below the melting point. water-related defects increase olivine plasticity .1137 1137 . it does not seem to be sensitiveto oxygen fugacity but the creep-rateincreases with increasingiron and aluminum content [37]. is a confirmation of its limited usefulnessas a criterion for the determination of the physical mechanism of creep).). however. thus forming thin lamella: of calcic clinopyroxene [26].0 3. For single crystals of olivine treated in a hydrous environment at 1300°C under a hydrostatic pressure of 300 MPa. the glissile dislocations with Burgers vector [OOl] can dissociate on (100) [52].8 6.1321 Slip on (110) Hedenbcrgite 1020 . In experiments on high-temperature creep of pure diopside. primarily on the (100) plane in the [OOl] direction. The crystals then becomemuch more creep-resistant than would be expectedfrom the extrapolatedlower-temperaturecreep law. The easiest slip system of orthorhombic enstatite as well as of monoclinic diopside is (lOO)[OOl]. 11 P = 5-15 kbar.1050 1020 .1 x 1O-4 7.5. High-temperaturecompression creepof single-crystalpyroxenes Crystal T (“c> 1350 .3. High-temperaturecreep of (Mg. their plastic properties have been much less studied than those of olivine.0 x 10-l* 1.244 PLASTIC RHEOLOGY OF CRYSTALS TABLE 4.1 8.6 x 1011 n m Q W/ml) Ref Enstatite (En99) Enstatite (En96) Diopside Diopside Slip on (100) 3. During hightemperature deformation.2 x lo* phenomenologically the creep behavior over the whole range of experimental conditions. Mechanical twinning.

Fe)Si03 perovskite and (Mg. does not provide quantitative information on their strength.POWER 245 TABLE 5. Magnesiowiistite has the NaCl stucture and is stable at ambient pressure. All phasesother than magnesiowiistiteare stable only at high pressures and.87 . 3. The fluid droplets may effectively act as obstaclesto dislocation slip. higher than for olivine or enstatite. the only information we have so far on the plastic properties of the silicate high-pressurephasescomes from experiments that were performed at room temperature. there is as yet no high-temperature creep apparatus operating at these pressures.0. in air or vacuum are compatible with climb-controlled dislocation creep. There is also qualitative information extracted from the examination of dislocation structures of the phasesby transmission electron microscopy. it does at least provide reliable qualitative information on the .0. the other end-member.0.98 415 292 274 444 -11 -39 -37 -92 1 2. [251 performed microhardness tests on metastable MgSiO3 perovskite single crystals at room temperature. Q = 290 kJ/mol) compatible with dislocation creep controlled by the diffusion of oxygen-related point defects whose nature varies with temperature. experiments at about 0.0. so that the dominant slip system at room temperature may not be the same at high temperature. High-Pressure Mantle Minerals Despite their importance for the rheology of the transition zone and the lower mantle. is always non-stoichiometric and Fedeficient. -0. and majorite garnet in the transition zone.0.8. The essential high-pressure phases are (Mg.78 0.67 . either on the metastable phases at ambient pressure or in-situ in a diamond-anvil cell. recent high-temperature creep experiments performed at various controlled oxygen fugacities [24] give results (n = 4.Fe)#iO4 P-phaseand y-spinel. there is no information on the plasticity of the high-pressure mantle minerals in the relevant conditions of temperature and pressure. prepared in a laser-heateddiamond-anvil cell. with n = 4 and Q = 400 kJ/mol [8].84 . They found that at room temperatureperovskite was stronger than spine1 olivine. High-temperaturecompressioncreepof single-crystaloxides with perovskite structure Crystal Orientation of stressaxis (pseudo-cubic) <l lO> <llO> <llO> <l lO> <loo> <lOO> 0. or However.78 0. Wiistite Fefwx 0.3 5.02 c m c 0. thus causing the observedhardening.3 21 15 24 192 14 melting point of diopside. from the pressuregradient in the cell.6 3.99 0.92 Atm In iO (0 in Pa) n Q Wmol) g Ref.67 .70 . Finally. experiments on isostructural compounds presumably belonging to isomechanicalgroups may provide some basis for speculation.99 0.5 3. Karat0 et al. There are good reasonsto believe that deformation of magnesiowiistite at lower mantle conditions is not very difficult: crystals formed by decomposition of olivine at high pressure in a diamondanvil cell contain a high density of dislocations[47].0. perovskite and yspinel. There are however no experiments at very high temperatures in controlled oxygen partial pressure conditions. and (Mg.4. the dependence on temperature of the CRSS may differ considerably for the various slip systems of one mineral (let alone for the slip systems of different minerals). MeadeandJeanloz[42] estimatedthe yield strengthat room temperature of polycrystalline olivine. on the six{ 110) planes in the cl 10~ directions.5Tm. in their stability field. they found a high value of the Vickers hardness(Hv= 18 GPa). Although transmission electron microscopy of phases deformed at high temperature.There havebeennumerousinvestigations on the plastic properties of the MgO end-member (magnesiaor periclase). BaTi KNbO3 KTa03 CaTi CaTi NaNbO3 Argon Argon Argon Air Air Air -38 -43 3.which is easily deformable even at low temperatures. it should be emphasized the yield strength of that crystalsdependson the critical resolvedshearstress(CRSS) of the available slip systems.75 .and the ranking of minerals according to their yield strengths at room temperature cannot be assumedto remain the sameat high temperature.11.Fe)O magnesiowtistitein the lower mantle.7 469 30 38 [41 r51 [51 [531 [531 [531 0.

C. Rheology of the lithosphere: selected topics. and dissociationfrom which educated guesseson the deformability can be attempted. 6. 24. Prior. 97123. Res. J. pointing to glide control of the deformation. S.287-14. 7. 108. 263-274. Christie. Av6 Lallemant. and M. McCormick. N. Interiors. Y. and J. Plasticity of MgSi03 perovskite: the results of microhardness tests on single crystals. 1983. Res.B. Water solubility in quartz and its influence on ductility. Bull. Frost. E.. and J. High temperature creep of Felsx 0. Plasticity and hydrolytic weakening of quartz single crystals. 5755-5770. J.B. A comparison of the creep properties of pure forsterite and iron-bearing olivine. High-temperature deformation of diopside single-crystal. Goetze. 21.H. 14..D.. Geophys. Tl5T18. 45. 182-198.B. 89. Doukhan. H. Durham. Jaoul. Dresen. the dislocation Geophys. 31 --. 2. S. H. J. J. 27.F. Doukhan. FitzGerald.5. 48. Ito. Hobbs. 13. The strength of quartz in the ductile regime. deformation. 206. 1. Monty. Kirby. 1. Lett. 1989. 187-189. REFERENCES 1. Mechanical results for buffered samples. 40.. Experimental deformation of diopside and websterite. K.. Hightemperature creep of forsterite single crystals. 8. 124-137. 425-443. 419-442. 9. P. 221-237. Deformation of Earth materials: six easy Reviews of Geophysics pieces. 1964. 5. Goetze. 28. 1991. Bull. 19. Beauchesne. the successof the analogueapproach to try elucidating the plastic properties of MgSi03 at high temperature is contingent on the existence of a good analogue(yet to be identified) of MgSi03 perovskite. stacking faults and dislocations similar to those found in MgA1204 spine1 are observed [39]. Durham. Exsolution of Ca-clinopyroxene from orthopyroxene aided by Chem. Mineralogy. 1987. Durham.297. and A. 96. J. I. Cannon. probably due to the fact that the distortions and the dislocationcore structuresare different: creepparameters can be very different even for apparently similar perovskites (Table 5). Geophys.. Ord and B. 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Microstructures in water-weakened single crystals of quartz.Transmission electron microscopy investigation of the defect microstructure. Boland. 29 . High-temperature creep of olivine single crystals. Res. Res. 1978. Hightemperature creep of olivine single crystals. High-temperature creep behavior of nearly stoichiometric alumina spinel. 17. 96. 55. . and J. Plastic flow of oriented single crystals of olivine.M.N. dislocationsare very and straight. W. Thus. 11. S.J. Interiors. 1981. Froidevaux 0. Geophys.W. Materials Sci. 1991. and J. Creep of hydrolytically weakened synthetic quartz crystals oriented to promote (2TfO)cOOOl> slip: a brief summary of work to date. and Y. 20. Kohlstedt.C. Oxford. 765-775. McLaren. A.G.W. 22. Geophys. Tectonophysics.J. 96. S. 12. J. J. There is no information on the plasticity or dislocation structures of MgSi03 perovskite at high temperature. 10. 5737-5753. A 45. Griggs. Darot. but crystals of perovskite structure certainly do not constitute an isomechanicalgroup [S. Burnley. 1989.. in natural y-spine1 (ringwoodite) formed at high temperature in shocked meteorites. Phys. Geophys. 1. 2. Darot. 1991. Geophys. Amer. Eur. 1740-1748. 7. Fujino and E. 531.H. 1991..B. Phys. Mineral. Green II and D. 82. Pergamon Press. W. 17.. Res. Geophys. Ashby. Doukhan. A. W. Phiios. 82. J.J. 1985. 64.P. 102. 1977b.. 26. Mackwell and D. T&pied. Res. Karato. it is reasonableto assumethat the slip systemsare the sameas in other perovskites. Doukhan and J. Tectonophysics. Minerals. J. 18. l-50. Gueguen. 2. Mag. Blacic. Evans. 15. 102... 61. Transient and steady-state creep of pure forsterite at low stress. 823-843. and C. and C. Les dislocations dans la for&rite deformee B haute temperature.H. density.. 4. 0. Escaig. Doukhan and B. 1979. 1977. 1981. Poirier. Creep of ceramics. 1991. 1978. N. Therefore. titanate Creep of baryum perovskite: a contribution to a the systematic approach to viscosity of the lower mantle. 1992.K. 3. In search of a systematics for the viscosity of perovskites: creep of potassium tantalate and niobate. Q. J .C.L. Union. and C. Etheridge. Earth planet. P. Beauchesne.C. 96.. W.. Gueguen. 95. and M. S. There is also evidencefor the (lll)cllO> slip system as in MgA1204 1121. Poirier. l-29. and J. J.G. 3.. Res. Phys. 13. 1990. Kronenberg. D. 18. and 16. 25. Trans.D. Res. Supplement. and M. Philos. 105-109. 2139-2155. Q. Multicomponent diffusion and creep in oli&e.

... Kohlstedt. 1992.P. l. Fe)2Si206. Kohlstedt and M. J. Ord and J.C. Anisotropy in the rheology of hydrolytically weakened synthetic quartz crystals. 135142.. F. 1984. 14. Geol. Press. Earth planet.L. 1991. C. Ricoult. The strength of metal silicates at high pressures and room temperature: implications for the viscosity of the mantle. Kol1S. N. Blacic. 2027-2030. Washington D. J. 46. Mantle phase changes and deep-earthquake faulting in subducting lithosphere. Ratteron. and J. 90 . 36. Logan and D.Licbermann. 39..H. in Mechanical Behavior of crustal rocks (The Handin volume) . J.. Jaoul. Phys.286. Interiors. High-temperature rheology of enstatite: implications for creep in the mantle. JStruct. Dislocation-controlled ffow processes in hedenbergite. 30. J. Chem. Wright. Unwin Hyman. Carmichael. and P. J. 4241-4255. Res. J. in Rheology of solids and of the Earth. Jeanloz. 79.P. Poirier. 1985. and Poirier. M. 33...M. 533-535. 32. and R. 34. Karat0 and M. Minerals. Cambridge University Press. and J.W. Gerretsen. 2045-2051. and S. D.Sotin and S. 38. 9-22. edited by N. 74. J. S. Poirier. 3. 1985. Madon.P. Oxford.J. A. Washington.D. 2. Kirby.P. pp 101-107.D. in Deformation processes in minerals.G. Philos. 35.S. 51. Barber and P. D. Effect of oxygen partial pressure on the creep of olivine. Florida.J. Analysis of high-temperature creep experiments by generalized non-linear inversion. Science. Mackwell. 1984. Lowstress.J. Res.C. Christie. Res. Geophys. 87.J. 1982.Beauchesne. On the activation volume for creep and its variation with depth in the Earth’s lower mantle. Sotin. Toriumi. 1991. Paterson.C. G.Mechanical data. M. Phys. and A.. Nicolas. J. 283-293. A.. American Geophysical Union.. Experimental deformation and data processing.S. Mechanical twinning in diopside and hedenbergite.C. McLaren. 1989.H. Stern. Hornack.D. CRC Press. 16. Kirby. Minerals.. Science. K. Res. 1983. and J.S. Boca Raton.L. Geophys. . M. 31.J.POIRJER 247 29.I.P. P. 1991. Deformation of single-crystal clinopyroxenes: 1. 79-93. 216-225. 4019-4034. 47. 35.A. Kolle. Doukhan. 53. 348... Geophys. Kohlstedt. edited by S.L. 41. The role of water in the deformation of olivine single crystals. D. Van Duysen. 2381-2393.. Earth planet. 252. M. 1986.. Price and J. 89. S.F. 1989. 1980. Stearns. Geophys. Eutectoid phase transformation of olivine and spine1 into perovskite and rock salt structures. Res. 45. Transmission electron microscopy of minerals and rocks. Doukhan and J. Meade. Friedman. Peyronneau. Poirier.D. J. C. Phys. 321. Paterson. Transmission electron microscope study of dislocations in orthopyroxene (Mg. J. 52. D. M. 1981. 49.. 465-482.H. 1984. High-temperature creep of the perovskites CaTi and NaNb03.. 311-317. edited by R. 42.. S. W. edited by D. pp 179-189.J. Creep of Crystals. Dislocations in spine1 and garnet high-pressure polymorphs of olivine and pyroxene: implications for mantle rheology. 50. Shear localization and shear instability in materials in the ductile field.. Kirby. Mechanics of Materials. J. Res. Effects of compression direction on the plasticity and rheology of 37. and 0. Guyot. 18. 1974. Paterson and A. hydrolytically weakened synthetic quartz crystals at atmospheric pressure. 603-605. J. Madon. edited by F. 1985. 1991.L. high-temperature creep in olivine single crystals. London. Goetze. Linker. Carter. pp 107-142.. Interiors.W. Cambridge. 1980. in Handbook of physical properties of rocks. Blacic.P. in Anelasticity of the Earth .. ceramics and rocks. 48.B.. 1984. McLaren. 88.D. D.L. S.an overview. J. Kohlstedt. Poirier. J.P. pp 139 . M. Res. J.F.P.280. Deformation of single-crystal clinopyroxenes: 2. Nature. and C. Geophys. Geophys. and J. 12.. Durham and L. Dislocation nucleation and multiplication in synthetic waterrelevance to quartz: weakening. 43. Creep of Fe2SiO4 and Co2SiOq single crystals in controlled thermodynamic environment. Poirier. Nature.L. vol HI.. A. 39-44. Poirier. 51.. 1981. American Geophysical Union. McCormick. 1990. 1985. J. FitzGerald and J. The interaction of water with quartz and its influence on dislocation flow . M. pp 29-48. 1990. Lett. and D. Linker. 207.C. Meredith. Chem. . 44.. Mug. Stacey. S. Inelastic properties of rocks and minerals: strength and rheology. Hightemperature deformation of diopside single-crystal. Phys. Mackwell. Kirby. 96. and R. Poirier.H.C.S. Cambridge University Cambridge.27714. Oxford University Press.M. Geophys. 40. Rcvcolevschi. C. 11319-11333.C. 66-68.

Phase Diagrams of Earth-Forming Minerals Dean C. (1) For several of the mineral groups. C. they have usually been left as originally published.5083-0688 Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union. only representative phase diagrams are shown. 122. 50. Dallas. Gilbert et al. Reviews of these subsolidus phase relationships and thermodynamic data for calculating the phase diagrams have been presented elsewhere [13. 1541. (3) Many subsolidus phase diagrams important to metamorphic petrology and thermobarometry are excluded. TX 7. and silicates at high pressures. Richardson. Minor drafting errors and topological imperfections that were found on a few of the original diagrams have been corrected in the redrafted diagrams shown here. Pro- 248 . oxides. (2) The presentation of more complex phase diagrams that show mutual stability relationships among the various minerals and mineral groups has been minimized. D. Presnall. [60] and Huckenholz et al. Liu and Bassett [104] for elements. [74] for amphiboles. The phase diagrams are arranged as follows: Figure 1 2-7 8-13 14-16 17-20 21-23 24 25 25 26-27 Silica Feldspars Pyroxenes Olivine Garnet Iron-titanium oxides Pargasite Serpentine Phlogopite Iron The compilation has been compressed in three ways. POB 830688. and Phase Diagrams for Cerumists [129-1371. It will be noted that some diagrams are in weight percent and others are in mole percent. Geoscience gram. Presnall The purpose of this compilation is to present a selected and compact set of phase diagrams for the major Earthforming minerals and to show the present state of knowledge concerning the effect of pressure on the individual mineral stabilities and their high-pressure transformation products. University of Texas. Other useful reviews and compilations of phase diagrams are Lindsley [96] for oxides. 70.

Silica has been synthesized in the FezN structure at 35-40 GPa. GPa Fig. and at 35 GPa. 2. 31. SiO2. 89. 16. which is shown in Figure 1.PRESNALL 249 Pressure. 941.[178]. [105]. Liq. kyanite. 4 . Isopleth for the composition. Coesite. The temperature of the high quartz-low quartz-coesite invariant point is from Mirwald and Massonne [ 1131. I 3 I I 4 Pressure. Fig. 500-1000°C by Togaya [162].63 GPa.1 GPa higher than the curve of Boettcher and Wyllie [22]. Locations of dashed lines are inferred. Qz. CaAI. ‘“““I’ Fig. The albite = jadeite + quartz reaction shown by Bell and Roseboom [12] and in this figure is about 0. NaAlSi206. grossular. and from Zhang et al. Phase relationships for SiO2. 3 . Gr. Cor. The melting curve is from Jackson [77] at pressures below 4 GPa. 1131. quartz. Liu [loll synthesized NaAlSigOg in the hollandite structure at pressures from 21 to 24 GPa. 1. from Kanzaki [83] at pressures between 4 and 7 GPa. corundum.4 GPa higher at 1300°C than the pressure given by a linear extrapolation of the curve of Bohlen and Boettcher [24].?SizOs [67. 23. T>lOOO”C by Liu et al. 600°C for this reaction [81]./ 2 . The curve of Bohlen and Boettcher would intersect the albite = jadeite + quartz curve at about 1300°C rather than the jadeite + quartz (coesite) = liquid curve.[160]. Isopleth for the composition. At about lOOO”C. The . Numbers beside curves refer to the following sources: 1 . 5 10 15 GPa Pressure. The high quartz-low quartz curve is from Yoder [172]. GPO . Jadeite. Ky. NaAlSigOs [12. 62. 331.[4]. Boundaries for the tridymite and cristobalite fields are from Tuttle and Bowen [164] except that the cristobalite-high quartz-liquid invariant point has been shifted to 0. and a mixture of NaAlSi04 (CaFezOa-type structure) + stishovite above 24 GPa. 2 . Tsuchida and Yagi [ 1631 reported a reversible transition between stishovite and the CaC12 structure at 80-100 GPa and T> 1000°C. The quartz-coesite transition is from Bohlen and Boettcher [24] but note that their curve lies toward the low-pressure side of the range of curves by others [5. 1000 0 I I I I .latter passes through the “consensus” value of 1. 3.7 GPa to accomodate the data of Jackson [77]. [178] at pressures above 7 GPa. liquid. the quartz-coesite curve shown by Bell and Roseboom [12] and in this figure is about 0. However. Also.[168].

and they synthesized the hollandite structure of KAlSi3Os at 9OO”C. 164. albite. 151-153.1 GPa and temperatures from 800 to 9OO”C. Fig. 142.OB Mole percent Or KAISi. 39. Note that the phase boundary is essentially isothermal except in the Ab-rich portion of the diagram. 1751. anorthite. An. An CaAlzSizOe Ab NaAISi. 5. Or. Compositions of coexisting alkali feldspar and plagioclase at 0. 139. 1491. 12 GPa. 58. In experiments from 8-10 GPa and 700”-lOOO”C. [144] synthesized KAlSi3Os in the hollandite structure. 75. KAlSi30s [93.250 PHASE DIAGRAMS Leucite + Liquid High Sanidine IIOOI 0 I I I I 2 Pressure. Ab. 156. [88] synthesized the assemblage K2Si409 (wadeite-type structure) + kyanite (A12Si05) + coesite (SiO2) from the composition KAlSi30s. Isopleth for the composition. I GPa I 3 I I 4 _ Fig. and at 700°C 11 and 11. 1651 and ternary feldspar phase relationships [68. At 12 GPa. 4.O. Many others have discussed ternary feldspar geothermometry [lo. 121. 900°C Ringwood et al. 54. as indicated [49]. 80. 66. 63. . orthoclase.5 GPa. Kinomura et al.

1 GPa.PRESNALL 251 1800 I I I I 1 I I 1 I I 17001600 Liquid t Corundum _ Liquid + Corundum 7 7001 NaAlSi308 Albite I IO I 20 I 30 I 40 Mole I I 60 50 Percent I 70 I I 80 9gaA. 6. 941. 1751. .5 GPa [79. 2 si o 28 Anorthite Fig. 1171.CaA12Si208 (anorthite) under anhydrous conditions at 1 atm [26. 2 GPa [33. Temperature-composition sections for the join NaAlSigOs (albite) . and under H20-saturated conditions at 0.

KAlSi308 (orthoclase) under anhydrous conditions at 1 atm [148]. albite.O. Liq. vapor.Or II \ 20 30 40 Weight 50 60 percent 70 80 90 KAISi. liquid. Fig. V.2 GPa [29] and 0. Locations of dashed lines are inferred. 1751. and under HZO-saturated conditions at 0.5 GPa [ 119. Temperature-composition sections for the join NaAlSigOg (albite) . 7. Ab. .252 PHASE DIAGRAMS 130( Liquid 120( / Leucite t Liquid I lO( Feldspar + Liquid lOO( Feldspar Liquid t Vapor / / Orthoclase t Liquid tVapor 70( t Vapor / Orthoclase tVapo 60( 2 Feldspars + Vapor 50( Na*lSi.

Position of dashed curve is inferred. Isopleth for the composition MgSi03 [7. 8. GPa Fig.PRFBNALL 253 Orthoenstatite Protoenstatite 5 IO Pressure. 76. For additional data on melting temperatures up to 58 GPa. For additional data at pressures above 15 GPa.1 GPa and lOOO”-1200°C.5 GPa. 140.13 GPa below which enstatite melts incongruently to forsterite + liquid [45]. 56.7 and 42. For CaMgSi206 composition. [ 1lo] found a mixture of perovskite (MgSi03) and glass at 21. Melting curve for diopside. and curve 2 is from Boyd and England [33]. 57. see Zerr and Boehler [ 1771. Mao et al. See also Yoder [173] for data below 0. 9. 9. 65. . They interpreted the glass to be a second perovskite phase of CaSi03 composition which inverted to glass on quenching [see also 1021. 35. 13001 I I I 2 I 3 I 4 I 5 Pressure. 127. see also Sawamoto [147]. CaMgSi& Curve 1 is from Williams and Kennedy [ 1661 uncorrected for the effect of pressure on thermocouple emf. 1691. 45. 92. 15 GPa 20 25 Fig. Not shown is a singular point at about 0.

+ Gt Di + a . 56. protoenstatite. forsterite. 128. 14.95 GPa. 91. MgzSi04.O. orthoenstatite. Cpx. 1501. Pv. . Fig. Fo. clinopyroxene. ilmenite. orthopyroxene. perovskite.254 PHASE DIAGRAMS 1601 I atm 20 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ II?Gt II + CaSi03Pv CM CaSiL3Pv _ -. Pen. 170. CM. 41. Di. Mole percent Fig. Pressure-composition section for the system Garnet and MgSiOs-CaSQ at 1650°C [55. C. 106. 36. liquid. 8OOV 20 40 60 80 CaMgSi.‘CPX IO -_ CaSi03 Pv _ Pen + Di I 3p 1 Mole \ percent Casio. 10.x 0 $ 14 -. 441. 571. Opx. 11. The thermodynamic models are based on data from other sources [37. 1711. are the same phases. Opx. See also data of Biggar [ 151 from 1 atm to 0. Many others have also discussed phase relationships on this join [9. Thermodynamically modeled subsolidus phase relationships for the system Mg2Si206 (enstatite) CaMgSi206 (diopside) from I. Pig.OB 2o 40 60 80 CaMgSi. u Oen + Di \ Mg. when they are free of Ca on the left-hand margin of this diagram. 98. Gt. 5c I Di 60Casio -3 ‘Oen I I I Oen + Di I I I I I’ Mg. a high-pressure phase of unknown structure. pigeonite. respectively. 118. The join MgzSi206 (enstatite) . diopside.5 to 10 GPa [56. garnet. 42.Si.SI. 11. 12. 123. Oen. clinopyroxene. Di.O. 78. as majorite and high-P clinoenstatite on Figure 7. Liq. diopside. orthopyroxene.Oe Mole percent Fig.CaMgSi206 (diopside) at 1 atm [43].

Lindsley and Andersen [97] should be consulted for correction procedures required before plotting pyroxenes on these diagrams for geothermometry. ferrosilite (FeSiO3). Periclase + Liquid 2500 1 Anhydrous ite ie Spine1 Forsterite 1 /I: / / Spine1 \ ] -L I / I 5 Pressme. Hd. 1. .5 GPa. En. Additional studies of the melting relationships are Ohtani and Kumazawa [126] and Kato and Kumazawa [84-861. Lindsley [95] has presented three other similar diagrams at 0. Phase relationships to the right of the forbidden zone boundary are metastable relative to augite + olivine + silica. and 1. orthopyroxene + augite + pigeonite. Isopleth for the composition Mg2SiOd [48. Locations of dashed lines are inferred. 13. 14. G Pa Fig.PRESNALL 255 Mole percenl Fig. and pigeonite + augite equilibria at 1 atm and 500-1300°C [95]. 1411. hedenbergite (CaFeSi206). diopside (CaMgSi206).5. Fs. enstatite (MgSi03). Orthopyroxene + augite. Di. 57.

O. 821. Mole percent AI.!?10~ Mole percent 101 MgSiO. lOOO”-14OO”C. Liu [loo] subsequently revised this result and found that pyrope transforms to the ilmenite structure at about 24-25 GPa. stishovite (SiO2).2000 t Llquld Pyrope iti E I400 c 13001000 I200 0 I I I 2 / 3 .SIO. 1571 give additional data and discussion of these phase relationships. Sp. Phase relationships for the system Mg2Si04 (forsterite) . Locations of dashed lines are inferred. 1 1 5 1 1 IO 1 1 15 1 h 20 k ” 1 25 ’ 30 ’ - I AI. [3]. . 5 GPo Mg. 16. For additional data along the boundary between the garnet and clinopyroxene + garnet fields at 1OOO”C.see Akaogi and Akimoto [2]. Mod Sp. . Mw.essure. 341. Phase relationships at pressures less than 5 GPa are from Boyd and England [32]. 18.O. . 01. perovskite (MgSiOg-FeSiO3 solid solution). . Fig. SP I- PV Pv + Gt \ P\ \ Gt Al:o. 87. 6 7 8 9 IO OLIVINE Fig. . 1 Gt \ \ \ Mg. [125]. . Fig. and that ilmenite then transforms to perovskite at about 30 GPa. magnesiowiistite (MgO-Fe0 solid solution). Locations of dashed lines are inferred. the A1203 content of pyroxene in equilibrium with garnet increases with decreasing pressure to at least 15 mole percent [30. 200800°C. . The melting curve at 5 GPa and above is from Ohtani et al.5 GPa. Liu [99] reported that pyrope transforms to perovskite + corundum at about 30 GPa.S. St.FezSiO4 (fayalite) in equilibrium with Fe at 1 atm [27]. olivine.O. Isopleth for Mg3A12Si3012. 15. PvtMw 25- I I 1 .o. Pressure-composition sections for the join Mg2Si04-Fe2Si04 at various temperatures. spinel. pyrope garnet. Pressure-composition section for the join MgSiOjAl203 at 1000 and 1650°C [57.?. 20 40 60 80 Fe. 17. Other references [51. Pv. modified spinel. Phase relationships above 21 GPa are from Ito and Takahashi [76] and those below 21 GPa are from Akaogi et al. . At 1100 and 1600°C for pressures between 2 and 6. 1 /&LPv+Mw+St /&j-Pv+Mw+St Fig. IO 20 30 40 Weight 50 60 percent 70 80 90 Fe.

Wollastonite CaMgSi.PRESNALL 257 A’. 9. enstatite. Grossular. Ca-Tschermak’s molecule. Di. Pyrope.03 Corundum 1200 OC. Wo. Ca3A12Si3012. Ca-Gt. wollastonite. 20. Enstatite Fig. Ca-rich pyroxene (Cpx). diopside. and Ca-poor pyroxene (Opx or Cpx) at various pressures and temperatures [69]. 19. En. 2000. MgSiO.3 GPa [30]. Compositions (unsmoothed) of coexisting garnet (Gt). .O. Diopside Weight percent MgSiO. Mg3Al$Si3012. Mg-garnet. corundum. Mg-Gt. Co. Fig. Labels of the type. +- Grossular. indicate pressure (GPa) followed by temperature (“C). Pyrope GPa GPa Diopside Mole % CaSiO. 3 GPa CaSiO. CaAl$i06. The system CaSi03-MgSi03-Al203 at 12OO”C. Cagarnet.

.-.p?-.-.IRON + MAGNETITE I 1 1 -I lC20-.. --I”.- Cl!.- - -‘-‘~ y. 1381..g?-.800CY-IRON + WkTlTE __.- ..- - 600--‘-.-..py(f=JF.--pJ t -. n! (u 1200 2 I “+ aJ u “J k-/-l.-.-. -.-.-.0-l” .. 7.. 21.-ic3L..-.-.@C.-.lDrlhl / + \A/iicTlrc -.Fe0 23 -. -.. -L- lC24.6’1.i’ AIR .IQUID Fe /I . -.-.-. 64.-..-. section for the system Fe-O at 1 atm [46.-.-. Temperature-composition lines are oxygen isobars in atm.-.-.-.258 PHASE DIAGRAMS I L..-.. Fig...\.p-.o-14-.. . - 24 Weight 25 26 % Oxygen 27 FesO. )- .. pL.- .O.~ .-.-.-. 29 Fe.--. Light dash-dot .-.3 (/!L.Cj-E.-.Fe 0.- .$!L.1 0._-_-_-I .47. 120.-.__. -.I I I-.cB -..

magnetite (Fe304).PREBNALL 259 Rutile TiOo 1 * . ilmenite (FeTiOs). Fpb. 22. Mt. Psb. Hem. The system TiOz-FeO-FqO3 at 13OO”C. wiistite (Fed3 . hematite (FezOg). Wiis. ferropseudobrookite (FeTi205). Light dashed lines are oxygen isobars labeled in log oxygen fugacity units (atm). 1300°c One atm Mole percent Hem Fig. pseudobrookite (FezTiOs). 1 atm [161]. Ilm. ulvospinel (FezTi04). Usp.

ulvospinel. Ilm. indicate mole % ilmenite in the ilmenite (FeTiOs) . magnetite. . Temperature-oxygen fugacity (&) grid for coexisting magnetite-ulvospinel solid solution and ilmenite-hematite solid solution pairs [ 1551. hematite. 23. Usp. “C Fig. ilmenite. Lines with labels of the type. Mt.magnetite (Fe304) solid solution. indicate mole % ulvospinel in the ulvospinel (Fe2Ti04) . U-70.260 PHASE DIAGRAMS r o”-1: k 0 -: i -2c ) Temperature. Lines with labels of the type. Hem.hematite (Fe203) solid solution. I-70.

Pa-out (0. (0.F)2. melting in the presence of a pure Hz0 or H20-CO2 vapor with Hz0 mole fractions of 1. 25. See Yoder and Kushiro [174] for an earlier study of the stability of phlogopite.5). KMg3AISi30to(OH)2 (curves 3-6). so that the curve above this pressure is metastable. I 5oc 800 900 1000 1100 Temperature.[28]. The univariant curves labeled Pa-out (1 . Mg$i205(OH)4 (curves I and 2) and phlogopite. Curves 36 are not univariant [114]. and Oba [124]. 2 .[90]. 0. and the patterned areas labeled F430H57 and Ftoo are from Holloway and Ford [72] and Foley [52].PRESNALL 261 Pa-out 400 / 800 Temperature”C I 1000 1200 IL IO / .3) are from Gilbert [59].5 GPa on curve 4. . Small concentrations of other constituents in the vapor are ignored. The dashed curve labeled OHtnu. Pressure-temperature projection showing the upper temperature stability limits for serpentine.5.5) . and give the maximum stability of pargasite during Fig. and represent more closely the stability of phlogopite in the mantle. stability limits. and show the breakdown of pargasite during vapor-absent melting for different proportions of fluorine and hydroxyl in the pargasite. 24. Curves 5 and 6 give the maximum stability of phlogopite in the presence (curve 5) and absence (curve 6) of vapor. 3-6 . and Paout (0.“C 1200 Fig.< ‘Pa-out .[115]. Holloway [71]. Curves 3 and 4 give the corresponding maximum stability of phlogopite in the presence of forsterite and enstatite.3. (Pa) NaCa2Mg4A13Si6022(OH. and 0. 1400 . / 1300 . . Numbers beside curves refer to the following sources: 1 . Pressure-temperature projection of pargasite. Montana and Brearley [ 1161 speculated that a singular point exists at about 1.0.O).

M. that is stable along the liquidus at pressures above Acknowledgements. 27. (Ross et al. 2 . about 170 GPa. 143. Numbers beside curves refer to the following sources: 1 [159]. 108. 3 . Analysis of shock temperature data for iron. GPa Fig. Fig. 381. T.[112]. inner-outer core boundary (329 GPa).. Geosciences Program. High pressure melting curves for iron.. For reference to Figure 26 at low pressures. [176] (not plotted but located at 6350 K. 1977. Matsui [ 11 l] has also proposed the existence of a new phase at 300 GPa and temperatures above 5000 K. Ito. Res. and Boehler [ 171 are used for the a-&-y phase relationships. and J.[25. core-mantle boundary (136 GPa). Gallagher and Ahrens [54] found that earlier shock data from their laboratory [ 1l] are 1000°K too high. IOC.[20. Saxena et al. 211. Akimoto. 3. CM.[17-19. Akaogi. Several additional references [61. Bass. 15. Ahrens..40]..[II]. REFERENCES 1. 5 .[I]. Olivine-modified spinel-spine1 transitions in the system Mg2SiOq-Fe2SiO4: Calorimetric measurements. 90106. 300 GPa) are at slightly higher temperatures than the data of Brown and McQueen.[17. Bundy [40]. Preparation of this compilation was supported by Texas Advanced Research Program Grants 009741007 and 009741-066. E. Tan.[109]. 2 . On the basis of molecular dynamics calculations. center of Earth (364 GPa). Pyroxene-garnet solid-solution equilibria in the systems Mg4Si4012-Mg3A12Si3012 and Fe4Si4012-Fe3A12Si3012 at high pressures and temperatures. and geo- 2... 103. 9 . High-Press. The shock data of Yoo et al. Low pressure phase relationships for iron. and A. . 738. the curves of Mirwald and Kennedy [ 1121. 1791 also discuss the WE transition. 4 . University of Texas at Dallas. J. C. M.[73]. Numbers beside melting curves and brackets refer to the following sources: 1 . [145] and Anderson [8] have proposed the existence of a new phase. [146] have suggested that al-iron is the liquidus phase down to a pressure of 60-70 GPa. 1531. 3 . Contribution no. Int. Akaogi.[167]. [l l] and Brown and McQueen [38] into agreement. and by National Science Foundation Grants EAR-8816044 and EAR-9219159. 4 . 5 . H.[6]. 145157. Phys. and S. al-iron. 8 . 200 GPO Ethcp) Pressure. 7 [107]. 235 GPa and 6720 K. D. 6 . 21. thermochemical calculation.[103]. Earth and Planet. 26. 2. Navrotsky.262 PHASE DIAGRAMS 6000 - CM IOC I I 300 100 Pressure. which brings the data of Bass et al.

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35. H. W. 74. S. 273. 70. Contrib. L. Geol Sot. Application of the solid-helium pressure medium in a study of the CI-E Fe transition under hydrostatic pressure. A. Williams. T.. Am. 1981. Herzberg. Jr.. J. 1962. 159. 3I. No. 173.. Phys. Mineral. Zhang. M. and Boehler. 259-270. 4359-5366.K20 . J. Hannemann. Taylor. Suito.. S. R. 160. J. 267-A. Chaney. A. The melting curve of iron to 250 gigapascals: A constraint on the temperature at Earth’s core. 157. B. 1977. Strong. T. Change of melting point of diopside with pressure. S. High pressure 162. D. Mineral.56.. 168. D. No. 1989. 66. J. 1958. hydroxy-clinohumite and 10 A-phase. 179. 1969. Tectonophys. Stixrude. H. 1993. J. R. 172. J. E.. Stewart. 74. H. Ahrens.. 73. 1989. Direct determination of coesitestishovite transition by in-situ Xray measurements. H.. Whitney. Jeanloz. Gasparik. Manghnani and S. Ge02. W. Yoder. 1977... C. Stability of iron-free pigeonite at atmospheric pressure.. J. generation and phase transformations of SiO2 and 163 164 165 166 167. 62.. Mineral. Symp. Tsuchida. 154.. Am.. Sci. 49. Q. and J. Stability of (Mg. 19. Jr. L. H. MacCrone.. Res. J. Ternary feldspars.. 1964. 1981. 16. H. J.. 1992. Bell. Roseboom. 1950. 175 Yoder. 60. Bass. Petrol. Science.. and T. 3. and R.. .Fe)Si03-perovskite under hydrostatic. Fei. A new post-stishovite high-pressure polymorph of silica. and E. 161. 155. Mem. Jr. Smith. H. edited by M.-Y. Lower temperature terminations of the threephase region plagioclase-alkali feldspar -liquid. R. 57. J. inert conditions to 580 kbar (abstract). Sci. Webb. 340. 1992. M. C. and H. and M. Tuft. 0. Metall.. 217-220. Liebermann. 1976. F. Tuttle. Washington Year Book 80.. E. AGU. 174. R. Carnegie Inst. C. 488-497... Am.. K. 1969. 1975. 1232-1241. 272274. Jr. 14.. Crystallization of iron-free pigeonite in the system anorthite-diopside-enstatite- silica at atmospheric pressure. 280315. Academic Press. 1993.. 158. Williams..78519.793.. Geol.. 17 1. Lett. Yang.MgO .. 255-266... in High-Pressure Research. 687-691. Mat. J. H. Melting of a hydrous phase: phlogopite. 19. Am. Yoder. Whalley. R. Phase equilibria in the system FeO-Fe203-Ti02 at 13OO”C. Yamamoto. Yagi. Res. Am.. Stormer. 1987.-Y. Eos Trans. and T. D. 178. 1972. K.. C. 98. Am. B. Trans. Shock temperatures and melting of iron at Earth core conditions. and S.. J. A m Mineral. Mao. edited by C. Svendsen. and I.H20. Spencer. J. pp. Am. 277. 10161030.Fe)SiOj perovskite and the structure of the lowermost mantle. A petrogenetic grid for pelitic schists in the system Si02-A1203Fe0 . K. and C. Melting of (Mg. 22. T. Lindsley. Mineral. F. IOI. High-low quartz inversion up to 10. Y. B. Stewart.. Rev. and E. S. 74. 1973. AGU. R. 169. Geophys. Carnegie Inst. Pike. 667-674. C. Akimoto. 558582. Lett. The iron fusion curve and the triple point. Jr. A solution model for coexisting iron-titanium oxides. and S. and W. AGU. Ross. Kushiro. Petrol.. The system MgO-Si02-H20 at high pressures and temperatures Stability field for hydroxyl-chondrodite. R. R. 2657-2611. and N. 149-164. Melting curve of diopside to 50 kilobars. in High Pressure in Science and Technology. Eos Trans. Spear. 168-169. J.268 PHASE DIAGRAMS wiistite (abstract).. 1189-1201. Melting and subsolidus relations of SiO2 at 9-14 GPa. 153 pp. Jr. 1957. 288-312. 60. 4. Bowen. C.. C. Bukowinski... and D.. K. Res. 1973. 177. D. Holmes. Origin of granite in the light of experimental studies in the system NaAlSi308-KAlSi30g-SiO2H20.. K. 827-835.. Foster.. G... Yang. Yagi.. Proc. Yoder. 10571060. A practical two-feldspar geothermometer. S. Washington Year Book 56. Trans. 176 Yoo. G. and Kennedy. Am. and J. Geophys. Stormer. and J. Zerr. 364-374. and Y. H. 236. Res. 1977. Akimoto.000 bars. Jr. Nature. 1984. 206-214. 368.. S. 1. Phase relations of pure Mg2SiO4 up to 200 kilobars. M. The distribution of NaAlSijOg between coexisting microcline and plagioclase and its effect on geothermometric calculations. S. N. T.. Togaya. Zou. 1993.. Geophys. P. H. T. Mineral. 181-183.. Akimoto. 373-376. 170. Homan. 3931-3934. Sci. 1952. M.

Diffusion Data for Silicate Minerals.. B. (2) Diffusion is the thermally-activated. On a macroscopic scale. the complexity of describing diffusion in multicomponent systems rises 269 J. and Liquids John B. linear equations appear to be adequate for relating each diffusive flux to the set of operative forces [137.g. 1281.J. 32. 121. therefore. Glasses. p. FORCES AND FLUXES energy. The reader is urged to read one or more diffusion texts [e. Brady. the application of the resulting diffusion coefficients to complex geologic problems may not be straightforward. MA 01063 of Geology. a brief summary of the equations required for a phenomenological (macroscopic) description of diffusion follows. the movement of An i moles of chemical component i from a region (II) of high chemical potential (/. a chemical potential gradient provides a therm odynamic force for atom movement. relative movement (flux) of atoms or molecules that occurs in response to forces such as gradients in chemical potential or temperature. Smith College. 2. ncomponent system with respect to reference frame R may be described by (3) where x (m) is distance and the n2 terms L: (moles of i/m. must lead to a net decrease in free Thus. Department ampton. North- Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union. 13. p. For example. This compilation is intended to be a guide to recent experimentallydetermined diffusion coefficients and. through the papers cited. The instantaneous. to important older literature. Diffusion is spontaneous and. and application of diffusion data. To provide a context for the tables.451. one-dimensional. . Because each component of the system may move in response to a gradient in the chemical potential of any other component. Although the equa tions for well-constrained experiments are relatively straightforward. isothermal diffusive flux JR (moles of i/m2s) of component i in a single-phase. Brady 1.s) are “phenomenological diffusion coefficients” [36]. 99. estimation.51 before attempting to use the data presented here.Li”) to a region (I) of lower chemical potential (pi’) will cause the system Gibbs energy (G) to fall since and using the definition of pi [ 139. 147. INTRODUCTION Diffusion is an integral part of many geologic processes and an increasing portion of the geologic literature is devoted to the measurement.

Joesten 194. 16. 17. 971. 99. More complicated boundary conditions and geometries may require numerical approximation [32. 96. 98. Most experimentalists achieve this by their experimental design..: . 55. 81. Additional ways to simplify the treatment of multicomponent systems are addressed in Section 5. 1341 (4) 3. fluxes.1) and the number of diffusion coefficients to (n-1)2. ) (9) [ 1341. The next two sections present definitions and equations used to describe these binary (Zcomponent) experiments. Although equations (3)-(5) are theoretically satisfying. (3 relates the instantaneous flux Ji (moles of i/m2s) of component i to the one-dimensional gradient of the concentration of i. Similar analytical solutions exist for related boundary conditions and/or other geometries. then equation (4) may be simplified to (%). # DF so that (n-1)2 diffusion coefficients Di (m2/s) are needed for (6). the isothermal.g. All of the equations (7)-(13) implicitly assume constancy of volume. and others [e. 1331 showed that if the forces. the number of required diffusion coefficients to 1. If Di is not a function of composition (Ci) and. In semi-infinite cases such as (10) and (1 I). unless the experiment attains a steady state.270 DIFFUSION DATA rapidly with the number of components.1). First. p.=Iq$). not a function of position (x). 321. The most obvious simplification of (6) is to limit the number of components to 2 and. for which the fixed laboratory reference frame is a mean volume reference frame. In finite . Some commonly used solutions to (5) for planar geometries are given in Table 1 and two of these a~ shown graphically in Figure 1. It is clear from Table 1 and Figure 1 that the parameter fi may be used to characterize the extent of diffusion. and reference frame are properly chosen. FICK’S LAWS Adolf Fick’s [50] empirical equations were used to describe binary diffusion experiments long before the more general equations (3) and (6) were developed. which has many analytical solutions [6. Onsager [ 132. components. the matrix of coefficients relating the forces and fluxes is symmetrical L. time (t) is also a variable and a continuity equation (Fick’s Second Law) (8) reducing the number of independent diffusion coefficients to (2n. = L. but unfortunately D.. and defines the diffusion coefficient Di (m2/s). most workers use empirical equations related to (3) that involve measurable compositions Cj (moles of j/m3) must be solved. Only (n-l) compositions are independent. Fisher [Sl]. the distance x that has attained a articular value of Ci after time t is proportional to P Dit . Chap. Two impor tant results help limit this complexity. in part because chemical potential gradients are not directly measurable in most cases. However. and must be modified if the sample volume does change [lo]. However. dCi/dx (moles of i/m4). l] have applied these equations successfully in modeling the diffusion evolution of coronas and other textures in some rocks. Second. therefore. isobaric Gibbs-Duhem equation [ 139. they are not generally used to describe diffusion experiments. notably spherical and cylindrical cases. Fick’s First Law Ji =-Di for the single phase in which the diffusion occurs reduces the number of independent gradients to (n. therefore.

and liquids. Therefore. In such cases the Di calculated with these equations will be at best a compositional “average” and equation (8) should be considered. This is accomplished either (a) by using a measurement technique (typically involving radioactive tracers) that can detect very small changes in Ci. A commonly-used analytical solution to (8).Fixed SurfaceComposition cases such as (12) and (13). These fi relations provide important tests that experimental data must pass if diffusion is asserted as the rate-controlling process. 4. Approach (a) yields a “tracer diffusion coefficient” for the element that is specific to the bulk composition studied. or (b) by using diffusional exchange of stable isotopes of the same element that leave the element concentration unchanged.00 for x = 0 as t + 0 Semi-infinite Pair Solution Ci =CO for x>O at t=O 1C. Approach (b) yields a “self-diffusion coeffi cient” for the isotopically doped element that is also specific to the bulk chemical composition. glasses. 3. DIFFUSION COEFFICIENTS In general. They also provide simple approximations to the limits of diffusion when applying measured diffusion coefficients to specific problems [ 1471. was obtained by Matano [122] using the Boltzmann [8] substitution (x=x/& 1: Equation (14) can be evaluated numerically or graphi tally from a plot of (Ci .BRADY 271 Table 1. Both approaches generally ignore the opposite or exchange flux that must occur in dominantly ionic phases such as silicate minerals. observed compositional profiles might not match the shape of those predicted by (9)-(13).CO) versus x. =0 for x=0&L Finite Sheet.CO)/(Cl . the fractional extent of completion of homogenization by diffusion is proportional to a. =Cl for x<O at t=O 1 Finite Pair Solution Ci =Cl for O<x<h Ci =CO for h<x<L Solution (y)=&exp[&) where cx=lL”(Ci -CO)dx (10) (E) = ierfc[--&=j (11) at t=O at t=O (ilC. equations (9)-( 13) may be used with confidence only if Ci does not change appreciably during the experiment. for the same boundary conditions as for equation (1 1)./~x). one must assume that Di is a function of Ci. Experiments in which composition does change significantly are often termed “interdiffusion” or “chemical diffusion” experiments. Commonly-usedsolutions to equation(9) BoundaryConditions Thin-film Solution Ci + CO for Ix]> 0 as t + 0 } c. If Ci does change significantly in the experiment and Di is a function of Ci. where the point x = 0 (the Matano interface) is selected such that (15) .

113.2 0.’ and BZ represents BzbZ. = (N. For binary. Plotting (Ci -CO)/(Cl CO) as a function of x/L normalizes all casesto a single dimensionless graph.6 0.0 0.8 0. Darken’s analysis showed that in the presence of inert markers the D AB-. For minerals that are not . Darken [35] and Hartley and Crank [83] showed that for electrically neutral species. who studied the interdiffusion of Cu and Zn between Cu metal and Cu7&&~~ brass. lo]: 1 + I[ (17) which requires vacancy diffusion if a#b.4 and various values of Dt/L2 (labels on curves). This expression permits interdiffusion coefficients to be calculated from more-easily-measured tracer diffusion coefficients..272 DIFFUSION DATA 0. If a=b. for which neither (8) nor (14) is correct. between ionic crystals. (A) The “thin film” solution of equation (10) is shown with a=1 for various values of fi (labels on lines). x 3 g 0.0 0.0 s u . cation exchange [32.8 1. Darken developed his analysis in response to the experiments of Smigelskas and Kirkendall [ 1481. the binary (AtiB) interdiffusion coefficients (D.D.4 0.230-2341.Z + NBZD. A similar analysis for binary cation interdiffusion (AZ w BZ where AZ represents Al”Z. (B) The “finite pair” solution of equation (12) is shown for h/L=O.Z) D AB-. Smigelskas and Kirkendall observed that MO wires (inert markers) placed at the boundary between the Cu and brass moved in the direction of the brass during their experiments. therefore.4 x/L 0.CO) as a function of x2 at any time yields a straight line of slope -l/(4Dit).0 1.0 0.0 (4 s u 3 9 -1.2 0.“) in appreciably ionic materials such as silicate minerals yields [5. Plotting ln(Ci .-. Ii I + (18) [ 12 I].) for the interdiffus ing speciesare related by independent fluxes and.8 1.Di + NADIR) where N A is the mole fraction and YAthe molar activity coefficient of component A.4 X2 -2.6 0. ) obtained in a Boltzmann-Matano type experiment and the tracer diffusion coefficients ( Da and D*. indicating that more Zn atoms than Cu atoms crossed the boundary. Diffusion experiments that follow the Boltzmann-Matano approach have the advantage of determining Di as a function of Ci and the disadvantage of risking the complications of multicomponent diffusion. The initial boundary between the two phases is marked by a dashed vertical line. p. 112. Figure 1. the “tracer” diffusion coefficients of Cu and Zn can be determined in addition to the interdiffusion coefficient DCuZnm.6 0.. the Matano interface is the original boundary between the two crystals. Graphical solutions to equation (9).5 1.2 0. then ( 17) simplifies to (Daz)( Diz ) = (NA.

” The @t test can be used if data are gathered at the same physical conditions for at least two times. dislocations. see also 1611 has generalized the relationship (17) to multicomponent minerals. liquid.g.BRADY 213 ideal solutions. 46. EXPERIMENTAL DESIGN Rarely is diffusion in geologic materials binary. 201. 95. Therefore. usmg tracer diffusion A few additional considerations should be mentioned regarding the collection and application of diffusion data.” l l l l l . and other crystal defects may have profound effects on diffusion rates [e. Experiments involving grain-boundary diffusion [e.Cooper [75. 167. Multicomponent diffusion presents the possibility that diffusive fluxes of one component may occur in response to factors not included in (7)-( 1S). coupling of diffusing species. 13.. Another approach. In general. a matrix of diffusion coefficients must be determined before the analysis can proceed. preferably differing by a factor of four or more. If the mineral. crystal interfaces. Dg or Li. The full expression is quite long. then the contributions of “extrinsic” grain-boundary diffusion must be shown to be negligible. and 6il = 0 if i#j. it is essential that the mineral being studied is well-characterized. In (19) zi is the charge on cation i. Diffusion in rocks or other polycrystalline materials may occur rapidly along grain boundaries. Water can have a major effect on diffusion in many geologic materials. The offdiagonal (i#j) diffusion coefficients. Because many kinetic experiments cannot be “reversed. Vacancies. 301 who discuss diffusion in ternary glasses and present criteria to be satisfied to obtain “effective binary diffusion coefficients” from multicomponent diffusion experiments. The form of this tensor is constrained by point group symmetry and the tensor can be diagonalized by a proper choice of coordinate system [ 13I].g. 49. Garnet is the one mineral for which offdiagonal diffusivities are available [ 19. and its inverse offer the most hope for diffusion analysis of multicomponent problems [ 115. 73. 251. Lasaga [105. diffusion may be a function of crystallographic orientation and the diffusion coefficient becomes a second rank tensor. One approach used by many is to treat diffusion that is one-dimensional in real space as if it were onedimensional in composition space. 102. It should be noted in using equations ( I6)-( 19) that the tracer diffusivities themselves may be functions of bulk composition. 47.g. then an equilibrium oxygen fugacity should be controlled or measured because of its effect on the vacancy concentration. 5. 154. I 1. etc. 19.” every effort should be made to demonstrate that diffusion is the rate-controlling process. 6. In these cases. This approach was formalized by Cooper and Varshneya [28. If polycrystalline materials are used in experiments to measure “intrinsic” or “volume” diffusion coefficients. Although some simplification in data presentation is achieved in this way. but simplifies to (19) if the solid solution is thermodynamically ideal. water fugacities are an essential part of the experimental data set. or glass contains a multivalent element like Fe. In anisotropic crystals. 411= 1 if i=j. 150. 1581 are beyond the scope of this summary. is to diagonalize the diffusion coefficient matrix for (6) through an eigenvector analysis. equation (6) or (3) must be used. 103. MULTICOMPONENT DIFFUSION coefficients Dy to calculate multicomponent interdiffusion coefficient matrices. The often-overlooked “zero time experiment. Important tests include the m relations noted in equations (lo)-( 13) and the “zero time experiment.. 711. or surfaces and will not necessarily record intracrystalline diffusivities. 121. even in small quantities [e. 1641. the “thermodynamic factor” in brackets on the right side of (l6)-( 18) can significantly change the magnitude (and even the sign!) of interdiffusion coefficients from those expected for an idea1solution [ 12. developed by Cullinan [33] and Gupta and . 291. diffusion coefficients obtained with this procedure are functions of both composition and direction in composition space. such as gradients in the chemical potentials of other components. If water is present. This approach. 201 and they were found to be relatively small.. are unknown for most materials and most‘workers are forced to assume (at significant peril!) that they are zero.

commonly reveals sources of systematic errors. J. and Harrop [81]. J. Some good data also exist for important non-silicate minerals such as apatite [ 157. Askill [2]. . for ease of comparison log D is listed for a uniform temperature of 800°C (1200°C for the glasses and liquids). and their uncertainties. exp (20) AH (J/mole) is the “activation energy.K) and Acknowledgments. 451 and magnetitetitanomagnetite [65. DATA TABLE Due to space limitations. Giletti. but are not included [see 156.591. Note that other closure temperatures would be calculated for different crystal sizes. cooling rates. The closure temperature given is a solution of the Dodson [38] equation for a sphere of radius a=O. Interdiffusion (chemical diffusion) experiments involving minerals are not numerous and interdiffusion data sets do not lend themselves to compact presentation. Vondell provided considerable help with the library work.274 DIFFUSION DATA which duplicates the sample preparation. 3. 21. No attempt was made to reevaluate the data. Also listed are the conditions of the experiment as appropriate including the temperature range. Finally. 1211and may be related for groups of similar materials [162. Use these tabulated log D numbers with caution. S. However. pressure range. glasses.R) is the slope of the line where R is the gas constant (8. B. J.) has been calculated for the silicate mineral diffusion data. m2/s) and form (log D. E. Neither are non-isothermal (Soret) diffusion data [see 1081. Cherniak. 7. and AH have significance in the atomic theory of diffusion [see 32. even though this temperature may be outside of the experimental range.” D. Cooper. 51 problems. Chap. J. Many good. the fit. or the uncertainties given (or omitted) in the original papers. but the silicate minerals offered the clearest boundary for this paper. Interdiffusion data for silicate liquids and glassesare more abundant. and fit by a straight line on a graph of log D (m2/s) as a function of l/T (K-i) [147. heating to the temperature of the experiment. and liquids. the data included in this compilation have been restricted to comparatively recent experimental measurements of diffusion coefficients for silicate minerals. Hofmann [86]. Older data may also be found by consulting the compilations of Freer [56. This paper was improved by helpful comments on earlier versions of the manuscript by D. 23. Logarithms are listed to 3 decimal places for accurate conversion. older data have been left out. Almost all of the data listed are for tracer or selfdiffusion.3143 J/mole. Diffusion data are listed in terms of AH and log D. a sample “closure temperature” (T. R. but can be found by following the trail of references in the recent papers that are included. 1061. and data analysis of the other diffusion experiments. 571. oxygen fugacity. These and other important features of diffusion experiments are described in Ryerson [141]. AHl(2. and an anonymous reviewer. B.l mm and a cooling rate (dT/dt) of 5 K/Ma. even though the original data may not warrant such precision. Kozak. Extrapolation of the data using (20) to conditions outside of the experimental range is not advisable. Log D.303. coefficients for diffusion by a single mechanism at different temperatures may be described by an Arrhenius equation D = D. Ganguly. Chap. Watson. quenching (after “zero time” at temperature).) of this compilation. (m2/s) is the intercept of the line on the log D axis (l/T = 0). R. 136. Freer. 41. The example closure temperatures were included because of the importance of closure temperatures in the application of diffusion data to petrologic [107] and geochronologic [123. and sample geometry. In many cases data were converted to the units &I. N. A. Because diffusion is thermally activated. Diffusion data listed for silicate glasses and liquids have been further restricted to bulk compositions that may be classified as either basalt or rhyolite. and boundary conditions. 82.

Mineral. m E 4 Y WI . Glass. (or D) (m*/s) log D 8oo”c ‘IT. (MPa) 4 (kJ/mole) log D.” (“C) Experiment/Comments Ref. or Liquid Orientation Diffusing Component Temperature Range (“C) P (MPa) 0.

or Liquid Orientation Diffusing Component Temperature Range (“C) P (MPa) 02 (MPa) ma (kJ/mole) log D. Glass. (or D) (m2/s) log D 800°C ‘IT.” (“C) Experiment/Comments Ref.Mineral. u 7 [l@l [loll ? 2 .

0 233 [541 -7.21 -7. reference) biotite powder powder powder I c 88 171.6 -19.6(+10.1 t t 163 (f21) 172 (+25) -11. bulk analysis.854 -16.7 t c L .3 ‘80 650-800 180 4oAr Sr 650-800 750-900 800 “wet” 100. bulk analysis.5) Exchange with CO*. Glass.1) NO uB/ NO -7.4 305 [541 I powder 1’2”‘:’ -5.9 t muscovite (see paper for camp.452) -5.620 (f0.” (“C) 199 Experiment/Comments Ref. cylindrical model. bulk analysis.) powder -16.699(f1.OOO(f1. cylindrical model (AV =1.523 (f0. biotite (see paper for camp. bulk analysis.506) D=lxlO-*’ -19. cylindrical model.98 163 (+21) -8. or Liquid nepheline Orientation powder Diffusing Component Temperature Range (“C) P (MPa) O2 (MPa) 4 (kJ/mole) log Do (or D) (m*/s) -12.4 L c m F 4 Y 4 239 (k8) UB/ NO UBo r 268.Mineral.7 121. bulk analysis & ion [27] -9.322) -19.4~10-~ m3/mole) Exchange with 41KC1 soluon.) phlogopite (Ann4) (see paper for camp.) biotite (An& (see paper for camp. cylindrical model.20 2000 “wet” 100 “wet” 100 “wet” 200 “wet” NO uB/ NO 104.1 t -18.2 (k7.114 ’ i 373 t621 671 [771 281 powder F371 chlorite (sheridamte) (see paper) mucovite powder -13. ion probe too Exchange with 180-enriched water.zO m3/mole) Degassing into water.041 -16. ion probe too Degassing into water.3 “T.204) -1l.229 log D 800°C -17. bulk analysis Exchange with ‘*O-enriched water.6 powder -13. (AV. spherical model.) phlogopite (see paper for camp.

I Sermanite (syn) lc-axis 02MgSi207) lkermanite (svn) I c-axis (CazMgSizb. Rutherford backscatter.2-17. u ii 1180 “wet” 0. Ion probe.1 co2 atmosphere. Rutherford backscatter. or Liquid Orientation Diffusing Component Temperature Range (“C) 500-800 P (MPa) 0.1 w.ii Mineral.: I I N2 N2 N2 UhMgSi207) Sermanite (syn) 02MgSi207) lkermanite (syn) 02MgSi207) &ermanite (syn) GbMgSbO.1 0.) /c-axis /c-axis /c-axis N2 i .1 0. ion probe profile (CO)/ co.) 1 Sermanite (syn) ///c-axis 1x0 ‘80 / 45Ca 54Mn 59Fe 6oCo 1000-1300 800-1300 1100-1300 1100-1300 1100-1300 1100-1300 0.1 O2 (MPa) -12.” (“C) Experiment/Comments Ref. sectioning.1 0. =I@‘4 1 I robe.1 0.9 UB 4 (kllmole) log Do (or D) (m2/s) log D 800°C ‘IT. m. Glass.

” (“C) Experiment/Comments Ref. (or D) (m*/s) log D 800°C “T. or Liquid Orientation Diffusing Component Temperature Range (“C) P (MPa) 02 (MPa) 4 (kJ/mole) log D. Glass.Mineral. .

43 (rt36.222 (*0.36) -5. -8.1000 800-1000 1300-1500 800.0 -21. nd.1 evac. 193 (f10) 243 208. ion probe profiles Exchange with 145Nd water solution.288 -1.8 ! 403 78 1 702 [l-m [1261 [128] [581 I311 [341 VOI isotropic isotropic isotropic isotropic (couple) isotropic (couple) isotropic (couple) isotropic 1050 850 8001000 750-900 1300-1480 800 200 100 200 29004300 29004300 29004300 100 100 3000 100 4000 UB UB uB/ MH UBI GrPC UB/ GrPC UB/ GrPC UB UB UB/ GTPC UB UBI GrPC n.2 act + 2. D’s extrapolated to pure Fo Microprobe profile.(Co2 SiO.Te. fo2 Microprobe profile.8xlO-2’ . other interdiffusion coefficients Exchange with t80-enriched water. = 5.194 -22.602) -12.1400 1200-1450 air air 196 526 414 to 444 -18.6 . g 2 -18. tube 0.690 2.3 -21.5(*0.523(*0.8 604 WI Mn 1300-1480 -7.1 x [Mg/ log Do (or D) (m2/s) n. “sphere” Exchange with 167Er water solution.5 -18.55) 253. / 404 432 D59i+ = -10.4 -21. autoradiography.959 -20.602) -11.d.1000 1300.” (“C) log Experiment/Comments Ref. 301 (+46) 239 (*16) 275.763) . model fits of alm-rich composition G'61 [I41 ~1241 9 j! Wg+Fe)l olivine(MgzSi04) .5) D=2. ion probe profiles ! Calculated from interdiffusion experiments using model. Glass.44 (k37.3(+3.5~10-~~ D=4.3) x10-4) .292 -19.d.1 O2 (MPa) lo-to10-12 UB lo-l3 UB =a (kJ/mole) n.=5.9)x10e6 m3/mole) Calculated from interdiffusion experiments. (AV. ion probe profiles Microprobe profiles.Mineral.8) +9.52 (T37.+) forsterite liebensbergite grossularite C&9 Fe. or Liquid olivine Wd%o-Faloo~ olivine Orientation sintered powder //c-axis Diffusing Component 59Fe Ni Fe-Mg interdiffusion Fe-Mg interdiffusion Co-Mg interdiffusion Ni-Mg interdiffusion ‘80 ‘80 25Mg Fe Temperature Range (“C) 1130 1149-1234 1125-1200 900-1100 P (MPa) 0.6 725 5 14 / 588 Mg 13001480 -6. (AV.9 -19..5 -21.0)x10-6 m3/mole) Exchange with %r water solution. D varies w/direction. anisotropy found Microprobe profile. )Fo91Fa9) //c-axis (couple) //c-axis (couple) //c-axis (couple) //c-axis (couple) Thin Ni film.0 616 ! 562 321 605 57 1 [311 1311 WI [311 [411 ) isotropic powder isotropic isotropic (couple) tslSm 167ET Fe-Mn interdiffusion .1480 -12.5~10-~m~/mole) Microprobe profile. composition.10.009 -7.3 (k20.652 log D 800°C “T. ion probe profiles Exchange with silicate melt.1 0.1 Ah$hPd almandine (Al67SP2xAns b2) ww E’m%GrdJrI ) AlmsoPYPzo Spess94Almg AlmzoPYPzo Spessa4Alm6 AlmsoPYPzo Spessa4Alm6 almandine b’%SPd% pY2 almandine b%SP2dnd’Y2) wope almandine @l&Pd@Y2) AlmsoPYPzo Spess94Alm6 1150-1300 1300.6(f2.-8.7Fa6.6 526 m 86Sr 145w 800.585 -10.Fas> powder (Fa. microprobe profile.5(+18. (AV.6 -20.759 Do= 1.4 -17.1x [Mg/(Mg+Fe)] -8. ion probe profiles Thin 25Mg0 film.1.705 [Fe/(Fe+Mg)] [851 (Fo93.d. tube 0..086 -22. ion probe profiles Exchange with ‘*O-enriched water.6~10-~ m3/mole) Calculated from interdiffusion experiments.959 (f0. D also varies with direction and P (AV a=5.1 evac.740) -8.3) olivine fayalite olivine divine (Fo.143 + 0.000(&0. = 5.301(?0.49) 284.2 -23.19) 205 (+17) 184 (+29) 140 230 (f38) 224.

Zircon dissolution. (or D) (m2/s) log D 1200°C “Tc” (“C) Experiment/Comments Ref.Mineral. Glass. . or Liquid Orientation Diffusing Component Temperature Range (“C) P (MPa) O2 (MPa) =a (kJ/mole) log D.

40) 75(?21) log Do (or D) (m*/s) 2.770 (k1. counting surface Monazite dissolution. 14CGz Thin film.8 -18.3 141.4 .59) -2. counting surface Thin film.439 -0.1 -10.1 0.7 (k5.6 -11. OR rhyolite (obsidian) Mono Craters rhyolite (obsidian) New Mexico rhyolite (obsidian) Lake County.1 1000 0.7 -13. thermo-gravimetric balance Reduction by graphite. B-track profiles of cross section Thin film of 45CaCl.8 -10. ion probe profile of cross section Oxidation/reduction of bead.56) -7.6 -14.3 -10. low water Thin film of Na2 14C03.4) 293(+29) 360(+_25) 297 (+59) 213 (k17) 251 (+29) 113.5) -5.2 -12.081) -0.187 log D 1200°C -14.284 -3. B-track profiles of cross section [91] [91] [1381 [1381 [1661 1931 11551 6Li 0 0 0 0 0 ‘80 Ar 24Na 45Ca 45Ca 45Ca 45Ca 1300-1400 1160-1360 1280-1400 1280-1450 1350-1450 1300-1450 1320-1500 1300-1450 1300-1400 1260-1440 ilOO-14cKl 1100-1400 1100-1400 0.3) 510.59) -10.02 (f0. B-track Thin film of 45CaCl.362 (f0. bulk Fe0 analysis by titration Reduction by graphite.1 looo3000 0. (MPa) air air UB/ GrPC UB/ GrPC Nz air UBI GrPC air IW to co2 UB/ GrPC UBI GrPC uB/ GrPC uB/ GrPC Co2 ‘3202 aa @J/mole) 490.1 800 800 0.1 -11.87) -3. serial sectioning by etching. bulk analysis of sphere Method not described Thin film.8 -10.1 0. counting surface Thin film. OR rhyolite (obsidian) Lake County.2 (k7. or Liquid rhyolite (dehydrated) NM rhyolite (dehydrated) NM rhyolite (obsidian) Lake County.90 (+0.22) -4.0 208.72 (f0.638 (k1. serial sectioning by etching.8 -10.6 [ [116] [1601 ]401 ]401 ]401 [401 [I51 r391’ [116] [891 [152] ’ [152] 1 --I t15211 I air air UB UB UB 163 (+13) 184.3 -11.5 1) 1.2 -10.9(+59.2 -9. microprobe profiles Dehydration in Nz.5(*42.9 .0) 251.436) 3.46) -4.11 (0.48 (fl 1.790 (k2. microprobe profiles Monazite dissolution.0) 103@5) 46. bulk Fe0 analysis by titration Reduction by graphite. bulk Fe0 analysis by titration Reduction by graphite.3 -10.301 -5. Btrack profiles of cross section Thin film of 6LiC1.1 0.1 400 1200 2000 1200 0.450 (t0.854 -6.629) -14.2 -11.1 106.1 0.5 215.211 -9. FTIR profile. “Tc” (“C) Experiment/Comments Ref. OR basalt (alkali) basalt Goose Island basalt (alkali olivine) BC basalt (alkali olivine) BC basalt (alkali olivine) BC basalt (tholeiite) 1921 Kilauea basalt (FeTi) Galapagos “basalt” (Fe-free) (synthetic) basalt (“alkali”) Tenerife basalt (tholeiite) 1921 Kilauea “basalt” (Fe-free) (synthetic) “basalt” (Fe-free) (synthetic) “basalt” (Fe-free) (synthetic) Orientation glass and melt glass and melt melt 6% water melt 1% water glass glass melt with 8% water melt melt melt melt melt melt melt melt melt melt melt melt melt Diffusing Component Ce Eu LREE LREE Hz0 H20 Temperature Range (“C) 875-1100 700-1050 1000-1400 1000-1400 400-850 510-980 800-1100 P (MPa) 0.1 0. bulk Fe0 analysis by titration Exchange with tsO-selected gas.5 -9.140 (kO.1 1000 2000 115.99) -3.Mineral.9 (f13.068) -4.4 (f23. equilibrium model Dehydration in air.9) 288.272 -6.3 -13. Glass. serial sectioning by grinding.010 (YkO. B-track profiles of cross-section on film Thin film of 45CaCl. bulk weight loss.125 -2.59 (f1.

1 0.1 0. but near nickel-nickel oxide due to the cold seal pressure vessel . but fo2 limited by the graphite-bearing piston-cylinder assembly Unbuffered.1 O2 (MPa) air air air air air air air air air air air ul3/ GrPC fia (kJ/mole) log D.1 profiles of cross section.1 0.1 133& ‘Ts ‘=Eu. 0. Key to oxygen fugacity or atmosphere abbreviations in data table CQGM IW h4HN2 - NO - UB UBlGrPC UB/NO Pure carbon dioxide atmosphere Graphite-methane buffer Iron-wustite buffer Magnetite-hematite buffer Pure nitrogen atmosphere Nickel-nickel oxide Pure oxygen atmosphere Quartz-fayalite-magnetite buffer Unbuffered oxygen fugacity Unbuffered.1 0.1 0. Glass. or Liquid basalt (“alkali”) Tenerife basalt (“alkali”) Tenerife basalt (“alkali”) Tenerife basalt (tholeiite) 1921 Kilauea basalt (“alkali”) Tenerife basalt (tholeiite) 1921 Kilauea basalt (“alkali”) Tenerife basalt (tholeiite) 1921 Kilauea basalt (“alkali”) Tenerife basalt (“alkali”) Tenerife basalt (tholeiite) Orientation melt melt melt melt melt melt 1 1 melt melt melt melt melt Diffusing Component 46Sc 54Mn 59Fe 6OCo 6OCo *%r sSSr 133& Temperature Range (“C) 1300-1400 1300-1400 1300-1400 1260-1440 1300-1400 1260-1440 1 1300-1400 1260-1440 1300-1400 1300-1400 1320-1440 T P (MPa) 0. hin film. serial sectionin 0.1 0.1 0. (or D) (m2/s) log D 1200°C “Tc” (“C) Experiment/Comments Ref.1 0.Mineral.

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Santa Cruz. visible or ultraviolet region of the spectrum.998 x lOlo cm/se@. VIBRATIONAL INFRARED AND RAMAN SPECTROSCOPY: TECHNIQUES Q. Here.to the wavelength of light (in cm) by taking its inverse. three separatetypes of light-mediated spectroscopies of interest to geophysics and mineral sciences examined: 1) infrared spectroscopy. molecules or crystals. Electronic transitions may occur in the infrared. Institute of Tectonics. h (6.The role of electronic transitions in controlling the electrical conductivity and in reducing the radiative thermal conductivity of minerals at high temperaturesis briefly reviewed. noneof which have had significant impact to date in the Earth sciences . 2. 291 The primary feature of importance in vibrational spectroscopyis the interaction between the electric field associated with a photon and changes induced by vibrational motions in the electronic charge distribution within a material.and 3) optical absorptionspectroscopy.theseare associated with the electric field of an incident photon interacting with the vibrational or electronic statesof materials. Williams 1. the vibrational spectrum provides basic information on the bond strengths present within a material. and to energy by multiplying by c and Planck’sconstant. we focus on infrared and Raman spectroscopic characterization of vibrational states: in this discussion. Additionally. Williams. INTRODUCTION There are a number of ways in which light interacts with condensed matter.626 x 1O-34 J-W). In most cases. the configurations of electronic states. Moreover. University of California. The presenceand strength of theseinteractions are principally dependent on bonding properties. The bonding properties which produce infrared and Raman-active vibrational bandsprovide not only a useful fingerprinting techniquefor determining the presenceor abundance different functional groups. electronic transitions) is inverse centimeters. CA 95064 Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Geophysical Union. such of as hydroxyl or carbonateunits. observations of optical transitions may be used to constrain the energetic effects of different electronic configurations on element partitioning between sites of different symmetries and distortions. including their heat capacity. Here.Infrared. and local symmetry of ions. Each of these techniques provides complementary information on the vibrational and electronic propertiesof Earth materials. but also (in a bulk sense) fundamentally control a variety of thermochemical properties of materials. The most common unit utilized to describe the frequency of these vibrational motions (as well as. Santa Cruz. and their relation to spectroscopic observations summarized. Mineral Physics Laboratory. and commonly produce the colors of many minerals: theseare dictated by the local bonding environmentsand electronic configurations of different elements in crystals or molecules. we explicitly treat only normal Raman scattering and disregardnon-vibrational effects suchas Ramanelectronic and magnon scattering and non-linear effects such as the hyper-Ramanand resonance Ramaneffects.2) Raman are spectroscopy. c (2.or wavenumbers(cm-‘): thesemay be readily converted to Hertz by multiplying by the speedof light. in many cases. Raman and Optical Spectroscopy of Earth Materials Q.

which have more possible vibrational modes beyond simple stretching motions (see Figure 1): becauseof the more complex interatomic interactions. Such computationsof lattice dynamics where K is the force constantassociated with stretchingof the diatomic bond. That different force constants are required to describe these vibrations is apparent from the atomic displacements illustrated: for . For crystals. such as neutron scattering techniques. which effectively alter the masses involved in the vibration without significantly affecting the force constants.the symmetric stretch of the tetrahedrondepends predominantly on the strength of the Si-0 bond. and p is the reduced mass of the vibrating atoms. For the simplest case of a vibrating diatomic species. and in the number of different interatomic interactions included in thesecalculations. as some vibrations may be symmetrically equivalent(or energeticallydegenerate) with one another. Broadly. Approximate equationsrelating theseforce constantsto the frequencies of vibration for different polyatomic moleculeshave been reviewed and developedby Herzberg [ 121. The primary difficulties with such calculations lie in determining adequate potential interactions.These shorter wavelength probes are used to characterize the dispersion (or change in energy) of vibrations as the periodicity of vibrations becomeslonger than the unit cell length-scale (that is. The primary mcasurcment is thus of the intensity of transmitted or reflected infrared light as a function of frequency. the calculation of the vibrational frequenciesof a lattice entail examining the interchangebetween the kinetic energiesof the atomic displacementsand the potential energyinduced by the bonding interactions present in the crystal.sensitivedetection techniques. Considerableinsight in distinguishing vibrations such as those shown in Figure 1 from one another has been derived from isotopic substitution experiments. vibrations occurring away from the center of the Brillouin zone). in which example. the Raman effect is rather weak: only about 1 in lo5 to lo6 incident photons are Raman scattered. Such dispersionis characterizedby vibrations of adjacent unit cells being out-of-phasewith one another [6]. Raman measurements rely on monochromatic light sources (which.292 INFRARED.Because wavelengthof even the visible light is long relative to the size of crystallographic unit cells. the number of vibrations potentially accessible through either infrared or Raman spectroscopyin 3n-3.while a detailed review of the frequencies of vibrations of different moleculesis given by Nakamoto [18]. with three degrees of translational freedom of the entire unit cell being associated with acoustic(Brillouin) vibrations. the magnitude of which is dictated in turn largely by repulsive interactions between the oxygen anions. where n is the number of atoms in the unit cell of the material. and others may not be active in either the infrared or Raman spectra. Within crystalline solids. necessitating relatively high powered monochromaticsources. For comparison. the crystal symmetry (or atomic locations). a photon of light interacts inelastically with an optic vibrational mode and is either red-shifted towards lower frequency (Stokeslines) or blueshifted to higher frequency (anti-Stokes lines) by an amount corresponding to the energy of the vibrational mode. the effect is called Brillouin spectroscopy(see the section on elastic constants in this volume).this relation may be described using Hooke’sLaw. and the massesof atoms within the unit cell are generally required to solve for the different vibrational frequencies occurring in the unit cell. have almost always been lasers) to provide a discrete frequency from which the offset vibrational modesmay be measured.Furthermore. RAMAN AND OPTICAL SPECTROSCOPY (see[ 101for discussionof theseeffects). both infrared and Ramanspectroscopyprimarily sample vibrations which are in-phase between different unit cells (at the center of the Brillouin zone). a range of different force constants are required to treat more complex molecules. The vibrational modesmeasuredin infrared and Raman spectroscopymay be describedas a function of the force constant of the vibration or deformation and the mass of the participating atoms.the symmetric bendingvibration is controlled principally by the 0-Si-0 angle bending force constant.different stretching and bendingforce constantsare necessitated.a photon of energy below -14000 cm-l (and most often below 5000 cm-‘) is either absorbed or reflected from a material through interaction with interatomic vibrations. Characterizing vibrational modes that are out-of-phase to different degreesbetween neighboring unit cells requires shorter wavelength probes. These3n-3 vibrations represent the maximum number of observable vibrational modesof a crystal. Figure 1 shows the vibrational modes expected for an isolated silicate tetrahedra. a range of bonding interactions (and thus force constants). which comprise symmetric and antisymmetric stretching and bending vibrations. This simply results from the n atoms in the unit cell having 3 dimensional degreesof freedom during displacements. since the 1960’s. In the caseof infrared spectroscopy.or both. Notably. Clearly. With Raman spectroscopy. When such an interaction occurs with an acoustic mode (or sound wave).

highly symmetric vibrations are often inactive or weak in infrared spectra: for example. Whether a given vibrational motion is spectroscopically active underinfrared or Ramanexcitation is governed by selection rules associated with a given crystal structure. and the differing propertiesof Raman andinfrared activity.Thus. However. It is this change in the electric field associatedwith the unit cell which interacts with the electric field of the incident photons. Raman Fig. The physical origin of Raman scattering may be viewed from a simple classical perspective in which the electric field associatedwith the incident light interacts with the vibrating crystal. then the vibration is Raman active.WILLIAMS 293 vl -symmetric stretch 800-950 cm-l Raman (often strong) v2-symmetric bend 300-500 cm-l Present in Raman v3-asymmetric stretch vq-asymmetric bend 400-600 cm-l 850-1200 cm-l Infrared. both Ramanand infrared activities are governedby interactionsof the electric field of the incoming light with vibrationally producedchanges in the charge distribution of the molecule or unit cell. Infrared activity is produced when a changein the dipole moment of the unit cell occurs during the vibration. within isolated tetrahedra. Raman Infrared (strong). The normal modesof vibration of an SiO4-tetrahedra. These selection rules are primarily governed by the symmetry of the unit cell. the two sets of vibrations are not always mutually exclusive: for non-centrosymmetric molecules (or unit cells). and it is the symmetric properties of this tensor which allow the prediction of which families of modes will be active when observed along different crystallographicdirections. Because of this dependence on vibrational changes in the charge distribution. Notably. both the symmetric stretching and symmetric bending vibrations shown in Figure 1 are infrared-inactive. while only the v3 and v4 vibrations are active in the infrared. despite Raman active vibrations depending on changes in the polarizability tensor and infrared active vibrations being generated by changes in the dipole moment. all vibrations are Raman-active. Yet. have contributed major insight into the characterizationof different types of vibrational modes in complex crystals: the precise equations and means by which such calculationsare carried out have beenreviewed elsewhere 13.Within isolated tetrahedra. its ability to produce an induceddipole in an electric field. It is the relation of the change in the polarizability tensorand shifts in the dipole moment to the symmetry of the lattice which enables different vibrations to be associated with different symmetry species. Finally. 1. the polarizability is a secondrank tensor. some vibrations can be both Raman and infrared-active. as well as with possible crystallographic directionality for the infrared and Raman modes. this interaction occurs through the polarizability of the material: that is. the intensities of different vibrations in the two different types of spectroscopymay be related to the magnitudeof the changesproducedin the dipole moment or polarizability tensor in a given vibration. It is the oscillations in the polarizability produced by vibrations which causeRaman scattering: if a vibrational motion produces a change in the polarizability of a material. 91. while the induceddipole is a vector. In particular. environments with non-tetrahedral symmetries frequently produce infrared activity of the VI and v2 vibrations in silicate minerals[modified from [121and [1811. The way in which this characterization of vibrational mode symmetries is conductedis through an applicationof group theory called .

For many minerals. such absorbanceor transmission data are often generated from suspensions of powdered minerals or glasseswithin matrices with indices of refraction which approximate those of minerals. while absorption spectroscopy ideally samples only the transverse modes. and so-called external modes.are designedto model the extreme changesin the optical constants(expressed the as frequency dependentand complex index of refraction or dielectric constant) occurring over the frequency range of an optically active vibration. and correlation tables between different symmetry groups to determine the number. Frequently. and symmetry of infrared and Raman vibrations of a crystal. and I. Such internal modes are typically associated with the most strongly bonded units in a crystal. or an iterative classical dispersion analysis. Reflection spectra of crystals sample two components of each vibrational modes: transverseoptic and longitudinal optic modes. such data are reported as per cent transmittance. Character tables for different symmetriesare given in many texts (for example.and is definedas A = -log(&). These data are generally inverted for TO andLO frequencies oscillator strengths and (a measureof the intensity of the reflection of the band) using one of two types of analyses:Kramers-Kronig. or reflection. and thus with the highestfrequency vibrations of a given material. That there are two types of modes in reflection is becauseeach vibrational motion may be described either with atomic displacements oriented parallel (longitudinal modes) and perpendicular (transverse modes) to the wavevector of the incoming light.294 INFRARED. in The International Tables of Xray Crystallography).displacementsof the Si04 tetrahedra against their surrounding magnesium polyhedra in forsterite would constitute an external motion of the . coupled with character tablesof the site symmetry and crystal symmetry group. Internal modes are vibrations which can be associated with those of a molecular unit. a silica symmetric stretching vibration such as is shown in Figure 1 will involve a stretching motion of the adjoining A104 tetrahedra. describedin [ 171and elsewhere. 183-188 of [7]). (2) where / is the intensity of light transmitted through the sample. Lattice modes comprise both a range of (often comparatively low-frequency) vibrations not readily describable in terms of molecular units. Such transverseand longitudinal modesare thus separated from one another by long-rangeCoulombic interactionsin the crystal [3. is the intensity of light transmitted through a non-absorbing reference material. Those with their atomic displacements oriented parallel to the wavevector of the incoming light can be subject to an additional electrostatic restoring force producedby the differing displacementsof planesof ions relative to one another.and vibrations of thesetwo speciesmust be viewed as coupledwithin suchstructures. Infrared spectra may be presentedfrom two different experimentalconfigurations: absorption(or transmission).Becauseof the intensity of many of the absorptions in rock-forming minerals (greater than -2 p.while the higher frequencydrop in reflectivity of a peak is near the frequency of the longitudinal optic vibration. shifted (and possibly split) by interaction with the crystalline environment in which the molecular unit is bonded: the vibrations of the silica tetrahedra shown in Figure 1 are typical examplesof the types of motions which give rise to internal modes. activity. While relative absorption intensities and locations can often be accurately determined using these techniques (highly polarizablecrystals can presentdifficulties: seepp. A secondmeansby which infrared spectraare measured is through measurementof reflection spectra. with the lowest frequency onset of high reflectivity of a peak correspondingapproximately to the transverse optic frequency.which is simply the ratio I/I0 multiplied by 100 (note that vibrational peaks are negative features in transmittance plots and positive features in absorbance). In practice. This is a meansof utilizing the site symmetries of atoms in the primitive unit cell of a crystal (as given. For example. absolute absorption intensity is compromisedand orientation information is lost.6]. External modes are those which involve motions of a molecular unit against its surrounding lattice: for example. RAMAN AND OPTRXL SPECTROSCOPY factor group analysis. We note also that even the simple picture of molecular vibrations is often complicated by the presenceof interacting molecular units within a crystal. and correlation tablesare given in [73 and [8]: the latter text provides a number of worked examples of factor group analysisapplied to mineralsand inorganic crystals. an effect not generatedby shear. 5).rn thicknesses in the midinfrared (>-4OO cm-‘) often render samples effectively opaque).Nujol (paraffin oil) or teflon). for example. it is difficult to associatedifferent bands in feldspars with stretching vibrations of distinct A104 or SiO4 tetrahedra: becauseof the interlinking tetrahedra. Typical examplesof such matrices are pressedsalts (typically KBr. the types of vibrational modes may be divided into two loose categories: internal and lattice modes. reflection spectra generally have broad flattened peaks. KI or CsI) and hydrocarbons(for example. Sampleabsorbanceis dimensionless. Such analyses.

WILLIAMS 295 tetrahedral unit. Within the Raman spectrum. For calcite. or coupled vibrations of different functional groups may occur. the LO-TO splitting of the asymmetric stretching vibration of the carbonate group is clearly visible in the reflectance spectrum. Two features are immediately apparent from these spectra: first. d. This may be expressed as c = (M .for someapplicationsa more appropriatemeasure of the number of speciespresent is not the amplitude of absorption. with four being Raman-active (A1 symmetry type). Typically. while the strongest high frequency vibrations in quartz lie near 1100 cm-l (the asymmetric stretches of the silica tetrahedra) and 680-820 cm-l (correspondingto Si-0-Si bending vibrations). A fundamental limitation on such techniqueslies in that infrared and Raman spectraaccess only vibrations which have the periodicity of the unit cell (that is. Specific examples include the determination of the dissolved molecular water and hydroxyl content of glassesand crystals. in mineral spectra. while that within quartz is predominantly a displacement of the bridging oxygens between tetrahedraat 464 cm-l. with units of length2/mole. infrared spectroscopyhas been extensively utilized as a quantitative technique for determining the concentration and speciation of volatile components within samples. such lattice modes are of critical importance in controlling the heat capacity of minerals at moderate temperatures (of order less than -1000 K). E). (3) in which c is the weight fraction of a dissolvedspecies. there is a general decreasein frequency with decreases bond strength for in different isoelectronicand isostructural groupings.such as occurs in the P04-Si04-A104 sequenceof tetrahedral anions. Second.and E is the molar absorption coefficient of the suspended species. and theseare not included in Figure 3. but rather the integrated intensity underneath an absorptionband (see[21] for a mineralogically-oriented discussionof eachof theseeffects in hydratedspecies). along with a powder infrared absorption spectrum of quartz and an unpolarizedinfrared reflectance spectraof calcite. The factor group analysisof quartz predicts 16 total optically active vibrations. . Severalcomplications exist in the straightforward application of Equation 3: first. Moreover. the most intense vibration of calcite is the symmetric stretching vibration of the carbonategroup at -1080 cm-l. in that the amount of absorption can depend on the structural environment in which a given speciesoccurs. and four doubly degenerate Es symmetry modes) and eight infrared-active vibrations (3Azu and 5 doubly degenerateE. It is the determination of this last parameter on which the quantitativeapplicationof Equation3 depends:typically. Such determinations depend on an application of the Beer-Lambert Law. the differencesbetweenthe vibrations of the silicategroup and those of the carbonategroup are immediately apparent:in the infrared. of p is the density of the matrix in which the species is suspended. and the amount of impurities within crystals such as diamond and a range of semiconductors. Figure 3 shows representativevibrational frequencies of different functional. A is the absorbance a diagnosticband of the dissolvedspecies. such an analysis predicts five Ramanactive vibrations (lAl. normal modes involving motions of the entire lattice. At lower frequencies than are shown in Figure 2 in the infrared spectrum.groups. While both infrared and Raman spectroscopyrepresent useful techniquesfor characterizingbondingenvironments. the asymmetric stretching and out-of-plane bendingvibrations of the carbonategroup are presentnear 1410 and 870 cm-l.M is the molecular weight of the dissolvedmaterial. effects of dispersionare ignored).d is the path length through the sample. considerableeffort hasbeen devoted to designing methods to extract thermochemical parameters such as the heat capacity and the Grtlneisen parameter(the ratio of thermal pressureto thermal energy per unit volume) from vibrational spectraat ambient and high pressures [13]. At lower frequency (below 400 cm-‘). the amount of dissolved CO2 relative to COs2. the extinction coefficient canbe frequency-dependent. A)/@. vibrational mode frequencies and the molecular species present within minerals. four being infrared-active (A2 symmetry).). As it is the thermal excitation of vibrational modeswhich producesthe temperaturedependence the of lattice heat capacity. or molecular-like groupings. in which the amount of absorption is assumedto be proportional to the number of absorbing species present in the sampled region. both lattice-type vibrations of the calcium ions relative to the carbonate groups and displacementsof the carbonategroups and the calcium ions both against and parallel to one another OCCIE. RepresentativeRaman spectraof quartz and calcite are shown in Figure 2. As expectedfrom Equation 1. the spectrum of the carbonate has Raman bands associated with external vibrations of the carbonate group relative to stationary calcium ions. In the case of many minerals with complex structures. a non-vibrational meansof analysis is used to quantify the amount of dissolved specieswithin a sequence samples of in order to calibrate the value of E. and eight being both Raman and infrared-active (E symmetry: doubly degenerate).

The infrared spectrumof quartz is an absorptionspectrum from powderedmaterial. Both Ramanspectraare from single crystal samplesusing 514.SiO2: Quartz 465 cm-l Raman CaC03: Calcite :03-symmetric stretch Si-0-Si symmetric stretch 1089 cm-1 Raman Lattice modes Lattice modes Si04-asymmetric stretch 1083 cm-1 Si-0-Si bend 807 cm-1 I 207 128 / 1 1 284 cm-1 CO3-asymmetric stretch In-plane bend 713 cm-1 155 cm-l i Powder Infrared LO 1435 cm-1 TO Infrared.1) Fig.5 nm excitation. while that of calcite is an unpolarized reflectance spectrum from a singlecrystal. 2. Infrared and Raman spectraof SiO2-quartzand CaC03-calcite. Reflectance Out-of-plane 874 cm-1 In-plane bend 1300 1200 I100 1000 900 I ecu I 700 600 MO 300 I ma IDO 1 I640 / 1500 I I400 I 1300 I 1200 I II00 I IOrn I 900 I ml I 700 I 600 r MO I1 IQI 3w t 2m !m 1 Frequency (ccl) Frequency (cm. .

15. The application of Raman spectroscopyto quantitative measurement of molecular species is complicated by practical difficulties in determining the absolute Raman scattering cross-section of different species. Asymmetric Stretches t In-Plane’ O-H Bends SZ.I. The three processes of primary importance for minerals are: 1) crystal-field absorptions.I. the dx2y2 and dz2 orbitals.. and 3) charge transfer or absorption into the conduction band (4. for analysisof sampleswhose sizesare of the order of the wavelength of infrared light (such as some fluid inclusions).Yet.. as opposedto their quantitative abundance. .g.(or in somecasesf-) electron shell being incorporated into a crystalline environment whose symmetry produces a difference in energy between the different orbitals. which have lobes of electron density .. non-destructivecompositional probe of fluid inclusion compositions [e.1 v3 Iv 1000 1600 1400 1200 800 600 400 200 Frequency (cm-l) Fig. Its utility has thus been principally in determining what speciesare present in a sample.. For tetrahedral species. 3.Considerableeffort has thus been devoted to characterizing Raman scattering cross-sections of gas-bearing mixtures.WILLIAMS 297 bends . that for octahedralsilicon is from [24].. The first of these processesinvolves an ion with a partially filled d... 201.. and Bums in [2]). 2) intervalence transitions.I.I. diffraction of incident infrared light limits the usefulnessof infrared techniques.the mode designationsare identical to those shown in Figure 1. oxides and other functional groups within minerals. and in maintaining a constant volume of Raman excitation from which scatteredlight is collected.. A representative example of this phenomenonis shown in Figure 4: when the five atomic d-orbitals are octahedrallycoordinatedby anions. OPTICAL SPECTROSCOPY There are a number of different processeswhich may generateoptical absorption (see [19] for a discussion of different causes of color) in the visible and ultraviolet wavelength range. with the motivation of establishing Raman spectroscopy as a quantitative. Most of the spectralrangesare derived Tom [3].. ketches Hydroxides O-H Bends Out-oLG!ne Wane Bends Bends Stretches Carbonates Polymerized Silica Networks Inosilicates Orthosilicates Sulfates Orthophosphates I II.l. Approximate frequency rangeof common vibrations of silicates. 3. -Bends/Stretches SiOg-octahedra I Elm’ V & Non-Bridging 0 I t I I v3 Vl I bends HH v4 bends l---r+ v2 11ml1....

. Among major transition elements.The re ulsive effect producedby close proximity of the negatively chargedoxygen cations to the dx2-v2 and dzf orbitals separatesthese in energy from the d. Thus. Historically. Essentiallyno experimentalevidence . oriented towards the anions. Cg+.. Estimates of the spin-pairing energy in iron-bearing minerals are poorly constrained. For comparison. gems and laser crystals. as each orbital can contain two electrons of opposite spins. Ti3+. and dxz orbitals by an amount referred to as the crystal field splitting energy (also as 10 Dq or 4).Y dYz 7 d x2 Fig. and electronsenter into the higher energy unoccupieddx2-v2 and dz2 orbitals (eg states) rather than pairing in the lower energy three-fold t2g states.iron essentiallyalways occurs in the high spin configuration in minerals: this is simply a consequence the energy required to pair spins of in divalent iron being larger than the crystal field stabilization energy. energylevels. electrons in low spin configurations fully occupy the t2g states before entering the eg levels. The preferential occupation of the lower energy levels produces a net crystal field stabilization energy (CFSE) which contributes to the thermochemicalenergeticsof transition metal-bearingcrystals.298 INFRARED. in which the energy required to pair two electronswithin an orbital is greater than the crystal field splitting energy. d. ruby (Al203 with C2+) and both silicate and aluminate garnets (which may contain a range of transition elements). The effect of octahedralcoordination on the different d-orbitals of a transition metal cation (labelled M). For comparison. RAMAN AND OFWCAL SPECTROSCOPY Energy bZ /x I I 0 P AZ Y -0 X o- AZ Y 05 -> Y M -o- Q BI M c-v --o-M-OP a -e3 . the high spin to low spin transition of iron in crystalline silicates has been frequently invoked as a possible high pressurephenomena. thus producing a net preference of many transition metal ions for octahedral sites. characteristic cohesive energies of divalent transition metal ions octahedrally coordinatedby oxygen are on the order of 3000-4000Id/mole [4. tetrahedrally coordinated cations typically have CFS energies between -30 and -70% that of octahedrally coordinated cations. The surfacesof the d-orbitals representcontours of constantprobability that an electron lies within the boundaries.. optical absorption may be producedby excitation of electronsinto andbetweenthese separated. Furthermore. and is associatedwith both the colors and fluorescent properties of a range of minerals. 163. Fe3+. 4. Mn2+. but representativevaluesfor this quantity are generallygreater than 100 Id/mole at ambient pressure. 15. crystal-field split. the energetic or separationbetween which is often referred to as 10 Dq or A Such crystal-field effects are observed within c&pounds containing such transition metal ions as Fe2+.O % 0 I d. that for octahedralC2+ (d3) is generallybetween 200 and 275 M/mole. Characteristic octahedral CFSE values for other transition metal cations with unpaired delectrons generally lie in between these extremes. The characteristicmagnitudeof the CFSE for Fe2+ (d6 configuration) in octahedral coordination in minerals is between about 40 and 60 Id/mole. two possible configurations are possible for octahedrally coordinated cations containing between three and eight d-electrons: high spin configurations. lie at higher energy than the remaining three orbitals becauseof the larger repulsive interactions between the dx2-y2 and dz2 orbitals and their neighboring anions. including forsteritic olivines (peridot: Mg2SiO4 with Fe2+).

For example. a larger number of crystal field bandsmay be observedbecause further splitting of of the d-levels.5 0 I I I I I I I I I1 I ! I I 500 1000 1500 Wavelength (nm) Fig.The primary selectionrules are related to spin multiplicity (involving conservation of the number of unpaired electrons between the ground and excited state) and to conservation of parity (or. the dx2-y2 and dZ2 orbitals lie at lower energy than the three remaining dorbitals.000 1. discussedin detail elsewhere[4. In more complex environments. 15. and the type and symmetry of the site in which the ion sits. An exampleof spectraproducedby different polarizations of light incident on Fe#i04-fayalite. in a manner directly analogous to Equation 3. that indicates that such an electronic transition occurs over the pressure and compositional rangeof the Earth’smantle. is shown in Figure 5. combined with an interpretation of the observed transitions in terms of the Ml and M2 cation sites of Fe2+ in olivine [from 41.g. 161. the anion present(as the chargeand radius of the anion will also control the amount of crystal field splitting which takes place). such crystal field bandsare frequently orders of magnitude less intense than the vibrational bandsdiscussed above. Inter-valence. The values of the crystal-field splitting. a material with distorted octahedralsites. and by a combination of the symmetry of the cation environment and quantum mechanical selection rules. These selectionrules may be relaxed through a range of effects which include orbital interactions.0 8 $ e Fz 2 Octahedral Splitting Ml Site Splitting M2 Site Splitting 0.chargetransfer. transitions being only allowed between orbitals which differ in the symmetry of their wavefunction: the Laporte selection rule).and lack of a centrosymmetricion site. producing both weak spin-forbidden and Laporteforbidden transitions. The dotted spectrum is taken parallel to the b-axis of this phase. non-centrosymmetric environments (e. as well as contributing to the amount of cation-anion interaction. The intensities of crystal-field absorption bands can vary over four orders of magnitude: these are governed both by the abundance of the absorbing cation. Polarized crystal field absorption spectra of Fe2SiO4-fayalite in three different crystallographic orientations.000 10. additional splitting beyond that shown in Figure 4 occurs for the d-orbitals of iron ions within fayalite: this is shown in the insets. The lower than octahedral symmetry of the Ml and M2 sites produces more extensive splitting of the energy levels than occurs in sitesof ideal octahedralsymmetry.WILLIAMS 299 exists. combined with an interpretation of the different crystal field transitions present in this material [4]. by .clearly dependon the valence of the cation (as this controls the amount of occupancyin the d-orbitals. Short arrows in insets representelectrons occupying each d-orbital (Fe2+ has six d-electrons). however. vibrational and magneticperturbations. and the solid line parallel to a.such as distorted octahedraor dodecahedral sites. Indeed.000 cm-’ are generated spin-forbiddentransitions. 5. and valenceto conduction band transitions are all terms used to describeabsorption mechanismsof similar origins: the transfer of electrons between ions in non-metals via an input of energy in the Frequency (cm-l) 25. The sharp bandsabove 20.000 15. tetrahedrally coordinated cations) generally produce more intense absorptions. the dashedline parallel to c. Such effects of symmetry are demonstratedby a comparisonbetweenoctahedraland tetrahedral sites: in tetrahedral sites. As the Ml and M2 sites are each distorted from perfect octahedral symmetry. through the cation-anion bond strength).

they also induce effective opacity of most ! Charge-Trmsfer and Band-Gap 1.tm. Such crystal-field absorption bands tend to broaden markedly at high temperatures. such charge transfer bands appear as an absorption edge. 00. or attractive force between the photo-excited electron and its ion of origin. k is Boltzmann’s constant (1. but also occur in excitation of electrons between cations and anions. these bands occur in the visible region of the spectrum. The dependence of blackbody emission on wavelength at different temperatures. Among the most intense crystal field absorptions of iron in minerals are those occurring near 1 j. Characteristically. such as the M2 site in pyroxenes. and relatively short metal-metal distances. 6.+3) and Ti (+3. Within oxides. and represents the intercept of a plot of the log of the conductivity and the inverse of temperature. such as are shown in Figure 5.0 A . such oxygen-to-metal charge transfer absorption bands typically occur at high energies in the ultraviolet.and moderate-temperature electrical conductivity of insulators and semiconductors: in materials in which the electrical conductivity is not dominated by defect-related processes. Effectively. is generally treated as a constant (although both it and the band gap may be temperature dependent: these dependences are. There is an intimate association between such processes of electron delocalization and the high. however. and T is temperature [e. with bands in relatively iron-rich phases (such as magnesiowtistite) shifting strongly to longer wavelength with increasing pressure. Such absorptions generate an effective means of impeding radiative conductivity under lower mantle pressure and temperature conditions.300 INFRARED. if hydroxyl or carbonate units are present. (4) frequently small). with the wavelength ranges of electronic and vibrational absorptions which inhibit radiative heat transport in mantle minerals illustrated.. similarly. and are extremely intense: often three to four orders of magnitude more intense than crystal field transitions. especially those which are able to adopt multiple valence states in minerals.g.g. the thermal excitation of electrons into the conduction band represents the primary means by which charge carriers are generated. .+4). increasing the efficiency with which they prevent radiative heat transport. rather than a discrete band: this edge is simply generated because all photons with an energy above that of the edge will produce electron delocalization. The term inter-valence transition is generally used to describe processes associated with the transfer of an electron between transition metal ions. 11. or photoexcitation of an electron into the conduction band of a material: the separation in energy between the valence and conduction band of materials is commonly referred to as the band gap. and produce the opacity or deep red color in the visible of many such minerals. Vibrational absorptions (both single vibrational transitions and overtones) absorb strongly at wavelengths longer than about 5 urn. and are most intense in those minerals which have large quantities of transition metals. is the energy of the band gap.010 lo-’ 1 IO Wavelength ( p m) Fig. This relationship is expressed through Q = 00 exp(-Eg/2kr). Absorptions generated by such cation-anion charge delocalization processes are common in ore minerals such as sulfides and arsenides. These bound electron states are referred to as excitons. such as Fe (+2. iron in the dodecahedral site of garnets can absorb at longer wavelengths than 2 pm (see Bums in [2]). then such vibrational absorptions may extend to 3 pm. The pre-exponential factor.. in which d is the electrical conductivity of the material. E. Within many materials. such charge transfer between anions and cations is often associated with delocalization of an electron. these transitions produce the coloration of many iron and iron/titanium-rich oxides and hydroxides. RAMAN AND OPTICAL SPECTROSCOPY form of a photon. can occur at wavelengths above 4 pm. Furthermore. This edge may be accompanied by discrete bands at slightly lower energy than the edge: such bands are often associated with a binding.381 x 1O-23 J/K). As such. Crystal field absorptions of divalent iron in distorted octahedral sites. 221. The location of charge-transfer bands is known to be highly sensitive to pressure. Charge transfer transitions not only occur between transition metal ions. and are discussed in greater detail in solid state physics texts [e.z 2 3 5 0.

Chapman University Press. London.along with the wavelengthrangeof different absorption mechanismsoccurring in minerals relevant to the Earth’s upper mantle.K. Burns. Hawthorne.New York.WILLIAMS 301 silicates in the far ultraviolet.T. 8. F. Ashcroft. Vaughan (eds. London.. Chemical Applications of Group Theory. and D. 1970. Infrared and Raman Selection Rules for Molecular and Lattice Vibrations: The Correlation Method. Mermin. 383 pp. the intensity of radiative thermal emission is described by the Planck function. New York. Spectroscopic methods in . Fateley. Calif. 1981. Born. as well as the black.. Boltzmann’s constant and temperature. Clearly.. Interscience. it becomeseasierto delocalize electrons as the distance between ions decreases). radiative conductivity is unlikely to provide a rapid mechanismof heat transport within the deep Earth. Thus. This effect is illustrated in Figure 6.C. I.) Reviews in Mineralogy. Berry. J.. 1977. San Diego. I(v) = 2mhc2v5(exp[hvlkr] . New York. 1972.. 11. 9. 325 pp.. Plan&s constant.. A.. Cambridge 391 pp. Knittle for helpful comments. The actual radiative thermal conductivity of mantle materials naturally incorporates both a frequency-dependent absorption coefficient and index of refraction of the material. Harvey. the optical properties of mantle minerals play a passive but seminal role in the thermal and tectonic evolution of the planet: were radiative conductivity an efficient meansof heat transport through the deep Earth. Farmer. 7. and an anonymous reviewer. REFERENCES 1. Solid-State Physics.C. Wiley- 2nd Ed. Chemical Applications of Nonlinear Raman Spectroscopy. 6. N. Bentley. (Ed. F. thermal convection (and its geochemical and geodynamic consequences) would not be necessitated. This is contribution #207 of the Institute of Tectonics at UCSC. Mineralogical Society. A. 4. Figure 6 shows representative values of emitted intensity for a range of temperatures. McGraw-Hill.B.O) may have a significant effect on the electrical conductivity of the deepmantle. Decius. M.C. 420 pp. Acknowledgments. respectively.. 589 pp. Huang. however. (Ed.. 1976. Academic Press.S.W. e representsthe emissivity of the material (assumedto be unity in the caseof a blackbody.G. Saunders College Publishing. Kothari. 826 pp.. Ghatak. 224 pp. in addition to producing an absoluteimpediment to radiative thermal conductivity at thesedepths. Mineralogical Applica-tions of Crystal Field Theory. Not shown in Figure 6 are the grain boundary scattering effects which may also act to reduce radiative conductivity over a broad frequency range. h. 222 pp. 3. 1974. Among lower mantle minerals. 386 pp. I thank the NSF for support.R. F. is a function of frequency (v). Philadelphia.J. and D. New York.A. 18. New York. Wesley. k and T are the speedof light. and to lie at a wavelength-independentvalue between zero and one for a greybody).J. W. the absorptionof magnesiowiistiteat both ambient and high pressures has been wellcharacterized [14]..J.1)-l (5) in which the emitted intensity. Molecular Vibrations in Crystals.. Oxford Press. 5.M.). T.. 1985. Cotton. Ahrens and E. The Dynamical Theory of Crystal Lattices. R. McDevitt and F.or greybody emission of Equation 5 [23]. and K. and L. V.. Hexter.).F. and R. the effect of a lower energy absorption edge in compressed magnesiowiistite (MgxFel-.New York.along with absorption mechanismsof minerals relevant to the Earth’s upper and lower mantle.. 10. The role of pressure (in most cases)is to decrease energy at which such bandthe gap related absorptionsoccur (that is.. Dollish.It is generally believed that among relevant deepEarth constituentsonly relatively iron-rich materials (such as FeO) will have absorption edgeswhich decrease to zero energy and metallize over the pressure and temperature interval of the Earth’s mantle. 1971. Chemical Bonding and Spectroscopy in Mineral Chemistry. An Introduction to Lattice Dynamics. given the wavelength rangesover which crystalfield absorptions (which broaden in width at high temperatures) charge-transfer and bandsoccur in transitionmetal bearing minerals. 234 pp. Addison and Hall. and c. no optical absorption data have been reported for silicate perovskite.. N.). (Ed.G. 1954. WileyInterscience. Figure 6 shows representative values of emitted intensity for a range of temperatures. However. The Infrared Spectra of Minerals. 2. 1972. F. Vol.

edition.in The at Physics Minerals and Chemistry of and Rocks.. Wopenka and J. New York. and J. Solid State Phys. 1988. R. Vibrational spectrum of MgSi03-perovskite: Zero pressure Raman and infrared spectra to 27 GPa. Hofmeister.. 632 pp. RAMAN AND OPTICAL SPECTROSCOPY mineralogy and geology. 24. D. pp. Wiley. 484 pp. Hemisphere.. Vibrational spectrum of MgSi03 -perovskite: Zero pressure Raman and infrared spectra to 27 GPa. Oxford Univ.J. Washington. R. Seitz. Part II. 92. 14.D.C. D. Sot. D.... 1988. Paterson. and D.. 14. McMillan. Mineral. 13. 17. P.C. 8116-8128.. Hcrzberg.. Cosmochim.. McMillan. Mao.New York. 1979. McClure. Electronic spectra of moleculesand ions in crystals. Solymar. 20-29. The determination of hydroxyl by infrared absorption in quartz. 21. Am.. New York. Infrared and Raman Spectra of Polyatomic Molecules. M. 454 pp.. 1985. 1976. and A.C.65-126. K.. Res. Mineral. 352 pp. 22.. 1988... 19. 1992. Jeanloz and P. R. Practical aspects of 3rd Ed.. Hemisphere. 9. Res.G.M.K. Washington. 1072 pp. L. edited by Springer-Verlag. Thermal Radiation Heat Transfer. Infrared and Raman Spectra of Inorganic and Coor-dination Compounds. Walsh. Howell. R.S. Jeanloz and P. 24. 3rd Ed. Siegel. New York. 8116-8128. 1959. Nakamoto. 979-988.C. Charge transfer processes high pressure..S... 16. New York. 1992. J.. Marfunin. B. 23. Spectroscopy. 399-525. 1987. 12. Spectra of ions in crystals. K. H.. Pasteris. 15. 1987. 482 pp.F. Washington. 18. 92. 1982. Van Nostrand Reinhold. 1983. 1072 pp. 1945. J. The Physics and Chemistry of Color: The Fifteen Causes of Color. Kieffer. Q. PP.. New York. Infrared and Raman Spectroscopy. Luminescence and Radiation Centers in Minerals.. Lectures on the Electrical Properties of Materials. Bull. A. Molecular Specfra and Molecular Structure: II. McMillan. Mineral. Wiley..302 INFRARED. silicate glasses and similar materials. 105. J. J.. 573-581. 52. 698 Min. WileyInterscience.. 18. 1986.... Acta.Rev. Williams. G. Nassau. Geophys. ... J. 1992. Heat capacity and entropy: Systematic relations to lattice vibrations. Strens. Rev. S. Geophys.. 4th quantitative laser Raman spectroscopyfor the study of fluid inclusions. Geochim. 20. Williams. Press. 99-159.W. Q.R. 5th Ed. D.

and is particularly useful in amorphousmaterials and liquids. and to tabulate the most useful data. INTRODUCTION The purpose of this chapter is to very briefly summarize the applicationsand limitations of NMR spectroscopy in the study of the silicates and oxides that make up the earth’s crust and mantle.g. F. be observedby NMR. Stebbins. like techniquessuch as x-ray absorptionand Mossbauerspectroscopy. spin quantum number. NMR is an element specific spectroscopy.33. 1411. Stanford University.42.11.experimentsmust be carried out carefully to be accurately quantitative. ties and correspondingly broad NMR spectra.29. but these are now well understoodin a qualitative sense. infrared and Raman).Nuclear Magnetic Resonance Spectroscopy of Silicates and Oxides in Geochemistry and Geophysics Jonathan F.116. by the distributions of other neighboring spins (electronic or nuclear). regardlessof the structure. More extensivereviews havebeenpublishedrecently that give backgroundon the fundamentals.Another limitation of NMR is a severeone for the study of natural silicate minerals: paramagnetic ions in abundancesgreater than a few tenths of one percent can broadenNMR spectrato the point of being impossibleto observeor interpret [87].and spectra are primarily sensitive to short-range effects. which contain a simple comparisonof the relative easeof observation in a liquid sample. and by the time dependenceof theseinteractions. Stebbins I. Detection of signalsfrom nuclideswith low natural abundanceand low resonantfrequencyis often difficult or impossible.118. In practice.34.56. The samecan be true for even abundantnuclidesof heavyelements. although isotopic enrichment can be useful. NMR is a good complement to diffraction methods. visible. . but the practicality of the experimentvariestremendously. CA 94305-2 115 Mineral Physics and Crystallography A Handbook of Physical Constants AGU Reference Shelf 2 Copyright 1995 by the American Department of Geology. which may have extremely wide rangesof frequen- J. NMR can be highly quantitative. Most of the data reported in the tables has been collected by high resolution magic angles spinning (MAS) techniques. Extensive tabulations of NMR data on silicates have also beenpublished [34.as well as details of applications [2. however (especially for solids). A major drawback of NMR is its low sensitivity when comparedto spectroscopiesinvolving higher energy transitions (e.88. that some of the orientational information that 303 Geophysical Union.Potentially interesting nuclides are listed in Tables 1 and 2. The utility of NMR in understanding chemistry and the physics of materials comes from the small perturbations of nuclear spin energy levels (non-degenerateonly in a magneticfield) that are causedby variationsin local electron distributions. and abundance.128. however.62. with important contributions from the new technique of dynamic angle spinning (DAS).78.43. with a 1 to 1 correlation between signal intensity and the abundance of a nuclide in a given structural site. based on resonant frequency. Interpretationsof solid-state NMR spectra still rely primarily on empirical correlations.161]. in principle.Any nuclidewith non-zeronuclear spin thus can.Figure 1 suggests.61. becausethey contain no material-specific information on relaxation rates and line widths. Stanford.These data serve only for rough comparison. of course. Thus. and from singlecrystal and static powder spectra.

less favorable isotopesof elementslisted. causedby screeningof the external magnetic field by the surroundingelectrons.010 2252 100 4. Quantitative local structural information on minerals and melts is important to many problems in geochemistry and geophysics.6 230.4 16.lanthanides. nuclides with large quadrupolarmoments (Table 2).1 0. For many geochemically interesting pro- cesses.6 7.2 126.1 0.1 2.7 12. viscous flow.2 12.8 70.4 0. NMR parametersfor somenuclidesof interest in geochemistry: spin l/2 nuclides Isotope 1H 1% 15N 19F 29Si 31P 57Fe 77Se 89Y lo3Rh losAg 113Cd l19Sn 125Te 129Xe l@Trn 171Yb 183~ Natural abundance. Noble gasses. A secondnearly uniqueutiliiy of NMR.99 NMR frequency at 9.3 14. and unfavorableradioisotopes excluded.4 79.7 149.7 377 5.13 3.4 100 100 48. the fundamental rate may be within this range.7 195pt 199Hg *05T1 *07Pb Notes for Tables 1 and 2: Data are primarily from tabulation in [49].2 Receptivity relative to 29Si 2700 0. is lost in MAS may prove to be useful in characterizing anisotropic materials.3 8.3 19.09 0.6 71. and displacive phase transitions.43 0.4 T.2 33.6 1 180 0.6 40.8 16. In particular.0 100.0 26.7 18. MHz 400.6 376.6 85.1 70.002 1.5 22.NMR has proven to be very useful in this area.4 1.2 7.9 12. such as diffusion.5 2.1.7 100 2. that is just beginning to be applied in the geosciences.304 NMR OF SILICATESAND OXIDES TABLE 1.48 1. is in studying dynamics at the time scale of seconds to nanoseconds.6 is genemlly .Line width and relaxation behavior in solid samples can make this estimates quite misleading.4 33.4 100 14.8 76.Relativereceptivity is are calculated for low-viscosity liquid samples. 1. and heavynuclideswith very large chemical shift ranges may be difficult to observein solids.03 9. Definitions The chemical shift 6 is the perturbation in the resonant (Larmor) frequency v of a nuclide in a particular chemicalenvironment. % 99.6 88.6 111.5 161.2 6.5 83.1 15.7 12.32 0.

5 27.7 39.8 100 49.4 131.3 0. % 0.58 80.8 1.4 59.3 98.23 475 750 0. NMR parameters for some nuclides of interest in geochemistry: quadrupolar nuclides. Isotope Spin Natural abundance.11 174 96 0.4 28.7 Receptivity relative to 29Si 0.15 -0.1 Quadrupolar moment x102*.6 0.03 0.4 22.7 2H 6Li 7Li 9Be 1OB 1lB 14N I70 23Na 25Mg 27A1 3% 35Cl 37Cl 39K 43Ca 4ssc 47Ti 49Ti 5lV 53Cr 55Mn 59co 61Ni 63cu 65cu 67Zn 71Ga 73Ge 75As 81Br 87Rb 87Sr 91Zr 93Nb 95Mo 99Ru lolRu 1 1 312 312 3 312 1 512 312 512 512 312 312 312 312 712 II2 512 712 712 312 512 712 312 312 312 512 312 912 312 312 312 912 512 912 512 512 512 .29 0.3 17.8 75.05 0.32 152 0.20 0.7 560 0.9 24.STEBBINS 305 TABLE 2.1 113.44 NMR frequency at 9. See Table 1 for notes.3 22.0 97.3 1 0.4 0.04 100 10.4 35.6 56.7 18.16 -0.026 0.24 -0.4 37.5 10.9 7.2 -0.0 68.1 30.15 100 7.04 0.6 100 100 1.4 20.5 99.5 104.08 0.3 30.30 69 133 133 0.2 14.18 0.02 819 0.7 27.2 32.22 0.1 0.38 0.2 18.7 17.9 1320 1.5 93.041 0.6 7.8 9.12 -0.0 11.2 105.9 54.7 0.7 25.6 1035 0.02 7.0 155.10 0.3 -0.0 128.10 -0.5 24.6 105.21 -0.29 0.08 0.01 -0.6 360 2.5 22.2 43.6 98.1 39.4 T.6 1.3 5.2 69.7 737 37.05 0.4 0.0008 -0. me2 0.2 100 15.13 0.0028 -0.2 26.21 -0.8 94.22 fO.7 108.8 106.4 92.22 0.1 122.9 4.4 0. MHz 61.5 1 2.03 250 0.004 1.05 9.12 0.085 0.055 -0.4 99.4 0.13 100 0.6 100 19.16 0.05 0.7 12.

8 31.44 -0. center spectrum shows effect of strong preferred orientation in a quartz mylonite [132].The frequenciesof thesetransitions are controlled by the energy of interactionswith the L \ +qof& &random powder *.8 16.9 expressedin parts per million relative to a standard. Siso. .and in solids by rapid sample spinning (MAS NMR) at the “magic” angle 8 with respect to the external field (t3 = 54.7 99 238 1. NMR frequency at 9.4 88.8 44.99 62. The chemical i r’‘2 .with 6 = ~06hnple . For nuclides with spin I > l/2. a total of 21 transitions may be observable.2 0.22 4.7 100 13.4 7.4 T.306 NMR OF SILICATES AND OXIDES TABLE 2 (continued) Isotope Spin Natural abundance.1 62.3 100 100 11.38 18.70.2 100 0.0 91. Sisois observed experimentally in liquids where molecular rotation producesrapid isotropic averaging.8 1.6 6. 1.v J i /$-LAN .83 -0.7 56.5 381 I”5Pd l 151n 512 912 121Sb 1271 133CS 512 512 712 137Ba 139La 177Hf 181Ta 187Re 18gOS 312 712 712 712 512 312 312 312 lg31r lg7Au 201Hg 209Bi 312 912 22.2 95.2 80.0 0./’ r I mykmicc shift is orientation dependent. For spin l/2 nuelides.1 96.822. whose principle components are usually denoted 611. 1 163 0. Static (non-MAS) 2gSi spectra for quartz. The isotropic chemical shift. MHz Receptivity relative to 2gSi 0. and is described by the chemical shift anisotropy (CSA) tensor.Vstandard)/Vstandard.28 0.2 48.06 0.9 18.’ Fig.6 64. l-3cos28 = 0). Top spectrum shows three magnetically inequivalent Si sites: bottom spectrum shows spectrum for randomly oriented powder.5 99.8 0.07 0.79 -0.9 26.59 0.7 57.5 3 2.7 910 251 257 130 2.3 99.28 -0.003 0. and S33 and which has a unique orientation with respect to the local structure (or with respect to crystallographic axes in a crystalline material).9 16.5 52.0 0.is the averageof these three components. Scalesin this and other figures are in ppm.

103. eQ is the nuclear quadrupolar moment.112. Similar approacheshavebeentaken for SiO6 groups[47. in DAS NMR. In MgSiOg ilmenite and perovskite.146]. Thus. often summarizedby the nuclear quadrupolarcoupling constant QCC=e2qQ/h. and data are listed in Tables6 and 7. Very recently.If bridging oxygens are consideredas thosesharedwith tetrahedralSi or Al (or B or P) neighbors. as shown in Figure 2 [101. Signals near to -150 ppm are probably from SiO5 groups [58. APPLICATIONS TO CRYSTALLINE SILICATES AND OXIDES 2.72]. In severalcases. As for 29Si isotropic shifts for 27Al in oxides (now determined most commonly by high resolution MAS NMR) are most strongly influenced by coordination number. careful combinationof NMR spectroscopy with calorimetric observation has provided new insights and details of the energetic control and consequences Si/Al disorder of [17. 29Si MAS NMR has begun to be applied to high pressure mantle phases that contain SiO6 groups. bond angles.102. 6 for SiO6 groups is in the rangeof about -180 to -220 ppm relative to tetramethyl silane (TMS). but is not broadened. and non-bridging oxygens to be those shared with larger and/or lower charged M cations.1063. partially overlapping peaks for Si sites with varying numbers m of Al neighbors [Q”(mAl)].the field gradient and the quadrupolar interaction averageto zero and Gire is observed. The full description of the quadrupolarinteraction requires the electric field gradient tensor and its orientation relative to the structure. higher frequencies.146]. The secondmost important effect is that of the number and identity of first cation neighbors.103. For a few systems.20. which varies from 0 to 1.52. Mg. Increasing the mean Si-O-T angle systematically decreases A numberof semi-empiricalcorrelations 8. asymmetry parameters. but somewhat overlapping range of 6.53.discrepanciesin thermodynamicdatathat had beententatively ascribed to underestimates the entropy of disorderedsynof thetic phaseshavebeendisplacedto other parts of the data baseby findings of nearly completeorder./Si disorder hasnot beendetected[63. In silicates. 2. but without precise isotropic chemical shifts. 27A 1 NMR studiesof 27Al in minerals have beenreviewed recently [66]. Most early studies of this nuclide were of single crystals.104.169]. Here. The bond anglebetween tetrahedrahasa relatedeffect. Structures correlations have been usedto derive important constraints on Al/Si ordering in a number of minerals. 2.and 6 have beendevelopedthat allow rather preciseestimatesof 6 for tectosilicate structures 1343. Single-crystal work on MgAl204 spine1 allowed quantification of octahedralandtetrahedralAl site occupancies and ordering state [ 141. where it has often provided the key to unraveling quite complex Al/Si ordering patterns. In geochemistry. The quadrupolar parameters have been shown to be roughly correlated with the extent of distortion of the Al site for both octahedral and tetrahedral geometries [43]. decreasingn by one tends to increase 6 by about 10 ppm to less negative. other tectosilicates [12.60. and eq is the principle componentof the electric field gradientat the site of interest. an Si04 site can be labeled as Q”. where n designatesthe number of bridging oxygens(and Q standsfor quaternary). and is in nearly all cases between about -65 and -120 ppm for SiO4 groups. Each Q” speciesthus has a distinct. the most important examples have been in determining the ordering state in feldspars [64. In liquids with sufficiently rapid isotropic rotation of molecules. The greatestefforts havebeenon synthetic zeolites.140] and prehnite [139]. with complete determinations of quadrupolar coupling constants. For a fixed M cation type.148]. . and for Al06 groups in the range of -10 to 15 ppm. but both Mg/Si and WA1 disorder are significant in majorite and majorite-pyrope solid solutions.146].160]. and electric field gradient tensors. againbest calibratedfor tectosilicates.118]. 29Si MAS NMR spectra of aluminosilicates often have multiple.the largesteffect of structure on chemical shift is that of coordinationnumber.STE!BBINS 307 electric field gradient.1. and pMg2SiO4. Siso is shifted by the isotropic averageof the secondorder quadmpolarinteraction. 29S i Isotropic chemical shifts for 29Si and CSA data are listed in Tables 3 through 5. cordierite [107] and sheet silicates [5. suchas for sillimanite [59. This effect is particularly obvious and well-exploited in tectosilicates. As a result. the substitution of tetrahedral Al for a tetrahedralSi neighbor tends to increase 6 by about 5 ppm. The deviation from cylindrical symmetry of this tensor is given by the asymmetry parameter n.53.2. among number of Al neighbors. few correlationshave been A developed for Si04 groups in general that allow estimation of 6 for most silicate structures [56. 6 values for Al04 groups fall roughly in the range of 50 to 90 ppm relative to aqUeOUS fi@20)(j3+. In MAS NMR.74.117.120. In a similar fashion. the central l/2 to -l/2 transition remains shifted and broadened a secondorder by quadrupolar interaction. because of their tremendous technological importance [34.127.95.166].

9 66 66. [781 [78.128] [781 11181 WI [781 chondrodite forsterite(s) (s) monticellite(s) 6) 6) majorite garnet(s)g 6) 6) afwillite lamite(s) PyropeW Ca-olivine(s) 6) (9 phenacite rutile titanite andalusite kyanite zircon piemontiteg grossular topaz Q’ sites.4 85.3.6.6 38.308 NMR OF SILICATES AND OXIDES TABLE 3.2 77.5H20 Mg4SiV1Si1V3012e Ba2SiO4 cKa2Si04 Ca3(HSi04)2.8d 44 55.3 60 95.5 74.159] L'81 W81 b'81 [781 [101.6 81.8 82.5 83.3 71.8 68 to 90f 70.3 70.9 64.4 72.7 74.5. Q’. 6) (s) MgdSQh(OKF)2 MgzSiO4 Li2SiOq CaMgSiOq NaHgSiO4 Na2H2Si04.H20 a-Y2Si207 a-La2Si207 Ca&O7(OH)6 68.4 67.76.124] [781 [781 u391 11181 [78.0 73.2 79. and Q2 sitesin crystalline silicates.5 69 to 75h j3.461 .5 73.73.H20 p-Mg2SiO4 CaA1$$07(OH).6 79.MnPeh (Si207)(Si04)OH Ca3A12(SiO& Al$i04(0H..6 122 134 74 84 20 1 123 92 28 109 109 35 WI r341 WI WI [781 [781 11461 [I281 r341 [781 [34.F)2 61.4 72.3. mineral (s)=synthetic Q” sites: CSAb nominal formula 4soa 6oc -611 422 433 ref.4 72.0 81 81.128] [118.4 94 45 50 78 79 116 120 gehlenite(s) akennanite(s) m&bite(s) hemimorphite 6) lawsonite 6) 6) 6) Na6si207 Ligsi207 Ca2A12Si07 Ca2MgSi207 Ca3Si207 ZnqSi207(OH)2.3 71.83.1461 [781 [781 [341 1781 UOll [781 [78.2 82.83.0 77.8.2H20 P-Ca2SiOq Mg3A1$G3012e Y-CaTSi Ca3SiOg CaNaHSi04 Be2SiOq ~1% SiO2 in Ti02 CaTiSiOg A12Si05 A12Si05 ZrSi04 ~a2(Al.9 83. 29SiNMR data for Q”.2 81.9 79.

3 84.MnPe)3 (Si207)(Si04)OH In2Si207 p-Y2Si207 SqSi207 A113Si502($OH)14F4Cli -&ma -611 422 433 ref.2 86.4 85.4.4 86.5 76.9 E'81 [781 [781 U181 orthoenstatite clincenstatite(s) diopside omphacite spodumene jadeite pyroxenephase(s)g alamosite prehniteg tchermakitic amphibole(s)g triple-chain phase(s)g SC-Fpargasite(s) LizSiOg Na2SiO3 BaSi03 SrSi0-j MkZSi206 %X&206 CaMgSi206 (Ca.8.136] W81 W81 L7781 [56.3 86.3 84.4 91.1281 [781 [781 [781 [781 WI Ca$i03(0H)2 Ca2NaHSi309 CaqWMOW2 Ca6Si6017@Hh CagSi309 Ca3Si309 P-Ca3Si309 24 85 158 Cl181 1781 .8 73.3 86m 87. 79.86.8 85.91.8 80 85 82c 81.8 92.3 91.86.87.6 84.8.78.6.90.4.9 95. 94.7l 89.1.SSiIV206 Pb12Si12036 Ca2A12Si301o(OH)2 Ca2(Mg4Al)(AlSi70&KW2 N~2W&kQ 74.6k 83.2.84.8.0 87.5.128] [1181 ill81 1-W w61 WI u391 [181 WI N31 tdW2 NaCa2MgqScSigA12022F2 Ca2MMWh1)2(OW2 (Q2+Q3) tremoliteg hillebrandite(s) pectolite(s) foshagite(s) xonotlite(s)g walstromite phase wollastonite P-wollastonite(s) 50 77 137 [18..1.0 18 29 30 4oi 31 53 59 71 71 73 73 81 156 140 154 132 148 142 c781 [78.STEBBINS 309 TABLE 3 (continued) CSAb mineral (s)=synlhetic piemontiteg (9 6) thortveitite zunyiteg Q2 sites.4 91.2 84.128] [118.SSiV1g. UW 86.7 92.97.Na)(Mg.5.Al)Si$I& LiAlSi206 NaAlSi206 NaMgg. (s) w 6) (s) nominal formula Ca2W.4 87.96.

9 97 . 108.406 (CaO)XSiVSi1”04 e-Na2Si205 CaSiV1SP05 Na2Siv1Si1”207 [-Na2SiV1Si1”0g Naz(SiV1.9 1581 11461 . (j) CSA data are meansfor two sites. -107. Main peak is at -74. 107. (q) CSA components:-49. (cc) Narrow peak consistent with complete Mg/Si order. (5) partially disordered.4 ppm. -161 ppm [128] . (f) Multiple peaksdue to partial disorder among octahedralSi and Mg. (c) Broad peak (at least5 ppm width). (r) CSA components: -107. 109.TABLE 3 (continued) CSAb mineral (s)=synthetic Q2 sites.4.3H2. (a) Chemical shifts are in ppm relative to tetramethylsilane.Si1”)409 75.Al-avoidanceviolated.14:1 ee ee ee Notes for Tables 3. (k) Two additional peaks indicate a small amount of Si/Al disorder. 622 = 633 = -183.Li.4 97.Gisoand CSA data are from different sourcesand may therefore appearto be slightly discrepant [&so should= (61I+622+633)/3]. (ee) Kanzaki. (x) Overlapping peaks due to multiple sites. (bb) all=-173.9 94.81. (v) CSA componentsfrom single crystal study: 102. Si-O-B bonds are consideredas “bridging”.5 94. -72. Referencecontains data on solid solution with pyrope.andare of relatively low precision. (dd) Somewhat broadenedpeak consistentwith some Mg/Si disorder.0. uncertain structure: “phaseE” (s) “phaseY” (s)g 6) (SF (SF (SF (SF WmSii. orientation of tensor with respect to crystallographic axesmay not be known.lOBaCl2 BaTiSis K2SiV1SiIV309 -&ma -611 422 433 ref.(4) fully ordered or nearly so.6. (e) Additional data on solid solution seriesgiven in reference. -70. (y) End member: complex seriesof peaksfor intermediatecompositions. rings: nominal formula a-CajSi309 W-W4012 Na(Mg.7m 80 80. (aa) 8 peaks for 8 sites. this is generally not significant. In somecases.(b) Unless otherwise noted. (g) Data for another type of Si site listed elsewherein table or in Table 4 or 5.-59. . 0'81 ]71. (p) CSA components: -43. (d) CSA basedon single crystal study. (t) CSA components: -56. (w) Approximately 5 peaksresolved for 12 sites. (m) Broad peak consistentwith considerable disorder.781 ps-wollastonite(s) 6) tourmaline 6) benitoite wadeitephase(s)g 83. (s) small peak due to triple-chain site in partially disorderedphase. principle componentsof CSA tensor are derived from fitting spinningsidebands. (2) orderedaccordingto Al-avoidance only.(n)Ordering schemes be complex. -59 ppm [128] .0. -83. Given typical errors in CSA measurements.A1)3AlgSi6018@03h@KF)4i Ba7Si702I. (1)First peak is for Tl site. placing the Si sites in beryl and datolite in the Q4 and Q3 groups. (u) CSA components: -54. and 5: tMost intense peak. respectively. 7 resolved peaks. -151 ppm [128] . (3) more orderedthanrequiredby Alavoidance.8 88.5 87.2 95.1 ppm.5 88.but canbe characterizedfor tetrahedralSi and Al can as (1) disordered. secondfor T2+T3. (h) Nine Si sites.(0) Split peak reported by [4].0 63 63 141 U181 1341 [781 W61 High P phases.7.6.107. (z) Approximately 8 peaks for 15 possiblesites.3 ppm. -147 ppm [1281. Stebbinsand Xue.1 [132] . unpublished data. (i) Approximate formula.1 92. -129 ppm [128] .

other silicates: sapphirinee datolite sillimanite tremoliteg tremolite(s)g tchermakitic amphibole(s)g triple-chain phase(s)g apophyllite serpentine talc tMg3.2.9 91. -hoa ej sites.S 93.4 92. SeeTable 3 for notes.2 97.3S401otOHh .7.3Si2.H20 WsWMOW4 WsS401o(OW:! Ca6tSi6017)(0H)?.5 94.OH)2 A4Si&o(OHh Aldi4Oio(OH)8 A4S4Olo(OHho~8H20 AWWAotOHh (Al.OH)2 KMg3AlSi301o(OH)2 MgAlSi401o(OH)2~4H20 Nao.90. Data for end-membercompositions only.7Na0.9.94 89.4Si1. layer aluminosilicates: margarite phlogopite phlogopite(s)e palygorskite beidellite muscovite illitee lepidolite dickite kaolin& endellite pyrophyllite montmorillonite sepiolite hectorite CaA12(A12Si201o)(OH)2 KMg3AlSi301o(F.OP 86.2H20 (Mg.7. 96.4H20 Q-?sites.91. 73m 83.0 94.6 92.81 91m 89m 90.94.110 101.5 5 4 r191 W81 [59. mineral (s)=synthetic nominal formula ordering state” 4 5 3 ref. zeolites.101.87.Mg)2S401o(OH)2. 29Si NMR data for Q3 and Q4 sites in crystalline silicates.118] 1181 [I81 1181 H81 L’81 U81 U181 1781 r941 [941 1941 [941 WI r341 xonotlite(s)g 6) 6) 6) 6) 6) 6) Li2Si205 BaSi205 a-Na2Si205 K2Si205 p-HzSi205 a-H2Si205 .4.7 84.havebeenexcludedfor brevity.9s 92.118] WI WI WI KAl~SiAl~O~~(OH)~ KA12SiA1301o(OH)$ KLi2Al(AlSi301o)(F.50 93.6)020 CaBSi04(0H) A12Si05 Q@kWdh1)2(OH)2 ~azMgdS4011)20-02 Ca2(Mg4Al)(AlSi7022)(OH)2 Na2Mg&60idOH)2 KFCaqSig@o. as well as silicateswith organic ligands. Data for some clay minerals and synthetic silicas.98 95.85?.1 94.Y 91.0 97.0t.5 98.TABLE 4.0 93.93.9.3 C'81 WJW Lm [341 [341 [I 121 Km V81 [341 [781 F’81 [112.4)tA14.95.6A14.Li)2.5 84 to 87 83.4s 91.7 92.8 88.3A12(Alo.91.8.1 87.701o) (OW2 15.5.4HZO Mg&j015(OH)2.96.7’ 91.

95.6. zeolites: NaAlSiO4 Na8Al&jO2&12 Na3KAk+i40t& KAlSi04 Na8Al&i6024CO3 Na4Al$i9024ClCa4Al&jO24CO3 NaAlSi206.&0 KAlsi206 82.113.100.0.101.2t.100t 79 to 112aa 87c 4 1 w71 r1071 [781 .97.6.1271 WI WOI [1021 carnegieite(s) scdalite nephelinee kalsilite(s)e cancrinite scapolitee analcite leucite Q4.9 85.6.96.106.6 97.88.7 87.8t.97.2H20 N~Al2Si4012.ow [118.5 109.7.3HZO Na2Al2Si3010.99.6H20 CaAl2Si3010.4?.101m 82.98.0 78.2 84.6Nao.northitee @.7H20 BaA1&016. Q4.4.4 88.4” 108.8.4 92.104.5 to 104Sx [103.1+.0aa [1181 UN U181 VI WI L'21 1721 11181 cordierite cordierite petalite Mg2&Si5018 (ordered) Mg2Ak&Olg (disordered) LiAlSi4010 79.6.96.89.72 3 3 D481 [1181 11481 H481 [1181 [1171 r951 1951 thomsonite scolectite natrolite gmelinite chabazite stilbite harmotone heulandite @.3 91 to 112X 95.8 98.l02.0.9 108. silica polymorphs: q- coesite cristobalite tridymite @.0.4AlSi308 CaAl2Si2Og CaAl2Si208(disordered) 92. feldspathoids: NaAlSijOg NaAlSigOg KAlSi-jOg Ko.3-l 14.9.8 86. others: NaCa2AlgSi5020.6H20 86.5t.3 92.102.7 86.108 95.5 94.4.312 NMR OF SILICATES AND OXIDES TABLE 4 (continued) mineral (s)=syntbetic nominal formula -6isoa ordering state” ref.91.6H20 CaAl2Si4012.3x 82.108 95.88.126] W61 low albitee high albitee microclinee sanidinee anorthitee a.7.6. feldspars: SiO2 SiO2 SiO2 SiO2 107.95.104.2y 91.127] [1691 [103.7 to 106.6H2O CaAl$Gi701g.1.6H20 CaAl2Si7018.3.126] W61 [118.89.102.6.7t.0 to 108.84.

[48. a ref. 89 98.5 194.4 199. mineral (s)=synthetic SiO6.6 zunyite 102.8 200.l4?1 “phaseY” (Ca0)XSiVSi1V04g 150.6 U461 ee ee .1 214.3 100.7= 197.4 202. uncertain structure: CaSivWv05 [-Na2SiV1SiIV0g Na2Siv1SiW207 Na2(SiV1SiIv)40g OQxs~ .6 128.7= 194.4 208.0 11461 .STEBBINS 313 TABLE 4 (continued) mineral (s)=synthetic danburite prehnite belyle Kleddelite nominal formula -hoa ordering WI 4 ref.0 22oc WI 11461 11461 [101. 217.0.‘VIQ2 193. uncertain structure: w 179. known structures: nominal formula -6.6bb 181. Data for end-member compositions only.6dd 203.1391 0461 U461 thaumasite ilmenite phase(s) stishovite(s) perovskitephase(s) perovskitephase(s) pyroxenephase(s)g majorite gamet(s)g wadeitephase(s)g 6) 6) SiO6.3 191.146] U461 IX81 Cl581 (SF (SF w “phaseX” (s) SiOj.5 D391 u191 4 m U181 TABLE 5. SeeTable 3 for notes. 29Si NMR data for SiO6 and SiOs sites in crystalline silicates.0cc 191.

6) Q” sites.79. Al”] nominal formula QCC.314 NMR OF SILICATES AND OXIDES Si’” Si”’ I Fig. TABLE 6. 2. BasA1208 neighbors: 2.0 72c 64 66 62 64 70 1921 1431 BaAlV19AlVA11V20t9 [43.sheetsilicates.163] [921 [921 [921 1921 [921 KA102.47 6.5 3..6 0. 27Al NMR data A104 sites in crystalline silicatesand oxides.Al)w(A1.1SH20 5.4 5.8 80 [921 zunyite garnetphase(s) garnetphase(s) spine1 (disordered)(s) 0) 6) 6) 6) 6) Q’ sites: (9 Q2 sites: (9 Alv1t~A11vSi~020(OH)t4F4Cl Gd3A12”tA131V0t2 Y~A1~VIA1~lVOt~ (Mg.25 81 [921 6) KA102.5 0. 29Si MAS spectrum for a high pressure.0 0.1 0. Black dot marks spinning side band. The multiplicity of tetrahedral sites results from partial disorderamong six-coordinatedSi and Mg neighbors[ 1011.Mg)v1204 P-A1203 ?-A1203 “l-A1203 X-A1203 72 5.andphosphates havebeenexcludedfor brevity. Mineral (s)=synthetic Q” sites. MgSiOg garnet. 6.H20 a-BaA1204.2H20 I. Data for a number of clay minerals.3 0.9 83 81 80 WI WI [921 .02 0 0 76.92. synthetic zeolites. q bayb ppm ref.129] [86.

4)(A1’“4.64.62 0.73.21 0.65 0.53 0.Allv)~Ot~(OH)~f 4.75 44.8 76 69c 72 72.OH)2 KAIV*~SiAIrV~O~~(OH)~ KA12SiA13010(OH)2f (Mg.2 2.601 WI [731 [731 6) sillimanite sapphirine @ sites.32 62.731 [531 11171 [731 mw .66 63. layer aluminosilicates:d margarite phlogopitee muscovite illitee hector& penninite xanthophyllite e-7 sites.53 77 85 64.5 39.63.0.5 61.103.5 75c [921 [921 [43.5 143.1 2.64.69~ P’3961 153.0 60.STEBBINS 3 15 TABLE 6 (continued) QCC. feldspars: All’04 APO4 AlP04 4.2 0.76 0.42 0.gS401o(OH):!.9 62.9 61.95 0.75 0. silica analogs: AlV1AlrVSi05 (Mg3.88 0.6 0.qSii.5 7.8 66C 72 76 r733 [20.6)02o 5. Mineral nominal formula @ sites.6A1”‘4.7 58.73.60.5 4.22 8.0c 59.61j.75 1.37 0.8 2.4 2.4 6. feldspathoids: NaAlSi308 KAlSi30s CaA12Si208 3. others: 6) CaAIV1~(AllV~Si~O~o)(OH)~ KMg3AlSi301o(F.55c [43. V hsoavb ref.169 [133lw41 sodalitee nepheline kalsilite(s)e scapolitee analcite leucite Na8Al&j024Cl2 Na3KAk&0t(jf KAlSi04 NaqAl3Si9024Cl-CaqA16Si6024C03 NaAlSi&*H20 KAlSi$Qj 0.8 6.94 0.29 3.Mg .731 [I91 berlinite(s) tridymite phase(s) cristobalitephase(s) @ sites.8 42.4 6 1.90 4.6 11 6. OziO ozoo OOiO mOO0 mOi0 mzO0 mzi0 @ sites.169 [43.1111 [731 [54.09 0.4H20 (Mg Al”‘)b(Si A11V)40to(OH)8f Ca2.3 5.931 [931 1931 albitee microclinee anorthite.AIV1)~(Si.77 0 0.Li)3Nao.103.2 0.66 0.

CaA120qh CaA1407. Al(l) II . Al( 1) ” .4 1.5 78.1 76.5 69.88 0. (f) Referenceincludesdata on other solid solution compositions.7 0. others: 1.9 59.0 1.45 0. .3 6.4 64.6 5.25 9.56 0.55 2. AV) CaAIV1~AIVAllV~O~~ Q” 9 8.8 2.8 5.0 0.3 80. &so at slightly higher frequency.4 1.40 0.66 0. ppm thomsonite scolectite natrolite gmelinite chabazite mordenite gismondite & sites. (b) Peakpositionscorrectedfor secondorder quadrupolarshift have beenincludedwhere possible.0 69 [431 r431 [139. (d) See [162] for extensive data on clay minerals.34 0.5-4.32 0.7 3.3 78 79 81.6 9. Mineral (s)=synthetic Q4 sites. (h) Rangeof data for six sites. (c) MAS peak position.2-86.5 0.30 9. zeolites: nominal formula v hsoalb ref.2-1.4 [731 [731 [43..50 62. Al(l) 11 7442) Ca4A16013 Ca4A16013~3H20 .38 0.66.1 2.4 55. (e) Approximate formula.4 60 83. Where this correction is not made.2 1.316 NMR OF SILICATES AND OXIDES TABLE 6 (continued) QCC. (g) Reference includes high T study of phasetransition.2 75. Tt T5 prehnite 6) 6) 6) 6) (s) 6) Ca-aluminates: 6) 11 6) 11 6) 6) 6) 6) II 6) Mg2AlqSi501 gnH20 Ca2A1V1A11VSi30to(OH)2 p-LiAlO2 y-LiA102 P-NaA102 KA102 BaAl204 TlA102 10.2 80. MAS peak positions and widths will dependsomewhat on the magnetic field used.0 81.731 [731 r731 r731 [731 cordiertite.25 85.125] [921 [921 ~921 [921 ~921 ca3&06.8 56.9 3.4 2.69 9.9 80.70 0.5.82 4 79. Al(2) CanAll4033.5 0.95 0.5 65 WI WI W31 11231 [911 [911 [911 W31 W31 W31 [911 Notes for Tables 6 and 7: a) Relative to A1(H20)63+.7 0.0 0.0 59.54 0.7 62.4 0.0 78.#179] [92.

STEBBINS 317 TABLE 7.1 [411 [3.andphosphates havebeenexcludedfor brevity. Mineral (s)=synthetic A105 sites: 6) andalusite.17 <l 2.61 1.2 0.8 7.5 5.7 -2.5 0.0 12 gc 0.0 30.59 0.79. T &soa’b ppm ref.H20 &Ge207 LaAlGe207 Ca19A111Mg2Si18068(0H)~of 10.139] r431 [43.129] 143.70 6.9 5.5 6c [43.129] [431 [431 [82.0 7.4c .46 0. Data for a variety of synthetic zeolites.6 <O.5 13 4.0 11e -6.85 3.39 2.5 4.68 3. Al”2Si207 Alv1AlvSi05 Alv1Alv(OH)$04 A1V1A1V(OH)$‘Oq.09 5.95 10.70 0.431 u91 [431 [43.3 29 36.08 0 0 0 0 15 5.63 3. All A12 A13 A14 2.43.89 0. 27A1 NMR data for A105 and A106 sites in crystalline silicates and oxides.37 8.l 0.0 36 35 41.9 36.85 0.8 0 0.101] 3.A12 augelite senegalite 6) 6) vesuvianite A106 sites: corundum chrysoberyl.7 8. All A12 nominal formula QCC.04 3.38 0.731 r43.94 0.68 2.AIt sapphirine e-net 6) garnet“YAG” (s) grossular almandine wropef 2.731 VI PI [801 [801 ml o-Al*03 BeAl Mg&Q ZnA1204 = 1% Al203 in TiO2 A12Ti05 Be$412Si@t8 HBeAlSiOs Ca19A111Mg2Si18068(OH)10f Ca2Alv1A11vSi~Oto(OH)2 LiAlsi206 A12Si05 spine1 (ordered) (disordered) gahnite rutile 6) t=-Yl euchse vesuvianite prehnite spodumene kyanite.6 0.27 0.731 [43.0 16.53 9.94 0.129] [43.70 2.8 sillimanite andalusite.4 0.731 123. sheetsilicates.85 2.551 [431 [431 [431 [86. SeeTable 6 for notes.51 0 0.163] [431 11431 Cl431 1431 f431 [1W [66.93 15.76 0 0 1.

by collection of spectraat more than one magnetic field [73.7 0.5 9.Al)8020(OH)qf 1. and.09 =a 4-l 0.10 11.103].66. The more subtle effects of bond anle and secondneighbor identity are similar to those for 49Si [2.4 2.Na)(A1. by fitting of quadrupolar line shapes [34].5 <l 0.73 0.44 1.but canbe almost negligible in many minerals at high magnetic fields.19 10.Mg AlV1)6(SiA11v)40to(OH)4f A4SWioW-h ’ A12%01 AWO3.2 1.46 0.97 4. 11 o(OW2 Al(l) t AW (Ca. [431 r431 [431 [431 r431 MHz 8.36 10.9 10 11 4c 4c 4c 10. or even lost entirely becauseof instrumental dead time. Mineral (s)=synthetic zoisite. All.5 0.6 1.88].3 2.318 NMR OF SILICATES AND OXIDES TABLE 7 (continued) QCC.5 ~3.7 r731 [731 [54@1 r731 [731 WI m KQI W33 W31 r71 [71 augelite senegalite Ca-aluminates: 6) 6) 6) 6) ethingite(s) 6) 2.8 1. for sites with relatively large QCC (quadrupolar coupling constant) values. Many MAS NMR studies of 27A1of solids have reported only peak positions.36 1.4 11. Al1 A12 topaz margarite muscovite illitee penninite xanthophyllite kaolinite pyrophyllite smectite gibbsite (s) A12Si04F2 (A104F2 site) CaAIV12(A11”2Si20~~)(OH)2 KAlV12SiA11V30~~(OH)2 KA12SiA13010(OH)2f (Mg A1V1)&i. MAS studiesat .71 1.79].67 6.A11V)40~o(OH)gf Ca2.3 1.0 ppm epidote.8 4.45 4. Quadrupolar shifts can be as large as 20 or more ppm for data collected at relatively low magnetic fields and/or for siteswith large field gradients.2 Al3 nominal formula II 0.Mg)4(Si.2 0.16 0.0 11 5 5.20 9 16 13.4 0.80 W31 11231 W31 E911 1911 WI W31 Al05 groups in a few known structureshave S values of about 35 to 40 ppm.05 18.34 0. Determination of Sisofrom MAS spectra can be done in some casesby detailed analysisof spinning sidebands for the satellite transitions [55.38 Sisoayb ref.2 12.8 0. Quadrupolar effects can broadenpeaksto the extent of being inadequatelynarrowed by MAS. which are generallyshifted to frequencieslower than &so by the secondorder quadrupolar interaction.

Featuresother than the two labeledpeaksare s inning side bands.86. for example. Indeed. 45Sc. 13C.20. The distinctions among octahedral and tetrahedral Al have in some casesallowed quantification of disorderand Al site occupancy in silicates and oxides. have been L 250 0 14oov -150 Fig. In MgAl204 spine1 [45.14.52.For group II oxides and both bridging and non-bridging oxygens in silicates. Most of these studies have been done at relatively low magnetic fields and consist primarily of relaxation time measurements.163]. 31P. Many applications of this relationship.1381. 93Nb) [8. 7Li. 27Al.155. 25Mg. the latter can be quite informative. or static spectra.154]. 89Y.1621. DAS and DOR spectrahaverecentl beenshown to be remarkably effective for resolving 170 NMR peaks for structurally similar but crystallographically distinct sites in silicates [89]. there are good correlations between increasing cation size and decreasedshielding (higher frequencies or larger chemical shifts) [153.103] as well as aluminofluoride minerals [24]. and *07Pb. l’0 Although 170 can be observedat natural abundance in liquids and in highly symmetrical sites in crystalline oxides [6].and four-coordinatedboron.153. The large differencesbetweenelectric field gradientsfor three.152.23Na. 2. but haverecently included 9Be. 93Nb. applications to silicateshave generallybeenlimited by the necessityof working on isotopically enriched samples.g. DAS spectra. 47Ti. 19F. As such. For some materials. and on phasetransitions in materialswith abundant nuclides of high Larmor frequency (e. 35Cl. In a number of sheet silicates. 2. MAS NMR has also been used to estimate the effect of temperatureon disorder(Figure 3). 2.The increasein the intensity of the Al1B peak indicatesan increasein disorder with temperature[86].109. 51V. 27Al MAS spectrafor MgAl204 spine1 quenched from the two temperaturesshown.STEBBINS 3 19 very high magnetic fields (e.3.154]. 129Xe. l19Sn.The former generally have much larger QCC values. CP MAS NMR has been shown to work well for enhancingsignals from oxygensnear to protons [ 1571. 19F. The data assembledin Table 8 have been obtained at high magnetic fields by the fitting of MAS. similar effects on 6iso have been detected for 23Na in silicates [53.136.170]. for example. 27Al MAS NMR data have been shown to agree well with site assignments basedon stoichiometry [5. Isotropic chemical shifts for nonbridging oxygensvary widely (over 1000ppm) depending on the nature and number of the coordinatingcations.164]. 39K. dynamical studieshaveconcentrated on the mechanismsand rates of diffusion of both cations (especially7Li+ and 23Na+)and anions(especially 19F-). Studies of other nuclides in silicates and oxides are too numerousto mention in detail. made to borate and borosilicate glasses [ 11. Other Nuclides NMR studiesof a variety of other nuclei in solid geological materials have provided important structural information [61]. allow these sites to be easily distinguished by l1B NMR. QCC is well correlated with the electronegativity of the neighborcationsand thus with the covalent character of the M-O bonds [ 115. The first of these reports extensive work on perovskite-structured oxides. The new techniquesof “dynamic angle spinning” (DAS) and “double rotation” @OR) NMR may prove to be very useful in improving resolution [90.4. but neglect of chemical shift anisotropycan lead to discrepancies1311.g.60. quantification of results often requires . Dynamics in Crystalline Phases In oxides and silcates. 3. [ The most obvious effect on 170 spectra of silicates with tetrahedral Si is the distinction betweenbridging and non-bridging oxygens.5. as well as the effect of coordination number on &so.1 Tesla) can be very helpful. Recently.

rl hsoa’ ref.17 1.320 NMR OF SILICATES AND OXIDES TABLE 8.55 0.8 1.402c 383c -355d 267. OA4 site ~~-Al203.Somedata for synthetic zeolites.2 4.1.0.2 0. site 3 4 4 <0.3 co.1541 [I541 r1541 @I El WI El [I151 [I151 r1151 11151 periclase(s) 6) w 6) rutile(s) anatase(s) 6) baddeleyite (s) 6) 6) 6) MgO CaO SIO TiO2 Ti02 Ti203 m2 Z102 (tetragonal) 87ZrO2.6 <0. “NBO” non-bridging are oxygen.815~ -18b 11541 [I541 [I541 [I541 [I541 El 161 WI WI @I WI @I @I WI [61 El [6.9 -60 121e 251c 294c -193 -277 1197 437 429 422 &a0 KMnO4 K2WO4.13MgO(cubic) HfO2 La203 (octahedralsite) ” (tetrahedralsite) Ce02 v02 ZllO Cd0 HgO(yellow) SnO PbO cu20 <. OA4 site y-Al2O3.1.5 <l. OA13 site 11A1203. 6) nominal formula QCC.“BO” signifiesbridging oxygen.014 26b 47b 294b 390b 629b 59oc 558c 503c 325. OA4 site II .4 aluminum oxides: corundum(s) 6) 6) 6) 6) p-alumina(s) CX-Al2O3.6 1..9 <1. In silicates.2 6) 6) zincite(s) 6) 6) 6) litharge(s) cuprite(s) 6) 6) (s) 4 =0.9. site 2 11 .0 <1.Na20 2.4 c2.02 zo.13 7.005 <.4 <1. site lf 11 .156] [1561 11561 [I561 [1561 [1561 161 .335c 469c 59oc 878c ~755. ppm =0. Mineral (s)=synthetic miscellaneous oxides.0 c2. OA4 site &Al2O3.l c2.005 COO5 <1.6 1.1 ~2. as well as oxysalts and oxide superconductors excludedfor brevity.6 75C 73C 73C 72c 72c 79c 76c [13. OA4 site t%Al2O3. 170 NMR data for crystalline oxides and silicates.

2h 2.9h 2.BO a-Casio+.13 0.1 2.lh 0.1561 U561 WI [I571 Mg2Si04. I.2h 2. NBO 11 .1 2. .9h 3.BO 11 . NBO I.6h 2.3 3.. . . 0 htrnite(s) AlO( 11 Al(OH).P 2..gh 72i 64i 49i 134i 12gi 122i 122i if391 WI WY 1891 F391 P391 1891 chain silicates: diopside(s) 9.BO .1 0. NBO II .00 0. 11 I.* NBO . NBO I.0 7o. caMgsi206.8 0. NBO . NBO II . II II ps-wollastonite 11 11 (s) 19 I.. NBO 11 . II $9 8. NBO .8 2.3h 2.BO Ca3Si309.5 0. 9. NBO II .7h 2.9h 2. Mg(W2 OA4 site A120H site Al2OH site 1.15 5. bayerite(s) brucite orthosilicates: forsterite(s) t.BO NBO .74 4.1 0.39 2.6h 4.13 0.BO 11 . . NBO 2. 11 wollastonite(s) 11 11 11 It 0 I. NBO 9.8h 4. . hydronides: boehmite(s) .8h 3.3 0.3h 2.6h 4.36 . NBO I.7h 2. NBO II . NBO 11 . . NBO I.4 86i 64 69’ 57i 61i 59’ 62’ 7oi 7oi 115i 114i 107i 97’ 103i 88i 75’ 75i 67’ 94c 91c 75c 10gc 105c 80c E391 1891 WI F391 [891 WI WI [891 WI WI if391 P391 E391 [891 WI F391 WI [891 r1531 [I531 r1531 u531 u531 [I531 . rl hoa’ ref.STEBBINS 321 TABLE 8 (continued) Mineral nominal formula QCC. NBO . clinoenstatite(s) I.0h 2..oh 2.8h 4.1 0.1 0. NBO I. 11 11 Mg2si&j.2 0. .BO a-SrSiOgj. NBO 11 .83 2.0 6.6h 3.2h 5.1 0. NBO 3. .0 6.2 4.I-0 .BO 5.NBO Ca2SiO4. .oc 4oc 4oc 25g [125.

5 [I651 [I651 U651 a) Relative to H20.o-j3=217 ppm. and the frequent model-dependent nature of the structural conclusions. NBO 11 . for site 3: 011=561 a22=497.2 3. 033=-10 ppm. PQ’ QCCx( l+ IJ2/3) li2. as well as extensivediscussionof silicate. (c) From simulation of MAS data. 3.4 0 0 0 &soa’ ppm 169c 159c 87c 4og 5og og ref. (f) For site 1: 011=564.These contain information on studies of nuclides not included here.Separate .1 1.87<QCC<p~ [891. oxide. I have tabulated only a few 29Si MAS data on glasseswith the stoichiometry of end-member crystalline phases(Table 9). AMORPHOUS SOLIDS. (d) Uncorrected for QCC.45 4. (h) QCC given is actually the “quadrupolar product”. corrected using QCC from static spectrum.7 3.1 0. (e) From MAS.2 0.3 v 0. borate.35 0.6 0. MgOH site framework silicates: QCC.2 5.for example [57.l l. and non-oxide glasses [lO.1 0.CSA not included.Si-O-Al. BO (seereference).62.145].0 109.8 1. complex models. 29S i The relatively clear relationshipsbetween&so and Q speciesin crystalline silicates has led to a number of attempts to quantify their abundancein glasses. high resolution studies of silicates. AND MELTS Techniquessuch as NMR becomeparticularly important when the absenceof long-range structure limits the 3.144].3 3. Other recent reviews do include some tabulations [34].2 0. (b) From MAS data.a22=530. and can have an important influence even in ortho. a33=202 ppm. the direct observation of exchangeamong multiple sites in a crystal offers the possibility of simpler.Si-O-Al.BO 11 . 19F. Alkali cation dynamics have beenstudied in a number of framework silicates.Because of the wide and continuous rangesof compositions studied. 23Na9and 31P. @Derived from DAS data at two magnetic fields. little or no correction for QCC needed.131]. Structural and dynamical changesoccurring during displacivephasetransitions in silica polymorphs and their aluminum phosphate analogs have been explored in some detail [99.13 0.and chain-silicates[38]. APPLICATIONS TO GLASSES.1. BO 5.130.6 3. BO II . ts33=208ppm. MHz 2. ~iIV-O-SiVI SiO2 4.50 0. especially llB.322 NMR OF SILICATES AND OXIDES TABLE 8 (continued) Mineral (s)=synthetic nominal formula BaSiOjj. [I531 P531 r1531 r1571 [I571 [I571 cristobalite(s) Na-A zeolite(s) Na-Y zeolite(s) *a high pressure silicates: SiO2 (seereference).29. (g) Basedon static spectrum. information obtainableby diffraction methods.61. more direct interpretations. 0.2 0.13 62.022=518. for site 2: all=567. NBO 11 .BO Mg$&Olo(OH)2. Si-O-Al.90 6. (k) Fit of static spectrum gives CJ~ 1=a22=6O.1 4.5 97. (i) More sites are presentthan are resolved in MAS spectra.1 4ok 32= 31c 44c u311 U521 U521 11521 wadeitephase(s) 19 stishovite(s) Notes for Table 8: K2SiV1SiIV309 Si*v-O-Silv 11 . In a few recent. NBO 11 .

94.7* 103.166] [771 [771 1771 1771 Na2Si409 K2Si409 105.981 [94. [44.92.8*.0.1* 99.981 r9a 1941 [941 [94.32. becauseof the contrasts in chemical shift anisotropy [9.88.76.but more orderedthan predictedby random mixing of bridging and non-bridging oxygens [94.9 83.32.981 1701 [701 r77.5 ppm in peakpositionsand widths.5 98.0.79.5* NazSiOg 84. Quantitative interpretations have usually dependedon assumptions of Gaussian line shapeand curve fitting.8* 11*. but interpretations have converged as data improves [26.6.3 80.134.3*.981 [94. and in aluminosilicate glasses. 29SiNMR data for glassesof simple.peaks for Q speciesare usually unresolvedin MAS spectrabecause greateroverall disof .7.10* 12*. crystalline stoichiometry.91.77].8 86.ll 11.134].5*. static spectra can permit quantification of Q species in glasses with fewer curve fitting assumptions than for MAS spectra.81.6 20 16 14 [701 [701 1701 Notesfor Table 9: Uncertainties are generallyat least 0.12.MI [77.77.11.7* 10*. It is now clear that speciation is more disorderedthan requiredby simplestoichiometry.1.3 80.2 105.135]. *Partially resolvedshoulder peaks for each Q speciesare often partially resolved in MAS spectra for alkali silicate glasses (Figure 4).5 87.7 92.7. ppm 12 16 18 13 15 15 11 17 13 13.1 FWHM.STEBBINS 323 TABLE 9.10.66X* MgSiO3 CaMgSi206 CaSiO3 82.5* ref.7*.28.5 1.4 82. Composition Si02 NaAlSigOg NaAlSi206 NaAlSiO4 KAlSi308 CaA12Si208 CaAlZSiOfj -&so7 mm 111.90.3 102.8.0 100.lO 14*. In a few favorable cases.135]. In binary silicate glasses of alkaline earths.3 81. A number of ther- modynamic mixing models for these systemshave been based on NMR data [9.

129]. it hasbeendemonstrated that 170 DAS NMR can accurately quantify bond angles and oxygen site distributions [36].For pure Si02 glass. is highly disorderedwith respectto local structure [1.94. order and variety of first neighbor cation arrangements. 3. This approachhas been usedto show that Q speciesdistributions. Water in Glass Both static “wideline” and high speed1H MAS studies have detected and quantified OH. high-coordinateAl hasbeendetectedin only slightly peraluminousglasses near to the MgA1204Si02 join [831. Six-coordinatedSi has alsobeenreported in alkali silicate glassescontaining large amounts of P205 [25.22].4. It may be impossible to distinguish theseeffects from thosecausedby disordered distribution of sites. studiesat varying magnetic fields can be useful. as well as overall disorder in bond angles.can againbe useful in determining isotropic chemical shifts [79. which is characterizedby obvious x-ray diffraction peaks and which therefore containssubstantiallong-rangeorder. labeled[166]. 3.and from different tetrahedralspecies.167].98].68].1353. Mg silicates [70.94]. Black are dots mark spinning sidebands.27]. . Fitting of spinning side bands.SiO2 ternary. Studiesof alkali silicate glasses quenchedfrom liquids at pressuresto 12 GPa have shown the presence six coof ordinated Si (Figure 4). The narrowing of NMR peaks as Al/Si is increasedto 1 suggeststhat some Si-Al ordering occurs.3. High coordinate Si has not been observed in NaAlSigOg or SiO2 glassesquenchedfrom liquids at high P [150.113] and in some phosphorus-richglasses[27] and boroaluminates[ 15.110.Al203 . Careful quantification of intensities is essential in determining whether all Al hasbeendetected[651.1%) in glasses formed at 1 bar pressure[137].324 NMR OF SILICATES AND OXIDES SP Several NMR studies have suggestedthat opal-CT. Systematic compositional effects on the chemicalshifts for NBO sites have been noted [61].65.0. 4.166. -160 -203 Fig. as have pressureeffects on 0 site distribution [ 1651. However.Very recently. 27Al As in crystalline materials. although again. 29Si MAS spectra for Na2Si409 glasses quenchedfrom liquids at 12 GPa and at 1 bar pressures. The most dramatic findings from 27Al MAS NMR in glasseshas beenthe clear detectionof five and six coordinated Al in a variety of compositions.98]. including those in the Si02-A1203 binary [105. do indeedbecomemore randomwith increasing T [9.In carefully quantified studiesof glasscompositions with M+l20/A1203 or M+*O/A1203 I 1. Static spectracan sometimes be more informative than MAS data.Studieshaveincludedextensivework on alkali and alkaline earth aluminosilicates [35. and has provided some dynamical in- 12 CPa I bar -80 -la.when theseare observable.166]. One approachto determining the effect of temperature on liquid structure is to quench liquids at varying rates to produce glasseswith different “fictive” or glasstransition temperatures (Tg). The latter has now also been detected at low abundance (~0. 3. making quantitativederivation of speciationhighly modeldependent. In the CaO . it has been shown that high coordinatedAl is undetectable and thus comprises less than a few percent of the total Al [65.and molecular Hz0 [30. non-tetrahedralAl is abundant only in compositions close to the Si02-A1203 join [ 1141.2. Signalsfrom Si with different coordination numbers.971. 2H NMR has distinguishedamong water species in glasses.bond angledistributions have been derived using empirical correlations between 6 and bond angles [44. probably becauseof at least partial “aluminum avoidance” [943. the primary distinction among 0 sites detectedby NMR of glassesis that betweenbridging and non-bridging oxygens(Figure 5).98] and Ca. The latter study usedthe CP MAS techniqueto study the distribution of silanol groups (Si-OH). 170 As in crystals.as well. and for the first time demonstrated the existence of five coordinated Si [147. which were detectablein most of the samplesstudied. interpretation of NMR spectra of quadrupolar nuclides in glassesis complicated by second-orderquadrupolarbroadening(possiblyleading to signal loss from highly distorted sites).

whereas in hydrous binary alkali silicate glasses[85. in favorable cases. I would like to thank my numerous colleagues who sent reprints and preprints and allowed me to include results prior to publication.145]. and fluorides melt. and 29Si NMR have been usedin severalstudiesof the interaction of silicate glasseswith water at ambient to hydrothermalconditions at a range of pH’s [16. especially H. and 29Si MAS and CP MAS spectra were interpreted as indicating that OH is bound soley to Na with the possibility of protonated bridging oxygens [67. In K2Si4O9 liquid. I thank the editor.81.STEBBINS 325 formation [31]. 5. and acknowledge the support of the National Science Foundation. assuminga simple Eyring model for flow [38. T. that and of 0 between bridging and non-bridging sites. in situ. rate The of exchangeof Si among various anionic species. and an anonymous reviewer. are fundamentally tied to diffusion and viscous flow. for example (Figure 5) simulations of high temperature 170 and 29Si line shapesgives results that can be used to accurately predict the viscosity. and have includedsystematic work on the effects of composition on the structure and dynamics in the CaO-A1203-Si02 system 121. high temperature NMR reveals only single 170. that when aluminum oxides. for which orientational effects that lead to broadeningin a solid.69]. . 27A1.169]. As a result. J. flow requiresthe breakingof the strongest bonds in the system (Si-0). At lower temperatures. B. narrow line causedby exchange species.J.incomplete exchange averand aging occurs.168.841.76].Under theseconditions. This approach has shown. therefore. silicate species are short lived.1511. 1 943 ‘C ---iAL 3.149.Note collapseto single. and that the interaction of alkali cation with the network can also be detected[38. 29Si NMR has clearly shown the presence of SiOH groups. grant #EAR9204458. 23Na. Jakobsen. for example. aluminates. 23Na.NMR line shapes can be analyzedto measurethe rates of exchange. the meanAl coordination number decreases [40. and X. 27A1. Silicate and Aluminate Liquids In ionic and partially ionic liquids suchas silicates(at least at high silica contents). The averagepeak position can still give structural information however. A series of relaxation time measurements shown that has Si dynamics are greatly affected by the transition from glass to liquid. Xue.Studieshave now been made to temperaturesgreater than 2 100° C. and. 2-D exchange NMR spectroscopy just above the glass transition also suggeststhat exchangeamong Q speciesis of key importance in flow even in the very high viscosity range [39].5. are fully averaged [38.75. llB. of Acknowledgements. with all cations and anions exchangingrapidly amongavailablesites. 170.81].23Na 27A1. Phillips. and 29Si peaks. In hydrous NaAlSigO8 glass. High temperature 170 spectra for K2Si409 liquid.121. Skibsted. at high temperatures where viscosities are low. A multi-nuclear high T NMR study of alkali aluminosilicate liquids has detectedsystematictempemtureeffects on averagedchemicalshifts that can be interpretedin terms of structural changes[ 1421. Fig. “bo” and “nbo” show contributions from bridging and non-bridging oxygens [ 1451.139] and in SiO2 [373. since it is a quantitative weighted meanover all species present.139. Ahrens.142. including chemical shift anisotropy and quadrupolar couplings.

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