High-Pressure Silicates and Oxides: Phase Transition and Thermodynamics

215 Pages·2022·9.464 MB·English

by  Masaki Akaogi

Advances in Geological Science
Masaki Akaogi
High-Pressure
Silicates and
Oxides
Phase Transition and Thermodynamics
Advances in Geological Science
Series Editors
Junzo Kasahara, Tokyo University of Marine Science and Technology, Tokyo,
Japan
Shizuoka University, Shizuoka, Japan
Michael Zhdanov, University of Utah, Utah, USA
Tuncay Taymaz, Istanbul Technical University, Istanbul, Turkey
Studies in the twentieth century uncovered groundbreaking facts in geophysics and
produced a radically new picture of the Earth’s history. However, in some respects
it also created more puzzles for the research community of the twenty-first century
to tackle. This book series aims to present the state of the art of contemporary
geological studies and offers the opportunity to discuss major open problems in
geosciences and their phenomena. The main focus is on physical geological
features such as geomorphology, petrology, sedimentology, geotectonics, vol-
canology, seismology, glaciology, and their environmental impacts. The mono-
graphs in the series, including multi-authored volumes, will examine prominent
features of past events up to their current status, and possibly forecast some aspects
of the foreseeable future. The guiding principle is that understanding the
fundamentals and applied methodology of overlapping fields will be key to paving
the way for the next generation.
Masaki Akaogi
High-Pressure Silicates
and Oxides
Phase Transition and Thermodynamics
Masaki Akaogi
Department of Chemistry
Gakushuin University
Tokyo, Japan
ISSN 2524-3829 ISSN 2524-3837 (electronic)
Advances in Geological Science
ISBN 978-981-19-6362-9 ISBN 978-981-19-6363-6 (eBook)
https://doi.org/10.1007/978-981-19-6363-6
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Preface
The high-pressure and high-temperature investigation of Earth’s materials is a rapidly
advancing research field. Experimental research has explained the pressure-induced
phase transitions of various mantle-constituent minerals, and the results have been
applied to elucidate the constitution of the Earth’s interior with implications for its
dynamics and evolution. Presently, pressure and temperature conditions beyond the
Earth’s center can be generated by means of high-pressure and high-temperature
experiments.
In materials science and solid state chemistry, high-pressure and high-temperature
techniques are widely used for the synthesis of materials that are stable at high
pressure, such as diamond, and for the exploration of new materials with novel
structures and physical and chemical properties. Techniques for generating pressure
higher than approximately 10 GPa have been developed mostly in the field of Earth
science and are now being applied for the synthesis of novel functional materials
with potential industrial applications.
Phase transitions of Earth’s materials and related compounds under high pres-
sures and high temperatures are expressed in terms of chemical thermodynamics.
Thermodynamic parameters, including enthalpy, entropy, and heat capacity, are
measured and used to calculate the high-pressure and high-temperature phase rela-
tionships in equilibrium conditions. The phase relationships obtained by thermody-
namic calculations are independent of those obtained by direct high-pressure and
high-temperature experiments, and the combination of the two methodologies can
determine the equilibrium phase relationships more accurately.
This book summarizes recent results on solid-state phase transitions of Earth’s
materials and various related compounds at high-pressure and high-temperature
conditions. Most of them have been accumulated primarily over the latest two
decades using high-pressure and high-temperature experiments and thermodynamic
calculations based on calorimetric measurements. In this book, a detailed discussion
of the Earth’s interior is not the primary focus, but the physics and chemistry of
high-pressure silicates and various oxide materials are discussed, focusing on the
v
vi Preface
accurate phase equilibrium relations of these substances. The book also contains
a large number of illustrations of phase diagrams for these materials as the basis
for discussing the Earth’s interior and synthesis of novel high-pressure oxides.
This book is primarily intended for graduate and senior undergraduate students of
Earth and planetary sciences and materials science and can also be useful for scien-
tists interested in the high-pressure phase transitions of silicates and various oxide
materials.
Chapter 1 presents the outlines of the structure and constituent minerals of the
Earth’s interior, the roles of high-pressure experiments, and the names of high-
pressure minerals. Chapter 2 discusses the crystal chemistry and elementary thermo-
dynamics of high-pressure phase transitions. Both chapters provide the background
information for the following chapters. In Chap. 3, experimental techniques of high-
pressure and high-temperature experiments are described for large-volume presses
using both quenching and in situ X-ray diffraction methods. Various calorimetric
measurements and lattice vibrational model calculations are discussed in Chap. 4.
Chapters 5 and 6 describe high-pressure phase transitions of magnesium and iron
silicates, which separate the mantle transition zone from the upper and lower mantles,
and conclude that the perovskite-type Mg-rich silicate is the most abundant mineral in
the lower mantle. Recently, the distribution of water (hydrogen) in the Earth’s interior
and its effects on the phase transitions, melting, and dynamics of the mantle have been
extensively investigated. Thus, Chap. 5 also includes the discussion of major hydrous
silicates in the transition zone. Chapter 7 discusses crystal chemistry, phase relations,
and energetics of various perovskite-type high-pressure ABO compounds. The post-
3
perovskite transition of Mg-rich silicate in the lowermost mantle, the post-perovskite
transition of various ABO and ABF compounds, and the post-rutile transitions of
3 3
AO compounds are discussed in Chap. 8. Chapter 9 presents the phase transitions of
2
spinel-type AB O compounds. Chapter 10 is concerned with the phase transitions
2 4
in mantle rocks with multiple components and phases. Chapter 11 provides examples
of natural high-pressure minerals, for which the formation pressure and temperature
conditions can be constrained using experimentally determined high-pressure phase
relations.
I gratefully acknowledge Syun-iti Akimoto and Alexandra Navrotsky for guiding
me in high-pressure geoscience and calorimetry. I would like to thank a number of
colleagues and my former students for their fruitful collaboration in these research
fields, particularly, Eiji Ito, Takehiko Yagi, Hiroshi Kojitani, Toshihiro Suzuki, Toru
Inoue, Hitoshi Yusa, Takayuki Ishii, Yuichi Shirako, Kiyoshi Fujino, Yoshiyuki
Inaguma, Kazunari Yamaura, Paul F. McMillan, and Ahmed El Goresy. I also thank
the continued support of my research through the grants from the Japan Society
for the Promotion of Science (JSPS) and the Ministry of Education, Culture, Sports,
Science and Technology (MEXT), Japan. Most parts of this book were written during
the COVID-19 pandemic. I am grateful to my colleagues, Kiyoshi Fujino, Hiroshi
Kojitani, Hitoshi Yusa, Takayuki Ishii, Yuichi Shirako, Toru Inoue, Naotaka Tomioka,
and Paul F. McMillan, for reading all or parts of the manuscript and providing their
Preface vii
invaluable comments and suggestions to improve it. Finally, I thank my family,
especially Etsuko, for her understanding and support during the preparation of this
manuscript.
Tokyo, Japan Masaki Akaogi
June 2022
Contents
1 Introduction .................................................. 1
1.1 Structure of the Earth’s Interior ............................. 1
1.2 Constituent Minerals of the Earth’s Mantle ................... 3
1.3 High-Pressure and High-Temperature Experiments
and Thermodynamic Calculations for Investigation
of Mineral Phase Transitions ............................... 5
1.4 High-Pressure and High-Temperature Experiments
for Synthesis of New Materials ............................. 6
1.5 Mineral Names of High-Pressure Silicates and Oxides ......... 7
References .................................................... 9
2 Crystal Chemistry and Thermodynamics of High-Pressure
Phase Transition .............................................. 11
2.1 Crystal Chemistry of High-Pressure Phase Transition .......... 11
2.1.1 General Features ................................... 11
2.1.2 High-Pressure Phase Transitions of AO Compounds .... 13
2.1.3 Pressure-Induced Electronic Spin Transition ........... 15
2.2 Thermodynamics of High-Pressure Phase Transition .......... 17
2.2.1 Gibbs Free Energy and Phase Transition .............. 17
2.2.2 Configurational and Vibrational Entropies ............. 18
2.2.3 Thermodynamic Formulation of High-Pressure
Phase Transition ................................... 19
2.2.4 Thermodynamic Formulation of High-Pressure
Phase Equilibria in a Binary System .................. 21
References .................................................... 23
3 High-Pressure and High-Temperature Experiments
with Large-Volume Apparatus ................................. 25
3.1 Large-Volume High-Pressure Apparatus ..................... 25
3.1.1 Piston-Cylinder Apparatus .......................... 26
3.1.2 Multianvil Apparatus ............................... 26
3.2 Materials of Anvils and Pressure Media ..................... 29
ix
x Contents
3.3 Pressure Calibration ...................................... 31
3.4 Cell Assembly for High-Pressure and High-Temperature
Experiments ............................................. 34
3.5 High-Pressure and High-Temperature Quenching
Experiments ............................................. 38
3.6 High-Pressure and High-Temperature In Situ X-Ray
Diffraction Experiments ................................... 39
References .................................................... 42
4 Calorimetric Experiments and Thermodynamic Calculation
of High-Pressure Phase Relations ............................... 47
4.1 Enthalpy Measurement .................................... 47
4.2 Low-Temperature Heat Capacity Measurement
and Determination of Entropy .............................. 53
4.3 High-Temperature Heat Capacity Measurement ............... 55
4.4 Lattice Vibrational Model for Heat Capacity Calculation ....... 57
4.5 Examples of Thermodynamic Calculations of Phase
Equilibrium Boundaries: Quartz-Coesite-Stishovite
Transitions in SiO ....................................... 61
2
4.6 Thermodynamic Database for Calculation of High-Pressure
Phase Equilibria .......................................... 64
4.7 Ab Initio Calculation of Thermodynamic Properties
of High-Pressure Phases ................................... 65
References .................................................... 67
5 Olivine–Modified Spinel–Spinel Transitions ..................... 71
5.1 Introduction ............................................. 71
5.2 Olivine-Modified Spinel-Spinel Transitions in Mg SiO ....... 73
2 4
5.3 Olivine-Spinel Transition in Fe SiO ........................ 75
2 4
5.4 Olivine-Modified Spinel-Spinel Transitions
in the Mg SiO -Fe SiO System ........................... 76
2 4 2 4
5.5 Hydrous Wadsleyite and Hydrous Ringwoodite ............... 82
5.6 Spinelloids with Spinel-Related Structures ................... 83
References .................................................... 87
6 Phase Transitions of Pyroxene and Garnet, and Post-spinel
Transition Forming Perovskite ................................. 93
6.1 Phase Transitions in MgSiO and FeSiO .................... 93
3 3
6.2 Post-spinel Transition in Mg SiO .......................... 98
2 4
6.3 Post-spinel Transition in the Mg SiO -Fe SiO System ........ 101
2 4 2 4
6.4 Phase Transitions in the MgSiO -Al O System .............. 103
3 2 3
6.5 Phase Transitions in CaSiO , CaMgSi O , and Other
3 2 6
Pyroxene and Garnets ..................................... 107
References .................................................... 109