Glikin A.E. Polymineral-Metasomatic Crystallogenesis
Подождите немного. Документ загружается.
Polymineral-Metasomatic Crystallogenesis
Arkady E. Glikin
Polymineral-Metasomatic
Crystallogenesis
Arkady E. Glikin
Crystallography Department
Geological Faculty
Saint Petersburg State University
University Embankment 7/9
199034 St. Petersburg
Russia
glikin@ag2460.spb.edu
ISBN 978-1-4020-8982-4 e-ISBN 978-1-4020-8983-1
Library of Congress Control Number: 2008933944
© 2009 Springer Science + Business Media B.V.
No part of this work may be reproduced, stored in a retrieval system, or transmitted in any form or by
any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written
permission from the Publisher, with the exception of any material supplied specifically for the purpose
of being entered and executed on a computer system, for exclusive use by the purchaser of the work.
Printed on acid-free paper
springer.com
Acknowledgments
I’d like to express my sincere gratitude to the fate that ensured my successful work
and happy human relations at the Crystallography Department of St Petersburg
State University and Russian Mineralogical Society. I express my gratefulness to
my teacher, Thomas G. Petrov, whose guiding influence has been invaluable for my
scientific outlook formation. With deepest appreciation for the school of thought I
treasure recollections about my late professors: Vitalii B. Tatarskii, Victor A.
Frank-Kamenetskii, Alexander A. Kukharenko, Alexey A. Shternberg, and
Vladimir V. Nardov.
I feel myself deeply indebted to my most devoted collaborators: Sergey N.
Bocharov, Valeria D. Franke, Elena V. Kiryanova, Vladimir G. Krivovichev,
Lyudmila Yu. Kruchkova, Julia V. Plotkina, Marina Yu. Sinai, and Alexei E.
Voloshin. I also thank students, postgraduate students, and researchers of
Department of Crystallography of St Petersburg University, who took part in the
research works and became coauthors of the cited publications.
My particular gratitude should be addressed to Prof. Vladimir V. Dolivo-
Dobrovol’skii, whose valuable remarks greatly helped me in preparation of Russian
version of the present monograph.
A considerable part of the investigations and preparation and publication of the
book itself were supported by the Russian Fund for Basic Research (projects 03-05-
78003, 07-05-00380, and others), programs “Russia’s Universities” of Ministry of
Education and Science of the Russian Federation, State Contract 02.523.12.3004
(project DN 08/07-03). Grants of DAAD (Germany), NWO-NATO (Netherlands),
and INTAS (EC) allowed me to present the results of the investigations to
International Society of Mineralogists and Crystallographers and to develop some
aspects of the problem in close collaboration with my foreign colleagues Profs.
Valter A. Franke, Peter Gille, Helmut Klapper, Andrew Putnis, and Cornelis F.
Woensdregt and Drs. Christine Putnis, Julius Schneider, and Robert Stark.
I am greatly thankful to the editors of both the versions. The Russian version of
the book was issued by Anton V. Voznesenskii, Svetlana A. Bulacheva, and Nina
R. Liberman (the company “Kolo,” formerly “Zhurnal Neva”). The primary transla-
tion into English was carried out by Tatyana Yu. Nikolaenko and the figures for the
English version were edited by Olga A. Temezhnikova. These preparations were
sponsored by the Geological Faculty of St Petersburg University under its Dean
v
vi Acknowledgments
Igor V. Buldakov’s initiation. The agreement of Springer to publish the book is of
a great honor for me.
I am particularly obliged to my wife Elena N. Kotel’nikova, mother Sofia E.
Glikina, and son Anton A. Glikin for long-standing and invaluable assistance.
I dedicate my work to the memory of my grandparents Cecil A. Glikina and
Karp F. Dvornikov.
Contents
Foreword ......................................................................................................... xi
Introduction On the Concept of Polymineral-Metasomatic
Crystallogenesis ......................................................................................... 1
1 Replacement of Monocrystals ................................................................. 7
1.1 Natural and Experimental Products of Replacement ........................ 7
1.2 Technique, Terminology, and Experimental Results ........................ 12
1.3 Metasomatic Transformations in Polymorphic Pair Retgersite–
Nickelhexahydrite (α–β-NiSO
4
·6H
2
O) ............................................. 25
1.4 Structural-Morphological Classification of Replacement
Products............................................................................................. 28
1.5 Genetic Nature of Replacement Products ......................................... 30
1.5.1 Types of Physicochemical Systems and Structure
of Replacement Products ...................................................... 30
1.5.2 Volume Effect of the Reactions ............................................ 34
1.5.3 Kinetic Factors and Shape of Replacement Products ........... 36
1.5.4 Imperfection of Protocrystals as a Factor
of Replacement Process ........................................................ 40
1.6 Mineralogical Aspects of the Problem of Crystal Replacement ....... 45
References .................................................................................................. 53
2 Joint Growth of Crystals of Different Phases ........................................ 61
2.1 Growth and Dissolving in Supercooled Solutions ............................ 61
2.1.1 Technique .............................................................................. 61
2.1.2 Crystal Morphology .............................................................. 64
2.1.3 Kinetics ................................................................................. 66
2.2 Physicochemical Model .................................................................... 72
2.2.1 Phase Equilibria in KCl–NaCl–MgCl
2
–H
2
O System ............ 72
2.2.2 Kinetic Effects and Peculiarities of Phase Equilibria ........... 76
References .................................................................................................. 82
vii
viii Contents
3 Formation of Mixed Crystals in Solutions ............................................. 85
3.1 Particular Characteristics of the Process and Historical Survey ....... 85
3.2 Material Balance and Mechanisms of Replacement ......................... 88
3.3 Physicochemical Model .................................................................... 96
3.3.1 Modified Concentration Diagrams........................................ 96
3.3.2 Formation of Crystals Under Equilibrium,
Quasi-equilibrium, and Non-equilibrium Conditions ........... 100
3.3.3 Heterogeneous Metastable Equilibrium Between
Crystals and Solutions........................................................... 107
3.4 Morphological and Kinetic Behavior of Monocrystals .................... 115
3.4.1 Tutton Salt Series (Co,Ni)(NH
4
)
2
(SO
4
)
2
.
6H
2
O ..................... 115
3.4.2 Series of Potassium–Rubidium Acidic Phthalates
(K,Rb)HC
8
H
4
O
4
.................................................................... 128
3.4.3 Arcanite-Tarapacaite K
2
(S,Cr)O
4
Series ............................... 137
3.5 Inhomogeneity of Crystals ................................................................ 141
3.6 Mass Precipitation of Mixed Crystals: Distribution
by Compositions and Sizes ............................................................... 145
3.7 On the Mechanism of Isomorphic Component Selection
during the Crystal Formation ............................................................ 147
References .................................................................................................. 149
4 Physicochemical Analysis of Metasomatic Crystallogenesis ................ 153
4.1 Brief Overview .................................................................................. 153
4.2 Isothermal Replacement in Ternary Systems .................................... 157
4.3 Isothermal Replacement in Complex Systems and Formation
of Poikilitic Crystals ......................................................................... 162
4.4 Polythermal Processes ...................................................................... 164
4.5 Common and Different Features of the Processes Proceeding
in Systems Containing either Isomorphic or Non-isomorphic
Components ...................................................................................... 167
4.6 Some Methods of Estimation of Reaction Volume Effect ................ 170
References .................................................................................................. 173
5 Metasomatic Transformation of Aggregates ......................................... 177
5.1 On Replacement and Growth of Monocrystals in the Course
of Transformation of Aggregates ...................................................... 177
5.2 A Model of Formation of Rapakivi-Type Structures ........................ 182
5.3 Recrystallization of Polymineral Aggregates ................................... 195
5.3.1 Natural and Experimental Products of Recrystallization ...... 195
5.3.2 Technique and Experimental Results .................................... 197
5.3.3 General Regularities and Possible Mechanisms ................... 212
References .................................................................................................. 223
Contents ix
6 Epitaxy and Quasiepitaxy in Solutions .................................................. 229
6.1 Principle Phenomena ........................................................................ 229
6.2 Technique .......................................................................................... 231
6.3 Epitaxial Regularities on a Growing or Dissolving Substrate .......... 235
6.4 Regularities of Orientation of CaCO
3
Microcrystals Adhered
to a Substrate ..................................................................................... 240
6.5 Model of Formation of Epitaxial and Quasiepitaxial Textures ......... 241
References .................................................................................................. 245
7 Crystal Faceting ....................................................................................... 249
7.1 Stationary Forms of Faceting ............................................................ 249
7.2 Crystal Habit under Nonstationary Growth Conditions .................... 260
7.3 Regularities of Fluorite Faceting....................................................... 266
7.4 Structure-Chemical Model of Crystal Faceting ................................ 275
7.5 Effect of Infrared Radiation on Crystal Growth Kinetics
in Solutions ....................................................................................... 279
7.6 Kinetic Anomalies of Crystal Growth in Solutions .......................... 282
7.7 Nature of Kinetic Anomalies and Crystal Growth Mechanisms....... 284
References .................................................................................................. 294
Conclusion On Interrelation between Crystallogenesis
and Geological and Mineralogical Sciences .............................................. 301
Index ................................................................................................................ 305
Foreword
A vast list of publications concerning the influence of formation conditions upon
the process of crystal growth begins with the work concerning the supposed rela-
tionship between the shape of natural galenite and its silver content published by
Abraham G. Werner (1774) and with experimental findings of Jean-Baptiste L.
Romé de l’Isle and Sieffert, who observed in 1780 the effects of impurities on
sodium chloride and alum crystal shape.
Crystallogenesis as a term to denote a branch of science dealing with correlations
between conditions of crystal formation and its properties was introduced as early as
in the beginning of the nineteenth century by an outstanding American mineralogist
James D. Dana. It was he who outlined the main tasks of crystallogenesis in his
famous book A System of Mineralogy. Intensive development of crystallogenesis
started from the beginning of the twentieth century. At present, crystallogenesis
(crystallogenesis, crystallogeny, crystal genesis) is a subject of official activities of
the International Union of Crystallography, although the use of the term is compara-
tively infrequent and predominately used in Russian publications.
In Russia, in the 1910s, there were organized two scientific institutions for
studying crystallogenesis, which have been developing in parallel ever since.
The first institution was founded in St. Petersburg University by the Head of its
Mineralogical Department Piotr A. Zemyatchenskii who from 1909 to 1914 carried
out the first object-oriented observations of crystal growth. His investigations of
influence of solution impurities upon crystals of alum and sodium chlorate were
summarized in the first specialized monograph concerning this field Crystallogenesis
Essays. For many years, this work had served as a tabletop manual for everyone
who dealt with growing crystals.
Development of crystallogenetic school of St. Petersburg University was mainly
influenced by geologists, who, nevertheless, paid great attention to the physical
aspect of the art. The founder of Crystallography Department in Leningrad/
St. Petersburg University Osip M. Ansheles was taught by the famous crystallo-
grapher Evgraf S. Fedorov, who, of course, influenced his ideas. In particular, he
was probably the first to observe in situ a macrostepwise growth of crystals (in
hyposulfite). That allowed him and his followers and colleagues Vitalii B. Tatarskii
and Alexei A. Shternberg to pioneer development of a fast method for growing
single crystals of Seignette salt, which was successfully applied in the defense
xi