Bergaya F. Handbook of Clay Science
Подождите немного. Документ загружается.
FOREWORD
Clay science has emerged after a few millennia of clay use and a century-long
accumulation of written information about clays and clay minerals. No other min-
erals currently attract so great an interest, or are being subjected to such an intensive
examination as clays. The focus of clay research has long been on the geological,
geotechnical, and mineralogical aspects of clays. It is onl y relatively recently that
clay science has assumed a physico-chemical orientation. The rapid development
of clay science over the past few decades is attested to by the voluminous literature
on clays. It is also reflected by the establishme nt of clay groups and societies in many
countries. New information is regularly communicated in a variety of journals and
through numerous national, regional, and international conferences and symposia as
well as by dissertations, lect ure notes, technic al reports, and patents. At a rough
estimate, several hundred scientific communications on clays and clay minerals are
published annually.
The two main features that evoke interest in clays are: (1) their common avail-
ability, a nd (2) their extraordinary properties. Archaeological research has indicated
that the first use of clays by humans coincided with ancient agrarian settlements. As
humans sowed the first grain seeds, they also began to make bricks, utensils, and
artistic objects from clay. Pottery developed into an important and respected pro-
fession, the associated skills and experien ces being handed down from one gener-
ation to the next. Likewise, the technological improvements were transmitted from
decade to decade. Over time, empirical technology has been systematical ly converted
into scientific procedure based on sound theoretical principles.
Clays and clay minerals represent the youngest members of the family of minerals
in the Earth’s crust. Being formed from different parent rocks under variable con-
ditions, clay minerals vary in chemical composition, structure, and modes of occur-
rence. Clay minerals are irregularly distributed in the lithosphere, while their
concentration steadily increases due to weathering and/or hydrothermal alteration.
Clay minerals in nature also undergo spontaneous modificat ion and transformation
as environm ental conditions change. These processes are driven by physical, chem-
ical, and biological forces, including anthropogenic effects.
Natural clays are highly heterogeneous in composition and, almost invariably,
contain ‘impurities’ in the form of associated miner als and X-ray amorphous
materials. The mineralogical composition of clays is also influenced by particle size,
the smaller the size the larger the contribution of X-ray amorphous material.
The fineness of clays predetermines both their vu lnerability an d reactivity. By the
same token, clay particles are sensitive to mechanical and chemical treatments.
These features raise the question of scale. A small sample of material examined
xix
under laboratory conditions may react and behave differently from its bulky coun-
terpart. Issues of heterogeneity aside, minor constituents in clays and the scale and
conditions of testing can give rise to discrep ancies in the results of measurements
carried out in different laboratories. A variety of spectr oscopic and instrumental
techniques have been used to analyse and characterize clays and clay minerals.
Improvements in sensitivity, selectivity, and accuracy are constantly being sought.
The development of new techniques and the refinement of old ones create a complex,
multidimensional problem. Verification of the reproducibility of results, obtained in
different laboratories, is not an option but a necessity. The chemical and mineral
composition of clays is more difficult to quantify than other hard rocks. Differences
in clay mineral populations, structural imperfections, variations in crystallinity, and
the presence of impurities are problems that are specifically associated with the
identification and quantitative analysis of clays.
Experimenting with artificial mixtures of clay minerals is popular in soil and
geotechnical testing. Mixtures of clay minerals of different origin would be expected
to behave like natural, multiphase clay material. However, it is difficult, if not im-
possible, to simulate the natural fabric and the intimacy of contact between neigh-
bouring particles formed over geological periods of interaction. Likewise, computer
modelling has become important over the past decade or so. This approach to
research can be rewarding if the model is properly validated, and not used to justify
or prove a preconceived notion.
The different aspects of clays mentioned above refl ect the unique nature of clays
and clay minerals. No other group of inorganic materials have so many specie s, show
such a wide range of reactivity and propensity for modification, or enjoy such a
diversity of practical applications as clay minerals. In addition to their conventional
uses, as in ceramics and paper coating, clays have found many novel applications.
Clay minerals are naturally occurring nanomaterials, abundant, inexpensive, and
environmental friendly. As such, they have a huge potential for the synthesis of clay-
polymer nanocomposites with superior mechanical and thermal properties. The op-
timization of adsorption properties, swelling behaviour, colloidal and rheological
properties, and the design of new types of organo-clays also open prospects of using
clay minerals for pollution control and environmental protection. Many clay
scientists and geotechnical engineers are also aware of the negative side of clays as
manifested in the form of landslides, mudflows, and the deterioration of clay-based
construction materials. In so far as it is impossible to control nature, prevention, and
remediation are the only practical ways of responding to such destructive natural
processes.
Clay science is a multidisciplinary endeavour, combining geology, mineralogy,
crystallography with physics, geotechnology, and soil mechanics together with in-
organic, organic, physical, and c olloid chemistry. The contributions to clay science
of the biological, medical, and pharmaceutical sciences are increasing, and this trend
will continue.
Forewordxx
These considerations reveal the strong need for bringing together the scattered
literature on the many and varied disciplines that make up clay science. The Hand-
book of Clay Science fulfils these requirements. Leading scientists covering a wide
field of expertise have given much of their time and energy to write critical accounts
of the current state of knowledge. All manuscripts have been carefully edited and
coordinated. Besides being a reference text and a source of information on clays and
clay minerals, the Handbook of Clay Science provides a point of first entry into a
unique and very important field of materials science for research scientists, university
teachers, industrial chemists, physicists, graduate students as well as the environ-
mental engineers and technologists, including people with political responsibility.
Radko A. Ku
¨
hnel
Foreword xxi
CONTENTS
List of Contributors by Country of Residence..................................... xi
Acknowledgements ........................................................ xiii
Contributing Authors ...................................................... xv
Foreword . ............................................................. xix
R.Ku
¨
hnel
Chapter 1. General Introduction: Clays, Clay Minerals, and Clay Science . . ........... 1
F. Bergaya and G. Lagaly
Chapter 2. Structures and Mineralogy of Clay Minerals . . . ...................... 19
M.F. Brigatti, E. Galan and B.K.G. Theng
Chapter 3. Surface and Interface Chemistry of Clay Minerals ..................... 87
R.A. Schoonheydt and C.T. Johnston
Chapter 4. Synthetic Clay Minerals and Purification of Natural Clays ............... 115
K.A. Carrado, A. Decarreau, S. Petit, F. Bergaya and G. Lagaly
Chapter 5. Colloid Clay Science . . . ....................................... 141
G. Lagaly
Chapter 6. Mechanical Properties of Clays and Clay Minerals ..................... 247
R. Pusch
Chapter 7. Modified Clays and Clay Minerals ................................ 261
F. Bergaya, B.K.G. Theng and G. Lagaly
Chapter 7.1. Acid Activation of Clay Minerals ................................. 263
P. Komadel and J. Madejova
´
Chapter 7.2. Thermally Modified Clay Minerals ................................ 289
L. Heller-Kallai
Chapter 7.3. Clay Mineral Organic Interactions ................................ 309
G. Lagaly, M. Ogawa and I. De
´
ka
´
ny
Chapter 7.4. Clay Minerals and the Origin of Life. . . ............................ 379
A. Brack
Chapter 7.5. Pillared Clays and Clay Minerals ................................. 393
F. Bergaya, A. Aouad and T. Mandalia
Chapter 8. Properties and Behavior of Iron in Clay Minerals...................... 423
J.W. Stucki
vii
Chapter 9. Clays, Microorganisms, and Biomineralization . . ...................... 477
K. Tazaki
Chapter 10. Clays in Industry ............................................. 499
F. Bergaya, B.K.G. Theng and G. Lagaly
Chapter 10.1. Conventional Applications ...................................... 501
C.C. Harvey and G. Lagaly
Chapter 10.2. Clay Minerals as Catalysts ...................................... 541
J.M. Adams and R.W. McCabe
Chapter 10.3. Clay Mineral– and Organoclay–Polymer Nanocomposite................. 583
E. Ruiz-Hitzky and A. Van Meerbeek
Chapter 11. Clays, Environment and Health. . ................................. 623
F. Bergaya, B.K.G. Theng and G. Lagaly
Chapter 11.1. Clays and Clay Minerals for Pollution Control . . ...................... 625
G.J. Churchman, W.P. Gates, B.K.G. Theng and G. Yuan
Chapter 11.2. Clays and Pesticides ........................................... 677
S. Nir, Y. El-Nahhal, T. Undabeytia, G. Rytwo, T. Polubesova,
Y. Mishael, O. Rabinovitz and B. Rubin
Chapter 11.3. Clay Liners and Waste Disposal . ................................. 693
K. Czurda
Chapter 11.4. Clays and Nuclear Waste Management . ............................ 703
R. Pusch
Chapter 11.5. Clays and Human Health ....................................... 717
M.I. Carretero, C.S.F. Gomes and F. Tateo
Chapter 11.6. Clays and Clay Minerals as Drugs................................. 743
M.T. Droy-Lefaix and F. Tateo
Chapter 12. Critical Assessment of Some Analytical Techniques..................... 753
F. Bergaya, B.K.G. Theng and G. Lagaly
Chapter 12.1. Mo
¨
ssbauer Spectroscopy of Clays and Clay Minerals . . ................. 755
E. Murad
Chapter 12.2. Identification and Quantitative Analysis of Clay Minerals ................ 765
J. S
´
rodon
´
Chapter 12.3. X-ray Absorption Spectroscopy. . ................................. 789
W.P. Gates
Chapter 12.4. X-ray Photoelectron Spectroscopy ................................. 865
H. Seyama, M. Soma and B.K.G. Theng
Contentsviii
Chapter 12.5. Small-angle Scattering Techniques ................................. 879
D. Tchoubar and N. Cohaut
Chapter 12.6. Fourier Transform Infrared Spectroscopy ........................... 909
S. Petit
Chapter 12.7. Nuclear Magnetic Resonance Spectroscopy .......................... 919
J. Sanz
Chapter 12.8. Transmission Electron Microscopy ................................ 939
F. Elsass
Chapter 12.9. Surface Area and Porosity ...................................... 965
L.J. Michot and F. Villie
´
ras
Chapter 12.10. Cation and Anion Exchange ..................................... 979
F. Bergaya, G. Lagaly and M. Vayer
Chapter 12.11. Thermal Analysis ............................................. 1003
F. Rouquerol, J. Rouquerol and P. Llewellyn
Chapter 13. Some Other Materials Related to Clays . ............................ 1019
F. Bergaya, B.K.G. Theng and G. Lagaly
Chapter 13.1. Layered Double Hydroxides ..................................... 1021
C. Forano, T. Hibino, F. Leroux and C. Taviot-Gue
´
ho
Chapter 13.2. Parallels and Distinctions between Clay Minerals and Zeolites . . ........... 1097
D.L. Bish
Chapter 13.3. Cement Hydrates ............................................. 1113
H. Van Damme and A. Gmira
Chapter 14. Genesis of Clay Minerals ....................................... 1129
E. Gala
´
n
Chapter 15. History of Clay Science: A Young Discipline . . . ...................... 1163
F. Bergaya, G. Lagaly and K. Beneke
Chapter 16. Teaching Clay Science: A Great Perspective .......................... 1183
R. Berry, F. Bergaya and G. Lagaly
Subject Index ............................................................ 1197
Contents ix
CONTRIBUTING AUTHORS
J.M. ADAMS
School of Engineering, University of Exeter, Harrison Building, North Park Road, Exeter, Devon EX4
4QF, UK
A. AOUAD
CRMD, CNRS-Universite
´
d’Orle
´
ans, F-45071 Orle
´
ans Cedex 2, France
K. BENEKE
Institut fu
¨r
Anorganische Chemie, Universita
¨t
Kiel, D-24118 Kiel, Germany
F. BERGAYA
CRMD, CNRS-Universite
´
d’Orle
´
ans, F-45071 Orle
´
ans Cedex 2, France
R.W. BERRY
Department of Geological Sciences, San Diego State University, San Diego, CA 92182-1020, USA
D.L. BISH
Department of Geological Science, Indiana University, Bloomington, IN 47405-1405, USA
A. BRACK
Centre de Biophysique Mole
´
culaire, CNRS, F-45071 Orle
´
ans Cedex 2, France
M.F. BRIGATTI
Dipartimento di Scienze della Terra, Universita
`
di Modena, I-41100 Modena, Italy
K.A. CARRADO
Chemistry Division, CHM 200, Argonne National Laboratory, Argonne, IL60439-4837, USA
M.I. CARRETERO
Departamento de Cristalografı
´
a, Mineralogı
´
a y Quı
´
mica Agrı
´
cola, Facultad de Quı
´
mica, Universidad de
Sevilla, ES-41071 Sevilla, Spain
G.J. CHURCHMAN
School of Earth and Environmental Sciences, University of Adelaide, Glen Osmond, S.A. 5064, Australia
N. COHAUT
CRMD, CNRS-Universite
´
d’Orle
´
ans, F-45071 Orle
´
ans Cedex 2, France
K. CZURDA
Angewandte Geologie, Universita
¨
t Karlsruhe, D-76128 Karlsruhe, Germany
A. DECARREAU
UMR 6532, HydrASA, F-8602 Poitiers Cedex, France
I. DE
´
KA
´
NI
Department of Colloid Chemistry and Nanostructured Materials Research Group of the Hungarian
Academy of Sciences, University of Szeged, H-6720 Szeged, Hungary
M.T. DROY-LEFAIX
Beaufour-IPSEN, F-75016 Paris, France
xv
Y. EL NAHHAL
Environmental Protection and Research Institute (EPRI), PO Box 1175, Gaza, PNA (Palestinian
National Authority)
F. ELSASS
INRA, Unite
´
de Science du Sol, Centre Versailles-Grignon, F-78026 Versailles, France
Present addrress: CNRS, Centre de Geochimie de la Surface, 1 rule Blessig, F-67084 Strasbourg, France.
C. FORANO
Laboratoire de Mate
´
riaux Inorganiques, CNRS UMR 6002, Universite
´
Blaise Pascal, F-63177 Aubie
`
re
Cedex, France
E. GALA
´
N
Departamento de Cristalografı
´
a, Mineralogı
´
a y Quı
´
mica Agrı
´
cola, Facultad de Quı
´
mica, Universidad de
Sevilla, ES-41071 Sevilla, Spain
W.P. GATES
Centre for Green Chemistry, School of Chemistry, Monash Univerisity, Clayton, VIC 6800, Australia
A. GMIRA
CRMD, CNRS-Universite
´
d’Orle
´
ans, F-45071 Orle
´
ans Cedex 2, France
C.S.F. GOMES
Departamento de Geocie
ˆ
ncias, Universidade de Aveiro, P-3810-193 Aveiro, Portugal
C.C. HARVEY
Institute of Geological and Nuclear Sciences, Wairakei Research Centre, Private Bag 2000, Taupo,
New Zealand
L. HELLER-KALLAI
Institute of Earth Sciences, The Hebrew University of Jerusalem, IL-91904 Jerusalem, Israel
T. HIBINO
Ecological Materials Group, AIST, 16-1 Onogawa, Tsukuba 305-8569, Japan
C.T. JOHNSTON
Department of Soil and Environmental Sciences, Purdue University, West Lafayette, IN 47907-1150,
USA
P. KOMADEL
Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-845 36 Bratislava, Slovakia
R.A. KU
¨
HNEL
Burg. Merkusstraat 5, NL-2645 NJ Delfgauw, The Netherlands
G. LAGALY
Institut fu
¨
r Anorganische Chemie, Universita
¨
t Kiel, D-24118 Kiel, Germany
F. LEROUX
Laboratoire de Mate
´
riaux Inorganiques, CNRS UMR 6002, Universite
´
Blaise Pascal, F-63177, Aubie
`
re
Cedex, France
P.L. LLEWELLYN
Laboratoire MADIREL, UMR CNRS-Universite
´
de Provence Centre de St Je
´
ro
ˆ
me, 13397 Marseille
Cedex 20, France
Contributing authorsxvi
J. MADEJOVA
´
Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-845 36 Bratislava, Slovakia
T. MANDALIA
CRMD, CNRS-Universite
´
d’Orle
´
ans, F-45071 Orle
´
ans, Cedex 2, France
R.W. McCABE
Center for Materials Science, University of Central Lancashire, Preston PR1 2HE, United Kingdom
L.J. MICHOT
Laboratoire Environnement et Mine
´
ralurgie, BP 40, F-54501 Vandoeuvre Cedex, France
Y. MISHAEL
Faculty of Agricultural, Food and Environmental Quality Sciences, The Hebrew University of Jerusalem,
PO Box 12, IL-76100 Rehovot, Israel
E. MURAD
Bayerisches Landesamt fu
¨r
Umwelt, D-95603 Marktredwitz, Germany
S. NIR
Faculty of Agricultural, Food and Environmental Quality Sciences, The Hebrew University of Jerusalem,
PO Box 12, IL-76100 Rehovot, Israel
M. OGAWA
Department of Earth Sciences, Waseda University, Nishiwaseda 1-6-1, Shinjuku-ku, Tokyo 169-8050,
Japan
S. PETIT
UMR 6532, HydrASA, F-86022 Poitiers Ce
´
dex, France
T. POLUBESOVA
Faculty of Agricultural, Food and Environmental Quality Sciences, The Hebrew University of Jerusalem,
PO Box 12, IL-76100 Rehovot, Israel
R. PUSCH
Geodevelopment AB, Ideon, S-22370 Lund, Sweden
O. RABINOVITZ
Faculty of Agricultural, Food and Environmental Quality Sciences, The Hebrew University of Jerusalem,
PO Box 12, IL-76100 Rehovot, Israel
F. ROUQUEROL
Laboratoire MADIREL, UMR CNRS-Universite
´
de Provence Centre de St Je
´
ro
ˆ
me, 13397 Marseille
Cedex 20, France
J. ROUQUEROL
Laboratoire MADIREL, UMR CNRS-Universite
´
de Provence Centre de St Je
´
ro
ˆ
me, 13397 Marseille
Cedex 20, France
B. RUBIN
Faculty of Agricultural, Food and Environmental Quality Sciences, The Hebrew University of Jerusalem,
PO Box 12, IL-76100 Rehovot, Israel
E. RUIZ-HITZKY
Instituto de Ciencia de Materiales de Madrid, Campus de Cantoblanco, CSIC, ES-28049 Madrid,
Spain
Contributing authors xvii