Bergaya F. Handbook of Clay Science

Подождите немного. Документ загружается.

G. RYTWO

Tel Hai Academic College, Biotechnology and Environmental Sciences Department, Upper Galilee

IL-12210, Israel

J. SANZ

Instituto de Ciencia de Materiales de Madrid, CSIC, Campus de Cantoblanco, ES-28049 Madrid,

Spain

R.A. SCHOONHEYDT

Center for Surface Chemistry and Catalysis, Kuleuven, B-3001 Leuven, Belgium

H. SEYAMA

Environmental Chemistry Division, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba,

Ibaraki 305-8506, Japan

M. SOMA

Institute for Environmental Sciences, University of Shizuoka, 52-1 Yada, Shizuoka, Shizuoka 422-8526,

Japan

Present address: 6-8 Tsutsujigaoka, Aoba-ku, Yokohama 227-0055, Japan

J. S

RODON

Institute of Geological Sciences, PAN, PL-31-002 Krakow, Poland

J. STUCKI

Department of Natural Resources and Environmental Sciences, University of Illinois, W-321 Turner Hall,

1102 S. Goodwin Ave, Urbana, IL 61801-4798, USA

F. TATEO

Istituto di Ricerca sulle Argille, CNR, I-85050 Tito Scalo (PZ), Italy

C. TAVIOT-GUE

Laboratoire de Mate

riaux Inorganiques, CNRS UMR 6002, Universite

Blaise Pascal, F-63177 Aubie

Cedex, France

K. TAZAKI

Department of Earth Sciences, Kanazawa University, Kanazawa, Ishikawa 920-1192, Japan

D. TCHOUBAR

Expert CRT-Plasma Laser, Orle

ans, F-45160 Olivet, France

B.K.G. THENG

Landcare Research, Palmerston North, New Zealand

T. UNDABEYTIA

Instituto de Recursos Naturales y Agrobiologia, CSIS, Apdo 1052, ES-41080 Sevilla, Spain

H. VAN DAMME

Ecole Supe

rieure de de Physique et de Chimie Industrielle (ESPCI-PPMD), F-75231 Paris Cedex, France

A. VAN MEERBEEK

Advanced Elastomer Systems SA, B-1140 Bruxelles, Belgium

M. VAYER

CRMD, CNRS-Universite

d’Orle

ans, 1b Rue de la Fe

rollerie, F-45071 Orle

ans Cedex 2, France

F. VILLIE

RAS

Laboratoire Environnement et Mine

ralurgie, BP 40, F-54501 Vandoeuvre Cedex, France

G. YUAN

Landcare Research, Palmerston North, New Zealand

Contributing authorsxviii

LIST OF CONTRIBUTOR S BY COUNTRY OF RESIDENCE

AUSTRALIA G. Jock Churchman, Will P. Gates

BELGIUM Robert A. Schoonheydt, Andre

Van Meerbeek

FRANCE Amina Aouad, Faı

za Bergaya, Andre

Brack, Nathalie

Cohaut, Alain Decarreau, Marie The

se Droy-Lefaix,

Franc-oise Elsass, Claude Forano, Ahmed Gmira,

Fabrice Leroux, Philip L. Llewellyn, Tushar Mandalia,

Laurent J. Michot, Sabine Petit, Franc-oise Rouque

rol,

Jean Rouque

rol, Christine Taviot-Gue

ho, Denise

Tchoubar, Henri Van Damme, Maryle

ne Vayer,

Fre

ric Villie

ras

GERMANY Klaus Beneke, Kurt Czurda, Gerhard Lagaly, Enver

Murad

HUNGARY Imre De

ISRAEL Lisa Heller-Kallai, Yael Mishael, Shlomo Nir, Tamara

Polubesova, Onn Rabinovitz, Baruch Rubin, Giora

Rytwo

ITALY Maria Franca Brigatti, Fabio Tateo

JAPAN Toshiyuki Hibino, Makoto Ogawa, Haruhiko Seyama,

Mitsuyuki Soma, Kazue Tazaki

THE NETHERLANDS Radko A. Ku

hnel

NEW ZEALAND Colin C. Harvey, Benny K.G. Theng, Guodong Yuan

PALESTINIAN NATIONAL

AUTHORITY

Yasser El-Nahhal

POLAND Jan S

rodon

PORTUGAL Celso de Sousa Figueiredo Gomez

SLOVAKIA Peter Komadel, Jana Madejova

SPAIN Maria Isabel Carretero, Emilio Gala

n, Eduardo

Ruiz-Hitzky, Jesus Sanz, Tomas Undabeytia

SWEDEN Roland Pusch

UNITED KINGDOM John M. Adams, Richard W. McCabe

UNITED STATES OF AMERICA Richard W. Berry, David L. Bish, Kathleen A.

Carrado, Cliff T. Johnston, Joseph W. Stucki

ACKNOWLEDGEMENTS

The editors acknowledge all the people who have helped them to realise this

handbook, especially the contributing authors. Without their cooperation, enthu-

siasm, and dedication, this handbook would not have been possible. The editors are

grateful for their patience and forbearance, and acknowledge their great efforts in

condensing and summarising the vast amount of information in their individual

ﬁelds of expertise.

F. Bergaya wishes to acknowledge the ‘‘Conseil Re

gional du Centre’’ for their

ﬁnancial support without which this project would not have started. She than ks all

the contributing authors of this book. She is especially grateful to Benny Theng and

Gerhard Lagaly for accepting her proposal to share the task of editing this book, and

to Elsevier for their agreement to publish. Finally, she is deeply grateful to her

husband, Badreddine, whose patience and encouragement were invaluable since the

beginning of this pro ject, particularly during the last three years.

B.K.G. Theng acknowledges the efforts made by Faı

za Bergaya in obtaining

funds for him to spend 12 months, spread over three leave periods during 2001–2003,

in her laboratory (CRMD, CNRS-Universite

d’Orle

ans). He is grateful to Landcare

Research New Zealand for providing ofﬁce space and associated facilities as well as

some ﬁnan cial assistance, and to the Royal Soc iety of New Zealand for their support

under the ISAT Linkages Fund. He also thanks the following people from Landcare

Research: Nicolette Faville and Janie Jansen for drawing up ﬁgures, and Anne

Austin for editorial assistance. Lastly, he is grateful to his wife, Judith Theng, for

encouragement and support.

G. Lagaly thanks Faı

za Bergaya for the invitation to participate in editing this

handbook, and the kind hospitality provided by her family during his several visits

to Orle

ans. He is also very grateful to Klaus Beneke for furnishing literature ref-

erences, an d to Mrs. Britta Bahn for editorial assistance.

The author(s) of certain chapters wish to acknowledge the following persons and

agencies:

Part of the time for writing Chapter 4 was provided under the auspices of the U.S.

Department of Energy under contract #W-31-109-ENG-38 (to K.A.C.).

The author of Chapter 7.4 is very grateful to Professor J.P. Ferris for his helpful

comments.

The author of Chapter 8 expresses his thanks to the following agencies for their

recent ﬁnancial support of his research: The International Arid Lands Consortium,

Grant No. 03R-15; BARD, The United States-Israel Binational Agricultural Re-

search and Development Fund, Research Grant Award No. AG IS-3162-99R; the

National Science Foundation, Division of Petrology and Geochemistry, Grant No.

xiii

EAR 01-26308; and the Natural and Accelerated Bioremediation Research (NABIR)

Program, Biological and Environmental Research (BER) , U.S. Department of En-

ergy, Grant No. DE-FG02-00ER62986, subcontract FSU F48792.

The authors of Chapter 10.3 are indebted to P. Aranda for her critical review of

the manuscript and to S. Letaı

ef for editorial assistance. One of the authors (E. Ruiz-

Hitzky) thanks the CICYT, Spain, for ﬁnancial support.

In Chapter 11.2, the research was supported by Grant G-641.106.8/1999 from

G.I.F., the German-Israel i Foundation for Research and Development.

The authors of Chapter 11.5 are grateful to E. Gala

n (Seville University, Spain)

for helpful discussions and critical review of the manuscript. They also thank

F. Veniale (Pavia University, Italy) for useful suggestions, and L. Cima and F. Cozzi

(Padua University, Italy) for their comments on some aspects of this chapter.

One of the authors (F. Tateo) of Chapter 11.6 is grateful to L. Cima and F. Cozzi

(Padua University, Italy) for helpful discussions.

The author of Chapter 12.2 thanks W. Gates and B.K.G. Theng for their critical

comments and language corrections.

The author of Chapter 12.3 is grateful to F. Bergaya, G. Lagaly, an d B.K.G.

Theng for inviting him to submit this contribution, and to A. Manceau and J.W.

Stucki for providing the extended X-ray absorption ﬁne structure spectroscopy

(EXAFS) data used to illustrate spectral analyses.

The author of Chapter 14 thanks R.E. Ferrell (Louisiana State University, USA)

for his critical reading, discussion, and numerous suggestions, leading to consider-

able improvement of the manuscript, and for his assistance with style corrections. He

also thanks P. Aparicio (Seville University, Spain) for her helpful comments and

editorial assistance, as well as G.J. Churchman (University of Adelaide, Australia)

for his collaboratio n in the ﬁnal version an d editing. He would also like to thank the

editors, F. Bergaya, G. Lagaly, and B.K.G. Theng, for giving him an opportunity to

contribute to this handbook.

F. Bergaya, B.K.G. Theng and G. Lagaly

June 2005

Acknowledgementsxiv

Handbook of Clay Science

Edited by F. Bergaya, B.K.G. Theng and G. Lagaly

Developments in Clay Science, Vol. 1

Chapter 1

GENERAL INTRODUCTION: CLAYS, CLAY MINERALS, AND

CLAY SCIENCE

F. BERGAYA

AND G. LAGALY

CRMD, CNRS-Universite

d’Orle

ans, F-45071 Orle

ans Cedex 2, France

Institut fu

r Anorganische Chemie, Universita

t Kiel, D-24118 Kiel, Germany

The authors believe that clays and clay minerals, either as such or after mod-

iﬁcation, will be recognized as the materials of the 21st century because they are

abundant, inexpensive, and environment friendly. With that in view, this Handbook

of Clay Science has assembled core information on the varied and diverse aspects

that make up the discipline of clay science, ranging from the fundamental structure

and surface properties of clays and clay minerals to their industrial and environ-

mental applications.

Clay has been known to, and used by, humans since antiquity. Indeed, clay has

been implicated in the prebiotic synthesis of biomolecules, and the very origins of life

on earth. Clay has also become indispensable to modern living. It is the material of

many kinds of ceramics, such as porcelain, bricks, tiles, an d sanitary ware as well as

an essential constituent of plastics, paints, paper, rubber, and cosmetics. Clay is non-

polluting and can be used as a depolluting ag ent. Of great importance for the near

future is the potential of some clays to be dispersed as nanometer-size unit particles

in a polymer phase, forming novel nanocomposite materials with superior thermo-

mechanical properties. The diversity of structures and properties of clays, and their

wide-ranging applications, make it difﬁcult to compile a comprehensive reference

text on clay science.

1.1. AIM AND SCOPE

If the general knowledge and usage of clay have ancient roots, the scientiﬁc study

of clay (i.e., ‘clay science’) is a relatively recent discipline, dating back only to the

mid-1930s, following on the emerg ence and general acceptance of the ‘clay mineral

concept’. According to this concept, clays are essentially composed of micro-

crystalline particles of a small group of minerals, referred to as the clay minerals

DOI: 10.1016/S1572-4352(05)01001-9

(Grim, 1968). Since then, clay science or ‘argillology’ (Konta, 2000) has become an

autonomous, multi-faceted discipline.

Since people who work with clay come from diverse backgroun ds and have di-

verse interests, there are probably as many concepts and views of clay as there are

clay mineral species. It is not surprising, therefore, that clay scientists have varied

trainings, including geology, mineralogy, chemistry, physics, and biology, and hold

different perspectives. The multi-disciplinary nature of clay science is indicated by

the scope, contents, and multi-authorship of this handbook. It is also reﬂected in the

wide range and variety of scientiﬁc journals where papers on clays and clay minerals

are published. At the same time, individuals or groups who investigate and use

clay—whether they be in acad eme or industry—often fail to realize that they share a

common interest, or worse, are ignorant of one another’s existence. Similarly, in-

formation about clay is dispersed in many scientiﬁc conferences and symposia whose

themes (e.g ., nanotechno logy, rheology, and heterogeneous catalysis) often make no

reference to the experimenta l material used. Indeed, the word ‘clay’ in many pub-

lications is often subsumed into such terms as ‘microporous solid’ or ‘layered ma-

terial’. This is probably because in the mind of many people, clay is associated with

soil (dirt) and mud. By the same token, clay science is not generally considered to be

intellectually challenging. If clay science features at all in the syllabus or curriculum

of a university degree course, the focu s is usually on the mineralogy of clay, while its

colloidal and physico-chemical aspects are glanced over, if not ignored. The teaching

of clay scienc e also varies from school to school within a given country, and from

one country to another.

The ﬁrst two textbooks by Grim, Clay Mineralogy and Applied Clay Mineralogy,

were published some 4–5 decades ago (Grim, 1953, 1962, 1968). Since then a great

deal of information on clays and clay minerals has accumulated. Also, many ad-

vanced analytical and instrumental techniques have been developed as well as novel

industrial and environmental applications. Yet, no general reference text on clay

science in the English language has been published to date, although a number of

books on particular aspects are available (e.g., Weaver and Pollard, 1973; Farmer,

1974; Theng, 1974, 1979; van Olphen, 1977; Brindley and Brown, 1980; Chamley,

1989; Wilson, 1994; Velde, 1995; Moore and Reynolds, 1997).

The Handbook of Clay Science aims to provide up-to-date information on the

fundamental structural and surface properties of clay minerals, their industrial and

environmental applications as well as analytical techniques, and the teaching and

history of clay science. The book is intended to be a critical review and not just a

compilation of the published literature. To our knowledge, this holistic multi-dis-

ciplinary approach does not exist in any other clay book. Here, we describe some

generally held concepts and working deﬁnitions of clay and clay mineral that might

be acceptable to most disciplines and practitioners of clay science.

The structures of clays and clay minerals together with their surface-chemical prop-

erties are summarized in Chapters 2 and 3. Synthetic clay minerals and clay puriﬁcation

are described in Chapter 4, while Chapter 5 deals with the colloid chemistry of clays,

Chapter 1: Clays, Clay Minerals, and Clay Science2

and Chapter 6 with their mechanical properties. Chapter 7 describes modiﬁcations of

clays and clay minerals by acid activation (Chapter 7.1), thermal treatment (Chapter

7.2), and pillaring (Chapter 7.5), and has subchapters on the clay-organic interaction

(Chapter 7.3), and the possible involvement of clay in the origins of life (Chapter 7.4).

The properties and behaviour of iron in clay minerals are discussed in Chapter 8, while

Chapter 9 reviews the role of clays in biomineralization. Chapter 10 deals with clays in

industry with subchapters on the conventional applications of clays (Chapter 10.1),

catalysis by clay minerals (Chapter 10.2), and the formation and properties of clay-

polymer nanocomposites (Chapter 10.3). The role of clays in environmental and hu-

man health protection is discussed in Chapter 11 with six subchapters covering a wide

range of topics from pollution control to clays as drugs. The eleven subchapters of

Chapter 12 give a critical assessment of spectroscopic and analytical techniques com-

monly used in clay studies. The handbook also contains in subchapters of Chapter 13,

reviews on layered double hydroxides (LDH) (Chapter 13.1), zeolites (Chapter 13.2),

and cement hydrates (Chapter 13.3) because these materials are related to smectite

clays in structure and certain properties. Clay mineral formation and the genesis

of the principal clay deposits are described in Chapter 14, while the last two chapters

are concerned with the history (Chapter 15), and teaching (Chapter 16) of clay

science.

This handbook will therefore provide a point of ﬁrst entry into the clay science

literature for research scientists, university teachers, postgraduate students, indus-

trial chemists as well as people in agriculture, environmental engineering, industry,

and waste disposal, who need to know about clays and clay minerals. This book will

also be useful to commercial users of clays.

1.2. CLAY

There is, as yet, no uniform nomenclature for clay and clay material. Nonetheless,

we do not seek a consensus

about the meaning of the terms ‘clay’, ‘clays’, and ‘clay

minerals’ (Table 1.1). Indeed, the quest for a unifying terminology that is acceptable

to all disciplines, users, and producers would be a fruitless exercise (R.A. Ku

hnel,

personal communication). Rather, here we aim to highlight the common meaning of

these terms, and the impact of these materials on our actual daily life together with

their potential for the ever-growing number of practical applications (Ku

hnel, 1990;

Murray, 1999 ).

Georgius Agricola (1494–1555), the founder of geology, was apparently the ﬁrst

to have formalized a deﬁnition of clay (Guggenheim and Martin, 1995). The latest

effort in this direction was made nearly ﬁve centuries later by the joint nomenclature

One of the authors (FB) is a member of the AIPEA nomenclature committee dealing with deﬁnitions

of clay and clay mineral. However, the views expressed here are the entire responsibility of the authors and

do not necessarily reﬂect those of the nomenclature committee.

1.2. Clay 3

committees (JNCs) of the Association Internationale pour l’Etude des Argiles

(AIPEA) and the Clay Minerals Society (CMS). The JNCs have deﬁned ‘clay’ as ‘‘y

a naturally occurring material composed primarily of ﬁne-grained miner als, which is

generally plastic at appropriate water contents and will harden with ( sic) dried or

Table 1.1. Current names of clays

Current

names of clays

Origin

Main clay mineral

constituents

Remarks

Ball clay Sedimentary Kaolinite Highly plastic, white burning

(Grim, 1962)

Bentonite Volcanic rock

alteration or

authigenic

Montmorillonite

Bleaching

earth

Acid-activated

bentonite

Decomposed

montmorillonite

Common clay Sedimentary or

by weathering

Various, often

illite/smectite

mixed-layer

minerals

General for ceramics excluding

porcelain

China clay Hydrothermal Kaolinite Kaolins from Cornwall plastic,

white burning

Fire clay Sedimentary Kaolinite Plastic, high refractoriness

(Grim, 1962)

Flint clay Sedimentary

with subsequent

diagenesis

Kaolinite Non-slaking, not plastic, used

for refractories (Grim, 1962;

Keller, 1978, 1981, 1982)

Fuller’s earth Sedimentary,

residual, or

hydrothermal

Montmorillonite,

sometimes

palygorskite,

sepiolite

Primary

kaolin

Residual or by

hydrothermal

alteration

Kaolinite

Secondary

kaolin

Authigenic

sedimentary

Kaolinite

Refractory

clay

Authigenic

sedimentary

Kaolinite With low levels of iron, alkali

and alkali earth cations for

refractories (Grim, 1962)

Laponite Synthetic Hectorite-type

smectite

Nanoclay Mostly

montmorillonite

Superﬂuous term for clays used

for nanocomposites

See Chapter 14 for more details.

Chapter 1: Clays, Clay Minerals, and Clay Science4

ﬁred’’ (Guggenheim and Martin, 1995). (The authors have italicized some words to

alert the reader, and ind icate that these words will be commented on below ). By this

deﬁnition synthetic clays and clay- like materials are not regarded as clay even though

they may be ﬁne grained, and display the attributes of plasticity and hardening on

drying and ﬁring.

Although particle size is a key parameter in all deﬁnitions of clay, there is no

generally accepted upper limit. Some disciplines and professions, however,

have conventionally set a maximum size of clay particles. In pedology, for exam-

ple, the ‘clay fraction’ refers to a class of materials whose particles are smaller than

2 mm in equivalent spherical diameter (e.s.d.). In geology, sedimentology, and geo-

engineering the size limit is commonly set at o4 mm e.s.d. (Moore and Reynolds,

1997), while in colloid science the value of o1 mm is generally accepted. Indeed,

Weaver (1989) has suggested that the term ‘clay’ should only be used in the textural

sense to indicate material that is ﬁner than 4 mm.

Although plasticity is a pa rt of the JNCs’ deﬁnition, some non-plastic clays (e.g.,

‘ﬂint clays’) are still regarded as ‘clay’ because of past usage.

The JNCs also state that the plastic properties of clay do not need quantiﬁcation

since plasticity is affected by many factors, including chemical composition

and particle aggregation. Operationally, ‘plasticity’ may be deﬁned as the ability

(of a clay material) to be moulded into a certain shape without rupturing when stress

is applied, and for this shape to be retained after the stress is removed. However, in

the ceramics industry, plasticity is commonly measured in terms of the ‘water

of plasticity’ (liquid and plastic limits) (see Chapter 5). In engineering, plasticity is

measured or expressed in terms of the ‘plasticity index’ (PI), that is, the difference in

water content between the liquid and plastic limits of the clay material. As a rule of

thumb, a clay with a PI>25% would tend to expand or swell when wet.

In industrial applications of clays one distinguishes four types of clays: (i) bent-

onites with montmorillonite as the principal clay mineral constituent, (ii) kaolins

containing kaolinite, (iii) palygorskite and sepiolite, and (iv) ‘common clays’ which

often contain illite/smectite mixed-layer minerals, and are largely used for ceramics

(see Chapter 10.1).

1.3. CLAY MINERAL

Likewise, the term ‘clay mineral’ is difﬁcult to deﬁne. As a ﬁrst approximation, the

term signiﬁes a class of hydrated phyllosilicates (Tables 1.2 and 1.3) making up the

ﬁne-grained fraction of rocks, sediments, and soils. The deﬁnition that the JNCs

have proposed is ‘‘y phyllosilicate minerals and minerals which impart plasticity to

clay and which harden upon drying or ﬁring’’ (Guggenheim and Martin, 1995). Since

the origin of the material is not part of the deﬁnition, clay mineral (unlike clay) may

be synthetic.

1.3. Clay Mineral 5

Nor does grain size feature as a criterion in the JNCs’ deﬁnition of clay mineral.

Accordingly, phyllosilicates of any size, such as macroscopic mica, vermiculite, and

chlorite may be regarded as clay minerals. Indeed, much of our basic and detailed

understanding of clay mineral structures is derived from X-ray diffraction analysis of

Table 1.2. Classiﬁcation of planar hydrous phyllosilicates

Interlayer material

Group Octahedral

character

Species

1:1 Clay minerals

None or H

O only,

x0

Serpentine-

kaolin

Tri Amesite, berthierine, brindleyite, cronstedtite,

fraipontite, kellyite, lizardite, nepouite

Di Dickite, halloysite (planar), kaolinite, nacrite

Di-tri Odinite

2:1 Clay minerals

None, x0 Talc-pyrophyllite Tri Kerolite, pimelite, talc, willemsite

Di Ferripyrophyllite, pyrophyllite

Hydrated

exchangeable cations,

x0.2–0.6

Smectite Tri Hectorite, saponite, sauconite, stevensite,

swinefordite

Di Beidellite, montmorillonite, nontronite,

volkonskoite

Hydrated

exchangeable cations,

x0.6–0.9

Vermiculite Tri Trioctahedral vermiculite

Di Dioctahedral vermiculite

Non-hydrated

monovalent cations,

x0.6–1.0

True (ﬂexible)

mica

Tri Biotite, lepidolite, phlogopite, etc.

Di Celadonite, illite, glauconite, muscovite,

paragonite, etc.

Non-hydrated divalent

cations, x1.8–2.0

Brittle mica Tri Anandite, bityite, clintoni te, kinoshitalite

Di Margarite

Hydroxide sheet, x

variable

Chlorite Tri Baileychlore, chamosite, clinochlore, nimite,

pennantite

Di Donbassite

Di-tri Cookeite, sudoite

Regularly interstratiﬁed 2:1 clay minerals

x Variable Tri Aliettite, corrensite, hydrobiotite, kulkeite

Di Rectorite, tosudite

Source: Adapted from Martin et al. (1991).

x ¼ net layer charge per formula unit.

tri ¼ trioctahedral, di ¼ dioctahedral.

Chapter 1: Clays, Clay Minerals, and Clay Science6