CLAY MINERALS
IN NATURE – THEIR
CHARACTERIZATION,
MODIFICATION AND
APPLICATION

Edited by Marta Valášková
and Gražyna Simha Martynková







Clay Minerals in Nature – Their Characterization, Modification and Application

Edited by Marta Valášková and Gražyna Simha Martynková

Contributors
Oluwafemi Samuel Adelabu, Shu Jiang, Burhan Davarcioglu, Károly Lázár, Zoltán Máthé,
Miloš René, Markoski Mile, Tatjana Mitkova, Milan Gomboš, Carla Eloize Carducci,
Geraldo César de Oliveira, Nilton Curi, Eduardo da Costa Severiano, Walmes Marques Zeviani,
Fabienne Trolard, Guilhem Bourrié, Hideo Hashizume, Marta Valášková,
Gražyna Simha Martynková, Masashi Ookawa, Hisako Sato, Kenji Tamura
,
Akihiko Yamagishi,
Zuzana Navrátilová, Roman Maršálek, Miloš Vasić, Željko Grbavčić, Zagorka Radojević

Published by InTech
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Copyright © 2012 InTech

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First published September, 2012
Printed in Croatia

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Additional hard copies can be obtained from


Clay Minerals in Nature – Their Characterization, Modification and Application,

Edited by Marta Valášková and Gražyna Simha Martynková
p. cm.
ISBN 978-953-51-0738-5








Contents

Preface IX
Section 1 Clay Minerals in Deposits 1
Chapter 1 Documentation, Application and Utilisation
of Clay Minerals in Kaduna State (Nigeria) 3
Oluwafemi Samuel Adelabu
Chapter 2 Clay Minerals from the Perspective
of Oil and Gas Exploration 21
Shu Jiang
Chapter 3 Kolsuz-Ulukisla-Nigde Clays,
Central Anatolian Region –
Turkey and Petroleum Exploration 39
Burhan Davarcioglu
Chapter 4 Claystone as a Potential Host Rock
for Nuclear Waste Storage 55
Károly Lázár and Zoltán Máthé
Chapter 5 Distribution and Origin
of Clay Minerals During Hydrothermal

Alteration of Ore Deposits 81
Miloš René
Section 2 Clay Minerals in Soils 101
Chapter 6 Soil Moisture Retention Changes in Terms
of Mineralogical Composition of Clays Phase 103
Markoski Mile and Tatjana Mitkova
Chapter 7 The Impact of Clay Minerals
on Soil Hydrological Processes 119
Milan Gomboš
VI Contents

Chapter 8 Relations of Clay Fraction Mineralogy, Structure
and Water Retention in Oxidic Latosols (Oxisols)
from the Brazilian Cerrado Biome 149
Carla Eloize Carducci, Geraldo César de Oliveira, Nilton Curi,
Eduardo da Costa Severiano and Walmes Marques Zeviani
Chapter 9 Fougerite a Natural Layered Double Hydroxide in Gley Soil:
Habitus, Structure, and Some Properties 171
Fabienne Trolard and Guilhem Bourrié
Section 3 Clay Minerals Characterization,
Modification and Application 189
Chapter 10 Role of Clay Minerals in Chemical
Evolution and the Origins of Life 191
Hideo Hashizume
Chapter 11 Vermiculite:
Structural Properties and Examples of the Use 209
Marta Valášková and Gražyna Simha Martynková
Chapter 12 Synthesis and Characterization
of Fe-Imogolite as an Oxidation Catalyst 239
Masashi Ookawa

Chapter 13 Application of Clay Mineral-Iridium(III) Complexes
Hybrid Langmuir-Blodgett Films for Photosensing 259
Hisako Sato, Kenji Tamura

and Akihiko Yamagishi
Chapter 14 Application of Electrochemistry for Studying
Sorption Properties of Montmorillonite 273
Zuzana Navrátilová and Roman Maršálek
Chapter 15 Methods of Determination for Effective Diffusion
Coefficient During Convective Drying of Clay Products 295
Miloš Vasić, Željko Grbavčić and Zagorka Radojević









Preface

Clay and clay minerals represent the youngest minerals in the Earth’s crust. Clays are
irregularly distributed in lithosphere, as their concentration increases due to the
weathering, hydrothermal changes, including anthropogenic influences. Clay minerals
occur in all types of sediments and sedimentary rocks and are common in
hydrothermal deposits. The interdisciplinary character of clay science follows from the
information obtained from the methodology and theory of other natural and technical
sciences. These include physics, physical chemistry, colloid chemistry, inorganic,
organic and analytical chemistry, mineralogy, crystallography, petrology, geology,

sedimentology, geochemistry, soil science, soil mechanics and technology of silicates.
The clay minerals when occurring in very small grain size are very sensitive to the
mechanical and chemical treatments. Their structures are built from the tetrahedral (Si,
Al, Fe
3+
) and octahedral (Al, Fe
3+
, Fe
2+
, Mg) coordinated cations forming sheets. The
major subdivision of the layer lattice silicates is based upon the combination of the
tetrahedral and octahedral sheets. Additional subdivision is based on the octahedral
sheet. Dioctahedral sheet contains two cations per half unit cell and trioctahedral sheet
contains three cations per half unit cell.
The clay mineral type 1:1 consists of one tetrahedral and one octahedral sheet. These
sheets are approximately 0.7 nm thick. The 1:1 clay minerals are divided into kaolinite
minerals (dioctahedral) and serpentine (trioctahedral). The different members of
kaolinite minerals are characterized by the manner of stacking of the 1:1 layers.
The clay mineral type 2:1 layer consists of two silica tetrahedral sheets and between
them is an octahedral sheet. The 2:1 layer is approximately 1 nm thick. The unshared
oxygens of the tetrahedra point towards the center of the octahedral sheet and
substitute two-thirds of the coordinated hydroxyls in octahedra. The 2:1 clay minerals
include the mica and smectite groups. The pure end members of this type are talc
(hydrous magnesium silicate), pyrophyllite (a hydrous aluminum silicate) and
minnesotaite (a hydrous iron silicate). The mica group is subdivided to muscovite
(dioctahedral type) and biotite (trioctahedral type). The most common illite mineral is
diocathedral and has lower total negative charge 0.75 per O
10(OH)2 in comparison with
the charge 1 per O
10(OH)2 of muscovite. The dioctahedral iron illites are glauconite and

celadonite. The clay-sized minerals are usually mixed-layer biotite-vermiculite formed
when the interlayer cations were leached from the interlayer of biotite.
X Preface

The expandable 2:1 clay minerals contain loosely bound cations and layers of water or
organic molecules between the silica sheets. The interlayer cations are usually Na, Ca,
H, Mg, Fe and Al. The interlayer water can released at temperature between 120 and
200°C.
The low-charged expanded minerals montmorillonites belong to the group of
smectites. The layer charge ranges from 0.2 to 0.6 per O
10(OH)2 originates in the
octahedral sheet. Dioctahedral smectites with the layer charge 0.4 (or higher) were
named beidellites and their ferric ion-rich variety is called nontronite. Trioctahedral
low-charge smectites are hectorite which contains Mg and Li in octahedral sheet and
saponite with substitution Al in tetrahedral sheet.
Trioctahedral expanded 2:1 clay minerals with layer charge between 0.6-0.9 are
vermiculites. Vermiculites are coarser grained. Their negative layer arises mostly from
the substitution of Al
3+
for Si
4+
in tetrahedra.
Chlorites consist of a 2:1 layer and an octahedral interlayer sheet which a unit
periodicity is 1.4 nm. Chlorites are mostly trioctahedral while some chlorites have both
dioctahedral and trioctahedral sheets.
In nature there are number of clays which are not pure clay minerals but contain
interstratified units of different chemical composition and are called mixed-layer clays.
Interstratifications between non-expandable layers of illite and expandable layers of
smectite (montmorillonite) are the most abundant mixed-layer clay. Other mixed-layer
clays are chlorite-montmorillonite, biotite-vermiculite, chlorite-vermiculite, illite-

chlorite-montmorillonite, talc-saponite and serpentine-chlorite. A regular
interstratifications of one layer of illite and one layer of smectite is in rectorite while
one layer of smectite and three layers of illite are in tarasovite.
Allophane and imogolite are clay-size hydrous alumino-silicates of short-range order.
They are abundant in soils derived from volcanic ash.
Palygorskite and sepiolite are clay minerals with a chain structure. They contain a
continuous two-dimensional tetrahedral sheet and lack continuous octahedral sheets.
The non-clay minerals can significantly affect the properties of a clay material. For
example the presence of fine quartz particles affects the abrasiveness of the kaolin,
organic material in a clay affects the color and other properties. The exchangeable ions
and soluble salts affect the physical properties of a clay material: a calcium
montmorillonite presents very different viscosity and gelling characteristics than a
sodium montmorillonite.
The texture of a clay material refers to the particle size distribution of the constituents,
the particle shape, the orientation of the particles with respect to each other, and the
forces which bind the particles together. The definition of clays according to the size
particles varies for geologists (2µm), chemists (1µm) and for sedimentologists (4µm).
Preface XI

Pure clays do not usually occur in nature. Clays often referred to as the “common
clays” have engineering applications. They contain mixtures of different clay minerals
such as illite/smectites, kaolinites, smectites, micas and associated minerals. Other so-
called “industrial kaolins” contain relatively high amounts of kaolinite (kaolins), and
sometimes a small proportion of high-quality kaolin minerals. The class named
‘bentonite’ has a high montmorillonite (smectite) content. The “palygorskite-sepiolite
clays” are similar to bentonites and are used because of their surface properties and
reactivity.
Clay minerals may be utilized in their as-mined state, as low-cost impure materials
because of their engineering, physical and or chemical properties. The refined high-
purity clay minerals are an integral part in the highest technological achievements in

pharmacy, medicine and catalysis.
Soil science is an interdisciplinary science that integrates knowledge of physical,
chemical, and biological processes which interact across a large range of spatial and
temporal scales. Clay minerals together with organic matter in soils form a humus
complex which is very significant for the life of the majority of plants. The clay
minerals in soils are an important source of nutrients and water.
This book first introduces the reader to the basics characterization of clay minerals in
deposits and their utilization. The topics as distribution and origin of clay minerals in
ore deposits, characterization and documentation as well as exploration clays at oil
production are discussed. The second section includes four chapters about the clay
minerals in soils, where mineralogical composition or water retention are described.
The third section implements the structural modifications of clay minerals for the
purpose of further clay minerals applications and unconventional methods of
characterization.

Dr. Marta Valášková D.Sc and Dr. Gražyna Simha Martynkova
Nanotechnology Centre, VŠB-Technical University of Ostrava,
Ostrava-Poruba
Czech Republic

Section 1




Clay Minerals in Deposits