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 http://dx.doi.org/10.5772/b.bookID 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 Janeza Trdine 9, 51000 Rijeka, Croatia Copyright © 2012 InTech All chapters are Open Access distributed under the Creative Commons Attribution 3.0 license, which allows users to download, copy and build upon published articles even for commercial purposes, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. 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Publishing Process Manager Ivona Lovric Typesetting InTech Prepress, Novi Sad Cover InTech Design Team First published September, 2012 Printed in Croatia A free online edition of this book is available at www.intechopen.com Additional hard copies can be obtained from orders@intechopen.com 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). . CLAY MINERALS IN NATURE – THEIR CHARACTERIZATION, MODIFICATION AND APPLICATION Edited by Marta Valášková and Gražyna Simha Martynková Clay Minerals in Nature – Their Characterization,. non-metallic, earthy and naturally- occurring resources abounding throughout Nigeria's sedimentary basins and on the Clay Minerals in Nature – Their Characterization, Modification and Application. pipe clay; sculptor's clay, or modeling clay, a fine potter's clay, sometimes mixed with fine sand; brick clay, an admixture of clay and sand with some ferruginous (iron-containing)