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Relation between structural disorder and other characteristics of kaolinites and dickites
Apparent long spacings from clay-water gels, glasses, and crystalline materials due to total reflection of X-rays
Hydrobiotite, a regular 1 : 1 interstratification of biotite and vermiculite layers
Tarasovite, a mixed-layer illite-smectite which approaches an ordered 3:1 layer ratio
Interaction of uranyl ions with synthetic zeolites of type A and the formation of compreignacite-like and becquerelite-like products
Chemical compositions of berthierines; a review
Report of the Clay Minerals Society Nomenclature Committee for 1980-1981; nomenclature for regular interstratifications
Adsorption of uranium from solutions by montmorillonite; compositions and properties of uranyl montmorillonites
Long-spacing organics for calibrating long spacings of interstratified clay minerals
Formation, compositions, and properties of hydroxy-A1- and hydroxy-Mg-montmorillonite
Intracrystalline swelling of montmorillonites in water-dimethylsulfoxide systems
Hydrothermal alteration of a serpentinite near Takovo, Yugoslavia, to chromium-bearing illite/smectite, kaolinite, tosudite, and halloysite
Thermal behavior of hydrotalcite and of anion-exchanged forms of hydrotalcite
Summary of recommendations of AIPEA nomenclature committee
Front Matter
Abstract T HE hydrous layer silicates commonly known as clay minerals are part of the larger family of phyllosilicates. The layer silicates considered here contain continuous two-dimensional tetrahedral sheets of composition T 2 O 5 , (T = tetrahedral cation, normally Si, Al, or Fe 3+ ), in which individual tetrahedra are linked with neighboring tetrahedra by sharing three corners each (the basal oxygens) to form an hexagonal mesh pattern (Fig. 1.1 a ). The fourth tetrahedral corner (the apical oxygen) points in a direction normal to the sheet and at the same time forms part of an immediately adjacent octahedral sheet in which individual octahedra are linked laterally by sharing octahedral edges (Fig. 1.1 b ). The common plane of junction between the tetrahedral and octahedral sheets consists of the shared apical oxygens plus unshared OH groups that lie at the center of each tetrahedral six-fold ring at the same z-level as the apical oxygens. F may substitute for OH in some spccies. The octahedral cations normally are Mg, Al, Fe 2+ , and Fe 3+ , but other medium-sized cat:ons such as Li, Ti, V, Cr, Mn, Co, Ni, Cu, and Zn also occur in some species. The smallest structural unit contains three octahedra. If all three octahedra are occupied, i.e . have octahedral cations at their centers, the sheet is classified as trioctahedral . If only two octahedra are occupied and the third octahedron is vacant, the sheet is classified as dioctahedral . The assemblage formed by lirking one tetrahedral sheet with one octahedral sheet is known as a 1 : 1 layer . In such layers the uppermost, unshared plane of anions in the octahedral sheet consists entirely of OH groups.
Abstract C HAPTER 1 has reviewed the regular or ordered structures of layer silicates determined mainly by single crystal, X-ray diffraction methods. The present chapter and the two following chapters are concerned with irregular and disordered structures mainly in the 0.1–10 μ m particle size range. X-ray powder diffraction methods are commonly used in studying these clay-grade materials, but single crystal, electron diffraction analysis furnishes additional important information (see Gard, 1971; Zvyagin, 1967). Structural disorder is so prevalent in clay minerals that its recognition and evaluation are important aspects of the identification process. Some acquaintance with the fundamental concepts of diffraction by disordered systems is very helpful in understanding the phenomena involved. A full treatment would go far beyond what can be given in the present monograph, but from the simple treatment presented it is hoped that the main features of powder patterns from disordered layer structures will be more clearly recognized and interpreted than would be possible from a purely descriptive treatment. The theoretical discussion is presented in Sections 3, 4, 5 and 6 and its application is given in Sections 7 and 8. Inevitably there will be some overlap between the theoretical sections and their application to different mineral groups. It may be remarked that macro-crystalline minerals are not devoid of structural disorders, but in single crystal methods of structure analysis the investigator can usually select “good” crystals with a minimum of disorder. In studying clay minerals it is usually necessary to study them as formed in Nature and without the option of selecting “good” materials.
Abstract I NTERLAMELLAR complexes of caly minerals are formed by the introduction of inorganic and organic meterials between the structural layers, the relatively weak bonding between the layers as compared with the strong ionic-covalent bonding within the layers facilitating their formation. The most common of the interlayer materials is water which is normally present between the layers of smectites and vermiculites, and in the hydrated form of halloysite. The extent to which inorganic and organic materials enter the silicate structures varies greatly and depends on many factors related to the detailed structure and composition of the layers, and the nature of the materials. In the early stages of the structural study of these complexes attention was focused principally on the swelling–shrinking behaviour with respect to water, and the complexes formed with simple organic liquids, notably ethylene glycol and glycerol. The use of these liquids became a standard identification test. From these simple beginnings, a wide range of investigations has developed oriented towards the understanding of the formation, structure and properties of the complexes, as well as the refinement of identification procedures and the development of new procedures. Both aspects will be treated in this chapter. As regards research on the complexes themselves, Xray diffraction is the major method of investigation, but other techniques, notably infrared absorption spectroscopy, are being increasingly applied. In keeping with the particular theme of this monograph, X-ray studies will be considered with rare references to other methods. For purposes of X-ray identification of clay minerals, it will often be necessary to utilize no more than a fraction, possibly a small fraction, of the total knowledge now available on the interlamellar complexes of clay minerals.
Abstract T HE terms interlayzring, mixed-layering, and interstratification describe phyllosilicate structures in which two or more kinds of layers occur in a vertical stacking sequence, that is, along c* or a line normal to (001). Phyllosilicate layers are strongly bonded internally but rather weakly bonded to each other. Thus, each layer approximates a one-dimensional “molecule” in the c* direction, and a two-dimensional crystal in the a and b directions. The basal surfaces of different kinds of layers are geometrically very similar and consist of sheets of oxygen or hydroxyl ions in quasi-hexagonal array. Consequently, layers with different internal arrangements can stack together and still articulate well at their interfaces. These structural factors are almost unique to the clays and phyllosilicates generally, and doubtless are responsible for the common occurrence of interstratified species. The existence of interstratified clay minerals has been known for many years. Early papers include the work of Gruner (1934), Alexander, Hendricks, and Nelson (1939), and Nagelschmidt (1944). The widespread occurrence of interstratified minerals was documented by the comprehensive study of Weaver (1956). Reported instances of interstratified clays comprise a relatively small number of tlpes despite the large number of possibilities. Dominant species involve two components, although three component minerals have been reported (Weaver, 1956; Jonas and Brown, 1959; Foscolos and Kodama, 1974). It will be shown later that small amounts (~5%) of some types of layers in three-component systems can easily escape detection by routine X-ray diffraction methods. Consequently, three-component (or more?) minerals may be more common than a reading of the contemporary literature would suggest.
Abstract P REVIOUS chapters have surveyed the structures of ordered and disordered clay minerals and related layer silicates, their swelling in water and organic liquids and interstratified layer structures. We come now to consider how this detailed information can be used to identify clay minerals. This means that we must consider how to prepare clay materials for X-ray examination. how to utilize X-ray diffraction equipment to obtain the necessary data, and finally how to compare these data with the accumulated information so as to arrive at an identification suitable for the purpose involved. Many aspects of sample preparation, of diffraction analysis, and of material identification apply to the study of crystalline materials generally. Here we shall emphasize those aspects which relate to the particular class of materials under consideration. It will be assumed that readers have access to books dealing generally with X-ray diffraction procedures, particularly powder methods of analysis; the following may be mentioned specifically: Elentents of X-Ray Diffraction , Cullity (1956, 1978); X-Ray Diffraction Procedures for Polycrystalline and Amorphous Materials , Klug and Alexander (1954, 1974). No single identification procedure, not even X-ray diffraction, gives all the answers on all occasions. Consequently diffraction analysis is combined almost always with other methods, partly chemical and partly physical, Much depends on whether very detailed information is required on a few samples, or less detailed information on a very large number of samples. At one extreme, identification is more or less synonymous with mineralogical and crystallographic study of minerals; at the other extreme, it becomes one aspect of a broad geological or soil survey. In this chapter we enkavour to keep in mind this range of interests.