The origin and formation of soil clay minerals, namely micas, vermiculites, smectites, chlorites and interlayered minerals, interstratified minerals and kaolin minerals, are broadly reviewed in the context of research over the past half century. In particular, the pioneer overviews of Millot, Pedro and Duchaufour in France and of Jackson in the USA, are considered in the light of selected examples from the huge volume of work that has since taken place on this topic. It is concluded that these early overviews may still be regarded as being generally valid, although it may be that too much emphasis has been placed upon transformation mechanisms and not enough upon neoformation processes. This review also highlights some of the many problems pertaining to the origin and formation of soil clays that remain to be resolved.

This article reviews that clay literature from the last ten years, which is devoted to the applications of clay minerals in the interpretation of geological processes in sedimentary basins. The results, selected by the author as being of particular interest, are presented, arranged according to the successive phases of the rock cycle.

The clay minerals kaolin, smectite and palygorskite-sepiolite are among the world's most important and useful industrial minerals. Clay minerals are important in a number of geological applications such as stratigraphic correlations, indicators of environments of deposition and temperature for generation of hydrocarbons. In agriculture, the clay minerals are a major component of soils and determinant of soil properties. The clay minerals are important in construction where they are a major constituent in brick and tile. The physical and chemical properties of the clay minerals determine their utilization in the process industries.

What about tomorrow? Processing techniques will be improved and new equipment will be available so that improved clay mineral products will be available. Pillared clays and nanocomposites will become important. Further developments in organoclay technology and surface treatments will provide new usages for these special clays. Tomorrow will see further growth and utilization of the clay minerals.

Reagent-based selective separations of minerals are of great industrial importance. The basis of these separations is the competitive differential adsorption of the reagent onto a number of minerals. An X-ray photoelectron spectroscopic (XPS) study of the adsorption of polyacrylamide onto kaolin, feldspar and quartz is described. Initial data confirmed the utility of XPS for the study of polyacrylamide adsorption onto silica glass slides. Further results indicated the utility of the technique for the direct measurement of adsorption of polyacrylamide onto individual aliquots of kaolin, feldspar and quartz. Adsorption was relatively greatest onto kaolin. Feldspar displayed less adsorption and quartz very little. An imaging method was used to characterize, at least relatively, the competitive adsorption of polyacrylamide onto kaolin in the presence of mixtures of kaolin and quartz. This is a potential new technique for study of competitive adsorption.

Naturally occurring sepiolite has been used as a support in the preparation of Ni and Pd catalysts. A precipitation procedure has been applied for both metals to deposit the precursor on to the support surface. The interaction between the sepiolite and the metal precursor has been studied by use of IR and solid-state MAS-NMR. Results show that SiOH groups are consumed in forming the Ni precursor whereas no specific interactions occur in the case of the Pd. However, strong interactions between metal precursor and the tetrahedral sheet occur for both metals leading to precursors which show a high stability under reducing conditions.

The Cu,Cr-, Zn,Cr- and Cu,Al-layered double hydroxides have been synthesized by the coprecipitation method and characterized by elemental analysis, PXRD, SEM/EDS and BET. The mixed oxide materials obtained upon calcination at 873 K show very high catalytic activity for the combustion of toluene and ethanol. The best sample is derived from the Cu,Cr-LDH precursor with a Cu:Cr ratio of 2, composed of copper oxide and copper chromite. This catalyst gave 50% conversion of toluene and ethanol at temperatures of 45 and 15 K lower, respectively, than the reference commercial catalyst. Catalytic tests with a mechanical mixture of CuO and CuCr2O4 demonstrate that the use of an LDH precursor is essential for optimum results. The importance of the simultaneous presence of both Cu and Cr, the influence of the Cu:Cr ratio on the catalytic activity and the role of the interface boundaries in the CuO-CuCr2O4 mixed oxide system are discussed.

Catalytic properties of Cu-doped alumina-pillared montmorillonite samples have been tested in the liquid phase oxidation of toluene, o-, m-, and p-xylene with hydrogen peroxide. The results show that the clay samples possess significant activity for both the oxidation of methyl groups and hydroxylation of the aromatic ring. Physicochemical characterization of the catalysts using XRD, BET, ESR and ICP-AES techniques show that they are porous materials with Cu species located in the interlayer, present either as isolated Cu2+ ions anchored at alumina pillars or as patches of amorphous CuO. The dependence of the overall yields on the amount of Cu dopant is discussed and explained in terms of the catalyst structural properties.

X-ray diffraction (XRD), infra red (IR) spectroscopy, gloss goniophotometry and stylus profilometry were used to investigate the alignment of kaolinite applied as a thin coating on a polyester film substrate. The principles and applicability of the analytical methods are reviewed and discussed in the context of a kaolinite coating. X-ray diffraction and transmission IR were used to measure kaolinite misalignment and orientation distribution in the coating. Transmission IR measures the coating bulk; XRD data are surface biased, but contain contributions from the bulk. Attenuated total reflectance-IR (ATR-IR) provides a direct measure of kaolinite alignment within ~1 µm of the coating surface and also allows an assessment of surface smoothness. Gloss goniophotometry and contact profilometry measure surface microroughness and macroroughness, respectively, rather than kaolinite particle orientation. However, the properties of roughness and orientation are related. Bulk and surface texture are not necessarily correlated and a combined approach using both bulk and surface sensitive techniques is required for a full understanding of coating structure.

The Tinto river is one of the most polluted stream environments in the world, as a result of both acid mine drainage and natural acid rock drainage. Two representative samples from the phyllosilicate-rich rocks exposed in the drainage basin (Palaeozoic chlorite-bearing slates and Miocene smectite-rich marls) were treated with acid river water (pH = 2.2) for different times to constrain the effects of extreme hydrogeochemical conditions on clay mineral stability. Illite and kaolinite did not show appreciable variations in their crystal chemistry parameters upon treatment. Chlorite underwent an incipient chemical degradation evidenced by the progressive loss of Fe in octahedral positions coupled with a shortening of the b unit-cell parameter, although no weathering products of chlorite were observed. Smectite and calcite were rapidly and fully dissolved thus neutralizing the water acidity, and subsequently Fe and Al oxy-hydroxides and opaline silica precipitated from the aqueous solution, together with a neoformed amorphous silicate phase largely enriched in Al and Mg.

Textural, mineralogical and chemical parameters of clays belonging to the Upper Cretaceous ‘Argilas de Aveiro’ formation were determined and correlated, using geostatistical analysis, with some relevant geotechnical parameters. The data obtained made it possible to subdivide the region under study into distinctive sectors on the basis of geotechnical behaviour. Clay fraction content and composition control geotechnical parameters such as the expandability and the Atterberg plastic and liquid limits. A positive correlation was found between both expandability and the Atterberg plasticity index values and the total phyllosilicates, smectite, MgO and Al2O3. However, Atterberg plasticity index values were relatively independent of the diverse clay mineral assemblages.

An artificial neural network with back-propagation architecture has been applied to the problem of the quantitative analysis of simulated clay mixtures from synthetic X-ray diffraction (XRD) data. A ‘clay characterization function’ (CCF) has been devised that combines information from two clay XRD peaks into a single peak that simplifies the problem which the neural network must solve. In addition, it eliminates peaks from non-layered minerals. A neural network with 17 neurons in the hidden layer and log-sigmoid transfer functions in each layer is sufficiently successful at predicting the compositions of binary and ternary mixtures of the three model clays to demonstrate the potential of the method. Moreover, training is accomplished in relatively short times using a Levenberg-Marquardt algorithm.

Although the problem ‘solved’ by this neural network is rather simple, the approach has the potential for the much more complex problem of the quantitative phase analysis of mixtures of real clay minerals. In this study, only the CCF peak heights have been used, but the positions and peak widths also contain important information. It may be practical to include as variables not only the concentrations of clay phases, but also compositional information to which XRD is sensitive.

The construction and operation of a spray drier is described where the spray is produced using an air brush, essentially a miniature spray gun. The spray-dried products consist of spheres 50–60 µm in diameter and typical product recoveries are 80%, a marked improvement over simple two-nozzle systems. The spray-dried samples are easy to load into XRD powder holders and present a smooth surface and relatively constant bulk density to the X-ray beam. Problems of preferred orientation are effectively eliminated and the resulting X-ray powder patterns are completely reproducible by different operators.

Back-scattered electron images of clay minerals from sandstones are used, together with complementary micro-analytical methods, to identify and quantify mineral microporosity and geochemistry. Clay minerals typically have a range of microporosity from 10 to >90% dependent on texture and paragenesis. Fibrous clays are highly microporous; detrital clays have low microporosity but specific clay minerals have broad ranges of microporosity. The often quoted mineral-chemical association between thorium (Th) and kaolinite cannot be substantiated by micro-analysis. The Th content of clay minerals is associated with micro-inclusions within the kaolinite which form diagenetically or are derived from precursor minerals.

Early Cambrian sediments on the East European platform in North Estonia, represented mostly by clays and silty clays, were deposited under normal marine conditions. The sediments were never affected by significant tectonic or thermal events after sedimentation 530 Ma ago, and the clays still have high water contents. The clay fraction, divided into four sub-fractions, was studied using X-ray methods and Rb/Sr dating. Decomposition of the XRD curves was used to quantify the amounts of illitic minerals in the sub-fractions. Dating by Rb/Sr showed that the finest fraction (<0.06 µm) was formed 50–150 Ma after sedimentation. The coarser fractions also contain considerable amounts of diagenetically formed minerals. This shows that neoformation of illitic minerals in marine sediments with high water/sediment ratios is a very important process even at temperatures <35°C.

Soil clay mineralogy at Rothamsted began in the early 1930s, and quickly focused on technique, swelling minerals, micas and sorption phenomena. By the mid-1940s interest had extended to the formation and spatial distribution of soil clays with the move of the Soil Survey of England and Wales to Rothamsted. These themes continued for the next 40 years. Considerable contributions were made to crystal chemistry and structure determinations, and the relationship of these to the sorption and desorption of water and organic molecules, and the behaviour of soil K. The pattern of soil clay mineralogy was determined for large parts of England and Wales, and absorbed into soil mapping. The work on X-ray diffraction appeared in the Mineralogical Society Monographs on this subject. These, and the Monograph on Clay Chemistry, which reached their final form in the 1980s, are the lasting monuments to soil clay mineralogical research at Rothamsted.

An informal overview is given of the development of the fundamental particle model, where, in a series of papers published from 1982-1987, researchers from the Macaulay Institute presented a radical model for the interpretation of the crystal structure, chemistry, and genesis of interstratified clays. The model reconciled electron microscopy and X-ray diffraction (XRD) data from a variety of sedimentary clay specimens, and proposed that these minerals were composed of nano-crystalline ‘fundamental particles’ whose adsorptive interfaces were responsible for the expanding smectite layers observed by XRD. The term ‘interparticle diffraction’ was used to describe this phenomenon. Experiments were reported which proved the model, by producing randomly interstratified illite-smectites from combinations of ordered illite-smectite and smectite clay dispersions. The model was extended to propose that fundamental particles were the primary units of crystallization, and that changes in the particle population were responsible for the commonly observed evolution in XRD character of these minerals with increasing depth of burial and temperature.

The kaolinized granites of St. Austell, England, are worked to produce a range of china clay products, for some of which the kaolin has to meet stringent particle shape and size specifications. Systematic petrographic study indicates that kaolin occurs in the form of two textural types: (i) finely crystalline kaolin (typically <5 µm in average diameter), which infills dissolution porosity of granitic feldspars, and (ii) coarsely crystalline vermiform aggregates (up to 100 µm or more in length), which are closely associated with expanded micas. The vermiform aggregates are characterized by an intergrowth of mica and kaolin crystals, which can be observed at scales of resolution offered by TEM. Textural and chemical evidence suggest that the expanded mica texture is probably the result of preferential precipitation of kaolin along mica cleavage planes and is not simply a process of chemical replacement.

Petrographic examination of kaolin slurries sampled at different points in a typical refinery circuit indicates that platy products with high aspect ratio are derived exclusively from raw materials rich in vermiform aggregates. The fine scale intergrowth of kaolin and mica within the aggregates results in circumstances where mica persists through to fine grained products. Furthermore, the absence of Fe or other chemical components in the kaolin structure suggests that any iron reported for the final products may be a consequence of the presence of Fe-bearing mica within a very fine grained intergrowth.