Some characteristics of the kaolin→metakaolin reaction have been studied by applying nuclear magnetic resonance, X-ray fluorescence, and acid dissolution techniques to samples at intermediate stages of dehydroxylation. Nuclear magnetic resonance spectra enabled the average distance between hydroxyl groups to be computed, while X-ray fluorescence provided information on changes in the co-ordination number of aluminium and acid dissolution demonstrated the reduction in cohesion between individual layers during dehydroxylation. The last technique appears to be useful in studying the development of new solid phases. The main conclusions are that the reaction proceeds in a stepwise manner by complete removal of constitutional water from octahedral sheets and not by the growth of randomly distributed nuclei, that six-fold coordinated aluminium is gradually transformed into four-fold coordinated aluminium, and that the internal surface becomes progressively accessible to the acid reagent as dehydroxylation proceeds. The ‘ring structure’ of the silica layer remains.

UV-visible light absorption spectra of dilute suspensions of standard and commercial montmorillonites (bentonites) and of nontronite, hectorite and pyrophyllite, were studied.

All montmorillonites exhibit either an absorption band or a shoulder at a wavelength of 245 nm. The absorption peak for nontronite is shifted to 260 nm and absorption intensity is very high. Hectorite exhibits a very slight shoulder whereas pyrophyllite shows almost none. Absorption intensity in the UV range was found to be in direct correlation to structural octahedral Fe(III) contents. Direct evidence for the role of Fe(III) in the specific UV absorption of smectites was obtained by the fact that reduction with hydrazine fumes resulted in the disappearance of the peak and reoxidation with H2O2 caused its reappearance with even stronger intensity than originally. Mössbauer spectra showed that the Fe(III) disappeared almost completely in the reduced clay.

Extensive drying of smectites can cause the interlayer space to break down (collapse). This can affect the properties of bentonites as geotechnical barriers of HLRW (highly radioactive waste) repositories. If and to what extent the collapse occurs depends strongly on the type of interlayer cation. In particular K is known to lead to ready dehydration, in contrast to Ca and Mg. In the present study, various bentonites and one illite/smectite clay were dried/heated at 90ºC for 1.5 a and in a different experiment at 120ºC for 4.5 a and investigated with respect to mineralogical and geochemical changes of the smectite.

Smectite alteration after extensive drying was restricted to changes of the exchangeable cations. The CEC decreased by 9% (90ºC test) and 14% (120ºC test). A slight decrease of exchangeable Na+ was observed following the 90ºC test. No significant further decrease was observed after the 120ºC test. In contrast, the larger cation exchange capacity (CEC) decrease after the 120ºC test could be explained by increased Ca/Mg fixation. A possible mechanism for the observations is presented.

The adsorption of the silane coupling agents N-(2-amino-ethyl)-3-aminopropyl- trimethoxysilane (Z-6020), N-(2-(vinylbenzyl-amino)-ethyl)-3-amino-propyl-trimethoxysilane (Z-6032) and 3-glycidoxy-propyl-trimethoxysilane (Z-6040) onto the surface of kaolinite has been studied using the solvents water and ethanol. The adsorbed silanes were analysed using diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy and FT-Raman spectroscopy. When the silane coupling agents are dissolved in water, silanol groups are formed. Raman spectra of aqueous solutions of the silanes show that condensation of the silanols into oligomers occurred. The peak at 1000 cm-1 assigned to Si–O–Si vibrations indicates that polymerization has occurred. A similar behaviour is observed when the silanes are dissolved in ethanol. The DRIFT spectra show that the silane coupling agents adsorb onto the surface of kaolinite. It is proposed that the oligomers are bonded to the kaolinite surface only by hydrogen bondings with no covalent bonds formed.

As a unique tubular nanoclay, halloysite nanotubes (HNTs) have recently attracted significant research attention. The HNTs have outer diameters of ∼50 nm, inner lumens of ∼20 nm and are 200–1000 nm long. They are biocompatible nanomaterials and widely available in nature, which makes them good candidates for application in biomedicine. Compared with other types of nanoparticles such as polymer nanoparticles and carbon nanotubes, the drawbacks associated with HNTs include brittleness, difficulty with fabrication, low fracture strength, high density and inadequate biocompatibility. Preparation of polysaccharide-HNT composites offer a means to overcome these shortcomings. Halloysite nanotubes can be incorporated easily into polysaccharides via solution mixing, such as with chitosan (CS), sodium alginate, cellulose, pectin and amylose, for forming composite films, porous scaffolds or hydrogels. The interfacial interactions, such as electrostatic attraction and hydrogen bonding, between HNTs and the polysaccharides are critical for improvement of the properties. Morphology results show that HNTs are dispersed uniformly in the composites. The mechanical strength and Young's modulus of the composites in both the dry and wet states are enhanced by HNTs and the HNTs can also increase the storage modulus, glass-transition temperature and thermal stability of the composites. Cytocompatibility results demonstrate that the polysaccharide-HNT composites have low cytotoxicity even for HNT loading >80%. Therefore, the polysaccharide-HNT composites show great potential for biomedical applications, e.g. as tissue engineering scaffold materials, wound-dressing materials, drug-delivery carriers, and cell-isolation surfaces.

The Cretaceous fuller's earth of Southern England has been studied using sedimentological, petrographical and X-ray diffraction techniques, and by 40Ar-39Ar radiometric dating. The results indicate that the ultimate sources of the fuller's earth were basic to intermediate, alkaline pyroclastic materials, perhaps stemming from volcanicity associated with the Mesozoic rifting of the North Atlantic. The Wolf Rock phonolite is considered as a potential pyroclastic source. Deposition occurred under normal sedimentary processes, with partial re-working of land-fall ash, and incorporation of orthoclastic debris.

IR spectra of antigorite and sepiolite show an absorption band at ∼ 1200 cm−1. Spectra of palygorskite show several small absorptions between 1140–1200 cm−1. Since these three minerals are the only layer-silicates which show this absorption this band was assigned to Si-O-Si groups which serve as bridges between alternating alumino-Mg-silicate ribbons. By comparing the location of this band to bands observed in the spectra of P=O groups it was concluded that the contribution of π bonding in the bridging Si-O-Si group is of a high order. Similar conclusions were drawn after comparing the spectra of antigorite, sepiolite and palygorskite with those of various pyrosilicates. An inversion of the tetrahedral sheet requires an Si-O-Si angle of 180° which can be stabilized by dπ-pπ bonding in the Si-O-Si group. Due to the inductive effect of the octahedral sheet this type of bonding may occur in trioctahedral clay silicates, but is not to be expected in dioctahedral clay silicates.

Nickel ions play similar roles to magnesium ions in nickel-containing hydrous layer silicates. The extent of the replacement of Mg by Ni ranges from small proportions to complete, or almost complete, replacement. Particular interest attaches to the micro-crystalline, clay grade, minerals formed by processes of lateritic weathering. The multiplicity of names proposed in pre-X-ray-diffraction times must be re-evaluated in terms of modern identification procedures. Many of these minerals can now be placed in series such as:

Garnierite is now used mainly as a field term, prior to more specific identification, and terms such as 7 Å- and 10 Å-garnierite are useful when identification can proceed no further than recognition of basal spacings. Further study is required of schuchardtite, and of nickel-containing smectites and sepiolites. Consideration also must be given to the composition ranges of the end-member names.

Upper Jurassic Piper Formation sandstones of the Outer Moray Firth Basin, UK North Sea, form the main reservoir for the Piper and Tartan Fields, and are sealed by either the Kimmeridge Clay or Cretaceous marls. The main reservoir sandstones can be broadly considered as stacked coarsening-upward units that accumulated in a predominantly high-energy, shallow marine complex with depositional waters of inferred normal marine salinity, Eh and ionic composition. The amount of porosity and its distribution throughout these sandstones differs between the individual structural entities of the Piper and Tartan Fields. On the Piper structure all the sandstones are highly porous. Oil-zone porosities average 25% and are only slightly reduced in the water zone. Sandstones in the upthrown block of the Tartan structure are also generally porous but porosities are typically reduced to below 20%. Porosities are the most variable in the Tartan downthrown block and in the 15/17-9 well, off-structure Piper, where porous sandstones with between 14 and 18% porosity are associated with highly compacted and cemented sandstones with <5% porosity. Thin-section and SEM textural evidence indicate that much of the porosity in these sandstones is secondary, produced through the dissolution of an intergranular cement that provided support for the detrital framework, was peripherally replacive with respect to most detrital grains, and extensively replaced feldspars. Nodular concretions and sporadic, irregular crystals of ferroan calcite are inferred to be the remnants of this intergranular cement. The distribution of porosity zones in the Tartan downthrown block is related to the present structure and oil-water contact, supporting the interpretation of a secondary origin for much of the present porosity. Highly compacted sandstones interbedded with the porous sandstones result from a combination of early compaction, brittle framework collapse following the generation of secondary porosity and late grain-to-grain contact dissolution. Aggressive fluids responsible for the generation of the cement dissolution porosity are inferred to have been expelled from the Kimmeridge Clay in the adjacent Witch Ground Graben. The preservation of secondary porosity in Piper Formation sandstones is due to the relative timing of secondary porosity generation and subsequent hydrocarbon migration.

Two outcrops were studied which showed granite in the early stages of weathering. Reactions between specific mineral species were observed, and especially the formation of an illite-like phase which is similar to that of sedimentary illite. This phase has a composition distinct from that of the initial micas in the rocks, notably in its iron and magnesium content. This suggests solution-solid equilibria which involve ionic transfer beyond the grain bondary region where the mineral is found.

In the three previous papers of this series the role played by the exchangeable cations in the adsorption of methanol by homoionic montmorillonites has been investigated by different techniques, namely desorption isotherms, X-ray determination of the basal spacings and IR spectroscopy. In this last paper, models based on the previous discussions are presented. In the adsorbed state, methanol shows a strong tendency to form on the clay surface, hydrogen-bonded zig-zag chains analogous to those in crystalline CH3OH. The exchangeable cations perturb this arrangement to different extents. For Li+ the perturbation is negligible, for Ca2+ a complete rearrangement is observed and for Na+ and Ba2+ the chains are broken into smaller fragments.

The formation of kaolinite from Al hydroxy interlayered Garfield nontronite has been carried out at 225°C in hydrothermal conditions. The kaolinitization process, which proceeds through mixed-layer kaolinite/smectite intermediates, was followed by XRD, IR and ESR spectroscopy, chemical analysis and charge properties. The smectite content of the clay products decreases regularly with the duration of the hydrothermal treatment. The CEC and the structural Fe content of the deferrated products show a similar trend. IR features specific to nontronite disappear and are barely detectable as the smectite content of the mixed-layer clay falls below 30%. In contrast, the ESR spectrum of nontronite is characterized by a broad g2 signal that remains even after prolonged hydrothermal treatment. The calibration of the g2 ESR signal, due to Fe-smectite, shows that the synthetic kaolinites have low Fe contents (∼ 1% Fe2O3) indicating that the kaolinitization process involves destruction of the 2:1 layers and the subsequent neoformation of kaolinite and Fe oxides. As illustrated by the study of deferrated soil clay samples, representing a weathering sequence Fe-smectite → kaolinite + Fe oxides, ESR spectroscopy proved to be a powerful Fe probe for detecting Fe-rich smectite in kaolinite/Fe-smectite mixed-layer clays.

The acid strength and the number of acid sites on various clays were determined by observing the colouration of Hammett indicators adsorbed on them and by titrating benzene suspensions of them with n-butylamine, respectively. H(Al)-saturated allophane behaves as a strong acid (Ho; −5·6 ∼ 1·5) in a relatively dry environment (relative humidity 10-55%), but its acid strength is very much reduced either by increasing its water content or by saturating it with alkali or alkali earth metal cations. Imogolite shows only a very weak acidity (Ho; 4·6 ∼ 6·8) under medium dry to moist conditions (relative humidity; 30-100%). Both allophane and imogolite show a marked enhancement of acidity (Ho; −8·2 ∼ 1·5) when they have been dried over P2O5 or heated to result in dehydroxylation. H(Al)-saturated montmorillonite, kaolinite and halloysite show stronger acidities (Ho; −5·6 ∼ 1·5) than allophane (Ho; 1·5 ∼ 6·8) in a relatively moist environment (relative humidity; >60%). The n-butylamine titre and CEC show a good agreement for montmorillonite, but a poor agreement for allophane. The latter discrepancy which is larger for allophane when it has been heated at 150 and 300°C, is also found for imogolite when similarly heated. In these titrations, excess butylamine is found in supernatants at end-points. Therefore, the n-butylamine titre as such can not be used for the estimation of the number of acid sites on imogolite and allophane. The origin, structure and transformation of the acid sites on these clays is discussed.

The work outlined in this paper was undertaken to show how, by a consideration of the energy changes involved, some insight may be gained into the reactions occurring when kaolin minerals are heated.

Activation energies have been determined experimentally for the dehydration of various kaolin minerals. The fireclay mineral is distinctive and it is suggested that it does not form part of a halloysitekaolinite series. It is further thought possible that there is a series of fireclay minerals.

From thermochemical and thermodynamic considerations the heat of formation of kaolinite has been calculated approximately and enthalpy and free energy changes have been estimated for the exothermic reaction at 980°C. These indicate that, if a compound is produced during dehydration, the most probable explanation of the exothermic reaction is the simultaneous production of mullite, γAl2O3 and SiO2. Finally the lattice energies of kaolinite and its thermal decomposition products have been calculated.

A method is described for calculating, and then subtracting, the background from X-ray diffraction patterns of oriented clay mineral samples. Ti-Kα radiation is used and, to minimize the absorption of this radiation by air, a vacuum and helium-flushed device has been developed. This device can be used with other X-ray sources, offering a considerable increase of intensity—e.g. Co-Kα radiation is increased by 125%. With the background-eliminated patterns a better semi-quantitative estimate of the composition of clay mineral mixtures is possible. Small differences in composition of two samples can be identified by subtracting one of the background-eliminated patterns from the other. Using this method, peak maxima of smectite-group minerals can also be accurately determined.

Se estudia la interacción del isocianato de butilo y del isocianato de fenilo con sepiolita, utilizando las técnicas de espectroscopía IR y anáilisis químico. En determinadas condiciones experimentales se produce un injerto de grupos orgánicos sobre la superficie mineral por formación de enlaces tipo uretano ≡ Si-O-CO-NH-R. Se ha puesto de manifiesto que el agua adsorbida sobre la superficie mineral, tiende a formar ureas simétricamente disustituídas como sub-producto de la reacción.

The adsorption of Cd and Zn on a standard montmorillonite (SAZ-1) in the presence of the cationic pesticide chlordimeform, both in solution (simultaneous adsorption) and when the pesticide is previously adsorbed on the clay (successive adsorption) has been studied. The adsorption of Zn decreases when the chlordimeform concentration increases in both simultaneous and successive adsorptions, following the sequence: chlordimeform-free solutions > successive > simultaneous. In the adsorption of Cd the sequence is different: successive > chlordimeform-free solutions > simultaneous, indicating that a small amount of pesticide adsorbed favours Cd adsorption. In all cases, the apparent affinity of the metal for adsorption on montmorillonite, on the basis of distribution coefficients, KD, is higher for lower metal surface coverage, and decreases largely with the amount of the metal adsorbed. This indicates the existence of high affinity sites on the clay, probably those of variable charge edge regions. The contribution of edge and interlamellar positions to adsorption of Zn and Cd on SAZ-1 has been studied.

In a paper to the Faraday Society (1946), Mering showed that the temperature to which one required to heat montmorillonite to produce irreversible collapse of the c-axis depended on the exchangeable cation. With Na-montmorillonite irreversibility began at about 550°C but with Ca-montmorillonite below 350°C During a study of the liquid phase sorption of pyridine by montmorillonite, the writer obtained evidence that irreversible collapse occurred at 200°C with Li-montmorillonite.

The source of montmorillonite was a sample of Wyoming bentonite, which was purified by passing through a Sharples supercentrifuge. The resultant exchange capacity to ammonium acetate at pH 7 was about 90 m.e./100 gms. and the displaced ions chiefly consisted of Na+ and Ca++.

The clay mineral assemblages and microtextures of a suite of mudrocks from the Lias Group of England and Wales indicate important regional differences in burial history.

Samples from the northern Cleveland Basin are characterized by illite-smectite (I-S, 90% illite) and little carbonate whilst samples from the southern Worcester and Wessex basins contain less mature discrete smectite and are often calcite- and dolomite-rich. Lias Group rocks have been buried to 4 km in the Cleveland Basin but to <2 km in the Worcester and Wessex basins. Burial in the Cleveland Basin is deeper than previously estimated and does not need a local heating event. Illite- smectite (80% illite) detected in samples from the East Midlands Shelf suggests burial to 3 km, again deeper than previous estimates for this region.