Expanding and non-expanding layers of interstratified clay minerals have been examined by high-resolution transmission electron microscopy. Permanent expansion of swelling layers under the electron beam was achieved by intercalation of n-alkylammonium ions, especially the octadecylammonium ion. Oriented flakes of clay minerals were prepared by embedding the expanded or non-expanded clay minerals in epoxy resin, followed by centrifugation before hardening of the resin. The minerals were then cut perpendicular to 001 using an ultramicrotome. Crystals of macroscopic trioctahedral vermiculites show homogeneous interplanar distances of 24 Å after intercalation of octadecylammonium ions. Crystals of dioctahedral soil vermiculites often show a central zone with non-expanding 10 Å layers; the outer zone shows a disturbed layer sequence extensively expanded by n-alkylammonium ions. After embedding in epoxy resin, vermiculites show stable 9·2 Å interplanar spacings but smectites expand to 13 Å. Montmorillonites of the Wyoming type show curved stacks of layers. Most of the layer stacks of montmorillonites of the Cheto type are split and disordered aggregates of single layers are formed. Crystals of illites and glauconites are built up of aggregated small stacks of 10 Å layers, the layer stacks consisting of 10 layers. Mostly the boundaries of the layer stacks are parallel to their 001 planes; sometimes low-angle boundaries are found. The dimensions of the layer stacks, ∼ 100 Å thick and some hundreds of Å in plane, are equal to the dimensions of the domains of coherent scattering of X-rays. The border layers between the layer stacks are identical with those 5 to 10% of layers which swell with glycerol or ethylene glycol during X-ray analysis. Some of the layer stacks of illite and glauconite crystals are expanded by octadecylammonium ions within a fortnight. The other stacks show unchanged 10 Å spacings. The different expanding behaviour of different layer stacks reflects the heterogeneity of the layer-charge distribution in the mica clay minerals. K-bentonites show the same expanding behaviour as illites and glauconites but the number of layers expanding with octadecylammonium ions is greater in K-bentonites than in illite crystals. Expanded mixed-layered minerals of the illite-smectite type show a different layer stacking sequence from illites. Random irregular stacking of mica layers with expanded layers are recognized rather than coherent stacks of mica layers. The crystals have a stepped morphology, perhaps effected by translations along the 001 plane. After reaction of the rectorite from Garland County with octadecylammonium ions, the non-expanded mica layers and the expanded smectite-like layers can be distinguished. The heterogeneity of the interlayer charges of the smectite layers is documented by the formation of alkyl double-layers with 17 Å spacings and alkyl triple-layers with 21 Å spaces in irregular sequence. The ‘rectorite’ from the Goto Mine expands nearly homogeneously in comparison with the rectorite from Garland County. After reaction with octadecylammonium ions, interplanar spacings of mostly 31 Å are observed but rarely spacings of 27 Å. The smectite layers of the corrensite from Kaubenheim are expanded by tetradecyl-ammonium ions to 18 Å spacings by formation of alkyl double-layers. A regular 1 : 1 layer structure of 14 Å chlorite layers and expanded 18 Å smectite layers with total spacing of 32 Å can be observed. Muscovite and pyrophyllite are not expandable by n-alkyl-ammonium ions within a fortnight. However, sporadic layers of celadonite crystals are expanded. Generally the 10 Å or 9·2 Å layers extend over the whole crystals of the three minerals. In celadonite crystals, disorder is caused sporadically by interrupted layers or slightly enlarged layer spacings.

Syntheses of ferric smectites were performed at low temperature (75° C by aging coprecipitated gels of silica and Fe2+-sulphate under initially reducing then oxidizing conditions. Under strictly reducing conditions only nuclei of a trioctahedral ferrous stevensite were observed and crystal growth did not take place. When a spontaneous oxidization, in contact with air, was effected, the ferrous smectite nuclei transformed rapidly into a ferric, nontronite-like, smectite. Crystallogenesis of the ferric smectite was studied by XRD, IR, DTA, Mössbauer and EPR spectroscopies. The end-synthesis smectite contained only Fe3+ ions, all located in the octahedral sheet. This clay was mixed with a cryptocrystalline iron oxide phase containing one-third of the iron atoms and undetectable by XRD.

The structure of synthetic aluminosilicates prepared at pH 6 has been investigated by 29Si and 27Al high-resolution solid-state nuclear magnetic resonance (NMR) spectroscopy. Fourier transform infrared (FTIR) spectroscopy and electron microscopy have also been used to characterize the products. The amount of Si and Al in protoimogolite, disordered allophane and other structures has been measured. There is a fair correlation between the intensity of the 349 cm−1 band in the FTIR spectra and the proportion by weight of protoimogolite Si measured by NMR. It is shown that disordered allophanes have similar structures to those proposed by van Reeuwijk and de Villiers (Soil Sci. Soc. Am. Proc. 32 (1968) 238–240), i.e. octahedral Al surrounding a tetrahedral core. Moreover, it is clear that at high Al:Si ratios (⩾1:1), protoimogolite can compete with disordered allophane precursors for aluminum. The driving forces for formation of protoimogolite rather than allophane appear to be long range Al-Al repulsive forces through oxygen.

The surface free energy of Ca-montmorillonite has been determined from measurement of the contact angle of water on an oriented deposit immersed in n-alkanes; the oriented deposits were equilibrated at different relative humidities. These experiments provided the polar, γSP, and dispersive, γSD, components of the surface free energy γs. The results indicate that: (1) γs is mainly due to dispersive forces (γSD ≃ 145 mJ.m−2) and, to a lesser degree, polar forces (γSP ≃ 35 mJ.m−2). (2) The value of the apparent surface free energy of the clay, γα, tends towards that measured for water when the solid water content exceeds 50 wt%. (3) The sorption of water molecules substantially modifies the surface free energy of the solid; γs decreases from 180 mJ.m−2 to 60 mJ.m−2 when the water content increases from 0 to 50%. These results agree with other observations made on solids whose surface characteristics are similar to montmorillonite, i.e. micas, silicates and glasses. In addition, variations of γs with water content can be related to the hydration processes of smectites. Finally, these results show that the silicate no longer influences the surface properties when the montmorillonite water content exceeds 60%.

Low-dip fractures in the Lac du Bonnet granite pluton, SE Manitoba, contain abundant illite. Petrographic examination showed that the illite has three modes of occurrence: (i) alteration product of biotite, (ii) microfracture (< 1 mm width) filling, (iii) macrofracture (> 1 mm) filling. Microprobe analyses of these three types of illites in a single sample gave distinct compositional characteristics that defined an evolutionary trend, depicting Al2O3 enrichment, on an Al2O3−(K2O + Na2O)−(MgO + FeO) triangular diagram. White micas in the rock matrix adjacent to illite-bearing fractures have higher K and Al contents than all the three types of illites, implying that they formed under different conditions. The sorption of four radionuclides, 137Cs, 147Pm, 241Am and 90Sr, under oxic conditions on illite-bearing polished sections was also investigated, using autoradiography combined with petrographic examination. Illite showed greater sorption compared with other minerals present in the polished sections.

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.

Authigenic chlorites occurring as pore linings in reservoir sandstones have been investigated by XRD and TEM/EDAX. Both methods identified the Ib (β = 90°) polytype. TEM/EDAX analyses suggest that the chlorites are Al-rich, Mg-chamosites with Fe/(Fe + Mg) > 0·47. Octahedral Al exceeds tetrahedral Al, resulting in octahedral totals of less than the theoretical 12·0. Compositions were estimated from XRD data using the equations after Brindley (1961) and Shirozu (1958). XRD-determined compositions are relatively enriched in tetrahedral Al and octahedral Mg, giving Fe/(Fe + Mg) > 0·4 and suggesting that the chlorites are Al-rich clinochlores. XRD estimates plot in the same compositional area as authigenic Ib (β = 90°) chlorites of Hayes (1970), but also within the compositional area of metamorphic chlorites. Caution should be exercised when estimating the composition of sedimentary chlorites by XRD as results appear to overestimate Mg content because of the excess of octahedral R3+ over tetrahedral R3+.

On treatment with dodecylammonium chloride, a synthetic Na-saturated phyllomanganate undergoes a cation-exchange reaction in which the structure expands from a collapsed basal spacing of 7 Å or a hydrated one of 10 Å to ∼ 25·5 Å. The exchange reaction is strongly influenced by the saturating cation in the original manganate and by the degree of hydration of the interlayer zone in which the exchangeable cations are located. Of the 12 cations tested, from Groups IA, IIA and IIB of the Periodic Table, only Co-manganate undergoes alkylammonium exchange when fully-dehydrated by evacuation. The results are discussed in the context of existing knowledge of the synthetic phyllomanganate and, by extrapolation, the potential value of the technique in the characterization of natural manganates has been assessed.

A synthetic phyllomanganate saturated with a series of primary alkylammonium cations has been examined using XRD, chemical analysis and X-ray photoelectron spectroscopy. A linear relationship exists between the basal spacing of the saturated alkylammonium-manganate and the hydrocarbon chain length in the interlayer, and from the gradient it is concluded that the alkyl chains are perpendicular to the manganate sheet. This orientation is a function of both the charge density and the presence of a layer of water molecules immediately adjacent to the manganate basal surfaces. Evacuation results in the loss of this interlayer water and the structure of the organo-manganate is considerably disrupted. The extent to which the interlayer arrangement can be reinstated by rehydration is dependent on the chain length of the saturating organo-cation. For cations of chain length > C6 the C contents suggest that cation in excess of the exchange capacity is present in the interlayer, but the absence of any compensating anion and the release of amine on evacuation suggests that the excess C arises from the presence of free amine.