On NH4- as well as on (C2H5)3NH-montmorillonite EDA was adsorbed in protonated form. The extent of protonation depended on the relative basicities and concentrations of the interacting compounds. In the systems exposed to EDA vapor a proton transfer process took place. A similar mechanism, involving probably a water molecule which remained associated with the EDAH+ ion, occurred on air-drying (C2H5)3NH-montmorillonite treated with aqueous EDA, whereas no adsorption was observed when the suspension was washed. On the contrary EDA added, in quantities not exceeding the CEC, to a suspension of NH4-montmorillonite was adsorbed almost exclusively as EDAH22+ ion. This is explained in terms of ion-exchange between NH4+ and EDAH+ present in aqueous medium and protonation of the second amine function through the dissociation of water molecules near the clay surface.

Hydrogen-bonding between protonated and neutral EDA was observed when the extent of adsorption was higher than the extent of protonation.

Bulk (lump) densities of 31 kaolins were measured on the clay in the natural or raw state after drying at 100°C and after firing to 1510°C (2700°F). The kaolins were selected from such diverse origins as surface-weathered and sedimentary accumulations, hydrothermally altered bodies and flintclay deposits. The sedimentary group ranged in density from 0·82 to 1·85 in the dried raw clay, and 1·93 to 2·63 when fired. The hydrothermally altered clays ranged from 1·83 to 2·50 in the dried raw state, and 2·02 to 2·66 when fired. Flint clays ranged from 2·20 to 2·60 in the dried raw state (a “toasted clay” from Russia, 1.75), and 1·99 to 2·70 when fired. The effect of the genetic process on bulk density values is discussed and related.

The t-plot method has been applied to the results of nitrogen adsorption at 76°K on sepiolite first heated in vacuo at various temperatures. Heating sepiolite samples in vacuo at 427°K results in a large decrease in surface area compared with samples outgassed at 373°K. A change in structure and a consequent collapse of micropores is postulated. However, the t-plots indicate that some microporosity remains. Outgassing at 623°K appears to destroy completely the micropores.

Determination of the mineralogical composition of six highly weathered soils of the Central Plateau of Brazil showed that the sand content (predominantly quartz) was not related to the relative amounts of gibbsite and kaolinite in the clay (< µm) fractions. The latter is in agreement with kinetic considerations of the involved mineral species, but in disagreement with thermodynamic considerations. However, that dissolution of quartz has been operative in these soils is indicated by an excellent relationship (r2 = 0·96) between the amount of sand-size quartz and the reactive SiO2 content of the clay fractions.

Hexafluorotitanic acid (H2TiF6) selectively dissolves kaolinite and most other phyllosilicate minerals of soils and sediments, concentrating free crystalline (Ti,Fe)O2 minerals (partially substituted anatase and rutile) in the residue. A series of H2TiF6 reagents was standardized by analysis of the Ti content and by tests with pure anatase and commercial kaolinites. The Ti in the H2TiF6 solution selected (made from 49% HF + reagent TiO2) was 16·5% by weight as analyzed by the Tiron method. Treatment of pure anatase with the reagent H2TiF6 resulted in a 98% by weight recovery of TiO2 in the residue. The fraction of TiO2 recovered in the residue of commercial Georgia kaolinites was 88–101% after treatment with the selected H2TiF6 reagent. Isolates from nine Georgia kaolinite samples with varying amounts of TiO2 and Fe2O3 were examined by X-ray powder diffraction, scanning electron microscopy and elemental analysis. The main constituent of the (Ti,Fe)O2 isolates was anatase for all samples, with minor amounts of coarser rutile and mica from coarser kaolinite. The anatase and rutile isolates contained 74–93% (Ti,Fe)O2 with 0·5–3·1% Fe. The other constituents of the isolates were muscovite of mica (0·3–7%), quartz (0–9%) and amorphous relics of vermiculite and/or kaolinite (6–19%). Rutile, muscovite and quartz appear to be detrital but the anatase and relics are probably authigenic. Fine anatase appears to stick on the muscovite flakes as revealed by scanning electron microscopy and heavy liquid data for separation of these two minerals. The (Ti,Fe)O2 isolates from kaolinites which passed with the first magnetic concentrate of anatase were coarse, on the order of a few microns dia., as revealed by the scanning electron microscopy. Those passed with subsequent extensive magnetic concentrates from the same samples were finer. The anatase isolated from kaolinite purified by removal of as much of the impurities as possible by magnetic means was extremely fine, most of the particles being on the order of 0·1 µm dia. More than one third of the total Fe2O3 in kaolinites magnetically separated in the first pass was extracted by the citrate-bicarbonate-dithionite treatment after hot NaOH dissolution of 52–74% of the kaolinite, showing that the Fe2O3 had been mainly associated within the kaolinite. Only 2–6% of the total Fe2O3 was extracted from magnetically purified kaolinite after 40–50% of this kaolinite had been dissolved, indicating that most of the Fe is in the anatase and rutile fraction.

Accelerated soil erosion from construction sites and the resulting increase in downstream sediment load constitute a significant environmental problem. Laboratory studies indicate that small percentages of hydrated lime or of Portland cement will stabilize clay soils against rainstorm erosion by preventing particle detachment. Coordinated measurements of the size distribution of water-stable aggregates, of pore size distribution by mercury porosimetry and of microstructure by scanning electron microscopy and energy dispersive X-ray spectrometry were used to clarify aspects of the mechanisms responsible for the development of erosion resistance. Attainment of such resistance was marked by aggregation of a significant part of the clay into water stable aggregations of the order of several mm in size and of minimal change in porosity and pore size distribution on exposure to the test rainstorms. At least some of the clay particles in the aggregations appeared to be partly converted to calcium-bearing reaction products and formation of the “reticulated network” variety of calcium silicate hydrate gel linking adjacent particles was demonstrated.

Fibrous sepiolite crystals derive much of their commercial value from their molecular size channels and grooves. The crystals fold upon drying and these channels and grooves are lost. A model for the folding and unfolding of the crystals is presented. Extensive i.r., X-ray and thermogravimetric evidence shows that folding occurs when approximately half of the water of hydration, which is coordinated to the edge magnesium atoms inside of the channels, is removed. This occurs near 175°C under vacuum and near 300°C in air. When the crystals fold, all remaining water molecules enter a new environment, that of the hexagonal holes of the neighboring silica surface. A true anhydride is produced at about 500°C under vacuum when the final water is lost, but this final dehydration produces no important structural change. Rehydration of the anhydride to the normal hydrated sepiolite does not occur at room temperatures in 100% r.h. However, above, 60°C rehydration does occur.

Based on X-ray powder diffraction measurements of swelling, thermodynamic analysis of adsorption and kinetics, a mechanism of interaction between xylene isomers and two organoclay complexes was derived. The work is intended to resolve the factors which make possible the chromatographic separation of the xylene isomers with organoclays. Significant differences between the behavior of fresh organoclays and xylene vapor-conditioned organoclays were noted. Only small differences were apparent between the montmorillonite and the hectorite organoclays. Force constants, enthalpy changes, entropy changes, free energy changes and two specific rate constants were derived from the information obtained from this study.

The reaction products obtained when montmorillonites react with potassium halide at elevated temperatures, which were described in a previous publication, are further characterized. On the basis of their X-ray powder diffraction patterns, i.r. spectra, CEC and chemical composition they could be regarded as montmorillonite-illite interstratifications. Changes in morphology of various montmorillonites heated with and without K halide are related to the size, charge and position of interlayer cations. Scanning electron-micrographs of samples heated with KBr resemble those of well-crystallized illite. It is speculated that reactions of clay minerals with halides or other proton acceptors may account for some diagenetic processes in nature, e.g. the conversion of montmorillonite to illite on deep burial.

This work describes the separation of alunite from natural alunitic kaolins by applying a selective flocculation procedure. In order to determine the most efficient separating procedure preliminary experiments were performed with artificial mixtures of alunite and kaolin. The same procedure was then applied to natural alunitic kaolin which enabled the preparation of kaolin of considerable purity.