Mössbauer and i.r. spectra of a series of nontronites show that Fe3+ and Al3+ are distributed between tetrahedral and octahedral sites. The Mössbauer results have reaffirmed the occupation by Fe3+ of octahedral sites at which these ions are coordinated to pairs of OH groups in both cis and trans configurations. The distribution of Fe3+ between these two sites varies considerably but in all of the nontronites some Fe3+ occurs in the trans site in contrast to the all cis occupancy of the centro-symmetric structure proposed by Mering and Oberlin (1967). In one of the nontronites the distribution of Fe3+ between these two sites approaches that in the ideal non-centrosymmetric structure proposed for montmorillonite.

Complexes of 1,4-diazabicyclo [2.2.2] octane (triethylene diamine) with smectite and vermiculite were made for the purpose of exposing the internal surfaces of the clays for adsorption of gases and possible catalytic activity. When the diprotonated form of the amine saturated the exchange sites, internal surfaces of the clays were found to be available to nitrogen, ethane, and 2,4-dimethyl pentane. Proton lability in the smectites was studied with NH3, D2O, and C6D6 experiments. Catalytic function was demonstrated in the conversion of acetonitrile to acetamide in the smectite.

A new magnetic separation technique combines high magnetic fields, extreme gradients, and controlled retention time to separate feebly magnetic mineral contaminants from kaolin.

Extraction of pyrite, siderite, hematite, iron stained anatase, and mica by magnetic filtration of kaolin significantly upgrades brightness of many sub-marginal deposits and reduces consumption of reagents in processing.

A method using the bombardment of samples with protons and other positive ions of energy in the MeV range is described: the prompt atomic (γ-rays) and nuclear (γ-rays and charged particles) events generated during the bombardment, are detected with energy sensitive solid state detectors: cooled Ge(Li) for γ-rays and hard γ-rays, cooled Si(Li) detectors for soft γ-rays (3–20 keV) and Si-barrier detectors for charged particles. These 3 types of detectors can be simultaneously used for multipurpose experiments. These techniques are particularly useful for simultaneous detection of all the elements of interest in the sample. Comparisons are made with other microtechniques. Analyses of Li, Na, K, Ca, Rb, Cs and Cl exchanged in appropriate chloride solutions have been achieved for several clays (Geisenheim, Isola di Ponza, Layton). A new phenomenon relative to the anion contribution in cation exchangers is observed. A method of profile analysis of Na by resonant nuclear reactions is discussed.

Well developed smectite “crystals” up to 10 mm long, which probably are pseudomorphic after titaniferous hornblende phenocrysts, are present in a weathered dike in a Melbourne clay pit. The pseudomorphs contain 77 per cent of montmorillonite as determined by X-ray powder diffraction, differential thermal analysis, thermo-gravimetric and chemical analysis. The pseudo-hexagonal shape of the pseuodomorphs probably reflects the original crystal habit of the hornblende. The mechanism of alteration of an amphibole to a smectite is discussed.

For very small crystallites diffraction theory shows not only broadening of powder lines, but generally also a shift of the line position, depending on the change of the structure factor over the range of broadening. For decreasing thickness of kaolinite crystals (less than 50 layers) an increasing shift of reflections is found: the lines (001), (002), (004) and (006) are shifted to apparently larger spacings, the lines (003) and (005) to smaller spacings, resulting in a nonintegral series. Presuming a known crystallite size, tables are given for evaluating true spacings from measured values of 2θ.

Electron spin resonance (ESR) spectroscopy is used to investigate the nature of exchange sites on kaolinite. ESR spectra of exchangeable Cu2+ and Mn2+ on kaolinite indicate that divalent exchange ions are about 11–12Å apart on kaolinite surfaces and that planar Cu (H2O)42+ ions are oriented parallel to the surfaces. Solution-like spectra for exchangeable Cu2+ and Mn2+ are observed at high relative humidities, suggesting a high degree of mobility of exchange cations on kaolinite surfaces. The evidence seems to eliminate edge sites as being active in cation exchange at least in the acidic range of pH. Similar conclusions are derived from ESR studies of Cu2+-saturated talc and pyrophyllite. It is proposed that most exchange sites arise from ionic substitutions or mineral impurities in phyllosilicates.

A steady state reaction of apparent equilibrium of K mica + Ca2+ ⇄ Ca vermiculite + K+ was indicated by prolonged dissolution extractions from Blount soil clay (from northern Indiana) abundant in dioctahedral mica and vermiculite, with log Keq = 2.92 for the reaction when extrapolated to infinite time. From this and published free energies of formation of mica and kaolinite, a mineral phase stability diagram depicting the phase joins of Ca vermiculite, muscovite, and kaolinite was constructed with the solute activity functions pH-pK+, 2pH-pCa2+, and pSi(OH)4. These solute functions for 14-day reactions of calcareous (and dolomitic), poorly drained Harps soil (from central Iowa) fell near the calcite-dolomite-CO2-H2O phase join, suggesting equilibrium. These functions for Harps soil and the control minerals muscovite, biotite, and (or) vermiculite plus calcite were plotted on the mica-vermiculite stability diagram for various CO2 partial pressures. The points fell on the vermiculite-stable side of the mica-vermiculite plane at CO2 partial pressures of 0.15 and 0.20 atm (similar to soil air that would exist under frozen soil during winter and early spring; 2pH-pCa2+ ≃ 10.3). They fell on the muscovite-stable side of the muscovite-vermiculite plane at CO2 partial pressures of 0.0001 and 0.001 atm (similar to soil air under natural summer conditions; 2pH-pCa2+, 13.6 and 12.6, respectively) and therefore K+ (and 137Cs+ in rainfall) would be expected to be fixed.

The 2pH-pMg2+ values determined for Harps soil at the various CO2 partial pressures plotted either in the Mg montmorillonite stability field or on the Mg-montmorillonite-kaolinite phase join, in concordance with the abundance of montmorillonite and some kaolinite in the medium and fine clay fractions. The solute values for the nearby Clarion soil (upland, noncalcareous) plotted on the montmorillonite-kaolinite join, or with higher CO2 partial pressure, in the kaolinite stability area. The Gibbs free energy of formation (△Gf0) for a dioctahedral Ca vermiculite of −1303.7 kcal per 010 was determined from the Keq. The solute functions for the Blount soil showed kaolinite to be the thermodynamically stable phase with respect to dioctahedral mica and (or) vermiculite. The 14-day solute values for the Harps and upland Clarion soils were also on the kaolinite stability side of the kaolinite-vermiculite join. The kinetics of kaolinite formation in the upper midwestern U.S.A. are apparently slow on a scale of ~ 104 years.