The crystal structure of a synthetic boehmite sample has been refined to an R of 0.047 in the space group Amam from X-ray powder diffraction data. Inclusion of hydrogen atoms and/or refinement in the space group A21am gave poorer results. Cell dimensions were determined as a = 3.6936 (± 0.0003), b = 12.214 (± 0.001), c = 2.8679 (± 0.0003) Å. All Al-O(OH) distances lie between 1.88 and 1.91 Å. Shared octahedral edges are 2.51–2.52 Å, and unshared octahedral edges are 2.86–2.87 Å, in excellent agreement with those for layered silicates. The O-H … O distance between contiguous octahedral sheets is 2.71 Å. The computed X-ray pattern matches closely with the experimental pattern, indicating the degree to which the crystal structure has been determined.

Cation-exchange capacities determined by methylene blue adsorption (CEC MB) and by the amount of K displaced from a K-saturated clay by NH4 (CEC K//NH4) correlate closely in five soil clays from Pennsylvania, but differ greatly in two soil clays with a large content of amorphous material. CEC MB was found to provide a more precise distinction between montmorillonite and vermiculite than CEC K//NH4. Synthetic aluminosilicate gels showed CEC K//NH4 > CEC Ca/Mg > CEC MB, but no relation to the behavior of the two soil clays with a large content of amorphous material was found.

The electron spin resonance (ESR) spectra of varying quantities of vanadyl ion (VO2+) adsorbed on hydrated hectorite indicated that hydrolysis of VO2+ was promoted at low levels of adsorption. The hydrolyzed product was adsorbed on the clay surfaces, with a ligand environment that was partially aqueous and partially hydroxide in nature. Greater amounts of VO2+ adsorbed on wetted hectorite obscured the ESR spectrum of the strongly adsorbed hydrolysis product with a solutionlike spectrum. An approximately 50% reduction in rotational mobility of VO2+ relative to solution was indicated by the linewidth of this spectrum. Loss in mobility occurred with reduction of the interlamellar spacing until, under strongly dehydrating conditions, the VO(H2O)52+ ions became aligned with the V=O bond axis normal to the plane of the clay platelets.

The electron spin resonance (ESR) technique has been used to study the motion and segregation of an organic spin probe cation (4-amino-2,2,6,6-tetramethylpiperidine N-oxide) on K+-hectorite as a function of average surface concentration. The organic cation tends to concentrate in certain interlayers of aqueous hectorite suspensions even when it occupies a small fraction of the cation-exchange sites. This demixing effect is not evident in methanol-solvated hectorite. The average mobility of the probe increases at higher adsorption levels as a result of the shift of the equilibrium in favor of the solution state. Calculated time-averaged orientations of the probe on the clay surfaces are quite different for methanol- and water-solvated systems, emphasizing the importance of the solvent in modifying the surface-cation interaction.

Aluminum-substituted hematites (Fe2−xAlxO3) were synthesized from Fe-Al coprecipitates at pH 5.5, 7.0, and in 10−1, 10−2, and 10−2 M KOH at 70°C. As little as 1 mole % Al suppressed goethite completely at pH 7 whereas in KOH higher Al concentrations were necessary. Al substitution as determined chemically and by XRD line shift was related to Al addition up to a maximum of 16–17 mole %. The relationship between the crystallographic a0 parameter and Al substitution deviated from the Vegard rule. At low substitution crystallinity of the hematites was improved whereas higher substitution impeded crystal growth in the crystallographic z-direction as indicated by differential XRD line broadening. At still higher Al addition crystal growth was strongly retarded. The initial Al-Fe coprecipitate behaved differently from a mechanical mixture of the respective “hydroxides” and was, therefore, considered an aluminous ferrihydrite.

Acidified suspensions of Al-saturated kaolinite, montmorillonite, mica, illite, and biotite in 10−3 M NaNO3 were potentiometrically titrated with 0.1 N NaOH and 0.1 N HNO3 in succession in a CO2-free nitrogen atmosphere. The resulting curves were compared with those for Al(NO3)3 solutions of similar Al concentration in the supernatant solution and corrected for Al in the entrained solution in the clay.

Base titrations of Al ions adsorbed on all the minerals, except montmorillonite, showed two pH inflections separated by a buffering range. With montmorillonite, there were three pH inflections similar to those for Al in solution. The first inflections in the titration of suspensions occurred at lower pHs and were less pronounced than for Al in solution. These represent the titration of H3O+ sorbed during the pretreatment. The buffering by adsorbed Al ions is also less than that by Al in solution.

The OH− used up by adsorbed Al ions between the first and last inflections was equal to, or slightly greater than, the CEC of the minerals, except for mica where it was more than twice the CEC, because new interlayer surfaces were formed during the acid pretreatment. Acid titration curves of Al ions in the adsorbed and solution states showed hysteresis when related to the base titration curves. The use of two titration speeds (3 and 0.3 pH units/hr) only slightly affected the titration curves of the minerals suggesting that the observed effects were not caused by lack of equilibrium with added base or acid.

Exchange reactions of Na-montmorillonite with zirconyl chloride solutions give products with basal spacings near 18 Å which are stable to 500°C and have surface areas of the order of 300–400 m2/g. The Na ions are exchanged with tetrameric hydroxy cations [Zr4(OH)14•nH2O]2+. The high surface area is attributed to the porosity formed by stable zirconium oxide “pillars” formed by dehydroxylation of the complex cation. The nitrogen adsorption isotherms are of Langmuir type and are consistent with adsorption in interlayer micropores. Reduced-charge montmorillonites, formed by application of the Hofmann-Klemen procedure, give either similar or slightly smaller surface areas.

The conditions under which an exchanger phase will behave as an ideal mixture are established from thermodynamic principles. It is shown that, if a stoichiometric cation-exchange reaction is reversible, the exchanger phase will exhibit ideal behavior if the Vanselow selectivity coefficient is independent of the exchanger composition. This criterion is applied to some recently published data for Na+-trace metal cation exchange on Camp Berteau montmorillonite. An analysis of the data suggests that, so long as the exchange process is reversible, Na+-trace metal cation exchange produces an exchanger phase that behaves as an ideal mixture.

Montmorillonite-aminocaproic acid complexes (monomer complexes) were prepared by the intercalation of 6-aminocaproic acid to various homoionic (Na+, Ca2+, Mg2+, Co2+, and Cu2+) montmorillonites. Infrared spectra of the monomer complexes indicated that the interaction between the exchangeable cations and the 6-aminocaproic acid increased in the following order: Na-, Ca-, and Mg- < Co- < Cu-montmorillonite-aminocaproic acid complex. Montmorillonite-nylon complexes (polymer complexes) were prepared by thermal treatment of the monomer complexes, which was confirmed by X-ray powder diffraction and infrared spectroscopy the results of which indicated the condensation of 6-aminocaproic acid in the interlayer space.

Thermal degradation of montmorillonite-nylon complexes was studied by thermogravimetry. It was found that the thermal stability of the polymer complexes increased in the following order: Cu- < Co- < Na- < Mg- < Ca-montmorillonite-nylon complex.

It was suggested that the difference in thermal stability depended upon the length of the polymer chain which might be influenced by the interaction between the exchangeable cations and the 6-aminocaproic acid. The activation energy for the thermal degradation of each montmorillonite-nylon complex was obtained, and the value for Cu-montmorillonite-nylon complex was smaller than that for the other cation-exchanged montmorillonite-nylon complexes.

Nephelometric (light scattering) methods for the determination of Ca and Ba in the 0–30 ppm range, and their application to the estimation of the cation exchange capacity (±10%) of small (≤30 mg) samples of clay minerals, are described and evaluated.

The diffusion of water in the title intercalate has been measured by quasielastic neutron scattering. The diffusion coefficient (6.1 × 10−7 cm2 s−1 at 23.5°C) is one order less than that found previously for a sodium-exchanged montmorillonite which, however, contained 4 times as much water in the interlamellar space. The activation energy for the motion has been deduced to be 18 kJ mol−1. Also it has been demonstrated that upon the time scale of the neutron scattering events (faster than 10−9 s) the hydroxyl groups of the clay lattice are not in motion.

Adsorption isotherms for water vapor, c-spacing and heat of immersion in water of mixed Na/Ca-montmorillonite were measured at 25°C at various RH. There was good agreement between the calorimetric data, the heat calculated from the isotherms by use of BET equation, and the calculations from the ion-dipole model. It was concluded that the electrostatic forces between the adsorbed cations and the water molecules are the dominant forces in the hydration of the clay. Thus, at low moisture content, only the adsorbed Ca-ions are hydrated. The heat released when Na-platelets condense to form Ca-packets was measured, and it was suggested that this energy term is the driving force for the demixing phenomena.