New information is presented relating to the hydrothermal stability, lattice parameters, and adsorptive, electrical, and catalytic properties of synthetic and natural faujasite. Present concepts concerning the nature and relationship of synthetic and natural faujasite are restated to be consistent with the experimental evidence and the developed physical model. The major structural and physicochemical properties reflect the close similarities and smooth gradations expected of substitutional members of a continuous series. The existing division of the range (2–6) of SiO2/Al2O3 mole ratios (S/A) at 3 into two compositional subranges is shown to be unjustifiable and rather misleading. Individual compositions from these two subranges do not represent distinctly different zeolite species; instead, it is demonstrated that they are members of a continuous series with smoothly changing properties over the studied range of SiO2/Al3O3. Some of the properties of the natural mineral faujasite are found to be very similar to those of the synthetic analogs with the same SiO2/Al2O3 mole ratio.

Finally, a plea is made for a uniform nomenclature which will serve to identify specific (single) compositions (instead of ranges of compositions); reflect the continuity, close similarities and interrelationships in their main structural and physicochemical properties; and also identify the characteristics of the faujasite group.

A theory for the quantitative analysis of multicomponent mineral systems by means of X-ray diffraction is presented. A linear interaction between mineral pairs is postulated. The theory is verified experimentally for bicomponent and tricomponent systems using a variety of sample preparation techniques including random powder mounts, suspensions sedimented onto glass slides, and pressed powder pellets. The minerals studied include quartz, fluorite, kaolinite, glauconite, illite, and montmorillonite.

The determination of the linear interaction factors for mineral pairs is treated theoretically and experimentally. Emphasis is placed upon techniques that are applicable to naturally occurring mineral systems. Four approaches are presented for determining linear interaction coefficients for various types of such mineral systems. These approaches are applied to the experimental data and the results are compared. Results accurate within 2 per cent are commonly obtained.

Experimental techniques are discussed and a qualitative and quantitative error analysis is presented. It is shown that the indicated quantities present may not be particularly sensitive to the value of the linear interaction coefficient.

The migration of small cations into the empty octahedral sites of dioctahedral clays allows one to study the local effects in the trioctahedral structure and the consequences of the exchange capacity decrease on the solvation properties. The results concern essentially the montmorillonite saturated by lithium. Computations based on a point charge model shows the necessity for the OH groups to undergo a reorientation when the lithium ions are within the octahedral sites. This change of orientation was studied by i.r. spectroscopy which permits one to estimate the amounts of lithium present in the structure. By analogy with i.r. results obtained for the Li, Mg, Ca and K montmorillonites, one can say that the non-exchangeable lithium which is not within the octahedral sites must be in the bottom of the hexagonal cavities. Moreover, it is shown that the solvation properties of the clay depend on the number of exchangeable cations and on the nature of the solvent. The clay does not swell with water when the amount of exchangeable cation is lower than 50 per cent of the exchange capacity. This limit is 30 per cent with glycerol, and 20 per cent with ethylene glycol.

Under appropriate conditions, both surface areas and cation exchange capacities of clay minerals can be measured by absorption of methylene blue from aqueous solutions. The method has been applied to two kaolinites, one illite, and one montmorillonite, all initially saturated with Na+ ions. For Na-montmorillonite, the total area, internal plus external, is measured. For Ca-montmorillonite, entry of methylene blue molecules appears to be restricted by the much smaller expansion of the Ca- clay in water. X-ray diffraction data clarify the absorption behavior in Na- and Ca-montmorillonite, and in particular it is shown that two orientations of the methylene blue molecules are involved.

Scanning electron microscope observation of endellite from Bedford, Indiana, discloses the existence of globular clusters of quasi-tubular endellite particles radiating from common centers. Individual clusters are of the order of 10 μ in overall diameter. The individual quasi-tubular particles are irregularly flattened in cross section, and some may be plugged at the ends. Conventional oven drying at 105°C results in partial unrolling and incomplete flattening of the quasi-tubular particles of some of the clusters. The globular cluster microstructure is taken to represent the result of in-situ crystallization from solution. If this is so, these hollow tubes cannot have arisen by the mechanism of repeated extrusion of concentric zonal crystallites as postulated by Chukhrov and Zvyagin.

The petrography of shale partings in carbonate rocks from eleven cores in the Illinois (Jeffersonville Formation) and Michigan Basins (Detroit River Formation) of Indiana indicates the presence of a K-bentonite which is interpreted as the Tioga Bentonite, an important stratigraphic marker in the middle Devonian rocks throughout the central and eastern United States. The clay mineral composition of the Tioga Bentonite of Indiana is interstratified illite and smectite, usually with admixed kaolinite. This composition stands in striking contrast to the simple illite suite without kaolinite in the normal terrigenous shale partings in the Devonian rocks of Indiana. Euhedral sanidine, high temperature albite, zircon, apatite, and the angularity of quartz grains found associated only with the interstratified clay mineral suite support the volcanic origin of these clay partings.

Bound water of sepiolite dehydrates in two steps in the temperature range of 250-650°C, as shown in the TG-curve. These steps are described here as steps II and III. At step II, half of the bound water is removed; other half at step III. From step II to III, discontinuous changes are confirmed in such properties as activation energy of dehydration, a-dimension, axial ratio, and intensities and spacings of X-ray powder reflections. A structural state at step II may be recognized as a distinct phase in the dehydration process.

Al-substituted goethites were prepared by rapid oxidation of mixed FeCl2-AlCl3 solutions at pH 6.8 in the presence of CO2 at 25°C. A combination of Al substitution and adsorption of CO2 reduced crystal size (except for an increase at small additions of Al) and produced unusual thin, porous particles. Product goethites had surface areas up to 283 m2/g and unit-cell expansions induced by hydration. Substitution of Al for Fe reduced the 111 spacing and increased infrared OH-bending vibrational frequencies. Al substitution split the goethite dehydroxylation endotherm during differential thermal analysis into a doublet and increased the temperature of all reactions. Both cold and hot alkali solutions dissolved Al from the goethite structure.

After drying the product in vacuo at 110°C. X-ray powder diffraction data indicated minimal deviation from Vegard's law for the goethite-diaspore solid solution up to about 30 mole % Al substitution. Goethite prepared in the presence of 40 mole % Al had a 111 spacing of 2.403 Å corresponding to 36 mole % structural Al if Vegard's law was obeyed. Rapid oxidation of mixed FeCl2-AlCl3 solutions appears to be conducive to a higher degree of Al substitution in goethite than alkaline aging of hydroxy-Fe(III)-Al coprecipitates.

Although the specific outcrop from which the original kaolin at Kauling (Gaoling) Mine, China, was collected cannot now be relocated, samples were collected and studied from the mine tunnel, country rock, and pegmatite which constitute the sources of kaolin in this region. The kaolin is a residual product of weathering. Where the parent rock was a granite the clay is a mixture of platy and elongate kaolin-group minerals, whereas from the pegmatite portion of the parent rock it is halloysite(10Â) with elongate morphology. These mineral identifications are based on X-ray powder diffractograms, scanning electron micrographs, differential thermograms, and an infrared spectrum hitherto not documented for material from this area.

Although the Kauling locality is the region for which kaolin is named, the mineral kaolinite is a defined species without a specific type locality. The 11th century Chinese locality was not mentioned in the two classic research papers defining kaolinite. The data on the Chinese kaolin, therefore, cannot be used directly to provide criteria for sharply differentiating the otherwise vague boundary between the minerals kaolinite and halloysite(7Å). Pertinent questions on these kaolin-group mineral relationships are brought into clearer focus.

The cation exchange process between tris(ethylenediamine)cobalt(III) and Na+ on mont-morillonite was studied by atomic absorption spectrophotometry, X-ray diffraction, differential thermal analysis, and nitrogen sorption at 78°K. The exchange of Co(en)33+ for Na+ was found to be extremely favorable, with a tendency toward segregation of the two kinds of cations in the mixed clays studied. Small amounts of Co(en)3+3 were found to lower the nitrogen sorption capacity of Na+ mont-morillonite while clays with high Co(en)3+3 content had greatly enhanced sorption. An explanation is offered in terms of a dual role of the Co(en)3+3 in determining the kind and amount of nitrogen sorption in the exchanged montmorillonite.

The ESR spin probe, TEMPAMINE+, was used to study the interlamellar behavior of adsorbed organic cations on hectorites solvated with water, ethanol, and water-ethanol mixtures, and saturated with several monovalent and divalent metallic cations. The mobility and orientation of the probe was affected greatly by the solvent, and to a lesser extent by the predominant exchangeable cation on the silicate surface. Most of the effects could be interpreted in terms of the basal spacings of the hectorite. In all instances, the adsorbed probe was much less mobile than in solution despite the different interlamellar volumes available for molecular motion.

A method for the determination of the cations of Na, K, Mg and Ca adsorbed on clay minerals mixed with CaCO3 and MgCO3 is described. An ethanolic solution of LiCl-CsCl is used to displace the exchangeable cations. Blank determinations performed using either a second ethanolic leach or a second LiCl-CsCl leach, are used to correct for carbonate dissolution. Details of the methods development are given.

The method has been tested using mixtures of homoionic forms (Na, K, Mg, Ca) of smectite and kaolinite with either CaCO3 or MgCO3. The smectite and kaolinite were found to have total CECs (with standard deviations) of 765 (4.4) and 39.8 (0.52) mequiv kg−1, respectively. The amount of cation exchanged was found to vary directly with the proportion of clay mineral in the mixture; regression coefficients consistently greater than 0.997 were obtained.

Other tests with smectite-CaCO3 mixtures in sea-waters of various salinity vindicated the use of the method with heteroionic forms of smectite. These tests also suggest that the phenomenon of fixation observed in most other studies of clay minerals in estuarine conditions might be redundant. It is contended that there is an urgent need for this suggestion to be tested.

X-ray diffraction patterns for mixed-layer kaolinite-glycerine-saturated montmorillonite were calculated, taking into account the differences of scattering power of kaolinite and montmorillonite layers. The data were compared with the experimental results for two kaolinite-montmorillonite mixed-layer minerals. The probability parameters and the total number of layers in crystals were established.