The thermal transformation of a Brazilian antigorite heated dry from 600° to 1300°C, was studied by high resolution electron microscopy and selected area electron diffraction (SAD). Below 600°C, the antigorite particles did not change morphologically or crystallographically, as evidence by the presence of the superlattice in the SAD patterns and lattice images. At 650°C, traces of antigorite remained, although the superlattice structure had disappeared and the first indications of forsterite formation were observed in the same SAD. Diffraction patterns of the transition phases showed various topotactical relationships between antigorite and forsterite. At 800°C, the crystallization to forsterite was much more pronounced. At 900°C, the individual particles retained their original shapes, but they were actually pseudomorphs, for their SAD patterns showed only forsterite. Between 1000° and 1300°C various topotactical relationships were observed. Although the overall transformation to forsterite appears to be similar for both chrysotile and antigorite, the transformation of antigorite took place at a slightly higher temperature (~50°C) with a larger number of topotactical relationships than for chrysotile. Enstatite was formed at 1300°C, but it was impossible to determine the topotactic relations between enstatite and forsterite, which was possible with chrysotile.

Twenty-nine chlorites, seventeen lithium-free micas, and twenty-two lithium-bearing micas from diverse localities have been studied by X-ray diffraction, microprobe, and optical second harmonic generation (SHG) techniques to determine which are noncentric and the cause of acentricity. Manandonite (B-rich chlorite) and cookeite, both crystallizing in the Ia form, are acentric. Sudoite-IIb gave a questionable SHG signal, possibly indicating acentricity. All other chlorites gave null signals. Bityite, a Li, Be mica similar to margarite, was determined from the positive SHG response to be acentric. It crystallizes in the 2M1 form and, by analogy to margarite, is ordered tetrahedrally in subgroup symmetry, Cc. Masutomilite-1M and “cryophyllite“-1M (a zinnwaldite high in Al and Si, but low in Fe) are acentric and most probably crystallize in space group C2, thus allowing a noncentric octahedral ordering pattern. Lepidolites showed a diversity in SHG response with only a few being acentric; a lepidolite-1M from Mesagrande, California, a lepidolite-3T from Windhuk, South West Africa, and a lepidolite-2M2 from Nagatare, Japan, gave positive SHG responses. The Japanese material is complexly intergrown and twinned, and intergrain reflection or refraction may have produced spurious signals.

Most lithium-free micas showed diversity in SHG response and, although most were non-emitters, clintonite from Amity, New York, showed a positive response, but this sample is twinned and shows stacking disorder. A “manganophyllite”-1M (manganoan phlogopite) from Langban, Sweden, showed a very weak positive response; however, the presence of Mn alone is not suffcient to produce octahedral cation ordering in noncentric subgroup symmetry. Two manganoan phlogopites from Japan were refined in subgroup symmetry, and the higher order and ideal symmetry of C2/m was confirmed.

Smectites exchanged to various degrees with mono- or biprotonated 1,4-diazobicyclo(2,2,2)-octane (Dabco) have a porous structure in which the organic molecule acts as a “pillar.” Less Dabco2+ than Dabco1+ was necessary both to initiate and to complete expansion, whereas for both Dabco1+ and Dabco2+ the threshold for expansion increased with the charge density of the clay. Interstratification of 9.7-Å and 14.5-Å (Dabco1+) or 14.1-Å (Dabco2+) layers was observed before full expansion occurred.

Nitrogen sorption isotherms on partially exchanged Dabco1+- and Dabco2+-clays are of the BET II and Langmuir type respectively, whereas n-butane adsorbed according to BET type II for both cationic forms. The specific surface area was governed by the number of Dabcoz+ pillars, irrespective of the inorganic cation, and increased with Dabcoz+ content even beyond the composition where full expansion was reached and notwithstanding the increasing number of silicate layers in the c direction of the crystal units. This relationship is explained by an enhanced random interleaving of clay platelets in the stacking units containing Dabcoz+.

Mineralogical and 57Fe Mössbauer spectroscopic analyses were made on seven terrae rossae and two terrae fuscae samples of Pliocene to Early Pleistocene age from Slovakia and limestone residues from their parent materials. In most of the samples, no mineral weathering or clay mineral formation could be detected by optical or X-ray powder diffraction investigation, compared with their parent limestone residues; only one terra rossa showed a strong weathering of primary feldspar and phyllosilicates and a high rate of clay formation, especially kaolinite. Mössbauer measurements between 5° and 300°K showed that hematite and goethite are the dominant color pigments in the rubified terrae rossae and their corresponding limestone residues. The mean particle size of hematite and goethite was estimated from Mössbauer effects and X-ray powder diffraction data to be 95 and 250 Å, respectively. Reduced values of the hyperfine fields at 5°K of the soil iron oxides, as compared with those of the pure oxides, indicate a partial substitution of Fe(III) by Al. The hematite content correlates with the Munsell color notation of 5 of the 7 terrae rossae samples and their corresponding limestone residues. All terrae rossae samples showed higher hematite contents than their corresponding limestone residues, indicating that the rubification of such materials is independent of the degree of weathering.

Storage of ferrihydrite in aqueous suspensions at 24°C and pHs between 2.5 and 12 for as long as three years resulted in the formation of goethite and hematite. The proportions and crystallinity of these products varied widely with the pH. Maximum hematite was formed between pH 7 and 8, and maximum goethite at pH 4 and at pH 12. The crystallinity of both products, as indicated by X-ray powder diffraction line broadening and magnetic hyperfine field values and distribution widths, was poorer, the lower the proportion of the corresponding product in the mixture. The existence of two competitive formation processes is suggested: goethite is formed via solution, preferably from monovalent Fe(III) ions [Fe(OH)2+ and Fe(OH)4−], and hematite by internal rearrangement and dehydration within the ferrihydrite aggregates. This concept relates the proportions of goethite and hematite to the activity of the Fe(III) ion species in solution, and implies that conditions favorable for the formation of goethite are unfavorable for that of hematite and vice versa.

57Fe Mössbauer spectra of a cleaned Weipa, Australia, kaolin showed that a considerable fraction of the structural iron exhibits paramagnetic relaxation between 4°K and 300°K, the first time that this has been observed for ferric ions in a mineral. The sample also contained a very fine particle ferric oxide/oxyhydroxide phase, probably of secondary origin.

57Fe Mössbauer spectra have been used to interpret the effects of different cleaning processes on the iron mineralogy of a Weipa, Australia, kaolin. A magnetically separated fraction contained 28% of its iron as hematite likely of secondary origin. An initial centrifugal size separation was shown to give an improved final product, and oxalic acid was found to be more efficient at removing Fe from the kaolinite surface than dithionite bleach. The Mössbauer spectra clearly show that beneficiation steps which give a substantial increase in kaolin brightness result in only minor changes in the clay iron mineralogy. Similar results were also obtained for two commercially available kaolins.

A hydrated alumino-phosphate mineral was identified in thin, kaolinitic clay beds of the Cretaceous Dakota Group and the overlying Mowry Shale in the Dakota hogback west of Denver, Colorado. It occurs as 1–3-μm size euhedral crystals and makes up as much as 15% of the rock. Sr is by far the dominent divalent cation present, ranging from 9.4 to 13.1%, confirming the X-ray powder diffraction identification of this mineral as goyazite, the Sr member of the plumbogummite group. The characteristic pseudo-cubic, rhombohedral morphology of this mineral is plainly visible in scanning electron micrographs. On the basis of its euhedral morphology and its occurrence in volcanic ash-derived kaolin beds, the goyazite probably formed during early diagenesis, before or during the alteration of the ash, and before much compaction of the beds.

Ion-exchange isotherms between hydrotalcite-like compounds (HT) of the NO3-, Cl-, and SO4- forms and F−, Cl− Br−, I−, OH−, SO42−, CO32−, and Naphthol Yellow S (NYS2−) ions were determined, and the spacing and the width of the 003 reflection were measured as a function of HT composition. The ion-exchange equilibrium constant for HTs of monovalent anions are in the sequence OH− > F− > Cl− > Br− > NO3− > I−, those for divalent anions are in the sequence CO32− > NYS2− > SO42−. The ion-exchange equilibrium constants tend to increase as the diameters of the anions decrease, and the crystallite size in the 001 direction tends to increase with anions having higher selectivity. The OH-form of HT has the smallest basal spacing and the largest crystallite size in the 001 direction.