The adsorption of n-octane and water vapor on natural kaolinite was measured. From adsorption isotherms film pressures were determined which were then used to calculate the dispersion and nondispersion components of the kaolinite surface free energy. In addition, thermodesorption of water from the kaolinite surface was determined. These results suggest that physically adsorbed water remained on the kaolinite surface, even at temperatures as great as 125°C. Therefore, experimentally determined dispersion and nondispersion components appear to relate to the surface precovered with a film of water. These values are: γSf(w)d = 34.4 mJ/m2 for dispersion interactions and γSf(w)n = 60.2 mJ/m2 for nondispersion interactions. Assuming a kaolinite surface precovered with a film of water, which decreased the free energy by the work of spreading, the following components of the energy for the bare surface were calculated: γSd = 67.6 mJ/m2 and γSn = 103.4 mJ/m2, for dispersion and nondispersion components, respectively.

The heavy atom content and distribution in chlorite were estimated using the relative intensities of basal X-ray powder diffraction (XRD) peaks. For these peaks to be meaningful, however, corrections had to be made for the effects of sample thickness, sample length, and preferred orientation of the mineral grains, all of which are 2θ dependent. The effects of sample thickness were corrected for by a simple formula. The effects of sample length were accounted for by using rectangular samples and by ensuring that the sample intersected the X-ray beam through the range of diffraction angles of interest. Preferred orientation of mineral grains were either measured directly or estimated. Estimated values were quicker and easier to obtain and were within 5% of measured values. A comparison of the compositional parameters of chlorite estimated before correcting for these sample effects with those estimated after the corrections had been applied indicate that the uncorrected values differed from the corrected values by as much as 55% of the latter values. Mounts of a single sample prepared by different filter-membrane peel and porous-plate techniques yielded widely different compositions until the measurements were corrected for sample effects. Analyses in triplicate indicated that the XRD intensity ratio 003/001 is preferred for calculating heavy atom distributions and abundances in chlorite because of the relative strength of the 001 peak.

The <0.1-μm size fraction of an Ordovician K-bentonite from northern Kentucky was characterized by X-ray powder diffraction (XRD). Using A.I.P.E. A. criteria for interstratification nomenclature and Reynolds’ computer algorithm the dominant clay mineral proved to be an R2 ordered illite/smectite. The best fit of observed and calculated XRD tracings was obtained using 12 > N > 5, where N is the number of layers within a diffracting domain.

Sections of the K-bentonite were prepared by ion-beam milling and examined in an analytical transmission electron microscope (ATEM). One-dimensional lattice images observed parallel to the a-b plane showed subparallel packets, about 50–100 Å thick, each of which consisted of about 10-Â thick unit layers. Somewhat thicker unit layers (as much as 14.5 Å) were also seen. The former are presumed to be illite, whereas the latter may be partially collapsed smectite. Selected-area electron diffraction patterns suggested simultaneous diffraction from several packets, each containing at least five layers. Both h0l and 0kl spacings were usually present, indicating that the stacking of the subparallel packets was random. Quantitative analysis by AEM and electron microprobe show the clay to be low in tetrahedral Al but high in octahedral Mg, the latter presumably contributing largely to the interlayer charge responsible for K fixation. The TEM data are broadly reconcilable with the accepted XRD interpretation of a two-component, mixed-layer clay. Alternatively, the TEM images may be interpreted as a single phase having numerous packet boundaries, the latter being responsible for swelling behavior. These two interpretations will not be fully reconciled until greater analytical precision and resolution permit individual packets to be studied. This work suggests that mineral definitions based purely on XRD interpretations may have to be reconsidered as more electron microscope data become available.

Phenamiphos interacted with homoionic montmorillonites of Ca2+, Mn2+, Co2+, and Ni2+ to form interlayer complexes having basal spacings of about 16.5 Å. In the infrared spectra, the ν-PO bands were displaced towards lower frequencies suggesting that this group interacted with the exchange cations. Moreover, a small shoulder at 1600 cm−1 indicated the partial protonation of the phenamiphos. After heating the complexes to 110°, 160°, and 200°C, however, the bands corresponding to δ-NH2+ and ν-NH intensified because of increased protonation, whereas the ν-PO bands had the same intensity as in pure phenamiphos. The fundamental implication of these observations is that phenamiphos interacts with exchange cations through molecules of coordinated water, possibly by means of the P=O group.

A series of synthetic goethites containing varying amounts of Si and P dopants were characterized by X-ray powder diffraction, electron diffraction, microbeam electron diffraction, and Mössbauer spectroscopy. Very low level incorporation produced materials having structural and spectral properties similar to those of poorly crystalline synthetic or natural goethite. At higher incorporation levels, mixtures of noncrystalline materials were obtained which exhibited Mössbauer spectra typical of noncrystalline materials mixed with a superparamagnetic component. Microbeam electron diffraction indicated that these mixtures contained poorly crystalline goethite, poorly crystalline ferrihydrite, and a noncrystalline component. If the material was prepared with no aging of the alkaline Fe3+ solution before the addition of Na2HPO4 or Na2SiO3, materials were obtained containing little if any superparamagnetic component. If the alkaline Fe3+ solution was aged for 48 hr before the addition, goethite nuclei formed and apparently promoted the precipitation of a superparamagnetic phase. The Mössbauer-effect hyperfme parameters and the saturation internal-hyperfine field obtained at 4.2 K were typical of those of goethite; however, the Mössbauer spectra indicated that the ordering temperature, as reflected in the relaxation rate and/or the blocking temperature, decreased with increasing incorporation of Si and P. The complete loss of crystallinity indicates that Si and P did not substitute for Fe, but rather adsorbed on crystal-growth sites, thereby preventing uniform crystal growth.

This paper presents thermal conductivity data for highly compacted Ca-smectite, Na-smectite, illite, and palygorskite as a function of density (i.e., compaction pressure), water content, and temperature. All the clays behaved similarly: thermal conductivity increased directly with density and water content. Specifically, the thermal conductivity increased from 0.63 to 1.32 W/m·K as the dry density increased from 1.2 to 1.8 g/cm3 (for a water content of 17%). An increase of water content from 6 to 17% resulted in an increase in thermal conductivity from 0.63 to 1.22 W/m·K (for a dry density of 1.6 g/cm3). Differences from one clay to the other were less important. The thermal conductivity (in W/m·K) for constant conditions of 12% of water and a dry density of 1.6 g/cm3 were: Ca-smectite 0.80, Na-smectite 0.74, palygorskite 0.71, and illite 0.69. Heating to 188°C produced only a 10% increase in the thermal conductivity.

The infrared absorption spectra of a palygorskite sample from Cáceres, Spain, showed two previously unreported bands in the OH-stretching region at 3420–3440 and 3220–3230 cm−1 after evacuation at 90°–230°C. These bands, which reached maximum intensity after the sample was heated at 150°C, were assigned to OH in the

$$\begin{array}{*{20}{c}} H \\: \\ {Si - O - Si\,and\,} \\ \end{array}\begin{array}{*{20}{c}} H \\: \\ {Si - O - A1} \\ \end{array}$$

An X-ray thermodifferential powder diffraction method for the quantitative determination of goethite and hematite in lateritic bauxites has been developed and consists of measuring the integrated intensities of the 012 line of hematite before and after heating the sample at 900°C and of correcting the obtained values by the X-ray mass absorption coefficient of either the untreated or heated matrix. From the corrected line intensities and the chemical analyses, the amounts of iron to be allocated to goethite and hematite in the untreated samples can be estimated. The actual content of goethite and hematite in a sample is calculated by taking into account the degree of Al substitution in each of these minerals. The method was tested on artificial mixtures of goethite and hematite and subsequently used to analyze 98 auger drill samples from lateritic bauxites of Guinea Bissau. The estimated precision of the determination of goethite and hematite content was ±2% (absolute). The method can not be applied to samples containing < 10% Fe2O3 (on a whole weight basis) unless preconcentration is carried out.

The influence of manganese oxide minerals (cryptomelane, hausmannite, and pyrolusite) on the formation of iron oxides was studied in the FeCl2-NH4OH system at different Mn/Fe molar ratios (0, 0.01, 0.1, and 1.0) and pHs (3.0, 4.0, 5.0, and 6.0) by X-ray powder diffraction, infrared absorption, transmission electron microscopic, and chemical analyses. In the absence of Mn minerals, lepidocrocite (γ-FeOOH) precipitated at pHs 5.0 and 6.0; however, no precipitate formed at lower pHs. All the Mn minerals studied promoted the precipitation of iron oxides and oxyhydroxides. In the presence of Mn oxides, Fe2+ was oxidized to Fe3+, which hydrolyzed and precipitated as noncrystalline and/or different crystalline iron oxides and oxyhydroxides, depending on the nature of the Mn oxides present in the system. Simultaneously, Mn2+ was detected in solution after the reaction by electron spin resonance spectroscopy. The presence of cryptomelane and hausmannite resulted in the formation of åkaganeite (β-FeOOH) and magnetite (Fe3O4), respectively. Thus, the effect of Mn oxides on the formation of Fe oxide minerals in the weathering zone merits attention.

The sintering of montmorillonites pillared by hydroxy-Al species was investigated by several techniques. The change of the microporosity of the pillared interlayer clay with temperature shows that sintering was mainly due to the loss of microporosity. On calcination of the parent clay at 760°C, the X-ray powder diffraction pattern did not change; the 060 line shifted only slightly from 8.988 to 9.017 Å. The infrared (IR) spectrum suggested some dehydroxylation, but the structure appears to have been preserved. On calcination of the pillared clay at >700°C, the intensity of the 001 line decreased steadily, the 060 line broadened, and the b parameter decreased slightly from 8.988 to 8.928 Å. Fe3+ ions apparently occupied only one site after calcination at 300°C and two sites after calcination at 700°C. Smaller isomer shifts and higher quadrupole splittings in the Mössbauer spectra suggest that calcination produced more covalent bonding of Fe3+ and a highly distorted structure. The IR spectrum was significantly modified by calcination of the sample, and the 935- and 1125-cm−1 bands disappeared and the 1035-cm−1 band broadened. These results suggest that at <700°C the pillars sintered and that the clay progressively decomposed at >750°C. The pillaring-induced decrease of thermal stability of the clay was likely due to the introduction of protons during the first step of the preparation. The thermal stability of these Al-pillared interlayer complexes is comparable to that reported for hydroxy-silicoaluminum montmorillonites and fluorhectorites.

Iron impurities in the Hohen Hagen nontronite (NG-1) were identified as maghemite and goethite. The phase identified as maghemite was magnetically ordered at both room temperature and 87 K, with hyperfine magnetic fields of 48.6 and 50.7 tesla, respectively. Due to the magnetic properties of this phase, it was easily separated from aqueous dispersions of the clay using a hand magnet. X-ray powder diffraction analysis revealed maghemite, quartz, and phyllosilicate in the magnetically separated phase. The impurity identified as goethite remained in the non-magnetic <2-μm fraction of the clay, displayed magnetic order only at 87 K (47.44 tesla hyperfine field), and accounted for about 8% of the total area of the Mössbauer spectrum.