Samples of nacrite, dickite, kaolinite, and halloysite were investigated using X-band electron paramagnetic resonance (EPR) and Mössbauer spectroscopy. Fe3+ gave rise to EPR signals at g ≃ 4 which differed with the individual polytype. Only nacrite had no resonance in this region of the spectrum, but it had one at g ≃ 2. Dickite had a quadruple line, kaolinite a triple line, and halloysite a single line in this region. The EPR spectra of these minerals are apparently dependent also on the orientation of adjacent layers in the structures. Other resonances were attributed to (1) clusters of ferric ions giving rise to broad resonance near g ≃ 2, (2) trapped holes, and (3) free radicals linked with organic matter. The Mössbauer spectroscopic results suggest that iron occurs in the ferric state (except in nacrite where Fe2+ is present also) as an ionic substitution (IS) in octahedral layers. This suggestion follows from the difference is the IS values between octahedral and tetrahedral symmetry sites occupied by Fe3+ equal to ∼0.4 mm/sec. Linewidths depend mainly on the way the layers stack; for monoclinic modifications represented by nacrite and dickite, the linewidths are narrow (Γ = 0.45 mm/sec and 0.56 mm/sec, respectively); pseudomonoclinic halloysites also gave narrow linewidths (Γ = 0.39 mm/sec and 0.48 mm/sec). The widest line was observed for triclinic kaolinite (Γ = 0.62 mm/sec and 0.71 mm/sec).

The recent determination of the three-dimensional crystal structure of a dickite:formamide intercalate allows insight into the clay:organic bonding schemes of amides and other small organic molecule intercalates of the kaolin minerals. It is demonstrated that the observed basal spacings of intercalates with these molecules are consistent with hydrogen bonding schemes in which, if possible, triple hydrogen bonds from the clay hydroxyls to 0=C< are formed. Variations in basal spacing within a series of amides can be explained by considering the maximization of hydrogen bonding while avoiding close van der Waals contacts.

Three samples of bluish chromium-bearing dickite and chromium-bearing kaolinite were examined by X-ray powder diffraction, chemical analysis, electron microprobe, optical, and infrared techniques to determine whether chromium is part of the mineral structure or present in an impurity phase. Two of the samples studied contain a single dominant chromium-bearing phase (either dickite or kaolinite); the third contains equal proportions of both minerals. The optical absorption and infrared spectra are consistent with the presence of octahedrally coordinated chromium. The range of Cr3+-Al3+ substitution is rather limited: up to 0.06 atoms per unit cell. The electron microprobe study revealed the presence of very rare, minute grains of chromite, as well as a uniform distribution of chromium in dickite and kaolinite, indicating that chromium occupies octahedral sites in the structure of these minerals.

The effect of pH, time and temperature on the interaction of zinc with acid and base saturated dickites has been investigated. Increase in pH resulted in an increase in adsorption of zinc in the higher concentration range. The adsorption increased rapidly and then slowly with increase in the time of interaction. The variation of rate constants and the half times of reaction suggested an exchange process controlled by film and possibly particle diffusion and thereafter fixation processes. The inferences found support from the nature of adsorption isotherms. Temperature affected adsorption with exothermic interactions. The activation energy of adsorption of zinc on Na-dickite was 14.0 kcal mole−1.

The crystal structure of kaolinite(Pl, a = 5.153(1), b = 8.941 (1), c = 7.403 (1)Å, α = 91.692(3)°, β = 104.860(3)°, γ = 89.822(3)°, specimens from Keokuk geodes) has been refined in detail and that of dickite (Cc, a = 5.1460(3), b = 8.9376(5), c = 14.4244(6) Å, β = 96.761(5)°) has been re-refined, both from powder diffraction data with the Rietveld method. Except for the hydrogen atoms, the layer structures in both clays are very similar and are much as inferred or determined previously by others. The rotation in the tetrahedral sheet is 7(1)°. The two inner hydroxyl O-H bonds in kaolinite are differently oriented; one points into an octahedral vacancy and the other somewhat away from the octahedral sheet and toward the unoccupied center of an oxygen triangle formed by the two apical oxygens and shared basal oxygen of two adjacent SiO4 tetrahedra. All six of the inner surface hydrogen atoms appear to be nearly equally involved in the hydrogen bonding between kaolinite layers in kaolinite.

Near-infrared (NIR) reflectance spectra for mixtures of ordered kaolinite and ordered dickite have been found to simulate the spectral response of disordered kaolinite. The amount of octahedral vacancy disorder in nine disordered kaolinite samples was estimated by comparing the sample spectra to the spectra of reference mixtures. The resulting estimates are consistent with previously published estimates of vacancy disorder for similar kaolin minerals that were modeled from calculated X-ray diffraction patterns. The ordered kaolinite and dickite samples used in the reference mixtures were carefully selected to avoid undesirable particle size effects that could bias the spectral results.

NIR spectra were also recorded for laboratory mixtures of ordered kaolinite and halloysite to assess whether the spectra could be potentially useful for determining mineral proportions in natural physical mixtures of these two clays. Although the kaolinite-halloysite proportions could only be roughly estimated from the mixture spectra, the halloysite component was evident even when halloysite was present in only minor amounts. A similar approach using NIR spectra for laboratory mixtures may have applications in other studies of natural clay mixtures.

Authigenic, well-crystallized kaolinite and dickite occur within sulfide mineral deposits (mine-size to hand-specimen size occurrences) of the Mississippi Valley type in Arkansas, Kansas, Missouri, Iowa, Wisconsin, Illinois, and Indiana. Fluid inclusions in these rocks indicate temperatures of formation as high as 140°C. These authigenic kaolin-group minerals are probable geologic indicators of a regional thermal event. Such elevated temperatures are probably the result of heated waters derived from deeply buried sedimentary or tectonic basins, of passage of the region over a hot spot, or of an episode of thinning of the crustal plate in the mid-continent region.

Gibbs free energies for phases in the system Al2O3-SiO2-H2O have been calculated from reversed experiments in order to correct earlier values and to calculate a phase diagram consistent with more recent experiments. An internally consistent diagram could not be calculated that agreed with all published experiments, and choices of preferred data were made. The following Gibbs free energies, relative to the elements at STP (298.15 K, 1 bar), have been derived

The above values were calculated assuming literature values for corundum, quartz, and H2O (v).

Examination of available thermodynamic, experimental, and observational data on the aluminum hydroxides gibbsite, boehmite, bayerite, and nordstrandite suggests that these minerals are metastable with respect to diaspore + water at STP and at higher temperatures. Similarly, halloysite and dickite are metastable with respect to kaolinite at these conditions. The occurrence of these minerals in soils must therefore be ascribed to nonequilibrium processes, and the use of equilibrium phase diagrams to explain their occurrence is inappropriate.

A suite of Georgia kaolinites, ranging from well-ordered to very poorly ordered samples, were studied to explore correlations between degree of structural disorder, geological environment, Fe3+ content, Fe3+ electron paramagnetic resonance (EPR) spectrum, and infrared (IR) hydroxyl-stretching band frequencies and bandwidths. Samples from different localities showed a wide range of disorder which appears to be related to differences in their geological environments. High iron content correlated strongly with low degree of order. The areas of both the I and E components of the EPR spectrum and the fractional I area correlated inversely with degree of order. Fourier-transform IR studies of kaolinites and dickites showed that (1) interlayer hydrogen bonding is weaker in dickite than in kaolinite; (2) frequency of the ν11 stretching band of the inner-surface hydroxyls increases sequentially from well-ordered kaolinite through the disordered structures to well-ordered dickite, which is consistent with a model for disorder based on vacancy displacement; and (3) the character and temperature dependence of the inner hydroxyl-stretching band is not compatible with the crystal structures of kaolinite and dickite as refined by Suitch and Young.

Single-crystal Fourier-transform infrared (FTIR) spectra of Keokuk kaolinite and Ouray dickite were obtained with an FTIR microscope. Although numerous IR, FTIR, and Raman spectra of polycrystalline kaolinite and dickite can be found in the literature, the present data represent the first reported single-crystal vibrational spectra for these clay minerals. The orientation of the crystallographic axes of dickite was determined using a cross-polarizing optical microscope fitted with an 550-nm optical retardation plate. Assignment of the inner hydroxyl group OH1 to the 3623-cm-1 band was confirmed, and the angle of this OH group to the b-axis was determined to be 47° based upon the measured dichroic ratio. The 3702-3710-cm−1 absorption feature appeared to consist of two closely spaced bands having slightly different polarization behavior. The inner-surface hydroxyl group OH3 was assigned to the absorption bands at 3710 cm−1. The calculated angle of the OH3 groups to the b-axis was found to be 22°, which agrees well with the angles determined by X-ray powder diffraction and neutron diffraction. The remaining hydroxyl groups, OH2 and OH4, were assigned to the 3656 cm-1 band; the angle of the OH2 and OH4 groups to the b-axis was measured at 45°. The polarization behavior of the OH-deformation bands of dickite at 911, 937, and 952 cm−1 was found to be similar to that observed in the OH-stretching region. Single-crystal FTIR spectra of Keokuk kaolinite showed that rotation of the electric vector around the c/z axis in the ab plane of kaolinite resulted in a behavior distinct from that of dickite. The OH-stretching bands of kaolinite were found to be considerably more polarized than the corresponding bands of dickite. This is related directly to the fact that dickite possesses a glide plane (space group Cc) compared with kaolinite, which does not (space group C1).

A comparison of the structural characteristics of the kaolin-group minerals, mainly kaolinite and dickite, shows that they differ in both the two-dimensional periodicity in the 1:1 layers and the rotation angles of the polyhedra. Distortions in a real 1:1 layer, compared with an idealized layer, do not allow such stacking faults as ± 120° layer rotations and vacancy displacements, because the second layer is incommensurable with the first. The 1:1 layer structure and the fact that the unit cell is symmetrical with respect to the plane passing through the long diagonal of the unit cell suggest the possibility of defects resulting from the two stacking sequences for the same layers. For a regular alternation of translations, a halloysite-like structure should be the end-member of such a series of defect kaolinite types.

The formation of layers having vacant octahedral C-sites is another possible type of fault. Because of the minor dilference between γ and 90°, dickite-like layers should exist. A regular alternation of B and C layers yields dickite as the end-member structure. In materials containing few defects, stacking faults of both types lead to similar X-ray powder diffraction patterns. Thus, the nature of the stacking faults is difficult to determine experimentally. In materials containing many defects, however, the two models lead to different calculated diffraction patterns. Therefore, only a study of defect-rich types of kaolinite can determine which types of defects exist in natural kaolinite samples.

The 16-8-, 8-5-, 5-2-, 2-1-, 1-0.5-, 0.5-0.3-, 0.3-0.1-, and <0.1-μm size fractions were centrifuged from a Georgia (U.S.A.) sedimentary kaolin and a hydrothermal kaolin from the Sasso mine (Italy) and analyzed by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), infrared spectroscopy (IR), differential thermal analysis (DTA) and thermogravimetry (TGA) together with the corresponding whole rocks. All size fractions of the Georgia sample consisted dominantly of well-crystallized, fine-grained kaolinite, associated with minor quantities of smectite. Some halloysite-like elongate particles were noted by SEM in the intermediate size fractions, minor amounts of quartz were identified in the coarsest size fractions, and < 1% noncrystalline material and traces of organic material were suspected in the finest size fraction. The crystallinity of the kaolinite as measured by XRD and IR varied moderately with size. IR suggested that nacrite-like stacking disorder increased with decreasing size for particles < 5 μm in size.

In the Sasso sample kaolinite dominated all size fractions and was accompanied by dickite in the coarse and by halloysite in the fine size fractions. Regular mixed-layer illite/smectite (I/S) was present in all size fractions and dominated in the finest. Abundant quartz and traces of alunite were identified in the whole rock and coarsest size fractions. The kaolinite in this sample showed marked variation in stacking order and crystallinity, as shown by changes in XRD, IR, and DTA patterns.

The observed compositional and structural variations in the size fractions of the Georgia sedimentary kaolin are small, as expected from formational environment, which was characterized by low temperatures and relative stable genetic conditions. The much more marked differences in composition within the size fractions of the Sasso hydrothermal kaolin are likely a result of the broad range of temperatures and fluid chemistry of its formational environment. The sequence dickite-well-crystallized kaolinite-kaolinite-halloysite is probably temperature-dependent.

Orientations of OH-vectors in structural hydroxyl groups of layer silicates were defined both from diffraction data and calculations of electrostatic energy. The comparison of the results showed that for the hydroxyls of the 2:1 layers of chlorites and micas the positions of the hydroxyl protons are mainly determined by electrostatics. For the hydroxyls of dickite, amesite, and the brucitic sheets of chlorite, the results derived by the two methods differed systematically from each other, pointing to a change in the nature of the bond in these OH-groups.

The structure of kaolinite (non-hydrogen atoms only) from Keokuk, Iowa, was refined in space group C1 using CuKα X-ray powder diffraction data and Rietveld refinement techniques (Rwp = 12.3%). A distance least-squares (DLS) model for the initial atomic coordinates avoided a false minimum and unrealistic results characteristic of previous Rietveld refinements of kaolinite. All Keokuk samples examined contain small amounts of dickite. The profile of the mixture was calculated using a fixed set of dickite atomic parameters and by constraining the dickite profile parameters to those refined for kaolinite. Results indicate that the individual kaolinite layer is very similar to the dickite layer; bond distances, which are similar to dickite and nacrite, are: Si-O, 1.60-1.63 Å; Al-O, 1.87-1.97 Å. The tetrahedral rotation angle is 6.9°, compared with 7.3° for dickite and 7.4° for nacrite. Previous Rietveld refinements apparently suffered from poor preferred orientation models, failure to consider the presence of dickite as a second phase, and, most importantly, refinement to a false-minimum structure. The conclusions based on the earlier refinements must therefore be reevaluated, especially regarding the kaolinite space group and hydrogen positions. Existing X-ray and electron diffraction and spectroscopic data support the presence of C-centering in kaolinite.

The resolution of the infrared spectra of structural OH in kaolin-group minerals increases with decreasing temperature. Poorly crystalline kaolinite gives typical infrared spectra, which suggest the existence of kaolinite-, dickite-, and nacrite-like configurations. The relative amount dickite- and nacrite-like configurations compared with kaolinite-like configurations increases with decreasing crystallinity. Low-temperature infrared spectroscopy is a more sensitive means of estimating the degree of order of poorly crystalline kaolinite than is X-ray powder diffraction.