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.

Previous studies of the defect structure of kaolinite have examined samples having a restricted level of defects. This study examined nine kaolinite samples having a large diversity of defect contents, as indicated by Hinckley indexes ranging from 1.44 to 0.18. The samples were chosen so as to cover this range in as regular a manner as possible. The types and abundances of the defects were determined by examining the X-ray powder diffraction profiles for the 02,11 and 20,13 bands. The diffraction intensities were measured by counting for a fixed time in steps of 0.01°2θ. Analysis of these diffraction profiles indicated that (1) the major defect is the existence of a translation between adjacent layers, which is not the usual (approximately a/3), but is related to that translation by the pseudo-mirror plane coincident with the long diagonal of the unit cell; (2) the existence of a few C layers among the B layer stacking is a minor defect; (3) many of the samples could be accurately modeled only by assuming the existence of two kaolinite phases; (4) the existence of only a few C layers in some samples does not support the idea of a continuous series from kaolinite to dickite through disordered intermediates; and (5) the Hinckley indexes of several samples depend on the relative proportions of the two types of kaolinite in the mixture.

The nine kaolinite samples fall into three groups: those having a low to moderate abundance of defects (Hinckley index > 0.43) are mixtures of two types of kaolinite (one almost free of defects, the other richer in defects); those having low Hinckley indexes (0.43 to 0.18) are single phases with different proportions of defects; and those which contain a single type of kaolinite, unlike the others in the nature of the interlayer translations and the greater abundance of C layers. The agreement between calculated and observed X-ray diffraction profiles is excellent for all specimens, except one sample (from Charentes) for which the fit is acceptable but not perfect.

The orientation of the OH-vectors in hydroxyl groups of micas of different compositions, polytype modifications, and symmetry were calculated by the method of minimization of electrostatic energy. The orientations are strongly affected by the peculiarities of structures, and even slight deviations from the ideal dioctahedral periodicity can introduce a correction of as much as 10° to the value of the polar angle. Ordering of cations in octahedra lead to twisting of the OH-bond towards the octahedron with lower charge and larger dimension. The latter is less true for cation ordering in tetrahedra. Because of these factors and the dependence of the hydrogen position on the coordinates of heavy atoms, such calculations can give reliable results only if the structure has been refined with high precision. Different polytypes of micas displayed the same orientation of the OH-vectors with respect to the axes of a separate layer, if the stacking sequence did not introduce specific distortions of the 2:1 layer.

Several new minerals, structurally and chemically similar to the hydrotalcite-manasseite group, have been found in the saline deposits of the central pre-Caspian depression and in those of Middle Asia. Their structures consist of layers of (Mg1-xAlx)(OH)2 plus interlayers of anions and molecular water. In addition to manasseite itself, [(Mg4Al2)(OH)12][(CO3)-3H2O], having unit-cell parameters of a = 3.042, c = 2 × 7.56= 15.12 Å and a calculated density of Dc = 2.15 g/cm3, other varieties were identified whose interlayers contain alternately SO42− or SO42− and CO32− anions. The following new phases were recognized: (1) an 8.85-Å phase having the composition [(Mg4Al2)(OH)12][(SO4)·3H2O], subcell dimensions of a' = 3.04, c' = 8.85 Å, and Dc = 1.96 g/cm3; (2) an 11-Å phase having the composition [(Mg3.96Fe0.06Al1.98)(OH)12][Na0.56(SO4)1.30·7.3H2O], hexagonal unit-cell parameters of a = √3 · 3.042 = 5.28 Å, c = 11.16 Å, and Dc = 1.90 g/cm3; (3) a 16.5-Å mixed-layer phase having the composition [(Mg4Al2)(OH)12][(SO4)0.5(CO3)0.5·3H2O] and an ordered ABAB... alternation of 7.56-Å layers (i.e., a brucite-like layer + a CO32−-containing interlayer) and 8.94-Å layers containing SO42− anions in interlayers; this phase has unit-cell dimensions of a' = 3.05, c' = 16.5 Å and Dc = 2.06 g/cm3; and (4) an 18.5-Å ordered mixed-layer phase having the ideal composition [(Mg8Al4)(OH)24][M+0.5(SO4)1.25(CO3)1.0·9H2O] and an alternation of 7.56-Å, CO3-containing layers and 11-Å layers having SO42− anions and Na and Mg cations in interlayers (M+0.5 corresponds to interlayer cations). This last phase has unit-cell dimensions of a = 3.046, c = 3 × 18.54 = 55.62 Å and Dc = 1.99 g/cm3. Some of the varieties containing SO42− in the interlayers swelled with ethylene glycol or glycerol.

For this diverse family of minerals whose structures are based on brucite-like layers of the composition (R2+1-xR3+x)(OH)2, a unifying system of nomenclature is offered for consideration. In describing these brucite-like structures intercalated with anion- and cation-containing interlayers, the composition of the hydroxide sheet and the interlayers, the periodicity of the layers, and the mixed-layer nature of the material should be described. By means of symbols, a single term might be used to describe the crystal chemistry of any member of the group having a given cation composition for the brucite-like layers, for example, manasseite, a 2H polytype of hydrotalcite that has a repeat distance of 7.56 Å and CO3-containing interlayers, might be designated as 7.56-Å CO3-hydrotalcite-2H.

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.

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.

A new approach to the interpretation of Mössbauer spectra of Fe3+-phyllosilicates having vacant trans-octahedra is based on (1) crystal structure simulation methods that allow for the size and the shape of a Fe3+-octahedron as a function of the nearest surrounding cations; and (2) calculations of electric field gradients (EFG) on Fe3+ in terms of the ionic point-charge model. Calculations were performed by direct summation within the region of radius ≤50 Å. Coordinates for the anions in the coordination octahedra have been assigned to take into account the nearest cationic environment. Atomic coordinates for the rest of the summation volume are those for the average unit cell. EFG calculations for cation combinations responsible for the visible quadrupole splitting Δvis in the spectra of nontronite, “red” muscovite, and celadonite have led to good agreement between Δvis and Δcalc. Computer fitting of the nontronite and celadonite spectra based on EFG calculations for the rest of the possible cation combinations suggests that the distribution of tetrahedral cations in nontronite obeys the Loewenstein rule, and in celadonite, the distribution of R3+ and R2+ over cis-octahedra is predominantly ordered, in agreement with electron diffraction and infrared spectroscopy data. The Mössbauer spectrum of one of the glauconites suggested the presence of celadonite-like and muscovite-like domains in its 2:1 layers.

Structural and diffraction criteria for distinguishing between t-1M, c-1M, m-1M, and 3T illite varieties are described. The t-1M illite corresponds to a one-layer monoclinic structure with vacant transsites. The c-1M illite has vacant cis-octahedra forming one of two symmetrically independent point systems; the other cis-octahedra as well as the trans-octahedra are occupied; and the m-1M illite corresponds to the structure in which cations are statistically distributed over available trans- and cis-sites. For t-1M, c-1M, and m-1M, the values of |c cos β/a| are equal to 0.39–0.41, 0.29–0.31, and 0.333, respectively. Application of these criteria demonstrates that illite samples described in the literature as the 3T polytype usually are c-1M instead. The relatively common occurrence of c-1M illite in association with t-1M and 2M1 polytypes has been recognized in illite from hydrothermal alterations around uranium deposits located in the Athabasca basement (Saskatchewan, Canada). The c-1M illite from these deposits was previously described as 3T one.

A new approach is described to computer simulate cation distribution in octahedral sheets of dioctahedral 2:1 layer silicates with vacant trans-octahedra. This approach makes use of the information on cation distribution at the one-dimensional level provided by integrated IR optical densities for the region of OH-stretching frequencies. By using this program it is possible to show that (1) the Mössbauer spectrum of glauconite B. Patom conforms to the structural model composed of celandonite-like and illite-like domains whose dimensions are limited by approximately 2 or 4 unit cells; (2) non-equivalency of “left” and “right” cis-positions (with fixed b-direction) with respect to R2+ and R3+ occupancy is a characteristic feature of a celadonite-like domain.

A new model for the interpretation of dioctahedral mica infrared (IR) spectra in the OH stretching vibration region is proposed. It is based on the analysis of the main factors responsible for the observed sequence of the OH frequencies. In terms of this model, the simple analytical dependence between the OH frequencies and the mass and valency of cations bonded to OH groups has been found. The specific character of the interaction between octahedral Al and OH groups in the mica structures is assumed.

Integrated optical densities of the OH bands determined by the decomposition of the studied mica IR spectra are used for the quantitative analysis, that is, for the determination of a number of each type of octahedral cations per unit cell of the sample under study. A good agreement between the octahedral cation contents of 2:1 layers found from the IR spectra decomposition and the chemical analysis has shown that this technique may be used to study the local order-disorder of isomorphous cation distribution in mica structures.

The essential result obtained by the quantitative analysis of the mica IR spectra is the determination of Fe3+ cations in the tetrahedral sites of some samples. This means that the conventional presentation of structural formulae for Al-Fe3+-containing 2:1 layer silicates is unacceptable without consideration of tetrahedral Fe3+ by spectroscopic techniques and by the quantitative analysis of the IR spectra, in particular.

Layer stackings in the ideal and real kaolinite structures are considered in terms of layer orientations i = 1, 2, … 6, intra- and interlayer displacements of adjacent 0- and T-sheets, si and tk, distortions of these displacements δ1 and δ2, deviations of unit cell parameters ηi = b2i/a2i − 3, εi = γi − π/2, and normal projections cn of the axis vector c on the ab plane.

The ideal monoclinic angle of dickite (cnx = −1/3) and the deviation α - π/2 ≠ 0 for kaolinite are explained by combinations of the δ1 and δ2 values in the sequence of symbols si and tk defining the corresponding structures. Twenty stacking variants in the 3 successive layers of the kaolinite structure are derived, incorporating layer orientations of the same parity, displacements t+, − = [0, ± 1/3] and reflection operations in planes normal to the axis b3. Two deformation mechanisms are proposed for the accommodation of successive layer unit cells adjusting either angular or linear parameters at the agreement of either linear or angular parameters corresponding.

A modified version of the Bertaut-Warren-Averbach (BWA) technique (Bertaut 1949, 1950; Warren and Averbach 1950) has been developed to measure coherent scattering domain (CSD) sizes and strains in minerals by analysis of X-ray diffraction (XRD) data. This method is used to measure CSD thickness distributions for calculated and experimental XRD patterns of illites and illite-smectites (I-S). The method almost exactly recovers CSD thickness distributions for calculated illite XRD patterns. Natural I-S samples contain swelling layers that lead to nonperiodic structures in the c* direction and to XRD peaks that are broadened and made asymmetric by mixed layering. Therefore, these peaks cannot be analyzed by the BWA method. These difficulties are overcome by K-saturation and heating prior to X-ray analysis in order to form 10-Å periodic structures. BWA analysis yields the thickness distribution of mixed-layer crystals (coherently diffracting stacks of fundamental illite particles). For most I-S samples, CSD thickness distributions can be approximated by lognormal functions. Mixed-layer crystal mean thickness and expandability then can be used to calculate fundamental illite particle mean thickness. Analyses of the dehydrated, K-saturated samples indicate that basal XRD reflections are broadened by symmetrical strain that may be related to local variations in smectite interlayers caused by dehydration, and that the standard deviation of the strain increases regularly with expandability. The 001 and 002 reflections are affected only slightly by this strain and therefore are suited for CSD thickness analysis. Mean mixed-layer crystal thicknesses for dehydrated I-S measured by the BWA method are very close to those measured by an integral peak width method.

Area-weighted thickness distributions of fundamental illite particles for samples of illite and illite-smectite from seven locations (including bentonites and hydrothermally altered pyroclastics) were measured by Pt-shadowing technique, by transmission electron microscopy. Most thickness distributions are described by lognormal distributions, which suggest a unique crystallization process. The shapes of lognormal distributions of fundamental illite particles can be calculated from the distribution mean because the shape parameters α and β2 are interrelated: β2= 0.107α − 0.03. This growth process was simulated by the mathematical Law of Proportionate Effect that generates lognormal distributions. Simulations indicated that illite particles grow from 2-nm thick illite nuclei by surface-controlled growth, i.e., the rate of growth is restricted by how rapid crystallization proceeds given a near infinite supply of reactants, and not by the rate of supply of reactants to the crystal surface. Initially formed, 2-nm thick crystals may nucleate and grow within smectite interlayers from material produced by dissolution of single smectite 2:1 layers, thereby transforming the clay from randomly interstratified (Reichweite, R = 0) to ordered (R = 1) illite-smectite after the smectite single layers dissolve. In this initial period of illite nucleation and growth, during which expandable layers range from 100 to 20%, illite crystals grow parallel to [001]* direction, and the dimensions of the (001) plane are confined to the size of the original smectite 2:1 layers. After nucleation ceases, illite crystals may continue to grow by surface-controlled growth, and the expandable-layer content ranges from 20 to 0%. This latter period of illitization is characterized by three-dimensional growth. Other crystal-growth mechanisms, such as Ostwald ripening, supply-controlled growth, and the coalescence of smectite layers, do not produce the observed evolution of α and β2and the observed shapes of crystal thickness distributions.

Polytype diversity of hydrotalcite-like minerals is mainly a function of the nature of the interlayer anion. Among the varieties with CO32− anions, only two- and three-layer polylypes having the same structure as manasseite and hydrotalcite have been confirmed. Stichtite and reevesite, which have been previously identified as six-layer polytypes, are in fact three-layer polytypes.

Among SO42− varieties, one-layer and three-layer polytypes have been identified, but the one-layer types are only present in more hydrated minerals with larger interlayer spacings. The three-layer varieties are of three different polytypes, with both P- and O-types of interlayers. Both rhombohedral and hexagonal varieties exist. Interlayer type may change during hydration-dehydration or anion exchange. Thus, in contrast with the CO32−-bearing minerals, a complete description of the polytype of the SO42−-bearing minerals cannot be made by simply indicating the number of the brucite-like layers in the unit cell.

The two-layer unit cell seen in refined crystal structures of some minerals with SO42− interlayers is not due to a doubled periodicity of alternation of brucite-like layers but to periodicity of interlayer anions, or layer cations.

A very simple technique is proposed for a quantitative or semiquantitative interpretation of X-ray diffraction (XRD) patterns for two-component mixed-layer structures. It is suitable for a determination of the Reichweite (R) values and proportions of component layers from graphical simulations of basal peak positions for mixed-layer structures with definite layer types. This technique can be successfully used for illite-smectites, but the accuracy of the results obtained for other mixed-layer structures is somewhat lower. In addition to the graphical technique, simple linear relationships are proposed for the calculation of layer proportions. Such relationships can be easily obtained for any mixed-layer structure with any R and any thicknesses of interstratified layers.

Structural parameters reported in the literature for mixed-layer illite-smectites, kaolinite-smectites, etc., were used to check the reliability of the method presented. It is concluded that the technique works well and produces parameters that are in agreement with those published.

An improved model for the interpretation of thermal effects during dehydroxylation in aluminous dioctahedral 2:1 layer phyllosilicates considers trans-vacant (tv) and cis-vacant (cv) 2:1 layers and leads to very different temperatures of dehydroxylation for these tv and cv vacant modifications. In particular, smectites and illites consisting of cv 2:1 layers are characterized by dehydroxylated temperatures which are higher by 150°C to 200°C than those for the same minerals consisting of the tv 2:1 layers. A considerable lengthening of the OH-OH edges in cv 2:1 layers in comparison with the OH-OH edges in the tv 2:1 layers is postulated as the reason for the higher dehydroxylation.

Dehydroxylation in aluminous cv 2:1 layer silicates should occur in two stages. Initially, each two adjacent OH groups are replaced by a residual oxygen atom and the Al cations, which originally occupied cis -and trans-sites, become 5- and 6-coordinated, respectively. The structure of 2:1 layers corresponding to this stage of the dehydroxylation is unstable. Thus the Al cations migrate from the former trans-sites to vacant pentagonal prisms. The resulting dehydroxylated structure of the original cv 2:1 layers is similar to that of the former tv 2:1 layers.

Diffraction and structural features of the cv dehydroxylates predicted by the model are in agreement with X-ray diffraction effects observed for cv illite, illite-smectite and montmorillonite samples heated to different temperatures. In particular, the diffusion of Al cations to empty five-fold prisms during dehydroxylation of the tv 2:1 layers explains why dehydroxylation of reheated cv montmorillonites occurs at temperatures lower by 150°C to 200°C than samples that were not recycled.

Structural transformations of illite-smectite samples of hydrothermal genesis with increasing contents of illite layers were studied by X-ray powder diffraction. The samples were K-saturated and subjected to wetting and drying cycles to increase three-dimensional structural ordering. Diffraction profiles were analyzed with the help of a specially devised computer program based on the approximation of individual diffraction reflections by “bell-shaped” functions, with minimization of the differences between experimental and simulated profiles. The data indicate that the transformations of these illite-smectite samples were accompanied not only by variations in the proportion of illite and smectite layers and in the pattern of their alternation, but also by a change in structure within 2:1 layers.

A model to compensate the 2:1 layer having excess negative charge owing to the reduction of Fe3+ to Fe2+ by sodium dithionite buffered with citrate-bicarbonate in nontronite, beidellite, and montmorillonite is proposed. This model is based on reassessing published experimental data for Fe-containing smectites and on a recently published structural model for reduced Garfield nontronite. In the reduced state, Fe2+ cations remain six-fold coordinated, and increases of negative charge in the 2:1 layer are compensated by the sorption of Na+ and H+ from solution. Some of the incorporated protons react with structural OH groups to cause dehydroxylation. Also, some protons bond with undersaturated oxygen atoms of the octahedral sheet. The amount of Na+ (p) and H+ (ni) cations incorporated in the structure as a function of the amount of Fe reduction can be described quantitatively by two equations: p = m/(1 + K0mrel) and ni = K0mrel/(1 + K0mrel); with K0 = CEC (9.32 − 1.06mtot + 0.02mtot2), where mtot is the total Fe content in the smectite, m is the Fe2+ content, mrel is the reduction level (m/mtot), CEC is the cation-exchange capacity, and K0 is a constant specific to the smectite. The model can predict, from the chemical composition of a smectite, the modifications of its properties as a function of reduction level. Based on this model, the structural mechanism of Fe3+ reduction in montmorillonite differs from that determined in nontronite and beidellite owing to differences in the distribution of cations over trans- and cis-octahedral sites.

X-ray phase analysis of clays is difficult because these materials generally consist of a mixture of different phases, i.e., mixed-layer minerals, individual clay minerals (non mixed-layer), and associated minerals, such as calcite and quartz. The analysis requires knowledge that presently is incorporated in a computer-based expert system. This expert system is capable of a) identification of associated minerals; b) identification of individual clay minerals; c) identification of the nature of the mixed-layer minerals; d) approximate structural characterization of the mixed-layer minerals; and e) precise structural determination of the mixed-layer minerals by comparison of experimental X-ray diffraction (XRD) patterns with calculated patterns for different models. Accuracy of the conclusions drawn by the expert system has been verified with literature data. Programs for the structural characterization of mixed-layer minerals must allow a) modification of the structural characteristics, abundances, and order-disorder distribution of the layers; b) modification of the distribution of the sizes of coherent scattering domains; and c) consideration of mixed-layer clays with more than two components. Two programs were written to calculate the XRD patterns of two- and three-component mixed-layer minerals consisting of any layer type and without any limitation in the order-disorder relationships.