Infrared spectra of two minerals; Urkut quartz (Hungary) and a Swedish feldspar, of different origin with different physical characteristics and crystallinity were studied. Samples were taken after appropriate grinding, and infrared spectra, X-ray powder diffraction and water vapor absorption measurements were made along with electronmicrographs. Quantitative conclusions were drawn from changes of particle size and the ratio of bands of the Si—O groups and also the degree of crystallinity and changes of the particle size, respectively.

“Kaolinites” from classic, large deposits of kaolin are shown commonly in scanning electron micrographs to be mixtures, at least in part, in microdimensions, of kaolin-mineral polymorphs.

Artificial mixtures of selected kaolin polymorphs simulating the natural mixtures, also micrographed, show crystallinities intermediate between the crystallinities of the end members in X-ray powder diffractograms. Thus, apparent crystallinity interpreted from diffractograms of a kaolin specimen may be a product of kaolin-mineral mixture in microdimensions as well as from ordering in the crystals. Evaluation of the crystallinity of a kaolin from powder diffraction may be suspect if independent means, such as SEM, are not used to assess the monomineralic character of that kaolin specimen.

Analogous to the apparent crystallinity of a “kaolinite” being the product of a mixture, so may other widely ranging properties of “kaolinite” be products of kaolin-mineral mixtures in microdimensions. These properties include DTA, IR, chemical composition, free energies of formation, and industrial applications.

Specifications for a monomineralic, nearly ideal kaolinite are considered—the Keokuk geode variety possesses desired crystallographic and chemical properties.

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.

Goethites were synthesized from ferrihydrite in 0.7 M KOH between 4° and 90°C. As temperatures increased, the goethite crystals became larger and of less domainic character, and surface areas decreased from 153 to 9 m2/g. Surface area, oxalate-soluble Fe to total Fe ratios, chemisorbed water, Mössbauer parameters, and dissolution rate in 6 M HCl at 25°C are particle-size controlled, whereas mean crystallite dimensions, a-dimension of the unit cell, differences between the two OH-bending modes, and dehydroxylation temperatures suggest the existence of a low-temperature (high-a-dimension) and a high-temperature (low-a-dimension) goethite, with a narrow transition range at a synthesis temperature of 40°–50°C. Hydrothermal treatment at 125°–180°C of a low-temperature goethite led to a healing of the multidomainic, microporous high-a-dimension goethite into a monodomainic low-a-dimension goethite of similar overall crystal size with the properties of a low-a-dimension goethite.

Riet veld X-ray powder diffraction (XRD) analysis has been evaluated as a procedure for characterizing Al-substituted goethite according to the Rietveld scale factor, unit-cell parameters, and atom positional parameters. The study was conducted with three synthetic goethite samples for which the degree of Al substitution for Fe determined by chemical analysis was 8.0 ± 0.4, 12.0 ± 0.4, and 20.1 ± 0.4 mole %. The weight fractions of crystalline material (WFCM) in the specimens, determined from the Rietveld scale factors after correcting for adsorbed water and impurities, were 0.878 (esd = 0.014), 0.919 (0.014), and 0.965 (0.015), respectively. The Al mole % substitutions, inferred from the Rietveld cell parameters according to the method of Schulze (1984), were 10.4 ± 2.5, 16.5 ± 2.6, and 17.1 ± 2.6, respectively. The cause of the significant difference between the second value and the chemical analysis result is not known. The atom positional parameters did not differ significantly within the sample suite and agreed satisfactorily with literature values. The results have demonstrated the value of using Rietveld XRD analysis to determine simultaneously the WFCM and Al mole % substitutions, as well as to confirm the non-hydrogen atom positions.

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.

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.

Mineralogy, kaolin crystallinity, Fe content, δO18, and δD were determined for late Cretaceous “soft” and early Tertiary “hard” Georgia kaolins. The crystallinity of the <0.5-, 0.5–1.0-, and 1.0–2.0- μm size fractions of soft kaolins was higher than that of equivalent size fractions of hard kaolins. δO18 and δD of the soft and hard kaolins ranged between 18.5 to 23.1‰, and −64 to −41‰, respectively, and could not be used to discriminate soft from hard kaolins. The trends of crystallinity vs. δO18 were different for kaolins collected at different localities, and, for a given sample, δO18 generally decreased with increasing crystallinity and with increasing crystallite size. These data indicate that the Tertiary kaolins could not have been simply derived from the Cretaceous kaolins by winnowing unless post-sedimentation recrystallization of one or both occurred. δD vs. δO18 systematics indicate that the late Cretaceous to early Tertiary Georgia kaolins crystallized over a temperature range of about 15°C in the presence of waters that varied little in isotopic composition.

The lower Permo-Triassic sediments of the Maláguide Complex contain abundant dickite. Whole rocks were studied by optical microscopy, scanning electron microscopy, and X-ray powder diffraction. The 2–20 µm and < 2 µm size fractions were extracted and analyzed by scanning and transmission electron microscopy, X-ray powder diffraction, infrared spectroscopy, differential thermal analysis, and thermogravimetry.

In the coarse-grained samples, the 2–20 µm size fraction consisted of well-crystallized dickite associated with minor quantities of kaolinite, illite, quartz, and hematite. XRD patterns of the fine-grained samples and the <2 µm fractions showed the existence of well-crystallized minerals in which several reflections of dickite (11l, 02l) were absent and the 132/13$\bar 2$ reflections were shifted. These patterns suggest the presence of an intermediate member between well-crystallized dickite and well-crystallized kaolinite. Only locally high-order reflections are present at 10.5 Å and 18–22 Å. DTA and IR data agree with those from XRD.

The observed compositional and structural variations are a function of the lithology and the particle size of the sample. The sequence kaolinite → kaolinite/dickite → dickite is proposed for the development of these materials during Alpine metamorphism.

Minerals in surface environments form in both turbulent and non-turbulent systems. This study compares the properties of Al goethite formed from ferrihydrite at 60°C in 0.3 M KOH with and without mechanical stirring. Compared to the static system, stirring increased crystal order and needle thickness, decreased unit cell edge length a, but not b and c, reduced the separation between the 2 OH-bending vibrations, increased Al substitution and promoted hematite formation.

Synthetic goethites studied by high-resolution thermogravimetry (HRTGA) show variability in surface characteristics and structural stability as a function of aging conditions. Goethites were synthesized at either pH 6 or 11, at temperatures of 40 or 70°C, and in the presence or absence of sorbed Mn or Pb. Data from HRTGA analysis revealed at least four distinct weight-loss events near goethite dehydroxylation that relate to 1) three events involving the evolution of water associated with surface Fe-O functional groups and 2) bulk dehydroxylation of goethite during transformation to hematite. The relative mass of evolved surface and bulk structural water was related to the predominant particle morphology as determined by transmission electron microscopy (TEM). Differentiation of surface and bulk decomposition reactions allowed the identification of bulk structural dehydroxylation. Goethite crystallin-ity, estimated by the bulk dehydroxylation temperature, appeared to depend on the kinetics of crystallization. This trend was most evident for systems aged at pH 11 and 40°C. Greater concentrations of coprecipitated Mn or Pb dramatically improved goethite crystallinity as indicated by higher dehydroxylation temperatures and smaller widths of the (110) Bragg reflection. Comparison of bulk dehydroxylation temperatures for these samples to other preparations suggests that structural defects predominated over the effects of particle size and Mn/Pb substitution in determining goethite thermal stability. A conceptual model is proposed to account for the disparate dehydroxylation profiles displayed by goethites of varying crystallinity.

Alteration of the crystal structure of Mulhacén antigorite caused by dry, vibration grinding was investigated by X-ray diffraction (XRD), infrared spectroscopy (IR), thermal analyses (TG), grain-size distribution, and transmission and analytical electron microscopy (TEM, AEM). Grinding for 1 min reduces particles to a size ideal for IR and TG. With prolonged grinding, XRD and electron diffraction patterns showed that the crystal structure was affected mainly along the c axis, causing a partial loss of crystallinity. TG analyses revealed that vibration grinding modified mineral dehydration, accelerating the dehydroxylation process and transforming the structural OH to adsorbed water in the resulting matrix. IR spectra and AEM showed that grinding affected the tetrahedral sheet to a lesser extent than the octahedral sheet. Partial release of Mg by preferential destruction of the octahedral sheet after 10 min grinding produced an increase in the Si/Mg ratio in semi-crystalline particles, whereas the amorphous material product after 120 min showed the same composition as the initial antigorite. TEM and grain-size distribution results revealed that grinding led to a general decrease in particle size at the beginning of the experiment followed by the agglomeration of ultrafine particles as grinding proceeded.

Investigation of material from three core sections of the RWTH-1 drill-hole in the Wurm syncline of Aachen, Germany, shows mineralogical and structural evidence of intensive hydrothermal activity in the footwall of the Aachen thrust. Mineral and microstructural data indicate minimum temperatures of 200–250°C. CISillite 001 values of 0.45–0.61 (Δ°2θ) and insignificant amounts of smectite indicate a late diagenetic grade for illite pointing to temperatures <200°C. Chlorite, mainly formed in veins and cleavage planes, has CISchlorite 002 values between 0.35 and 0.26 (Δ°2θ) which only in part point to anchizonal grade. In contrast to these illite and chlorite data, maximum temperatures up to 370°C can be expected based on comparison with recently published fluid inclusion and mineral thermometric data. Illite is neither significantly affected by the hydrothermal event nor by deformation, and mirrors the burial history of the Wurm syncline.

Chlorite grew syntectonically as is shown by bent and predominantly stretched sheets which do not, however, have deformed structures. Syntectonic hydrothermal growth by incipient nucleation along crystal edges limited domainsize and thus also the CISchlorite 002 values. The hydrothermal event did not last long enough to allow further crystal growth. The retarded CISillite and CISchlorite grades can be best explained by limited duration(probably <5000 y) of the hydrothermal event which for a short time reached epithermal temperatures. The hydrothermal fluid flow was caused by dewatering of sedimentary rocks during thrusting and tectonic thickening within the Variscan orogen and it was focused along the Aachen thrust which represents the frontal Variscan thrust.

The mineralogical properties of goethite and clay minerals from the Shewushan supergene gold deposit have been studied using X-ray diffraction (XRD) and transmission electron microscopy (TEM). These results show that in the weathering zone of the Shewushan supergene gold deposit the mineral assemblage is mainly composed of quartz, kaolinite, halloysite, minor illite and goethite. The coexistence of these minerals is apparently indicative of weak laterization. The Al content in goethite from XRD data is ∼10.0%, suggesting formation by weak desilicification. Observation by TEM shows that the flakes of clay minerals with larger particle size usually have extremely rounded outlines, indicating intensive dissolution of clay minerals. Halloysite is derived from the decomposition of kaolinite and the micrographs of curling, tubular, and club-shaped halloysite strongly suggest significant hydration and thus a water-saturated environment. Both the XRD data of goethite and the micrographs of the clay minerals show that the environment in Shewushan is characteristic of high [H2O] activity and high [SiO2] activity. The high dynamic hydraulic conditions may facilitate the downward migration of the primary gold particles during their mechanical concentration, resulting in the accumulation of gold in the lower portion near the water table.

Because relatively little information about the crystal-growth process of smectite is available, the process was assessed here by studying the size and shape of nontronite particles synthesized at six different temperatures from 75 to 150°C over a period of 4 weeks.

The morphology of nontronites was studied using low-pressure isotherms of argon adsorption at 77 K, a method which enables the measurement of the basal and edge surface areas of the nontronite particles and of their mean diameter and thickness. During the crystal growth of nontronite, the mean particle length increased whereas their thickness (and the number of stacked layers) did not vary significantly.

A specific two-dimensional crystal-growth process was observed for smectite via the lateral extension of the layers. This process also appears to occur during the growth of neoformed natural smectite.

Adsorption of the ${\text{AuCl}}_4^{-}$ complex by kaolinites of different crystallinities (Kao-1 and Kao-2) from 100 mL of AuCl3·HCl·4H2O solutions containing 10,000, 500 and 50 µg/L Au and 1 g of kaolinite was measured at pH 3 to 9 at ambient temperature and 120°C. Adsorption from the 50, 500 and 10,000 µg Au/L solutions ranged from 64 to 100% at ambient temperature and from 68 to 100% at 120°C for both kaolinites. Adsorption was pH dependent with a maximum at pH <5 and a minimum at neutral and alkaline pHs. Up to 1 mg Au/g kaolinite was adsorbed by the kaolinites at both ambient temperature and 120°C. In a separate Au adsorption experiment using 100 mL of 4000 µg Au/L solutions and 0.02 to 1.0 g of Kao-1, up to 8.55 mg Au/ g of kaolinite was adsorbed. The pH dependence of Au adsorption suggests that surface complexation of Au to alumina sites at the edges of kaolinite particles might be involved. Protonation of kaolinite surface sites might facilitate adsorption of the anionic Au complex. Both kaolinites adsorbed ~100% of added Au at low pH values, but the less crystalline kaolinite (Kao-2) adsorbed more Au at high pH. Greater Au adsorption would be expected for the less crystalline Kao-2 sample if adsorption occurred at the edges of kaolinite particles.

The purpose of this report is to describe the appropriate use of indices relating to crystallinity, such as the ‘crystallinity index’, the ‘Hinckley index’, the ‘Kübler index’, and the ‘Árkai index’. A ‘crystalline’ solid is defined as a solid consisting of atoms, ions or molecules packed together in a periodic arrangement. A ‘crystallinity index’ is purported to be a measure of crystallinity, although there is uncertainty about what this means (see below). This report discusses briefly the nature of order, disorder and crystallinity in phyllosilicates and discusses why the use of a ‘crystallinity index’ should be avoided. If possible, it is suggested that indices be referred to using the name of the author who originally described the parameter, e.g. ‘Hinckley index’ or ‘Kübler index’, or in honor of a researcher who investigated the importance of the parameter extensively, e.g. ‘Árkai index’.

The objectives of this study were to investigate the effects of chemical parameters on the characterizationof W-type zeolite crystals and their intergrowths with other types of zeolites. The crystal size and purity ofW-type zeolites are affected significantly by the gel composition with respect to the molar ratios of SiO2/Al2O3 (aluminosilicate module, α), H2O/K2O (alkainity, β), and water content (H2O/SiO2, γ). The effects of these gel parameters ont he synthesis and characterizationof W-type zeolite were investigated.

Crystalline W-type zeolite of high purity was synthesized using a gel with a molar ratio of Al2O3:6.4SiO2:5.6K2O:164.6H2O at T = 165°C for a period of 72 h. The effect of excess K2O/SiO2 ratio ina mono-cation (K)-SiO2-Al2O3 gel-composition system on the nanoparticle size and purity of the product was also investigated. Experiments were carried out using the following levels of alkalinity: 21.4, 29.4, and 51.9; aluminosilicate module: 5.0, 6.4, and 10.0; water content: 16.5, 25.7, and 32.9; and excess K2O/SiO2 ratio: from 0.65 to 3.33. The results showed that by increasing the aluminosilicate module at high K2O/SiO2 ratio, the crystallinity and crystal size of the zeolite synthesized increased, while at low alkalinity, the crystallinity and crystal size decreased. Decreasing alkalinity at low aluminosilicate module increased the crystallinity and decreased the crystal size, while at high aluminosilicate module, both decreased. Finally, by increasing the water content at all aluminosilicate module and alkalinity values, the crystallinity and crystal size of the W-type zeolite increased. Excess K2O/SiO2 ratio was the key factor that should be adjusted int he range 0.7–1.0 for synthesis of pure crystals of W-type zeolite.

Despite the numerous studies on geomaterials in Tunisia, quite a few clay varieties are not yet well defined. In fact no detailed geological, mineralogical, or geochemical characterizations of Tunisian palygorskite deposits have been carried out to date. The purpose of the present work was to study the continental Eocene clay deposit at the southern end of the Tunisian North axis, between Jebel Rheouis and Jebel Boudinar, to determine its potential as a clay reserve. Nine samples were collected from the Cherahil formation representing the lower, middle, and upper levels. The analytical results obtained using several techniques (chemical analysis, X-ray diffraction, specific surface area measurements, Fourier-Transform infrared spectroscopy, scanning electron microscopy) revealed that palygorskite is the dominant clay mineral. Dolomite and quartz are present as associated minerals. Chemical analysis of sample AR9 showed a smaller potassium content compared to other samples. Sample AR9 consists essentially of dolomite associated with palygorskite and quartz. Other samples (AR5, AR6, and AR7) collected from the same Cherahil formation contained palygorskite as the main phyllosilicate mineral (80%). The important reserve of palygorskite was found in the middle of the Cherahil formation. Dolomite and quartz associated with palygorskite reduced the length and crystallinity of the fibrous clay morphology. Analysis by scanning electron microscopy proved that the crystallinity of palygorskite was less in the lower and upper parts of the Cherahil formation. The central palygorskite deposit may be of interest for pharmaceutical (adsorbent drug) and other applications. The two other levels of Cherahil formation are mineralogically heterogeneous and considered economically less important than the middle level, which is rich in palygorskite.