Measurement of clay particle size invariably presents data in the form of equivalent spherical diameters. For asymmetric particles the equivalent spherical diameter varies with the method of measurement. Based upon an understanding of the theoretical concepts involved, a method has been proposed whereby comparison of data on a given sample from two different techniques can reveal information about the minor dimension of the particle. Theoretical expressions are given for the equivalent spherical diameter of cylindrically symmetric rods and discs from which it is shown that some of the existing measurement methods are more dependent upon size than the degree of non-sphericity whilst for others the reverse is true. It is shown how for rods and discs one can obtain information on both an average axial ratio and the distribution of this parameter for heterogeneous samples. Illustrated data are given for three kaolin samples. Far from showing inconsistency between the variable spherical diameters yielded by different instruments, the data produce compatible size and thickness parameters which match those observed in supplementary, unreported electron microscope experiments. A method of measuring particle major and minor parameter distributions is indicated.

Replacement of kaolinite by dickite has been observed to occur with increasing depth of burial in sandstones from three different basins on the Norwegian continental shelf. In the Garn Formation (Middle Jurassic) of Haltenbanken, samples from 1.4-2-7 km below the sea floor (110°C) contain kaolinite, whereas deeper than 3.2 km (130°C) mainly dickite is present. In the Statfjord Formation (Late Triassic-Early Jurassic) from Gullfaks and Gullfaks Sør Fields, transformation of kaolinite to dickite occurs at ~3.1 km below the sea floor (120°C) From the Stø and Nordmela Formations (Lower to Middle Jurassic) to the Troms Area, kaolin polytypes have been identified in only two shallow and two deep samples, but the results are consistent with the transformation depth determined in two other areas studied. These occurrences are significant because they allow the temperature of the kaolinite/dickite transformation to be established with greater confidence than had been possible previously. Also the observation of this transformation in all three areas so far examined indicates that it may be a general and predictable feature of kaolinbearing sandstones worldwide and therefore a potentially reliable paleogeothermometer. In most cases, the kaolinite occurs as relatively large vermicular crystals, whereas dickite forms more euhedral, blockier crystals. This morphological difference, together with the nature of the structural difference in octahedral occupancy between the kaolinite and dickite, suggests that the transformation occurs by dissolution and reprecipitation, rather then in the solid state.

Synthetic 2-line and 6-line ferrihydrite and feroxyhite samples prepared from ferric salt solutions have been investigated by EXAFS spectroscopy. All these materials have been found to be short-range ordered, consisting of Fe octahedra linked by comers, edges, and faces. Their local structures are related to those of well-crystallized (oxyhydr)oxides, and the absence of hkl reflections in some samples is attributed to the small size of coherent scattering domains. The presence of face sharings indicates that these materials have structural similarities with hematite. Based on Fe-Fe distances and the analysis of the static disorder, it has been concluded that the local structure of feroxyhite is close to that of hematite, whereas ferrihydrite has common structural features with both hematite (αFe203) and cdβFeOOFI. The local structure of ferrihydrite thus differs from that of aqueous Fe polymers obtained by the partial hydrolysis of ferric nitrate and chloride solutions. Differences of local structures among hydrous Fe oxides and aqueous polymers have been interpreted on the basis of a room temperature stability phase diagram established for well-crystallized (oxyhydr)oxides.

Laponite RD forms stable, coherent films which adhere strongly to glass slides. Such films are capable of supporting liquid drops allowing the direct measurement of contact angles for five liquids of which, two were apolar (0:-bromonaphthalene and diiodomethane) and three were polar (water, formamide, glycerol); surface tension components and parameters (γLw, γ⊕ and γ⊖) were determined by solving the Young equation. These determinations were made for homoionic samples saturated with Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba and NH4 as well as the natural material. Whereas the values of γLw (the apolar Lifshitz-van der Waals component) varied only within narrow limits (41-44 mJ/m2), the Lewis base parameter varied comparatively widely (24-41 mJ/m2). The Lewis acid parameter was small and relatively constant (1·3-3·0 mJ/m2). The variation of γ⊖ as a function of the exchangeable cation suggests that the divalent cations are shielded from the silicate surface by the water molecules of their sphere of hydration, whereas the monovalent cations are in direct contact with the oxygen atoms of the silicate surface. Furthermore, the divalent cations may screen the Lewis base sites to a greater degree than do the monovalent cations. Lithium behaves anomalously and this may indicate that it physically enters into the ditrigonal hole in the silicate layer.

Evidence obtained from ESR and IR studies is presented for the presence of structural Cr in two natural kaolinites (MILO and GEY) formed in an hydrothermal environment in Sonoma County, California. The XRD patterns show a greater structural disorder for GEY than for MILO, but both have the usual hexagonal shapes as shown by TEM observations. On the basis of EDX analysis of different particles, GEY, on average, appears to be richer in Cr (2.1% Cr203) than MILO (0.6% Cr203). The presence of Fe oxide particles containing some Cr, Ni and V is also indicated by EDX analysis. By FT-IR observation, the octahedral Cr 3+ position was easily detected by a well resolved spectral feature at 3586 cm -1. The adsorbed Cr 3+ kaolinite (KMRXCR) presents no band at 3586 cm -1, but two other bands situated at 3527 and 3477 cm -1. The main features of the ESR spectra of these two kaolinites are a set of resonances near geff4; a broad resonance centred near geff2 with some modulations; and a set of resonances near gcffl. The broad resonance centred near geff2 is interpreted as the free iron oxide signal with modulations due to VO 2+. The set of resonances near geff4 is similar to that observed for octahedral Fe 3+, but the position is shifted compared to that of octahedral Fe 3+. This set of resonances near geff4 is, therefore, interpreted as belonging to Cr 3+ in octahedral position. The resonances at geff1 are also interpreted as belonging to Cr 3-. Comparison with the Cr 3+ surface-adsorbed ESR signal of a Cr-saturated kaolinite (which is a broad resonance centred near geff2) strengthens the interpretation of the geff4 resonances belonging to Cr 3+ in the octahedral position. The results obtained by the combination of FT-IR and ESR spectroscopics indicate that Cr 3+ is present in the octahedral position of the MILO and GEY kaolinites.

Characterization of platiness of kaolin pigments was derived from the divergence of measurements of their particle size distribution by two different techniques: sedimentation and light scattering. A numerical shape factor, which is related to the ratio of kaolin particle face diameter to its thickness, can be calculated to provide a quantitative measure of such platiness. Two sets of kaolin pigments were prepared from a Middle Georgia kaolin: delaminated and non-delaminated. Shape factors of delaminated samples were higher than those of non-delaminated ones. Maximum platiness was found between equivalent volume diameters of 1·0 and 2·0 μm. Examples are presented where properties of coated paper are correlated with the size and shape of kaolin pigments.

A basic lead carbonate-montmorillonitec omplexw as prepared by treating a natural montmorillonite hydrothermally for 120 h at 250°C with lead powder, dry ice and lead nitrate solution. The product is a non-swelling material showing well-outlined, hexagonal, thin plates <1 µm in size; the symmetry is pseudo-orthorhombic, a = 5·141(7) Å, b = 9·005(5) Å, c = 17·420(4) Å, and Z = 2. The X-ray powder pattern is characterized by a 17·4 Å reflection and an integral series to the 14th order. The TG-DTA curves of this 17 Å-mineral showed one endotherm around 400°C accompanied by weight loss and two exthotherms at about 680 and 780°C By applying hightemperature X-ray diffractometry (XRD) and infrared (IR) spectroscopy, it was found that the endotherm is due to decomposition of carbonate hydroxide in the interlayer, while the two exthotherms are caused by crystallization of a hexagonal phase of PbAl2Si2O8 and by the conversion of this phase into lead feldspar, respectively. The crystal structure of the 17 Å-mineral was determined and refined as a 2:1 dioctahedral smectite interlayered with a hydrocerussite-like layer by a one-dimensional Fourier synthesis method.

The structure of 6-line and 2-line ferrihydrite (Fh) has been reconsidered. X-ray diffraction (XRD) curves were first simulated for the different structural models so far proposed, and it is shown that neither of these corresponds to the actual structure of ferrihydrite. On the basis of agreement between experimental and simulated XRD curves it is shown that Fh is a mixture of three components: (i) Defect-free Fh consisting of anionic ABACA . . . close packing in which Fe atoms occupy only octahedral sites with 50% probability; the hexagonal unit-cell parameters are a = 2-96 Å and c = 9-40 Å, and the space group is P1c. (ii) Defective Fh in which Ac1Bc2A and Ab1Cb2A structural fragments occur with equal probability and alternate completely at random; Fe atoms within each of these fragments have identical ordered distribution with in the hexagonal super-cell with a = 5.26 Å. (iii) Ultradispersed hematite with mean dimension of coherent scattering domains (CSD) of 10-20 Å. The main structural difference between 6-line and 2-line Fh is the size of their CSD which is extremely small for the latter structure. Nearest Fe-Fe distances calculated for this new structural model are very close to those determined by EXAFS spectroscopy on the same samples.

The effect of temperature on the swelling of clay was studied by determining (1) the relation between the interlayer spacing, λ, and the swelling pressure,Π, at different values of the temperature, T, using the method of Viani et al. (1983) as modified by Wu et al. (1989); (2) the relation between λ and T at different values of Π; and (3) the relationship between Π and mw/mc, the mass ratio of water to clay, at different values of T using the method of Low (1980). The results showed that λ was essentially independent of T but that mw/mc decreased slightly with T at any value of Π. Such results are not consistent with electric double-layer theory. Therefore, it was concluded that the decrease in mw/mc with increasing T was due primarily to the thermal breakdown and consequent loss of water from the larger pores outside of the interlayer region.

Large quantities of clay minerals (and other micron-sized mineral powders) are used widely in materials science. Mineral fillers are major components, for example, of paints, rubber, plastics and paper and board. While the original object of such incorporation was to reduce costs, performance is now being “engineered” by design or choice of the relevant mineral particles. This paper concentrates on the use of mineral powders in polymer and paper science. In both application areas, the size and shape of the mineral particles can affect mechanical properties such as stiffness and tensile and impact strength. However, other characteristics are also modified. For example, the drainage rate in paper formation and the rheology of a polymer melt, properties which are critically important to the rate of processing of the relevant materials, can be greatly affected. Finally, the size and shape of the mineral particles also affect appearance, i.e. the smoothness, uniformity, optical properties etc. Mechanical and rheological data are presented for mineral-filled polypropylene, as are mechanical and optical data for filled and coated paper.

Powder X-ray diffraction (XRD) curves were calculated for the different structural models so far proposed for feroxyhite (δFeOOH). The influence on XRD features of different structural parameters, including site occupancy of Fe atoms, atomic coordinates, content and distribution of stacking faults, and dimension of coherent scattering domains, were considered. On the basis of agreement between experimental and simulated curves it is shown that δFeOOH is a mixture of feroxyhite proper and ultradispersed hematite in the 9 : 1 volume ratio. Feroxyhite proper consists of hexagonal close packing of anions containing 5% stacking faults. Iron atoms occupy only octahedral sites and are distributed in such a way that face-sharing filled octahedral pairs regularly alternate with vacant octahedral pairs along the c axis. This distribution of Fe atoms is quite similar to that established by Patrat et al. (1983), but in each pair, Fe atoms are displaced by the same value of 0.3 Å in opposite directions away from the centre of their octahedron. Nearest Fe-Fe distances calculated for the model proposed (2.88, 3.01, 3-39 and 3-73 Å) practically coincide with those found by EXAFS spectroscopy for the same sample (2-91, 3.04, 3.41 and 3.7-3.8 Å).

A method of infrared (IR) analysis for quantitative determination of tubular halloysite in mixtures with kaolinite was investigated for drill hole samples collected during an assessment of paper-coating kaolin resources at the Mount Hope Kaolin Deposit, Eyre Peninsula, South Australia. Tubular, dehydrated halloysite from the deposit does not readily intercalate formamide, and the proportion of tubes in <2 μm size-fractions was determined initially from scanning electron micrographs. For samples showing a range of tube contents, a strong correlation between IR spectral response and counts of halloysite tubes was established using partial leastsquares analysis. This provided a rapid technique suitable for routine determination of tubular halloysite in samples from the Mount Hope deposit. Although the universality of the method remains to be tested, it offers an alternative approach to other analytical techniques for assessment of kaolin deposits where the presence of halloysite is suspected.

The efficiency of removal of the free iron from kaolinite-group minerals by means of acid leaching was followed by chemical, AES, XRD and ESR analyses. Structural Fe responsible for the g = 4 ESR signal represented only a small fraction of Fe impurity in the natural samples. The remaining non-structural Fe was found to exist both as forms easily extractable with acid, as well as deposits that were moderately resistant to the acid treatment. At least part of the latter could be associated with the broad g ~- 2 ESR signal typical of clustered Fe 3+ ions, which in most samples persisted even after prolonged acid leaching. The data demonstrate that procedures commonly used to clean kaolinite of free iron are by no means 100% efficient. In particular, frequently encountered quantitative association of the Fe remaining in the deferrated solids with purely structural Fe, homogeneously distributed in the kaolinite matrix, is probably significantly overestimated and should be treated with great caution.

Calcium-cadmium and calcium-zinc exchange equilibria were studied at 20°C and constant ionic strength (0·015) on four clay minerals, viz. montmorillonite, bentonite, illite and vermiculite. Vermiculite and, to a lesser extent, illite and bentonite showed the strongest affinity for Cd2+ or Zn2+ over Ca2+ ions, whereas on the Camp Berteau montmorillonite nearly nonpreferential exchange isotherms were observed. With this one exception, selectivity for the heavy metals was greatly enhanced in the trace Cd or Zn regions, suggesting the presence of specific adsorption sites in these clays. Generally, the adsorption increased with the polarizing power of the exchangeable cation. Thermodynamic equilibrium constants and standard free energy changes for the complete exchange of Ca-clay to Cd- or Zn-clay were calculated.

Dissolution in HCl of hematite particles with different morphologies led to sigmoidal dissolution vs. time curves. The rate of dissolution was directly proportional to the sample surface area and independent of crystal morphology. Hematites produced by heating goethite at 600 or 800~ dissolved more rapidly per unit area than did hematites grown from solution. TEM showed that some platy crystals developed central holes after prolonged acid attack; the hole formation was attributed to enhanced dissolution at screw dislocations present on the (001) faces of the crystals. Except where particularly susceptible regions involving strained areas or dislocations were present, there appeared to be no preferential acid attack at any particular crystal face. The original morphology was usually maintained during the reaction.

Modem disc centrifuge technology has extended the range of application of sedimentation particle size analysis to include the submicron region. An overall size range of approximately 10 nm to 100 pm is now accessible. The principles of both the disc centrifuge photosedimentometer, which employs optical detection with full Mie light scattering corrections, and the X-ray disc centrifuge are described. Examples of their application to a variety of samples are given to illustrate the performance characteristics of the instruments including a direct comparison of resolving power with that of the laser diffraction technique.

Authigenic clay minerals in the German Rotliegend formed mainly at burial depths >1.5 km. Illite is the dominant cement, although kaolinite, dickite and early radial chlorite are abundant locally. Illites contain more AI and late chlorites more AI and Fe in sequences showing extensive grain dissolution. This relationship between clay chemistry and grain dissolution suggests that clay cementation is linked to grain dissolution. Sequences at relatively shallow burial depths (<3-5 km) contain less clay cement. In the more deeply buried sections, increased illite and kandite cementation, together with extensive grain dissolution, is evident where the Rotliegend is juxtaposed against Carboniferous Coal Measures. Faults also acted as important conduits for acidic fluids. Illite and kandite growth occurred at similar depths and from waters of similar isotopic composition (618O = 1-6‰ SMOW) throughout most of the Southern Permian Basin. However, the timing of illite growth varied between areas and corresponded to periods to tectonic activity.

In Moroccan calcareous mountains, red soils are distinguishable from brown soils, not only by their colour but also by their microaggregated structure. Clay mineral dispersion studies of these soils were carried out by increasing pH, after different treatments. The formation of the pseudo-particles appears to be dependent on the fixation of amorphous Fe on clay and on the chemical binding of those clays by amorphous Al-hydroxy-polycations. This can be explained by the high isoelectric point of ferric compounds such as ferrihydrite which are soluble in ammonium oxalate. Based on these results and using techniques of granulometric analysis, red clays aggregated in pseudo-particles were separated from less rubified clays. Hematite was identified in pseudoparticles from red soils and an increase of amorphous Fe has been shown in aggregated clays. These microstructural conditions characterizing rubification could also favour it, by creating microsites where water activity decreases and allows the crystallization of hematite by dehydration of ferrihydrite.

The use of transmission electron microscopy in association with other methods is described for the characterization of Brazilian industrial clays, especially kaolinitic-halloysitic clays. Examples are presented from: (a) tubular 7 Å-halloysites and the characterization of mixtures with ordered and disordered kaolinites in residual china clays; (b) tubular kaolinitic clay from Piedade, São Paulo; (c) platey 10 Å-halloysite from Poģos de Caldas, Minas Gerais; (d) rolled forms similar to 10 Å-tubular halloysite formed by repeated K Ac intercalation in well ordered kaolinite; (e) use of particle shape and size of kaolinite crystals in the São Simão, São Paulo ball clays as orientation for good sanitaryware ball clays; (f) characterization of gibbsite crystals in high alumina gibbsite/kaolinite clays; (g) antigorite as a clay mineral; (h) electron optical studies of thermal phase transformations involving tubular kaolinite, halloysites, antigorite, chrysotile, talc and pyrophyllite mono crystals.

Amines are strongly adsorbed by the crystalline silica H4Si20O42·4H2O and are intercalated into the interlayer spaces. The adsorption of butyl-, hexyl-, octyl-, and decylamine from alcoholic solutions (ethanol, butanol…decanol) is competitive as both types of molecules, amines and alcohols, are adsorbed in the interlamellar space. The adsorption isotherms are presented as composite isotherms showing the specific reduced surface excess of amine, n°(n)/m, as a function of the molar fraction of amine in the equilibrium solution. These isotherms increase to a plateau-like section (n°(n)/m≈1·4 mmol/g) when the interlamellar adsorption is restricted to formation of monolayers of flat-lying molecules (in water, ethanol and butanol). In the presence of longer chain alcohols, the isotherms increase stepwise to a second "plateau" (at n1°(n)/m = 2·2-2·7 mmol/g) which corresponds to paraffin-type bilayers of amine and alcohol molecules. The composition of the adsorption phase is estimated from the specific reduced surface excess of amine on the basis of the interlamellar structure derived from basal spacing measurements.