The transference numbers of the counter ions in montmorillonite paste are determined as a function of the thickness of the water film (h) and of the diffuse double layer (1/κ).

From measured E.M.F. values of a cell with two liquid junction potentials (C′KCl solution-paste-C″KCl solution) and by applying the Henderson equation, the transference numbers t+ were calculated. It is shown that the transference numbers of the counter-ions, t+ → 1 if hκ → 0.

X-ray diffraction patterns obtained from montmorillonite-dextran complexes prepared with either B-512F or Polytran dextran showed maximum oven-dry crystal expansions of about 5·3 Å. X-ray diffraction patterns of individual complex preparations containing < 20 per cent dextran showed evidence of both expanded and collapsed crystals. The observation of expanded and collapsed crystals in individual preparations has not been previously reported and was apparently related to clay preparation. An estimate of the quantity of dextran which could be interacting with the silicate surface was obtained using polymer adsorption weights and volumes. At maximum adsorption almost all adsorbed B-512F could be in contact with the mineral surface, but only two thirds of the adsorbed Polytran could be in contact with the mineral surface.

The chemical and mineralogical properties of six soils previously believed to be developed from coastal plain sediments were found to be significantly influenced by thin loess overlays and admixtures. The study included two profiles each of the Atwood, Lucedale and Savannah series. Atwood formed primarily in deep loess over coastal plain sediments, Lucedale showed definite loess influence to a depth of 10 in. and possible mixing to a greater depth, whereas the Savannah indicated the presence of slight loess to a depth of 20 in. Both the Atwood and Lucedale soils are well drained, whereas Savannah is moderately well drained and contains a fragipan.

The mineralogy of the coarse clay (2-0·2 μm) appeared to be the most diagnostic feature indicating genetic differences among the soils. Montmorillonite in this clay fraction was most abundant in Atwood, diminished in Lucedale and occurred only in trace amounts in Savannah. In both the Atwood and Lucedale soils very little montmorillonite was found at depths of 35 in. where coastal plain influence apparently predominates. Conversely, aluminous vermiculite-chlorite intergrade minerals were least abundant, in Atwood, increased in Lucedale and occurred in greatest amounts in Savannah.

Accompanying these changes in mineralogy were corresponding changes in the chemical properties. Although no consistent differences in Ca and Mg content were found between the Atwood and Lucedale soils, both Atwood and Lucedale were much higher in exchangeable Ca and Mg than Savannah. Soil pH and base saturation increased in the order Savannah, Lucedale and Atwood.

The ammonia electrode serves as the basis of a simple, accurate method for determination of cation exchange capacity of small (ca. 50 mg) samples of clays. The technique is also capable of accurate measurement of CEC values on the order of 0·01 m-equiv/100 g if larger (ca. 500 mg) samples are used. The procedure, which requires saturation of the exchange sites with ammonium as in the usual methods, utilizes the electrode in the determination of ammonia released by treatment of the ammonium clay by strong base. For a Wyoming bentonite, the technique gave a CEC of 86 m-equiv/100 g with an S.D. (four determinations) of 0·83 m-equiv/100 g. Duplicate runs on the same sample by the conventional Kjeldahl method gave results of 86·0 and 85·5 m-equiv/100 g.

Electrochemical treatment of kaolinite-glass bead plugs in the presence of water and CaCl2 solutions produces dissolution of the glass beads, corrosion of the anodes, and transport of the released elements toward the cathodic zone. In this area, new mineral phases (both amorphous and crystalline) are synthesized. Most of these new phases, and especially the calcium silicate hydrate (CSH-1), are well known to exhibit important cementing properties. The nature and the extent of the modifications brought about by the treatment are dependent on the nature of the electrodes, the pH and the ionic strength of the circulating electrolyte, and the duration of the treatment.

The crystal structure of a sample of talc from Harford County, Maryland, has been determined by least squares refinement from X-ray diffraction photographs. A triclinic cell with a = 5·293, b = 9·179, c = 9·496Å, α = 90·57°, β = 98·91°, γ = 90·03, space group C1̄ is adopted. The layers of the structure have almost monoclinic symmetry but the nearly hexagonal rings of oxygen atoms on the surfaces of the layers, formed by the bases of the silica tetrahedra, are not held in register by interlayer ions as they are in micas but are partly displaced so that the stack of layers forms a triclinic crystal. The hexagons of surface oxygens are distorted by a 3·4° twist of the tetrahedra so that the b axis is 0·2 per cent shorter than in a structure with regular hexagons, and the twist brings the oxygen ions a little closer to the octahedral magnesium ions.

The magnetic behavior of some biotite samples, from volcanic rocks of W. Thrace area, N.E. Greece, was studied in the temperature range from 85 to 270°K and compared with the chemical composition. The magnetization of the samples depends linearly on the applied field, and the magnetic susceptibility obeys the Curie law, showing a typical paramagnetic behavior which is due to Fe2+, Fe3+ and Mn2+ The effective magnetic moment was calculated from the structural formulas of the samples and deviation from the experimental values is discussed.

X-ray diffraction patterns of garnierites indicate that most samples resemble serpentine-group minerals or a talc-like mineral, or a mixture of these forms, and give respectively 7 Å and 10 Å basal reflections. From a survey of some 40 garnierites, four of predominantly serpentine type and seven of predominantly talc-like type were selected for detailed study. The talc-like garnierites exhibit little variation of the 10 Å basal spacing with low-temperature heating or with immersion in liquids, though some may contain a small proportion of expandable layers. Chemical analyses show considerable deviations of octahedral/tetrahedral cation ratios from the values 3/2 and 3/4 for normal serpentine and talc minerals, and may be interpreted in terms of mixed 1:1 and 2:1 layer types, either as separate phases and/or as interstratifications, or as defect structures of various kinds. The H2O + contents of the talc-like forms of garnierite are considerably greater than that of normal talc and point to a mineral of composition 3(Mg, Ni)O·4SiO2. 2H2O or [(Mg, Ni)3Si4O10(OH)2]H2O—a talc mono-hydrate formula. The green color of garnierites is related to the NiO weight per cent and a color index is derived based on the Munsell color charts.

Aluminum ions as well as hydroxide precipitates promote improved extraction of iron from kaolinites during leaching. Selective aggregation of ultrafine particles in kaolinites, seemingly induced by precipitation of aluminum hydroxide, gives brightness improvement in excess of that which can be ascribed to iron extraction. Aggregation of anatase, a primary discolorant confined mostly to the fine end of the kaolinite particle size distribution, is the suggested mechanism for complementary brightness improvement.

Precipitation of aluminum hydroxide in kaolinite systems substantially changes flocculation characteristics, surface area (methylene blue), and rheology. Edge-edge and edge-face flocculation are promoted where sulfate retention is high, becoming progressively more face-face with sulfate removal. The character of the flocculation can be interpreted by the combined use of surface area and low shear viscosity data.

The extent to which kaolinites can be dispersed after processing increases with increase in sulfate retention. Stability of suspensions deflocculated with polyphosphates shows an inverse relationship, decreasing with increase in sulfate retention.

This article emphasizes the influence of crystal-chemical composition on the ease of transformation of micas to vermiculite or more smectite-like minerals. The swelling test, with glycerol, of Mg-saturated mineral is used to characterize the degree of transformation.

The main structural factors of this evolution are tetrahedral substitution of Si by Al, and total charge. There is a relation between these two factors, i.e. the lower the tetrahedral substitution, the greater can be the charge without affecting the smectite swelling behavior.

In this respect there is a contrast between tri and dioctahedral micas. In the first, tetrahedral Al is so high (> 1·20 for Si4O10) that transformation into smectite must imply modification of the tetrahedral layer. For dioctahedral micaceous phyllites (illites, glauconites) where tetrahedral charge is lower, transformation can be easier. Only a lowering of total charge is needed and reduction-oxidation seems to play a very important role in this process.

Clayey fragments colored deep bluish-green are widely found in glassy rhyolitic tuffs at Oya, Tochigi Prefecture. In room-air the color changes to black or gray within one hour and finally to brown in a few weeks. The fragments are composed of an intimate mixture of two kinds of smectite: a ferrous iron-rich smectite (IR) with b0 = 9·300 Å; and an iron-poor smectite(IP) with b0 = 9·030 Å. Microscopic examination shows a vesicular texture and that IR occurs at the core and IP at the marginal parts of each vesicle. Analysis by EPMA gave the following structural formulas: IR, (Na0·60K0·04Ca0·44) (Mg2·04Fe3·982+Al0·02) (Si6·36Al1·64)O20(OH)4; IP, (Na0·52K0·08Ca0·26) (Mg0·90Fe0·952+Al2·54) (Si7·66Al0·34)O20(OH)4. IR has a much larger amount of iron in trioctahedral sites than that found in any earlier data. Acid-dissolution data, infrared absorption spectra, Eh-values, and DTA and TG curves are also given. Ferrous iron in the structure is easily oxidized in room air with loss of protons from the clay hydroxyls and with contraction of the lattice. We call the IR before and after oxidation the ferrous and ferric forms, respectively, of iron-rich saponite. They strongly suggest the existence of the iron-analogue of saponite. On exposed weathered surfaces in the field, brown fragments tend to be differentiated into two parts: one light yellow montmorillonite-beidellite; the other a brown incrustation due to hisingerite.

Artificial weathering of biotites, which contain various levels of structural ferric iron, by NaCl and NaBPh4 solutions produces minerals and structures similar to those described for naturally weathered biotites. Oxidation of structural iron leads to K removal from alternate layers and development of hydrobiotite. The growth of order with increasing ferric iron content has been assessed by comparison with theoretical calculations for random and most ordered interstratified structures. There is evidence for the existence of two layer types in biotite prior to oxidation. The depression in rates of K release due to oxidation has been confirmed.

The structure of a dioctahedral 2M2 mica was defined by high voltage electron diffraction. The cell parameters are: a = 8·965, b = 5·175, c = 20·31 Å, β = 100° 40′, Z = 4, space group C2/c. Despite the peculiar character of the layer disposition (σ4 σ5 σ4 σ5), the oxygens of the layers are packed according to the cubic law. Consequently, the interlayer cations K have a trigonal prismatic coordination. The angle of tetrahedral twist is 11° 20′. The interatomic distances T-O indicate ordered replacements of Al for Si.

Infrared absorption spectra show important changes in the positions and form of the absorption bands of a film of attapulgite after it has been pumped out. An attempt to differentiate among some of the multiple frequencies due to OH groups is based on the information obtained from dehydration and deuteration experiments. The 1198 cm−1 shoulder, characteristic of attapulgite, is assigned to a Si-O vibration. When attapulgite is refluxed with 5N HCl for 5 hr the octahedral layer is dissolved. The acid attack causes the disappearance of the Si-O-Si absorption bands from attapulgite giving rise to a characteristic vibration at 1090 cm−1, as well as another absorption at 960 cm−1. The latter indicates the presence of silanol groups.

Electron micrographs of 7 Å-type and 10 Å-type garnierites have been recorded at 5·104–105X magnifications to show the morphological character of these minerals, and at 106X magnification to show structural features of the particles. The 7 Å, serpentine-like minerals show a greater variety of morphological forms including tube- and rod-shaped particles and also platy forms and poorly defined, fluffy particles, probably aggregates. The 10 Å, talc-like minerals show mainly platy forms and fluffy aggregates, and generally very few tube or rod-shaped particles. At 106X magnifications, the 7 and 10 Å layer spacings are seen directly. In the samples examined, the 7 Å spacings are more clearly and more regularly defined than the 10 Å spacings.

The autoradiographic method at the electron microscope level has been applied successfully to locate the position of sorbed ions and compounds associated with kaolinite and dickite particles. For suitable isotopes, the limit of resolution was about 0·2 μm and would be conceivably less in the most favorable conditions.

Judged by the location of iodide-125 and strontium-85, the majority of positive sites and also the most reactive negative sites were situated at the edges of the clay particles. These conclusions were supported by normal electron microscope examination of mixtures of clay with charged gold and silver iodide sols.

Iron (III) ions, which have been shown to react with kaolinite by chemisorption mechanisms in 0·15 M systems and by both ion exchange and chemisorption in 0·01 M systems, were, in either case, located at edge-sites on the clay. When intentionally precipitated onto dickite, iron (III) hydroxides were distributed evenly over the clay surfaces. However, precipitation was probably initiated at the particle edges.

Minor exceptions to the above conclusions appeared to be caused by basal surface features such as fracture or stress lines, outgrowths or cavities, and if the clays had not been cleaned, by strongly associated impurities such as iron hydroxides.

The basal spacings of long chain n-alkanol complexes of nontronite saturated with Li+, K+ Mg2+, Ca2+, Sr2+ and Ba2+ were measured for temperatures increasing from −70°C up to 130°C. With rising temperatures the complexes rearrange from a low temperature form into a high temperature form.

In the low temperature form the alkyl chains of the alkanol molecules form bilayers with their chain axes perpendicular to the silicate layers. The chains may not be in all cases in the planar all trans conformation but in special ‘kink’-conformations.

The transition into the high temperature form is explained by cooperative transition from a form with a low number of ‘jogs’ to one with a high number of ‘jogs’ and ‘kinks’.

The ability of a clay mineral surface to function as an acid is not represented by bulk pH measurements. A method using u.v. analysis and organic indicators has been developed to monitor surface acidity. The u.v. organic indicator method enables sensitive in situ quantification of surface-induced protonation in wet or dry clay systems. The clay preparation procedure used yields reproducible acidic behavior.

The sorption of anisole and some related aromatic ethers on the interlamellar surfaces of Cu(II) hectorite has been investigated by i.r. and e.s.r. spectroscopy. In addition to physical adsorption, anisole forms two distinct types of Cu(II) complexes which are analogous to the type I and II species previously reported for benzene-Cu(II) smectite systems. These complexes can be transformed to type I and II complexes of 4,4’-dimethoxybiphenyl. Possible mechanisms are proposed for the oxidation process. Butyl phenyl ether formed a type II complex with Cu(II)-hectorite, but no dimerization reaction was noted in this system. Phenyl ether and benzyl methyl ether form a type I π complex with Cu(II)-hectorite. No type II analog was noted. E.S.R. spectra of each of the type II ether-Cu(II)-hectorite systems showed a single, narrow band with g near the value expected for a “free spinning” electron. The type I phenyl ether and benzyl methyl ether complexes also exhibited this e.s.r. band. Ag(I) hectorite adsorbs anisole by forming exclusively a type I complex. Na(I) and Co(II) hectorite adsorb anisole by physical means only, indicating association with the silicate surface.

An interstratified mineral (mica-montmorillonite) from a hydrothermally altered andesite in the southern part of Satsuma Peninsula, Japan fully rehydrates after having been heated to 800°C.