The structure of a lepidolite-2M1 from Biskupice, Czechoslovakia, has been redetermined. Violations of systematic extinctions and of monoclinic equivalences plus the results of a second harmonic generation test indicate that the true symmetry most likely is C1̄. The deviation of the data set from C2/c symmetry, however, proved to be too small to permit a statistically significant refinement in C1̄. Refinement in C2/c symmetry indicated no ordering of tetrahedral cations but ordering of octahedral cations so that M(1) = Li0.93R2+0.06Fe3+0.01 and M(2) = Al0.58Li0.35□0.07. The tetrahedra are elongated to form trigonal pyramids with a rotation angle of 6.2°. The anomalous orientation of the thermal ellipsoid for the F,OH anion plus the large equivalent isotropic B value of 2.58 for F,OH and of 1.74 for the interlayer K cation, whose position is partly restricted in C2/c symmetry, suggest a lower symmetry than C2/c.

The compositions of this sample and of a second lepidolite-2M1 from Western Australia fall outside the stability field of lepidolite-2M1 in the synthetic system. Structural control of the stacking sequence is discounted on the basis of the structural similarity of the lepidolite unit layers. Crystallization parameters are considered more important than composition or the structure of the unit layer in determining the stability and occurrence of different layer-stacking sequences in lepidolite.

Cross-linking of Li-montmorillonite by hydroxy-aluminum oligomers was performed in a specially constructed mixing apparatus. Observations on flocculation and solution composition were carried out during and after the cross-linking reaction; the dry product was studied by scanning electron microscopy.

Flocculation was most pronounced at Al/montmorillonite ratios between 0.98 and 2.45 mM/g; below and above this range, flocculation was much less intensive. These observations can be explained by heterocoagulation and protecting colloid action. A complete neutralization of the montmorillonite charge was estimated at 1.9 mM adsorbed Al per g clay, and in order to account for the electrical charge of the hydroxy-Al, polymers with an average charge of 0.5 per Al atom must be assumed on the montmorillonite surface. Assuming that the hydroxy-aluminum form in the unreacted solution is Al6(OH)3+12, the adsorbed polymer will be Al24(OH)12+60. Alternatively, assuming Al6(OH)3+15 in the unreacted solution, this form will remain unchanged upon adsorption onto the montmorillonite surface.

Differences in the microfabric of dry Al-CLM as a function of Al/montmorillonite ratio can be explained along the lines of the interpretation of the flocculation studies.

Li-bearing smectite minerals occurring as hydrothermal alteration products of magnesium silicate minerals in skarns associated with the Moldova Nouǎ, Romania, porphyry copper deposit were examined by X-ray powder diffraction, infrared spectroscopy, and thermal and chemical analyses. Li-bearing smectite containing 0.45–0.50 Li/unit cell is common, whereas smectite containing 0.21–0.33 Li/unit cell is less common. Both materials coexist with talc and kerolite. The Li-bearing smectite minerals (b = 9.111 Å) contains semi-ordered or ordered stacking and is highly crystalline, similar to saponite. After 3-yr storage under laboratory conditions in an air-dried state (RH = 50%) or after heating for 2 hr at 100°, 200°, 300°, or 400°C, the Li-bearing smectite minerals showed charactenstics of a regular 1:1 interstratification of anhydrous and dihydrate layers. Some segregation of the anhydrous, monohydrate, and dihydrate layers was noted.

The amount of Li-for-Mg substitution was found to be close to that in hectorite, and the number of octahedral vacancies was similar to that in stevensite. This Li-bearing smectite apparently formed directly from colloidal suspensions at atmospheric temperature and pressure.

Sedimentologic zones that are differentiated by changes in lithology, mineralogy, chemical composition, and crystal morphology observable in scanning electron micrographs occur in Missouri high-alumina clay deposits. These properties and changes suggest that the high-alumina materials originated from Pennsylvanian-age, paludal sediments deposited in depressions underlying Paleozoic carbonate rocks. Alumina was relatively enriched in zones of the deposits by leaching of silica and of alkali and alkaline earth metals from the sediments. The most intense leaching occurred on the highest parts of the Ozark Dome.

Diaspore is the predominant high-alumina mineral. Boehmite, although far less abundant than diapsore, may have paragenetically preceded diaspore in some deposits. Chlorite, presumably an Al-rich variety because the content of MgO is typically <0.5%, is also present. Li, which is sporadically present, is inferred to have accumulated in the chlorite which may be a proto-variety of cookeite. Because Li+ and Al3+ are similar in size, Li is inferred to have accompanied Al as a resistate element in contrast to K and Na which were leached from parent phyllosilicates.

Lithium-bearing donbassite and tosudite were found in veins in hydrothermally altered granite (Beauvoir granite) in the northern part of the Massif Central, France. The two minerals are characterized by their high Li contents and low Mg and Fe contents; their structural formulae are: $${\left( {S{i_{3.81}}A{l_{0.19}}} \right)_{\Sigma = 4.00}}{O_{10}}{\left( {A{l_{3.81}}L{i_{0.52}}Fe_{0.01}^{2 + }C{a_{0.02}}M{g_{0.01}}} \right)_{\Sigma - 4.38}}{\left( {OH} \right)_8}{\left( {N{a_{0.07}}{K_{0.04}}} \right)_{\Sigma = 0.11}}$$ for donbassite and $${\left( {S{i_{3.50}}A{l_{0.50}}} \right)_{\Sigma = 4.00}}{O_{10}}{\left( {A{l_{2.95}}L{i_{0.22}}Fe_{0.01}^{3 + }T{i_{0.01}}} \right)_{\Sigma = 3.19}}{\left( {OH} \right)_5}{\left( {C{a_{0.01}}N{a_{0.15}}{K_{0.18}}} \right)_{\Sigma = 0.34}}$$ for tosudite.

These chemical compositions indicate that the donbassite is an intermediate member of the donbassite-cookeite solid solution series and that the tosudite consists of interstratified Li-donbassite and beidellite. Both Li-bearing minerals show thermal behavior distinct from those previously reported for dioctahedral chlorite and tosudite.

Petrographie investigation of drill cuttings from the Echassières area indicates that the two minerals were formed in an intermediate stage of hydrothermal alteration following an early stage characterized by formation of muscovite (2M1) at >350°C and before the latest stage characterized by deposition of kaolinite and randomly interstratified illite/smectite at < 100°C. Moreover, tosudite occurs in the upper part of the granite, whereas donbassite is restricted to the lower part, suggesting the formation of tosudite at lower temperatures.

Twenty-nine chlorites, seventeen lithium-free micas, and twenty-two lithium-bearing micas from diverse localities have been studied by X-ray diffraction, microprobe, and optical second harmonic generation (SHG) techniques to determine which are noncentric and the cause of acentricity. Manandonite (B-rich chlorite) and cookeite, both crystallizing in the Ia form, are acentric. Sudoite-IIb gave a questionable SHG signal, possibly indicating acentricity. All other chlorites gave null signals. Bityite, a Li, Be mica similar to margarite, was determined from the positive SHG response to be acentric. It crystallizes in the 2M1 form and, by analogy to margarite, is ordered tetrahedrally in subgroup symmetry, Cc. Masutomilite-1M and “cryophyllite“-1M (a zinnwaldite high in Al and Si, but low in Fe) are acentric and most probably crystallize in space group C2, thus allowing a noncentric octahedral ordering pattern. Lepidolites showed a diversity in SHG response with only a few being acentric; a lepidolite-1M from Mesagrande, California, a lepidolite-3T from Windhuk, South West Africa, and a lepidolite-2M2 from Nagatare, Japan, gave positive SHG responses. The Japanese material is complexly intergrown and twinned, and intergrain reflection or refraction may have produced spurious signals.

Most lithium-free micas showed diversity in SHG response and, although most were non-emitters, clintonite from Amity, New York, showed a positive response, but this sample is twinned and shows stacking disorder. A “manganophyllite”-1M (manganoan phlogopite) from Langban, Sweden, showed a very weak positive response; however, the presence of Mn alone is not suffcient to produce octahedral cation ordering in noncentric subgroup symmetry. Two manganoan phlogopites from Japan were refined in subgroup symmetry, and the higher order and ideal symmetry of C2/m was confirmed.

Reference smectites were examined to determine relationships between Li uptake, cation-exchange capacity (CEC), and octahedral layer charge after Li saturation and heating at 250°C (Hofmann-Klemen effect). Direct measurements of exchangeable Li after heating led to overestimates of charge reduction due to entrapment of Li in collapsed interlayers. Expansion of interlayers by sequential washings with 1 N MgCl2, 0.01 N MgCl2, and ethanol and subsequent determinations of exchangeable Mg provided accurate measurements of reduced charge. The CEC reductions observed in dioctahedral samples as a result of Li saturation and heating equaled octahedral charge values derived from published mineral formulae, and interlayer charge estimates obtained by alkylammonium exchange confirmed that measured CEC reductions were a consequence of uniform decreases in octahedral layer charge.

Dioctahedral specimens retained 1 to 10 meq/100 g of non-exchangeable Li in excess of CEC reduction and were acidified in direct proportion to their total Fe contents, apparently as a result of the deprotonation of structural hydroxyl groups. Mild acid treatment reprotonated these hydroxyl groups, released excess Li, and resulted in total Li contents comparable to measured CEC reductions. Heating (250°C) Mg-saturated hectorite induced a loss of octahedral Li, acidification, and a reduction of CEC, indicating that Mg had partially replaced octahedral Li. These results suggest that octahedral Li is mobile at low temperatures and that cation movement into or out of the octahedral sheet is favored if the layer charge is reduced.

A layered double hydroxide with a chemical composition [Al2Li(OH)6]+X− · nH2O, where X− is an interlayer anion, has been synthesized hydrothermally at 130°C from aluminum-tri-(sec-butoxide) and lithium carbonate. Electron micrographs showed the product to have a platy morphology with distinct hexagonal symmetry, which has been corroborated by selected area electron diffraction patterns corresponding to a projection of the structure on its (001) plane. Evidence for a superlattice with a = 5.32 Å was obtained, indicating cation ordering among octahedral sites. X-ray powder diffraction data also can be interpreted by reference to a hexagonal supercell with dimensions a = 5.32 Å and c = 15.24 Å. The arrangement of the octahedral sites appears to be that of gibbsite, but with the vacancies filled with lithium cations. Anions must be present between the sheets to balance the charge. A complete assignment of the observed infrared lattice vibrations can be made for the anion [Al2LiO6] with the ideal D3d symmetry for motions within one octahedral sheet. The results show that [Al2Li(OH)6]+X− · nH2O is a hydrotalcite-like compound with the octahedral cations largely ordered. The general formula for hydrotalcite-like compounds, [M2+1−xM3+x(OH)2]x+Xm−x/m · nH2O, should be extended to include the monovalent lithium cation.

When Li-saturated montmorillonite is heated to 200–300 °C, the Li ions migrate from interlayer positions to sites in the layer structure. However, the identity of these sites has not been clearly established. Here we have investigated the migration of Li ions in montmorillonite, after heat treatment at 250 °C, using chemical and instrumental analyses. The latter include X-ray diffractometry (XRD), 7Linuclear magnetic resonance (NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Heating causes a large reduction in cation exchange capacity (CEC) and an almost complete loss of interlayer expansion with glycerol as shown by XRD. Static and magic angle spinning (MAS) 7Li-NMR spectroscopy shows that the quadrupole coupling constant of Li increases markedly over the corresponding value for unheated Li-montmorillonite (where Li occupies exchange sites in the interlayer space) and for hectorite (where Li is located in the octahedral sheet). This would indicate that, in heated montmorillonite, Li occupies structural sites of low symmetry which, however, cannot be identified with octahedral vacancies in the layer structure as is commonly assumed. XPS shows that the binding energy (BE) for Li in unheated montmorillonite is comparable to that for other exchangeable cations. Heating broadens the Li 1s band and decreases the BE. The BE for Li in heated montmorillonite is significantly higher than that in either spodumene or lepidolite, where Li is known to occupy octahedral sites. The combined data suggest that heating induces Li to migrate from interlayer sites to ditrigonal cavities in the tetrahedral sheet, rather than into vacancies in the octahedral sheet, of montmorillonite.

Cation exchange experiments were carried out on phlogopite, biotite, and muscovite using cryptand [222] as a complexing agent, dioxane as solvent, and Li as the exchanging cation. The results indicate greater than 90% exchange of the analyzed cations K+, Rb+, and Sr++ in phlogopite and biotite after two days. Similar results for the exchange in muscovite are observed but it is apparently slower. The amount of exchange observed for mica depends mainly on pH, time and the exchanging cation at a constant temperature. Residues of the mineral phase were also investigated by X-ray diffraction and a significant change of the interlayer spacing was detected. Some samples of the residue were analyzed for Li content. The compositions of the treated samples were in good agreement with the determined exchange of K+.