Smectites synthesized from experiments at 5.5 GPa and 1500°C are of high quality, crystals are large at >10 μm, and the 2:1 layers may have a homogeneous charge distribution. Smectite was exchanged with various cations (Na+, Li+, K+, Ca2+, and Mg2+) and the hydration behavior of each sample was observed by an in situ powder X-ray diffraction method under precisely controlled relative humidity (RH). The smectite showed distinct stepwise (discontinuous) hydration versus RH. During the transition between two hydration states, the coexistence of the two states was observed. Randomly interstratified structures with one and two planes of H2O are time-dependent phenomena and relate to hydration and dehydration processes.

The effect of cooling rate on the formation of smectite crystals with high crystallinity was investigated using two different types of high-pressure and high-temperature apparatus, a modified belt type and a uniaxial split-sphere type. The cooling rate was changed after a treatment of the sample at 5.5 GPa and 1500°C. Smectite crystals were obtained at faster cooling rate, coexisting with coesite, kyanite, jadeite, corundum and/or glass. In the slowly cooled process, no smectite crystals were obtained but coesite, kyanite, jadeite and clinoenstatite were formed. These results indicate that smectite crystals are formed metastably during the quenching of the high-pressure and high-temperature hydrous silicate melt.

Trimethylammonium ions (TMA+) with formula CH3(CH2)n-1N+(CH3)3, with n = 4, 8, 12, 16, 18 and 22 were intercalated into synthetic Li-fluorotaeniolite (Li-FTN) and Li-fluorohectorite (Li-FHT) by cation exchange. The products were analyzed by thermogravimetric (TGA) and X-ray powder diffraction (XRD). XRD patterns exhibited variable (001) spacings of the TMA+/mica complexes depending upon the exchange ratio of TMA+/Li+ and the carbon number of TMA+. Detailed inspection of these XRD patterns clarified the structures of the complexes and also the intercalation mechanism, as follows: The fundamental structure of the complexes is the commonly known intercalation structure where the “paraffin-type bilayers” of TMA+ are in the mica interlayer and their long chains incline at approximately 30° to the silicate sheet. This structure appeared at the final stage of the intercalation reaction. During the intermediate stage of the reaction, units of this structure and those of hydrated mica formed randomly and regularly interstratified structures. Variable (001) spacings in XRD patterns showed the structural change of the complex with an increasing number of TMA+-intercalated units.

Hydration behavior of Na-smectite crystals synthesized at a pressure of 5.5 GPa and temperatures of 1400°–1500°C was examined by X-ray powder diffraction at various relative humidities (RH) in the range of 0–100%. The basal spacing of the Na-smectite crystal increased stepwise with increase in RH. The reflections observed were only normal reflections of a single or dual hydration states of smectite. No irrational, intermediate, or asymmetrical reflections were observed. The simple hydration behavior, not known for natural smectite with fine particle sizes and low crystallinity, indicates that the Na-smectite crystals are as perfect as common inorganic crystals with an ordered structure.

Smectite single crystals of superior quality were synthesized at high pressures and temperatures using a modified belt type high pressure apparatus. Pressure-temperature conditions were established for smectite formation by quenching experiments in the pressure range from 2–5.5 GPa and temperatures of 700°–1000°C. Smectite crystals with extraordinary quality were formed beyond 3 GPa and 1000°C with coexisting phases of coesite, kyanite, jadeite, and in some cases with mica and glass. Smectite was confirmed from the XRD taken after intercalation of ethylene glycol. The smectite crystals were considered to be quenched crystals metastably from the hydrous silicate melts formed at high pressures and temperatures.

Transformation of montmorillonite was experimentally investigated using a model system of montmorillonite-alanine at 100 MPa and up to 500°C. Sodium-montmorillonite changed to a mixed layer mineral of sodium- and ammoniumn-montmorillonites (Na/NH4-Mnt) in the temperature range from 150 to 400°C. Ammonium ions were the decomposition product of alanine above 150°C. The Na/NH4-Mnt transformed to regularly and randomly interstratified minerals of NH4-montmorillonite and NH4-mica (o. NH4-Mnt/NH4-Mic and d. NH4-Mnt/NH4-Mic) at 400°C. These mixed layered minerals transformed to ammonium-mica at 500°C. Ammonium-analcime appeared and coexisted with the smectites at temperatures over 200°C, and with albite for those over 400°C.

In comparison with the results of previous experiments in which there was no organic component, the present results revealed that (1) some uncommon mineral phases appeared by replacement of sodium ions in montmorillonite with ammonium ions, i.e., NH4-Mic, o. and d. NH4-Mnts, o. and d. NH4-Mnt/NH4-Mics, and (2) ammonium-analcime appeared. The mineral assemblages and alteration sequences correspond better with those observed in the natural system than those known from experimental results in aluminosilicate-water system.

A glass in the intermediate composition of montmorillonite and beidellite, 50/50 in mole ratio, was treated under a hydrothermal pressure of 100 MPa, in the temperature range from 250 to 500°C and durations from 2 to 129 days. The phases identified in the products were plotted in a time-temperature-transformation (TTT) diagram. The TTT diagram showed that the regularly interstratified montmorillonite-beidellite (r.i.M-B) was a metastable phase above the temperature of 350°C and changed to the assemblage of Na-rectorite + saponite + quartz, through the intermediate assemblage of beidellite + saponite + quartz. The TTT diagram suggested also that the r.i.M-B might be a stable clay mineral below the temperature of 300°C in the middle region of montmorillonite-beidellite pseudo-binary system, although the laboratory confirmation of the mineral stability was not easy for the sluggish reaction.

A series of hydrothermal experiments were performed to determine the phase relations on the beidellite-saponite pseudo-binary join. Quenched glasses with stoichiometric dehydrated compositions of an Na-rich smectite on the join were heated at 250–500°C for durations of 1–151 d at 100 MPa. Time-temperature diagrams showed that immiscibility occurs between dioctahedral smectite (beidellite) and trioctahedral smectite (saponite) below 400°C. Thus, smectite with intermediate chemical composition was considered as metastable in this system. Above 400°C the assemblage of regularly interstratified saponite-chlorite, quartz, and feldspar was recognized in the intermediate chemical compositional region of this join. On the beidellite side of this join, beidellite and mixed-layer phases of smectite and a regular interstratification of montmorillonite-beidellite, are possible phases that occur at <300°C. They readily reacted to form a mixture of dioctahedral rectorite plus quartz at 300°C. This assemblage then reacted to a dioctahedral “mica”, which can expand with glycol and quartz. On the saponite side of this join, a single phase, saponite, existed at <400°C, and transformed to saponite plus trioctahedral rectorite with aging and increasing temperature of synthesis. The alteration was affected strongly by the chemical composition of the binary system.

A scanning X-ray analytical microscope was constructed using X-ray guide tube(XGT). XGT is a glass capillary which guides and focuses x-rays by total external reflection at the inner wall. The nature of X-ray beam passed through XGT is varied depending on the form of XGT. The cylindrical and conical types were used for the present setup. A small area (10μm × 10μm) of the sample was irradiated by the X-ray microbeam formed by XGT. Fluorescent and diffracted X-rays from the small area were detected by SSD. By scanning the sample in the plane normal to the X-ray microbeam, the intensity distributions of such secondary x-rays were measured and used as picture elements for constructing x-ray mapping images. The sample was a thin-section of an old chinaware. The images suggest a wide application of this instrument.