The hydrothermal synthesis of kaolinite was examined in the Al2O3-SiO2-H2O system to study inhibitory effects of additional ions on the formation of kaolinite. Syntheses were carried out with amorphous starting materials and salt solutions of various concentrations in Teflon pressure vessels at 220°C for 5 days. The reaction products were characterized by XRD, IR, DTA-TG, NMR and TEM. In all of the runs using solutions with cation concentrations less than 0.001 M, no significant effect on the formation of kaolinite was observed. The inhibitory effect of the univalent cations Li+, Na+ or K+ was less than that of divalent cations such as Mg2+ or Ca2+. The addition of trivalent Fe3+ or excess Al3+ ions interfered with the formation of kaolinite significantly. Sulfate and acetate solutions interfered with the formation of kaolinite more than chlorides and nitrates. No crystalline product was obtained using a 1.0 M basic solution of carbonate or hydroxide. The addition of the lithium ion to the system affected the crystallization of kaolinite only slightly. The use of 0.1 M LiCl and LiNO3 solutions for the syntheses improved crystallization of kaolinite along the [001] direction.

The formation of iron-rich phyllosilicates can occur at different natural or engineered settings. In this study, the influence of pH in the hydrothermal synthesis of iron-rich phyllosilicates was investigated in the pH range 8.50–12.10 after the ageing of the precursor. The synthesized samples were characterized by powder X-ray diffraction, Raman and Mössbauer spectroscopies and transmission electron microscopy. Three domains of pH were identified, and these correlated with silica availability and its speciation in the solution. The formation of 1:1-type FeIII/FeII phyllosilicate was observed between pH 9.67 and 10.75. Above pH 10.75, two types of phyllosilicate-like mineral phases were observed. In addition to 1:1-type FeIII/FeII phyllosilicate, 2:1-type FeIII/FeII phyllosilicate was observed. Below pH 9.67, mainly amorphous silica and iron oxides were observed. The findings show that pH governed the crystallinity and nature of the obtained phyllosilicate-like phases.

A comparative study is reported in which kaolinite has been hydrothermally synthesized at several pH conditions. The syntheses were carried out at 220 °C for 3 to 10 d with distilled water or acidic solutions using a mixture of silica-gel derived from alkoxide and gibbsite with a Si/Al ratio of 1:1 as the starting material. Use of acidic solution for the synthesis promotes the dissolution of the starting materials and leads to kaolinitization at an earlier stage of the reaction. However, the rate of kaolinitization is found to be rather slow, in comparison to the reaction with distilled water. The synthetic kaolinite was characterized by X-ray powder diffraction pattern. Kaolinite synthesized with distilled water was poorly grown for direction of the stacking. For example, crystallite size along the c*-axis = 155 Å, whereas kaolinite synthesized with acidic solution gave a higher crystallite size along the c*-axis, such as 253 Å in the case of the synthesis with 0.1 N HCl. Hinckley index of the synthetic kaolinite was varied from 0.35 to 0.80 by the acidity of the reaction. Different kaolinitization processes are implied by differences observed in the rate of kaolinitization, which has an influence on the nature of the stacking faults of the kaolinite.

In the chemical system Na2O-Al2O3-SiO2-H2O, the stability field of Na-beidellite is presented as a function of pressure, temperature, and Na- and Si-activity. Na0.7-beidellite was hydrothermally synthesized using a stoichiometric gel composition in the temperature range from 275° to 475°C and at pressures from 0.2 to 5 kbar. Below 275°C kaolinite was the only crystalline phase, and above about 500°C paragonite and quartz developed instead of beidellite. An optimum yield of 95% of the Na0.7- beidellite was obtained at 400°C and 1 kbar after 20 days. Gels with a Na-content equivalent to a layer charge lower than 0.3 per O20(OH)4 did not produce beidellite. They yielded kaolinite below 325°C and pyrophyllite above 325°C. With gels of a Na-content equivalent to a layer charge of 1.5, the Na-beidellite field shifted to a minimum between temperatures of 275° and 200°C. This procedure offers the potential to synthesize beidellite at low temperatures. Beidellite synthesized from Na1.0-gel approach a Na1.35 composition and those from Na1.5- and Na2.0-gels a Na1.8 composition.

Hydrothermal synthesis experiments were conducted to study the transition from smectite to corrensite. A mixture of oxides with the bulk composition of corrensite—Na0.4(Si6.4Al1.6)(Mg7.8Al1.2)-O20(OH)10—was sealed in platinum capsules with 29–37 wt. % water. One set of samples was treated in cold-seal vessels at 500°C and 2 kbar for durations of 2, 3, 6, 12, and 24 h; the other set was treated at 350°C and 2 kbar for periods of 12 to 89 d. X-ray diffraction patterns (XRD) of oriented aggregates from treated products were obtained from ethylene glycol-solvated and air-dried preparations. Samples were also heated to 350°C either in a calibrated muffle furnace, removed and quickly placed in a nitrogen filled chamber on the diffractometer, or were heated at 350°C by using a calibrated heating stage mounted on the diffractometer.

Initial mineral assemblages at both temperatures contained only saponite and serpentine. In experiments at 500°C, saponite transformed to corrensite within 6 h; in experiments at 350°C, the transformation occurred as early as 22 d. Increased experiment times at both temperatures produced increasing amounts of well-crystallized corrensite, as indicated by several well-defined XRD peaks. No evidence of a randomly interstratified chlorite-smectite (C-S) precursor to corrensite was found. The identification of pure smectite, as opposed to highly-expanded randomly interstratified C-S, was possible only when clays were dehydrated on a heating stage on the diffractometer.

These results call for a new examination of hydrothermally-altered basalt that has been reported to contain randomly interstratified C-S as an intermediate step in the reaction of smectite to corrensite or chlorite. These results also strengthen the view held by increasing numbers of investigators that corrensite should be regarded as a single phase, not as a mixed-layered phyllosilicate.

Kaolinite was hydrothermally synthesized from two kinds of silica-alumina gels to examine the effect of the structure of the starting material. Two kinds of gels were prepared by precipitation at different pH conditions (pH = 9.6 and 4.2) from solutions containing water glass and aluminum sulfate. Na ions in the gels were removed with a resin before the hydrothermal treatment, but a slight amount of sulfate ions was still present in the gels. The nuclear magnetic resonance spectra of the starting gels suggested that the gel prepared at pH 9.6 consists of networks with alternating SiO4- and A1O4-tetrahedra (partially AlO6-octahedra), whereas the gel prepared at pH 4.2 consists of a sheet structure related to allophane. After the hydrothermal treatment at 220°C for 9 days, kaolinite particles with spherical shape were obtained from the former gel, and platy kaolinite was crystallized from the latter one. The difference in morphology of synthetic kaolinite was attributable to the structures of the starting gels, and the pH values in the hydrothermal reactions were not very significant to the morphology.

Hydrothermal syntheses were performed at various pH values and temperatures to induce variability in kaolinite defect density. Temperature of synthesis ranged from 200 to 240°C, for 21 d. Initial pH at room temperature ranged from 0.5 to 14. The starting material was a hydrothermally treated gel, with an atomic Si/Al ratio of 0.93, partly transformed into kaolinite.

Kaolinite was obtained for a wide range of pH. Although no influence of temperature on “crystallinity” (i.e., defect density) was observed, the effect of pH was important. A continuous series was obtained from a low-defect kaolinite, with high thermal stability and a hexagonal morphology for the most acidic final pH, to a high-defect kaolinite, with low thermal stability and lath shape for the most basic final pH. These variations of kaolinite properties appear related to the pH dependence of kaolinite surface speciation. Increasing pH value results in increased cation adsorption on the kaolinite external surfaces and increases in the elongation of particles.

Smectitic clay minerals are unique indicators of paleoenvironmental conditions and exhibit a unique reactivity in the mineral world. Smectites may exhibit tetrahedral substitutions (Al3+, and sometimes Fe3+, can substitute for Si4+ in tetrahedral sites), resulting in a layer-charge increase, thereby impacting their properties (e.g. swelling and sorption capacities, catalytic properties, expandable abilities). The objective of the present study was to determine the influence of pH conditions on the hydrothermal production of smectite end-members exhibiting tetrahedral Al substitutions (saponite, beidellite, and nontronite), using X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) methods. The results of a series of syntheses conducted at various pH values allowed discussion of the crystallization pathways of these smectites from a mechanistic point of view. Altogether, the present study provided easily reproducible protocols for the hydrothermal production of pure saponite, nontronite, or beidellite (i.e. with no other mineral). The successful synthesis of pure saponite was achieved by exposing the starting gels to 230°C for 4 days in solutions at pH ranging from 5.5 to 14. The successful synthesis of pure beidellite was achieved by exposing the starting gels to 230°C for 9 days in a solution at pH 12. The successful synthesis of pure nontronite was achieved by exposing the starting gels to 150°C for 2.5 days in a solution at pH 12.5. Although extrapolating experimental results to natural settings remains difficult, the results of the present study may be of great help to constrain better the geochemical conditions existing or having existed on extraterrestrial planetary bodies.

Dioctahedral smectite was prepared hydrothermally from dickite [Al2Si2O5(OH)4] as a starting material by autoclaving in a closed stainless steel vessel with variable temperature, pressure, time and pH conditions. Highly crystalline smectite can be obtained at 290°C under a pressure of 69 bar for 48 h. The pH of the solution was an important factor and should be maintained at 10 to 11 for the successful formation of smectite. Characterization by X-ray powder diffraction, scanning electron microscopy, infrared spectroscopy, thermogravimetric analysis, differential thermal analysis and the Greene-Kelly test showed that the smectite synthesized was Na-beidellite, mostly because of the heat treatment of the starting material and the stoichiometric batch composition.

Control of the structure and morphology of clay crystals presents a challenge in the synthesis of materials for adsorption and catalysis. In the present study, direct crystallization of a phyllosilicate grafted with organosilyl (methylsilyl and phenylsilyl) groups on the surface of monodisperse spherical silica particles (2.6 μm) is reported. Methyl- and phenyltriethoxysilanes were allowed to react hydrothermally in a Teflon-lined autoclave with silica, MgCl2, and LiF in the presence of urea for 2 or 4 days. X-ray diffraction patterns revealed that the fine platy particles formed were a trioctahedral hectorite-like layered silicate. Greater temperature (150°C) was required to achieve homogeneous coverage of the original spherical silica particles with the hectorite-like particles. The diameter of the initial silica grains increased slightly to 3.0 μm after the hydrothermal reactions, while the original spherical shape and size distribution were maintained. Solid-state 29Si nuclear magnetic resonance analyses confirmed that the presence of resonances attributed to the RSi(OMg)(OSi)2 and RSi(OMg)(OH)(OSi) (R = methyl or phenyl) environments of the silicon proved the formation of covalent bonds between phyllosilicate sheets and the organic moieties. The crystallinity of the layered silicates increased when the reactions ran for a longer time (4 days).

Minerals such as quartz, present widely in various volcanic ashes, remain unaltered throughout the low-temperature hydrothermal process currently used in industry to obtain zeolites, causing an incomplete hydrothermal transformation of the starting solid. This study presents a novel and cost-effective procedure which improves the reactivity of ash toward the generation of zeolite by increasing the availability of silica and alumina components. This method leads to a final product with a large zeolite content. The transformation consisted of an ash-activation step followed by hydrothermal zeolitization. The influence of the structural, chemical, and morphological characteristics of the volcanic ash as well as the effect of the activation procedure on the ash reactivity were studied. A collected sample (VA) and an amorphous fraction obtained after VA sieving (VA40, retained on #40 mesh) were used for zeolite production. These solids were alkaline-treated separately, aged, and reacted under controlled conditions of temperature at autogenous pressure. Throughout the process, the solid phases were characterized by X-ray diffraction, energy dispersive X-ray microanalysis, scanning electron microscopy, Fourier-transform infrared spectroscopy, and N2adsorption-desorption porosimetry measurements. After activation and alkaline aging, the presence of quartz and plagioclase minerals in the natural ash seemed to improve the growth of NaAlSiO4 polymorphs, which in turn were transformed easily to zeolite structures. Even under adequate pretreatment and suitable synthesis conditions, the coarse non-crystalline fraction led to low conversion, while the highest conversions to zeolites A and X were obtained from the natural ash. The outcomes of the present study could be used to improve the conversion levels of other non-conventional aluminosiliceous minerals into zeolites.

Two varieties of Zn-smectite were synthesized hydrothermally: sauconite, with an ideal composition of Na0.4Zn3(Si3.6Al0.4)O10(OH)2·nH2O; and a Zn equivalent of hectorite, with an ideal composition of Na0.4 (Li0.4Zn2.6)Si4O10(OH)2·nH2O (referred to here as Zn-hectorite). For comparison, hydrothermal synthesis of the related trioctahedral smectites of hectorite, Na0.4(Li0.4Mg2.6)Si4O10(OH)2·nH2O and hectorites containing Cu, Co or Ni in the octahedral sheets instead of Mg were also attempted. The results showed that sauconite, Zn-hectorite and hectorite could be synthesized in the temperature range 100–125°C but hectorites containing Cu, Co or Ni in the octahedral sheet, under the same conditions or even at a temperature of 150°C, could not.

At present, no production of zeolites is ongoing in Colombia; thus, because of the high demand in the industrial sector, ~2500 tons is imported annually from other countries such as Cuba, Ecuador, Mexico, and the United States. In order minimize the need for these costly imports, the present study sought to evaluate the viability of producing low-silica zeolites through the hydrothermal synthesis of a Colombian kaolin, which contains quartz (40%) and iron-oxide impurities. The kaolin was subjected to a milling process to reduce the particle size to the order of 11 μm, and was heat treated to transform it to metakaolin. Optimization of the synthesis variables (Na2O/SiO2 and H2O/Al2O3 ratios, time, and temperature) was accomplished by applying an experimental design based on the ‘Response Surface Methodology’ technique. The degree of crystallinity and the cation exchange capacity (CEC) were used as response variables. The CEC was determined from the NTC 5167 standard. In addition, the mineralogical composition and the zeolite microstructure were evaluated using techniques such as scanning electron microscopy, X-ray diffraction, and solid state nuclear magnetic resonance spectroscopy. The results indicated that synthetic type A zeolites with a CEC value of 442 cmol(+)/kg can be obtained from the Colombian kaolin, with the following optimal processing conditions: Na2O/SiO2 molar ratio of 2.7, H2O/Al2O3 molar ratio of 150, temperature = 66°C, and processing time = 8 h. Note that this value (442 cmol(+)/kg) is greater than that reported for an imported commercial zeolite (408 cmol(+)/kg) of the same type, which is currently being used in industry in Colombia. The nationwide availability of the raw material and the quality of the final product present opportunities to make this material available to the Colombian market.

Cobalt (II) and Al (III) layered double hydroxides were precipitated from homogeneous solutions using urea hydrolysis under hydrothermal conditions. The particle sizes were controlled successfully by changing the reaction temperature and period. It was found that larger particles formed by reactions at lower temperatures over longer reaction periods because the slow urea hydrolysis at lower temperatures suppresses the formation of nuclei in the solution. When the reaction was conducted at 60°C for 100 days, particles >40 µm wide were obtained.

Rapid dissolution of partly amorphized kaolinite in the systems kaolinite + NiCl2, kaolinite + Ni(OH)2, and kaolinite + NiCl2 + Ni(OH)2, at a temperature of 200°C and at pH between 5.3 and 7.4, leads to the precipitation of Ni-poor kaolinite, Ni-rich kaolinite and Al-Ni-serpentine. Identification of the phases was carried out using a combination of X-ray diffraction and transmission/analytical electron microscopy. Ni-bearing kaolinite shows variable morphologies in the systems studied: stacks of kaolinite with relatively small Ni contents and fine-grained curved particles of Ni-rich kaolinite dominate in the Cl-bearing system; spherical particles with a disordered structure and relatively uniform Ni contents (in the order of 0.15 atoms per formula unit (a.p.f.u.)) and platy particles of Al-Ni-serpentine characterize the products formed in the Ni(OH)2-richest systems. The presence of Ni(OH)2 in the systems (with and without Cl) favors the dissolution process as well as rapid precipitation of spherical particles, and the formation of serpentine. A difference from Mg systems studied previously is a well defined phase intermediate in composition between kaolinite and serpentine which originated in the Ni-bearing systems. Increasing Ni content is clearly reflected in the parallel increase in the b cell parameter of kaolinite. The average composition of the coexisting Al-Ni-serpentine is: (Al1.24Ti0.01Fe0.02Ni1.31) (Si1.58Al0.42)O5(OH,Cl)2.

Mesoporous materials have a wide range of applications in the fields of nanotechnology, biotechnology, information technology, and medicine, but historically, the resource materials used for their synthesis have been expensive. Natural silicate minerals are characterized by their abundance, low cost, and large SiO2 contents, making them an alternative silicon source for mesoporous silica. The objective of the present study was to determine the utility of natural chlorite as the source of Si for synthesizing hexagonal mesoporous silica materials (MCM-41). The natural chlorite was pretreated by acid leaching and calcination, followed by a hydrothermal reaction with cetyltrimethylammonium bromide (CTAB) as the template, and subsequent calcination to prepare MCM-41. The structures and the porosity of MCM-41 were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), 29Si magic-angle spinning solid-state nuclear magnetic resonance spectroscopy (29Si MAS NMR), and N2 adsorption–desorption measurements. The mechanism of structural evolution from natural chlorite to MCM-41 was investigated using these techniques. Calcination of chlorite results in amorphization and partial structural breakdown, while subsequent acid leaching dissolves the Mg and Al in the octahedral sheets to leave the Si–O framework as a silicon source. 29Si MAS NMR results revealed that the ratio of Q4/Q3 increased from 0.91 to 1.21 after hydrothermal synthesis of MCM-41 from leached chlorite, demonstrating more polymerization of the Si–O structure in MCM-41. The final MCM-41 products were amorphous SiO2, with a large surface area of 630 m2/g, a pore volume of 0.46 mL/g, and a narrow pore-size distribution of 2.8 nm. MCM-41 showed favorable adsorption toward methylene blue (MB) with a monolayer adsorption capacity of up to 302 mg/g, indicating potential for application in adsorption.

Mg-rich kaolinite and Mg+Ni-rich kaolinite have been synthesized in hydrothermal experiments (200 and 400°C) from poorly crystalline kaolinite and Mg- and Mg+Ni-bearing solutions. Al-rich serpentine and Al-rich chlorite were obtained as sub-products of the reactions. The formation of these phases occurred through a dissolution-precipitation mechanism that led to spherical kaolinite after short reaction times. A morphological evolution towards platy particles and stacks occurred at increasing run times.

Identification of the several phases was carried out using a combination of X-ray diffraction and transmission/analytical electron microscopy. Analytical data indicate that the Mg content in kaolinite increased as a function of the reaction time and temperature, reaching up to 0.46 atoms per half formula unit (a.p.h.f.u.). The measured (Mg+Ni) content reached up to 0.56 a.p.h.f.u.. Both the gradual increase of the b-cell parameter of kaolinite at increasing Mg contents and the presence of new bands on the FTIR spectra of the synthesized kaolinite point to a Mg-for-Al replacement in the octahedral sheet rather than to the presence of serpentine-like layers interstratified in the kaolinite structure.

The formation conditions and stability fields of Fe-serpentines are still poorly understood in both terrestrial (natural or anthropic) and extraterrestrial environments. Knowledge of the effects of physical-chemical parameters on compositional and structural features of Fe-serpentines is lacking, and only a few thermodynamic parameters of these minerals are available in the literature. To fill these gaps, the synthesis of these minerals, while controlling all the physicochemical experimental parameters, was undertaken. Two hydrothermal syntheses were carried out at 90°C to investigate the effect of two different starting mineralogical mixtures on the nature of Fe-serpentines. The run products were identified by several analytical techniques (powder X-ray diffraction, transmission, and scanning electron microscopy). Berthierine crystals were synthesized from a starting mixture of kaolinite and metal iron. The berthierines synthesized show different morphologies and iron contents (~3–38 at.%). From a starting mineralogical mixture composed of quartz and metal iron, cronstedtite crystallizes. Most of the crystals are 1M polytypes. Magnetite is always associated with both berthierine and cronstedtite. Lepidocrocite was observed only in the experiment with kaolinite. These experimental results demonstrated that Fe enrichment in serpentines depends on the silicate precursor (kaolinite or quartz) of the starting mixture. The results are also in agreement with the geochemical equilibrium predicted by thermodynamic modeling, i.e. the formation of berthierine and cronstedtite in association with magnetite at the expense of metal iron and silicates.

Eudialyte-related compounds have been synthesised hydrothermally at T = 600°C and P = 2 kbar from a stoichiometric mixture of Na2CO3, CaO, Fe2O3, ZrOCl2 and SiO2 using the Na:Ca:Fe:Zr:Si ratios corresponding to the eudialyte end-member Na15Ca6Fe3Zr3Si(Si25O73)(OH)Cl2⋅H2O, in the presence of 1 M aqueous solutions of NaCl and NaF. The synthesis was carried out in platinum ampoules over 10 days. Natural raslakite (a Ca-deficient member of the eudialyte group) was used as a seed and added in amounts corresponding to 2 wt.% of the whole charge. The products were characterised by powder X-ray diffraction, IR and Raman spectroscopy, morphological features, and electron probe microanalyses. In experiments with NaCl, almost pure eudialyte-type compounds were obtained. Synthesis in the presence of a NaF solution resulted in the formation of a F-dominant eudialyte-type compound related to raslakite as the main product and aegirine, vlasovite and lalondeite as by-products. All synthesised eudialyte-type compounds are Zr-rich and Fe-deficient, similar to eudialyte-group minerals from hyperagpaitic rocks related to foyaites. The increased NaCl contents in the reaction system results in increased Ca content in the synthesised eudialyte-related compounds. The crystal-chemical formulae of the synthesised eudialyte-type compounds are derived based on general regularities established earlier for eudialyte-group minerals.