Smectite growth is of importance across various fields due to its abundance on the surface of both Earth and Mars. However, the impact of the crystallinity of initial materials on smectite growth processes remains poorly understood. In this study, the kinetic processes of smectite growth were examined via experimental synthesis of trioctahedral Mg-Ni saponites. Mg-Ni saponites were synthesized using mixed precursors, specifically end-member Mg-saponite and Ni-saponite, which exhibit different crystallinities. The crystal chemistry and morphology of samples were analyzed using X-ray diffraction, Fourier-transform infrared spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy. The experimental results converge towards these main conclusions: (i) the formation of Mg-Ni saponite solid solutions are promoted when the precursors are small particles, whereas large-particle precursors limit their own dissolution and do not yield Mg-Ni saponite solid solutions under the experimental conditions; (ii) because Ni exhibits a greater stability within the saponite structure compared to Mg, the Mg-Ni-saponite solid solutions formed more easily from the mixture of Ni-saponite germs and well-crystallized Mg-saponite precursors than from the mixture of Mg-saponite germs and well-crystallized Ni-saponite precursors; (iii) the dissolution extent (DE) of precursor mixtures increases with longer synthesis time, higher synthesis temperature, and larger gap between synthesis temperature of precursors and of samples, and stabilizes once it reaches a certain value. Thus DE can be used to estimate the kinetics of Mg-Ni saponite crystallization from precursor mixtures. These results obtained from the experimental Mg-Ni saponite system are useful for predicting the evolution processes of smectite in natural systems.

The presence of Al hydroxy species in solution during the synthesis of lepidocrocite had been previously found to influence the reaction towards goethite formation. However, under certain conditions, which are not unrealistic in terms of the natural soil environment, this influence does not occur, and Al appears to substitute for Fe(III) in the lepidocrocite structure. This substitution causes the unit-cell dimensions to decrease along the “a” direction and to increase along the “b.” From the differential line broadening of X-ray powder diffraction peaks, the incorporation of Al was found to inhibit crystal growth preferentially in the b-axis direction, the hkl peaks being more broadened the higher the value of k relative to h and l. Al-substituted lepidocrocites have been suggested to occur in soils, and although they can be synthesized under conditions approaching those expected in soils, it is considered that their formation in nature is unlikely or restricted to unusual environments.

Glauconite has been synthesized at low temperature by precipitation of Fe-hydroxides from Si-, Fe-, Al-, and K-containing solutions under reducing conditions. The compositions favorable for the synthesis at 20°C and pH 8.5 are 1 ppm Fe, 0.15 ppm Al, 13 ppm Si02, 1000 ppm KC1, and 1000 ppm dithionite. The K-content of the solutions must be sufficiently high to fix K in the precipitate.

Under special early diagenetic conditions glauconite is formed in marine sediments, probably at the interface between reducing and oxidizing zones in the muddy sediments. The silica content of pore waters seems to control the formation of glauconite or chamosite rather than depth or temperatures of the bottom waters.

Noncrystalline aluminosilicate gels with Al2O3/(Al2O3 + SiO2) weight ratios from 0.3 to 0.5 were reacted in 0.1 N KOH at temperatures varying from 125° to 175°C. The pH of the solutions dropped sharply with increasing gel:solution ratios, indicating that the coordination number of Al in the products changed from IV to VI. The degree of hydrolysis appeared to be higher with KOH than with NaOH. X-ray powder diffraction and infrared spectroscopy showed that disordered kaolinite was the only crystalline product formed. Thermal data and surface area measurements indicated that the kaolinite was formed by a condensation process.

Thirty two boehmites, synthesized at temperatures ranging from room temperature to 300°C, were examined by scanning electron microscopy, transmission electron microscopy, electron diffraction, X-ray powder diffraction, differential thermal analysis, and infrared spectroscopy. The results show that boehmite exhibits a continuous gradation in crystallite size ranging from single octahedral layers or a few unit cells to about 65 unit cells in the y-direction. This conclusion suggests that the term pseudoboehmite is inappropriate for finely crystalline boehmite. Finely crystalline boehmite contains more sorbed water than coarsely crystalline boehmite; this water is commonly intercalated between octahedral layers, usually randomly but sometimes regularly. The regularly interstratified boehmite gives rise to a diffuse “long spacing” X-ray diffraction reflection. Calculated 020 X-ray diffraction peaks approximate closely those observed experimentally when a range of crystallite sizes is taken into account.

Hydrotalcite solid solutions were prepared by coprecipitation followed by hydrothermal treatment between 150° and 250°C. Based on the structural formula [Mg1−xAlx(OH)2]x+[(CO3)x/2 • mH2O]x−, pure solid solutions were formed in the range A1/(A1 + Mg) = 0.2 to 0.33, where m = (1 − 3x/2). Maximum crystallite size was achieved by hydrothermal treatment between 180° and 200°C, with x = 0.337 to 0.429. Crystal strain was also minimized at these values of x. The adsorption capacity for Naphthol Yellow S increased as x increased and reached a maximum (1.56 × 10−6 moles/m2) when x = 0.287, a value eight times larger than that of Mg(OH)2. A weak endothermic DTA peak at about 350°C is probably due to the loss of structural water in the main layer of the structure. On calcination between 400° and 700°C, only periclase was detected, probably containing Al in solid solution. Hydration of the calcined product resulted in the reconstruction of the original hydrotalcite structure.

The equilibrium diagrams developed for Al-hydroxide and for kaolinite by Garrels and Christ (1965) have been modified by taking into account the existence of gels. From the stability zones obtained, the “appropriate” concentrations can be deduced and utilized for synthesizing these species, provided the requirements to insure good crystal growth are observed. Among procedures to promote these crystallizations, homogeneous precipitation processes (La Iglesia et al., 1974, 1976) appear to be particularly adequate.

The theoretical considerations provide an explanation for most of the processes observed until now, both successful and unsuccessful syntheses, and also give an explanation for many field observations. The crystallizations, however, remain poorly reproducible, indicating that many factors are still poorly known. Some points requiring further investigation include (i) better values for ΔGr0, (ii) the influence of organic complexes, (iii) the effect of preexisting crystalline phases, (iv) those involving dehydration processes in these systems.

The crystal structure of a synthetic boehmite sample has been refined to an R of 0.047 in the space group Amam from X-ray powder diffraction data. Inclusion of hydrogen atoms and/or refinement in the space group A21am gave poorer results. Cell dimensions were determined as a = 3.6936 (± 0.0003), b = 12.214 (± 0.001), c = 2.8679 (± 0.0003) Å. All Al-O(OH) distances lie between 1.88 and 1.91 Å. Shared octahedral edges are 2.51–2.52 Å, and unshared octahedral edges are 2.86–2.87 Å, in excellent agreement with those for layered silicates. The O-H … O distance between contiguous octahedral sheets is 2.71 Å. The computed X-ray pattern matches closely with the experimental pattern, indicating the degree to which the crystal structure has been determined.

The low temperature synthesis of iron silicate minerals with clay structures is possible at surface temperatures only under reducing conditions. Under oxidizing conditions clay minerals could not be synthesized. Instead quartz and quartzine were found in these X-ray amorphous Fe III hydroxide-silica precipitates after 14 days at low temperatures (20° and 3°C) as well as geothite or X-ray amorphous iron hydroxides. Only from solutions containing Fe-II could the different iron-containing clay minerals be built up within days at low temperatures. The presence of Fe-II enables an octahedral layer of the brucite-gibbsite type to be formed. This is necessary for the bidimensional orientation of SiO4-tetrahedra leading to clay mineral formation. The presence of Fe2+- and/or Mg2+-ions is necessary for the formation of the Al3+- and Fe3+-containing octahedral layers. The reducing conditions were obtained in the experiments by addition of dithionite. With a high content of silica (ca. 20 ppm SiO2,7 ppm Fe) nontronite and lembergite, the di-Fe-III and tri-Fe-II octahedral, three-layer silicates, were built up in several days at low temperatures. With a lower silica content, that is, a lower Si/Fe ratio (15 ppm SiO2 and 20 ppm Fe), the two-layer silicate minerals greenalite and chamosite could be synthesized. A higher Mg content and more reducing conditions in the solutions favored the tri- as well as dioctahedral chamosite synthesis.

The conditions of formation of recent naturally formed nontronite fit well with the synthesis conditions. Chamosites in sedimentary iron ores are characterized by a low content of SiO2, between 15–30% SiO2. This low content of silica cannot be the result of primary precipitation from seawater. The iron and silica ratio in seawater or in river waters would lead to a precipitation of ~60% SiO2 in the iron hydroxide precipitates. A probable origin for chamosite iron ores, which explains the low SiO2 content, is diagenesis of the lateritic weathering crust. Indeed, investigations of recent tropical shoreline sediments and in particular their trace element content confirm that chamosite minerals have formed diagenetically from lateritic particles in reducing sediments.

Al-substituted goethites were prepared by rapid oxidation of mixed FeCl2-AlCl3 solutions at pH 6.8 in the presence of CO2 at 25°C. A combination of Al substitution and adsorption of CO2 reduced crystal size (except for an increase at small additions of Al) and produced unusual thin, porous particles. Product goethites had surface areas up to 283 m2/g and unit-cell expansions induced by hydration. Substitution of Al for Fe reduced the 111 spacing and increased infrared OH-bending vibrational frequencies. Al substitution split the goethite dehydroxylation endotherm during differential thermal analysis into a doublet and increased the temperature of all reactions. Both cold and hot alkali solutions dissolved Al from the goethite structure.

After drying the product in vacuo at 110°C. X-ray powder diffraction data indicated minimal deviation from Vegard's law for the goethite-diaspore solid solution up to about 30 mole % Al substitution. Goethite prepared in the presence of 40 mole % Al had a 111 spacing of 2.403 Å corresponding to 36 mole % structural Al if Vegard's law was obeyed. Rapid oxidation of mixed FeCl2-AlCl3 solutions appears to be conducive to a higher degree of Al substitution in goethite than alkaline aging of hydroxy-Fe(III)-Al coprecipitates.

Feroxyhite (δ′-FeOOH) in association with goethite and lepidocrocite was found as a dominant mineral in some rusty precipitates from Finland. These precipitates formed in the interstices of sand grains from rapidly flowing, Fe(II)-containing water which was very quickly oxidized as it flowed through the sediment. The mineral is distinguished from other FeOOH forms and from ferrihydrite mainly by its X-ray powder diffractogram. Further characteristics are an acicular morphology (possibly thin, rolled plates), an internal magnetic field at 4°K of ∼510 kOe, Fe-OH stretching bands at ∼2900 cm−1 and Fe-OH bending bands at 1110, 920, 790, and 670 cm−1, and an oxalate solubility between ferrihydrite and goethite or lepidocrocite. Feroxyhites with very similar properties were synthesized by oxidation of an Fe(II) solution with H2O2 at a pH between 5 and 8.

Kaolinite is synthesized in approximately the same time in three temperature ranges: (1) from 200–250° to 350–400° (hydrothermal processes); (2) from 120 to 175° (semihydrothermal ones); (3) at ordinary temperature. It is thus evident that the rate process cannot be explained by the Arrhenius equation only, but is explained well by considering that kaolinite formation obeys the laws of crystal growth. It occurs only in slightly supersaturated solutions in which the nucleation process is possible and in which a slow and regular rate of growth has been insured. Concentrations calculated from the thermodynamical equilibria correspond to those of the experimental conditions for the low temperature processes. For the higher temperature ones, a similar relationship is delineated, at least as far as the thermodynamical treatment can be carried out.

Mixed-layer kaolinite/smectites containing 40–90% kaolinite layers have been synthesized from Wyoming smectite. Run times were 4 months at 156°C in solutions of A1C13∙6H2O and KCl or CaCl2. Similar KCl runs devoid of Al3+ yielded mixed-layer illite/smectites. The supply of Al3+, rather than pK or pH, seems to control the alteration of smectite toward kaolinite or illite.

A series of mixed iron and titanium oxide coprecipitates ranging in composition between 0 < Ti/Ti + Fe < 1 was synthesized and aged under varying conditions of pH, temperature and time in order to establish a working model for pedogenic titanium and titano-ferric oxides. X-ray powder diffraction (XRD), selective chemical dissolution, magnetic susceptibility, charge distribution and electron optical data indicate that the freshly prepared Fe-Ti oxides consist of an Fe-rich (Ti-ferrihydrite) phase (Ti/Ti + Fe ⩽ 0.70) having pH-dependent positive charge and a Ti-rich phase (Ti/Ti + Fe ⩾ 0.7) with permanent and pH dependent negative charge.

Synthetic Ti-ferrihydrite and amorphous TiO2 were completely soluble in acid ammonium oxalate (2 hr extraction in the dark) whereas poorly crystalline anatase (width at half height, WHH > 2.0°2θ) was partly oxalate soluble. NH4-oxalate soluble Ti was particularly high in soils developed under a cool montane climate (afro-alpine) and lower in soils of warmer subtropical climate, which contain anatase and rutile.

Several mixed Fe-Ti crystalline phases were identified after aging NH3 coprecipitates of Fe and Ti nitrate at 70°C and pH 5.5 for 70 days:

1. (1) goethite and hematite in the composition range 0 < Ti/Ti + Fe ⩽ 0.20; at low Ti concentrations (<5 mole %) goethite was favored and/or hematite inhibited

2. (2) microcrystalline pseudorutile in the composition range 0.20 ⩽ Ti/Ti + Fe ⩽ 0.70

3. (3) anatase and ferriferous anatase in the range 0.70 ⩽ Ti/Ti + Fe < 1.0; with decreasing proportion of Ti the crystal-Unity of anatase decreased.

The results suggest that secondary or pedogenic Ti-Fe oxides can form by coprecipitation and crystallization in the weathering solution, and emphasize the essential role of water (as opposed to dry oxidation) in the alteration of primary titaniferous minerals.

After a temperature-dependent period when little dissolution occurs, the dissolution of rhyolitic glass can be described by dC/dt = k(Cs − C), where Cs is the concentration of dissolved silica at saturation, C is the instantaneous silica concentration, and k is a rate constant equal to 1.6 × 10−5, 3.0 × 10−5, and 4.5 × 10−5 sec−1 at 115°, 130°, and 140°C respectively, in 2 M Na-K carbonate solution at 1 kbar pressure. At 130°C, a Cs value of 0.177 M SiO2 is reached in 30 hr, and phillipsite, clinoptilolite, and mordenite begin forming at 34, 64, and 76 hr, respectively, in 2 M CO3, 1:1 Na/K. During glass dissolution and zeolite formation, the concentration of Al as Al(OH)4− is buffered at 3.7 × 10−4 M by an unidentified phase. The ratio of SiO2 to Al(OH)4− at the onset of zeolite formation is 475. In 2 M CO3 solution, phillipsite crystallization begins at 144 hr at 115°C, at 34 hr at 130°C, and at 20 hr at 140°C. Phillipsite crystallization begins at 48 hr in 1.5 M CO3, at 168 hr in 1.0 M CO3, and in excess of 550 hr in 0.2 M CO3 at 140°C. In addition to OH− catalysis, CO32- appears also to catalyze the glass-dissolution and zeolite-formation processes.

Thermodynamically, phillipsite is unstable relative to clinoptilolite and mordenite in silica-rich alkaline hydrothermal solutions. Phillipsite forms first, followed by clinoptilolite, and then mordenite. Phillipsite formation is favored by runs of one-week duration, temperatures less than 150°C, and K-rich fluids. Clinoptilolite formation is favored in runs of more than one week, temperatures less than 150°C and K-rich fluids. Mordenite formation is favored by runs of more than one week, temperatures greater than 140°C, and Na-rich fluids. In 8-day runs at 140°C, clinoptilolite formation was favored by liquid: solid reactant (volume: mass) ratios less than 1.0, mordenite by ratios from 0.85 to 1.5, and phillipsite by ratios greater than 1.5. The mechanism of formation of the different zeolites, particularly phillipsite, may involve silica-cyclic tetramers which are abundant in concentrated solutions under alkaline hydrothermal conditions but which are almost absent in dilute low-temperature solutions. Thus, the results of hydrothermal experiments may not be directly applicable to zeolite formation at low temperatures.

The crystallization of calcium zeolites was carried out in an open hydrothermal system at 100°–250°C, using reactants that in nature are known to alter to calcium zeolites and 0.1 N CaCl2, 0.01 N CaCl2, and 0.01 N CaCl2 + 0.01 N NaOH (1:1) solutions. The following calcium zeolites were identified by X-ray powder diffraction:

• Rhyolitic glass: heulandite, phillipsite, epistilbite, wairakite;

• Basaltic glass: phillipsite, scolecite, wairakite, levynite;

• Nepheline: thomsonite, wairakite, gismondine;

• Oligoclase: heulandite, phillipsite, wairakite.

Factors that influenced the type of zeolite formed were: Si/Al ratio of the starting material, calcium/alkali ratio of the starting material, calcium activity of the reacting solution, presence of an open alteration system, and temperature. The Si/Al ratio of the starting material was of special importance in that zeolites formed with Si/Al ratios similar to or smaller than that of the parent material. The calcium/alkali ratio of the starting material also influenced the kind of the early alteration products in the open system. As alteration progressed, the importance of the starting material decreased. The importance of the calcium activity of the reacting solution and the influence of the open system increased as alteration proceeded. Because of mass transfer during alteration in the open system, the calcium content of the minerals formed increased, while their Si/Al ratio decreased. Temperature was especially effective during prolonged alteration, in that the higher the alteration temperature the smaller was the H2O content of the alteration product. Initially, H2O-rich zeolites formed transitorily at higher temperatures.

The trimethylsilyl derivative from halloysite was prepared by the reaction of halloysite powder with a trimethylsilylating reagent. The product was organophilic and the results of its infrared spectrum, X-ray powder diffraction pattern, and elemental analysis indicated that the trimethylsilylation occurred on silanol groups in the tetrahedral layer of halloysite after the acid decomposition of the octahedral layer. The thermal stability of the product was evaluated by means of differential thermal analysis. It was not possible to obtain the organic derivative from kaolinite by the same procedure. It is suggested that the differences in the reactivity between halloysite and kaolinite is due to the difference in susceptibility of the clay minerals to acid attack.

Spherical and platy kaolinite crystals were prepared under several hydrothermal conditions. Spherical kaolinite was produced mainly at high solid/water ratio (1/4) and at low temperatures (150°-200°C). Platy kaolinite predominated in products from experiments with intermediate solid/water ratios (1/256-1/16) and at high temperatures. Boehmite predominated at low solid/water ratios (1/4096) at all experimental temperatures (180°-220°C). The results indicate that the growth of the spherical kaolinite was favored at high degrees of supersaturation, whereas the growth of the platy kaolinite was favored at relatively low degrees of supersaturation.

The influence of Mn2+ on the formation of Fe oxides at pHs of 6.0 and 8.0 and varying Mn/Fe molar ratios (0, 0.1, 1.0, and 10.0) in the FeCl2-NH4OH and FeSO4-NH4OH systems was studied by X-ray powder diffraction (XRD), infrared absorption, transmission electron microscopic, and chemical analyses. In the absence of Mn2+, lepidocrocite (γ-FeOOH) and maghemite (γ-Fe2O3) were the crystalline species formed at pHs of 6.0 and 8.0, respectively, in the FeCl2 system, whereas lepidocrocite and goethite (α-FeOOH) and lepidocrocite were the crystalline species formed at pHs of 6.0 and 8.0, respectively, in the FeSO4 system. The amount of Mn coprecipitated with Fe (as much as 8.1 mole % in the FeCl2 system and 15.0 mole % in the FeSO4 system) increased as the initial solution Mn/Fe molar ratio increased from 0 to 10.0, resulting in the perturbation of the crystallization processes of the hydrolytic products of Fe formed. At pH 6.0, the perturbation led to the formation of poorly ordered lepidocrocite, as reflected in the increasing broadening of its characteristic peaks in the XRD patterns. At pH 8.0, poorly ordered iepidocrocite and a honessite-like mineral (Mn-Fe-SO4-H2O) formed in the FeCl2 and FeSO4 systems, respectively.