Determination of water content in raw perlites: Combination of NIR spectroscopy and thermoanalytical methods.

A new approach to determination of water content in raw perlites, an industrially important material, and obsidian was proposed, utilizing diffuse reflectance spectroscopy in the near-IR region. The phase composition of the perlite of the perlite samples was over 94% rhyolitic volcanic glass, with only small admixture of other components. The observed volatile species contents detected from both thermogravimetric analysis (TG) and the loss of ignition method (LOI) varied from 3 to 7%. The samples with the highest content of volatiles released over the temperature interval 30-250 °C (based on thermogravimetric analysis) displayed sharp signals in the 1H MAS NMR spectra, with chemical shifts of 4.6-4.7 ppm attributed to water molecules of high mobility. Using IR spectra taken in the near-infrared region, the water content of perlites was evaluated using the combination mode (ν + δ)H2O near 5240 cm-1. The band area depended on the H2O content, with the highest value found for the sample which displayed the highest mass loss in the thermoanalytical experiments. The samples showed variations in properties depending on the location in the deposit they were taken from. The relationship between water content determined gravimetrically and calculated band areas showed a correlation coefficient of 0.78 and 0.74 for TG and LOI respectively. The correlation was significantly improved by adding internal standards, hexadecyltrimethylammonium bromide salt (HDTMA) or layered hydrosilicate talc, to the perlite samples, and then normalizing the spectra of the mixtures to selected bands of those standards (R2 = 0.89 and 0.88 respectively for TG methods). A better correlation between infrared and TG/LOI results was obtained for HDTMA-Br than for talc. The proposed method using standards could be a reliable way of estimating water content in raw perlites in processing plants.

Spectroscopic study of water adsorption on Li(+), TMA(+) and HDTMA(+) exchanged montmorillonite.

The potential of IR and NMR spectroscopy in characterization the interaction of water with natural and organically modified montmorillonites was introduced. Organoclays were prepared from Li-saturated montmorillonite (Li-S) and tetramethylammonium (TMA) or hexadecyltrimethylammonium (HDTMA) salts. The influence of organic cation size on the water vapour uptake was examined and a comparative study with natural clay mineral was provided. The near-IR spectra confirmed the reduced water content in TMA-S and HDTMA-S. After exposure of the samples to water vapour under various relative humidities (RH) the H2O content was determined. According to the adsorption isotherms the amount of water decreased in order Li-S>TMA-S>HDTMA-S. The intensities of the 2νOH and [Formula: see text] bands, corresponding to the vibrations of H2O, gradually increased in hydrated samples. The (13)C MAS NMR and near-IR of hydrated organoclays confirmed the presence of H2O close to the cation's headgroup. NMR signals of inner -CH2- groups in HDTMA-S were also affected by hydration: the intensity of disordered gauche conformers (31.1 ppm) overtook the intensity of ordered all-trans conformers (33.0 ppm).

The effect of acid treatment on the structure and surface acidity of tetraalkylammonium-montmorillonites.

The effect of tetrabutylammonium (Bu4N+) and tetrapentylammonium (Pe4N+) cations on the modification of the organo-montmorillonite structure upon acid-treatment was investigated. Samples were treated with HCl for various times (2-12 h). Structural changes were followed by MAS NMR spectroscopy. The 29Si MAS NMR spectra of initial Na-saturated form (Na-SAz) showed gradual decrease of the intensity of the resonance assigned to SiO4 cross-linked in the tetrahedral sheets Q3(0Al) while signals arising from the reaction product Q31OH and Q4(0Al) became more pronounced upon acid treatment. The Q3(0Al) signal almost completely disappeared for Na-SAz treated for 8 h on contrary to Bu4N-SAz and Pe4N-SAz showing signal of relatively high intensity even after 12 h. The 27Al MAS NMR measurement proved that more than one half of Al remained in the reaction product of Bu4N-SAz and Pe4N-SAz after 8 h treatment, while Al content dropped below 5% for Na-SAz. Formation of acid sites was investigated via pyridine adsorption. Only physically adsorbed and H-bonded pyridine was detected for acid-untreated samples. In contrast, the IR spectra of the samples partially decomposed in HCl revealed bands of pyridine adsorbed on Brønsted acid sites. Strongly bonded pyridine was able to bear up heating even at 230°C.