The influence of Cu(II) on the hydrothermal and thermal transformations of a synthetic hectorite was investigated by a combined approach using mainly X-ray diffraction, thermal analyses, and electron paramagnetic resonance spectroscopy. The presence of Cu(II) during hydrothermal treatment increased the crystallite size. Copper (II) was both structure-bound and associated with the inner surfaces of the particles. Upon heating, structural destabilization of the hectorite began at ∼400°C as indicated by the formation of free radicals. Between 600 and 700°C, the hectorite converted to enstatite, and in the presence of Cu(II), to enstatite and richterite. The formation of richterite as an additional conversion product is explained by the creation of structural weakness due to structure-bound Cu(II) in F-containing hectorite. Our results suggest that traces of Cu(II), typical of natural environments, may influence the conversion products in high-temperature geochemical systems.

The thermal stability of surfactant-modified clays plays a key role in the synthesis and processing of organoclay-based nanocomposites. Differential thermal analysis (DTA), thermogravimetric measurement and differential scanning calorimetry (DSC) were used in this study to characterize the thermal stability of hexadecyltrimethylammonium bromide-modified montmorillonites prepared at different surfactant concentrations. Analysis by DSC shows that the molecular environment of the surfactant within the montmorillonite galleries is different from that in the bulk state. The endothermic peak at 70–100°C in the DTA curves of the modified montmorillonites is attributed to both the surfactant phase transformation and the loss of free and interlayer water. With an increase of surfactant-packing density, the amount of water residing in the modified montmorillonite decreases gradually, reflecting the improvement of the hydrophobic property for the organoclay. However, the increase in the surfactant packing density within the galleries leads to a decrease in the thermal stability of the organoclays.

With an increase of initial surfactant concentration for the preparation of organoclays, the surfactant- packing density increases gradually to a ‘saturated’ state. It was found that the cationic surfactant was introduced into the montmorillonite interlayer not only by cation exchange but also by physical adsorption.

Antarctic algae are extremophilic organisms capable of surviving harsh environmental conditions such as low temperatures and deep dehydration. Although these algae have various adaptations for life in extreme environments, the majority of the molecular mechanisms behind their resistance to dehydration and freezing are not yet fully understood. The aim of our research was to observe the behaviour of bound water freezing in the free-living Antarctic alga Prasiola crispa. One way to avoid frost damage involves deep dehydration of the algal thallus. For that reason, a detailed analysis of water freezing at different sample hydration levels was carried out. Nuclear magnetic resonance investigation revealed two types of water immobilization: cooperative bound water freezing for samples with sample hydration levels above Δm/m0 = 0.40 and non-cooperative bound water immobilization for lower thallus hydration levels. In the differential scanning calorimetry experiment, 2-h incubation at -20°C suggested the diffusion and final binding of supercooled water to the ice nuclei and a lower hydration level threshold, at which ice formation could be observed (Δm/m0 = 0.21). Our research provides a new perspective on water sorption and freezing in Antarctic algae, which may be important not only in biological systems, but also in such novel materials as metal-organic frameworks or covalent organic frameworks.

A commercially available combined X-ray diffraction – differential scanning calorimetry (XRD-DSC) stage was adapted for studies of gas loading in microporous materials, including metal organic frameworks (MOFs). Insertion of a custom-built humid atmosphere swing chamber (HASC) between a humidity generator and the XRD-DSC stage facilitates both humid atmosphere and vacuum swing gas loading. The HASC is necessary to buffer between the humidity generator and the XRD-DSC stage, allowing the gas mixture to homogenize prior to sample exposure, so that both humid atmosphere and vacuum swings could be performed. The changes in XRD can be used to follow structural changes, including collapse, which is indicative of a lack of microporosity upon activation, and the flexibity of frameworks upon gas sorption–desorption cycles. Measurements of the area under the DSC curve allows for calculation of the isosteric heat of adsorption (Qst; kJ molGAS−1). Vacuum-atmosphere swing experiments performed at different pressure steps allow for the reconstruction of the enthalpy of gas adsorption before and after a phase transition. These modes of operation are illustrated in three case studies from a program of exploratory MOF synthesis used to discover novel materials for selective gas sorption from humid gas streams: (1) gas binding in Stony Brook metal organic framework-1, (2) zeolitic imidazolate framework-7 response to variable pressure vacuum-atmosphere swing, and (3) high throughput evaluation of the selectivity of novel MOFs synthesized from customized linkers.

Phenol red dyed bis thiourea cadmium acetate (BTCA) crystals of ∼30 × 10 × 6 mm dimension have been grown for the first time using the slow evaporation solution technique. Diffuse reflectance measurements show absorption bands at 363 and 563 nm in the doped crystal. Optical energy gap was calculated to be 4–5 eV. Photoluminescence spectra were recorded using 320 nm excitation source. The chemical etching study was done and etch pit density was found to be reduced from 4.5 × 103/cm2 (pure) to 3.0 × 102/cm2 (dyed). Mechanical strength is increased from 74.1 kg/mm2 for pure to 94.7 kg/mm2 for dyed crystals. The enriched properties of BTCA in the presence of dye suggest that the dyed crystals will be more applicable compared to pure crystals.

Basalt glass from Kilauea, Hawaii (SBG) starts to crystallize upon heat treatment in air at ∽840°C. In addition, oxidation takes place. The kinetics of both processes may be readily quantified though the mechanism is difficult to access. This work investigates the relationship between these processes, crystallization and oxidation, and the escape of volatiles from the glass/liquid upon reheating. Evolved gas analyses and differential scanning calorimetry are the techniques used. In addition, isothermal heat treatment in argon is carried out in order to eliminate the external reason for oxidation, the oxygen gradient, and to focus on intrinsic oxidation. Products are examined with 57Fe Mössbauer spectroscopy. As expected, degassing temperatures of SBG, and of two MORB samples, considered for comparison, are above the glass transition temperature. We find no convincing evidence of intrinsic oxidation. Degassing is likely to induce interface-controlled crystallization.

Compounds of poly(3-hydroxybutyrate) (PHB) and carbon black (CB) with CB content ranging between 0.5 and 10% were prepared in an internal mixer. The effect of heating and cooling rates on the crystallization and melting of PHB/CB compounds was investigated by differential scanning calorimetry (DSC), and its morphology analyzed by optical microscopy (OM). Results showed that PHB and its compounds partially crystallize from the melt during cooling and partially cold crystallize on reheating, with the amount of polymer crystallizing in each stage depending strongly on the cooling rate. Melting is usually shown in DSC scans as complex (double) peaks, which are influenced by the heating/reheating thermal cycles. The melting and cold crystallization temperatures, and the rates of phase change depend strongly on the cooling and heating rates and CB content. CB acts as a nucleating agent, promoting the melt and cold crystallization of PHB as well as increasing the number of spherulites, with a mild effect on the melting transition. Light microscopy images suggest that a secondary crystallization of PHB also occurs during storage at room temperature.

The effect of low temperature on Umbilicaria aprina collected from Schirmacher Oasis, East Antarctica, was determined over a wide range of hydration using proton free induction decays, proton nuclear magnetic resonance (NMR) spectra and differential scanning calorimetry methods. The proton NMR line is a superposition of the broad component from the solid matrix of the thallus and a narrower component from the averaged bound water pool. Proton free induction decays may be resolved into three components: a solid component well described by the Abragam function and two exponentially decaying components from water loosely bound and water tightly bound in the thallus. With decreased temperature the loosely bound water pool (freezing water) is transferred to the tightly bound water pool (non-freezing water), and vanishes below -40°C. Bound water freezing and melting temperatures decrease with the decrease of hydration level, suggesting that heterogeneous ice nucleation is responsible for water freezing. The onset of bound water freezing temperature is c. 10°C lower than the melting temperature. The U. aprina thalli do not reveal the ability to stimulated ice nucleation at higher temperature. Freeze-thaw cycles showed that for n > 5 cycles no substantial change occurs in the difference between melting and freezing temperatures.

The crystal structure of titanium-tin tellurium oxide Sn0.59Ti0.41Te3O8 has been determined using X-ray powder diffraction techniques. At room temperature, the title compound crystallizes in cubic space group Ia-3, with lattice parameter a=11.05515(6) Å. Rietveld refinement of the structure led to final confidence factors Rp=0.0395 and Rwp=0.0577. The structure of Sn0.59Ti0.41Te3O8 consists of isolated Ti/SnO6-octahedra slightly deformed in the a direction. The TeO4E [E=lone pair of Te(IV) atoms] groups are located between the octahedra ensuring the stability of the structure by Ti/Sn-O-Te bonding contacts. Only one peak in thermal behavior was detected for this compound at 488 K by differential scanning calorimetry experiment. An IR spectroscopic study is employed as a means to obtain preliminary structural information and shows the presence of the Ti/SnO6 and TeO4E groups. This result is later confirmed by X-ray diffraction studies.

The effect of peripheral halogenation is examined based on analytical transmission electron microscopy and thermal analyses of two chemical family structures, specifically the vanadyl-phthalocyanine family (VOPcX: X = H16, F14.5) and the copper-phthalocyanine family (CuPcX: X = H16, F16, Cl16, Cl8Br8), focusing on the process of molecular changes and crystalline disintegrations. To clarify the molecular transformations, electron energy-loss spectroscopy (EELS) is applied to two fluorinated phthalocyanines (VOPcF14.5 and CuPcF16), by monitoring mass changes as well as energy loss near edge structures (ELNES). The elemental mass of both VOPcF14.5 and CuPcF16 remain constant up to 0.5 C·cm−2, except in the case of mass reduction attributed to oxygen loss occurring in VOPcF14.5. It is expected that the released oxygen will induce higher radiation damage in VOPcF14.5. Although mass variation is not observed in CuPcF16, it is found from ELNES that the π resonant system of nitrogen is more radiation sensitive than that of carbon. These results imply that the electron sensitivity in VOPcX is triggered by eliminated oxygen or, thus, an induced larger empty space, whereas the sensitivity of CuPcX is dominated only by a large intermolecular empty space resulting in the following bond alterations. It is also found that the decomposition temperature (Td) measured by thermal analyses and the characteristic dose (D1/e) are exponentially correlated to the “effective molecular occupancy” (Oe) evaluated as a volume function of molecules in unit cells. By measuring Td and/or Oe, we discuss the durability of peripheral halogenation with respect to the radiation damage.