Influence of Moisture on the Glass Transition of A Spray-Dried Compound Using the Isosteptm Method

The interaction among moisture content, solvent loss and glass transition temperature is relevant for processing of spray-dried pharmaceuticals, since the glass transition temperature determines the application range of a compound. Conventional Differential Scanning Calorimetry (DSC) does usually not allow to separate glass transitions from common kinetic effects like evaporation or crystallization. Based on classical DSC methods, the IsoStep^TM method allows the independent determination of heat capacities and kinetic effects, and thus, the separation of kinetic effects from effects arising from heat capacity changes. This technique is used to separate glass transition and evaporation processes, and to find the relation between moisture content and glass transition temperature for a pharmaceutical sample based on a modified Gordon–Taylor equation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal expansion studies on some gamma-irradiated binary borate glasses

The thermal expansion, density and molar volume of some binary borate glasses were measured before and after exposure to a gamma-ray dose of 10³ kGy. The expansion curves for all glasses, which were measured from room temperature to above the softening temperature, displayed similar characteristics. Increase of the lead oxide content decreased the thermal coefficient of expansion, but the effects of different alkali metal cations were shown to depend on their ionic radii. The various proposed mechanisms of thermal expansion are dealt with. The experimental results could be explained by considering the bond strengths, the polarizing powers of the different cations and the damage produced by radiation. The possible compaction of the structure due to irradiation is also discussed.     

Sol-Gel Preparation of Silica Films with Controlled Surface Morphology and Their Application to a Low Reflective Glass

Silica coating films with various surface morphologies, such as flat, porous (with deep pores), concave-convex (with hills and valleys), and convex (with hills on flat plane) structure were prepared from a mixture of two kinds of sols derived from polymerized tetraethoxy-silane (TEOS) and methyltriethoxysilane (MTES). Different surface morphologies were obtained by varying the molar ratio r = MTES/TEOS of the coating solution. The surface was flat for r less than 2.5, porous for 2.5 r < 5, concave-convex for 5 r < 7.5, convex for 7.5 r < 13, and again flat for r larger than 13. For 2.5 r < 5, the apparent refractive index of the silica film with porous morphology was decreased to 1.23 by selecting the solvent and by controlling the relative humidity of the coating atmosphere and the heat treatment temperature. Coating of glass with silica films of low refractive index of 1.23 led to the low reflective glasses with visible light reflectance Rvis of less than 0.2%.     

Epoxy/poly(benzyl methacrylate) blends: miscibility, phase separation on curing and morphology

Diglycidyl ether of bisfenol-A (DGEBA)/polybenzyl methacrylate (PBzMA) blends cured with 4,4’-diaminodiphenylmethane (DDM) were studied. Miscibility, phase separation, cure kinetics and morphology were investigated through differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Non-reactive DGEBA/PBzMA blends are miscible over the whole composition range. The addition of PBzMA to the reactive (DGEBA+DDM) mixture slows down the curing rate, although the reaction mechanism remains autocatalytic. On curing, initially miscible (DGEBA+DDM)/PBzMA blends phase separate, arising two glass transition temperatures that correspond to a PBzMA-rich phase and to epoxy network. Cured epoxy/PBzMA blends present different morphologies as a function of the PBzMA content.     

A model for the fragility of the melts

The concept of fragility has been used widely to characterize the temperature dependence of the viscosity of glass forming materials. However, the physical background that determines the degree of fragility is still not well understood. In the present study an expression for the fragility is derived based on a simple model of the melt. According to the model, the fragility is determined by the relaxation of structural units that form the melt, and is described in terms of the bond strength (E ₀), coordination number (Z ₀), and their fluctuations (ΔE and ΔZ). It is shown that a strong system is characterized by large value of total bond strength (Z ₀ E ₀) and small value of its fluctuation ((ΔZ)²(ΔE)²). On the other hand, a fragile system is characterized by small value of total bond strength and large value of its fluctuation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Chromatographic peak broadening with a lab-made splitter: Reproducibility and accuracy studies

Sample inlet splitters are used in capillary column gas chromatography. We have investigated the sample band broadening in the splitter and studied reproducibility and accuracy in quantitative analysis using a simple lab-made splitter. It was found that the results were dependent upon the operating conditions such as split ratio, splitter temperature, glass wool plug, injected sample volume and solvent.     

Heat capacity and glass transition of ethylene oxide clathrate hydrate

The heat capacity of structure I ethylene oxide clathrate hydrate EO-6.86 H₂O was measured in the temperature range 6–300 K with an adiabatic calorimeter. The temperature and enthalpy of congruent melting were determined to be (284.11 ± 0.02) K and 48.26 kJ mol^–1, respectively. A glass transition related to the proton configurational mode in the hydrogen-bonded host was observed around 90 K. This glass transition was similar to the one observed previously for the structure II tetrahydrofuran hydrate but showed a wider distribution of relaxation times. The anomalous heat capacity and activation enthalpy associated with the glass transition were almost the same as those for THF-hydrate.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.Author for correspondence.     

Trace analysis of fungicides in grape juice and wine using glass capillary gas chromatography

The fungicides Bupirimate, Fenarimol, and Vinclozolin were sprayed on Vines. The fruits were harvested 8 and 21 days after the final application and processed to juice and wine. The fungicide residues were determined by filtration of the samples throug XAD-2 after pH adjustment, elution with methylene chloride, and glass capillary gas chromatography with SE-30 as stationary phase. Residue values of the three compounds were reported before and after fermentation. The precision of the analytical method was established by spiking portuguese white wine and spanish grape juice with the three fungicides and Triadimefon. The recoveries were in the range 80%-100%, except for Vinclozolin.     

Statistical evaluation of potash-lime-silica glass weathering

Two potash-lime-silica model glasses with compositions similar to those of medieval stained glass were exposed at 26 test sites all over Europe and in North America for 3–6 years. The objectives of this large-scale field exposure programme were: (a) a qualitative analysis of the weathering products formed on the surface of the samples in the (environmental) scanning electron microscope in combination with energy dispersive X-ray microanalysis (ESEM/EDX or SEM/EDX, respectively); (b) a statistical evaluation of the weathering phenomena by applying a multiple linear regression (MLR) analysis to find correlations between the degree of weathering, which was measured in terms of surface coverage with reaction products, and environmental parameters such as the concentration (c) of the acidifying gases SO₂, NO₂ and O₃, the temperature (T) and the relative humidity (RH); and (c) the calculation of a time-dependence function of the weathering process of these glasses. Mainly sulfates of calcium and potassium such as gypsum (CaSO₄·2 H₂O), arcanite (K₂SO₄) and syngenite (CaSO₄·K₂SO₄·H₂O) could be identified in the SEM and ESEM. Carbonates, nitrates and many particles deposited on the glass surface were found as well. MLR calculations exhibit significant dependencies of the degree of weathering on T, RH, c(NO_x), c(SO₂) and c(O₃). Applying a time-dependence function of the general form y=a·t^b (t=time) results in a value of approximately 0.42 for the exponent b, which comes close to values expected from various studies in the literature.     

The application of modulated differential scanning calorimetry to the glass transition

The modulated differential scanning calorimetry (MDSC) technique superimposes upon the conventional DSC heating rate a sinusoidally varying modulation. The result of this modulation of the heating rate is a periodically varying heat flow, which can be analysed in various ways. In particular, MDSC yields two components (reversing and non reversing) of the heat flow, and a phase angle. These each show a characteristic behaviour in the glass transition region, but their interpretation has hitherto been unclear. The present work clarifies this situation by a theoretical analysis of the technique of MDSC, which introduces a kinetic response of the glass in the transition region. This analysis is able to describe all the usual features observed by MDSC in the glass transition region. In addition, the model is also able to predict the effects of the modulation variables, and some of these are discussed briefly.Financial support has been provided by the DGICYT (Project no.PB93/1241). J.M.H. wishes to acknowledge financial assistance for a sabbatical period from the Generalitat de Catalunya.