Sylwester J. Rzoska

On the glass temperature under extreme pressures

The application of a modified Simon-Glatzel-type relation [Z. Anorg. Allg. Chem. 178, 309 (1929)] for the pressure evolution of the glass temperature is presented, namely, Tg(P)=Tg0[1+DeltaP/(pi+Pg0)]1/bexp[-(DeltaP/c)], where (Tg0,Pg0) are the reference temperature and pressure, DeltaP=P-Pg0, -pi is the negative pressure asymptote, b is the power exponent, and c is the damping pressure coefficient. The discussion is based on the experimental Tg(P) data for magmatic silicate melt albite, polymeric liquid crystal P8, and glycerol. The latter data are taken from Cook et al. [J. Chem. Phys. 100, 5178 (1994)] and from the authors dielectric relaxation time (tau(P)) measurements, which employs the novel pressure counterpart of the Vogel-Fulcher-Tammann equation: tau(P)=tau0P exp[DPDeltaP/(P0-P)], where DeltaP=P-PSL (PSL is the stability limit hidden under negative pressure), P0 is the estimation of the ideal glass pressure, and D(P) is the isothermal fragility strength coefficient. Results obtained suggest the hypothetical maximum of the Tg(P) curve, which can be estimated due to the application of the supporting derivative-based analysis. A hypothetical common description of glass formers characterized by dTg/dP>0 and dTg/dP<0 coefficients is suggested. Finally, the hypothetical link between molecular and colloidal glass formers is recalled.

The combined effect of high pressure and nisin or lysozyme on the inactivation of Alicyclobacillus acidoterrestris spores in apple juice

Alicyclobacillus acidoterrestris, a thermoacidophilic and spore-forming bacterium is one of the important target micro-organisms in the quality control of acidic canned foods. High pressure pasteurization (HPP) at 50°C was used for the inactivation of A. acidoterrestris spores in apple juice. Pressure applied both in a continuous and oscillatory mode gave the best results when 200 MPa was used. Increasing the pressure to 500 MPa, as well as lowering its value to 100 MPa, had an adverse effect on the effectiveness of the process. The best results were achieved with the use of a combined treatment, involving oscillatory pressurization at 200 MPa, followed by holding the sample for 60 min at atmospheric pressure and subsequent pressurization at 500 MPa, resulting in a reduction in the spore count of 6.15 log. Nisin significantly enhanced the effect of HPP at 300 MPa. Using pressure of 200 MPa for 45 min with a nisin concentration of 250 IU/mL enabled total spore inactivation (over 6 log). No significant effect of lysozyme at a concentration of 0.05 and 0.1 mg/L at 300 MPa was observed.

Unique effects of thermal and pressure histories on glass hardness: Structural and topological origin

The properties of glass are determined not only by temperature, pressure, and composition, but also by their complete thermal and pressure histories. Here, we show that glasses of identical composition produced through thermal annealing and through quenching from elevated pressure can result in samples with identical density and mean interatomic distances, yet different bond angle distributions, medium-range structures, and, thus, macroscopic properties. We demonstrate that hardness is higher when the density increase is obtained through thermal annealing rather than through pressure-quenching. Molecular dynamics simulations reveal that this arises because pressure-quenching has a larger effect on medium-range order, while annealing has a larger effect on short-range structures (sharper bond angle distribution), which ultimately determine hardness according to bond constraint theory. Our work could open a new avenue towards industrially useful glasses that are identical in terms of composition and density, but with differences in thermodynamic, mechanical, and rheological properties due to unique structural characteristics.

Pressure-Induced Changes in Interdiffusivity and Compressive Stress in Chemically Strengthened Glass

Glass exhibits a significant change in properties when subjected to high pressure because the short- and intermediate-range atomic structures of glass are tunable through compression. Understanding the link between the atomic structure and macroscopic properties of glass under high pressure is an important scientific problem because the glass structures obtained via quenching from elevated pressure may give rise to properties unattainable under standard ambient pressure conditions. In particular, the chemical strengthening of glass through K(+)-for-Na(+) ion exchange is currently receiving significant interest due to the increasing demand for stronger and more damage-resistant glass. However, the interplay among isostatic compression, pressure-induced changes in alkali diffusivity, compressive stress generated through ion exchange, and the resulting mechanical properties are poorly understood. In this work, we employ a specially designed gas pressure chamber to compress bulk glass samples isostatically up to 1 GPa at elevated temperature before or after the ion exchange treatment of a commercial sodium-magnesium aluminosilicate glass. Compression of the samples prior to ion exchange leads to a decreased Na(+)-K(+) interdiffusivity, increased compressive stress, and slightly increased hardness. Compression after the ion exchange treatment changes the shape of the potassium-sodium diffusion profiles and significantly increases glass hardness. We discuss these results in terms of the underlying structural changes in network-modifier environments and overall network densification.

Factors influencing the inactivation of Alicyclobacillus acidoterrestris spores exposed to high hydrostatic pressure in apple juice

Alicyclobacillus acidoterrestris, a thermoacidophilic and spore-forming bacterium, survives the typical pasteurization process and can cause the spoilage of juices, producing compounds associated with disinfectant-like odour (guaiacol, 2,6 – dibromophenol, 2,6 – dichlorophenol). Therefore, the use of other more effective techniques such as high hydrostatic pressure (HHP) is considered for preserving juices. The aim of this study was to search for factors affecting the resistance of A. acidoterrestris spores to HHP. The baroprotective effect of increased solute concentration in apple juice on A. acidoterrestris spores during high pressure processing was observed. During the 45 min pressurization (200 MPa, 50°C) of the spores in concentrated apple juice (71.1°Bx), no significant changes were observed in their number. However, in the juices with a soluble solids content of 35.7, 23.6 and 11.2°Bx, the reduction in spores was 1.3–2.4 log, 2.6–3.3 log and 2.8–4.0 log, respectively. No clear effect of age of spores on the survival under high pressure conditions was found. Spores surviving pressurization and subjected to subsequent HHP treatment showed increased resistance to pressure, by even as much as 2.0 log.

Dual field nonlinear dielectric spectroscopy in a glass forming EPON 828 epoxy resin

Results of the dual field nonlinear dielectric spectroscopy (NDS) studies in supercooled glass forming epoxy resin EPON 828 are presented. For the NDS, changes of dielectric permittivity induced by DC (rectangular) or AC (sine-wave) pulses of a strong electric field were probed by a weak radio frequency electric field. A clear stretched exponential (x < 1) decay after switching off the DC pulse and a single exponential decay (x = 1) after switching off the AC pulse were found. The same results are presented for preliminary studies in superpressed low molecular glass former di-isobutyl phthalate. This observation may be considered as an argument for the heterogeneous picture of supercooled glass forming materials. The temperature dependences of the stationary responses related to DC and AC strong electric field excitations are also shown. The sensitivity of the applied set up made it possible to detect NDS outputs even for electric fields E(strong) < 10 kV cm(-1), qualitatively weaker than in similar nonlinear, dielectric experimental studies on glass forming materials carried out so far.

Distortion-sensitive insight into the pretransitional behavior of 4-n-octyloxy-4?-cyanobiphenyl (8OCB)

Results of studies of the static and dynamic dielectric properties in rod-like 4-n-octyloxy-4-cyanobiphenyl (8OCB) with isotropic (I)-nematic (N)-smectic A (SmA)-crystal (Cr) mesomorphism, combined with measurements of the low-frequency nonlinear dielectric effect and heat capacity are presented. The analysis is supported by the derivative-based and distortion-sensitive transformation of experimental data. Evidence for the I-N and N-SmA pretransitional anomalies, indicating the influence of tricritical behavior, is shown. It has also been found that neither the N phase nor the SmA phase are uniform and hallmarks of fluid-fluid crossovers can be detected. The dynamics, tested via the evolution of the primary relaxation time, is clearly non-Arrhenius and described via τ(T) = τ(c)(T-T(C))(-φ). In the immediate vicinity of the I-N transition a novel anomaly has been found: Δτ is proportional to 1/(T - T*), where T* is the temperature of the virtual continuous transition and Δτ is the excess over the background behavior. Experimental results are confronted with the comprehensive Landau-de Gennes theory based modeling.

Temperature-dependent densification of sodium borosilicate glass

Densified glasses recovered from a high-pressure state are of potential technological interest due to their modified physical and chemical properties. Here we investigate the temperature-dependent densification behavior of a sodium borosilicate glass in a gas pressure chamber at 1 GPa. The temperature is varied for a 30 min treatment between 0.6Tg and 1.15Tg, where Tg is the glass transition temperature, and the treatment duration is varied between 10 and 10u2006000 min for compression at 0.9Tg. Permanent densification occurs for temperatures above 0.7Tg and the degree of densification increases with increasing compression temperature and time, until attaining an approximately constant value for temperatures above Tg. The same temperature and time dependence is also found for the glass mechanical properties (hardness and brittleness) and the network structure, i.e., fraction of three-fold versus four-fold coordinated boron atoms and ring versus non-ring trigonal boron atoms, and the extent of mixing of Si and B. The results provide insights into the temperature-dependence of the network densification and the relative roles of viscous flow and more localized rearrangements.

The effect of high hydrostatic pressure on the survival of Saccharomyces cerevisiae in model suspensions and beetroot juice

The inactivation of Saccharomyces cerevisiae NCFB 3191 using high hydrostatic pressure of 300 MPa at 20°C with a holding time of 0, 1, 5 and 10 min was investigated with model suspensions in phosphate-buffered saline and in beetroot juice. The reduction in S. cerevisiae NCFB 3191 in model suspensions was about 5 log after 10 min of pressurization, irrespective of the initial level of cell concentration in the samples (5.4–8.7 log cfu/mL). The baroprotective effect of beetroot juice on yeast cells during pressurization was observed; the reduction was lower and was only 3.5 log (the inoculum was 5.4 log cfu/mL). No sublethal injury among the surviving cells of the studied yeast strain was found.

Does the characteristic value of the discontinuity of the isotropic-mesophase transition in n-cyanobiphenyls exist?

Results of the extended Landau-de Gennes model analysis and experimental studies of the isotropic-nematic (I-N) and isotropic-smectic-A (I-SmA) phase transitions in rod-like liquid crystalline n-alkylcyanobiphenyls are presented. Experiments were carried out as a function of temperature and pressure using the static dielectric permittivity and its nonlinear (strong electric field related) counterpart-the low-frequency nonlinear dielectric effect. Precise estimations of the values of the discontinuity of the isotropic-mesophase transitions (ΔT) for nCB from n = 3-14 have been obtained. It is suggested that for each nCB a unique, characteristic minimal value of ΔT, associated with the I-N-SmA triple point, exists. For shorter nCBs it can be hidden in the negative pressures domain. The possibility of the extension of the melting curve into the negative pressures region as well as the appearance of the melting inversion at high enough pressures is indicated.