The baddeleyite-type high pressure phase of Ca(OH)2

Abstract

A phase transition from Ca(OH)₂ I (portlandite) to Ca(OH)₂ II at high pressure and temperature has been confirmed, using in situ x-ray diffraction in a multianvil high pressure device (DIA). The structure was determined at 9.5 GPa and room temperature from data collected after heating the sample at 300°C at 7.2 GPa in a diamond anvil cell. Both the Le Bail fit and preliminary Rietveld refinement suggest that the new phase, which reverts to Ca(OH), I during pressure release, has a structure related to that of baddeleyite (ZrO₁); it is monoclinic (P2₁/c) with a= 4.887(2), b= 5.834(2), c = 5.587(2), β = 99.74(2)°. The coordination number of Ca increases from six to seven (5 + 2) across the transition. At 500°C, the phase boundary is bracketed at 5.7 ± 0.4 GPa by reversal experiments performed in the DIA.     

Moderate hydrostatic pressure–temperature combinations for inactivation of Bacillus subtilis spores

We report the effect of using moderate hydrostatic pressure, 40–140?MPa, at moderate temperature (38–58°C) to inactivate Bacillus subtilis spores in McIlvaine's citric phosphate buffer at pH 6. We have investigated several parameters: pressure applied, holding time, pressure cycling, and temperature. The kinetics of spore inactivation is reported. The results show that spore inactivation is exponentially proportional to the time the sample is exposed to pressure. Spore germination and inactivation occur at the hydrostatic pressures/temperature combinations we explored. Cycling the pressure while keeping the total time at high pressure constant does not significantly increase spore inactivation. We show that temperature increases spore inactivation at two different rates; a slow rate below 33°C, and at a more rapid rate at higher temperatures. Increasing pressure leads to an increase in spore inactivation below 95?MPa; however, further increases in pressure give a similar rate kill. The time dependence of the effect of pressure is consistent with the first-order model (R²?>?0.9). The thermal resistance values (Z_T) of B. subtilis spores are 30°C, 37°C, and 40°C at 60, 80, 100?MPa. The increase in Z_T value at higher pressures indicates lower temperature sensitivity. The pressure resistance values (Z_P) are 125, 125 and 143?MPa at 38°C, 48°C, and 58°C. These Z_P values are lower than those reported for B. subtilis spores in the literature, which indicates higher sensitivity at pressures less than about 140?MPa. We show that at temperatures <60°C, B. subtilis spores are inactivated at pressures below 100?MPa. This finding could have implications for the design of the sterilization equipment.     

Pressure inactivation of fungal spores in aqueous model solutions and in real food systems

Abstract

Conidiospores from Penicillium expansum and ascospores from Eurotium repens were exposed to high hydrostatic pressure in isotonic salt solution, apple and broccoli juice. Kinetic measurements were done at 4,25 and 40 or 45°C. The shape of the inactivation curves was strongly dependent on the temperature. Asco- and conidiospores were found to behave in a contrary way. The fastest reduction for conidiospores was found at 4°C, for ascospores best inactivation was achieved at 45°C. High pressure inactivation of spores in apple or broccoli juice was nearly the same as in isotonic salt solution.     

Distribution of light alkanes in the reaction of graphite hydrogenation at pressure of 0.1–7.8 GPa and temperatures of 1000–1350°C

ABSTRACT

We studied the effect of pressure and temperature on the hydrocarbon (HC) chain length distribution and total amount of HCs in the reaction of direct graphite hydrogenation at pressures of 0.1–7.8?GPa and temperatures of 1000–1350°C. An increase in pressure was found to lead both to an increase in the absolute yield of HCs due to direct graphite hydrogenation and to chain elongation of HC products. Light alkanes predominate among HCs in the entire studied range of P–T parameters. However, their concentration in quenched fluids increases as pressure is elevated, from less than 10?rel.% at 0.1?GPa to more than 40–50?rel.% at P?≥?3.8?GPa. Methane is actually the only light alkane among reaction products at 0.1?GPa and 1000°C, while it is a minor component at 7.8?GPa and 1350°C. The most stable alkane at pressures above 3.8?GPa is ethane (C₂H₆).     

Synthesis of nano-polycrystalline diamond from glassy carbon at pressures up to 25 GPa

ABSTRACT

Nano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ～1700°C at 15?GPa to ～1900°C at 25?GPa. The NPD having grain sizes less than ～50?nm was synthesized at temperatures below ～2000°C at 15?GPa and ～2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions.     

Growth of he bubbles in al during annealing

Abstract

The temperature dependent growth of He bubbles in Al films implanted at room temperature to various He concentrations is investigated by electron energy-loss spectroscopy (EELS) and transmission electron microscopy (TEM). EELS reveals even the weakest changes in He density within the bubbles by measuring the pressure shift of the He 1¹S₀?2¹P₁ transition. This is applied to investigate the mechanisms driving the growth of bubbles in the temperature range 20°C ? T ? 500°C. For T?200°C indication is found that bubbles relax by emission of interstitial dislocation loops. At higher temperatures bubble migration and coalescence under absorption of thermal vacancies is evident. The final state is characterized by large cavities filled with He at low pressure as evidenced by the detection of the atomic He series.     

Comparison of the Raman pressure shift and the Raman temperature shift of benzene and diamond with the ruby soale

Abstract

In order to serve as substitute for the pressure ruby scale at high temperature, the breathing mode of bemsens (990 cm^?1) and the first order Raman mode of diamond (1333 cm^?1) have been studied as a function of pressure and temperature in the range of 0–15 GPa and 25–400°C. The diamond and bensene Raman frequency shifts are shoft to be of valuable use as a pressure scale at high temperature. A further advantage of bensene is to remain a suitable pressure transmitting medium up to 350°C and 15 GP.     

Diastereoselectivity and kinetics of hetero diels-alder reactions under high pressure

Abstract

The Hetero Diels-Alder reaction of enamino ketones and ethyl vinyl ether to give dihydropyrans is studied in different solutions under pressure up to 7 kbar. The kinetics is measured via on-line FT IR spectroscopy. The cycloaddition shows a remarkable pressure dependent increase in diastereo-selectivity. For the difference in activation volumes referring to the reaction to the two diastereomers, values up to 5.9 ± 0.5 cm³/mol are observed. The ratio of cis and trans diastereomers can be improved by almost one order of magnitude by changing pressure and temperature from 1 bar and 90 °C to 6 kbar and 0.5 °C.     

Effect of external pressure on Tc of as‐grown and thermally treated superconducting Rbx Fe2–ySe2 single crystals

We report on the effect of external pressure on the superconducting transition temperature (T_c) of as‐grown and thermally treated single crystals of superconducting iron chalcogenide Rb_0.85Fe_1.9Se₂. The superconducting transition temperature of 27.1 K at ambient pressure for the as‐grown sample was found to increase up to 33.2 K for the sample annealed for 3 h at 215 °C in vacuum. An increase of T_c up to 28.2 K was observed for the as‐grown sample at a pressure of 0.83 GPa. For all the studied crystals, annealed in the temperature range between 215 °C and 290 °C, the external pressure seems to decrease the superconducting transition temperature and a negative pressure coefficient of T_c was observed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of pH and high pressure at sub-zero temperature on the viability of some bacteria

The objective of this study was to investigate the viability of Escherichia coli and Staphylococcus aureus in apple juice after treatment with high pressure at sub-zero temperature and during subsequent storage at 5 and 20 °C. The viability of E. coli and S. aureus cells suspended in the apple juice with a pH of 3.8 did not decrease considerably after pressure treatment at 193 MPa and?20 °C. However, viability losses occurred during storage of samples after pressure treatment. Living cells of both strains were not detected in pressurized samples of apple juice stored for 10 days at 20°C. The lethal effect was lower when the samples after pressure treatment were incubated at refrigerated temperature; the number of E. coli and S. aureus decreased by 6 log cycles when the juice was stored for 10 days at 5 °C.     

Listeria monocytogenes cells injured by high hydrostatic pressure and their recovery in nutrient-rich or -free medium during cold storage

ABSTRACT

Cells of Listeria monocytogenes suspended in phosphate-buffered saline (PBS) were treated by high hydrostatic pressure (HHP; 500?MPa, 25°C, 10?min), diluted by ten folds using trypticase soy broth (TSB) or PBS, and stored at cold temperatures of 0–15°C. Viable cell count in TSB increased logarithmically close to the initial count at each storage temperature, while that in PBS increased temporarily and subsequently decreased to almost nondetectable level except the case at 15°C, where it showed logarithmic increase thereafter. Based on proliferation experiments where their healthy cells were inoculated to TSB or to PBS containing their heat-killed dead cells, it was suggested that increase in the viable count of HHP-treated cells in TSB and PBS could be ascribed to the recovery of colony forming ability and/or proliferation depending on the cold storage temperature.     

Birefringence of SbSI and SbSeI crystals at the region of antiferroelectric phase transition

Anomalous behavior has been observed in the temperature range of T = 140–145 °C. The electric current I(T) of SbSI and SbSeI crystals along the c(z) axis changes significantly at the region of the antiferroelectric phase transition when DC voltage is applied. The peak positions are observed at 140 °C and 145 °C for SbSI and SbSeI, respectively. The birefringence spectra show temperature-dependent changes upon retardation m, confirming the antiferroelectric phase transition for both crystals. The peak positions observed from the optical measurements do not differ from the electrical measurements, showing the transition point at 140?°C and 145?°C for SbSI and SbSeI, respectively.     

Phase Transformations in Nd–Fe–B-Based Alloys under High Pressure Torsion at Different Temperatures

In this work, we studied the behavior of the Nd–Dy–Fe–Co–Cu–B alloy for permanent magnets under high pressure torsion (HPT). In the initial state of the studied alloy, it mainly contained the crystalline phase τ₁ (Nd, Dy)₂(Fe, Co, Cu) ₁₄B. After HPT at room temperature (T_HPT = 30°C), a mixture of an amorphous phase with nanocrystalline inclusions of the τ₁ phase is observed in the alloy. In the equilibrium phase diagram, this state is equivalent to a mixture of the τ₁ phase with the melt at the temperature T_eff= ∼1100°C. The thus determined T_eff value is called the effective temperature. When the T_HPT temperature of the HPT treatment increases to 300 and 400°C, the amorphous phase disappears, and the Fe₂B and γ-Fe phases appear instead. In the equilibrium phase diagram, this state is equivalent to a mixture of phases τ₁+ Fe₂B + γ-Fe, which is observed in the temperature range from ∼950 to ∼1050°C. We explain this phenomenon by the fact that with an increase in the HPT temperature T_HPT, the rate of formation of defects during deformation remains constant, but the rate of their thermal relaxation (annihilation) increases. This is equivalent to decrease in the effective temperature T_eff in the equilibrium phase diagram. The previously predicted decrease in T_eff with an increase in T_HPT is observed for the first time.

     

Autoadhesion of High‐Molecular‐Weight Monodisperse Glassy Polystyrene at Unexpectedly Low Temperatures

Abstract

Healing of symmetric interfaces of amorphous anionically polymerized high‐ and ultrahigh‐molecular weight (HMW and UHMW, respectively) polystyrene (PS) in a range of the weight‐average molecular weight M _w from 102.5 (M _w/M _n = 1.05) to 1110 kg/mol (M _w/M _n = 1.15) was followed at a constant healing temperature, T _h, well below the glass transition temperature of the polymer bulk [T _g‐bulk = 105–106°C as measured by differential scanning calorimeter (DSC)]. The bonded interfaces were shear fractured in tension on an Instron tester at ambient temperature. Autoadhesion at symmetric HMW PS–HMW PS and UHMW PS–UHMW PS interfaces was detected mechanically after healing at T _h = 38°C for 107 hr, and even at 24°C (for longer healing times). The occurrence of autoadhesion between the surfaces of the UHMW PS with M _w = 1110 kg/mol at 24°C implies that the glass transition temperature at the interface, T _{g‐interface}, of this polymer was a least lower: by 82°C than its DSC T _g‐bulk, by 30–40°C than the Vogel temperature, T _∞—the lowest theoretical value of a kinetic T _g‐bulk at infinite long time—and by 20°C than T ₂ (a “true” thermodynamic T _g‐bulk corresponding to a second‐order phase transition temperature). To our knowledge, this is the first observation of such nature, which gives further evidence of the lowering of the T _g at polymeric surfaces and the persistence of this effect at early stages of healing of polymer–polymer interfaces.     

Calibration of berlinite (AlPO4) as Raman spectroscopic pressure sensor for diamond‐anvil cell experiments at elevated temperatures

Changes in the band position of the 462 and the 1111 cm^–1 A₁ modes of berlinite (AlPO₄) with temperature and pressure were determined in situ to 500°C and to 10 GPa using Raman spectroscopy and diamond‐anvil cells. These bands shift in opposite directions with pressure and, likewise, with temperature. At a known temperature, the relative difference of both band positions (Δν)_P,T can therefore be used as a pressure gauge that does not require calibration of the spectrometer. At ambient pressure, the observed temperature dependence of this relative difference of the line positions is very close to linear and can be described by (Δν)_{T, 0.1 MPa} (cm^–1) = 0.0181 T – 0.46 where 23 ≤ T (°C) ≤ 500. Along the 23°C isotherm to 10 GPa, pressure and relative wavenumber difference (Δν)_{P, 23°C} are related by the equation P (GPa) = 0.00083 [(Δν)_{P, 23°C}]² – 0.062 (Δν)_{P, 23°C}. Both equations can be combined to determine pressures at higher temperatures under the assumption that the change in (Δν)_P,T with pressure is insensitive to temperature. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of a high pressure stirring cell up to 2 GPa: a new window for chemical reactions and material synthesis

ABSTRACT

A new method for stirring under high pressure conditions has been developed and tested. The key component is a Teflon cell assembly equipped with magnetic stirring function, which is capable to operate across a wide pressure range, up to at least 2?GPa, in a large volume press. The setup enables adjustable stirrer rotation rate and detection of stirring in a sample, e.g. to observe liquid–solid phase transitions at high pressure. The viscosity limit of stirring is ca. 500 times that of water at room temperature (i.e. ～500?mPas). Moreover, we show that zinc oxide nanoparticles hydrothermally synthesized at 0.5?GPa and 100°C under stirring conditions show an order of magnitude smaller size (100?nm) compared to those synthesized under non-stirring conditions (1?μm). The wide pressure range for stirring of viscous media opens interesting possibilities to produce novel materials via hydrothermal synthesis and chemical reactions.     

Epitaxial growth and magnetic and electric properties of Co-doped thin films

In this research, c-axis oriented epitaxial anatase TiO ₂ thin films were grown on SrTiO ₃ (100) substrates using a ceramic Ti _0.95 Co _0.05 O ₂ target by Pulsed Laser Deposition (PLD). The film growth processes were monitored by reflective high energy electronic diffraction (RHEED). Microstructure, conductivity, and magnetism of these doped films are found strongly affected by the oxygen pressure and substrate temperature T_s. Grown at a T_s around 750 ^° C in an oxygen pressure of 0.2 mbar, the dopants are found existing as oxide inclusions. The doped film thus behaves as an insulator and shows diamagnetism in a magnetic field parallel to the film surface. However, in the doped film grown at a reduced temperature of 630 ^° C in a vacuum, no impurity phase can be identified. The film shows a saturated magnetic moment of 0.16μ _B / Co and a fairly good conductivity at room temperature. It is then concluded that nonequilibrium growth at lower temperatures in vacuum is essential for a high solubility of Co in the TiO ₂ lattice and thus the ferromagnetism.     

Investigation of domain behaviour in 0.7Pb(Mg1/3Nb2/3) O3-0.3PbTiO3 single crystals at different temperatures in the transmission electron microscope

Using transmission electron microscopy, in-situ changes in ferroelastic domains in 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ single crystals were observed at 60 to -163°C. At -163°C, the microscopic tweed morphology of the ferroelastic domains rotated by 90°, and certain orientation changes in the mesoscopic sawtooth domains took place. At this temperature, the ferroelastic domains became coarsened and certain S-shaped mesoscopic domains were reshaped. The disappearance and/or changes in the orientations of both the sawtooth and the ferroelastic domains were reversible upon return to room temperature. On heating to 60°C, both the mesoscopic sawtooth and the microscopic tweed domains were stable below 53°C. Above 53°C, the mesoscopic walls disappeared and the contrast of the tweed domains became blurred. Upon return to room temperature from 60°C, the mesoscopic domain patterns could not be retrieved, indicating that the transformation was irreversible. The morphology of the tweeds at this temperature indicated a structural transition from a two-variant domain state to a multivariant state, eliminating mesoscopic boundaries.     

Gasket temperature: an alternate technique for estimating sample temperature in a multi-anvil apparatus

It is common for sample temperatures to be estimated by the power input to the furnace in multi-anvil experiments in which a thermocouple cannot be used or the thermocouple failed during heating. Uncertainties using this technique are often on the order of ±85°C or larger. This paper describes a new method for estimating sample temperature using a second thermocouple outside all pressure media. Temperatures recorded at this external (gasket) thermocouple trend linearly with the internal (sample) thermocouple temperature. Because of thermal lag, it is necessary to determine the first gasket temperature (T₀) corresponding to the desired sample temperature. Accurate prediction of T₀ for the desired sample temperature can come from relatively few (5–6) gasket-temperature measurements made during the initial temperature ramp over a small temperature range (500–600°C). Using this method and manually ramping to T₀ allows for uncertainties in sample temperature estimation as small as ±20°C.     

Variable-Temperature and High-Pressure Micro-Raman Spectra of Inorganic Artists' Pigments: Crystalline Wulfenite,Lead(II) Molybdate(VI), PbMoO4

Variable-temperature (?150°C to 600°C) and high-pressure (up to ～5 GPa) micro-Raman spectra have been obtained for the mineral wulfenite [lead(II) molybdate(VI), PbMoO₄], a main constituent of the artists' pigment, orange molybdate. The spectra were quite similar in both the temperature and the pressure studies, except for broadening and shifting of some peaks. No phase changes were detected, although there is possibly some amorphization beginning at ～600°C. The photoacoustic IR spectrum in the 1950–450 cm^?1 region is reported for characterization purposes. The long-term stability of PbMoO₄ with respect to extreme changes in both temperature and pressure illustrates the importance of orange molybdate in artwork and protective coatings.