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.     

Interactive Effects of Pressure,Temperature and Time on the Molecular Structure of Ovalbumin,Lysozyme and β-Lactoglobulin

The structure of three food proteins, ovalbumin, lysozyme and g -lactoglobulin were investigated when subjected to pressure, temperature and holding time. Structural effects were determined by the examination of circular dichroism spectra. Experiments were performed using pressures of up to 105 MPa, temperatures up to 79 °C and holding times of 30 minutes using experimental design methodology and compared with ultra high pressures (600 MPa). Examination of the spectra showed that the structure of the three proteins behaved differently to the processing conditions. g -lactoglobulin was found to be the least stable protein while lysozyme was the most stable protein. The higher pressure of 105 MPa was not sufficient to cause structural change when used at ambient conditions but when used in conjunction with raised temperatures and holding time, the applied energy was found to be sufficient to disrupt the protein structure.     

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.     

Athermic movement of dislocations in KC1 single crystals under high pressure

Abstract

The influence of hydrostatic pressure up to 700 MPa on activationless movement of edge dislocations in KC1 single crystals under low applied stresses was studied. It was shown that the path length l of dislocations increase with pressure according to the pressure dependence of the shear modulus G.     

Direct Resinification of Two (1→3)-β-D-Glucans,Curdlan and Paramylon,via Hot-Press Compression Molding

Abstract

Hot-press compression molding was attempted to resinify two renewable source-derived linear (1→3)-β-D-glucan polymers, i.e., paramylon or curdlan via the generation of reactive aldehyde groups that tend to crosslink with hydroxyl groups of the glucans. As for the paramylon, the optimal molding temperature was found to be around 220?°C, keeping the pressure at 20?MPa for 3?min, due to its highly crystalline structure. On the other hand, the curdlan resin was producible in the temperature range of 180–240?°C at the same pressure and pressing time. Dynamic mechanical analysis revealed a large temperature dependence of the loss modulus, E’’, for the paramylon-based polymer resin whereas the semi-crystalline curdlan resin was stable in terms of both the storage and loss moduli, E’ and E’’, up to 160?°C. The vaporization of the water formed during the molding, due to the thermal decomposition, and the adsorption of moisture due to the hydrophilic property of the paramylon affected the thermal stability. The curdlan resin exhibited flexural strength and modulus extremely superior to those of regenerated and esterified curdlan films, and even a little superior to those of polyamide-12. The strain at break was comparable to the yield strain of an epoxy resin. On the other hand, the paramylon-based polymer resin was producible, but the resinification property and thermal stability of the paramylon resin was inferior to the curdlan resin due to the former’s highly crystalline structure.     

Mechanical relaxation of single crystal mats of polyethylene in a crystalline dispersion region

Stress-relaxation measurements have been conducted over the temperature range 15°–105°C on mats of single crystals of two linear polyethylene fractions. The single crystals were grown isothermally at several different temperatures. The relaxation modulus was observed to be strain dependent, indicating that the single crystal mats exhibited nonlinearity.

In spite of this appearance of nonlinearity, it was found possible, when the relaxation modulus was extrapolated to zero strain by an appropriate method, to obtain correct relaxation spectra for the mats of single crystals prepared by isothermal crystallization. This spectrum was then used to calculate the dynamic viscoelastic functions and, for the unannealed sample crystallized at 80°C, good agreement was found between experimental results and calculated ones. Two annealed samples showed multiple absorptions and, under these circumstances, strict application of the method of reduced variables for time and temperature was impractical.

The effect of molecular weight on the intensity of the relaxation spectrum was investigated. It was found that the single crystal with the higher molecular weight showed an increased spectrum intensity.

Observations were also made of the effect of increased lamellar thickness on both the relaxation spectra and the dynamic complex moduli and the results obtained on the fractions studied were compared with prior studies in whole polymer.     

Molecular mobility in compressed fluid n-butane

Abstract

An autoclave machined from a high strength titanium alloy for high pressure high resolution NMR studies is described. The autoclave has been used at pressures up to 600 MPa and temperatures between 150 K and 450 K. The molecular mobility of fluid n-butane has been studied by proton- and deuteron spin lattice relaxation time measurements of selectively deuterated butanes. Additional information about the dynamic is obtained from isotopic dilution experiments. The p, T dependence of the overall mobility and of the rotation of the methyl groups is derived from the data.     

Study of fast relaxation in a glassy polymer by far-IR spectroscopy

The temperature dependence of the far-IR spectra of glassy polymethylmethacrylate is studied in the range of ν = 10–130 cm^–1 at temperatures from 90 to 420 K. The analysis of the spectra revealed absorption corresponding to two rapid relaxation processes: (1) 180°-rotation of the OCO plane of the side groups and (2) reorientation of the links of the main chain. The activation energies of these processes are determined.

     

Investigation of Relaxation Process of Nylon 1212 Using Dielectric Relaxation Spectroscopy

The relaxation processes of α-form nylon 1212 from 50°C up to 160°C were studied by dielectric relaxation spectroscopy (DRS) in a wide frequency range of 63 Hz to 5 MHz. The α relaxation, the electrode relaxation, and the conductivity relaxation of nylon 1212 were observed and analyzed in detail using permittivity and modulus formalism. Electrode polarization and dc conductivity were the origin of high dielectric permittivity values at low frequencies and high temperatures. The strength of the imaginary part of the electric modulus of conductivity relaxation M″ _max was nearly independent of temperature. The distribution of local conductivity and relaxation time became broader with decreasing temperature.     

Investigations of texture formation in geomaterials by neutron diffraction with high pressure chambers

Abstract

This paper suggests a classification of texture in quartzitic rocks. Possible mechanisms of texture formation and their relation to tectonic processes are discussed.

A scheme for the experimental varification of some models describing the evolution of deformation structures in geological materials in dependence on various erxternal conditions (high pressures, temperatures, various loadings, etc.) acting on a sample is proposed.

To investigate “in situ” the mechanisms of texture formation in rocks, high pressure devices are under construction. They will be built of a special T_i ? Z_r alloy, which has zero coherent scattering lenght and therefore is well suited for neutron diffraction investigations. Two different devices are proposed. The first one allows neutron diffraction measurements of sample volumes up to 4 cm³, a hydrostatic pressure of 1, 5 GPa, a temperature of 300° C, and uniaxial compression up to 50 kN. Pressure temperature and axial load are measured inside the chamber. Besides during the experiment, diagrams of load, elastic wave velocities and acoustic emission will be recorded. The second chamber is designed to investigate the mechanisms of texture formation in polycrystal samples (rocks or their imitations) at temperatures up to 800° C and axial compression with a force of up to 150 kN.     

Boron–Carbon Nanocomposites Fabricated at High Pressures and Temperatures

Interaction of amorphous boron and C₆₀ fullerite is analyzed at pressures of 2.0 and 7.7. GPa and temperatures of 600–1800°C. Effect of pressure and temperature on the material structure is studied, temperatures for synthesis of boron carbide and diamond are found, and the sequence of transformations of the carbon component is determined. Ultrasonic method is used to measure elastic moduli of the samples, and the dependences of the moduli on the structure are analyzed. It is demonstrated that the boron–carbon nanocomposite synthesized at relatively low pressure (2.0 GPa) and temperature (about 1000°C) exhibits high elastic parameters (bulk modulus, B ≈ 75.3–84.0 GPa; Young modulus, E ≈ 108–119 GPa; and shear modulus, G ≈ 43–47 GPa at a density of about 2.2 g/cm³). The results can be used for development of novel nanocomposite materials.     

Electric strength of rocks at a pulsed voltage under high pressures at high temperatures

The electric strength of rocks (granite, limestone, and sandstone) for the first time has been measured under the simultaneous effect of the pressure up to 35 MPa and temperature up to 120°C in the system of rod-rod electrodes arranged on one sample surface and point-plane electrodes in the liquid medium of a drilling agent. With the simultaneous increase in pressure and temperature, the electric strength of rocks for point-plane electrodes continuously increases (especially rapidly in the pressure range of 10–24 MPa and temperature range of 35–85°C), while for rod-rod electrodes arranged on the same sample surface, the electric strength varies with a maximum at pressures of 5–12 MPa and temperatures 20–35°C.     

Dynamic Mechanical Properties of Aged Filled Rubbers

Abstract

It is well known that the macromolecular structure and the microstructure of the fillers play an important role in the mechanical properties of filled rubbers. This paper focuses on the dependence of the complex modulus of aged natural rubber vulcanizates on the filler network and polymer structure. Dynamic mechanical analysis (DMA) at 30°C, 50°C, and 70°C on the aged rubbers with/without prestrain showed the Payne effect, i.e., a storage modulus drop with increasing amplitude, and the appearance of a loss tangent maximum at strain of about a few percent. The storage modulus increased with the aging time at 70°C, 24 < 72 < 240 hr, in the case of nonprestrain. When the prestrain was applied, strain‐induced crystallization was generated that enhanced the storage modulus. As time passed, the prestrain relaxed and the crystalline structures began to disappear. After 72 hr, the crystalline structures had almost disappeared, and they had only a weak effect. Consequently, there existed a higher modulus for an aging time of 24 hr than 72 hr at testing temperatures of 30°C and 50°C. It was concluded that the storage modulus was determined by the postvulcanization, strain‐induced crystallization, aging, and relaxing time.     

High-precision measurements of the compressibility of chalcogenide glasses at a hydrostatic pressure up to 9 GPa

The volumes of glassy germanium chalcogenides GeSe₂, GeS₂, Ge₁₇Se₈₃, and Ge₈Se₉₂ are precisely measured at a hydrostatic pressure up to 8.5 GPa. The stoichiometric GeSe₂ and GeS₂ glasses exhibit elastic behavior in the pressure range up to 3 GPa, and their bulk modulus decreases at pressures higher than 2–2.5 GPa. At higher pressures, inelastic relaxation processes begin and their intensity is proportional to the logarithm of time. The relaxation rate for the GeSe₂ glasses has a pronounced maximum at 3.5–4.5 GPa, which indicates the existence of several parallel structural transformation mechanisms. The nonstoichiometric glasses exhibit a diffuse transformation and inelastic behavior at pressures above 1–2 GPa. The maximum relaxation rate in these glasses is significantly lower than that in the stoichiometric GeSe₂ glasses. All glasses are characterized by the “loss of memory” of history: after relaxation at a fixed pressure, the further increase in the pressure returns the volume to the compression curve obtained without a stop for relaxation. After pressure release, the residual densification in the stoichiometric glasses is about 7% and that in the Ge₁₇Se₈₃ glasses is 1.5%. The volume of the Ge₈Se₉₂ glass returns to its initial value within the limits of experimental error. As the pressure decreases, the effective bulk moduli of the Ge₁₇Se₈₃ and Ge₈Se₉₂ glasses coincide with the moduli after isobaric relaxation at the stage of increasing pressure, and the bulk modulus of the stoichiometric GeSe₂ glass upon decreasing pressure noticeably exceeds the bulk modulus after isobaric relaxation at the stage of increasing pressure. Along with the reported data, our results can be used to draw conclusions regarding the diffuse transformations in glassy germanium chalcogenides during compression.     

Isochoric measurement of the equation of state of solid argon at high pressure

Isochoric P-T traces have been measured for solid argon at eight different molar volumes by using a capacitance technique which records the radial expansion of the vessel due to pressure. These measurements extend from melting curve temperatures down to 4 °K at pressures ranging up to 7 kbar.Analysis of the data indicates that, for the high temperature region (above 80 °K) the thermodynamic derivative ?P/?T_r is independent of both temperature and density to within experimental errors. Using the fact that ?P/?T_r is constant, it is possible to generate PVT and isothermal bulk modulus data at high temperatures. These data are compared with X-ray diffraction measurements and piston displacement data and are found to be in good agreement with both. The data also agree quite well with current theoretical predictions. The high-temperature bulk modulus data were found to have a simple exponential dependence on the molar volume, prividing another convenient representation of the high-temperature equation-of-state data.     

Microwave heating in high pressure reaction vessels

Abstract

We report the use of microwave -hydrothermal processing to synthesize various ceramic powders. Microwave-hydrothermal processing is compared with conventional hydrothermal processing in the crystallisation of MoO₂. The presence of microwave field leads to accelerated kinetics of crystallization of the finely divided molybdenum dioxide particles. Existing microwave heated pressure vessels for chemical synthesis cannot be used above 250 MPa and 270°C because they contain parts made of polymeric materials. The objective of this work is to associate a microwave source to a high pressure vessel in a way such that it might be used to carry out reactions in aqueous media at pressures around 100 MPa and temperatures above the critical point of water.     

Effects of pressure and temperature on the survival rate of adherent A-172 cells

Preservation of cells under high pressure is an important alternative to cryopreservation. We studied the effect of temperature (4, 25, 37°C) and pressure (0.1–350 MPa) on the survival rate of A-172 glioblastoma cells. The survival rate was not changed by brief (10 min) pressurization of up to 150 MPa, but the survival rate began to decrease from 150 MPa, and most of the A-172 cells died when treated with over 200 MPa. Lengthy pressurization (4 days) at lower pressure (upto 20.1 MPa) without medium exchange showed complex results. The survival rate of cells preserved at 25°C showed two maxima at 1.6 and 20.1 MPa. After preservation, cells adhered and proliferated in the same way as normal cells when cultured at 37°C in a CO₂ incubator. The other two temperatures, 4° and 37°C, showed no maximum survival rate. Therefore, a high survival rate can be maintained with high pressure treatment.     

Evaluation of the importance of germinative cycles for destruction of bacillus cereus spores in miniature cheeses

Our objective was to determine the effect of high pressure on inactivation of spores of Bacillus cereus ATCC 9139 inoculated into cheese made of raw cow's milk. Inoculated miniature cheeses were manufactured under controlled bacteriological conditions, vacuum packed and kept at 8 °C for 15 days after pressure treatment. Cheeses were submitted to pressures of 300, 400 or 500 MPa at 30 °C, during 15 min. Some of them were treated with a germination cycle of 60 MPa at 30 °C for 210 min. Lethality was calculated comparing surviving sample counts to control ones. Adding the germinative cycle resulted in higher efficiency, and when applied with 500 MPa, lethality reached 2.0 log cfu/mL. We saw that with both cycles initial counts of spores diminish, but all of them were not inactivated. However, considering that in raw milk mesophilic spore counts are 2.6-2.9 log cfu/mL, this treatment may be useful.     

High pressure,high temperature them determination of triple point in CdSe

Abstract

Thermal investigation of melting in gas pressures (Nz) up to 17 kbar was used to determine p-T phase diagram of CdSe. The method, based on measurements of temperature gradient in the container wall during heating and cooling, allowed to obtain the temperature of fusion. The pressure dependence of the melting temperature was given for both low and high pressure phases. The triple point coordinates, equal to 10.90 kbar and 1221 °C confirm earlier measurements of Jayaraman et a1.     

New processes in material production under high pressure

Abstract

To investigate processes of producing high-quality materials using high pressures of gas VNIIMETMASH has developed 3-400 MN hot isostatic presses (HIPes) with working pressure up to 200 MPa and temperature up to 2000°C. Ar and N2 are used as working gases. Frame and vessel units of such machines are of multi-element structure which eliminates the possibility of its fragmentation failure and instant release of compressed gas energy. HIPes are intended for healing defects in casting and compacting metallic, ceramic and composite materials.