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.     

Anomalies in the temperature dependences of the bulk and shear strength of aluminum single crystals in the submicrosecond range

The results of measurements of the dynamic yield stress and the ultimate strength of aluminum single crystals in the temperature range from 15 to 650°C, which is only 10°C lower than the melting point, are presented. The measurements are made on samples under the action of plane shock waves with a pressure up to 5 GPa behind the front and of a duration of ～2×10^?7 s. It is found that the dynamic yield stress anomalously increases, attaining, in the vicinity of the melting point, a value four times as high as that measured at room temperature. The dynamic strength of the single crystals in this temperature range decreases approximately by 40%, a high strength being preserved in the state in which melting during extension is expected.     

Enhanced hardness of CVD diamond after high pressure and high-temperature treatments

The diamond thick layers prepared using chemical vapor deposition (CVD) methods have been treated at high pressures and high temperatures (HP-HT). It was found that the Vickers hardness of the HP-HT treated bulks was nearly two times as high as that of the starting CVD diamond samples. The hardness of the samples treated at 8?GPa and 1800°C is ～80?GPa at a loading force of 49?N, close to that of the single-crystal diamond (～100?GPa). In addition, the oxidation resistance of CVD diamond samples was also enhanced greatly after HP-HT treatments, and the diamondization of sp² bonded carbon in the CVD diamond samples could occur at 7–8?GPa and 1600–1800°C. The HP-HT conditions of diamondization in our works are much lower than the case of the graphite-to-diamond direct transformation without the presence of catalyst (>15?GPa and 2000°C).     

The Fe–Fe2P phase diagram at 6 GPa

Here, we report experimental results on melting and subsolidus phase relations in the Fe–Fe₂P system at 6?GPa and 900–1600°C. The system has two P-bearing compounds: Fe₃P and Fe₂P. X-ray diffraction patterns of these compounds correspond to schreibersite and barringerite, respectively. The Fe–Fe₃P eutectic appears at 1075°C and 16?mol% P. Schreibersite (Fe₃P) melts incongruently at 1250°C to produce barringerite (Fe₂P) and liquid containing 23?mol% P. Barringerite (Fe₂P) melts congruently at 1575°C. Maximum solid solution of P in metallic iron at 6?GPa is 5?mol%. As temperature increases to 1600°C, the P solubility in the metallic iron decreases to 0.5?mol%, whereas the P content in coexisting liquid decreases to 3?mol%. The composition of quenched phases from Fe–P melt coincides with the compositions of equilibrium phases at corresponding temperature. Consequently, the composition of quenched products of Fe-P melts in meteorites can be used for reconstruction of P–T conditions of their crystallization under ambient or low pressures or during shock melting by impact collisions.     

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.     

Convenient preparation of ITO nanoparticles inks for transparent conductive thin films

We synthesized Pt and Ag nanowires using a mesoporous silica, SBA-15, as templates. The obtained nanowires are a few micrometers (~4???m) long and 7?nm in diameter. The nanowires are free from bundling and, thus, can be separated as single nanowires. The successful synthesis of such nanowires requires a few considerations. In general, SBA-15 has microchannels on the walls through which the mesopores are interconnected when synthesized at 100?°C or higher. We, therefore, synthesized SBA-15 at a low temperature (80?°C) to eliminate the microchannels. Impregnation of the metal precursors and reduction of them into metals forms metal particles outside the pores in addition to the desired metal nanowires inside the pores. Surface alkylation of SBA-15 prohibits the nucleation of metal on the external surface and exclusively forms the nanowires. Finally, the introduction of surface passivating agent, an alkylthiol, during the removal of the template keeps the nanowires from interacting with one another. The Pt and Ag nanowires so-synthesized were characterized by electron microscopy.     

Insignificant influence of the matrix on the melting of ice confined in decorated mesoporous silica

For a critical examination of matrix effect on the melting of confined ice, mesoporous silica (SBA-15) are synthesised and decorated with n-Alkyl and aminopropyl groups to tune the surface hydrophobicity. Water contact angle to these decorated surfaces are estimated to be about 100° and 60°, respectively. By examining the melting of ice confined in these decorated samples, we find that the influence of the matrix is indeed not significant. The reported apparent matrix effect is more likely method effect in the determination of pore diameters as was demonstrated in our previous studies (Philos. Mag. 93 (2013), p. 1827).     

The system Na2CO3–MgCO3 at 3 GPa

It was suggested that Na–Mg carbonates might play a substantial role in mantle metasomatic processes through lowering melting temperatures of mantle peridotites. Taking into account that natrite, Na₂CO₃, eitelite, Na₂Mg(CO₃)₂, and magnesite, MgCO₃, have been recently reported from xenoliths of shallow mantle (110–115?km) origin, we performed experiments on phase relations in the system Na₂CO₃–MgCO₃ at 3?GPa and 800–1250°C. We found that the subsolidus assemblages comprise the stability fields of Na-carbonate?+?eitelite and eitelite?+?magnesite with the transition boundary at 50?mol% Na₂CO₃. The Na-carbonate–eitelite eutectic was established at 900°C and 69?mol% Na₂CO₃. Eitelite melts incongruently to magnesite and a liquid containing about 55?mol% Na₂CO₃ at 925?±?25 °C. At 1050 °C, the liquid, coexisting with Na-carbonate, contains 86–88?mol% Na₂CO₃. Melting point of Na₂CO₃ was established at 1175?±?25 °C. The Na₂CO₃ content in the liquid coexisting with magnesite decreases to 31?mol% as temperature increases to 1250°C. According to our data, the Na- and Mg-rich carbonate melt, which is more alkaline than eitelite, can be stable at the P–T conditions of the shallow lithospheric mantle with thermal gradient of 45?mW/m² corresponding to temperature of 900 °C at 3?GPa.     

Mechanical properties of kaolinite ‘macro-crystals’

The mechanical properties of a rare sample of kaolinite macroscopic crystals were evaluated using instrumented indentation. The crystals were also characterized by X-ray diffraction, scanning electron microscopy, atomic force microscopy and Fourier transform infrared spectroscopy before and after heat treatment at 1100°C. The results are explained in terms of the fracture process occurring in the layered structure of kaolinite, and of the effect of roughness on the hardness and elastic modulus. Data analysis using One-way ANOVA (p?<?0.05) showed that the values of hardness and elastic modulus obtained are statistically homogeneous. Before heat treatment, the sample was composed essentially of kaolinite, with hardness of 42?MPa and elastic modulus equal to 1.3?GPa. After calcination at 1100°C, the sample keeps its layered habit and consists of amorphous metakaolinite. The hardness increases to 360?MPa and the elastic modulus increases to 6.9?GPa.     

Some dielectric properties of monoclinic lysozyme crystals

The frequency dependences of the dielectric loss tangent and the magnitude of the impedance for monoclinic lysozyme single crystals and the solution used for preparing the crystals were investigated. The measurements were performed in the frequency range 1–10⁷ Hz under exposure of the crystals at a temperature of 25°C, cooling to ?20°C, and subsequent heating. The analysis of the experimental dielectric properties of the crystals demonstrated that drying of the crystals at room temperature in air initially led to the removal of “free” water with the content approximately equal to 65% of the total content. Further drying resulted in the removal of “bound” water. The solvent contained in the crystals (～26 wt %) was frozen at a constant temperature of approximately ?6.5°C. The permittivity of the dehydrated crystal at high frequencies was considerably higher than that of ice.     

Melting and Recrystallization of Nylon-6,10 Thin Films

The melting and recrystallization of nylon-6,10 thin films immersed in an aqueous solution of calcium chloride were investigated by DSC measurements. The crystal length, ζ, was determined as a function of the melting peak temperature, T _m . The end surface free energy of nylon-6,10 crystals used for the ζ–T _m conversion was derived thermodynamically. For films of 0.01 mm thickness, the original length of ζ (=7.6 structural units) at T _m decreased step by step with increasing immersion time by the length near the structural unit (2.24 nm) per step. However, the suppression of the recrystallization after melting of the original crystals formed during the first cooling by the adsorbed calcium ions did not occur completely, even for films immersed for 30～60 min at 50°C.     

Melting curve of black phosphorous

The melting curve of black phosphorus has been determined up to 5 GPa by a high-pressure high-temperature X-ray system using synchrotron radition. The curve has a maximum at 1 GPa and joins the orthorhombic-rhombohedral phase boundary at a triple point around 2.7 GPa and 900°C.     

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).     

纳米SiO2形成柯石英的p-T相图

 使用纳米SiO₂粉体为原料,在2.0～4.2 GPa、150～1200 ℃范围内进行了一系列的高压高温实验研究,得到了该压力温度范围内晶化产物α-石英与柯石英的p-T相图,而且该相图中的相边界在650 ℃以下斜率为负,在650 ℃以上基本水平。通过X射线衍射仪（XRD）、Raman光谱仪（Raman）、傅立叶红外光谱仪（FT-IR）、DSC-TGA差热分析仪（TG-DTA）-等表征手段,发现纳米SiO₂原粉中水分（包含Si－OH和吸附水）的存在能显著降低合成柯石英的温度和时间,在4.2 GPa压力下得到了目前合成柯石英的最低温度190 ℃。常压下,合成的柯石英在800 ℃以下能够稳定存在,在1 000 ℃以上转化为α-方石英。     

Behavior of thermocouples under high pressure in a multi-anvil apparatus

We have conducted experiments to study the behavior of W5%Re–W26%Re (type C) and Pt10%Rh–Pt (type S) thermocouples under high pressure in a multi-anvil apparatus. The electromotive force (emf) between four different or three identical thermocouple wires was measured up to 15?GPa and 2100?°C. Mechanical and chemical stability of the thermocouples was examined during and after the experiments. Due to the effect of pressure on the emf/temperature relation, the temperature reading of the type C minus that of the type S thermocouple rises to +5?°C then falls to ?15?°C between room temperature and 1500?°C at 5?GPa, and to +25?°C and then ?35?°C between room temperature and 1800?°C at 15?GPa. In addition, we observed variations in the emf/temperature relation caused by uncertainties in the position and geometry of hot junctions in a steep temperature gradient, and by variable distribution of pressure gradient and non-hydrostatic stress on the thermocouple wires. These errors are estimated at 1.6% for the type S thermocouple up to 1700?°C, and 0.8% for the type C thermocouple up to 2100?°C. Self-diffusion and chemical contamination of the thermocouples by high-purity insulating ceramics appear negligible for the type S thermocouple at 1700?°C for one hour, and for the type C thermocouple at 2100?°C for half an hour. In contrast, large-scale displacement of the hot junction due to dislocation of the type C thermocouple wires and plastic deformation of the type S thermocouple wires may lead to large errors in temperature measurement (±200?°C).     

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.     

Melting Point Elevation of Isotactic Polypropylene

The melting point of a conventional isotactic polypropylene (PP) was enhanced by a rapid annealing procedure of an extruded sheet composed of β trigonal form crystals having thick lamellae, which was prepared by T-die processing with a specific β-nucleating agent, N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide. Although the melting point of PP with α monoclinic form, prepared by a conventional processing method, is known to be located around at 165°C, the sample obtained by the present technique showed a higher melting point, 170°C. The phase transformation from β-to α-form crystals, retaining the lamellar thickness, was responsible for the melting point elevation.     

Experimental evidence of the ferroelectric nature of the λ-point transition in liquid water

We studied the dielectric properties of nano-sized liquid water samples confined in polymerized silicates MCM-41 characterized by pore sizes 3–10 nm. Freezing temperature suppression in nanopores helps keep the water samples in liquid form at temperatures well below 0°C and thus effectively study the properties of supercooled liquid water. We report the first direct measurements of the dielectric constant by the dielectric spectroscopy method and demonstrate very clear signatures of the second-order phase transition of ferroelectric nature at temperatures next to the λ-point in the supercooled bulk water in full agreement with the recently developed model of the polar liquid.     

Polyhedral carbon nanoparticles at high pressures

The solid-phase transformations of polyhedral nanoparticles at a pressure of 8.0 GPa and various temperatures have been investigated by X-ray diffraction, small-angle X-ray scattering, and transmission electron microscopy. It has been found that the graphene layers of the inner cavities of polyhedral particles are transformed into onion-like structures at temperatures above ～1000°C. This transformation gives rise to the formation of hybrid-type sp2 carbon nanoparticles, which combine the outer polyhedral shape with the quasispherical onion-like core. Polyhedral nanoparticles smaller than ～40 nm are completely transformed into onion-like particles at 1600°C.     

Kinetic peculiarities of diamond crystallization in K-Na-Mg-Ca-Carbonate-Carbon melt-solution

The kinetic peculiarities of diamond crystallization in multicomponent K-Na-Mg-Ca-carbonate-carbon system have been studied in conditions of diamond stability at 1500–1800°C and 7.5–8.5 GPa. It has been established that the diamond phase nucleation density at a fixed temperature of 1600°C decreases from 1.3 × 10⁵ nuclei/mm³ at 8.5 GPa to 3.7 × 10³ nuclei/mm³ at 7.5 GPa. The fluorescence spectra of obtained diamond crystals contain peaks at 504 nm (H3-defect), 575 nm (NV-center), and 638 nm (NV-defect), caused by the presence of nitrogen impurity. In the cathodoluminescence spectra, an A-band with the maximum at 470 nm is present. The obtained data make it possible to assign the synthesized diamonds in the carbonate-carbon system to the mixed Ia + Ib type.