Constant chemical potential,pressure and temperature profiles in liquid–vapour equilibrium obtained by spinodal decomposition

Constant chemical potential, pressure and temperature profiles across a slab of liquid in equilibrium with its vapour confirm that, the spinodal decomposition procedure carried on the NVT ensemble simulated via molecular dynamics produce an equilibrium system. An initial homogeneous crystalline configuration of fluid is kept in a cell with a parallelepiped shape at a density near the critical density and a temperature between the triple and critical temperatures, form a slab of liquid in equilibrium with its vapour by the spinodal decomposition phenomenon if the simulation is performed in the NVT ensemble. An elongated box favours the formation of two planar parallel surfaces along the largest side of the box. We show in this paper that the ‘three conditions’ for thermodynamic equilibrium: constant temperature, constant pressure and constant chemical potential are met for such a system.     

Preparation of copper–silicon dioxide nanoparticles with chemical vapor synthesis

Atmospheric pressure chemical vapor synthesis was used to produce copper nanoparticle composites in an amorphous silicon dioxide, i.e., either copper nanoparticles coated with amorphous silicon dioxide or copper nanoparticles embedded in amorphous silicon dioxide matrix. Synthesized metal–organic copper(I) complex was used as a precursor that provided well-defined ratio (1:2) of copper and silicon. The thermal decomposition of the Cu(I) complex molecule leads to homogenous nucleation and formation of copper nanoparticles which are subsequently coated with Si/SiO₂ in the gas phase. The decomposition was greatly enhanced when reductive atmosphere, i.e., H₂/N₂ 10 v% were used instead of pure nitrogen. A narrow size distribution with the geometric mean diameter of the particle agglomerates around 30 nm was observed while the primary size of the copper core particles was around 5 nm.     

Ceramic synthesis of 0.08BiGaO_3–0.90BaTiO_3–0.02LiNbO_3 under high pressure and high temperature

In this paper, the preparation of 0.08BiGaO_3–0.90BaTiO_3–0.02LiNbO_3 is investigated at pressure 3.8 GPa and temperature 1100–1200?C. Experimental results indicate that not only is the sintered rate more effective, but also the sintered temperature is lower under high pressure and high temperature than those of under normal pressure. It is thought that the adscititious pressure plays the key role in this process, which is discussed in detail. The composition and the structure of the as-prepared samples are recorded by XRD patterns. The result shows that the phases of Ba TiO_3, BaBiO_(2.77), and Ba_2Bi_4Ti_5O_(18) with piezoelectric ceramic performance generate in the sintered samples. Furthermore, the surface morphology characteristics of the typical samples are also investigated using a scanning electron microscope. It indicates that the grain size and surface structure of the samples are closely related to the sintering temperature and sintering time. It is hoped that this study can provide a new train of thought for the preparation of lead-free piezoelectric ceramics with excellent performance.     

Crystallographic aspects related to the high pressure–high temperature phase transformation of boron nitride

Crystallographic relations between different forms of boron nitride (BN) appearing at the high pressure–high temperature structural phase transformation have been revealed by high-resolution transmission electron microscopy (HRTEM). As starting materials, crystalline hexagonal BN (hBN) with different degrees of crystallinity, or with defects intentionally introduced, were used. Cubic BN (cBN) is formed only as a minor component, the rest consisting of different forms of sp ² bonded BN: hBN, compressed, monoclinic deformed hBN, or turbostratic BN (tBN). The small cBN crystallites (300–400?nm) contain many defects such as twins, stacking faults and nanoinclusions of other BN forms: tBN, rhombohedral BN (rBN) and wurtzite BN (wBN). The cBN phase grows epitaxially on the basal plane of hBN. The nucleation sites for cBN are revealed by HRTEM. They consist of nanoarches (sp ³ hybridized, highly curved nanostructures), frequently observed at the edges of the hBN crystallites in the starting materials. Based on HRTEM observations of specimens not fully transformed, a nucleation and growth model for cBN is proposed which is consistent with existing theoretical and experimental models.     

Condensed matter chemistry under ‘extreme’ high pressure–high temperature conditions

Improved techniques for high-pressure experiments have led to new studies of the structure and physical properties of materials compressed to extremely high densities. Now we must fully enable the field of condensed matter chemistry under extreme high-pressure conditions. This will require development of strategies for the analysis and control of the chemical composition during reactions between solid, liquid and fluid phases. Such approaches already exist within the fields of experimental geochemistry and petrology, and they can be readily adapted to the wider area of chemistry. The first consideration is the manipulation and determination of stable and metastable pressure–temperature phase diagrams, illustrated here for the one-component system Si. Next, relationships between P, T and the chemical composition, X, expressed in terms of the chemical potential (μ) or the activity–composition relations, can be used to constrain and determine components within the system. This is illustrated by examples drawn from our recent work on high-pressure syntheses of boron suboxides (B₆O_1???δ) and (Si, Ge)₃N₄ nitride spinels.     

Effects of Mg on diamond growth and properties in Fe–C system under high pressure and high temperature condition

Diamond crystal crystallized in Fe–Mg–C system with Archimedes buoyancy as a driving force is established under high pressure and high temperature conditions. The experimental results indicate that the addition of the Mg element results in the nitrogen concentration increasing from 87 ppm to 271 ppm in the diamond structure. The occurrence of the {100}plane reveals that the surface character is remarkably changed due to the addition of Mg. Micro-Raman spectra indicate that the half width of full maximum is in a range of 3.01 cm~(-1)–3.26 cm~(-1), implying an extremely good quality of diamond specimens in crystallization.     

The use of calcination in exposing the entrapped Fe particles from multi-walled carbon nanotubes grown by chemical vapour deposition

Multi-walled carbon nanotubes (MWCNTs) were synthesized a by chemical vapour deposition method. The effect of calcination at temperatures ranging from 300 to 550°C in exposing the metal nanoparticles within the nanotube bundles was studied. The degree of degradation of the structural integrity of the MWCNTs during the thermal process was studied by Raman spectroscopy, X-ray diffraction analysis, field-emission scanning electron microscopy, and transmission electron microscopy. The thermal behaviour of the as-prepared and calcined samples was investigated by thermogravimetric analysis. Calcination in air, at 400°C for 1 h, was found to be an efficient and simple method to extract metallic impurities from the amorphous carbon shells with minimal damage to the tube walls and lengths. The nanotubes were observed to be damaged at temperatures higher than 450°C.     

Fracture toughness evaluation of WC–10 wt% Co hardmetal sintered under high pressure and high temperature

This work focused on fracture toughness studies of WC–10?wt% Co hardmetal fabricated through the high pressure/high-temperature technique. A powder mixture of WC–10?wt% Co was sintered at 1500–1900°C under a pressure of 7.7?GPa for 2 and 3?min. Vickers hardness test at two different loads of 15 and 30?kgf was done and fracture toughness of the sintered bodies was measured using the indentation method to obtain the effect of sintering parameters. Structural analyses were also performed via X-ray diffraction to investigate structure-related properties. Full density was achieved for high sintering temperature along with abnormal grain growth that reduced hardness. High hardness was observed ranging from 1200 to 1670?HV and fracture toughness increased with increasing sintering temperature up to the highest value of 17.85?MPa/m^1/2.     

Nucleation of diamond on silicon wafers using C60 in the hot filament chemical vapour deposition system

Scanning electron microscopy and Raman shifts were used to study the process of diamond nucleation and growth using C60 in the hot filament chemical vapour deposition (HFCVD) system.The process of nucleation and growth of diamond films on silicon wafer using C60 as intermediate layer in HFCVD system is described.In order to increase the density of diamond nuclei on the wafers,it is not necessary to use negative bias.The UV-light pre-treatment is not beneficial for improving the diamond nucleation.The multi-layers of C60 molecules,but not a monolayer,can increase the density of diamond nuclei in the presence of H atoms.     

Blue–violet photoluminescence from colloidal suspension of nanocrystalline silicon in silicon oxide matrix

We report room temperature visible photoluminescence (PL), detectable by the unaided eye, from colloidal suspension of silicon nanocrystals (nc-Si) prepared by mechanical milling followed by chemical oxidation. The PL bands for samples prepared from Si wafer and Si powder peak at 3.11 and 2.93 eV respectively, under UV excitation, and exhibit a very fast (～ns) PL decay. Invasive oxidation during chemical treatment reduces the size of the nc-Si domains distributed within the amorphous SiO₂ matrix. It is proposed that defects at the interface between nc-Si and amorphous SiO₂ act as the potential emission centers. The origin of blue–violet PL is discussed in relation to the oxide related surface states, non-stoichiometric suboxides, surface species and other defect related states.     

Thermoelastic parameter αKT of sodium chloride at high pressure and high temperature

Two different potential models to the molecular dynamics (MD) simulations have been applied to investigate the thermoelastic parameter αK_T of sodium chloride (NaCl) under high pressure and high temperature. The first one is the shell model (SM) potential that due to the short-range interaction when pairs of ions are moved together as is the case in that polarization of a crystal due to the motion of the positive and negative ions, and the second one is the two-body rigid-ion Born–Mayer–Huggins–Fumi–Tosi (BMHFT) potential with full treatment of long-range Coulomb forces. Particular attention is paid to the comparison of the SM- and BMHFT-MD simulations with the Debye model for the first time, and this model combines with ab initio calculations within local density approximation (LDA) and generalized gradient approximation (GGA) using ultrasoft pseudopotentials and a plane-wave basis in the framework of density functional theory (DFT), and it takes into account the phononic effects within the quasi-harmonic approximation. Note that the MD calculated volumes using SM model is somewhat larger than both the DFT and experimental volumes despite not considering the temperature effect. Compared with SM potential, the MD simulated 300 K isotherm of NaCl with BMHFT potential is very successful in reproducing accurately the measured volumes and the GGA calculated volumes. Generally, it is found that there exist minor differences between the LDA and GGA computed the thermoelastic parameter αK_T of NaCl, with both average results giving good agreement with SM-MD simulations. At an extended pressure and temperature ranges, the variation of thermoelastic parameter αK_T which play a central role in the formulation of approximate equations of state has also been predicted. The properties of NaCl are summarized in the pressure range of 0–300 kbar and the temperature up to 2000 K.     

Double-sided laser heating system for in situ high pressure–high temperature monochromatic x-ray diffraction at the esrf

A new double-sided laser heating system optimized for monochromatic X-ray diffraction at high pressure and high temperature has been developed at beamline ID27 of the European Synchrotron Radiation Facility (ESRF). The main components of this system including optimized focusing optics to produce a large and homogenous heated area, optimized mirror optics for temperature measurements and a state-of-the-art diffraction setup are described in details. Preliminary data collected at high pressure and high temperature on tungsten and iron are presented.     

Specific features of thermal resistance of silicon in the temperature range 105–130 K

Careful experimental investigations into the behavior of the thermal resistance of single-crystal silicon are carried out in the immediate vicinity of the temperature of an anharmonicity sign inversion (T _i =121.1 K), where phonon thermal resistance approaches zero. An anomalous positive deviation of the total thermal resistance (W) from the linear part of the temperature dependence with a maximum at 121.1 K is found in the temperature range 105–130 K. The temperature behavior of W in this range indicates that the mean free path of phonons is limited by a characteristic size of structural defects and that its temperature dependence exhibits specific features in the vicinity of T _i . It is established that the character of the temperature dependence of W above and below T _i is different. A linear functional relation between the total thermal resistance and the isobaric thermal strain is revealed at positive and negative anharmonicities of atomic vibrations.     

Fundamental understanding of Na-induced high temperature embrittlement in Al–Mg alloys

Sodium is an undesirable impurity in aluminium–magnesium alloys. In trace amounts it leads to high temperature embrittlement (HTE), due to intergranular fracture, which results in edge cracking during hot rolling. In the present work, the results of a thermodynamic investigation to elucidate the mechanism are presented. Correlations between HTE, phase formation, temperature and composition in Al–Mg alloys were determined. It is suggested that: (i) HTE is related to the formation of an intergranular Na-rich liquid phase, which significantly weakens the strength of grain boundaries; (ii) for a given Mg content, there exists a maximum Na content above which HTE cannot be avoided; and (iii) for a given alloy, a proper hot-rolling temperature should be chosen with respect to Na and Mg contents to suppress HTE. The HTE sensitive zone and a hot-rolling safe zone of Al–Mg–Na alloys are defined as functions of processing temperature and alloy composition. The tendency of HTE formation was evaluated based on thermodynamic simulations of phase fraction of the intergranular Na-rich liquid phase.     

XPS study of the chemical bonding in hydrogenated amorphous germanium–carbon alloys

A systematic study of the chemical bonding in hydrogenated amorphous germanium–carbon (a-Ge_1-xC_x:H)alloys using X-ray photoelectron spectroscopy (XPS) is presented. The films, with carbon content ranging from 0 at. % to 100 at. %, were prepared by the rf co-sputtering technique. Raman spectroscopy was used to investigate the carbon hybridization. Rutherford backscattering spectroscopy (RBS) and XPS were used to determine the film stoichiometry. The Ge 3d and C 1s core levels were used for investigating the bonding properties of germanium and carbon atoms, respectively. The relative concentrations of C–Ge, C–C, and C–H bonds were calculated using the intensities of the chemically shifted C 1s components. It was observed that the carbon atoms enter the germanium network with different hybridization, which depends on the carbon concentration. For concentrations lower than 20 at. %, the carbon atoms are preferentially sp³ hybridized, and approximately randomly distributed. As the carbon content increases the concentration of sp² sites also increases and the films are more graphitic-like. Received: 4 May 1999 / Accepted: 24 November 1999 / Published online: 24 March 2000     

The application of high pressure–mild temperature processing for prolonging the shelf-life of strawberry purée

The aim of this study was to monitor the shelf-life and quality of strawberry purée preserved using combined high pressure processing (HPP)–mild temperature processing at 300 and 600?MPa for 15 min during cold storage (6°C). Increasing the pressure resulted in a prolonged shelf-life of from 4 to 28 weeks for HPP-preserved purée at 300 and 600?MPa, respectively. The highest inactivation of peroxidases, pectinesterases and polygalacturonases was noted when a higher pressure was used, whereas a lower pressure was more efficient for polyphenoloxidases. The degradation of vitamin C and anthocyanins was 20% and 5% higher at 600?MPa than at 300?MPa, respectively. Significantly fewer changes in the colour coefficient, expressed as ΔE, and the browning index, were observed in purée preserved at 600?MPa. Oxidative and hydrolytic enzymes are highly pressure-resistant, which suggests other inhibitors should be used to increase the shelf-life of good-quality fruit products.     

Development of new WC–Ni hardmetals for use in high pressure experiments

Ultrafine-grained (0.2–0.3?µm) WC–Ni hardmetals with a low Ni content (3–5?wt%) were developed using new production techniques based on adding an appropriate amount of VC and Cr₃C_2, combined with the strong mixing of raw materials. Their uniaxial compressibility was subsequently compared with that of existing WC–Ni and WC–Co hardmetals to assess their suitability for use as anvils in various high pressure experiments, particularly those associated with neutron or magnetic studies. The ultimate compressive strength of the newly developed hardmetals was over 7.7?GPa, which was higher by 1.2?GPa than that of the existing WC–Ni hardmetal ‘MF10’. When these hardmetals were used as anvils, a pressure of approximately 16?GPa was generated using a Paris-Edinburgh-type apparatus with φ8?mm culet, thereby proving that they can allow the physical properties of various materials to be measured at higher pressures than is possible with existing hardmetals.     

Electrically stimulated movement of edge dislocations in silicon in the temperature range 300–450 K

The movement of edge dislocations and the related acoustic emission of Si (111) carrying a direct current of density 0.5?5×10⁵ A/m² in the [110] direction are studied in the temperature range T=300–450 K. It is shown that the basic mechanism of dislocation movement is the electric wind determining the magnitude of the effective charge (per atom of the dislocation line) Z _eff=0.06 (n-Si) and ?0.01 (p-Si). Matching theory with experimental data has made it possible to determine the main contribution of edge dislocations to the acoustic-emission response of the silicon samples under investigation. The characteristic transition frequencies of dislocations in n-and p-Si from one metastable state into another are found to be f _max=0.1–0.5 Hz. The numerical values of the diffusion coefficient for atoms in the dislocation impurity atmosphere are estimated as 3.2×10^?18 m²/s (n-Si) and 1.5×10^?18 m²/s (p-Si).