Nitrogen-rich carbon nitride materials shock-synthesized from carbon tetrahalide and sodium dicyanoamide

Shock reactions between CX₄ (X=Br or I) and NaN(CN)₂ were investigated to prepare carbon nitrides. The post shock samples were characterized by the powder X-ray diffraction (XRD) technique. The XRD spectrum of the product showed a peak in the range of 0.324-0.336 nm in d-value corresponding to the (002) basal plane diffraction in graphitic structure. Elemental analysis (C, H, N, O) of the product showed that the atomic ratio of nitrogen to carbon (N/C) ranged from 0.38 to 1.3. Analysis of data revealed that the d-value increased and the nitrogen content decreased with the increase of the impact velocity.     

Observation of chemical reactions between alkaline-earth oxides and tungsten at high pressure and high temperature

The potential chemical reactions of alkaline-earth oxides (AeO with Ae: Mg, Ca, Sr, and Ba) and tungsten are studied at high pressure and high temperature. At pressures ranging from 5 to 10 GPa and temperatures of 2000 K, a noticeable reaction between AeO and powder tungsten (W) was detected. As a product of the reaction, scheelite-structured orthotungstates (AeWO₄) were formed. The reactivity of alkaline-earth oxides with tungsten increases in the order Ca<Sr<Ba, being the reaction not detected for MgO. Possible chemical reactions leading to the formation of alkaline-earth orthotungstates have been considered. Our results support the conclusion that the most probable reaction occurring under high-pressure and high-temperature conditions is AeO+W+3/2 O₂→AeWO₄.     

Synthesis, structure and luminescence of LaSi3N5:Ce phosphor

In this work, new LaSi₃N₅:Ce³⁺ phosphors have been synthesized by solid-state reaction. Rietveld refinement of the crystal structure of La_1−xCe_xSi₃N₅ reveals that Ce atoms substituted for La atoms occupy 4a crystallographic positions. Broad emission and excitation bands observed were attributed to the transitions between the doublet ground state of the 4f¹ configuration and the crystal field components of the 5d¹ excited state. At 77 K, the centroid and crystal field splitting ε_cfs of the 5d levels of Ce³⁺ in LaSi₃N₅:Ce³⁺ compounds were valuated at 33.4×10³ and 11.3×10³ cm⁻¹, respectively. The zero-phonon line and the Stokes shift were measured to be 26.0×10³ and 5.0×10³ cm⁻¹, respectively.     

Electronic band gap of SrSe at high pressure

The electronic band gap of SrSe, in the CsCl-stuctured phase, was measured to 42 GPa via optical absorption studies. The indirect electronic band gap was found to close monotonically with pressure for the range of pressures studied. The change in band gap with respect to pressure, dE_gap/dP, was determined to be −6.1(5)×10⁻³ eV/GPa. By extrapolation of our line fit, we estimate band gap closure to occur at 180(20) GPa.     

Phase transitions investigation in ZnTe by thermoelectric power measurements at high pressure

The pressure-induced phase transitions were studied in ZnTe by the thermoelectric power (S) technique. For the high-pressure trigonal phase P3₁21 cinnabar the large thermopower values S≈+400 correspond to semiconductor hole conductivity. During a transition into the orthorhombic structure Cmcm the value of S dropped by 40-50 times indicating metallic hole conductivity, like in the high pressure phases of other chalcogenides of II Group (HgSe, HgTe, CdTe) with Cmcm structure. In a transient region between the trigonal and orthorhombic phase (especially under decreasing pressure) a novel phase has been observed with a negative value of S. By analogy with other Zn and Cd chalcogenides whose NaCl phases have an electron type of conductivity the phase observed may have a NaCl structure.     

Properties of C60 polymerized under high pressure and temperature

60 polymers. Pure and mixed phase polymeric samples were synthesized by simultaneously subjecting microcrystalline C₆₀ powder or pellets to various pressures () and temperatures (). The optical spectra of the orthorhombic, tetragonal, and rhombohedral C₆₀ polymer phases are observed to be quite distinct and rich. These spectra exhibit numerous lines and an overall downshift in frequency relative to C₆₀ is observed, consistent with a loss of double bonds from the fullerene cage. The LDMS spectra of a sample synthesized at under hydrostatic conditions and , exhibited a succession of clear peaks at mass numbers corresponding to , similar to the LDMS data on the C₆₀ photopolymer. This is taken as further evidence for interfullerene bonds in these high-pressure polymers. The XRD pattern of this sample indicates the presence of a strong texture in the sample. Received: 14 November 1996/Accepted: 8 January 1997     

Diamond Structure BeO, Designable Super-Hard Materials and Semiconductor Be-Diamond

It is possible for Beryllium oxide （BeO） to have a cubic diamond structure although it normally has a hexagonal structure under ambient conditions. As the solution of cubic BN and diamond, the solid solution of cubic BeO- diamond or BeO-cBN-diamond can potentially be a kind of super-hard materials with designable hardness; and this solution has also been confirmed based on our preliminary first principles calculations. In addition, the nonstoichiometry of BeO could create a mobile carrier in the cubic BeO-C or BeO BN-C system and it might lead to a new type of semiconductor Be-diamond.     

Synthesis of crystalline SrMoO4 nanowires from polyoxometalates

Crystalline SrMoO₄ nanowires were synthesized via a facile hydrothermal process at 180 °C for 10 h. α-(NH₄)₆-P₂Mo₁₈O₆₂·nH₂O, one of polyoxometalates with Dawson structure, was employed as the source of molybdates. The diameter and length of the obtained SrMoO₄ nanowires are about 20 nm and 5-10 μm, respectively. HRTEM results show that the SrMoO₄ nanowires are of high crystallinity with rough surface. However, when Na₂MoO₄·2H₂O was used, there are only SrMoO₄ nanorods with smaller aspect ratio (200/70 nm) in the similar hydrothermal process. The probable growth mechanism was discussed.     

Compression behavior of the delafossite-type metallic oxide PdCoO2 below 10 GPa

The compression behavior of delafossite-type metallic oxide PdCoO₂ below 10 GPa has been investigated by in situ high pressure X-ray diffraction measurement using synchrotron radiation. It is found that the delafossite-type structure of PdCoO₂ is stable below 10 GPa. It should be noted that compression behavior of PdCoO₂ is anisotropic. Pressure dependence of the lattice parameters indicates that the a-axis is more compressible than the c-axis. The lattice parameter ratio c/a in the hexagonal unit increases with increasing pressure. The calculated zero-pressure bulk modulus is 224 GPa. It is found that the above characteristic compression behaviors of PdCoO₂ are the same as those of the delafossite CuFeO₂. The compressibilities of the a-axis of both PdCoO₂ and CuFeO₂ are highly different although those of the c-axis are almost the same.     

A high pressure distorted α-uranium (Pnma) structure in plutonium

Under pressure many rare earths and actinide metals transform to α-U type structure or its lower symmetry distorted forms. We have reinterpreted the diffraction data of Dabos et al. for Pu [S. Dabos et al. J. Alloys Compd. 190 (1993) 237] and find that an Am IV type distorted α-U structure in Pnma space group can explain its high pressure phase. The structures of both the high pressure Am IV type phase and α-Pu, the 0.1 MPa phase, are shown to have a distorted hcp topology. The upturn in the atomic volume of Pu at 0.1 MPa can also be rationalized on the basis of this proposal.     

Short pulse laser microforming of thin metal sheets for MEMS manufacturing

Continuous and long-pulse lasers have been used for the forming of metal sheets for macroscopic mechanical applications. However, for the manufacturing of micro-electro-mechanical systems (MEMS), the applicability of such type of lasers is limited by the long-relaxation-time of the thermal fields responsible for the forming phenomena. As a consequence of such slow relaxation, the final sheet deformation state is attained only after a certain time, what makes the generated internal residual stress fields more dependent on ambient conditions and might make difficult the subsequent assembly process for MEMS manufacturing from the point of view of residual stresses due to adjustment.The use of ns laser pulses provides a suitable parameter matching for the laser forming of an important range of sheet components used in MEMS that, preserving the short interaction time scale required for the predominantly mechanic (shock) induction of deformation residual stresses, allows for the successful processing of components in a medium range of miniaturization but particularly important according to its frequent use in such systems.In the present paper, a discussion is presented on the specific features of laser interaction in the timescale and intensity range needed for thin sheet microforming with ns-pulse lasers along with relevant modelling and experimental results and a primary delimitation of the parametric space of the considered class of lasers for the referred processes.     

Influence of high pressure on the ferromagnetic transition temperature of CrO2

The shift of the Curie temperature of CrO₂ with pressure was determined by ac-susceptibility measurements under hydrostatic pressure up to 5 GPa. These experiments show that ferromagnetism of CrO₂ is suppressed at a rate , which is close to recent theoretical estimates.     

Simulated equation of state of CaF2 with fluorite-type structure at high temperature and high pressure

The pressure-volume-temperature (P-V-T) equation of state (EOS), isothermal bulk modulus, and thermal expansivity of CaF₂ with cubic fluorite-type structure are investigated using the constant temperature and pressure shell model molecular dynamics (MD) method with effective pair potentials which consist of the Coulomb, dispersion, and repulsion interaction. It was shown that MD simulation is very successful in accurately reproducing the measured volumes of the CaF₂ over a wide range of pressures. The simulated P-V data matched X-ray diffraction experimental results up to 9.5 GPa at 300 K. In addition, volume thermal-expansion coefficient and isothermal bulk modulus were also calculated and compared with available experimental data and the latest theoretical results at ambient condition. At extended temperature and pressure ranges, The P-V EOS under different isotherms at selected temperatures, T-V EOS under different isobars at selected pressures, thermal expansivity, and isothermal bulk modulus were predicted up to 1500 K and 10 GPa. The detailed knowledge of thermodynamic behavior and EOS at extreme conditions are of fundamental importance to the understanding of the physical properties of CaF₂.     

Structural phase transition of ScSb and YSb with a NaCl-type structure at high pressures

By use of synchrotron radiation, powder X-ray diffraction of ScSb and YSb with a NaCl-type structure has been studied up to 45 GPa at room temperature. A first-order phase transition from the NaCl-type (B1) to a CsCl-type structure (B2) began to occur at around 28 GPa for ScSb and at around 26 GPa for YSb. Crystal data of the high-pressure phase of both antimonides are obtained. The high-pressure structural behavior of ScSb and YSb is similar to that of heavier LnSb (Ln=Dy-Lu). The B1-B2 transition for ScSb and YSb can be understood according to the rigid sphere model. The bulk moduli of ScSb and YSb are about 58 GPa at ambient pressure.     

Molecular dynamics of binary metal nitrides and ternary oxynitrides

Ternary systems incorporating metals with oxygen and nitrogen are examined using Tersoff potentials. The apparent success of treating some binary nitride systems using the Tersoff potential is used as a way forward to obtain a new parameter set incorporates atomic features into a series of Tersoff potential for binary nitrides and ternary oxynitrides.     

Comparative investigations of the P-V-T relationship of NaCl at high pressure and temperature

Two different potential models of molecular dynamics (MD) simulations have been applied to investigate the pressure-volume-temperature (P-V-T) relationship and lattice parameter of NaCl under high pressure and temperature. The first one is the shell model (SM) potentials in which due to the short-range interaction pairs of ions are moved together as is the case in 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) potentials with full treatment of long-range Coulomb forces. The P-V relationship at 300 K, T-V relationship at zero pressure, and lattice parameter a, have been obtained and compared with the available experimental data and other theoretical results. Compared with SM potentials, the MD simulation with BMHFT potentials is very successful in reproducing accurately the measured volumes of NaCl. At an extended pressure and temperature ranges, P-V relationship under different isotherms at selected temperatures, T-V relationship under different pressures, and lattice parameter a have also been predicted. The properties of NaCl are summarized in the pressure range 0-30 GPa and the temperature up to 2000 K.     

Chemical Synthesis and Characterization of Flaky h-BCN at High Pressure and High Temperature

Hexagonal boron carbonitrogen （h-BCN） compound is synthesized from a mixture of boron powder and CNH compound prepared by pyrolysis of melamine （CaH6N6） under high temperature （1400-1500℃） and high pressure （5.0-5.5 GPa）. X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and Raman spec- troscopy are used to determine the chemical composition and bonds of the product. The results show that the product has composition of B0.18C0.64N0.16 （near BC4N） and atomic-level hybrid. X-ray diffraction analysis indicates that the powder has a hexagonal network structure. Scanning and transmission electron microscopy results suggest that h-BCN compound morphology is mainly flaky in width about 1 μm and thickness 200nm.     

Photoacoustic characteristics of dynamical adhesion of films on a metallic substrate

In this communication, we report a numerical model that predicts the mechanical deformations associated with the pulsed laser irradiation of a film surface, based on thermal diffusion theory. The model is consequently advanced to produce a method for evaluating film adhesion strength. The epicenter surface displacements within the irradiated fields have been measured using a heterodyne interferometer. The comparison of the experimental data and the displacements calculated by the model shows good agreement. By investigating the propagating acoustic modes under non-destructive and destructive modes, we reveal that, with or without interface delamination, the phase structure of the longitudinal waves will be altered due to the change of reflection mode at the interface. Applying shock dynamics theory, we evaluate the adhesion strength of the TiN/stainless interface. We also indicate the strain rate can be up to 10⁵∼10⁶ s^-1 during film interface delamination. Received: 5 April 2002 / Accepted: 24 June 2002 / Published online: 26 February 2003 RID="*" ID="*"Corresponding author. Fax: +86-511/879-1919, E-mail: mzhou@ujs.edu.cn     

Materials science of Mg-Ni-based new hydrides

One of the advantageous functional properties of Mg alloys (or compounds) is to exhibit the reversible hydriding reaction. In this paper, we present our systematic studies regarding the relationship between nanometer- or atomistic-scale structures and the specific hydriding properties of the Mg-Ni binary system, such as(1) nanostructured (n)-Mg₂Ni, (2) a mixture of n-Mg₂Ni and amorphous (a)-MgNi,(3) pure a-MgNi, and(4) n-MgNi₂. Further studies on(5) an a-MgNi-based system for clarifying the effect of the short-range ordering on the structural and hydriding properties and(6) a MgNi₂-based system for synthesizing the new Laves phase structure are also presented. The materials science of Mg-Ni-based new hydrides will provide indispensable knowledge for practically developing the Mg alloys as hydrogen-storage materials. Received: 14 August 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001