Raman Spectra of Selenium Dioxide at High Pressures

Raman spectra of selenium dioxide at ambient temperature and at pressures up to 10 GPa are reported. There is no evidence of any structural phase transitions in this pressure range, and only minor perturbations of the electronic states are observed. Shifts of normal mode wavenumbers with pressure are used to deduce percentage changes in the principal force constants. Interchain interactions sharply increase with pressure, whereas the stronger interchain forces show smaller increases. the Se-O bonds in side branches slightly weaken as a result of charge transfer to neighbouring bonds. the effects of pressure and temperature on the spectra are briefly compared.     

Proton Diffusion in High Pressure Ice

We have developed a spectroscopic method for measuring proton diffusion process in ice at high pressure and temperature using a diamond anvil cell (DAC). It enables us to determine the self diffusion constant of proton (deuteron) from infrared reflection spectra collected as a function of time for a H 2 O/D 2 O ice bilayer prepared and pressurized in the DAC. A preliminary experiment for ice VII at 14 GPa and 400 K provided a diffusion constant D=1.2\times1^{-15} m 2 /s. This was the first measurement of the proton diffusion in pure ice.     

Miniature cryogenic diamond anvil cell

Abstract

The miniature cryogenic diamond anvil described previously [D.J. Dunstan and W. Scherrer, Rev. Sci. Instrum. 59, 627 (1988)] has been modified to facilitate its use, and has been taken to 26GPa. The modifications are described here, together with some details of operation.     

IR Study of the Pressure Induced Solid State DI- and Polymerization in 1,3-butadiene

The pressure induced chemical reaction of butadiene was studied in the crystal phase by means of FTIR spectroscopy using a Membrane Diamond Anvil Cell (DAC). Two different reaction products, vinylcyclohexene (dimerization) and trans-polybutadiene (polymerization), were obtained. The phase diagram of butadiene was investigated and the existence of an orientationally disordered phase, between the liquid and the ordered solid phase, was identified. The analysis of the time evolution of the integrated absorption of the product bands provides information on the reaction mechanisms. Distinct models are necessary to explain the polymer and the dimer formation.     

金刚石压腔高温高压原位谱学研究的评述

金刚石压腔 (DAC)已经可以达到 5 5 0 GPa的压力和 6 0 0 0 K的温度 ,其高温高压谱学原位测量已经成为现代科学的一种重要的手段和方法。目前利用 DAC可以进行光谱学 (拉曼光谱、红外光谱、荧光光谱 )、衍射 (X射线衍射和 XAFS)、布里渊散射、核磁共振 (NMR)以及穆斯堡尔谱的高温高压原位研究。设计用于各种不同需要的便宜的压腔、合适的谱学测量方法以及压力内标物质是进一步拓宽 DAC应用的发展方向。     

B-C-N Compound Synthesized Under High Temperature and High Pressure

Crystalline hexagonal B(N 1 m x C x ) and cubic B-C-N compounds have been synthesized from a precursor produced from melamine and boric acid by application of high temperature and high pressure. The synthesized products were characterized by X-ray diffraction. The lattice parameters for the hexagonal crystal are a=2.506 Å, c=6.657 Å, and that for the cubic crystal is a=3.596 Å. The X-ray photoelectron spectra of the B-C-N compound indicate the presence of B-N, C-N, C-C, and B-C bonds, which suggests that boron, carbon, and nitrogen atoms all bond with one another and that the B-C-N crystal is a compound in which the three kinds of atoms are mixed atomically. The composition of the B-C-N compound is B 0.47 C 0.23 N 0.30 . A strong absorption band at 1000～1120 cm m 1 attributable to the cubic B-C-N phase is observed in the infrared spectrum. The photoluminescence spectrum of hexagonal B-C-N powder measured at room temperature features a broad peak centered at 374 nm, corresponding to the band-edge emission of h-B-C-N, and is similar to that of w-GaN.     

High Pressure and High Temperature Studies on Manganese Oxides

High pressure and high temperature quench experiments on f -MnO 2 , Mn 2 O 3 and sol gel derived manganese oxides have been carried out to identify any new phases to which the materials may transform under high pressure and high temperature conditions. Results of ESR, DTA and TGA investigations on sol gel derived manganese oxide have shown it to be hausmannite Mn 3 O 4 , instead of n -Mn 2 O 3 as reported earlier in the literature. The sol gel derived manganese oxide transforms to n -Mn 2 O 3 when heated above 700°C. Sol gel derived Mn 3 O 4 , when quenched from 5 GPa and temperature range 800-1200°C, gives a mixture of Mn 3 O 4 (hausmannite) and a phase having CaMn 2 O 4 (marokite)-type structure. f -MnO 2 undergoes partial amorphization when pressure-quenched from 8 GPa at room temperature. The high pressure and high temperature quench experiments up to 5 GPa and 700°C showed that the decomposition temperature of f -MnO 2 increases with pressure. The new phase reported by Liu (1976) from diamond-anvil cell (DAC) experiments on pyrolusite MnO 2 is identified to be a low-density polymorph f -MnO 2 . This unusual result of formation of low-density f -MnO 2 , having an open structure at high pressure and high temperature, is probably due to quenching of a non-equilibrium phase in Liu's (1976) laser-heated DAC experiment.     

High Pressure Theoretical Studies of Actinide Dioxides

Actinide dioxides (ThO 2 , UO 2 , Pu 2 etc.) compounds have the CaF 2 -type structure at ambient pressure and temperature. Under high pressure, they exist in the PbCl 2 -type structure, belonging to space group Pnma [1]. We have studied crystal structures under high pressure in actinide dioxides by means of first-principles self-consistent total-energy calculations with the non-local Perdew, Burke and Ernzerhof (PBE) exchange correlation using the full-potential linear-muffin-tin-orbital (FPLMTO) method. The atomic equilibrium volume, bulk modulus and transition pressure for actinide dioxides were calculated, covering the full pressure range for which the mentioned experiments have been done [2].     

High Pressure Study of Dynamics in Tetraphenyltin

Measurements of proton NMR relaxation times as well as inelastic and elastic neutron scattering of tetraphenyltin (C 6 H 5 ) 4 Sn as a function of temperature and pressure were performed in the work. It allowed to determine activation volume j V * for a small amplitude reorientation/oscillation of the phenyl rings. The values of activation volume is very small and the ratio of j V */ V M ( V M is molar volume) is less than 1%.     

Determination of the Mode Grüneisen Parameter of AlN using different Fits on Experimental High Pressure Data

To investigate the pressure dependence of the AlN phonon frequencies Raman spectra of single-crystalline bulk AlN under hydrostatic pressure up to 10 GPa were recorded. The Raman peak positions of the A 1 (TO), E 1 (TO), E 2 (high), A 1 (LO) and quasi-longitudinal optical (QLO) phonons were plotted as a function of pressure. The experimental data was fitted using the traditional parabolic fit (M. Kuball et al . (2001) Appl. Phys. Lett., 78, 724 [1]) and fits to physical models, density, volume, etc. The mode Grüneisen parameters of the different phonons were determined for each fit and significant differences are found between the various fits. Results are compared with recent theoretical calculations (J.-M. Wagner et al . (2000) Phys. Rev. B, 62, 4526 [2]).     

高温高压下电解质溶液谱学研究的进展

高温高压下电解质溶液研究在理论和工业应用上都具有重要的意义，拉曼光谱、红外光谱、紫外可见光谱、中子和X射线衍射、以及X射线吸收精细结构方法都已经用于它的研究。随着温度升高，溶液的结构发生了变化，离子的缔合度增加，内层配位水的数目减少，出现了离子的多核簇组成。除了静态结构的研究外，也用拉曼光谱进行溶液的动力学探讨。水热金刚石压腔装置是高温高压电解质溶液研究的一个重要的进步，在水热金刚石压腔装置中，拉曼光谱和X射线吸收精细结构两种方法具有重要的应用潜力。     

Photo-induced Conversion of Furylfulgide Single Crystal Under High Pressures

We have studied pressure effects on single crystal of photochromic furylfulgide for researching the possibility of photo-induced structural change. Pressure dependence of the absorption spectra was investigated up to 8.2 GPa at room temperature. Pressure-induced conversion to C-form molecules was observed at 8.2 GPa in single crystal composed only of E-form molecules, while at 5.7 GPa in single crystal containing small amount of C-form ones. Photochromic reaction was observed under high pressure as well as the ambient pressure. The dependence of absorption intensity due to C-form molecules suggests the possibly of cooperative structural change in furylfulgide single crystal at 5.5 GPa.     

高温高压下文石和方解石的拉曼光谱研究

利用金刚石压腔结合拉曼光谱分析技术,研究了文石在18～388 ℃,71～2 014 MPa,以及方解石在19～351 ℃,96～1 823 MPa条件下的拉曼光谱特征,并得到文石和方解石的拉曼位移与温度、 压力三者之间的关系式。研究结果表明,文石和方解石的拉曼位移随温度压力的变化规律相似,都随压力升高向高频移动,除文石的704 cm-1外均随温度升高向低频移动。二者的晶格振动ν_i/T值均大于[CO₃]基团内振动的值,说明CaO₆八面体的热膨胀性大于[CO₃]基团的热膨胀性。二者的对称伸缩振动ν/T及ν/P值不同,由于该振动拉曼位移和C—O键的键长有关,方解石的C—O键的热膨胀性比文石小而可压缩性比文石大。另外升温升压过程中文石和方解石可以相互转化,伴随该过程发生的[CO₃]基团旋转变形等动力学因素也可以造成二者ν_i/T和ν_i/P值差异。     

Solid and Liquid AgI at High Pressure and High Temperature: A X-ray Absorption Spectroscopy Study

We report about recent X-ray absorption spectroscopy (XAS) measurements on solid and liquid AgI under high pressure. The structural behaviour of AgI has been investigated to pressures P～4.3 GPa at room temperature and to P～1.8 GPa at 1100 K. The high temperature/high pressure conditions have been obtained by means of a large-volume press of the Paris-Edinburgh type, coupled with a 10 mm boron/epoxy biconical gasket. The absorption spectra have been collected in transmission mode, both at the K-edge of Ag and I, and the samples have been characterized in situ by energy scanning X-ray diffraction at fixed angles. Our XAS results for solid AgI are compatible with previous X-ray diffraction measurements. For liquid AgI, we observe a slight change in the intensity and a shift in the frequency of the XAS oscillations with respect to what obtained in the case of the ambient pressure liquid.     

High Pressure Effect on Meat and Lupin Protein Digestibility

High pressure treatment is a mild treatment concerning the nutritional characteristics: for instance vitamins content is very few affected by high-pressure treatment. But the impact of high-pressure on protein digestibility remains poorly understood. This work presents effect of high-pressure treatment on in vitro digestibility of meat and lupin proteins. Two high-pressure conditions (200 and 500 MPa 10 min.) and a heat treatment of 95 °C, 30 min were studied. In vitro digestibility was evaluated with a pepsin reaction. Results show than for both type of proteins, samples pressurised at 500 MPa were the most hydrolysed. Meat proteins were less hydrolysed than control either after heat or 200 MPa treatment. Lupin proteins where more hydrolysed than control after heat or 200 MPa treatment. Thus we revealed that high-pressure treatment presents an effect on the in vitro digestibility of proteins, opening a new perspective of investigations.     

A New High Pressure - Low Temperature Process for the Synthesis and the Crystal Growth of Gallium Nitride

Gallium nitride can be synthesized by a solvothermal route using ammonia as solvent and a nitriding additive (such as hydrazine hydrochloride NH 2 NH 3 Cl or sodium azide NaN 3 ) encapsulated in melt gallium as chemical reagents. The involved temperature and pressure are respectively 600 °C and 150 MPa. The synthesized products are then characterized by X-Ray Diffraction and Scanning Electron Microscopy. The synthesis parameters influence the powder morphology and purity.     

High Temperature-High Pressure Structural Studies of Cerium

Energy dispersive X-ray-diffraction with the large volume press MAX 80 at HASYLAB/DESY is used in the present study for the determination of the p - V - T -relations around the critical point of the f - n -phase transition in Cerium. Furthermore the f - l -phase boundary is studied experimentally to remove the last question marks from the phase diagram of Cerium in the accessible region of pressure and temperature.     

Suppression of Jahn-Teller Distortion and Insulator-To-Metal Transition in LaMnO 3 at High Pressures

Structural, vibrational and electronic properties of LaMnO 3 under pressures up to 38 GPa have been studied by synchrotron X-ray powder diffraction, Raman spectroscopy, optical reflectivity, and transport measurements. The cooperative Jahn-Teller distortion of the MnO 6 octahedra of the perovskite-type structure is continuously suppressed with increasing pressure, a process which appears completed at ～20 GPa. The system remains insulating to 32 GPa, where an insulator-metal transition is observed. This transition is attributed to strengthened Mn--O--Mn interactions due to the increasing overlap of atomic orbitals.     

High Pressure Fluorescence of 2,5-diphenyl-1,3,4-oxadiazole Crystals

The dependence of the fluorescence of 2,5-diphenyl-1,3,4-oxadiazole (DPO) crystals under compression up to 7 GPa was experimentally studied. The knowledge of the structural behavior at high pressure allows to relate the variation of the fluorescence to the diminution of the inter-molecular distance.     

Effect of High Pressure on Acid Phosphatase in Milk

Acid phosphatase activity was measured in whole milk, skim milk, acid and rennet wheys before and after subjecting samples to high hydrostatic pressures for 10 min. Whole and skim milks exhibited a significant drop in activity following treatment at pressures in excess of 200 MPa. While rennet whey exhibited similar characteristics, acid whey was more pressure resistant and required pressures in excess of 500 MPa before exhibiting a net loss in activity. Most of the activity was lost in the first 10 min of pressurisation.