High-pressure storage of hydrogen fuel: ammonia borane and its related compounds

As a promising candidate material for hydrogen storage, ammonia borane（NH3BH3） has attracted significant interest in recent years due to its remarkably high hydrogen content. Subjecting this material to high pressure not only enables the formation of novel phases and compounds with exotic properties, but also improves our basic understanding of material’s behavior at different levels of atomic and molecular interactions. This review focuses on the perspective of high-pressure chemical hydrogen storage related to NH3BH3-based materials. Four main aspects are discussed： the structures and bonding of NH3BH3 over a wide pressure–temperature space, thermolysis of NH3BH3 at high pressure, the formation of a novel high-pressure H-rich compound as a result of storage of additional molecular H2 in NH3BH3, and the potential rehydrogenation of the thermally decomposed NH3BH3 under the extreme of pressure.     

Decompression-induced disorder to order phase transition in low-melting ionic liquid [OMIM][PF6]

In situ pressure-induced Raman spectral changes of 1-octyl-3-methyl imidazolium hexafluorophosphate （[OMIM][PF6]） have been investigated under the pressure up to 5.86 GPa at room temperature. The results indicated that [OMIM][PF6] experienced a phase transition at about 4.12 GPa during compression, and it was thought as a phase transition of liquid to a superpressurized glass. Upon decompression, from the obvious change of Raman spectra of [OMIM][PF6] at about 0.48 GPa, it could be inferred that a decompression-induced disorder to order phase transition in [OMIM][PF6] occurred. The phase behavior of [OMIM] [PF6] at low temperature under atmospheric pressure was also investigated in detail. The result showed that Raman spectra of [OMIM][PF6] varied slightly and no crystallization occurred upon cooling. These facts suggested that a disorder to order phase transition was induced by decompression in [OMIM][PF6], and [OMIM][PF6] served as a superpressurized glass under the pressure above 4.12 GPa, which was similar to the glassy state at low temperature.     

Synthesis of boron-doped diamond with laser heated diamond anvil cell

Boron-doped diamond has been synthesized from graphite mixed with different ratio of B₄C at high pressure high temperature (HPHT) using laser heated diamond anvil cell. The starting composition was transformed to diamond compound at pressure ∼9 GPa, 2300–2400 K as indicated by the in-situ X-ray diffraction pattern with synchrotron radiation source. Raman spectrum of the recovered specimen from HPHT state confirmed that boron has been doped into diamond lattice.     

TiN在高压下结构稳定性的研究

本实验利用金刚石压砧和同步辐射X衍射技术对TiN在高压下的行为进行了研究．通过实验获得的数据分析了TiN体积压缩曲线．结果表明：在0．45．4GPa的压力范围内,TiN样品的体积随着压强的增加曲线变化比较平滑,TiN没有发生相变．同时,通过三阶的Birch-Murnaghan状态方程,得出了TiN样品在相应的静水压下的体弹模量为B0=195＝4．6GPa,一阶导数B’0固定为4．     

光谱在晶体材料测试方面的应用

总结了目前用于检测晶体材料的四种常用的光谱分析方法:晶体衍射谱、红外光谱、拉曼光谱和THz光谱,及其各自的材料应用范围.分析实验所得的LiTaO3和LiNbO3拉曼光谱图,并计算LN晶体中Li的组分含量.     

MgCo2-D2 and MgCoNi-D2 systems synthesized at high pressures and interaction mechanism during the HDDR processing

MgCo_2 and MgNiCo crystallize with hexagonal Laves type intermetallic structures of the C14 type and do not form hydrides at ambient hydrogen pressures. However, applying high hydrogen pressures in the GPa range forces the hydrogen absorption and leads to the formation of multi-phase compositions, which contain approximately 2.5 atoms H per formula unit of MgCo_2 or MgNiCo and remain thermally stable under normal conditions.The hydrogenation of MgCo_2 resulted in its decomposition to a ternary Mg_2CoD_5 deuteride and metallic cobalt. Phase-structural transformations accompanying the vacuum desorption of deuterium in the temperature range of 27–500 °C were studied using in situ neutron powder diffraction. The investigation showed a complete recovery of the initial MgCo_2 intermetallic via a Hydrogenation-Disproportionation-Desorption-Recombination process. At 300°C, the Mg_2CoD_5 deuteride first decomposed to elementary Mg and hexagonal Co. At 400°C, a MgCo phase was formed by interaction between Mg and Co. At the highest processing temperature of 500°C, a solid-state interaction of MgCo and Co resulted in the recovery of the initial MgCo_2.The interaction of MgNiCo with deuterium under the synthesis conditions of 2.8 GPa and 200 °C proceeded in a more complex way. A very stable ternary deuteride MgNi_2D_3 was leached away while Co was separated in the form of Mg_2CoD_5 and the remaining nickel formed a solid solution with Co with the approximate composition Ni_(0.7)Co_(0.3).The thermal desorption of deuterium from MgCo_2D_(2.5) and from MgNiCoD_(2.5) has been studied by Thermal Desorption Spectroscopy with deuterium released into a closed volume. The observed effects nicely correlate with changes in the phase structural composition of the hydrides formed.MgCo_2 is a new example of the hydrogen storage alloy, in which a successful HDDR processing results in the reversible formation of the initial intermetallic at much lower temperatures than in the equilibrium phase diagram of the Mg-Co system.     

Progress in high pressure EDXD system and research at Beijing Synchrotron Radiation Facility

The synchrotron radiation from a new wiggler of BEPC has been used to high pressure research. Upgraded DAC apparatus and EDXD system have been operated to determine the pressure-induced phase transition of materials at BSRF since June 1998. The improved performance of the system and the preliminary results of the research were described.     

Structural stability and Raman scatterin g of CoPt and NiPt hollow nanospheres under high pressure

This paper reports that the high pressure in situ angle dispersive x-ray diffraction and Raman scattering studies on CoPt and NiPt hollow nanospheres are performed by means of a diamond anvil cell for generating external pressure at room temperature.The crystal structures of both the CoPt and NiP hollow nanospheres keep stable up to about 41 GPa.Moreover,it shows that the hollow nanospheres possess higher bulk moduli than their bulk counterparts by using the frst-principles density functional theory.     

高温高压下ZnO的相变及热力学性质研究(英文)

本文通过平面波赝势密度泛函理论研究了ZnO岩盐(B1)结构、CsCl(B2)结构、闪锌矿(B3)结构和纤锌矿(B4)结构的相变和热力学性质.通过计算得到了晶格常数、体弹模量及体弹模量对压强的一阶导数,与实验值和其他计算结果都符合地较好.根据等焓原理,发现从B4和B3结构到B1结构的相变压强分别约为8.9GPa和7.8GPa.通过准德拜模型,成功得到B4结构的热力学性质,包括不同压强和温度下的状态方程、热膨胀系数和热容.     

掺La铁酸铋粉体的晶体结构

用溶胶凝胶法成功制备Bi1-xLaxFeO3(BLFO,x=0.00～0.40)粉体样品,用X射线衍射谱和拉曼光谱表征样品的结构,并用Rietveld精修法拟合样品的XRD谱.结果显示随着掺La量x的增加,晶格常数逐渐减小,晶胞体积线性减小,当掺杂量增加到x=0.30时,BLFO粉体样品的晶体结构由R3c的三角相转变为Amn2的正交相结构.     

ZnO晶须的变温Raman光谱

采用浮区法制备微米量级的ZnO晶须,X射线衍射(XRD)和偏光显微镜分析表明,生长的ZnO单晶晶须为六方纤锌矿结构,沿(100)晶面择优生长取向.微区变温Raman光谱表明:当温度为93～706K时,声子频率随温度升高呈倒指数下降(红移);当温度超过500K时,E2high谱线随温度上升而加宽,ZnO分子较活跃,Raman模频率呈明显的硬化现象。     

碳化树木的微结构特征研究

对浙江温岭火山角砾岩中的碳化树木进行了高分辨电子显微镜、X粉晶衍射和激光拉曼光谱研究。高分辨电子显微像表明火山角砾岩中的碳化树木相当于微柱石墨—柔绉石墨过渡阶段。碳化树木的一级拉曼光谱D峰波数在1359.7～1369.2cm^-1之间,O峰波数在1594.5～1603.4cm^-1之间。根据峰面积比A_D/(A_D+A_O)计算得出其L_a在7.6～11.8nm之间,与高分辨电子显微像观察结果一致。     

Macro-and microscopic mechanical behaviour of flow of coal samples experimentally deformed at high temperatures and pressures

Coal samples from Qinshui Basin, Shanxi, China are experimentally deformed at temperatures and confining pressures of 200 - 500℃and 200 - 500 Mpa, strain rate of 0.5×10-5/s and total strain of 10%. The vitrinite reflectance of the coal samples varies from 3.04 to 1.79. It is shown that the strengths of the deformed samples change obviously with coeval increasing temperatures and pressures (T/P). At the experimental range of T/P, the effects of increasing temperature predominate over that of increasing pressure. Microstructural analysis indicates a brittle to ductile transition under experimental T/P conditions from 200 to 300℃, and 200 to 300Mpa. Brittle deformation microstruc-tures include macroscopic fracture zones and penetrative fracture associations. Elongation, undulose or irregular extinction, deformation lamellae and dynamic recrystallization of grains are the main ductile deformation microstructures. The variation of deformation mechanisms of the experimentally deformed coal samples is related to both the components of coals and T/P conditions. At low T/P, fractures occur in both inertinite and vitrinite of the samples. At higher T/P, crystalline plastic deformations are observed in the inertinite only.     

Compression behavior of Sm）2Ti2O7-pyrochlore up to 50 GPa：single-crystal X-ray diffraction and density functional theory calculations

Single-crystal X-ray diffraction at pressures up to 50 GPa has been employed to study the compression behavior of Sm2Ti2O7-pyrochlore. In contrast to earlier reports, we observed no pressure-induced amorphization or pressure-induced anion disorder up to 50 GPa. The experimental study has been complemented by density functional theory-based calculations. A combination of the theoretical and experimental data yields a bulk modulus of 185 GPa, significantly higher than a value which had been reported earlier. In comparison to earlier work, the current study provides more reliable data due to the use of neon as a pressure medium, which provides a more hydrostatic pressure than the aluminum, which had been employed as a pressure medium in the earlier studies. An analysis of the compressibility of Al2B2O7 pyrochlores shows an approximately linear dependence of the bulk modulus on the unit cell volume.     

P2O5对氟镓铟基玻璃析晶稳定性和结构的影响

以20GaF3-15InF3-20CdF2-15ZnF2-10SnF2-20PbF2(GICZSP)为基玻璃,用P2O5替代等摩尔含量CdF2,以改善玻璃的抗析晶能力.利用差示扫描量热分析、拉曼光谱和X射线衍射分析手段,表征不同含量P2O5对玻璃抗析晶性能及结构的影响.结果表明,P2O5的引入提高了玻璃的析晶稳定性.P2O5在玻璃中以不含P＝O双键的[PO(4-)4,Q0]四面体存在.随着P2O5量的增加,新出现了M[O,F]6八面体结构.     

Studies of mineral properties at mantle condition using Deformation multi-anvil apparatus

This paper reports recent studies of the rheological and viscoelastic properties of minerals at mantle pressure and temperature using Deformation multi-anvil apparatus (D-DIA). Stress-strain-time relations were measured using synchrotron X-ray radiation to determine these properties. Rheological properties of San Carlos olivine were measured at pressure up to 10 GPa and indicated that the effect of pressure on the viscosity of olivine is much smaller than previous reported. The unique capability of synchrotron X-ray can resolve the stress heterogeneity within a polycrystalline material as well as within a multi-phase mixture and elucidate the stress-strain distribution in an aggregate. Anelasticity measurements were carried out using olivine as the sample at mantle pressure and temperatures. The results showed that grain boundary activity rather than pressure dominate the relaxation processes. The aim of this paper is to illustrate the methods using new tools for high pressure research.     

Structure properties for the superconductor MgCNi3 under high pressure with synchrotron radiation

The recent discovery of superconductivity at 39 K in the superconductor MgB2[1] shows that intermetallic compounds with simple structure types are worth serious reconsideration as sources of new superconducting mate-rials. Subsequent to this discovery, He et al. observed a new intermetallic superconductor MgCNi3[2] at about 8 K. The perovskite crystal structure for MgCNi3 is shown in Fig. 1, with the atomic positions: Mg: 1a (0,0,0), C: 1b (0.5,0.5,0.5) and Ni: 3c (0,0.5,0.5). This mater…     

Structural stability of infinite-layer CaCuCO<Subscript>2</Subscript> under high pressure

Since the discovery of high temperature supercon-ductivity by Bednorz et al. in 1986[1], many series of cu- prate superconductors have been synthesized. Critical temperature has been improved continuously. But no verdict has been given upon what mechanism causes su- perconductivity. CaCuO2 conductive layers are the parent structure of the high Tc cuprate superconductors, such as Cu-12 (n-1)n[2], Tl-12(n-1)n[3] and Hg-12(n-1)n[4,5] super- conductor families. In 1988, infinite-layer (Ca0.86S…     

浮区法制备金红石单晶及其光谱特性

采用锐钛矿型二氧化钛为原料, 通过浮区法制备金红石型二氧化钛单晶. 通过X射线衍射（XRD）和拉曼散射（Raman）测试, 对单晶体的结构进行表征, 表明晶体为典型的金红石相. 在Raman光谱中可观测B_1g(143 cm^-1),E_g(446 cm^-1),A_1g(605 cm^-1)和B_2g(826 cm^-1)4个Raman活性模, 并观测到可能属于2级Raman散射峰, 如273,316,327,519,700 cm^-1.     

The effect of phase transition on the compressional wave velocity for a trachybasalt at high temperature and high pressure

Compressional wave velocities in a trachybasalt, from Yichuan County, Henan Province, have been measured at 2.0 GPa and up to 1 350℃ in a YJ-3000 t cubic-anvil high-pressure apparatus. The run products have been gained at the same pressure but different temperatures, the observation of the thin sections of the run products indicates that, corresponding to the variation of the compressional wave velocity in the trachybasalt, the phase transition has taken place. The relationship between the change of the compressional wave velocity and the hydrous mineral dehydration, solid-solid phase transformation and partial melting has been discussed. The experimental data presented here are of great importance to elucidating the geological process in the earth's interior.