Neutron Diffraction of Large-Volume Samples at High Pressure Using Compact Opposed-Anvil Cells

Neutron diffraction techniques of large-volume samples at high pressure using compact opposed-anvil cells are developed at a reactor neutron source, China's Mianyang research reactor. We achieve a high-pressure condition of in situ neutron diffraction by means of a newly designed large-volume opposed-anvil cell. This pressure calibration is based on resistance measurements of bismuth and the neutron diffraction of iron. Pressure calibration experiments are performed at room temperature for a new cell using the tungsten carbide anvils with a tapered angle of 30°, Φ4.5 mm culet diameter and the metal-nonmetal composite gasket with a thickness of 2 mm. Transitions in Bi(Ⅰ–Ⅱ 2.55 GPa, Ⅱ–V 7.7 GPa) are observed at 100 and 300 kN, respectively, by resistance measurements.The pressure measurement results of neutron diffraction are consistent with resistance measurements of bismuth.As a result, pressures up to about 7.7 GPa can routinely and stably be achieved using this apparatus, with the sample volume of 9 mm~3.     

基于铰链式六面顶压机的二级6-8模超高压大腔体内置加热元件的设计与温度标定

 首次报道了一种新型的基于铰链式六面顶压机的二级6-8模大腔体静高压装置的内置加热元件的设计与温度标定。此加热组装结构简单,升温快,保温效果好,并有效地解决了国外基于两面顶压机构架下的二级6-8模内加热组装中热电偶在施加压力时易断的问题。以低成本的碳管为加热元件,采用直接和间接两种加热方式,用双铂铑（Pt6%Rh-Pt30%Rt）B型热电偶进行温度测量,并根据实验过程中加热功率与腔内实际温度的关系,对不同压力下腔体内的温度进行了标定。实验结果表明：此加热系统的油压达到40 MPa（腔体压力约10 GPa）时,温度可以达到1 700 ℃以上;在油压为30 MPa、样品室温度为1 000 ℃时,保温时间可达2 h,甚至更长;实验中获得样品的直径可达3 mm,高度可达7 mm,实现了在高温超高压条件下大样品的制备,满足了实验对产生高温超高压条件的需要。     

Neutron powder diffraction and high-pressure synchrotron x-ray diffraction study of tantalum nitrides

Tantalum nitride(TaN) compact with a Vickers hardness of 26 GPa is prepared by a high-pressure and hightemperature(HPHT) method. The crystal structure and atom occupations of WC-type TaN have been investigated by neutron powder diffraction, and the compressibility of WC-type TaN has been investigated by using in-situ high-pressure synchrotron x-ray diffraction. The third-order Birch–Murnaghan equation of state fitted to the x-ray diffraction pressure–volume(P–V) sets of data, collected up to 41 GPa, yields ambient pressure isothermal bulk moduli of B'_0= 369(2) GPa with pressure derivatives of B 0= 4 for the WC-type TaN. The bulk modulus of WC-type TaN is not in good agreement with the previous result(B_0= 351 GPa), which is close to the recent theoretical calculation result(B_0= 378 GPa). An analysis of the experiment results shows that crystal structure of WC-type TaN can be viewed as alternate stacking of Ta and N layers along the c direction, and the covalent Ta–N bonds between Ta and N layers along the c axis in the crystal structure play an important role in the incompressibility and hardness of WC-type TaN.     

A pressure calibration method for a portable wide-access ＂panoramic＂ cell

A simple and convenient pressure calibration method is developed for a newly designed portable wide-access ＇panoramic＇ cell. This cell is adapted to angle-dispersive-mode high-pressure in situ neutron diffraction of reactor neutron sources. This pressure calibration method has established a relationship between the cell pressure and the anvil displace- ment （gasket compression） based on the fixed-point calibration technique. By employing TiZr gasket with a thickness of 3 mm and WC anvil with a culet of 4 mm diameter, the average anvil displacements are 1.31 mm and 2.22 mm for Bi phase transitions （2.55 GPa and 7.7 GPa）, and 1.85 mm for Ba phase transitions （5.5 GPa）, respectively. In this pressure range, the pressure increases quickly with decreasing gasket thickness, and undergoes a linear increase with the anvil displacement. By extrapolating the calibration curve, the cell pressure will achieve 10 GPa when the anvil displacement is around 2.5 ram.     

In-situ ultrasonic calibrations of pressure and temperature in a hinge-type double-stage cubic large volume press

Here, simultaneous in-situ calibration of pressures and temperatures was performed in a hinge-type second-stage cubic large volume press (LVP) up to 15 GPa and 1400 K by an acoustic travel-time approach. Based on the recently reported P-t_S and P-T-t_P-t_S equations for Al₂O₃ buffer rod, the cell pressures and temperatures in the chamber of LVP were in-situ determined, in comparison with those by conventional off-line (or fixed-points) pressure calibration method and direct thermocouple measurement, respectively. It is found that the cell pressures of the LVP chamber are significantly reduced after annealing at simultaneous high pressures and high temperatures, owing to the stress relaxation as accumulate in the LVP chamber. This acoustic travel-time method is verified to be a good way for precise determination of thermal (cell) pressures at high temperature conditions, and is of great importance and necessity to conduct in-situ physical property measurements under extreme high P-T conditions, especially when the precious synchrotron x-ray/neutron diffraction beams are not available.     

基于巴黎-爱丁堡压机的高压中子衍射技术

巴黎-爱丁堡压机(Paris-Edinburgh press)可配合中子衍射对物质在高压下的结构变化进行研究.自20世纪90年代开始,已在材料学、地学、化学等众多领域得到了广泛应用.本研究利用巴黎-爱丁堡压机在中国绵阳研究堆(CMRR)的高压中子衍射谱仪(凤凰)上成功开展了高压中子衍射实验.实验由一台载荷为200 MPa的单缸柱塞泵为巴黎-爱丁堡压机提供加载压力,并发展了一套与谱仪集成的自动定位系统对样品进行定位.利用铁作为样品,分别使用单凹曲面和双凹曲面两种碳化钨(WC)压砧,成功获得了约10 GPa压力范围内的高压原位中子衍射谱.实验结果显示,双凹曲面组装可以稳定地承受100 MPa的负载压力,而单凹曲面封垫在80 MPa左右的负载压力下就开始不稳定而发生放炮.研究结果表明,双凹曲面压砧的凹槽增强了封垫的侧向支撑能力,使双凹曲面组装比单凹曲面组装具有更好的稳定性.研究结果对进一步优化巴黎-爱丁堡压机的压砧及封垫具有重要的指导意义.     

基于铰链式六面顶压机的二级6-8型大腔体静高压装置

报道了一种新型二级6-8型大腔体静高压装置.该装置是以国产DS6×800T铰链式六面顶压机为构架,在其六面体压腔中直接放入二级6-8模(球分割)增压装置以产生10GPa以上的压力,还实验了不同规格的预密封边和不同密度的叶蜡石对压力产生效率的影响,在室温下用BiⅠ-Ⅱ(2.55GPa),Ⅲ-Ⅴ(7.7GPa)和SnⅠ-Ⅱ(9.4GPa)在高压下的相变对14／8(8面体传压介质边长／8面体压腔边长)规格压腔进行了压力标定.实验结果表明,该系统可以在加载压力(油压)约为3×10⁶N(～42 关键词： 铰链式六面顶压机 6-8型球分割大腔体静高压装置 压力标定     

Manipulating metal-insulator transitions of VO2 films via embedding Ag nanonet arrays

Manipulating metal-insulator transitions in strongly correlated materials is of great importance in condensed matter physics, with implications for both fundamental science and technology. Vanadium dioxide (VO₂), as an ideal model system, is metallic at high temperatures and shown a typical metal-insulator structural phase transition at 341 K from rutile structure to monoclinic structure. This behavior has been absorbed tons of attention for years. However, how to control this phase transition is still challenging and little studied. Here we demonstrated that to control the Ag nanonet arrays (NAs) in monoclinic VO₂(M) could be effective to adjust this metal-insulator transition. With the increase of Ag NAs volume fraction by reducing the template spheres size, the transition temperature (T_c) decreased from 68° to 51°. The mechanism of T_c decrease was revealed as:the carrier density increases through the increase of Ag NAs volume fraction, and more free electrons injected into the VO₂ films induced greater absorption energy at the internal nanometal-semiconductor junction. These results supply a new strategy to control the metal-insulator transitions in VO₂, which must be instructive for the other strongly correlated materials and important for applications.     

固态离子晶体β-K0.294Ga1.969O3的高压与变温拉曼光谱研究

β-镓酸盐（β-gallate）型化合物是一种非常有应用前景的固态离子导体,在储能领域具有重要的应用价值。该类型化合物导电层中往往可以容纳过量的碱金属离子,使得该体系体现出复杂的晶格动力学行为,这也为进一步理解其导电机制带来了困难。压力与温度两个参量均可以通过改变原子间的间距而影响材料的结构,在研究材料的动力学过程,尤其在研究离子的扩散过程方面有很大的应用价值。迄今为止,对于温度依赖的β-镓酸盐型化合物的特性研究很少,且尚无β-镓酸盐型结构化合物的高压研究。由于激光拉曼散射技术在研究物质晶格动力学方面的独特优势,尤其压力与温度依赖的拉曼光谱可以提供重要的结构信息,是研究物质晶格动力学行为的有效实验手段。使用大腔体静高压技术成功合成了一种新型的β-镓酸盐型K_0.294Ga_1.969O₃(KGO)晶体,利用扫描电镜、能谱对晶体进行了表征,通过单晶X射线衍射对其晶体结构进行了解析,并与β-Ga₂O₃的晶体结构进行了对比分析。利用高压和变温拉曼光谱研究了KGO导电层中无序碱金属离子的晶格动力学行为。研究发现,由尖晶石层与疏松的离子导电层交替排列而成的β-镓酸盐型KGO晶体结构在压力23.3 GPa条件下仍可保持稳定;由于振动模式不同,高频拉曼模与低频拉曼模的压力系数存在着显著差异,并表现出显著的对压力诱导非谐性。在约300 ℃,KGO中K+发生热激活,表现在与碱金属K+运动相关的低频拉曼模的强度迅速增加,而与Ga-O多面体相关的高频振动模强度增加缓慢,与此同时,K+在沿着导电平面的方向上发生了无序扩散过程。研究结果将有助于深入地理解β-镓酸盐型结构化合物的导电机制,而且对于实现β-镓酸盐型化合物精确的计算控制和掺杂尤为重要。     

三元铁基金属氮化物的高压复分解反应合成北大核心CSCD

以二元金属氧化物(氧化铁、氧化钴、氧化镍)和六方氮化硼为反应前驱体,在大腔体压机提供的高温高压条件下(5GPa、1 673K),通过发生复合高压固相复分解(HPSSM)反应合成组分可调控的三元铁基金属氮化物圆球状块体材料ε-Fe_(3-x)M_xN_(1+δ)(M=Co,Ni)。并利用X射线粉末衍射(XPD)、场发射扫描电子显微镜(FE-SEM)、高分辨率透射电子显微镜(HRTEM)等多种材料表征手段对高压合成的三元铁基金属氮化物进行结构表征,同时基于密度泛函理论(DFT)的第一性原理计算探究压力对HPSSM反应的影响。研究结果表明,高压密闭环境有利于制备高质量金属氮化物,HPSSM反应合成法是制备铁基金属氮化物块体材料的一种有效方法。