硼酸锂系列晶体的高压拉曼散射研究

本文进行了硼酸锂系列晶体的高压拉曼散射及其压致相变的研究。对于三硼酸锂（ＬｉＢ３Ｏ５），我们发现在５．０ＧＰａ有一可逆的晶态到晶态的相变，在２７．０ＧＰａ有一不可逆的晶态到非晶态的相变。二硼酸锂（Ｌｉ２Ｂ４Ｏ７）不可逆压致非晶相变发生在３２．０ＧＰａ附近。对于一硼酸锂，我们研究了０—５５．８ＧＰａ范围内的高压拉曼光谱，只在２．０ＧＰａ发现了一个晶态到晶态的相变，但未发现不可逆压致非晶化现象。在硼酸锂系列晶体中，不可逆压致非晶化的压力随Ｌｉ２Ｏ的含量的增加而升高。硼酸锂晶体中Ｌｉ２Ｏ的含量越高，压致非晶化越不容易发生，这与熔体急冷法制备硼酸锂玻璃的规律是一致的。     

晶体压致非晶化的拉曼散射研究

本文主要介绍压致非晶化研究的进展，其中包括我们对β—ＢａＢ＿２Ｏ＿４，ＬｉＢ＿３Ｏ＿５，Ｐｂ＿５Ｇｅ＿３Ｏ＿１１和Ｌｉ＿２Ｇｅ＿７Ｏ＿（１５）的拉曼散射研究结果。综述了压致非晶的结构特征，压致非晶转变机制和重新晶化过程。     

高压下Eu^3^＋：Gd2O2S的发射光谱,能级及晶体场

在室温下，０－１５ＧＰａ压力范围内，测量了Ｅｕ＾３＾＋：Ｇｄ２Ｏ２Ｓ的发射光谱。通过对７Ｆ０－６多重态能级结构的拟合，研究了压力对能级和晶体场的影响。     

γ－Fe_2SiO_4在静水压下的压缩行为的测定

采用同步辐射高压原位Ｘ光衍射技术及金刚石对顶压砧高压装置，对γ－Ｆｅ＿２ＳｉＯ＿４进行了静水压条件下等温压缩行为的测定，最高压力达２３ＧＰａ。γ－Ｆｅ＿２ｓｉＯ＿４在０～２３ＧＰａ压力范围内的ｐ、Ｖ数据表明，其等温压缩可分为两个阶段：若设Ｋ＇＿０＝４，在０～１８Ｇｐａ，Ｋ＿０＝１８９±２ＧＰａ；而在１８～２３０Ｐａ，Ｋ＿０＝２１３±２ＧＰａ。我们认为，样品在１８ＧＰａ以下处于较好的静水压状态，压力超过１８ＧＰａ，传压介质的静水压性质变坏，所以Ｋ＿０值偏高。在整个实验过程中并未发现样品有任何发生相变的迹象。最后，对一些虽然使用了液体介质但得不到静水压条件的实验现象进行了讨论。     

Gd＿（1－x）Ca＿xBa＿2Cu＿3O＿（7－y）高温超导体压力效应的研究

研究了Ｇｄ＿（１－ｘ）Ｃａ＿ｘＢａ＿２Ｃｕ＿３Ｏ＿（７－ｙ）（０．０≤Ｘ≤０．２０）高温超导体在常压和高压下的超导电性在１－３００Ｋ温度范围内，利用Ｂｒｉｄｇｍａｎ对顶砧获得压力达９．０ＧＰａ，测量了（Ｘ＝０．１０，０．１５，０．２０）样品的ｄＴ＿ｃ／ｄｐ分别为７．６８，７．８和４．４６Ｋ／ＧＰａ。发现Ｔ＿ｃ的压力导数随着ｃａ￣（２＋）含量的增加而下降，分析了氧含量对Ｔ＿ｃ和ｄＴ＿ｃ／ｄＰ的影响．利用常压下晶格参数精修值和阳离子与氧离子间距随压力的改变，说明ＣｕＯ＿２面在超导电性上的作用，用ＣｕＯ＿２面之间耦合解释Ｔ＿ｃ（Ｐ）曲线的非线性关系。     

成型压力对La0.7Sr0.3MnO3纳米固体内部缺陷结构影响的研究

应用溶胶凝胶法合成了平均尺寸为４０ｎｍ的Ｌａ０．７Ｓｒ０．３ＭｎＯ３纳米粉末，在０．２ＧＰａ到４．５ＧＰａ的压力范围内加压成型，制成＝６ｍｍ，厚为１ｍｍ的纳米固体样品。测量了不同成型压力下样品的正电子寿命谱，研究了纳米固体内部存在的三类空位缺陷随压力的变化规律。在低于１．０ＧＰａ的情况下，三类缺陷随压力的增加变化敏感，成型压力高于１．０ＧＰａ时，纳米固体内部的压致碎化导致十几个单空位尺寸大小的微孔洞缺陷数量的剧增，使纳米固体内部的缺陷密度增加，呈现反常的压力依赖关系。     

La1.65Sr0.35CaCu2O4+δCly在高压下的电学性质与相变

利用金刚石压砧中的电阻测量技术和Ｘ射线衍射分析了在室温下和２２ＧＰａ压力范围内氯氧化合物超导材料Ｌａ１．６５Ｓｒ０．３５ＣａＣｕ２Ｏ４＋δＣｌｕ的相变行为。观测到了包括由晶相向非晶相转变在内的一些不可逆的相变。     

静高压下非晶（Fe0.09,Mo0.01）74Si9B13合金晶化过程的热力学研究

在６００－９３０Ｋ，常压到７ＧＰａ的范围内，对非晶（Ｆｅ０．９９，Ｍｏ０．０１）７８Ｓｉ９Ｂ１３合金等温等压退火３０ｍｉｎ。实验表明；其晶化产物α－Ｆｅ（Ｍｏ，Ｓｉ）Ｆｅ３Ｂ和Ｆｅ２Ｂ相的析出与所加压力密切相关。压力使非晶（Ｆｅ０．９９Ｍｏ０．０１）７８Ｓｉ９Ｂ１３合金的晶化温度和亚稳Ｆｅ３Ｂ相的析出温度下降，在一定的压力和温度下，亚稳Ｆｅ３Ｂ相半向稳定Ｆｅ２Ｂ相转变其转变温度随压力而变化。     

Hg1-xCdxTe在高压下的电学性质、状态方程与相变

在金刚石压砧装置上,采用电阻和电容测量方法研究了Ｈｇ１－ｘＣｄｘＴｅ（ｘ＝０．１９,０．２２）在室温下、２０ＧＰａ内的电阻、电容与压力的关系。实验结果表明：它们分别在０．７～１．８ＧＰａ与８．６ＧＰａ左右以及在１．６ＧＰａ左右与８．３ＧＰａ左右发生了两次电子结构相变;分别在２ＧＰａ左右与８．６ＧＰａ以上以及在１．６ＧＰａ左右与８．３ＧＰａ以上发生了两次晶体结构相变。同时,还在活塞－圆筒式ｐ－Ｖ关系     

InvFevLiNbO_3晶体的全息存储性能研究

在 Ｌｉ Ｎｂ Ｏ３ 中掺进 Ｉｎ２ Ｏ３ 和 Ｆｅ２ Ｏ３ 用恰克拉斯基（ Ｃｚｏｃｈｒａｌｓｋｉ）法生长 Ｉｎｖ Ｆｅｖ Ｌｉ Ｎｂ Ｏ３ 晶体。测试表明， Ｉｎｖ Ｆｅｖ Ｌｉ Ｎｂ Ｏ３ 晶体抗光致散射能力高， 响应速度快， 存储保存时间长。研究了 Ｉｎｖ Ｆｅｖ Ｌｉ Ｎｂ Ｏ３ 晶体全息存储性能的机理， 测得的衍射效率最大值为 ７３％ 。     

相变及空位缺陷对高压下GeO_2光学性质的影响

本文采用第一性原理方法,在100 GPa的压力范围内,计算了GeO_2理想晶体和含锗、氧空位点缺陷晶体的光学性质.吸收谱数据表明,压力诱导的三个结构相变对GeO_2晶体的吸收谱均有影响:第一个相变将导致其吸收边蓝移,而第二和第三相变将使得其吸收边红移.锗和氧空位点缺陷的存在将导致GeO_2的吸收边红移,但氧空位点缺陷引起的红移更明显.尽管如此,分析发现,在100 GPa的压力范围内,压力、相变以及空位点缺陷等因素都不会导致GeO_2晶体在可见光区出现光吸收现象(是透明的).波长在532 nm处的折射率数据显示,在GeO_2的四个相区,其折射率均随压力增加而降低;而且,GeO_2的三个结构相变以及锗、氧空位点缺陷都会导致其折射率有所增大.本文预测,GeO_2有成为冲击光学窗口材料的可能.     

Pressure-induced increase in the ionic conductivity of Li, Na, and K zeolites of type A

The effect of pressure on the ionic conductivity of hydrated A-zeolites containing Li, Na, and K cations was investigated. Room-temperature experiments at pressures to 4.8 GPa show an increase in the conductivity, which attains its maximum value in the range of 1.7–1.8 GPa for the three zeolites. Further compression leads to a drastic decrease in the conductivity at 2.5–3.5 GPa. The decrease in the conductivity is associated with the pressure-induced transition to the amorphous state, as follows from previously reported IR spectroscopy data. It is believed that the increase in the conductivity with pressure and the subsequent transition to the amorphous state follow one or several of the following mechanisms: (1) cation conductivity involving hydroxyls, (2) hydroxyl-proton conductivity, and (3) enhanced cation mobility due to pressure-induced change in the degree of hydration. With decreasing pressure, the conductivity does not follow the compression curve. For pressure-cycled samples, the low-pressure conductivity during decompression is two orders of magnitude higher than its value at the same pressure during compression. Compression provides a new way for conductivity optimization in hydrated A-zeolites.     

Pressure-induced amorphization of Gd2(MoO4)3: A high pressure Raman investigation

High pressure Raman spectroscopic studies on Gd₂(MoO₄)₃(GMO) have been carried out at ambient temperature in the diamond cell to 10 GPa hydrostatic pressure. These experiments have revealed pressure-induced phase transitions in GMO near 2 GPa and 6.0 GPa. The first transition is from Pba2(β′) phase to another undetermined crystalline phase, designated as phase II, and the second transition is to an amorphized state. On releasing pressure there is a partial reversion to the crystalline state. The Raman data indicate that the amorphization is due to disordering of the MoO₄ tetrahedral units. Further, it is inferred from the nature of the Raman bands in the amorphized material that the Mo-O bond lengths and bond angles have a range of values, instead of a few set values. The results of the present study as well as previous high pressure-high temperature quenching experiments strongly support that pressure-induced amorphization in GMO is a consequence of the kinetically impededβ toα phase transition. The system in frustration becomes disordered. The rare earth trimolybdates crystallizing in theβ′ structure are all expected to undergo similar pressure-induced amorphization.     

Sr2Bi4Ti5O18的压致结构相变

 使用4∶1的甲醇-乙醇混合液作传压介质，利用金刚石对顶砧装置（DAC），研究了层状铁电体Sr₂Bi₄Ti₅O₁₈的在位高压拉曼光谱和压致结构相变（0～27 GPa）。发现在8.31 GPa，Sr₂Bi₄Ti₅O₁₈经历了一次结构相交。在23.13 GPa以上，Sr₂Bi₄Ti₅O₁₈似乎出现了压致非晶相交的先兆。并使用内模方法对Sr₂Bi₄Ti₅O₁₈的内模进行了指认。     

Structure of B2O3 Glass at High Pressure: A 11B Solid-State NMR Study

We report spectroscopic evidence for the pressure-induced structural changes in B2O3 glass quenched from melts at pressures up to 6 GPa using solid-state NMR. While all borons are tri-coordinated at 1 atm, the fraction of tetra-coordinated boron increases with pressure, being about 5% and 27% in the B2O3 glass quenched from melts at 2 and 6 GPa, respectively. The fraction of boroxol ring species increases with pressure up to 2 GPa and apparently decreases with further compression up to 6 GPa. Two densification mechanisms are proposed to explain the variation of boron species with pressure.     

若干钠锗酸盐晶体和熔体的温致结构变化及其锗配位数的拉曼光谱研究

本文测定了Na4GeO4、Na2GeO3、Na2Ge4O9和Na4Ge9O20等晶体从273K到1413K升温及熔体的拉曼光谱,结合分析金红石型GeO2的相关结构和光谱,研究了其微结构单元在升温过程中的变化、熔体中的形态和锗的氧配位数及其温致变化。Na4GeO4和Na2GeO3晶体结构单元为GeO4四面体,在升温过程及其熔体中锗维持四配位。Na2Ge4O9和Na4Ge9O20晶体结构单元为GeO4四面体和GeO6八面体共存,升温过程中,GeO6八面体将发生结构转变,在熔融状态全部转变为GeO4四面体,并产生与钠离子等摩尔分数的非桥氧,在熔体中锗的氧配位数为4。研究还表明,桥氧的对称弯曲振动模可以反映不同微结构单元间的连接,并且随着温致结构的变化而产生特征性的变化。     

Equation of state and pressure induced amorphization of beta-boron from X-ray measurements up to 100 GPa

The equation of state of boron has been measured up to 100 GPa by single-crystal x-ray diffraction with helium as the pressure transmitting medium. Rhombohedral beta-boron is the stable structure up to 100 GPa under hydrostatic conditions. Nonhydrostatic stress stabilizes a different rhombohedral structure. At about 100 GPa a pressure-induced amorphization is observed. The amorphous phase can be quenched to ambient pressure. An explanation is proposed based on the different stability under pressure between intraicosahedra and intericosahedra bonds.     

Synchrotron X-ray diffraction of SiO2 to multimegabar pressures

Abstract

α-Quartz was compressed at room temperature in a diamond-anvil cell without a medium to maximum pressures of 31 to 213 GPa and was studied by energy-dispersive synchrotron X-ray diffraction. Broad peaks observed in a previous high-pressure diffraction study of silica glass are evident in the present study of quartz compression, providing in situ confirmation of pressure-induced amorphization above 21 GPa. The 21-GPa crystalline-crystalline (quartz 1–11) transformation previously observed on quasihydrostatic compression of quartz is found to also occur under the current nonhydrostatic conditions, at the identical pressure. With nonhydrostatic compression, however, new sharp diffraction lines are observed at this pressure. The measurements show the coexistence of at least one amorphous and two crystalline phases above 21 GPa and below 43 GPa. The two crystalline phases are identified as quartz II and a new, high-pressure silica phase. The high-pressure phases, both crystalline and amorphous, can be quenched to ambient conditions from a maximum pressure of 43 GPa. With compression above 43 GPa, the diffraction pattern from quartz II is lost and the second crystalline phase persists to above 200 GPa.     

High pressure phase transitions and depressurization amorphization of Bi2Fe4O9

High pressure structural behavior of Bi₂Fe₄O₉ has been studied by in situ angular-dispersive X-ray diffraction (ADXD) measurements up to 51.3 GPa. Two phase transitions have been observed at 7.6 and 22.6 GPa, respectively. A second high pressure structure (HP2) involving the tripling of lattice parameter c has been identified. An unusual amorphization occurs after releasing pressure. The high pressure phase transitions can be understood in terms of the increase in the coordination number of Fe³⁺ ion. The depressurization amorphization results from the appearance of the metastable HP2 and its collapse after releasing pressure. The results extend our understanding of pressure-induced amorphization.