立方聚合氮(cg-N)的高压低温拉曼光谱研究

聚合氮是一种理想的高能密度材料。本工作在室温下将分子氮加压至136 GPa,利用激光加热至2000 K成功合成以共价N-N单键结合的三维网状立方聚合氮cg-N。采用自主设计的高压低温装置,在173 K到300 K的温度范围内测量了cg-N样品的变温拉曼光谱,观察到不同压力下cg-N的A模声子对温度具有不同的响应。基于多声子耦合模型,研究A模频率的蓝移现象和A模声子对温度的响应特性。结果表明低温条件下cg-N拉曼散射效应中三声子耦合过程占主导,133 GPa时的三声子耦合过程对声子模拉曼频移的影响要小于140 GPa,而四声子耦合过程对声子模拉曼频移的影响要大于140 GPa。     

快速加压引起的硒熔体结晶行为

开展了在513,523,533 K温度下硒熔体的快速压致凝固实验,分析了不同保温时间即0,30,60 min对凝固晶体尺寸及形貌的影响.发现随着保温时间的延长,晶粒不断发生聚集生长,晶粒尺寸变大.通过与相同温度、压力条件下非晶硒、超细晶体硒粉等温结晶的样品对比,否定了快压凝固结构为非晶硒、非晶硒晶化为晶体硒的可能性,认为硒熔体快压凝固的结构为晶体硒,在保温过程中晶体颗粒在晶界处可以发生聚集生长.分析发现熔体快速压致凝固法不能得到非晶硒的原因在于实验条件下非晶硒为不稳定相,非晶硒的晶化温度随压力关系在2 GPa前后表现出不同的变化趋势,推测压力对过冷液态硒的微观结构有影响.     

放电等离子烧结制备纳米Ni块体材料

 采用自悬浮定向流法制备纳米Ni粉体,利用放电等离子烧结技术制备出了直径10 mm、厚2 mm,致密度为96.8 %,显微硬度为4.17 GPa的纳米块体材料。用X射线衍射仪、扫描电子显微镜和显微硬度计分析了烧结块体样品的相组成、晶粒尺寸、微观形貌和显微硬度。研究表明：随烧结温度的升高,块体样品的致密度和晶粒尺寸增大,当烧结温度为650 ℃时,致密度最高,晶粒尺寸为44.8 nm;显微硬度随烧结温度的增高先增大后减小,当烧结温度为550 ℃时,显微硬度最大为4.33 GPa;较高烧结温度下,断口微观形貌的纳米级韧窝出现,显示了韧性断裂的特征。     

压致硼酸盐晶态物质的非晶化现象研究

 本文用X射线衍射、Eu²⁺的发射谱与激发谱、拉曼谱以及扫描电镜（SEM）颗粒形貌，研究了常压下合成的具有正交结构的SrB₂O₄:Eu²⁺晶体在3.0~7.0 GPa压力下的晶态非晶化现象。分析结果表明，压力导致晶粒细化和晶态非晶化。晶粒尺寸由常压下的微米量级细化为几十个纳米量级，随压力的变化为：2 μm（0.1 MPa），49.4 nm（3.0 GPa），29.7 nm（5.0 GPa），25.1 nm（7.0 GPa）。晶态与非晶态体积比随压力增加而减小，分别为：70/30（3.0 GPa），63/37（5.0 GPa），57/43（7.0 GPa）。在压力下Eu²⁺是处在晶态与非晶态两种不同的低对称的环境中。纳米级晶粒是以亚晶粒形式存在于微米级大晶粒中的，压致非晶态可能组成了纳米亚晶粒的界面区。     

压力诱导的层状结构二碲化钛电输运性质、结构演变和振动性质的变化（英文）

系统地研究了层状二碲化钛在压力(至43.4GPa)作用下的电输运、晶格振动和结构性质。室温下样品的电阻率在6、13和22GPa附近表现出一系列的异常。为更好地研究二碲化钛的电子结构,测试了样品的低温电阻,在约6GPa处观察到超导转变。综合拉曼光谱和X射线衍射(XRD)实验结果发现:二碲化钛在6GPa附近可能发生拓扑相变;继续加压至约13GPa,样品发生从三角晶系到单斜晶系的结构相变,相变到22GPa附近完全结束。XRD数据与电输运结果相互印证,揭示了样品在压力诱导下的结构演变和电子结构变化。因此,二碲化钛为人们了解过渡金属二硫化物提供了一个全新的视角。     

微区Raman光谱在TiO_2高压结构相变研究中的应用

本文以金红石单晶TiO2和锐钛矿多晶TiO2为研究对象,应用金刚石小压机和原位拉曼光谱测量技术,系统研究了室温高压下TiO2的结构相变。原位拉曼测量表明,金红石单晶TiO2在压力达到12.91GPa时开始发生由金红石结构向斜锆石结构(MI)的相变,当压力达到14.16 GPa时,相变完成;继续加压到21.65 GPa,没有发现进一步的相变;卸压时由斜锆石结构转变为PbO2结构,相变发生在大约7.11 GPa处。锐钛矿多晶TiO2在压力达到4.26 GPa时开始向PbO2结构转变,当压力达到8.34 GPa时相变完成;继续加压到12.94 GPa,样品开始发生由PbO2结构向斜锆石结构的相变,当压力达到18.74 GPa时相变完成;继续加压到21.39 GPa,没有发现进一步的相变;卸压时也由斜锆石结构转变为PbO2结构,起始相变压力点应高于8 GPa。     

顽火辉石的高温高压同步辐射研究

 采用同步辐射能量色散X射线衍射技术、激光加热技术和金刚石对顶砧（DAC）高压装置，在温度为2 000 K和压力为23 GPa的范围内，对采自地幔二辉橄榄岩中的顽火斜方辉石，进行了原位的高温高压能量色散X射线衍射（EDXRD）测量。实验结果表明：当压力为15.3 GPa、温度为1 600 K时（相当于地球内部410 km处的地震波不连续界面的温压环境），顽火斜方辉石转变为橄榄石的β相——瓦兹利石（Wadsleyite）相；继续加温加压至2 000 K、23 GPa时（相当于地球内部670 km处的地震波不连续界面的温压环境），顽火斜方辉石相变为钛铁矿（Ilmenite）结构和钙钛矿（Perovskite）结构的混和相。实验结果进一步证明，在地幔中存在的两个地震波不连续界面是由橄榄石、顽火斜方辉石等矿物的相变引起的。     

电场条件下氧化锌结晶特性及极化产物的拉曼光谱分析

开展高压电场调控纳米材料结构形貌和性能研究在功能材料领域具有重要的理论和实际意义.本文在高压电场条件下合成了氧化锌纳米粉体,并对粉末试片进行了后期电场极化处理,研究了电场对氧化锌的结构形貌、点缺陷、拉曼光谱的影响.以X射线衍射仪(XRD)、扫描电镜(SEM)和拉曼光谱仪对产物的结构形貌、拉曼位移、缺陷分布等进行了表征.结果表明,高压电场条件下氧化锌的完全晶化时间和温度比未施加电场时明显延长和升高,直流电场能够显著促进前驱物中氧化锌的形核,并降低晶化速度.不同电场强度下氧化锌具有不同的显微形貌.纳米氧化锌粉末试片在直流电场中极化后,其阴极面和阳极面的拉曼光谱表现出明显的差异.有明显漏电电流的情况下,阳极面在1050 cm~(–1)处的二级光学声子模A_1(LO)的强度显著提高,且拉曼强度I_1=438 cm~(–1)和I_2=1050 cm~(–1)的比值与极化电场的场强呈线性关系.当调转试片正反面进行二次极化时,原来在阳极面尖锐的1050 cm~(–1)峰经过阴极极化而消失.阳极面1050 cm~(–1)拉曼峰的锐化与氧化锌晶粒内的缺陷重新分布和双肖脱基势垒有关.     

金刚烷的高压拉曼光谱研究

对金刚烷(C_(10)H_(16))进行了常温原位高压拉曼光谱研究,最高压力为25 GPa。通过分析高压拉曼光谱,结合拉曼频移随压力的变化情况,得出在实验压力范围内C_(10)H_(16)发生了多次相变。0.6 GPa时,C_(10)H_(16)由常温常压下的无序相(α相)转变为有序相(β相);继续加压至1.7 GPa时,第2次结构相变开始,直至3.2 GPa,第2次相变完全结束;第3次相变开始于6.3 GPa,结束于7.7 GPa;22.9 GPa时发生了第4次结构相变。另外,首次在拉曼光谱上探测到第3次相变过程中晶格振动峰的变化,说明第3次相变并非前人报道的等结构相变。     

金刚石压腔结合拉曼光谱技术进行Pb掺杂对二氧化锡高压结构性能的影响研究

因稳定的分子结构和物理化学性质,近年来SnO2在光、电、磁等方面应用日益广泛。为拓宽SnO2应用范围,对高压条件下纯SnO2和Pb掺杂SnO2结构的相变行为和拉曼光谱活性振动模的变化进行了探究。实验采用水热法制备了纯SnO2和Pb掺杂量为10%的SnO2样品。扫描电子显微镜(SEM)图表明,上述制备样品由多个纳米棒从中心发散排列而成,整体成类花状。X射线衍射图谱表明,样品在常温常压下晶体结构为四方金红石型SnO2(空间群P 42)。采用Mao-Bell型金刚石压腔结合原位拉曼光谱探究了金红石型SnO2和Pb掺杂SnO2两种材料的高压相变过程。研究结果显示,两种材料加压至26 GPa过程中,纯SnO2和Pb掺杂的SnO2的活性拉曼振动模(B 1g,E g,A2g,B2g)均向高频移动。在14 GPa时,纯SnO2的E g峰分裂,563 cm-1处出现新峰,表明SnO2从常压四方金红石型结构向CaCl2型结构相变。Pb掺杂SnO2在常压拉曼谱图中出现了577 cm-1的拉曼峰。当加压至13 GPa时,B1g振动模向A g模转变,材料发生一级相变。上述对比表明Pb掺杂的SnO2具有更低的一级相变压力点13 GPa,结果归因于SnO2晶胞中Pb离子代替Sn离子,原子之间间距变小,离子大小不同造成掺杂后价态差异表面缺陷,导致SnO2结构稳定性降低,进而降低了相变压力。此外Pb掺杂SnO2在压力12 GPa时,晶体的对称性降低,577cm-1和639cm-1处特征峰宽化开始合并成包状峰,表明有部分晶体表面原子无序性程度增加,出现晶体向非晶的转变过程。继续加压至26 GPa,两种材料特征峰渐渐消失,并未观测到其他特征峰的出现。非静水压对相变压力也存在一定程度影响。非静水压条件下部分晶体更易趋向于非晶,晶界处存在较大的应力使纳米晶体在晶界处极易形成高压相成核点,导致相变发生,进而降低相变压力。本文研究不同条件下SnO2的相变行为,丰富了极端条件下SnO2的物理化学性质的多样性研究。     

聚苯硫醚熔体的压致凝固行为

采用施加压力的方法将聚苯硫醚熔体凝固,凝固后获得的聚苯硫醚样品经过降温和卸压后在常温常压下回收. X射线衍射和差示扫描量热分析表明:约20 ms时间的快速压缩过程可以抑制熔体结晶,制备出非晶态聚苯硫醚块材,样品的表面及中心都是非晶态.非晶态聚苯硫醚的玻璃化转变温度和晶化温度分别为318和362 K.常压下的退火实验表明,非晶态聚苯硫醚在425 K等温结晶的产物为正交相晶型.压致凝固法中熔体的凝固不是靠温度变化,而是靠压力变化,样品表面和内部处在一致的温度下同时受压凝固,避免了热传导对非晶尺寸的影响,因此非常有利于获得结构均匀的大尺寸非晶态材料.     

Spectroscopic evidence of polymorphism in vitreous B2O3

Brillouin and Raman spectroscopy were performed on B2O3 glass compressed to 57 GPa at 273 K. Upon compression the sound velocities increase smoothly and the boroxol ring Raman mode vanishes by 11 GPa. Upon decompression the sound velocities follow a different path and at 3 GPa a discontinuity of 3 km/s in V(p) and 2 km/s in V(s) returns the velocities to the values seen on compression. After the transition, the boroxol ring Raman mode reappears. A second pressure cycle produces the same behavior, suggesting the 3 GPa transition occurs between vitreous polymorphs with different boron coordination.     

Ultraviolet Raman analysis of the formation of diamond from C60

The ultraviolet (257 nm) Raman spectrum of C₆₀ compressed to 30 GPa in a Mao–Bell diamond anvil cell with no pressure transmitting medium at ambient temperature indicates the formation of diamond after release of pressure. Previously, more extreme non-hydrostatic compression was reported to be required to form diamond from C₆₀. These results provide confirmation of the transformation of C₆₀ to diamond upon non-hydrostatic compression at room temperature and illustrate the utility of UV Raman spectroscopy for the analysis of carbon phases containing both sp² and sp³ bonding.     

用多次冲击压缩方法研究稠密氢氦等摩尔混合气体的物态方程

采用液氮冷却以及气体增压技术，制备了～30MPa及～90K初始状态的氢、氦等摩尔混合气体样品.以二级轻气炮作为加载工具，用不同灵敏度设置的两套多通道瞬态高温计系统获得完整、清晰的稠密氢、氦混合气体多次冲击压缩过程的光谱辐射强度信号.并建立起相应的实验数据处理和分析技术，获得了5—140GPa范围内氢、氦混合气体一至五次冲击雨贡纽物态方程，以及一次、二次和四次冲击温度实验数据.流体变分理论和离解模型用来分析和解释所获得的测量结果. 关键词： 氢、氦混合气体 多次冲击压缩 光谱辐射强度历史 物态方程     

Photothermal-chemical synthesis of P-S-H ternary hydride at high pressures

The recent discovery of room temperature superconductivity (283 K) in carbonaceous sulfur hydride (C-S-H) has attracted much interest in ternary hydrogen rich materials. In this report, ternary hydride P-S-H was synthesized through a photothermal-chemical reaction from elemental sulfur (S), phosphorus (P) and molecular hydrogen (H₂) at high pressures and room temperature. Raman spectroscopy under pressure shows that H₂S and PH₃ compounds are synthesized after laser heating at 0.9 GPa, and a ternary van der Waals compound P-S-H is synthesized with further compression to 4.6 GPa. The P-S-H compound is probably a mixed alloy of PH₃ and (H₂S)₂H₂ with a guest-host structure similar to the C-S-H system. The ternary hydride can persist up to 35.6 GPa at least and shows two phase transitions at approximately 23.6 GPa and 32.8 GPa, respectively.     

Raman study of thaumasite Ca3Si(OH)6(SO4)(CO3)⋅12H2O at high pressure

Thaumasite, Ca₃Si(OH)₆(SO₄)(CO₃)⋅12H₂O, is an extraordinary mineral that possibly plays a special role in the carbonate–sulfate–silicate balance of the Earth's crust. Thaumasite, an undesirable component in concrete, remains a material poorly studied at high pressures in various media except for He medium (M. Ardit et al., Mineral. Mag., 2014). In the present Raman study, thaumasite samples were compressed in alcohol–water and KBr media at high pressures up to ~7 GPa: several phase transformations were identified. In samples compressed in alcohol–water, the wavenumbers of intense Raman bands of S O and С О symmetric stretching vibrations at 991 and 1074 cm⁻¹ proved to exhibit similar dependences on pressure: during a first transition I → II at 4.4 GPa, the wavenumbers of both bands exhibited a downward jump; at a second transition II → III, which occurred at 4.9 GPa, each band split in a doublet; and then, at a third transition III → IV, which was observed at 5.4 GPa, each doublet band transformed in a singlet. In KBr medium, these and other Raman bands of thaumasite showed similar (to those in thaumasite at compression in alcohol–water) dependences on pressure, revealing several phase transitions with slightly shifted transition points, the first transition I → II, however, being not distinguished. Taking into account the similar behaviors in both media, the transitions are assumed to be polymorphic: no noticeable overhydration in thaumasite compressed in water–alcohol occurred. In phase IV, gradual widening and weakening of each band were observed; those changes can be attributed to amorphization of the material. Considerable hysteresis was observed at thaumasite decompression. Copyright © 2016 John Wiley & Sons, Ltd.     

Raman and infrared investigations at room temperature of the internal modes behaviour in solid nitromethane‐h3 and ‐d3 up to 45 GPa

Raman and infrared spectra of internal phonons in solid nitromethane‐h₃ and ‐d₃ were measured as a function of pressure in the range 0–40 GPa at room temperature. Experiments were performed in diamond anvil cells. The evolution of the splitting of the various modes in condition of nearly hydrostatic compression supports the maintenance of the P2₁2₁2₁ crystal structure until the material chemically transforms into an amorphous phase. The observed pressure‐induced shifts of vibrational wavenumbers are consistent with computations recently reported in the literature. Infrared and Raman spectroscopies deliver complementary information on the internal modes behaviour. The continuous evolution of the infrared band shapes suggests a weak molecular distortion during the compression process. The strong modifications that are observed in the Raman bands of the nitro group are attributed to polarization effects arising from a rearrangement of the molecules inside the unit cell in the pressure range 10–12 GPa, a consequence of a close intermolecular O…H approach. Copyright © 2007 John Wiley & Sons, Ltd.     

下地幔温压下(Mg,Fe)SiO3钙钛矿的相稳定性——对冲击回收样品的微观分析

 在60~110 GPa冲击压力（估算温度为2 300~4 800 K）范围内进行了5发原始样品为(Mg_0.92,Fe_0.08)SiO₃顽火辉石的冲击压缩回收实验，对回收样品进行的X射线衍射（XRD）和红外吸收光谱（IR）分析结果表明：（1）回收样品的主相均是单链状结构硅酸盐，而非钙钛矿结构；（2）回收样品中均未观察到氧化物SiO₂和(Mg_0.92,Fe_0.08)O的XRD 和IR特征谱线；（3）回收样品的XRD、IR特征谱线变得简略，并发现了与原始样品有某些不同的特征谱线，随冲击压力增加，这种变化趋于明显；（4） 通过对比冲击压力在85 GPa以下和97 GPa以上回收样品的XRD、IR特征谱线，没有观察到明显的新谱线特征出现。结合先前的冲击Hugoniot状态方程实验数据分析，可以认为：在冲击压缩过程中样品处于钙钛矿结构，在冲击卸载过程中样品发生了由钙钛矿结构向单链状结构的逆转相变；特别是，在实验的温度压力范围内，不可能发生由(Mg_0.92,Fe_0.08)SiO₃向SiO₂和(Mg_0.92,Fe_0.08)O的化学分解相变，顽火辉石的高压相——钙钛矿结构是稳定的。回收样品和原始样品的谱线差异可能对应于高压加载或卸载过程引起的某种晶格畸变，而高压加载导致钙钛矿型顽火辉石晶格畸变的可能性更大。这一结果将对下地幔矿物学模型的建立和下地幔地震波探测结果的解释提供基础物理依据。     

Physical and mechanical properties of C60 under high pressures and high temperatures

The physical and mechanical properties of a C₆₀ fullerene sample have been investigated under high pressure–high temperature conditions using a designer Diamond Anvil Cell. Electrical resistance measurements show evidence of C₆₀ cage collapse at 20 GPa, which leads to the formation of an insulating phase at higher pressure. Energy dispersive X-ray diffraction (EDXD) data indicated that the characteristic fcc reflections gradually decrease in intensity and eventually disappear above 28 GPa. A C₆₀ sample was laser-heated at a pressure of 35 GPa to a temperature of 1910±100 K and, subsequently, decompressed to ambient conditions. The photoluminescence spectra and the Raman spectrum of the pressure–temperature-treated sample were measured at a low temperature of 80 K. Raman peak at 1322.3 cm^?1 with full-width half-maximum of 2.9 cm^?1 was observed from the sample, which is attributed to the hexagonal diamond phase in the sample. The room temperature photoluminescence spectra showed a symmetric emission band centered in the red spectral range with a peak at 690 nm. The structural analysis of the pressure–temperature-processed C₆₀ sample using EDXD method showed strong internal structure orientation and a phase close to hexagonal diamond. Mechanical properties such as hardness and Young’s modulus were measured by nanoindentation technique and the values were found to be 90±7 and 1215±50 GPa, respectively and these values are characteristic of sp³-bonded carbon materials.     

Pressure and temperature dependence of the structure of liquid Sn up to 5.3 GPa and 1373 K

Pressure and temperature dependence of the structure of liquid Sn has been measured up to 5.3?GPa and 1373?K using multi-angle energy-dispersive X-ray diffraction in Paris–Edinburgh cell. Under nearly isobar condition at ～1?GPa, liquid Sn displays a normal behavior with gradual structural changes with temperature up to 1373?K. Under isothermal compressions at 850 and 1373?K, however, the structure factors of liquid Sn both show a turn-over at ～3?GPa in the height of the first diffraction peak. According to the hard sphere cluster model, the structure of liquid Sn may be viewed as two different types of clusters. Below ～3?GPa, it is shown that the packing fraction of the dominant cluster (occupying ～0.94 fraction) changes with compression, while above ～3?GPa, the packing fractions and the hard sphere diameters of both clusters start to influence the structure, causing significant changes with increasing pressure. Our results suggest that the compression behavior of liquid Sn changes from localized densification only in one cluster below ～3?GPa to homogeneous structural changes in both clusters above ～3?GPa.