钙钛矿（GaTiO3）高压相变及等温压缩

 高温高压条件下对钙钛矿（Perovstsite）多晶进行了研究，在金刚石压砧设备上压力条件最高达38 GPa，YAG莱塞加热温度近1 000 ℃以上，用红宝石荧光校压系统进行压力标定。实验结果表明静水压条件X射线就位测量，GaTiO₃(Ⅰ)由斜方晶系在10 GPa时直接向六方GaTiO₃(Ⅱ)结构相变，体积变化为1.6％；1 000 ℃加热及其非静水压条件下GaTiO₃(Ⅰ)由斜方晶系首先转变为四方晶系GaTiO₃(Ⅲ)转变压力为8.5 GPa，体积变化为0％，继续增加压力导15 GPa，GaTiO₃(Ⅲ)向GaTiO₃(Ⅱ')转化成六方晶系，体积变化亦为1.6％。三种高压相，在压力降到一个大气压时都会消失，所以是逆转化的非淬火相。等温压缩在标准静水压条件下进行，压力应小于10.4 GPa，K₀'=5.6时，K₀=(210±7)GPa，此数据是根据Birch-Murnaghan状态方程求得的体模量。     

非静水压条件下铁从α到ε结构相变的第一性原理计算

采用基于密度泛函理论的平面波赝势方法,研究了三轴加载的非静水压力和静水压力对铁从体心立方结构（bcc,α相）到六角密排结构（hcp,ε相）相变压力和磁性的影响,结果发现：在0—18 GPa压力范围内,相对静水压力条件,随着压力的升高,bcc结构的原子磁矩在非静水压力下降低得更快;在非静水压力下,相变更容易发生,相变压力随着非静水压力程度的增加而降低;并且对非静水压力对相变压力影响的物理机理进行了讨论. 关键词： 相变 非静水压力 第一性原理 铁     

Anomalous behavior and phase transformation of α-GaOOH nanocrystals under static compression

The structural compression mechanism and compressibility of gallium oxyhydroxide, α-GaOOH, are investigated by in situ synchrotron radiation x-ray diffraction at pressures up to 31.0 GPa by using the diamond anvil cell technique. Theα-GaOOH sustains its orthorhombic structure when the pressure is lower than 23.8 GPa. The compression is anisotropic under hydrostatic conditions, with the a-axis being most compressible. The compression proceeds mainly by shrinkage of the void channels formed by the coordination GaO_3(OH)_3 octahedra of the crystal structure. Anomaly is found in the compression behavior to occur at 14.6GPa, which is concomitant with the equatorial distortion of the GaO_3(OH)_3 octahedra. A kink occurs at 14.6 GPa in the plot of finite strain f versus normalized stress F, indicating the change in the bulk compression behavior. The fittings of a second order Birch–Murnaghan equation of state to the P–V data in different pressure ranges result in the bulk moduli B_0= 199(1) GPa for P 14.6 GPa and B_0= 167(2) GPa for P 14.6 GPa. As the pressure is increased to about 25.8 GPa, a first-order phase transformation takes place, which is evidenced by the abrupt decrease in the unit cell volume and b and c lattice parameters.     

Deviatoric stress: a nuisance or a gold mine?

Both synchrotron radiation and deviatoric stress were once considered to be nuisances. Now synchrotron radiation is one of the most important tools available to scientists of all disciplines and deviatoric stress is one of the most useful aspects of x-ray diffraction at extreme conditions. Samples in high-pressure devices are under true hydrostatic pressure only when surrounded by a fluid, thus limiting true hydrostatic pressure studies at ambient temperatures to pressures below about 11?GPa. Elevated temperature is able to extend this limit but has rarely been used for this purpose. Instead, noble gases have been used as pressure media as their solids are especially soft. Deviatoric stress and resultant anisotropic elastic strain in solid samples and solid media have led to many subtle errors in determinations of elastic properties and crystal structures, especially in the days before it was realized that they could be measured and were potentially a valuable source of information. In recent years, measuring anisotropic elastic strain by x-ray diffraction has provided new insights into materials strength, elastic properties, crystal structures, mechanisms of phase transitions, slip systems, lattice preferred orientation, and, of course, ways to make corrections when deviatoric stress is indeed a nuisance.     

Simultaneous determination of mean pressure and deviatoric stress based on numerical tensor analysis: a case study for polycrystalline x-ray diffraction of gold enclosed in a methanol-ethanol mixture

It is known that the {100} and {111} planes of cubic crystals subjected to uniaxial deviatoric stress conditions have strain responses that are free from the effect of lattice preferred orientation. By utilizing this special character, one can unambiguously and simultaneously determine the mean pressure and deviatoric stress from polycrystalline diffraction data of the cubic sample. Here we introduce a numerical tensor calculation method based on the generalized Hooke's law to simultaneously determine the hydrostatic component of the stress (mean pressure) and deviatoric stress in the sample. The feasibility of this method has been tested by examining the experimental data of the Au pressure marker enclosed in a diamond anvil cell using a pressure medium of methanol-ethanol mixture. The results demonstrated that the magnitude of the deviatoric stress is ～0.07?GPa at the mean pressure of 10.5?GPa, which is consistent with previous results of Au strength under high pressure. Our results also showed that even a small deviatoric stress (～0.07?GPa) could yield a ～0.3?GPa mean pressure error at ～10?GPa.     

First-principles investigation on high-pressure structural evolution of MnTiO3

First-principle calculations using density-functional theory with linearized augmented plane wave method and projector-augmented method have been performed for the high-pressure MnTiO₃ polymorphs and their possible dissociation products. Theoretical results demonstrate that ilmenite-type MnTiO₃ transforms into perovskite phase at 27 GPa and 0 K. The lithium niobate phase of MnTiO₃ is confirmed to be metastable according to its higher Gibbs free energy compared with that of ilmenite at ambient conditions. In ilmenite and lithium niobate phases, MnO₆ octahedra become more distorted while TiO₆ octahedra become more regular with increasing pressure. In orthorhombic perovskite phase, the structural distortion deviated from the ideal cubic perovskite is enhanced at higher pressure. Based on the non-spin-polarized calculations, perovskite phase MnTiO₃ is predicted to dissociate into Fm3?m-MnO+P2₁/c-MnTi₂O₅ at 29 GPa.     

Hydrostatic pressure-induced phase transitions in RbMnCl<Subscript>3</Subscript>: Raman spectra and lattice dynamics

Raman scattering spectra of RbMnCl₃ are measured at room temperature under high hydrostatic pressure. The results are interpreted based on first principles lattice dynamics calculations. The experimental data obtained correlate with the calculations in the low frequency domain but disagree slightly in the region of high-frequency vibrations. The transition from the hexagonal to the cubic perovskite phase observed earlier (near 0.7 GPa) was confirmed, and new transitions to lower symmetry distorted phases were discovered (at 1.1 and 5 GPa).     

Pressure-induced phase transition in an orthorhombic C60 crystal

X-ray diffraction studies of an orthorhombic C₆₀ single crystal grown from CS₂ solution have revealed a phase transition to a monoclinic phase between 1.1 and 2.2GPa. Compressibility of three principal axes is measured up to 3GPa and found to be nearly isotropic. Its bulk modulus is obtained as 10.5±1.9GPa, and this crystal is more compressible than an fcc one. We discuss the structural characteristic differences under pressure between the orthorhombic crystal and the fcc crystal.     

Effect of hydrostatic and chemical pressure on BaF2 and BaF2: Eu2+ crystals

The effect of hydrostatic pressure on a BaF₂ crystal was studied within the shell model in the pair-wise potential approximation. The structural phase transition from the cubic to orthorhombic phase was simulated. The behavior of the unit-cell parameters of the α-and β-BaF₂ phases under hydrostatic pressure (from 0 to 12 GPa) was investigated. The fundamental vibration frequencies of BaF₂ under hydrostatic pressure (0–3.5 GPa) were calculated for both phases. The effect of chemical pressure on the BaF₂ crystal was studied by simulating Ba_1?x Me_xF₂ mixed crystals (Me=Ca, Sr). It was shown that at impurity concentrations up to 15–20 at. % the lattice constant varies in the same way as it does when hydrostatic pressure increases to P _c , which corresponds to a phase transition to the orthorhombic phase. The effect of chemical and hydrostatic pressure on BaF₂: Eu²⁺ doped crystals was also studied. The dependence of the absorption and luminescence zero-phonon line shift on the Eu²⁺-ligand distance was calculated.     

(111)轴向锑化铟单晶冲击相变研究

 利用气体炮加载方法研究了(111)轴向锑化铟（InSb）单晶的冲击相变以及剪力对冲击相变的影响。冲击加载应力为1.75~3.80 GPa。实验得到，InSb单晶相变的起始应力由静高压时的2.3 GPa下降到1.727 GPa，最大体积变化率为ΔV/V₀＝15.31%，对应的最大剪力为0.681 GPa，剪力水平为83%左右，相变平均静水压力由静高压时的2.3 GPa，下降到0.823 GPa。研究表明，剪力对锑化铟单晶相变的诱发水平有重大影响。     

Shear induced phase transition in PbO under high pressure

We have studied the structural behavior of lead monoxide (PbO) as a function of pressure via angular dispersive X-ray diffraction employing two different pressure transmitting media that were quasi-hydrostatic (N₂) and non-hydrostatic (MgO), respectively. Besides litharge (-PbO) and massicot (β-PbO), which are both stable at ambient pressure, there is an orthorhombic γ-PbO phase which appears upon application of pressure to -PbO. We have found that the orthorhombic γ-PbO phase is favored by shear stress under non-hydrostatic conditions. -PbO shows strong anisotropy in compressibility. The a-axis is rather incompressible with a linear stiffness coefficient of K_a0=540(30) GPa whereas the c-axis stiffness is K_c0=25(1) GPa. The bulk modulus of -PbO is K₀=23.1(3) GPa and its derivative .     

钙钛矿CaTiO3的超高压结构研究

利用同步辐射x射线衍射和 DAC 高压技术在室温下测量了钙钛矿CaTiO₃在压力0—44.53 GPa下的结构变化.结果表明，随着压力的增加CaTiO₃的三个晶轴都受到不同程度的压缩，a,b的压缩率相近且相对比较大，c的压缩率最小，但没有证据表明有相变的发生.在压力范围内CaTiO₃的P-V关系用Murnaghan状态方程表示，设定K′0=4，得到V0=0.2245(6)nm3和K0=222(9) GPa.应用赝立方角γpc与压力的关系，初 关键词： 3')" href="#">CaTiO₃ 结构 超高压 状态方程     

High pressure studies on α-cristobalite form of Al0.5Ga0.5PO4: hydrostatic versus non-hydrostatic conditions

High pressure angle-dispersive X-ray diffraction investigations have been carried out on α-cristobalite form of Al_0.5Ga_0.5PO₄. Our investigations show that the structural stability of this phase under high pressure depends on the nature of pressure conditions in the diamond anvil cell. Under hydrostatic pressure conditions using neon as a pressure transmitting medium, ambient orthorhombic C222₁ phase transforms to orthorhombic Cmcm phase at 4.9?GPa. The high pressure Cmcm phase remains stable up to the highest pressure in the experiment, i.e. 19?GPa. The values of bulk modulus for C222₁ and Cmcm phases are 19(2) and 126(4)?GPa, respectively. In contrast to this, under non-hydrostatic pressure conditions, transformation of ambient C222₁ phase to Cmcm phase has not observed up to 17.4?GPa. Instead, a new monoclinic phase P2₁ is observed which contains layers of six coordinated Al/Ga ions separated by less dense five coordinated Al/Ga ions.     

Ultrastiff cubic TiO2 identified via first-principles calculations

The crystal structures and compressibilities of fluorite- and pyrite-structured TiO2 under varying hydrostatic pressures are calculated using gradient-corrected density functional as well as hybrid density functional-Hartree-Fock formulations. The results suggest that fluorite TiO2 is a highly incompressible solid with a large bulk modulus value (K(0) approximately 395 GPa), approaching that of ultrahard cotunnite TiO2 (K(0)=431 GPa). The bulk modulus obtained for pyrite TiO2 is considerably smaller (K(0) approximately 220-260 GPa), nonetheless larger than the value determined experimentally for cubic TiO2. Calculated shear modulus values indicate that fluorite TiO2 has the potential to be an ultrahard material, if it could be stabilized under ambient conditions.     

Effects of hydrostaticity on the structural stability of carbonates at lower mantle pressures: the case study of dolomite

We have conducted high pressure far-infrared absorbance and Raman spectroscopic investigations on a natural iron-free dolomite sample up to 40?GPa. Comparison between the present observations and literature results unraveled the effect of hydrostatic conditions on the high pressure dolomite polymorph adopted close to 40?GPa, i.e. the triclinic Dol-IIIc modification. In particular, non-hydrostatic conditions impose structural disorder at these pressures, whereas hydrostatic conditions allow the detection of an ordered Dol-IIIc vibrational response. Hence, hydrostatic conditions appear to be a key ingredient for modeling carbon subduction at lower mantle conditions. Our complementary first-principles calculations verified the far-infrared vibrational response of the ambient- and high pressure dolomite phases.     

Pressure-induced structural change in orthorhombic perovskite GdMnO3

Structural stability of the perovskite-type GdMnO(3) has been investigated by the synchrotron angle-dispersive x-ray diffraction technique up to 63 GPa in a diamond anvil cell. GdMnO(3) stays in an orthorhombic structure but undergoes an isostructural phase transition with ~5% volume reduction at 50 GPa. In the parent orthorhombic phase, the compressions along a, b and c axes exhibit a large anisotropic behavior. With increasing pressure, our results show that the distortion and tilts of the MnO(6) octahedra are reduced continuously and the orthorhombic structure evolves towards higher symmetry. By fitting the observed pressure-volume data using the third-order Birch-Murnaghan equation of state, we obtain the bulk modulus B(0) = 156(3) GPa with B(0)' = 6.5(3) for the starting orthorhombic phase. Upon decompression, the starting orthorhombic phase is recovered.     

High pressure structural studies on SrRuO3

We have performed room temperature high pressure structural studies on the ferromagnetic perovskite SrRuO₃ to 34 GPa. We have also used three different pressure media (silicone fluid, 4:1 methanol:ethanol and argon) to test for possible effects of pressure media on compression data. The orthorhombic perovskite structure is stable to the highest pressure, and the data can be fit with a bulk modulus of with a pressure derivative of for all of the pressure media. We have also examined the high pressure behavior of the RuO₆ octahedra using a model that assumes the octahedra are not distorted. Various tilt angles around the ideal cubic perovskite axes are found and can be used to estimate the Ru-O-Ru bond angle that is known to be directly related to the ferromagnetic Curie temperature. For all pressure media, there appears to be a minimum in the Ru-O-Ru bond angle around 15 GPa. Implications for the observed high pressure magnetic behavior of SrRuO₃ will be discussed.     

High-density strontium hydride: An experimental and theoretical study

Powder x-ray diffraction experiments and first-principles calculations have been carried out to investigate the possibility of a structural phase transition, characterized by a change from ionic to covalent bonding, in strontium hydride at pressures greater than 50 GPa. The powder x-ray diffraction results confirm a previously reported transition from the cotunnite structure to the Ni₂In structure at approximately 8 GPa. The Ni₂In phase remained stable up to the maximum experimental pressure of 113 GPa. The first-principles calculations, however, predict that under hydrostatic conditions a transition from the Ni₂In structure to the AlB₂ structure will occur at 115 GPa. A comparison of the pressure-dependent volume yielded by the respective experimental and theoretical studies suggests that in many cases the bulk modulus obtained from experiments carried out under non-hydrostatic conditions may be overestimated. Raman spectroscopy experiments corroborated the previously proposed Ni₂In structure, as the spectra obtained at pressures greater than 8 GPa exhibited two Raman-active modes, consistent with those expected from the Ni₂In structure.     

金红石高温高压相变的Raman光谱特征

以Ar作压力介质,在准静水压力条件下,利用激光加热DAC技术和显微Raman光谱原位测试技术,在0～35 GPa压力范围开展金红石的高温高压相变研究。在室温条件下,金红石结构TiO₂于13.4 GPa开始转变成斜锆石相,于21 GPa时转变完全,并直到35 GPa时斜锆石相稳定存在。在压力分别为29.4和35.0 GPa时,用YAG激光器发出的波长为1.064 μm的红外激光束扫描加热样品,TiO₂斜锆石高压相转变成另一Pbca结构高压相。卸压时,Pbca相于26.3 GPa时转变成斜锆石相。斜锆石相转变成Pbca相需要加热才能发生,而卸压时却在较小的压力区间即迅速转变完全,两相转变压力边界在28 GPa左右。进一步卸压,斜锆石相直到11 GPa仍稳定,在7.6 GPa时斜锆石相与α-PbO2相两相共存,5 GPa时完全转变成α-PbO₂相,并直到常压该相以亚稳定态存在。     

Simulation of pressure distribution in a pyrophyllite high-pressure cell by finite-element analysis

The pressure-transmitting behavior and pressure distribution of a pyrophyllite cell in a cubic-anvil large volume high-pressure apparatus is investigated by finite-element analysis (FEA). The mechanical equations describing pyrophyllite under high pressure are given, which are composed of the Drucker–Prager criterion and a linear equation of state. The related material parameters such as cohesive strength, angle of internal friction etc. are experimentally measured. The FEA simulation includes the non-uniformity deviatoric stress caused by plastic deformation and the isotropy hydrostatic pressure of the pyrophyllite cell caused by volume compression. The results demonstrate that, in such a pyrophyllite cell, almost 90{%} of the pressure is isotropy hydrostatic pressure, and the pressure gradient mainly arise from non-uniform deviatoric stresses. Simulated data are displayed using the contour and the path plots.