白钨矿的原位高压X射线衍射研究

使用金刚石对顶砧高压装置(DAC)和同步辐射光源,对天然白钨矿进行了原位高压能量色散X射线衍射(EDXD)研究,实验最高压力为16.0 GPa.在实验压力范围内观察到了一次白钨矿结构→钨锰铁矿结构的可逆相变:压力小于5.3 GPa时为白钨矿结构(I4_1/a),在5.3～12.3 GPa压力区间内为白钨矿结构与钨锰铁矿结构(P2/c)并存,大于12.3 GPa时完全相变为钨锰铁矿结构.从键长、配位数和配位多面体角度对白钨矿→钨锰铁矿结构的相变机制进行了解释.     

榍石的高压结构研究

利用同步辐射和金刚石压腔(DAC)技术对天然矿物榍石进行原位高压能散模式X射线实验研究,结果表明榍石在3.9 GPa和10.9 GPa分别发生P 21/a→A 2/a和A 2/a→A 1结构相变,并首次确定10.9 GPa→25.1 GPa榍石结构很可能稳定保持A 1相。基于此认为榍石能在地球较深部位稳定存在,此外,本研究对探索地球深部T i和S i元素的地球化学行为也有一定帮助作用。     

霞石NaAlSiO_4的压缩性及其机理研究

NaAlSiO_4高压相CF相的结构和性质近年来被广为关注,然而对其低压相霞石的高压行为研究并不深入。为进一步认识碱金属在CF相中的赋存状态,采用金刚石压腔和同步辐射X射线衍射,开展了霞石NaAlSiO_4(P63,Z=8)常温、20GPa时的压缩性质研究。结果显示,在实验压力范围内,霞石没有发生结构相变,其三阶等温状态方程参数为:V0=0.715(2)nm~3,K0=53(3)GPa,K'=4.1(3),a和c轴的压缩系数Ka=3.8(1)×10~(-3)nm/GPa,Kc=2.42(6)×10~(-3)nm/GPa。通过第一性原理计算模拟,印证了实验压缩性的结果,揭示了霞石的压缩机制,即SiO_4和AlO_4四面体呈刚性行为,这些四面体之间的扭转导致结构中伪正交空隙通道的畸变。     

下地幔温压下(Mg, Fe)SiO3钙钛矿的相稳定性

在69～100 GPa冲击压力(估算温度为2600～4300 K)范围内进行了初始样品为(Mg0.92, Fe0.08)SiO3顽火辉石和MgO+SiO2的冲击压缩回收实验。对回收样品进行的X射线衍射(XRD)分析结果表明: 两发顽火辉石回收样品的主相均是单链状结构硅酸盐, 而非钙钛矿结构; 另外, 回收样品中均未观察到氧化物SiO2 和(Mg0.92, Fe0.08)O的XRD特征谱线; 两发MgO+SiO2回收样品中均观察到SiO2和镁橄榄石(Mg2SiO4)而没有氧化物MgO。实验结果表明: 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; 在实验的温压范围内, 不可能发生由(Mg0.92, Fe0.08)SiO3向SiO2和(Mg0.92, Fe0.08)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。高压加载或卸载过程引起的晶格畸变导致回收样品和原始样品的谱线差异, 而高压加载导致钙钛矿型(Mg0.92, Fe0.08)SiO3晶格畸变的可能性更大。     

透视石的原位高压单晶X射线衍射研究

采用同步辐射光源和金刚石对顶砧(DAC)技术,对透视石进行了室温下的原位高压单晶X射线衍射研究。实验的最高压力为11.7 GPa,在实验压力范围内,未观察到透视石发生相变。随着压力的升高,晶胞体积逐步被压缩,体积压缩率符合三阶Birch-Murnaghan状态方程,拟合获得体模量K0为114.6(5.3)GPa。压力低于9.3 GPa时,c轴的压缩率大于a轴;在9.3~11.7 GPa压力范围内,限制于透视石结构中的水分子在高压下会阻碍硅氧四面体六元环沿c轴方向的扭曲变形,导致c轴的抗压性增强,最终a轴与c轴的被压缩程度趋于一致。通过分析多种含水环状硅酸盐矿物的高压行为,发现高压下结构中水的存在形式对含水环状硅酸盐矿物的弹性性质有重要的影响。     

钛闪石的高压结构及其地质意义

利用同步辐射EDXD方法和DAc高压技术对采于新疆天山碱性玄武岩地幔捕虏体中的钛闪石进行了原位高压(达25．4GPa)结构研究：在室温下，随着压力的增加，钛闪石的轴长a、b、c被逐渐压缩；当压力为18、9GPa时，钛闪石可能由于“脱水”而导致结构发生相变，此相变应属于可逆的二级相变。结合钛闪石的地质产状，我们认为，钛闪石在上地幔一定深度范围内可以保持稳定，是上地幔中重要的含水矿物相之一，其被携带到地表是一个非常快速的过程，本文的结果对某些含钛矿物的高压行为研究提供了一定的参考。     

橄榄石的等温状态方程

利用金刚石对顶砧(DAC)高压装置产生高压,使用16∶3∶1的甲醇、乙醇和水混合液体作为传压介质,在室温下,40 GPa的压力范围内,对橄榄石(olivine)进行了原位高压同步辐射能量色散X射线衍射(EDXRD)研究。实验结果表明,在所研究压力范围内,采自张家口大麻坪天然新鲜橄榄石的结构稳定,未见相变和压致非晶现象发生。用Birch-Murnaghan方程对测得的V-p数据进行了数值拟合,当K′T0=4时,橄榄石的零压体弹模量为KT0=141.3±3.2 GPa。     

DS 6×1400 t二级6-8型大腔体高压装置压力标定

本文介绍了一种新型二级6-8型大腔体静高压装置。此装置基于国产DS 6×1400 t铰链式六面顶压机,在六面体压腔中直接放入10/4(八面体传压介质边长10 mm/末级压砧正三角形截面的边长4 mm)类型二级6-8型增压装置产生压力。在室温下利用Zn Te(Ⅰ-Ⅱ,5 GPa;Ⅱ-Ⅲ,8.9~9.5 GPa;半导体-金属,11.5~13 GPa),ZnS(半导体-金属,15.6 GPa)和GaAs(半导体-金属,18.8 GPa)的相变点标定了腔体压力。结果表明,该装置在油压为18 MPa时可以产生19 GPa的腔体压力,样品尺寸可以达到2 mm~3。     

硅磷镍矿的高压状态方程与相变研究

硅磷镍矿(Ni,Fe)8(Si,P)3是一种4元陨石矿物,对探寻地核中轻元素的存在形式具有一定指示意义。采用同步辐射X射线衍射并结合金刚石压腔技术,笔者开展了硅磷镍矿的等温状态方程及其相变研究。实验结果表明常温下在0.0001~41.9 GPa内硅磷镍矿没有发生结构相变,但在34 GPa时其晶胞参数呈现不连续变化。这一异常变化可能与硅磷镍矿的磁性转变有关。对34 GPa前后的p-V实验数据分别进行拟合,得到了硅磷镍矿的状态方程参数V0=1.446(3)nm3、K0=231(8)GPa(p33 GPa)和V0=1.414(6)nm3、K0=343(18)GPa(p35 GPa)。而在高温高压条件下,硅磷镍矿会发生结构相变或者分解。     

方钠石的原位高压X射线研究

在室温下使用金刚石对顶砧（DAC）高压装置和同步辐射光源，对架状硅酸盐矿物方钠石进行了原位高压X射线衍射实验，最高压力达到17．4GPa。在研究的压力范围内观察到在3GPa左右方钠石发生了一次相变，且压力大于6．3GPa时，d222出现异常增大。对方钠石在高压下相变以及d222增大的原因进行了分析，认为方钠石结构中存在着充填大阳离子的多面体笼和孔道，高压下这些笼和孔道容易扭曲变形，从而造成结构的改变。     

HgO at high pressures: the transition to the NaCl structure (HgO-III) and the equation of state of tetragonal HgO-II

The high-pressure behavior of HgO-montroydite was investigated up to 36.5 GPa using angle-dispersive X-ray diffraction. The tetragonal phase of this material (HgO-II), a distortion of the NaCl structure, transforms into the cubic NaCl structure (HgO-III) above ~31.5 GPa. The transformation of mercury oxide from the orthorhombic Pnma (HgO-I) structure to a tetragonal I4/mmm structure (HgO-II) is confirmed to occur at 13.5 ± 1.5 GPa. Neither of the high-pressure phases, HgO-II nor HgO-III, is quenchable in pressure. The derived isothermal bulk modulus of HgO-II and its pressure derivative strongly depend on the assumed zero-pressure volume of this phase, but our elasticity results on HgO-II nevertheless lie significantly closer to theoretical calculations than prior experimental results, and the measured pressure of the phase transformation to the NaCl structure is also in agreement with recent theoretical results. The general accord with theory supports the existence of significant relativistic effects on the high-pressure phase transitions of HgO.     

High-Pressure Behavior of Copper Carbonate: Data from Malachite

Abstract: In-situ high-pressure energy dispersive X-ray diffraction experiments of malachite have been performed using diamond anvil cell and synchrotron radiation. The highest recorded pressure is up to 17.4 GPa. The experimental results reveal that malachite experienced two phase transitions at 0.7 and 7.8 GPa, and the last one is reversible.     

Raman spectroscopic study of PbCO3 at high pressures and temperatures

Cerussite (PbCO₃) has been investigated by high-pressure and high-temperature Raman spectroscopy up to pressures of 17.2 GPa and temperatures of 723 K. Two pressure induced phase transitions were observed at about 8.0(2) and 16.0(2) GPa, respectively. The post-aragonite transition (PbCO₃-II) at 8.0(2) GPa is accompanied by softening of the v ₂-out-of-plane mode of the CO ₃ ^2? group and disappearance of the B_1g (v ₄-in-plane band of the CO ₃ ^2? group) mode. Stronger shifts of the carbonate group modes after the phase transition suggest that the new structure is more compressible. The formation of a second high-pressure polymorph begins at about 10 GPa. It is accompanied by the occurrence of three new bands at different pressures and splitting of the v ₁-symmetric C–O stretching mode of the CO ₃ ^2? group. The transitions are reversible on pressure release. A semi-quantitative phase diagram for PbCO₃ as a function of pressure and temperature is proposed.     

High-pressure behaviour of germanate olivines studied by X-ray diffraction and X-ray absorption spectroscopy

Germanate olivines Mg₂GeO₄, Ca₂GeO₄ and CaMgGeO₄ have been studied by high-pressure X-ray Diffraction and high-pressure X-ray Absorption Spectroscopy. The three compounds were compressed, in the 0–30 GPa pressure range, at room temperature in a diamond-anvil cell, silicon oil being used as the pressure transmitting medium. Values of K₀ are 166 ± 15, 117 ± 15 and 152 ± 14 GPa for Mg₂GeO₄, Ca₂GeO₄ and CaMgGeO₄ respectively. These olivines all exhibit compression anisotropy, the a axis being the least compressible. Crystal to crystal phase transitions have been observed in Mg₂GeO₄ and Ca₂GeO₄ above 12 GPa and 6 Gpa respectively. The nature of these structural changes remains unclear yet. The onset of amorphization has been observed in Mg₂GeO₄ and Ca₂GeO₄ at pressures above about 22 and 11 GPa respectively. These phase transitions and amorphization processes do not involve any detectable increase in the coordination number of germanium atoms. At higher pressure (P >23 GPa), we report the onset of a transition from a phase with fourfold coordinated germanium to a phase with higher germanium coordination number in CaMgGeO₄.     

Static compression of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>: linear incompressibility of lattice parameters and high-pressure transformations

The high-pressure behavior of -Fe₂O₃ has been studied under static compression up to 60 GPa, using a laser-heated diamond anvil cell. Synchrotron-based angular-dispersive X-ray diffraction shows that the sample remains in the corundum structure up to 50 GPa, but with the appearance of coexisting diffraction lines from a high-pressure phase at pressures above 45 GPa. A least-squares fit of low-pressure phase data to an Eulerian finite-strain equation of state yields linear incompressibilities of K _{a 0}=749.5 (± 18.4) GPa and K _{c 0}= 455.7 (± 21.4) GPa, differing by a factor of 1.6 along the two directions. The enhanced compressibility of the c axis may lead to breaking of vertex- or edge-sharing bonds between octahedra, inducing the high-pressure phase transformation at 50 GPa. Analysis of linear compressibilities suggests that the high-pressure phase above 50 GPa is of the Rh₂O₃ (II) structure. Continuous laser heating reveals a new structural phase transformation of -Fe₂O₃ at 22 GPa, to an orthorhombic structure with a=7.305(3) Å, b=7.850(3) Å, and c=12.877(14) Å, different from the Rh₂O₃ (II) structure.     

The high-pressure phase diagram of synthetic epsomite (MgSO4·7H2O and MgSO4·7D2O) from ultrasonic and neutron powder diffraction measurements

We present an ultrasonic and neutron powder diffraction study of crystalline MgSO₄·7H₂O (synthetic epsomite) and MgSO₄·7D₂O under pressure up to ~3 GPa near room temperature and up to ~2 GPa at lower temperatures. Both methods provide complementary data on the phase transitions and elasticity of magnesium sulphate heptahydrate, where protonated and deuterated counterparts exhibit very similar behaviour and properties. Under compression in the declared pressure intervals, we observed three different sequences of phase transitions: between 280 and 295 K, phase transitions occurred at approximately 1.4, 1.6, and 2.5 GPa; between 240 and 280 K, only a single phase transition occurred; below 240 K, there were no phase transformations. Overall, we have identified four new phase fields at high pressure, in addition to that of the room-pressure orthorhombic structure. Of these, we present neutron powder diffraction data obtained in situ in the three phase fields observed near room temperature. We present evidence that these high-pressure phase fields correspond to regions where MgSO₄·7H₂O decomposes to a lower hydrate by exsolving water. Upon cooling to liquid nitrogen temperatures, the ratio of shear modulus G to bulk modulus B increases and we observe elastic softening of both moduli with pressure, which may be a precursor to pressure-induced amorphization. These observations may have important consequences for modelling the interiors of icy planetary bodies in which hydrated sulphates are important rock-forming minerals, such as the large icy moons of Jupiter, influencing their internal structure, dynamics, and potential for supporting life.     

High-pressure metallization and electronic-magnetic propertiesof hexagonal cubanite (CuFe2S3)

^?57Fe Mössbauer studies at room temperature and temperature-dependent resistance studies have been performed on a natural specimen of cubanite (CuFe₂S₃) in a diamond-anvil cell at pressures up to ～10 GPa. An insulator-metal phase transition occurs in the range 3.4–5.8 GPa coinciding with a previously observed structural transition from an orthorhombic to a hexagonal NiAs (B8) structure. The room temperature data shows that the metallization process concurs with a gradual transition from a magnetically ordered phase at low pressure to a nonmagnetic or paramagnetic phase at high-pressure. The change in magnetic behaviour at the structural transition may be attributed to a reduction of the Fe-S-Fe superexchange angle formed by edge-sharing octahedra occurring in the high-pressure phase. The non-magnetic or paramagnetic metallic phase at high pressure is retained upon decompression to ambient pressure-temperature conditions, indicative of substantial hysteresis associated with the pressure driven orthorhombic→hexagonal structural transition. The pressure evolution of both the ⁵⁷Fe Mössbauer hyperfine interaction parameters and resistance behaviour is consistent with the transition from mixed-valence character in the low pressure orthorhombic structure to that of extended-electron delocalization in the hexagonal phase at high-pressure.     

A high-pressure neutron diffraction study of the ferroelastic phase transition in RbCaF3

The fluoroperovskite phase RbCaF₃ has been investigated using high-pressure neutron powder diffraction in the pressure range ~0–7.9 GPa at room temperature. It has been found to undergo a first-order high-pressure structural phase transition at ~2.8 GPa from the cubic aristotype phase to a hettotype phase in the tetragonal space group I4/mcm. This transition, which also occurs at ~200 K at ambient pressure, is characterised by a linear phase boundary and a Clapeyron slope of 2.96 × 10^?5 GPa K^?1, which is in excellent agreement with earlier, low-pressure EPR investigations. The bulk modulus of the high-pressure phase (49.1 GPa) is very close to that determined for the low-pressure phase (50.0 GPa), and both are comparable with those determined for the aristotype phases of CsCdF₃, TlCdF₃, RbCdF₃, and KCaF₃. The evolution of the order parameter with pressure is consistent with recent modifications to Landau theory and, in conjunction with polynomial approximations to the pressure dependence of the lattice parameters, permits the pressure variation of the bond lengths and angles to be predicted. On entering the high-pressure phase, the Rb–F bond lengths decrease from their extrapolated values based on a third-order Birch–Murnaghan fit to the aristotype equation of state. By contrast, the Ca–F bond lengths behave atypically by exhibiting an increase from their extrapolated magnitudes, resulting in the volume and the effective bulk modulus of the CaF₆ octahedron being larger than the cubic phase. The bulk moduli for the two component polyhedra in the tetragonal phase are comparable with those determined for the constituent binary fluorides, RbF and CaF₂.     

The high-pressure stability of Mg-sursassite in a model hydrous peridotite: a possible mechanism for the deep subduction of significant volumes of H<Subscript>2</Subscript>O

The stability of the high-pressure phase Mg-sursassite, previously MgMgAl-pumpellyite, in ultramafic compositions has been determined in experiments in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). The breakdown of Mg-sursassite + forsterite + enstatite to pyrope + vapour with increasing temperature was bracketed at 6.0 and 7.0 GPa. Below 6.0 GPa, Mg-sursassite + forsterite + vapour reacts to chlorite + enstatite. This reaction provides a mechanism for transfer of water from chlorite- to Mg-sursassite-bearing assemblages. At pressures of 7.0 GPa and above, the assemblage Mg-sursassite + phase A + enstatite was found. Phase relations involving Mg-sursassite and phase A are considered. For bulk compositions with a low water content, the vapour-absent reaction Mg-sursassite + forsterite = pyrope + phase A + enstatite determines the upper-pressure stability of Mg-sursassite, and provides a mechanism for the complete transfer of water from Mg-sursassite to phase A-bearing assemblages. Mg-sursassite plays an important role in peridotite compositions in the subducting slab because, at temperatures below 700 °C, it can transfer water from hydrous phases such as antigorite and chlorite to high-pressure stable phases such as phase A.