Time-resolved measurement of high-pressure phase transition of fluorite under shock loading

In situ time-resolved measurements of shock wave profiles for anisotropic fluorite crystals with two different crystal orientations were carried out up to a pressure of 34 GPa that is above the transition pressure for the fluorite to cotunnite phase. They indicate that the Hugoniot elastic limit varies with the crystal orientation and final pressure and that high-pressure phase transition from fluorite to a cotunnite-type structure occurs at 13 GPa in 10–20 ns for CaF₂ [100]-oriented crystals and at 17 GPa in more than 50 ns for CaF₂ [111]-oriented crystals, respectively. These results are in disagreement with those from static compression. The phase transition at static pressures has been known to be very sluggish, but the present results indicate a large sensitivity of kinetics to the relationship between crystallographic orientation and shock direction, supporting a martensitic mechanism for the fluorite to cotunnite phase transition that is enhanced by the effect of shock-induced shear. It is also helpful to explain the observation that the in situ emission spectra for shocked Eu-doped fluorite became weak and had no shift above ~15 GPa.     

三轴压缩蠕变试验下石英云母片岩各向异性蠕变特性研究

对石英云母片岩进行三轴压缩蠕变试验,研究丹巴水电站石英云母片岩的三轴蠕变特性及其各向异性特性。按轴向荷载与层理面关系加工成平行组和垂直组2组试件,开展分级加载方式进行不同围压条件下的蠕变试验。试验研究表明,石英云母片岩具有蠕变特性,包括瞬时变形、衰减蠕变、稳定蠕变和加速蠕变阶段;采用带Kachanov蠕变损伤律的蠕变模型来描述石英云母片岩的蠕变特性,并进行蠕变参数辨识,拟合结果显示此模型能很好地描述石英云母片岩的蠕变特性;根据试验结果获得2组试件的长期屈服强度、破坏形态、瞬时变形参数和稳定蠕变速率,分析表明石英云母片岩的蠕变力学特性具有明显的各向异性特性。层理面与轴向荷载垂直的试件较层理面与轴向荷载平行的试件的强度、弹性剪切模量、体积模量和黏性系数相对较大,表现出较高的抗变形和抗破坏能力;平行组以剪切破坏为主,垂直组破坏时出现侧向鼓胀现象,显示出延性破坏的特点;2组石英云母片岩试件的瞬时应变量和稳定蠕变速率都随着应力水平的提高而增大。     

Phase transition and compression behavior of gibbsite under high-pressure

In situ high-pressure synchrotron X-ray diffraction and infrared absorption experiments for gibbsite were performed at room temperature up to 53 and 25 GPa, respectively. A phase transition was confirmed at about 2.5 GPa. The high-pressure phase is indexed as an orthorhombic structure, rather than a triclinic structure as reported in previous studies. The compressibility of gibbsite and its high-pressure polymorph were studied, and their bulk moduli K₀ were determined to be 49 and 75 GPa, respectively with K₀ as 4. The in situ high-pressure infrared absorption spectra revealed the gradual disordering of hydrogen substructure above 15 GPa in quasihydrostatic compression.     

膏岩三轴压缩试验及高温相变特征研究

采用伺服刚性试验机对天然膏岩开展三轴压缩试验,研究了温度及围压对膏岩强度及变形特性的影响。结果表明,膏岩在不同围压下均具有良好的塑性流动特性,加载后无明显的剪切破坏面,而是出现明显的侧向膨胀。根据三轴试验结果,利用摩尔-库仑定律得到了膏岩的强度准则及抗剪强度参数。升高温度导致膏岩强度降低,且高温下石膏发生晶型转变,从二水石膏脱水转变为半水石膏,利用扫描电镜和X衍射对此过程进行了研究。脱水过程导致瞬间孔隙应力增加,膏岩破坏特性由延性转变为脆性。随着持续加载,破裂断面逐渐愈合。膏岩显著的塑性流动能力及快速的裂隙愈合能力对于天然气盖层的封闭稳定性具有重要意义。     

Absorption spectra of Cr3+ in Al2O3 under shock compression

Unpolarized absorption spectra of single crystals of Cr³⁺ doped Al₂O₃ (synthetic ruby) have measured using a new, time-resolving, dispersive, streak photographic system over the range ～350 to ～700 nm during a series of shock loading experiments. The crystal field absorptions assigned to the transition ⁴ A _2g→⁴ T _2g were observed to shift in a series of experiments from 555±1 nm at atmospheric pressure to 503±5 nm at 46 GPa. In a single experiment at 32 GPa the ⁴ A _2g→⁴ T _1g transition was observed to shift from 405±1 to 386±5 nm. The present data extrapolate downwards in compression toward the 10 GPa data of Stephens and Drickamer (1961) although both crystal field absorption energies increase considerably less with compression than predicted by the simple ionic point charge model. The single datum observed for the Racah parameter B, 588±38 cm^?1 at 32 GPa, is consistant with previous results to 10 GPa and the trend of decreasing B, with compression expected from the divergence of the data from the point charge model due to increasing covalancy.     

Clinopyroxene-perovskite phase transition of FeGeO3 under high pressure and room temperature

In order to confirm the possible existence of FeGeO₃ perovskite, we have performed in situ X-ray diffraction measurements of FeGeO₃ clinopyroxene at pressures up to 40 GPa at room temperature. The transition of FeGeO₃ clinopyroxene into orthorhombic perovskite is observed at about 33GPa. The cell parameters of FeGeO₃ perovskite are a=4.93(2) Å, b=5.06(6) Å, c=6.66(3) Å and V=166(3) ų at 40 GPa. On release of pressure, the perovskite phase transformed into lithium niobate structure. The previously reported decomposition process of clino-pyroxene into Fe₂GeO₄ (spinel)+GeO₂ (rutile) or FeO (wüstite) +GeO₂ (rutile) was not observed. This shows that the transition of pyroxene to perovskite is kinetically accessible compared to the decomposition processes under low-temperature pressurization.     

含钒金红石可见光下催化降解亚甲基蓝实验研究

利用含有钒等杂质的金红石可部分吸收可见光的特性,以500 W卤素灯作为光源,实验研究了其对亚甲基蓝的可见光催化降解,结果表明,该金红石具有催化活性,7 h后亚甲基蓝可降解71 2%。经过加热、粉碎改性方法处理后的金红石光催化活性明显提高,加热1 100 ℃的金红石样品7 h后可使亚甲基蓝的降解率达到90 4%。增加光照强度、加入适当的H2O2 都可提高降解效果。实验为充分开发利用天然金红石提出了新的途径,为环境污染治理提出了新方法。     

Anisotropic compression of edingtonite and thomsonite to 6 GPa at room temperature

Polycrystalline samples of natural edingtonite (New Brunswick, Canada) and thomsonite (Oregon, USA) were studied up to 6 GPa using monochromatic synchrotron X-ray powder diffraction and a diamond-anvil cell with a methanol:ethanol:water mixture as a penetrating pressure-transmitting fluid. Unlike natrolite, previously studied under the same conditions, edingtonite and thomsonite do not show any apparent pressure-induced hydration (PIH) or phase transitions. All these fibrous zeolites are characterized by their anisotropic compressibilities, with the linear compressibilities of the fibrous chains (c-axis) being as small as one third of those perpendicular to the chains (a-, b-axes); for edingtonite, ₀ ^a =0.0050(3) GPa^–1, ₀ ^b =0.0054(2) GPa^–1, ₀ ^c =0.0034(1) GPa^–1; for thomsonite, ₀ ^a = 0.0080(2) GPa^–1, ₀ ^b =0.0084(2) GPa^–1, ₀ ^c =0.0032(1) GPa^–1. The pressure–volume data were fitted to a second-order Birch–Murnaghan equation of state using a fixed pressure derivative of 4. As a result of the 0000-type connectivity of the chains, the bulk modulus of edingtonite is found to be about 40% larger than that of thomsonite; K^EDI ₀=73(3) GPa, K^THO ₀=52(1) GPa. Distance least-squares refinements were used to model the expected framework, following the observed linear compression behaviors. The chain-bridging T–O–T angle is proposed to be correlated with the different compressibilities across the chains in each framework type.     

The nonlinear anomalous lattice elasticity associated with the high-pressure phase transition in spodumene: a high-precision static compression study

The high-pressure behavior of the lattice elasticity of spodumene, LiAlSi₂O₆, was studied by static compression in a diamond-anvil cell up to 9.3 GPa. Investigations by means of single-crystal XRD and Raman spectroscopy within the hydrostatic limits of the pressure medium focus on the pressure ranges around ~3.2 and ~7.7 GPa, which have been reported previously to comprise two independent structural phase transitions. While our measurements confirm the well-established first-order C2/c–P2₁/c transformation at 3.19 GPa (with 1.2% volume discontinuity and a hysteresis between 0.02 and 0.06 GPa), both unit-cell dimensions and the spectral changes observed in high-pressure Raman spectra give no evidence for structural changes related to a second phase transition. Monoclinic lattice parameters and unit-cell volumes at in total 59 different pressure points have been used to re-calculate the lattice-related properties of spontaneous strain, volume strain, and the bulk moduli as a function of pressure across the transition. A modified Landau free energy expansion in terms of a one component order parameter has been developed and tested against these experimentally determined data. The Landau solution provides a much better reproduction of the observed anomalies than any equation-of-state fit to data sets truncated below and above P _tr, thus giving Landau parameters of K ₀ = 138.3(2) GPa, K′ = 7.46(5), λ _V  = 33.6(2) GPa, a = 0.486(3), b = −29.4(6) GPa and c = 551(11) GPa.     

受压煤岩破裂过程电磁辐射与能量转化规律研究

首先对煤岩单轴受压变形破裂过程产生的电磁辐射（EME）、声发射（AE）信号变化规律进行了试验研究,然后在试验测定结果的基础上分析研究了煤岩变形破裂电磁辐射与加载变形能量之间的转换关系。研究结果表明,EME值随着加载时间的增加而增强,声发射信号也呈现同样的规律;电磁辐射的幅值、脉冲数在煤岩主破裂前与应力基本成正相关的关系,出现峰值后降低,试验的各个样品均呈现此变化规律;电磁辐射能和机械能的转化曲线与煤岩单轴加载过程的应力-应变关系曲线是相对应的,且呈现三次多项式的关系。从能量转换的角度来研究煤岩变形破裂电磁辐射与应力之间的关系是可行的。     

南召泌阳金红石矿带金红石赋存规律

为了开发利用南召—泌阳金红石矿带的金红石,综合分析了以往资料,并在实地踏勘、样品测试和重点地段综合研究基础上,查明了各矿段金红石矿基本地质特征、金红石赋存状态、嵌布特征、粒度变化特征、金红石富矿体的主要赋存位置。区内粗粒易选富矿体位于矿带中段的左老庄组一段上部（北部）。采用以微生物提纯金红石粗精矿为标志的新工艺,取得了良好的选矿试验效果。刘岗矿区的1号和2号富矿体可作为进一步研究和开发利用的重点。     

High-pressure isosymmetrical phase transition in calaverite

Using density functional theory, we perform ab initio calculations of the behaviour of calaverite, AuTe₂, at high pressures. Calaverite has a distorted CdI₂ structure, that presents a pronounced two-dimensional character and a rather anisotropic response to pressure. Increasing the pressure, we predict an isosymmetrical phase transition between 55 and 60 GPa, that is accompanied by an important distortion of the structure, observed in all its geometrical parameters, especially the c lattice parameter. Relaxing the pressure, the reverse phase transition is observed between 30 and 25 GPa.     

紫外光及日光下天然金红石光催化降解苯酚的研究

研究了山西代县天然金红石在紫外光和日光照射条件下对苯酚的光催化降解性能,考察了光照时间、pH值、苯酚初始浓度以及H2O2添加量对降解过程的影响。在紫外光照射下,酸性条件(pH=3.5)利于光催化降解,中性和碱性条件下降解效率较低;当初始浓度为60mg/L时,降解速率可达1.922mg/(L.h);H2O2作为电子捕获剂可提高苯酚降解速率,最佳投加量为2mL/L。在日光条件下,天然金红石对苯酚表现出良好的降解性能,照射7h后,降解率达87.68%,仅略低于P25型TiO2(99.72%),可在14h内完全降解。根据电子探针和X射线衍射分析结果,认为天然金红石晶格中的V、Fe等杂质可能是提高其可见光响应效果和光催化活性的主要原因。     

Pressure-induced phase transition in synthetic trioctahedral Rb-mica

 The crystal structure of a synthetic Rb analog of tetra-ferri-annite (Rb–TFA) 1M with the composition Rb_0.99Fe²⁺ _3.03(Fe³⁺ _1.04 Si_2.96)O_10.0(OH)_2.0 was determined by the single-crystal X-ray diffraction method. The structure is homooctahedral (space group C2/m) with M1 and M2 occupied by divalent iron. Its unit cell is larger than that of the common potassium trioctahedral mica, and similar lateral dimensions of the tetrahedral and octahedral sheets allow a small tetrahedral rotation angle α=2.23(6)°. Structure refinements at 0.0001, 1.76, 2.81, 4.75, and 7.2 GPa indicate that in some respects the Rb–TFA behaves like all other micas when pressure increases: the octahedra are more compressible than the tetrahedra and the interlayer is four times more compressible than the 2:1 layer. However, there is a peculiar behavior of the tetrahedral rotation angle α: at lower pressures (0.0001, 1.76, 2.81 GPa), it has positive values that increase with pressure [from 2.23(6)° to 6.3(4)°] as in other micas, but negative values −7.5(5)° and −8.5(9)° appear at higher pressures, 4.75 and 7.2 GPa, respectively. This structural evidence, together with electrostatic energy calculations, shows that Rb–TFA has a Franzini A-type 2:1 layer up to at least 2.81 GPa that at higher pressure yields to a Franzini B-type layer, as shown by the refinements at 4.75 and 7.2 GPa. The inversion of the α angle is interpreted as a consequence of an isosymmetric displacive phase transition from A-type to B-type structure between 2.81 and 4.75 GPa. The compressibility of the Rb–TFA was also investigated by single-crystal X-ray diffraction up to a maximum pressure of 10 GPa. The lattice parameters reveal a sharp discontinuity between 3.36 and 3.84 GPa, which was associated with the phase transition from Franzini-A to Franzini-B structure. Received: 21 October 2002 / Accepted: 25 February 2003     

A room-temperature phase transition in maximum microcline

A type of hysteresis, similar to that observed in the heat capacity measurements (Openshaw et al., 1979), has been found in the room temperature unit cell parameters of a microcline sample 71104 and likewise indicates the existence of two forms of this microcline. The A-form (obtained on cooling the sample to approximately 80 K) has significantly different values of b, β and V to the B-form which is the more stable form above 300±10 K. The transition from the A- to the B-form occurs over a period of months and has an associated ΔV of ?0.0011 nm³. The cell parameters of the B-form have been measured up to 1278 K and show significant changes: a and V increase, b constracts, and c is unchanged on increasing temperature. The calculated thermal expansion ellipsoid is nearly uniaxial and similar in shape to that for sanidine. Below room temperature the isobaric thermal expansion coefficent α_p, for a natural microcline is nearly four times as large as that for sanidine. Above room temperature α_p for 71104 microcline decreases markedly with increasing temperature. This implies a rapid change in the thermal expansion behavior of microcline which has been correlated with the proposed phase transition.     

Polymorphic phase transition in Superhydrous Phase B

We synthesized superhydrous phase B (shy-B) at 22 GPa and two different temperatures: 1200°C (LT) and 1400°C (HT) using a multi-anvil apparatus. The samples were investigated by transmission electron microscopy (TEM), single crystal X-ray diffraction, Raman and IR spectroscopy. The IR spectra were collected on polycrystalline thin-films and single crystals using synchrotron radiation, as well as a conventional IR source at ambient conditions and in situ at various pressures (up to 15 GPa) and temperatures (down to −180°C). Our studies show that shy-B exists in two polymorphic forms. As expected from crystal chemistry, the LT polymorph crystallizes in a lower symmetry space group (Pnn2), whereas the HT polymorph assumes a higher symmetry space group (Pnnm). TEM shows that both modifications consist of nearly perfect crystals with almost no lattice defects or inclusions of additional phases. IR spectra taken on polycrystalline thin films exhibit just one symmetric OH band and 29 lattice modes for the HT polymorph in contrast to two intense but asymmetric OH stretching bands and at least 48 lattice modes for the LT sample. The IR spectra differ not only in the number of bands, but also in the response of the bands to changes in pressure. The pressure derivatives for the IR bands are higher for the HT polymorph indicating that the high symmetry form is more compressible than the low symmetry form. Polarized, low-temperature single-crystal IR spectra indicate that in the LT-polymorph extensive ordering occurs not only at the Mg sites but also at the hydrogen sites.     

Brittle failure of shale under uniaxial compression

Shale gas reservoirs are characterized by tight matrix, well-developed micro-fissures, and laminations. The study about the failure of shale under compression is of great significance to safe drilling operation and the subsequent reservoir stimulation. The variation of rock mechanical properties with the angle between the axial stress and bedding plane normal (coring angle) is analyzed based on laboratory tests. A failure criterion is applied and verified to describe the strength of shale. Moreover, ultrasonic technology is used to study the damage characteristics of shale during the uniaxial compression process. The experimental results show that shale strength decreases initially and then increases with the increase of the coring angle. The Young’s modulus and Poisson’s ratio increase with the increase of coring angle. In a compression process, damage is essentially the development of new micro-cracks induced by the compression. Shale failure is the microscopical reflection of the process of the generation and expansion of axial micro-cracks, so it is the result of damage accumulation. The variation of the lateral p wave velocity can function as a monitor of the development process of shale damage. The damage factor will increase in the linear elastic stage and then enlarge rapidly after entering the stage of unstable micro-crack expansion.     

The disproportionation of andalusite (Al2SiO5) to Al2O3 and SiO2 under shock compression

Shock-recovery experiments have been carried out on andalusite single crystals of gem quality in a pressure range from 300 up to 575 kbar. Infrared spectroscopic investigations indicate a progressive shock-induced transformation of andalusite into short-range-ordered Al₂O₃ and SiO₂ phases within a pressure interval from ～360 to ～575 kbar. Exposure to dynamic pressures of about 575 kbar results in andalusite breaking down into incoherently crystallized γ-Al₂O₃, well-crystallized α-Al₂O₃ and X-ray amorphous SiO₂. The shock disproportionation of andalusite is presumed to take place in three separate stages of reaction. The comparison of shock-induced reactions with results from static experiments on kyanite indicates significant differences in the transformation pressures and in the mechanism of the high pressure decomposition.     

岩石材料冲击压缩特性细观模拟方法研究

岩石材料的细观特性对宏观力学性能有着重要影响。为了分析岩石材料颗粒形态、孔隙和含水等细观特性对宏观冲击响应行为的影响规律,从岩石材料的细观特性入手,结合材料细观结构照片,经制图软件矢量化和轮廓处理,建立了能够反映材料细观分布特性的岩石材料有限元模型。基于AUTODYN有限元计算软件,对岩石材料冲击压缩细观行为进行数值模拟,获取材料颗粒形态、孔隙和含水等细观特性对材料宏观冲击压缩特性的影响规律。确定岩石材料冲击Hugoniot参数,应用于冲击开坑仿真中,并与已有的试验结果进行了对比。结果表明:数值仿真结果与已有试验数据吻合较好;孔隙率和含水率对岩石材料冲击波衰减规律有十分显著的影响;细观模拟确定的Hugoniot参数运用到岩石材料宏观动力学行为数值模拟中,可有效反映岩石材料中颗粒、孔隙和含水等细观特性对冲击开坑行为的影响规律。