Deformation of experimentally shock-loaded quartz powders: X-ray line broadening studies

Quartz powders (mean grain size: 22 μm) were pressed into sample discs of different green densities (ρ₀=1.65; 1.85 and 2.05 g/cm³) and subjected to shock pressure between 1.5 and 17.0 GPa. Peak shock pressures were determined by the impedance method using the Hugoniot curves of steel and quartz powders. Fourier techniques were used to analyse the line broadening of 5 X-ray reflections in each case. The Fourier coefficients were subjected to a Rothman-Cohen correction before further processing. The coherent domain size decreases abruptly from several thousand Ångström in the unshocked state to about 800 Å at 1.5 GPa, and reaches a constant mean value of about 200 to 300 Å at dynamic pressures of about 4 GPa. At very high dynamic pressures (?15 GPa) there is further fragmentation to very small domain size. There is no systematic correlation between sample density and coherent domain size produced by the shock event. A more or less linear dependency exists between microstrain and pressure for each starting density of the quartz powder. The observation that microstrain decreases with increasing starting density could be explained by the fact that increasingly larger portions of the input energy are consumed to create fresh surfaces by comminution. Consequently, less energy will be available for strain strengthening. The stored energies in the shocked quartz powders are of the same order as the surface energy. Shock-treated quartz should therefore be suitable for accelerating any activated process such as sintering.     

Deformation and transformation in experimentally shock-loaded quartz

Single crystals of quartz, shock-loaded along the a axis to pressures of 22 Gpa, 24 GPa, 26 GPa and 30 GPa were examined by high-voltage transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray diffraction. Asymmetric broadenings of X-ray lines indicate spatial inhomogeneity of shock effects. X-ray streaking angles in the reciprocal lattice planes h0 \(\bar h\) l, 0k \(\bar k\) l and hki0 indicate a slight tilting deformation by rotation about [00.1] in (0001). TEM reveals glass lamellae which are mostly in (01 \(\bar 1\) 2) orientation, and are correlated with optical planar elements and with surface steps seen in SEM. No dislocations are found. There are (0001) lamellar features, probably Brazil twins. The (01 \(\bar 1\) 2) glass lamellae develop directly from bands of quartz in which intense deformation has produced a fine-scale lamellar to blocky structure, possibly also originating by twinning. Relics of crystalline structure are found in almost completely vitrified lamellae. Stishovite occurs in heavily deformed parts of the 22 GPa and 24 GPa specimens, in patches of densified glass distinct from the sharply bounded lamellae. The nucleationless, pervasive transformation of lamellae to glass, with preservation of their sharp boundaries, is attributed to defect coalescence analogous to vitrification by radiation damage (metamictization). Some patchy glass may be due to melting.     

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.     

An X-ray photoelectron spectroscopic study of shock-loaded quartz

X-ray photoelectron spectra (XPS) for the Si 2p and O 1s signals of quartz recovered after shock-loading at pressures up to 55 GPa revealed the presence of stishovite in the pressure region between 10 and 34 GPa. The stishovite binding energy for both the Si 2p and O 1s is found to be independent of the shock stress level from which it is recovered. Moreover, the binding energy values obtained from 0.5 mm thick samples shocked in the laboratory for times of ca. 1 μs are equal, within experimental uncertainty, to stishovite produced by the Ries impact event. Variations of binding energies observed for the other phases (residual quartz and glass formed simultaneously with or by decomposition of stishovite) are discussed in the framework of previous results obtained by other methods such as X-ray diffraction and infrared spectroscopy. Although unequivocal interpretation of the variation in binding energy with exposure to different shock pressure is not always possible, the XPS method proves to be very well suited for recognition of high pressure phases and for distinction of pressure regions dominated by various shock or post-shock events.     

Deformation twinning and residual stress in calcite studied with synchrotron polychromatic X-ray microdiffraction

Microstructures of deformed calcite in marble from the Bergell Alps are studied by using a microfocused polychromatic synchrotron X-ray beam. The high spatial resolution, together with orientation and strain resolutions, reveals twin plane orientation, multiple twin lamellae, and strain distributions associated with the twins. Single and multiple mechanical twins on e = { 01[`1] 8 } e = \left\{ {01\overline{1} 8} \right\} systems are confirmed. Residual stresses are derived from the strain tensor that is derived from Laue diffraction patterns. Average lattice strains from several hundred to over one thousand microstrains are detected in a deformed marble from the Bergell Alps. Such strains suggest 60–120 MPa residual stresses. A detailed study of strain components shows that shear stresses on twin planes are completely released.     

Evolution of mineral–fluid interfaces studied at pressure with synchrotron X-ray techniques

In situ measurements of mineral surface evolution during the process of pressure solution are possible with the high brightness of synchrotron X-ray sources. This capability has been explored through the use of newly developed reaction vessels that allow transmission of the incident and scattered X-ray beam through a low atomic weight piston. Several new vessels are described, along with details of computational algorithms that are used to simulate X-ray scattering in this unconventional geometry. Results using calcite (CaCO₃) and halite (NaCl) as reactant crystals are presented and compared to other atomic-scale measurements of surface dissolution processes. Calcite was reacted with an unsaturated fluid at 30 bars of pressure for approximately 24 h. During reaction the root mean square surface roughness (σ) evolved from 13.7 Å (± 0.5 Å) to 19.5 Å (± 1.0 Å), giving a roughening rate of: dσ/dt = +6.3 × 10^− 5 Å s^− 1. This is consistent with other measurements made with free calcite surfaces and is driven almost entirely by chemical disequilibrium. Analysis of the surface ex situ post-reaction gives an identical σ value, showing that the in situ measurements are well-constrained. Experiments also at 30 bars but in a saturated solution indicate that the calcite surface does not significantly roughen, giving the result that pressure solution of calcite at this pressure cannot be monitored in experiments of several days duration. Experiments with halite, a much more reactive phase, in saturated solutions showed the reflectivity profile to be dynamic on a time scale of hours. This experiment was left to reach equilibrium over 108 days and then re-analyzed, showing that σ had increased from 34 Å (± 2 Å) to 41 Å (± 2 Å), giving a roughening rate of: dσ/dt ≤ +6.4 × 10^− 7 Å s^− 1. This is two orders of magnitude smaller than the calcite roughening rate caused by chemical disequilibrium and provides the first direct in situ atomic-scale measurement of the rate of surface roughening due to pressure solution.     

Graphitization of Korean anthracites as studied by transmission electron microscopy and X-ray diffraction

The different modes of high-resolution transmission electron microscopy (TEM) were applied to Korean anthracites, semi-graphites and graphites. Whereas X-ray diffraction data yield averaged values, TEM is the only technique able to bring out the heterogeneity of phases which are different in morphology and in microtexture. The thermal behavior of samples was studied using laboratory heat-treatments up to 2800°C. In heat-treated anthracites for example, an increasing degree of graphitization results in phase changes which can be quantified by TEM. The study of a larger sampling appears however necessary to relate crystallographic variations to geological data.     

X—ray Powder Diffraction Characterization of Pyrope

I332／I422，the intensity ratio of powder diffraction,is highly sensitive to variations in garnet compositon and can be taken as an identification criterion for pyrope:I332/I422-1 for pyrope while it is much smaller than unit for other members of the garnet group.     

Thermoluminescence of shock-loaded amethyst quartz

In natural amethyst samples subjected to shock pressures between 10 and 50 GPa (1 GPa=10⁹ Pa), thermoluminescence (TL) was observed after subsequent X-ray irradiation, in some cases even without high energy irradiation. The glow curves could be decomposed into at most five components of Gaussian shape, but no reliable activation energies could be determined from them, perhaps due to a wide distribution of trap depths. With increasing shock pressures traps of higher thermal stability were favored. Emission bands with maxima near 14000 cm^?1 were observed independent of shock pressure. They appear to be characteristic of defects created during the shock events, but it is uncertain whether the observed TL is connected with the iron impurities characteristic for amethyst. In natural amethyst samples of the same origin no TL could be observed, even after additional X-ray irradiation. It is concluded that TL in amethysts reported in the literature was actually caused by defects associated with aluminium impurities, not by destruction of Fe⁴⁺.     

田黄的X射线衍射研究

用X射线衍射分析的方法测定了12个田黄样品,其中,青田石1个,寿山石9个,昌化田黄石2个。确定青田石由叶蜡石(58%)、绢云母(36.1%)和高岭石(5.9%)组成;昌化田黄石由迪开石组成;寿山石分别由迪开石、高岭石、叶蜡石及绢云母组成。     

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。     

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。     

X-ray diffraction study of arsenopyrite at high pressure

The high-pressure X-ray diffraction study of a natural arsenopyrite was investigated up to 28.2 GPa using in situ angle-dispersive X-ray diffraction and a diamond anvil cell at National Synchrotron Light Source, Brookhaven National Laboratory. The 16:3:1 methanol–ethanol–water mixture was used as a pressure-transmitting medium. Pressures were measured using the ruby-fluorescence method. No phase change has been observed up to 28.2 GPa. The isothermal equation of state (EOS) was determined. The values of K ₀, and K′ ₀ refined with a third-order Birch–Murnaghan EOS are K ₀ = 123(9) GPa, and K′ ₀ = 5.2(8). Furthermore, we confirm that the linear compressibilities (β) along a, b and c directions of arsenopyrite is elastically isotropic (β _a  = 6.82 × 10⁻⁴, β _b  = 6.17 × 10⁻⁴ and β _c  = 6.57 × 10⁻⁴ GPa⁻¹).     

十字石的原位高压X射线衍射研究

利用原位高压同步辐射能量色散X射线衍射技术,在室温下对采自新疆阿尔泰地区冲乎尔递增变质带的天然十字石进行高压晶体结构测定,测量的压力范围为0.0001~3.9GPa,共11组有效数据。实验表明,在实验压力范围内,随着压力的增加晶胞参数β值逐渐增大,表明了十字石的结构对称性随压力增加而有所降低;同时,在1.5~2.7GPa压力范围内,十字石的晶体结构也发生了改变。     

Phase transitions in leucite: X-ray diffraction studies

Lattice parameters, and intensities of selected X-ray reflexions, have been measured as a function of temperature for natural leucite, to characterise the phase transformation behaviour. At low temperatures leucite has a large ferroelastic distortion, but the temperature evolution of lattice parameters cannot be explained in terms of a purely ferroelastic phase transition; in particular, the considerable change in volume with temperature implies an additional transition mechanism, which we correlate with off-centring of K-ions in the low-temperature phase, and a collapse of the 111 structural channels. The transition behavior can therefore be rationalised in terms of two competing mechanisms: (I) Ferroelastic (consistent with the change m3m 4/mmm); (II) Volume-changing (consistent with m3m 4/m). Coupling of the two order parameters Q_I, and Q_II gives rise to the intermediate 4/mmm tetragonal phase.Our results confirm the existence of an I4 ₁/aI4 ₁/acd transition, but the non-disappearance of the 200 reflexion at high temperatures implies that the expected transition from I4₁/acd to Ia3d (cubic) symmetry does not occur. We attribute this to a residual strain field conjugated to the order parameter, due to defects (with possible Al/Si order). Nevertheless, within our experimental resolution, the lattice becomes metrically cubic at 665° C.     

微区X射线衍射在矿物鉴定中的应用实例

介绍了微区X射线衍射仪发展的现状,给出了微区X射线衍射仪鉴定物相的研究实例,并讨论了微区X射线衍射法的优、缺点。通过配置有封闭3kWX射线光管、单毛细管透镜、Pixcel探测器和普通CCD视频的Panalytical X’Pert PRO MPDX射线衍射仪,对光片上的铍矿物进行了微区X射线衍射鉴定,结果确定该铍矿物为羟硅铍石。微区X射线衍射法具有微区、微量、原位和无损等优点,能够进行直径在100～300μm范围内的两种或两种以上矿物集合体的物相鉴定。与电子探针等微区手段相互结合、互相补充,鉴定结果更加可靠。     

X-ray diffraction studies of millerite NiS under non-ambient conditions

The high-pressure behaviour of millerite NiS up to 34.7 GPa was studied using single-crystal X-ray diffraction techniques. Under ambient pressure, 8.3, 19.2 and 26.8 GPa crystal-structure determinations were performed. No phase transition was observed and the fit of the Birch-Murnaghan equation of state gave a bulk modulus K=111(1) GPa and a pressure derivative K=5.0(1) at high pressure and room temperature. The high-temperature modification of NiS belongs to the NiAs type and has the smaller volume per formula unit. High-pressure–high-temperature X-ray diffraction studies on NiS powder indicate that the transition temperature is strongly dependent on pressure. Owing to the higher compressibility of millerite compared with that of the high-temperature phase, it is assumed that the NiAs-type is not the stable phase at high pressures.     

High-pressure single-crystal X-ray diffraction study of jadeite and kosmochlor

The crystal structures of natural jadeite, NaAlSi₂O₆, and synthetic kosmochlor, NaCrSi₂O₆, were studied at room temperature, under hydrostatic conditions, up to pressures of 30.4 (1) and 40.2 (1) GPa, respectively, using single-crystal synchrotron X-ray diffraction. Pressure–volume data have been fit to a third-order Birch–Murnaghan equation of state yielding V ₀ = 402.5 (4) Å³, K ₀ = 136 (3) GPa, and K ₀ ^′  = 3.3 (2) for jadeite and V ₀ = 420.0 (3) Å³, K ₀ = 123 (2) GPa and K ₀ ^′  = 3.61 (9) for kosmochlor. Both phases exhibit anisotropic compression with unit-strain axial ratios of 1.00:1.95:2.09 for jadeite at 30.4 (1) GPa and 1:00:2.15:2.43 for kosmochlor at 40.2 (1) GPa. Analysis of procrystal electron density distribution shows that the coordination of Na changes from 6 to 8 between 9.28 (Origlieri et al. in Am Mineral 88:1025–1032, 2003) and 18.5 (1) GPa in kosmochlor, which is also marked by a decrease in unit-strain anisotropy. Na in jadeite remains six-coordinated at 21.5 (1) GPa. Structure refinements indicate a change in the compression mechanism of kosmochlor at about 31 GPa in both the kinking of SiO₄ tetrahedral chains and rate of tetrahedral compression. Below 31 GPa, the O3–O3–O3 chain extension angle and Si tetrahedral volume in kosmochlor decrease linearly with pressure, whereas above 31 GPa the kinking ceases and the rate of Si tetrahedral compression increases by greater than a factor of two. No evidence of phase transitions was observed over the studied pressure ranges.     

赤铁矿高温原位X射线衍射研究

在空气和真空条件下对α-Fe_2O_3粉末进行了从室温到1 000℃的高温原位X射线衍射研究,分别修正了空气和真空条件下赤铁矿在27~1 000℃范围内的晶胞参数,从而得到了晶胞参数随温度变化的关系和赤铁矿在空气和真空条件下的热膨胀系数,并得出了热膨胀系数与温度的关系,即赤铁矿的热膨胀系数不随温度变化。赤铁矿在空气气氛下的热膨胀系数为αa=9.603 16×10~(-6)/℃,αc=6.647 67×10~(-6)/℃,β=2.606 33/℃;真空气氛下的热膨胀系数为αa=9.006 79×10~(-6)/℃,αc=6.891 23×10~(-6)/℃,β=2.511 51/℃。