Hydrogen in stishovite, with implications for mantle water content

Stishovite, the highest pressure polymorph of silicon dioxide, may be an important mineral in some regions of the Earth's mantle. Fourier transform infrared spectroscopy has been used to determine the hydrogen content of synthetic stishovite. The concentration of hydrogen depends on the aluminum content of the sample and reaches a maximum of 549 +/- 23 hydrogen atoms per 10(6) silicon atoms for an Al(2)O(3) content of 1.51 percent by weight. Stishovite could be a storage site for water in deep subducting slabs and in regions of the mantle that are too hot for hydrous minerals to be stable.     

Local structure and chemical shifts for six-coordinated silicon in high-pressure mantle phases

Most of the earth's mantle is made up of high-pressure silicate minerals that contain octahedrally coordinated silicon (Si(VI)), but many thermodynamically important details of cation site ordering remain unknown. Silicon-29 nuclear magnetic resonance (NMR) spectroscopy is potentially very useful for determining short-range structure. A systematic study of silicon-29 chemical shifts for Si(VI) has revealed empirical correlations between shift and structure that are useful in understanding several new calcium silicates. The observed ordering state of a number of high-pressure magnesium silicates is consistent with the results of previous x-ray diffraction studies.     

Pressure-induced landau-type transition in stishovite

A Rietveld structural analysis of stishovite, with angle-dispersive x-ray diffraction synchrotron source at the European Synchrotron Radiation Facility, confirmed a CaCl2 form of stishovite distortion at 54 +/- 1 gigapascals but confirmed no further phase transformation up to 120 gigapascals. The deviatoric stress that is usually encountered at such pressures was relaxed after yttrium-aluminum-garnet-laser heating. A single Birch-Murnaghan equation of state fits volumes of stishovite and a CaCl2 form, showing that the tetragonal distortion occurs without a substantial change in volume. At the 54-gigapascal transition, the pressure-induced lattice modifications were similar to those found in a Landau-type temperature-induced transition. It is proposed that, above the transition pressure, the critical temperature increases above 300 kelvin, so that the lower entropy form becomes stable.     

The Postspinel Phases in the Mg2SiO4-Fe2SiO4 System

Samples of olivine (Fo(0)Fa(100), Fo(60)Fa(40), Fo(80)Fa(20), and Fo(100)Fa(0)) and of spinel (Fo(50)Fa(50), Fo(2)Fa(100), where Fo is forsterite and Fa is fayalite) were subjected to pressures up to 250 kilobars in a diamond anvil press and were heated in situ up to ~ 1700 degrees C by an infrared beam from a continuous-wave YAG (yttrium-aluminum-garnet) laser. The brightness temperature was determined from the intensity of incandescence of the sample by means of an optical pyrometer. X-ray diffraction patterns of the samples, obtained after quenching and unloading, show conclusively that these compositions disproportionate to (Mg, Fe)O and SiO(s) (stishovite) under these conditions.     

5-coordinate si compounds as intermediates in the synthesis of silicates in nonaqueous media

Sodium silicoglycolate, an organosilicon compound in which silicon is in 5-coordination with respect to oxygen, is shown to be a reaction intermediate in the synthesis of a purely siliceous sodalite with ethylene glycol as solvent. The presence of silicon-29 nuclear magnetic resonances at -105.5 +/- 0.3 parts per million in solution and -102.7 parts per million in the solid state as well as x-ray powder diffraction patterns demonstrate that 5-coordinate silicon is intimately involved in the synthesis. Silicon compounds of the 5-coordinate type are highly reactive and are promising starting materials for the synthesis of novel silicone polymers, molecular sieves, glasses, semiconductors, and ceramics. We have used sodium silicoglycolate to prepare the molecular sieve silicalite as well as sodalites of different compositions.     

Coesite and Stishovite: Stepwise Reversal Transformations

Very marked differences in the metastable persistence of coesite and stishovite have been demonstrated; the former possibly persists indefinitely below 1000 degrees C at 1 atmosphere "dry," and the latter completely decomposes in minutes above 500 degrees to 600 degrees C to an amorphous or short range order phase. Quartz was grown (metastably) at temperatures well above its stability field from both coesite and stishovite, possibly by way of a short range order phase. The absence of stishovite in meteor-impact craters cannot be taken as evidence that it was not formed. If it has "reversed" in normal natural environments the product would almost certainly be a short range order phase or derivative.     

Shock effects in certain rock-forming minerals

Shock effects in quartz, plagioclase, biotite, amphibole, and some accessory minerals have been observed in rocks subjected to various degrees of meta morphism by meteoritic impact. The shock features described are unique; they are never observed in rocks from normal geologic environments. Such features are described: 1) Multiple sets of closely spaced planar microstructures occur in quartz, plagioclase, and other rock-forming minerals. Those characteristic of shock consist of alternating platelets, with a range of reduced mean index of re fraction and birefringence; they con sist of platelets that have been partially or completely transformed to an amor phous phase. 2) Quartz and plagioclase are selec tively and completely transformed to silica glass and plagioclase glass in the solid state, whereas the associated mafic minerals remained crystalline. There is no reaction between adjacent minerals. 3) High-pressure polymorphs occur, such as coesite or stishovite. Coesite oc Curs exclusively within silica glass; it has not been observed as a reaction or breakdown product. 4) Nickel-iron spherules occur in the fused glass or impactites. 5) The occurrence of droplets of ilmenite, rutile, pseudobrookite, and baddaleyite in impactites indicates a temperature of formation exceeding 150 degrees C. 6) Dense glass occurs, similar in composition to bulk rock, in which iron oxide, such as fine particles of mag netite, is completely dissolved. All these features are characteristic of a process involving the rapid rise and fall of extremiiely high pressures and temperatures. Minerals and mineral as semblages experiencing such high strain rates and sudden changes of pressures and temperatures react and change in dependently to the bulk chemical com position, under nonequilibrium condi tions. Many aspects of shock features re quire careful study. Kink bands in biotite and deformation lamellae in quartz occur in tectonically deformed rocks. These features should be studied with great care in order to determine whether reduction in mean index of refraction and total birefringence along the planar structures have resulted from vitrification or phase transition; their presence is additional evidence in favor of a shock mechanism. Vitreous phases or glasses formed by shock also have many unique prop erties; they have not been studied by such methods as thermoluminescence, electron spin resonance, low-angle x ray diffraction, or infrared spectroscopy. Shock-fused glass of high density needs to be studied in detail in carefully con trolled laboratory conditions. Experimental shock-wave studies of the equation-of-state of single minerals and mineral assemblages, under care fully controlled conditions, must pre cede estimates of peak pressures and peak and residual temperatures of shocked natural mineral assemblages. Detailed petrographic and mineralogic studies, however, have provided useful and definitive criteria for characteriza tion of impact events. Such data should be of paramount importance in the study of samples brought back from Moon.     

Compressibility, Phase Transitions, and Oxygen Migration in Zirconium Tungstate, ZrW2O8

In situ neutron diffraction experiments show that at pressures above 2 kilobars, cubic zirconium tungstate (ZrW2O8) undergoes a quenchable phase transition to an orthorhombic phase, the structure of which has been solved from powder diffraction data. This phase transition can be reversed by heating at 393 kelvin and 1 atmosphere and involves the migration of oxygen atoms in the lattice. The high-pressure phase shows negative thermal expansion from 20 to 300 kelvin. The relative thermal expansion and compressibilities of the cubic and orthorhombic forms can be explained in terms of the "cross-bracing" between polyhedra that occurs as a result of the phase transition.     

Zircon and chromite crystals in a muong nong-type tektite

Chromite, zircon, and quartz crystals (identified by x-ray diffraction) have been recovered from a 2.07-gram sample of Muong Nong-type tektite. The absence of eskolaite (Cr(2)O(3)) and baddeleyite (ZrO(2)) supports a previous conclusion that Muong Nong-type tektites were not heated as intensely as other tektite groups. X-ray asterism studies indicate that the crystals are shocked, which supports an impact origin. The presence of chromite and zircon together suggests that the Muong Nong-type tektite was produced from sedimentary material.     

青海不同产区大黄的X-射线衍射图谱研究（摘要）

[目的]为区分不同产地大黄药材的质量及鉴别提供依据。[方法]将供试材料青海玉树掌叶大黄（样品1）、青海海南唐古特大黄（样品2）与青海果洛唐古特大黄（样品3）分别粉碎成粉末,过100目筛,即可供X射线衍射试验用。设定管压30 kV,管流20 mA,2θ扫描范围3°～90°,扫描速度0.06°/s,每种样时间0.5 s,获得3种不同产区大黄的X-射线衍射图谱。试验数据以晶面间距d与特征峰相对强度L/Io表示,记为d/（I/Io）。将试验数据导入中药指纹图谱相似度计算软件,经选峰,设定匹配模板,将谱峰自动匹配,然后设定标准模板,进行谱峰差异性评价和整体相似性评价。[结果]样品1中所含的化学成分与样品2相同,但峰的强度（I/Io）不同,表明相同成分在两种样品中的含量不相等。同样把样品3的图谱与其他两个样品进行比较,也会得到相同的衍射峰值。表明不同产区的大黄中各化学成分的含量有差异,但其衍射图谱及衍射峰值具有一定的指纹特征。[结论]X-射线衍射法是鉴别不同产区的大黄及其他中药材的一种快捷有效的方法。     

采用变温X射线衍射技术对六方钛酸钡陶瓷材料的结构监控

对于由冷压陶瓷技术所开发的纯六方Ba（Ti0.95Fe0.05）O3-δ陶瓷，采用变温XRD技术测量该陶瓷在不同温度下的XRD谱，鉴定晶体结构．澄清了六方钛酸钡（BaTiO3）介电陶瓷材料的晶体结构是否在BaTiO3的居里温度（n=130℃）发生结构相变，并验证开发的变温X射线衍射（XRD）技术在无机粉体材料结构监控的可行性．结果表明：BaTiO3陶瓷在Tc发生四方-立方的结构相变，以45°附近两个分立的（002）／（200）衍射峰演变为单一对称的（200）衍射峰为标志；而六方Ba（Ti0.95Fe0.05）O3-δ陶瓷直到300℃都不发生结构相变．对于六方Ba（Ti0.95Fe0.05）O3-δ陶瓷，升高温度并不能导致吸附环境氧来填充氧空位，Fe3＋Vo-Fe3＋缺陷复合体所维持的晶格电中性仍占据统治地位，六方-立方结构相变不发生．该项研究为变温XRD技术在工业生产上对无机粉体材料的监控应用提供了技术依据．     

Closely Approaching the Silylium Ion (R3Si+)

The crystal structure of the tri-isopropyl silyl species, i-Pr(3)Si(Br(6)-CB(11)H(6)), where the brominated carborane Br(6)-CB(11) H(6)(-) is perhaps the least nucleophilic anion presently known, has revealed the highest degree of silylium cation character (R(3)Si(+)) yet observed. The average C-Si-C angle is 117 degrees , only 3 degrees short of the planarity expected of a pure silylium ion(120 degrees ). This value compares to 114 degrees recently reported for a toluene-solvated silyl cation, [Et(3)Si(toluene)](+) by Lambert and co-workers. The greater silylium ion character of i-Pr(3)Si(Br(6)-CB(11)H(6)) versus [i-Pr(3)Si(toluene)](+) is also reflected in the larger downfield shift of the silicon-29 nuclear magnetic resonance, 109.8 versus 相似文献   

A monoclinic post-stishovite polymorph of silica in the shergotty meteorite

A post-stishovite phase of silica was identified in the Shergotty meteorite by x-ray diffraction and field emission scanning electron microscopy. The diffraction pattern revealed a monoclinic lattice, similar to the baddeleyite-structured polymorph with the cell parameters a = 4.375(1) angstroms, b = 4.584(1) angstroms, c = 4. 708(1) angstroms, beta= 99.97(3), rho = 4.30(2) grams per cubic centimeter, where the numbers in parentheses are the maximum deviations. Transmission electron microscopy investigations indicate the presence of the alpha-lead dioxide-like polymorph, stishovite, and secondary cristobalite in the same silica grain. The mixture of high-density polymorphs suggests that several post-stishovite phases were formed during the shock event on the Shergotty parent body.     

Shocked quartz in the cretaceous-tertiary boundary clays: evidence for a global distribution

Shocked quartz grains displaying planar features were isolated from Cretaceous- Tertiary boundary clays at five sites in Europe, a core from the north-central Pacific Ocean, and a site in New Zealand. At all of these sites, the planar features in the shocked quartz can be indexed to rational crystallographic planes of the quartz lattice. The grains display streaking indicative of shock in x-ray diffraction photographs and also show reduced refractive indices. These characteristic features of shocked quartz at several sites worldwide confirm that an impact event at the Cretaceous-Tertiary boundary distributed ejecta products in an earth-girdling dust cloud, as postulated by the Alvarez impact hypothesis.     

Chemically induced fast solid-state transitions of omega-VOPO4 in vanadium phosphate catalysts

Vanadium phosphates are important catalysts for the oxidation of alkanes, and commercial catalysts comprise a complex range of V4+ and V5+ phosphates. We used three complementary in situ characterization methodologies-powder x-ray diffraction and laser Raman and electron paramagnetic resonance spectroscopies-to show that the metastable phase omega-VOPO4 is very sensitive to many of the reactants and products of butane oxidation. A rapid transformation from omega-VOPO4 to delta-VOPO4 occurs on exposure to butane at the reaction temperature, and hence the metastable omega-VOPO4 may play a role in the formation of commercial catalysts.     

中药材锁阳的X-射线衍射Fourier谱分析

本文采用粉末X-射线衍射法,首次对不同产地的锁阳样品进行了分析,获得了锁阳的标准X衍射Fourier谱及特征标记峰,为锁阳药材的鉴定提供了新的谱学分析依据。     

Macroscopic separation of dense fluid phase and liquid phase of phosphorus

Structural transformation between a dense molecular fluid and a polymeric liquid of phosphorus that occurred at about 1 gigapascal and 1000 degrees C was investigated by in situ x-ray radiography. When the low-pressure fluid was compressed, dark and round objects appeared in the radiograph. X-ray diffraction measurements confirmed that these objects were the highpressure liquid. The drops grew and eventually filled the sample space. Decompressing caused the reverse process. The macroscopic phase separation supported the existence of a first-order phase transition between two stable disordered phases besides the liquid-gas transition. X-ray absorption measurements revealed that the change in density at the transition corresponds to about 40% of the density of the high-pressure liquid.     

水分含量对玉米淀粉颗粒结晶度的影响

 应用X-射线衍射方法对不同水分含量的玉米淀粉颗粒的结晶度进行了研究。只有在玻璃态情况下,淀粉的无定型区域才产生X-射线衍射图样,衍射峰的强度、面积在某种程度上依赖于淀粉的含水量。玉米淀粉颗粒的X-射线衍射图形是由两部分组成的:微晶区域和无定型区域。随着水分含量的增加,样品的结晶度从小到大,并达到一个平衡值(约45%)。室温下,当水分含量处于低水平时(小于11.25%),玉米淀粉颗粒中的无定型区域处于玻璃态,衍射图形显示的是微晶区域和无定型区域两部分的衍射图形的综合。当水分含量处于较高水平时(大于18.55%),淀粉颗粒中的无定型区域处于橡胶态,其X-射线衍射图形仅由微晶区域形成。在较低水分含量时(小于18.55%),由于塑化作用的影响,增大含水量会导致更多的微晶的形成。当水分含量超过18.55%之后,再增大水分,就会导致微晶片层和剩余的无定型片层的同时分解。     

微波对板栗淀粉α度和结晶度的影响

采用X-射线衍射法、酶水解法就微波辐射对不同质量分数的板栗淀粉乳的α度及结晶度变化进行了研究.结果表明,微波辐射可有效影响板栗淀粉乳的α度和结晶度变化,在微波辐射功率一定的条件下,板栗淀粉乳的质量分数不同,经微波辐射后的样品α度和结晶度变化也不同,板栗淀粉乳的质量分数与经微波辐射后的样品α度呈负相关,与经微波辐射后样品的X-射线衍射图谱的结晶峰面积及样品的结晶度呈正相关.     

中药材半夏的X射线衍射Fourier指纹图谱分析

[目的]建立中药材半夏的鉴定分析新方法。[方法]采用X射线衍射Fourier指纹图谱法获取中药材半夏的微观衍射图形及相应衍射特征标记峰,分析不同种半夏样品鉴别、炮制品与原药材的差异以及相关组分含量的差异,实现对常用中药材的微观鉴定分析。[结果]对12个半夏药材及其炮制品样品进行试验,获得了半夏的对照X射线衍射Fourier指纹图谱及特征标记峰值,依次将其分为药材半夏、水半夏及其炮制品法半夏、清半夏、姜半夏5个组,将中药材质量标准化从宏观等性状显微定性鉴别推向以图形数据表征的可重复的微观信息。[结论]X射线衍射Fourier指纹图谱法可用于中药材半夏的鉴定。