滑石瓷相变及老化机理的探讨

滑石在加热过程中,当由层状结构转变为单链状结构的辉石时,可有三个晶相:原顽辉石、顽辉石和斜顽辉石。而在正常的滑石瓷中本文认为是以原顽辉石为主晶相。滑石瓷的老化现象主要是由于原顽辉石向斜顽辉石转变的结果,在转变的过程中因体积的收缩而产生内应力以改造成瓷坯的粉化和开裂。本文研究了原顽辉石和斜顽辉石的晶体结     

四川新康风化淋滤型海泡石的热相变研究

以四川新康风化淋滤型海泡石为研究对象，利用X射线衍射分析和红外光谱分析技术，对海泡石的热相变过程及特征进行了研究。结果发现，四川新康风化淋滤型海泡石的相变过程与沉积型、热液型海泡石相变过程明显不同，其相变过程可以划分为两个阶段：800℃以下保持海泡石相；800℃以上海泡石相转化为斜顽辉石相。     

海泡石相变的粉晶 X 射线衍射研究

摘 要　 利用粉晶 X 射线衍射分析方法‚研究了海泡石在热处理过程中的相变特征。研究发 现‚海泡石在受热后将向滑石转变‚并可分为4个阶段：室温～200℃‚为海泡石相;300～ 700℃‚为向滑石转化的过渡相;800～900℃‚为混合相;900～1000℃‚为顽火辉石相。     

安徽嘉山坡缕石加热相变的研究

研究样品产于安徽嘉山县的第三系沉积型粘土矿层。样品经分离提纯后分别加热,对不同温度的样品进行X射线衍射和红外光谱分析,结合坡缕石的热分析资料的综合研究,证明坡缕石的热相变过程为:200℃前脱失沸石水,对晶体结构没有影响;200—400℃配位水渐次脱失,晶体发生“折叠作用”,为无水坡缕石阶段;400-500℃时大部分羟基脱失,坡缕石结构随羟基脱失逐渐瓦解;700—800℃出现短暂的玻璃相,接着在800—900℃先后重结晶为顽火辉石和方英石。在高温结晶相中未发现硅线石。     

四川石棉蛇纹石猫眼热相变的Raman光谱和XRD研究

采用Raman光谱和X射线粉晶衍射(XRD)方法对四川蛇纹石猫眼的热相变过程和产物进行的研究表明,蛇纹石猫眼热相变的最终产物为镁橄榄石和顽火辉石。加热到500℃,蛇纹石猫眼的结构稳定;700℃,时,镁橄榄石的拉曼特征峰824cm^-1和854cm^-1出现,同时出现非晶质顽火辉石686cm^-1和341cm^-1附近的包络峰;800～900℃时,镁橄榄石的含量和结晶程度增强。晶质顽火辉石相出现,但强度较弱。1000℃时,镁橄榄石的含量明显降低。1100℃时,顽火辉石的含量和结晶程度显著增加。     

热处理电气石的物相转变

通过差热分析（DTA）、热处理和X射线衍射分析（XRD）等手段，研究我国西北某地区产的黑色电气石在热处理过程中的相转变过程，实验发现850℃热处理2h，电气石晶体结构的[Si6O18]复三方环和[BO3]三角结构已开始破坏，并出现新的物相－莫来石（Al2.35Si0.64O4.82)，铝硼氧化物（Al5BO9)和赤铁矿（Fe2O3)；890℃时，电气石分解形成的莫来石（Al2.35Si0.63O4.82)和赤铁矿（Fe2O3)量增加，并有新物相（Al2O3)9。97(B2O3)1.99形成；1010℃时，莫来石合成体系的Si、Al和O的原子个数比发生了变化（Al4.868Si1.132O9.566)，出现矽线石（Al2SiO5)、镁橄榄石（Mg2SiO4)、顽辉石（Mg(SiO)3)和镁铝硅硼酸盐（Mg2Al4Si4B4O37)等新物相。     

几种X射线物相定量分析法简介

本文介绍了以下几种X射线物相定量分析法:单相外标法,L.S.Zcvin无标定量法,复相X射线物相定量分析中两种改进的外标法,浓度稀释物相定量法。同时进行了种方法适用条件的讨论。这几种方法的应用,从不同角度完善了X射线物相定量分析工作。     

丁青和新喀里多尼亚玻安岩类的辉石及其超微结构

本文对西藏丁青玻安岩类深成岩的辉石和新喀里多尼亚玻安岩的斜顽辉石进行了矿物学工作及高分辨电镜观察。丁青斜方辉石堆晶岩辉石的超微结构包括:单斜辉石的(100)双晶、斜方辉石a/4平移畴结构及斜方辉石—单斜辉石相转变。玻安岩斜顽辉石典型超微结构是(100)双晶。由矿物的碎裂、错动以及斜方辉石—单斜辉石相变中只出现偶数倍单斜辉石等表明:矿物结晶及成岩过程中曾受应力作用、后者可能与岩石所处的构造位置有关。由辉石成分计算的地质温度表明,丁青堆晶斜方辉石岩的辉石是在高温下晶出、岩石固结温度是1013～1111℃,当它们在～1000℃下稳定时,斜方辉石出溶了单斜辉石片晶。将玻安岩斜顽辉石加热至1100℃后淬冷及按120℃/h速度冷却均未得到纯的斜顽辉石,可能斜顽辉石是原顽火辉石在应力环境中高温淬冷所成。     

X射线衍射-X射线荧光光谱-电子探针等分析测试技术在玄武岩矿物鉴定中的应用

玄武岩的鉴定通常采用显微镜镜下判定,鉴定结果容易受到鉴定人员的专业水平和主观因素、切片方位的影响,光性特征有差异,再者颗粒细小的矿物还受到光学显微镜本身放大倍数的限制也很难准确鉴定。当前的鉴定方法已由传统的显微镜向现代分析仪器(X射线衍射仪、电子探针、X射线荧光光谱仪等)综合研究方向发展。本文采用X射线粉晶衍射(XRD)和显微镜镜下观测相结合的方法,对安徽女山玄武岩(未经蚀变)和团山玄武岩(经过蚀变)进行鉴定,并采用X射线荧光光谱仪(XRF)和电子探针对鉴定结果进行验证。结果表明:女山玄武岩用显微镜鉴定主要由基质(74%,斜长石44%+辉石30%)和斑晶(13%)组成,还含有少量金属矿物(8%)及较大颗粒石英捕掳晶(5%);其中,基质部分的斜长石经XRD分析可进一步确定为拉长石,辉石主要为普通辉石(单斜辉石),少量金属矿物为钛铁矿。团山玄武岩用显微镜鉴定主要由基质(75%,斜长石50%+辉石25%)和斑晶(9%)组成,还含有少量绿泥石充填的杏仁体;其中,基质部分的斜长石经XRD分析可进一步确定为微斜长石,蚀变矿物为蒙脱石而非薄片鉴定中的绿泥石。综合XRD和相关技术鉴定结果可确定,女山玄武岩主要矿物为拉长石、辉石、钛铁矿;团山玄武岩主要矿物为微斜长石、辉石、蒙脱石。研究显示,单独的显微鉴定技术在含蚀变矿物的玄武岩鉴定中会产生较大偏差,而结合XRD等多种分析测定技术可以快速鉴定出矿物种类,尤其对颗粒较小的矿物鉴定的准确度更高。     

辽宁岫岩叶蛇纹石热处理产物的矿物学特征

对辽宁岫岩叶蛇纹石进行了热活化处理，通过差热—热重分析(DTA—TG)、X射线粉晶衍射分析(XRD)、红外光谱分析(IR)和扫描电镜分析(SEM)，发现热活化温度达到500℃时，叶蛇纹石八面体片中的羟基开始显著脱失，并出现镁橄榄石新物相，但仍然保持层的结构；当温度达到550℃时，叶蛇纹石的层状结构被完全破坏；温度升高到650℃时，镁橄榄石结晶度增高，并出现顽火辉石新物相；当温度达到1050℃时，镁橄榄石的含量略有减少，并出现较多的晶质顽火辉石物相。     

锡石的原位高压X射线衍射研究

利用同步辐射能量色散X射线衍射(EDXD)方法和金刚石对顶砧(DAC)高压技术对采于四川平武的锡石进行原位高压(达24.0 GPa)结构研究发现:压力加载过程中,锡石在13.8 GPa时发生了从金红石型结构(P 42/m nm)到C aC l2型结构(P nnm)的位移式相变;在19.9 GPa时又由C aC l2型结构相变为黄铁矿型结构(P a3),此相变为重构式相变。对于第Ⅳ主族元素氧化物(S iO2,G eO2,SnO2和PbO2)及过渡金属氧化物(M nO2和R uO2)的高压行为进行了讨论,它们具有相似的高压相变序列,这些成果对与斯石英同构氧化物的高压行为研究提供了有价值的参考。     

X射线粉晶衍射基体清洗法在矿物定量分析中的应用

为了消除层状硅酸盐矿物择优取向对检测结果的影响,本次X射线粉晶衍射定量分析采用基体清洗法,引入刚玉作为清洗剂,用滑石和绿泥石纯样品分别与刚玉以1：1的比例配制成参比样,测试参比样中刚玉、滑石、绿泥石的主衍射峰强度值,根据参比强度公式计算出滑石、绿泥石的参比强度.再把刚玉与定值样（滑石和绿泥石混合样）按1：1的比例配制成待测样,测试待测样中刚玉、滑石、绿泥石的主衍射峰强度值,把所得数据代入基体清洗法计算公式,剔除离散数据,计算出定值样中滑石的含量为81.5%,绿泥石的含量为14.6%;用EVA全谱拟合矿物半定量分析方法测试定值样中滑石的含量为92.9%,绿泥石的含量为5.8%.通过定值样中全岩化学分析铝元素含量换算,定值样中绿泥石的含量应在13%左右,接近基体清洗法的绿泥石矿物定值,与EVA全谱拟合矿物半定量分析方法绿泥石矿物定值相差较大.实验结果表明：利用基体冲洗分析混合物相中层状硅酸盐矿物含量是比较准确的.     

应用X射线衍射-红外光谱等技术研究滑石在机械力研磨中的形貌和晶体结构变化及影响机制

滑石的颗粒粒径、形貌、晶型等对其应用的实效性、终端产品的性能产生极大影响,目前主要研究其表面改性,而有关微观形貌及晶体结构研究较少。本文利用X射线荧光光谱、X射线衍射分析、红外光谱、粒度分析仪结合高分辨场发射扫描电镜(FE-SEM)技术对辽宁滑石粉在高强度机械力研磨作用下的微形貌和晶体结构变化特征进行系统研究。结果表明滑石粉原矿混合物中MgO与SiO2的分子个数比约为0.45,该数值明显低于纯滑石粉晶体中MgO与SiO2的分子个数比0.75。此类滑石为典型的单斜晶系,研磨作用使滑石粉由晶态转变为非晶态结构,其层状结构的有序化和键合作用发生了明显的变化。滑石粒度随研磨时间变化呈现减小-增大-减小的循环过程。研磨后粉体形貌存在差异,细化的小颗粒粉体因团聚而呈"准球体",且随着研磨的进行出现细化-团聚-细化的反复过程。此结论对于滑石的深加工与应用及其相关矿物粉体的研究具有一定的参考价值。     

X射线粉晶衍射仪在辽宁瓦房店金伯利岩蚀变矿物鉴定中的应用

瓦房店金伯利岩热液蚀变强烈,原岩矿物组分几乎蚀变殆尽,显微镜下对蚀变矿物鉴定相当困难.利用X射线粉晶衍射技术对蚀变金伯利岩物相进行系统检测,结果显示：42号岩管金伯利岩主要矿物为蛇纹石、金云母和滑石,有少量方解石、锐钛矿、磷灰石、石英、钛铁矿、钙钛矿、榍石、磁铁矿和绿泥石;石灰窑1号无矿金伯利岩岩管主要矿物为蛇纹石、金云母和白云石,有少量方解石、锐钛矿、磷灰石、滑石、磁铁矿和绿泥石;9号无矿金伯利岩岩脉主要矿物为方解石和石英,有少量绿泥石和重晶石;51号贫矿金伯利岩岩管主要矿物为蛇纹石和金云母,方解石化作用不均匀,白云石化作用普遍,有少量锐钛矿、滑石、磁铁矿、绿泥石、磷灰石、钛铁矿、石英;30号贫矿岩管样品风化严重,主要矿物为蒙脱石,有少量方解石、滑石、蛇纹石、榍石、磷灰石.实践证明,采用X射线粉晶衍射仪鉴定金伯利岩蚀变矿物组合是一种非常可行的技术手段.     

Phase diagram and thermodynamic properties of AIPO<Subscript>4</Subscript> based on first-principles calculations and the quasiharmonic approximation

We calculated the phase diagram of \(\hbox {AlPO}_{4}\) up to 15 GPa and 2,000 K and investigated the thermodynamic properties of the high-pressure phases. The investigated phases include the berlinite, moganite-like, \(\hbox {AlVO}_{4},\, P2_1/c\), and \(\hbox {CrVO}_{4}\) phases. The computational methods used include density functional theory, density functional perturbation theory, and the quasiharmonic approximation. The investigated thermodynamic properties include the thermal equation of state, isothermal bulk modulus, thermal expansivity, and heat capacity. With increasing pressure, the ambient phase berlinite transforms to the moganite-like phase, and then to the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases, and further to the \(\hbox {CrVO}_{4}\) phase. The stability fields of the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases are similar in pressure but different in temperature, as the \(\hbox {AlVO}_{4}\) phase is stable at low temperatures, whereas the \(P2_1/c\) phase is stable at high temperatures. All of the phase relationships agree well with those obtained by quench experiments, and they support the stabilities of the moganite-like, \(\hbox {AlVO}_{4}\), and \(P2_1/c\) phases, which were not observed in room-temperature compression experiments.     

The role of Al in the formation of secondary Ni precipitates on pyrophyllite,gibbsite, talc,and amorphous silica: a DRS study

Formation of secondary Ni precipitates is an important mechanism of Ni retention in neutral and alkaline clay/water systems. However, the structure and composition of these secondary phases, and their stability is still disputable. Using existing structure refinement data and new ab-initio FEFF 7 calculations we show that Ni-edge X-ray absorption fine structure spectroscopy alone may not be able to unequivocally discriminate four possible candidate compounds: α-Ni(OH)₂, the isostructural but Al-substituted layered double hydroxide (Ni-Al LDH), and 1:1 and 2:1 Ni-containing phyllosilicates. Hence, we investigated the potential of diffuse reflectance spectroscopy (DRS) in determining in situ the Ni phase forming in the presence of four sorbents, pyrophyllite, talc, gibbsite, and amorphous silica. The ³A_2g → ³T_1g(F) band (ν2) of octahedrally coordinated Ni²⁺ could be reliably extracted from the reflectance spectra of wet pastes. In the presence of the Al-free talc and amorphous silica, the ν2 band was at ≈14,900 cm⁻¹, but shifted to 15,300 cm⁻¹ in the presence of Al-containing pyrophyllite and gibbsite. This shift suggests that Al is dissolved from the sorbent and substitutes for Ni in brucite-like hydroxide layers of the newly forming precipitate phase, causing a decrease of the Ni-O distances and, in turn, an increase of the crystal-field splitting energy. Comparison with Ni model compounds showed that the band at 14,900 cm⁻¹ is a unique fingerprint of α-Ni(OH)₂, and the band at 15,300 cm⁻¹ of Ni-Al LDH. Although the complete transformation of α-Ni(OH)₂ into a Ni phyllosilicate causes a significant contraction of the Ni hydroxide sheet as indicated by band positions intermediate to those of α-Ni(OH)₂ and Ni-Al LDH, incipient states of silication do not influence Ni-O distances and cannot be detected by DRS. The first evidence for the formation of a precipitate was obtained after 5 min (pyrophyllite), 7 hr (talc), 24 hr (gibbsite), and 3 days (amorphous silica). For both pyrophyllite and talc, where sufficiently long time series were available, the ν2 energy slightly increased as long as the Ni uptake from solution continued (3 days for pyrophyllite, 30 days for talc). This may be explained by a relative decrease of relaxed surface sites due to the growth of crystallites. Our study shows that the formation of both α-Ni(OH)₂ and Ni-Al LDH may effectively decrease aqueous Ni concentrations in soils and sediments. However, Ni-Al LDH seems to be thermodynamically favored when Al is available.     

In situ study of the $$ R\overline{3} c \to R\overline{3} m $$ orientational disorder in calcite

The temperature dependences of the crystal structure and intensities of the (113) and (211) reflections in calcite, CaCO₃, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction data. Calcite transforms from to at about T _c = 1,240 K. A CO₃ group occupies, statistically, two positions with equal frequency in the disordered phase, but with unequal frequency in the partially ordered phase. One position for the CO₃ group is rotated by 180° with respect to the other. The unequal occupancy of the two orientations in the partially ordered phase is obtained directly from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x − 1. The a cell parameter shows a negative thermal expansion at low T, followed by a plateau region at higher T, then a steeper contraction towards T _c, where the CO₃ groups disorder in a rapid process. Using a modified Bragg–Williams model, fits were obtained for the order parameter S, and for the intensities of the (113) and (211) reflections. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A counter-clockwise P–T path for the Voltri Massif eclogites (Ligurian Alps, Italy)

Integrated petrological and structural investigations of eclogites from the eclogite zone of the Voltri Massif (Ligurian Alps) have been used to reconstruct a complete Alpine P–T deformation path from burial by subduction to subsequent exhumation. The early metamorphic evolution of the eclogites has been unravelled by correlating garnet zonation trends with the chemical variations in inclusions found in the different garnet domains. Garnet in massive eclogites displays typical growth zoning, whereas garnet in foliated eclogites shows rim‐ward resorption, likely related to re‐equilibration during retrogressive evolution. Garnet inclusions are distinctly different from core to rim, consisting primarily of Ca‐, Na/Ca‐amphibole, epidote, paragonite and talc in garnet cores and of clinopyroxene ± talc in the outer garnet domains. Quantitative thermobarometry on the inclusion assemblages in the garnet cores defines an initial greenschist‐to‐amphibolite facies metamorphic stage (M1 stage) at c. 450–500 °C and 5–8 kbar. Coexistence of omphacite + talc + katophorite inclusion assemblage in the outer garnet domains indicate c. 550 °C and 20 kbar, conditions which were considered as minimum P–T estimates for the M2 eclogitic stage. The early phase of retrograde reactions is polyphase and equilibrated under epidote–blueschist facies (M3 stage), characterized by the development of composite reaction textures (garnet necklaces and fluid‐assisted Na‐amphibole‐bearing symplectites) produced at the expense of the primary M2 garnet‐clinopyroxene assemblage. The blueschist retrogression is contemporaneous with the development of a penetrative deformation (D3) that resulted in a non‐coaxial fabric, with dominant top‐to‐the‐N sense of shear during rock exhumation. All of that is overprinted by a texturally late amphibolite/greenschist facies assemblages (M4 & M5 stages), which are not associated with a penetrative structural fabric. The combined P–T deformation data are consistent with an overall counter‐clockwise path, from the greenschist/amphibolite, through the eclogite, the blueschist to the greenschist facies. These new results provide insights into the dynamic evolution of the Tertiary oceanic subduction processes leading to the building up of the Alpine orogen and the mechanisms involved in the exhumation of its high‐pressure roots.     

Spontaneous strain below the I\bar 1 - P\bar 1 transition in anorthite at pressure

The phase transition between the and phases of anorthite has been studied at elevated pressure by single-crystal X-ray diffraction in a diamond-anvil cell. The phase transition is shown to be first-order in character for both end-member anorthite (CaAl₂Si₂O₈) and for an anorthite with a small amount of albite component (NaAlSi₃O₈) in solid solution. Reversals of the transition across the phase boundary at three other compositions show that the transition pressure (P _Tr) increases with increasing albite content. This behaviour is compared with that observed at elevated temperatures, and is analysed in terms of Landau theory.