α-石英晶体与刚玉晶体(0001)面腐蚀像的结晶学对称

晶体的腐蚀像是指晶面(或切面)在酸、碱溶液中被腐蚀后形成的具有一定形状的蚀坑。腐蚀像不仅可以揭示晶面及晶体的对称性,还可以揭示晶面的结晶学意义。本文对同属三方晶系,但对称型不同的α-石英晶体(点群32)和刚玉晶体(点群3m)的(0001)切面和晶面进行了腐蚀像的微分干涉显微镜(DIC)观察与研究。经研究发现,α-石英晶体(0001)切面的腐蚀像为等边三角形,与该面上出露三次对称轴的对称关系一致,等边三角形的三边分别平行于[0110]、[1010]、[1100]方向,即垂直于X、垂直于Y、垂直于U轴方向。该等边三角形腐蚀像与该切面边棱的方位关系表明在包含三次轴的方向上无对称面存在,与α-石英晶体的对称型是相符的。刚玉晶体(0001)晶面的腐蚀像亦为等边三角形,与该面上出露3次对称轴的对称关系一致,等边三角形的三边分别平行于[2110]、[1210]、[1120]方向,即X、Y、U轴方向。刚玉晶体(0001)面的腐蚀像与该晶面边棱的方位关系表明在包含3次轴的方向上有3个对称面存在,这3个对称面分别垂直于[2110]、[1210]、[1120]方向,即X、Y、U轴方向,与刚玉晶体的对称型相符。因此,同属于三方晶系同一单形平行双面{0001}的α-石英晶体与刚玉晶体(0001)晶面的蚀坑形态是一致的,均为等边三角形,但等边三角形腐蚀坑的方位不同,等边三角形腐蚀坑与边棱的方位关系反映该晶体的对称型特点。这一研究对认清三方晶系不同对称型矿物晶体(0001)面腐蚀像的对称关系,丰富同一晶系不同对称型矿物各面腐蚀像之间的关系研究具有理论与实际意义。     

红柱石腐蚀像立体模型及与对称的关系

采用摩尔比为1∶1的NaOH-KOH混合熔融物对红柱石晶体各不同结晶学方向的自然晶面和切面进行了腐蚀实验,建立了红柱石晶体腐蚀坑形态在三维空间分布的立体模型。相同腐蚀条件下,红柱石晶体同种单形的晶面(切面)腐蚀坑形态相同,不同单形的晶面(切面)腐蚀坑形态不同,故根据腐蚀坑形态可进行晶体定向。腐蚀坑形态能体现了晶体的对称性。红柱石晶体各晶面(切面)的腐蚀坑形态在三维空间分布的立体模型和投影图可用来进行红柱石晶体的定向及缺陷研究。     

红柱石腐蚀像立体模型及与对称的关系北大核心CSCD

采用摩尔比为1∶1的NaOH-KOH混合熔融物对红柱石晶体各不同结晶学方向的自然晶面和切面进行了腐蚀实验,建立了红柱石晶体腐蚀坑形态在三维空间分布的立体模型。相同腐蚀条件下,红柱石晶体同种单形的晶面(切面)腐蚀坑形态相同,不同单形的晶面(切面)腐蚀坑形态不同,故根据腐蚀坑形态可进行晶体定向。腐蚀坑形态能体现了晶体的对称性。红柱石晶体各晶面(切面)的腐蚀坑形态在三维空间分布的立体模型和投影图可用来进行红柱石晶体的定向及缺陷研究。     

α-石英晶体腐蚀形貌三维空间变化规律与晶体对称研究

通过对α-石英自然晶面六方柱面(100)和(010)、菱面体正形面(101)与菱面体负形面(011)、以及介于上述自然晶面之间的切面进行腐蚀形貌的观察研究发现,石英晶体同种单形的晶面(切面)腐蚀坑形态相同,但方位可以有变化,不同单形的晶面(切面)腐蚀坑形态不同;同一单形的正形与负形腐蚀坑形状不同;蚀坑形态能够反映晶体的对称性。α-石英晶体各晶面(切面)的蚀坑形态在三维空间分布的投影图可用于岩石中α-石英晶体的定向及缺陷研究。这一观察研究对厘清α-石英晶体腐蚀形貌立体全方位的对称关系、指导岩石中α-石英晶体的定向研究具有理论与实际意义。     

从矿物粉晶表面反应性到矿物晶面反应性——以黄铁矿氧化行为的晶面差异性为例

地球系统中各种矿物相的物理化学反应大多是从矿物表面或界面开始的。要揭示矿物表面反应性的本质,就需要从控制其反应性的表面结构入手。由于实验条件的限制,绝大多数关于矿物表面物理化学性质的研究主要采用粉晶作为研究对象。尽管粉晶方法在研究诸如硅酸盐、碳酸盐溶解和沉淀结晶等过程中被普遍采用,但这种基于矿物粉晶的研究方法还是有一定的不足。因为形成粉晶的破碎研磨过程会导致晶体高能面的出现,高能面所具有的高活性可能会加速其反应过程,应用于地球化学反应的计算结果就可能高估了实际的地球化学反应速率。本研究以黄铁矿表面氧化反应的晶面差异性为例,从晶面结构制约反应性的角度出发,重新审视了黄铁矿氧化的相关问题,弥补了传统"粉晶研究"中对黄铁矿氧化速率和氧化机理认识的缺陷。黄铁矿宽范围的氧化速率实测值很可能是由不同晶面间较大的反应性差异导致;水在黄铁矿的氧化过程中同时扮演着传递电子的催化剂和反应物的角色,也是黄铁矿氧化反应速控步(rate-limiting step)的核心物质。这些认识首次明确了黄铁矿不同晶面反应性差异的重要性,并提示我们应将传统表面矿物学的研究推向更为精确的晶面矿物学水平。这一从晶面角度考察发生在矿物表面的地球化学反应的研究方法可为构建更为精确的地球化学模型提供理论基础。     

橄榄石腐蚀像立体模型构建及其岩石组构研究之启示

利用20% 浓度的氢氟酸（HF）对橄榄石晶体不同方向之切面进行了腐蚀实验,以期建立三维立体构型。在晶体上选 取垂直任一结晶轴的单形,如（100）,（010）,（001）等平行双面,（110）,（011）,（101）等菱方柱和（111）菱方双锥进 行了腐蚀实验,由原子力显微镜记录各个切面腐蚀像。结果显示,相同切面上的腐蚀像具有固定的几何形状及角度,且在 晶面上的结晶学方向固定。各腐蚀像形状具有共性,即长轴为[010] 方向,短轴为[100] 方向。由不同切面腐蚀像的变化规律, 建立了橄榄石腐蚀像三维立体模型。相同腐蚀剂对不同晶面腐蚀的容易程度差异巨大,以蚀坑在DIC200× 下能清晰观察到 腐蚀像形态为标准,橄榄石各切面的腐蚀速率为v（010）>v（110）>v（100）>v（111）>v（101）>v（001）>v（011）。由橄榄石晶体腐蚀像的唯一 性及其结晶学定向,在橄榄岩切片中将橄榄石颗粒切面指数化,并获得其结晶学定向及结晶优选方向。由此,在大别山碧 溪岭石榴子石二辉橄榄岩中推断橄榄石[100] 主极密垂直面理面,[010] 主极密平行于线理面。腐蚀像所确定的晶体结晶优选 性为当地构造动力提供了一定有价值资料,开拓了腐蚀像的地质应用意义。     

矿物晶体腐蚀像的新应用

矿物晶体腐蚀像是一种研究晶体对称、晶格缺陷等传统的方法。对腐蚀像提出了一个全新的研究思路,建立各种不同矿物晶体的腐蚀像立体模型,从而可以在这个模型上进行：①腐蚀像的晶体对称理论意义及其在岩石中矿物晶体定向作用的研究;②腐蚀像所反映的晶格缺陷与定向及其地质意义的研究;③腐蚀像所反映的晶体溶解机理的结晶学各向异性特征的研究。这些研究充分挖掘了腐蚀像在地质学、矿物学中的新的研究意义。     

用面角公式标定锆石晶面符号初探

锆石晶体测量后,用面角公式计算相邻两晶面面角值来标定晶面符号是一个探索性的方法。锆石晶面符号这一测定方法的论证,也为不同成因的同种矿物对应面夹角的对比,提出了新的研究课题。     

影响晶体形态的因素

晶体具有各种各样的外形。同一种晶体可以呈树技状、骸晶,或以平滑晶面所围成的多面体外形。在多晶体晶形中,由于晶面的不同组合或晶体的畸形发育,故在外形上有千差万别的变化。     

晶面成键生长的动力学控制因素

通过对比霓石和钠铁闪石的晶面微形貌差异,结合这两种矿物的内部结构及外部生长条件的异同性,笔者认为晶面的成键生长机制不仅取决于外部环境的过饱和度,同时也取决于内部结构中化学健的强度。控制晶面成键生长约是过饱和度与键链强度的相对大小。这一结论反映了生长机制、过饱和度、键链强度三者的有机关系。本文还对这一结论的适用性进行了讨论。     

津巴布韦金刚石独特的形态及其“指纹”特征的意义

津巴布韦马朗金刚石矿床为近年来发现的特大型高品位金刚石砂矿。对津巴布韦马朗金刚石产区的金刚石样品进行了矿物学和宝石学研究。结果显示,津巴布韦金刚石的晶体形态、表面微细特征等与世界上主要产地的金刚石有较大差异。其中最新发现的“十字架”形熔蚀图像和红色斑点是该产地金刚石的典型特征。“十字架”是由大量大小不等的正方形熔蚀坑沿晶体[100]重叠排列而成的,红色斑点为铁质氧化物沿熔蚀坑棱线生长而成的。研究结果表明,津巴布韦马朗金刚石的形态特征具有产地“指纹特征”的意义,对中国地勘单位赴境外进行金刚石找矿具有借鉴意义。     

Partitioning of species-forming and impurity cations among growth pyramids of pinacoid and prism faces in crystals of beryl,cordierite, and beryllian indialite

The face effect was observed in all individual compounds with beryl structure having grown at a rate of 1–8 unit cells a second, with spontaneous crystallization in the system beryl (or cordierite)–Mg,Ca/Cl,F–impurity, where impurities are Ti, V, Cr and/or Fe oxides. By “face effect” is meant a difference in chemical compositions and symmetry of growth pyramids of crystallographically nonequivalent crystal faces. In the studied compounds of beryl structural type the simple crystal forms, prism and pinacoid, are characterized by hexagonal (pseudohexagonal in cordierite) and rhombic symmetry of face patterns. Degrees and characters of distinction of growth pyramids of prism and pinacoid faces of beryls, beryllian indialites, cordierites and their varieties vary in a wide range depending on the accumulation of species-forming and impurity elements. Most likely, this effect appears when crystallographically nonequivalent faces entrap chemically different “building units” (clusters spontaneously formed in a feeding medium and composed of fragments of beryl-type structure). It is supposed that the final isomorphous substitution of an impurity for the species-forming element occurs immediately on the face and/or attached unit. The character, direction, and degree of isomorphism depend on the initial composition of the medium, type of the main compound to be formed, and the presence of synchronous impurity phases. The same ratio of Si and Al concentrations in building units of the prism-pinacoid couple of cordierite with and without Ti and V suggests the persistent action of the patterns of these faces on the medium in the range of sampled concentrations of impurities and rates of growth. The contrasting face effect with respect to Si and Al in an indialite-cordierite individual is due to a drastic dissymmetry of the latter. The Ti- or V-related effects of cordierite faces are negligible. The study of beryllian indialite and its varieties showed that in some cases changes in Si-Al-Mg composition of units feeding faces with different crystallographic patterns are quite the same, with the considerable evolution of the total composition of the crystal-forming medium. As to the face effects of beryllian indialites (chiefly, with respect to Ti, V, Cr, and Fe impurities), they are owing to a considerable difference in degree of isomorphism with the participation of these elements in the building units that feed pinacoid and prism faces. Beryls demonstrate drastically contrasting face effects with respect to Ti (up to 0.20 f.u.) and in the presence of impurities, to Al (up to 0.21 f.u.); distinct effects were related to Cr (0.06 f.u.), in all varieties to Mg (up to 0.10 f.u.), and quite rarely, to Fe (0.01 f.u.), which is seen from comparison of the schemes of isomorphism implemented in prism and pinacoid. The effects under consideration and their evolution in the process of development of individuals are also clearly recognized from crystallochemical formulas of the building units feeding faces with different crystallographical patterns. By the example of beryl, it has been shown that the face effect inversion with respect to a component during the crystal growth indicates the inversion of the degree of isomorphous substitution of this element in the process of evolution of the individual (because of a drastic change in phase formation in the system) rather than the absence of relationship between face pattern and effect. Thus, in the system beryl–Mg,Ca/F,Cl–TiO₂ the inversion of Mg-related effect (resulting from inversion of degrees of substitution Al³⁺ → Mg²⁺) is linked to a drastic increase in rutile amount (TiO₂) crystallized together with beryl at a certain stage of solution cooling.     

湖南锡矿山锑矿床氧化带的自然硫

本文研究的自然硫产于锡矿山锑矿床氧化带底部。它的特点是晶体细小且晶面众多,其外貌颇似小的球状体。有关它的研究结果将为矿物学形态学以及晶体形态与成因的联系(成因形态学)提供新的资料,     

岩浆岩中石英晶体的对称性连生

矿物晶体连生是岩浆岩中晶体生长及岩石结构形成过程中的一个重要现象，可以提供岩浆演化过程信息.用电子背散射衍射技术(EBSD)分析了天堂寨花岗岩和梅川花岗闪长岩中石英晶体的结晶学取向关系.这2种岩石中石英的道芬双晶和交生(两晶体以某个相同的面重合连生)出现概率非常高.除了道芬双晶和交生外，还发现了一种特殊的石英晶体对称性连生现象.在这种特殊的对称性连生体中，考虑石英的劳埃群3 2/m(而不是石英的点群32)，两晶体形成的道芬双晶的双晶面(0001)或(1010)与第3个晶体的对称面(1120)重合.这样的重合使得这3个晶体的连生体保留了道芬双晶的某些对称性.这种双晶面与第3个晶体的对称面重合的现象在我们以前报道的NH₄Cl晶体聚集体和透辉石枝晶聚集体中也出现过.这种现象说明晶体的连生受控于对称性，即:晶体连生会选择对称性高的形式.由于劳埃群是与晶体空间格子的对称性相关而并不是与晶体结构的对称性相关的，所以，空间格子的对称性可能是控制晶体对称性连生的主要因素.      

Cyclic development of large,complex, calcite dendrite crystals in the Clinton travertine,Interior British Columbia,Canada

Bands of large (up to 4 cm long) three-dimensional crystallographic dendrites form the terrace fronts in an old travertine mound exposed near Clinton, British Columbia. The dendrites, with their long axes perpendicular to the terrace front, are characterized by numerous levels of branching. Each branch is formed of multitudes of skeletal rhombs, four- and six(?)-sided bipyramidal crystals, or prismatic hexagonal crystals that are precisely aligned along crystallographic precepts. Although individual branches are formed of one type of subcrystal, neighbouring branches may be formed of different subcrystal types.Highly supersaturated waters that were generated by rapid CO₂ degassing of the spring water during its turbulent flow over the steep terrace fronts probably drove dendrite precipitation. The presence of growth lines indicates that growth was episodic. Type I growth lines probably formed annually in response to seasonal climate changes whereas Type II growth lines, which formed less frequently, may reflect changes in the flow velocity and/or flow patterns of the spring waters.Early diagenetic modification of the dendrites involved crystal face enlargement, cements formed of trigonal prisms or needle-fiber crystals, microbial infestation that mediated substrate dissolution, and/or deposition of detrital calcite crystals that formed in the water column. Much of the diagenetic modification may have taken place during the periods when the dendrites had temporarily stopped growing.The dendrites in the Clinton travertine are an excellent example of complex, episodic calcite crystal growth that was extensively modified by early diagenetic processes in a surface environment. The same spring waters from which the dendrites were precipitated mediated much of the early diagenesis.     

山东金刚石晶体中氮片晶的分布特征及其表面微形貌

为研究山东蒙阴金伯利岩型金刚石晶体中氮片晶的分布特征,采用红外光谱仪对116粒宝石级金刚石晶体样品中的氮片晶进行分析,并采用微分干涉显微镜观察氮片晶在金刚石表面所具有的物理化学性质及其表面微细结构。结果表明,80.2%的金刚石样品中具有氮片晶;在个别浅褐色、八面体金刚石样品{111}面上观察到平行于[100]晶带方向的长条状蚀像,这些蚀像相互平行,大小不等。显微红外光谱对具长条状蚀像的金刚石样品{111}面的测试结果表明,该类晶体均具有较强的氮片晶的吸收峰（1359~1375cm-1）。综合浅褐色、八面体金刚石样品的红外光谱及其表面微形貌特征,推测长条状蚀像是由氮片晶的出露点受优先选择性腐蚀而致。     

Influence of lysozyme on the precipitation of calcium carbonate: a kinetic and morphologic study

Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO₃ was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω_calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL.Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces.     

Origin of quartz clusters in Vinalhaven granite and porphyry,coastal Maine

We use the crystallographic orientations of quartz crystals, as determined with EBSD, to provide new evidence for the formation of clustered quartz crystals during magma crystallization. Vinalhaven is dominated by granite, with minor porphyry that formed when granite remelted during input of coeval basalt. CL zoning suggests that most quartz clusters in granite and porphyry formed by synneusis, the “swimming together” of preformed crystals. In granite, most quartz pairs in clusters have random orientations—only about 10% have parallel or Esterel twin orientations. Porphyry has fewer quartz clusters, and all pairs have approximately parallel or Esterel twin orientations. CL zoning of quartz pairs in porphyry indicates that they attached prior to a major remelting event. Interpretation of the Vinalhaven quartz clusters leads us to propose that oriented synneusis occurs during crystal accumulation on a magma chamber floor. During hindered settling, some quartz crystals should have come into contact along their dipyramidal faces. Once in contact, continued settling and loss of interstitial melt may have rotated some quartz crystals such that lattices on their dipyramidal faces matched—producing parallel and Esterel twin orientations and creating strong bonds between pairs. Only a small proportion of pairs with matched dipyramidal faces formed in the granite and, during rejuvenation to produce porphyry, only these oriented pairs survived. Hence, the presence of oriented synneusis in a plutonic rock may demonstrate a history of crystal accumulation.