尼日利亚石类矿物的晶体化学研究及其意义

湖南省安化、临武、柿竹园等地区有一类含锡、镁、铁、锌、钛、锰、铝等多种元素的复杂氧化物矿物 ,它们是尼日利亚石、镁尼日利亚石 (彭志忠石 )等。本文从紧密堆积原理出发 ,深入探讨了尼日利亚石类矿物的晶体化学特征。它们的晶体结构可用O(阳离子八面体配位的层 )、T1(阳离子八面体配位与一种方向阳离子四面体配位的混合层 )、T2 (阳离子八面体配位与两种方向阳离子四面体配位的混合层 )堆积方式表征 ,O层与T层交替排列。尼日利亚石 6H的晶体结构表示为…OT2 OT1OT1… ,尼日利亚石 2 4R的晶体结构表示为…OT1OT2 OT2 OT1…× 3 ,等等 ;它们的晶体结构中既有尖晶石的…OT2 OT2 … ,又有铁钒矿的…OT1OT1…晶体结构单位。这类矿物研究在矿物学、宝石学、材料科学等方面有重要的理论和实际意义     

新矿物彭志忠石-6H的晶体结构和晶体化学研究

彭志忠石(镁尼日利亚石)是一种新矿物,除了Sn、Al外,过去发现的尼日利亚石都是以Fe、Zn为主的,而这次在湖南安化发现的,则是镁的端元矿物。矿物为三方晶系,P_(3m1),a_0=0.5692nm,c_0=1.3782nm。晶体化学式为:Mg_2(Zn,Fe,Al)_2(Sn,Fe)_2(Al,□)_(10)O_(22)(OH)_2。在全自动X射线射仪上,收集了单晶独立衍射强度数据443点进行结构计算,R=0.10。结构中氧沿c轴成…ABCACB…紧密堆积。阳离子充填四面体和八面体部分空隙,形式为…OT_2OT_1OT_0…。最后讨论了尼日利亚石—黑铝镁铁矿—塔菲石系列矿物的晶体结构和晶体化学。     

结构矿物学的新成果(续)

八、从氧离子最紧密堆积的观点研究氧化物矿物的晶体结构氧化物在地壳中分布广泛,到目前为止,巳发现300余种,其中除SiO_2外,主要为Al、Fe、Mn、Ti、Cr、Sn、Ta、Nb、TR等元素与氧结合的化合物.结构中的化学键主要为离子键.因此氧化物的结构一般可用最紧密堆积原理来阐述.离子最紧密堆积是阴离子和阳离子一起作最紧密堆积,其结构则服从鲍林法则(Pauling's Rule)和其补充法则波尔法则(Baur's Rule).但如果阳离子的配位数为4、6,即四面体配位和八面体配位,这种情     

国际矿物学会(IMA)新矿物与矿物命名委员会(CNMMN)通报

将相同部分分开。 (3)经修改的命名矿物包括了h gbomite(黑铝镁钛矿 )、nigerite(尼日利亚石 )和taaf feite(塔菲石 ) ,使整个矿物族得到完全一致的修订。2 接受提案 ,但保留 pengzhizhongite(彭志忠石 ) ,而不用magnesionigerite(镁尼日利亚石 )。投票结果 :同意 1,否决 19,弃权 1。部分评论意见 :(1)magnesionigerite(镁尼日利亚石 )的名称比较明了和具逻辑性 ,比 pengzhizhonggite(彭志忠石 )容易记忆。(2 )描述新矿物作用的个人意愿应该得到尊重。3 接受提案 ,但不应延伸到taaffeite(塔菲石 )族矿物。投票结果 :同意 1,否决 19,弃权 1…     

论尖晶石族矿物结构的转变

尖晶石族矿物结构的特征是;氧离子作立方最紧密堆积、阳离子占据八分之一的四面体空隙和二分之一的八面体孔隙。若将四面体位置叫做A位、八面体位置称作B位,其化学计量通式应为AB_2O_4。所有尖晶石族矿物都含有两种不同的阳离子,至少是两种价态的同种阳离子,其比例是2:1,根据含量较多的那种阳离子的分布,尖晶石结构又被划分为正尖晶石型和反尖晶石型,若较多的那种阳离子全部分布在八面体位置,则称之为正尖晶石型;若其平均分布     

钛钡铬石和钛钾铬石的晶体结构及晶体化学

本文通过结构的测定和修正。确定了各阳离子特别是Zr_+~4在钛钡铬石、钛钾铬石(蒙山矿)中的结晶学位置,证实了这两个矿物是锶铁钛矿族的分别以大阳离子Ba和K为主的两种新矿物。通过与锶铁钛矿族其他矿物的晶体结构和晶体化学特征进行对比,探讨了这两个矿物中M(4)-O M(5)O平均键长较同族其他矿物的偏大的原因,以及该族矿物晶胞的实际形态与理想形态(据最紧密堆积原理推测的)相比在堆积层内有些伸长而在堆积方向则有些收缩的原因。由于结构中较独立的M(0),M(1),M(2)配位位置的存在,故使具有共同结构特征的锶铁钛矿族矿物种类繁多,且化学成分复杂。     

金云母-蛭石间层矿物的酸浸取物与酸蚀机理研究

对采自新疆尉犁蛭石矿的金云母蛭石间层矿物样品进行了酸处理实验研究。在样品化学成分和XRD分析的基础上,研究了样品酸处理后酸浸取物的化学组成、含量及结构变化特征;分析讨论了金云母蛭石间层矿物在酸处理过程中不同阳离子浸出率的变化规律和酸蚀机理。结果表明,层间可交换性阳离子的氧化物CaO和Na2O的酸浸取率最高,层间不可交换性阳离子的氧化物K2O次之,八面体中阳离子的氧化物MgO、Fe2O3和Al2O3具有较高的酸浸取率,而四面体阳离子的氧化物Si O2的酸浸取率最低;金云母蛭石间层矿物中蛭石晶层含量高的样品酸浸取率高,金云母蛭石间层矿物的耐酸蚀性能不如金云母。     

黑云母的红外光谱研究

关于云母族矿物的红外光谱研究,国内外一些学者曾做过不少工作。笔者就近年来所收集到的一些产自宁芜地区、南岭地区花岗岩类岩石中27个黑云母样品,进行了红外光谱测定,确定了某些特征吸收峰的偏移及其与化学组分之间的关系,并探讨了黑云母矿物中主要金属阳离子的相互置换和晶体结构的关系。 黑云母属三八面体型的2∶1层状结构硅酸盐矿物。结构中上下四面体片(T)以尖顶相对,中间夹氢氧镁石型[Mg—O_4(OH)_2]八面体片(O),构成T—O—T型结构层。占有四面体晶位的阳离子主要为Si,约有1/4的Si可被R~(3+)(主要为Al~(3+)、次为Fe~(3+))取代。占有八面体晶位的阳离子主要为Mg~(2+)或Fe~(2+),次为Fe~(3+)、Al~(3+)、Mn~(2+)等。由T—O—T所组成的结构层则通过层间大阳离子K~+(少量的Na~+、Ca~(2+)等)彼此相连接。结构     

高温改性锌铁尖晶石的晶体化学与磁性研究

尖晶石型矿物因其阳离子在氧四面体和氧八面体中所占比例的不同而分为正尖晶石、反尖晶石和过渡的无序结构尖晶石。本文以微米级锌铁正尖晶石(Zn Fe2O4)为初始研究对象,通过扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线吸收精细结构谱(XAFS)、差热-热重分析(DTA-TGA)、磁性测试(M-H、ZFC-FC)等矿物学、热学和磁学测试手段综合分析了温度对其阳离子配位的影响。结果显示,随着温度的升高,原正尖晶石结构中四面体的ZnⅡ会逐渐与八面体中的FeⅢ发生交换,910℃左右时阳离子的交换速率出现最大值,并在1 200℃加热24 h后达到热动力学平衡,此时晶胞参数a从8.440 7减小到了8.437 2;同时尼尔温度(TN)由13 K升到了27 K,反映了由反铁磁性向亚铁磁性过渡的磁结构变化。本文研究认为,由粒径不同带来的体系能量的差异是造成微米级Zn Fe2O4在高温下阳离子交换行为与纳米级颗粒截然相反的根本原因。     

根据矿物薄片颜色判估铬尖晶石类型的方法

尖晶石族矿物为AB2X4型氧化物,因其阳离子A和B元素的不同,分属Cr、Fe、Al、Zn、Mn、Ti、Ni等不同种属,并有不同的产状。其中铬尖晶石仅见于幔源超镁铁岩和镁铁岩中。对岩石中副矿物铬尖晶石的薄片颜色与其矿物化学类型对比发现,二者存在着明显的专属关系,薄片中铬尖晶石的不同颜色可做为寄生岩体可能产出铬矿床或镍矿床的判据。副矿物和造矿铬尖晶石的化学通式是相同的,其中二价阳离子为Mg和Fe,三价阳离为Cr、Al和Fe。铬尖晶石以其三价阳离子含量百分比的不同分为不同的种属。岩石薄片下,铬尖晶石类矿物除含钛磁铁矿、铬磁铁矿和高铁…     

Crystal Chemistry Research of Minerals of Nigerite Group and Its Significance

SinceJacobsonandWebb (194 7)firstlyfoundthenigeriteinNigeria ,mineralogistshavefounditinmanycountriessuchasRussia (EastSiberia ,195 8) ,China(Hunan ,196 3) ,Portugal (196 5 ) ,Australia (1976 )andsoon .Greyetal.(1979)determinedaccuratelythecrystalstructureofnigerite (2 4R) .In 1988,Chenfoundakindofendmembermineralofnigerite ,whichisMg riched .ByapprovingofCommissiononNewMineralsandMineralNames (CNMMN) ,thismineralwasnamedpengzhizhongite .Inthepast ,somemineralogistsdidnotfurtherdis t…     

Structural relation of hydrous ringwoodite to hydrous wadsleyite

The sequential displacement mechanism based on the oxygen-lattice cubic closest packing (c.c.p.) in the < 2 0 1 > direction was proposed in this study. All displacements of cations are within the OT and the O layers with the length of displacement vector being around 1.7 or 2.9 Å, contrary to displacement of around 5.0 Å for models proposed previously. The difference in atomic arrangement between hydrous wadsleyite and hydrous ringwoodite is small. The atomic arrangement of the O layer of hydrous wadsleyite is essentially the same as that of hydrous ringwoodite when Mg vacancies preferentially exist in the O layer. The partial occupancies of normally vacant tetrahedral sites reported in the hydrous-β and hydrous-γ structures may possibly be caused by the existence of Mg vacancies at the octahedral sites through phase transition from hydrous-β to hydrous-γ or from hydrous-γ to hydrous-β phases.     

湖南香花岭矽卡岩中锡的矿物学行为与成矿过程

湖南香花岭矽卡岩型锡矿床是南岭地区一个重要的锡多金属矿床,发育有丰富的含锡矿物。在野外和显微镜下观察 基础上,文章利用电子探针技术系统分析了香花岭矽卡岩中含锡矿物的矿物学特征,探讨了锡的成矿过程、成矿流体以及 锡的来源。研究结果表明,香花岭矽卡岩中含锡矿物由锡矿物（锡石、尼日利亚石、孟宪民石等）和富锡矿物（韭闪石、 尖晶石、葡萄石、塔菲石等）组成。锡的成矿有三个阶段：矽卡岩早阶段,Sn进入尖晶石、韭闪石等造岩矿物中,形成富 锡矿物;氧化物阶段,锡矿物如锡石、尼日利亚石、孟宪民石等逐渐晶出;晚期热液阶段,早期含锡矿物热液蚀变原位析 出锡石,或富Sn热液交代早期矿物形成了富锡环边。矽卡岩中成矿流体富含F,CO2,Li等挥发组分,控制了Sn的富集、迁 移、结晶等过程。香花岭矽卡岩中Sn根本上来源于地层,锡的成矿过程反映了Sn在地壳中的地球化学循环过程。     

Structure and chemistry of (111) twin boundaries in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel crystals from Mogok

The atomic scale structure and chemistry of (111) twins in MgAl₂O₄ spinel crystals from the Pinpyit locality near Mogok (Myanmar, formerly Burma) were analysed using complementary methods of transmission electron microscopy (TEM). To obtain a three-dimensional information on the atomic structure, the twin boundaries were investigated in crystallographic projections and Using conventional electron diffraction and high-resolution TEM (HRTEM) analysis we have shown that (111) twins in spinel can be crystallographically described by 180° rotation of the oxygen sublattice normal to the twin composition plane. This operation generates a local hcp stacking in otherwise ccp lattice and maintains a regular sequence of kagome and mixed layers. In addition to rotation, no other translations are present in (111) twins in these spinel crystals. Chemical analysis of the twin boundary was performed by energy-dispersive X-ray spectroscopy (EDS) using a variable beam diameter (VBD) technique, which is perfectly suited for analysing chemical composition of twin boundaries on a sub-nm scale. The VBD/EDS measurements indicated that (111) twin boundary in spinel is Mg-deficient. Quantitative analyses of HRTEM (phase contrast) and HAADF-STEM (Z-contrast) images of (111) twin boundary have confirmed that Mg²⁺ ions are replaced with Be²⁺ ions in boundary tetrahedral sites. The Be-rich twin boundary structure is closely related to BeAl₂O₄ (chrysoberyl) and BeMg₃Al₈O₁₆ (taaffeite) group of intermediate polysomatic minerals. Based on these results, we conclude that the formation of (111) twins in spinel is a preparatory stage of polytype/polysome formation (taaffeite) and is a result of thermodynamically favourable formation of hcp stacking due to Be incorporation on the {111} planes of the spinel structure in the nucleation stage of crystal growth. The twin structure grows as long as the surrounding geochemical conditions allow its formation. The incorporation of Be induces a 2D-anisotropy and exaggerated growth of the crystal along the (111) twin boundary.     

蒙脱石晶体结构和水结构的矿物物理特征

本文利用矿物物理研究方法对我国内蒙、浙江、甘肃等地的钙基、钠基、镁基蒙脱石的物质成分、晶体结构和层间OH,H_2O的排布结构进行了研究,并获得下列结论: 1.由X衍射和拉曼分子光谱分析深入研究了蒙脱石阳离子配位体结构特征,提出其空间群为C_(2/m) 型。 2.建立了蒙脱石水结构模式,有3种主要类型:①层间大阳离子附近的束缚态水分子;②层间无大阳离子位置上的非束缚态水分子;③颗粒表面依靠氢键相连的水分子集合体。 3.利用群理沦,提出了蒙脱石OH～-的振动模式,由振动分析指出蒙脱石中OH～-具有12个振动模式。     

Lamellar nigerite in Zn-rich spinel from the Falun deposit,Sweden

Lamellar nigerite is found in Zn-rich spinel from a sample that contains chiefly anthophyllite + spinel + cordierite, lesser amounts of quartz and chlorite, as well as sphalerite, pyrite, pyrrhotite, and galena, and rare cassiterite and rutile. Nigerite can be described as interlayering of spinel-like (R²⁺Al₂O₄) and nolanite-like ((Sn, Ti)Al₄O₈) structures. In nigerite, the spinel-like part is also compositionally related to spinel, but in the nolanite-like part only the structural analogy exists. Stoichiometric assumptions that relate the anhydrous cation sum to the amount of R⁴⁺ cations present, allow Fe³⁺ estimates from microprobe analyses, and a representative analysis gives the following anhydrous formula: Mg_1.30Fe _0.65 ²⁺ Zn_3.03Mn_0.03Al_11.65Fe _0.35 ³⁺ Sn_0.32Ti_0.18O₂₄.The nigerite is Zn-rich with a Zn ratio (Zn/(Zn+Mg+ Fe²⁺)) of about 0.59, and the Sn ratio (Sn/(Sn+Ti)) that ranges from about 0.63 to 0.41. The Fe³⁺ content in these samples ranges from 0.35 to 0.52 (24 oxygen basis).Textures suggest that the nigerite could have formed by the breakdown of R ₂ ²⁺ (Sn, Ti)O₄ and R²⁺Al₂O₄ spinel components during more complex reactions. An experimental investigation of the MgAl₂O₄-Mg₂SnO₄ join indicates that the solubility of Mg₂SnO₄ component in spinel over the T interval 500 to 900° C is about 0.5 to 3.0 mole %. This, coupled with the increased solubility expected from the presence of Ti, gives good agreement with the 2.4 to 2.6 mole % R ₂ ²⁺ (Sn, Ti)O₄ component in spinel that is estimated to be the maximum necessary to form the compositions and amounts of observed nigerite.     

核-幔物质晶体化学、矿物学及矿床学初探

大量的高温、高压实验表明随着温度和压力的增加 ,地幔氧化物及硅酸盐的晶体结构会发生与其温度和压力相适应的多型转变 ,并导致元素金属性的增加 ,即氧离子半径的缩小以及硅和其他阳离子半径的增大。来自地核部分物质的晶体化学及晶体物理目前还很少涉及 ,根据其物质组成 ,可能具有金属及金属互化物的性质 ,即原子呈等大球最紧密堆积 ,具有高熔点、难溶性等特征。在地球形成时作为地核物质是最先凝聚的 ,并由于重力分异沉入地核 ,上升至浅部时不与其他元素化合 ,保持了零价状态 ;等大球最紧密堆积使其在地球各层圈中晶体结构保持恒定。地幔热柱使核、幔物质上升至地球浅部成为可能 ,并形成矿物及矿床。以西藏罗布莎铬铁矿床为例 ,已经发现了多达 5 0种的铂族元素矿物、铁族元素矿物及其金属互化物 ,包括成分复杂多变的Os Ir ,Os Ir Ru ,Pt Fe ,Ir Fe Ni,Fe Ni Cr及Fe Co等矿物 ,它们还与来自核幔边界的Si,Fe ,FexSiy,FeO和SiO2 矿物共生 ,其中铂属矿物及其金属互化物矿物应视为来自E层的地核矿物 ;探讨了该区矿物与陨石矿物在共生组合方面的相似性 ,地核矿物的聚集可能会形成新型的金属元素矿床     

从纳哥金矿地质地球化学特征探讨黔西南卡林型金矿成因

在黔西南相同地质背景下出现的纳哥金矿特殊地质和地球化学特征:矿区出露大量的与成矿有关的巨大石英脉体,脉体中CO₂含量很高,成矿温度与区域矿床类似,H、O同位素组成在岩浆水附近,认为该矿床是深部岩浆源成因。通过区域卡林型金矿床物源、成矿作用、控矿构造等方面的总结、分析和对比讨论,认为黔西南金矿床应有统一的成因,为深部岩浆源(少量地层中物质混杂)-深大断裂导矿-表层断裂、背斜控矿-交代充填成矿的中偏低温热液矿床。     

Crystal structural features of the olivine → spinel transition

Comparisons of structural features of olivine (α phase), spinel (γ phase), and the modified spinel (β phase) lead to predictions of possible mechanisms for the olivine → spinel transitions. In the olivine structure, rigid tetrahedral edges and shared octahedral edges form columns of corner-sharing trigonal dipyramids parallel to the a axis. These rigid columns are separated by weaker, unshared octahedral edges which may be stretched to reduce cation-cation repulsion. As a result, olivine has a relatively loose structure and is stable at low pressure. At elevated pressure, olivine transforms to the more compact spinel structure, in which the rigid tetrahedral edges and shared octahedral edges form a three dimensional network instead of aligned columns. These structural differences explain how compressibility and thermal expansion may be taken up mainly by octahedral sites in olivine, but are evenly distributed over both octahedral and tetrahedral sites in spinel. Because the closest packings of oxygens and interstitial cation distributions differ between olivine (h.c.p.) and spinel (c.c.p.), the olivine structure may have to disintegrate during its transformation to spinel, so that the olivine → spinel transition involves processes of nucleation and growth. The migration of atoms across the olivine-spinel interface is thus a complicated process of random walk without a definite path. In the β phase → spinel transition, however, the diffusion of cations may follow a definite path in restricted regions because oxygen closest packings and cation distributions are similar in the two structures. If the oxygen packing remains intact during the β → γ transition, the transformation will be an intracrystalline process leading to domain structure in the spinel product.     

Gaps in cubic closest packing: from MgO via spinel to the pharmacosiderite crystal structure type

Numerous ordered defect structures are known that are related to the sodium chloride (or MgO) structure type, thus they are basically cubic closest packed (ccp) arrangements with vacancies. For example the NbO type is an MgO type in which one quarter each of the anions and the cations are missing compared to the ccp in such a way that both anions and cations are in square-planar coordination. In spinel, Al₂MgO₄, one half of the octahedrally coordinated cations are missing compared with the MgO type and only one eighth of the tetrahedrally coordinated sites within the ccp are occupied. What these cases have in common is that all these derivatives are rather dense. This is different in pharmacosiderite, K[Fe₄(OH)₄As₃O₁₂]. 6 to 7H₂O, where one half of the anion positions, three quarters of the octahedral sites and five eighth of the tetrahedral sites remain vacant, compared to the spinel type. Pharmacosiderite is a wide open porous structure with zeolitic properties. We are illustrating these relationships using a Bärnighausen symmetry tree and by tables relating the various structure types to each other.