LnMsbO_6和Ln_2M_2O_7 (M = Zr, Ti)复合氧化物的合成、组成、结构及发光等性质的研究

在综合文献报导的基础上，我们选择了LnMsbO_6和Ln_2M_2O_7 (M = Zr, Ti)做为研究体系，对其合成、组成、结构以及稀土离子在其中的发光性质进行了较为系统的研究。用氢氧化物共沉淀的方法，在等摩尔阳离子原料配比条件下，我们制备了LnMsbO_6和Ln_2M_2O_7(M = Zr, Ti, Ln = La - Yb, Y除Ce和Pm)。根据对组成的分析结果并与文献对比，我们认为得到的化合物组成与给出的分子式是一致的。由热分析并结合x-ray衍射分析对LnZrsbO_6的形成反应进行了研究，其结果表明化合物的形成过程是一个较慢的固相反应过程。通过x-ray粉沫衍射物相分析并结合掺杂Eu~(3+)的发光光谱，我们确定了在不同条件下合成的LnMsbO_6和Ln_2M_2O_7化合物的结构类型，并计算了所有化合物的晶胞参数。在对上述结构特性及其变化规律进行研究后，我们认为Ln_2M_2O_7结构变化规律与ΔZ/(d~2) (Z为阳离子电荷，d为阳离子与阴离距离)有关，随ΔZ/(d~2)值由小到大，Ln_2M_2O_7(M = Zr, Ti)先是形成具有荧石结构的阳离子无序固溶体，然后逐渐过渡到荧石结构的变型——有序的立方烧绿石结构，最后变型到单斜晶系结构。LnMsbO_6(M = Zr, Ti)低温相结构与Ln_2M_2O_7(M = Zr, Ti)是有联系的，即基本保持了其立方晶系结构。然后锑的加入使这种结构变得很不稳定，因此在高温灼烧下上述立方相将不可逆地变为更稳定的高温结构相。利用磁天平对LnMsbO_6和Ln_2M_2O_7进行了室温条件下的磁学性质测量，其玻尔磁子数的实验值与Van Vleck理论值符合较好。由此也可说以说明化合物的组成与给出的分子式是一致的。用荧光光谱仪对Eu~(3+)在不同基质中做发光光谱，其结果表明Eu~(3+)在烧绿石结构的Ln_2M_2O_7中，Ln~(3+)是处于具有反演中心的D_(3d)格位，这时~5D_0 → ~7F_2的电体极跃迁（～610nm）是被禁阻的，因此Eu~(3+)主要的发光为~5D_0 → ~7F_1磁体极跃迁（～590nm），并劈裂为两条谱线。在其它不具有反演中心的格位中Eu~(3+)的~5D_0 → ~7F_2跃迁则是较强的。在La~(3+)有着多个较低对称性格位的La_2Ti_2O_7:Eu中，无论是Eu~(3+)的激发光谱，还是发射光谱，其~5D_0与~7F_0之间的跃迁谱线都不只一条，这与La~(3+)多对称性格位特性是一致的。在立方荧石结构的LnZrsbO_6:Eu中，用Eu~(3+)电荷迁移带激发的发光光谱与用其它激发带激发的很不相同，其~5D_1能级的跃迁谱线非常强，我们认为这可能是由于电荷迁移激发态，将大部分能量传递给3~5D_1能级的结果。另外，我们比较了在Ln_2Zr_2O_7和LnZrsbO_6中Eu~(3+)的发光强度，发现前者要比后者强许多。在研究Bi~(3+)对Eu~(3+)的敏化作用时，我们发现在Y_2M_2O_7:Bi, Bu中Bi~(3+)对Eu~(3+)有较好的敏化作用，而在YMsbO_6:Bi, Eu中则没有。同时我们注意到对于Eu~(3+)取代六配位La~(3+)格位时，其电荷还移带位置和符合Hoefdraad认为是不变的规律，而是随着基质晶格的不同发生变化的。对Dy~(3+)在LnMsbO_6和Ln_2M_2O_7基质中发光性质研究中，我们看到Dy~(3+)的发光主要为兰色的~4F_(9/2) → ~6H_(15/2)跃迁(～480nm)和黄色的~4F_(9/2) → ~6H_(13/2)跃迁(～580nm)。其黄光与兰光的强度比值（R）随基质晶格的不同可以有很大的变化。一般情况下R值总是要大小1，且不随湿度和Dy~(3+)掺杂浓度变化。同时我们比较了在Ln_2Zr_2O_7和LnZrsbO_6 (Ln = Y, Gd, La)基质体系中Dy~(3+)的发光强度，发现同Eu~(3+)类似前者较后者强许多。在论文中我们给出了在Y_2M_2O_7和YMsbO_6 (M = Zr, Ti)中Sm~(3+)的激发光谱与发射光谱，从中可以看到当Sm~(3+)在Y_2Ti_2O_7中取代占据D_(3d)格位的Y~(3+)时，其~4G_(5/2) → ~6H_(9/2) (～650nm)电体极跃迁是被禁阻的。同时还给出了在YZrsbO_6中H_0~(3+)和Er~(3+)的激发光谱与发射光谱。此外，我们研究了Eu~(3+)和Dy~(3+)在一些基质体系中发光强度随温度的变化规律。发现Y_2Zr_2O_7:Eu的临界猝来温度要比La_2Zr_2O_7:Eu的高，Ln_2Zr_2O_7:Dy (Ln = La, Y)的温度猝来曲线则大致相同，且随温度和猝来要比Ln_2Zr_2O_7:Eu缓慢，对于上述现象我们利用位形坐标给出了一定的解释。然而所有的样品发光强度从室温开始，随温度的升高都是单调下降的。

Ti-V-Cr固溶体储氢合金的结构及电化学性能研究

本论文首先研究了Ni、Zr分别对Ti-V－Cr固溶体储氢合金中Cr和Ti部分取代的影响，得到了性能良好的Ti0．17Zr0．08V0．35Cr0．10Ni030基质合金。在此基础上进一步研究了入甄、B、Fe、Co、Al元素的添加或取代对基质合金的结构及电化学性能的影响。采用XRD、ICP、SEM一EDX、XPS、EIS、线性极化和阳极极化等表征手段对Ti一V－Cr固溶体储氢合金的结构及电化学性能进行分析和表征，主要结果如下：①Ti一V－Cr合金自身在碱性电解液中几乎无电化学活性。当用Ni部分取代Cr后，合金中出现具有电化学活性的第二相，其电化学性能得到有效地改善和提高。②Ti0.25-xZr_xV0.35Cr0.1Ni0.3（x＝0．05-0．15）合金主要是由bcc相和c14Laves相组成。随Zr含量从0．05增加到0．08，合金电极的放电容量和倍率放电能力增加；当x继续从0．08增加到0．15时，其变化较小。合金电极的电荷转移电阻随x增加而降低，当x在0．08到0．15之间变化时，电荷转移电阻变化也比较小。表明电荷转移电阻的大小与合金的电化学性能密切相关。③经过50次充、放电循环后，Tio．17zr"sV时scrol0Ni03。合金电极在303K和313K的放电容量能保持在90％以上；在70℃时的放电容量仍能达到275mA扮g。根据不同温度时的交换电流密度，计算了Ti。，17Zr008V时SCr川0Ni030合金电极表面电化学反应的表观活化能，其值约为50kJ／mol。④通过Nln、B、Fe、C。、AI对Tio．17zroosvo35Crol0Nio3。合金基质的添加与取代的研究，得到了具有高容量的储氢合金。其中Tio．17Zr008Vo35Cro．10Ni020Mnol。合金室温最高放电容量达到390n1A扮g；在253一343K的温度范围内，Tiol7Zr08V035Cr0JONioz5Mnoos合金具有高的放电容量，其容量在167一298mA树g之间变化，但是这些合金的稳定性有待进一步的提高。⑤合金充、放电过程中，晶格的扭曲和膨胀、Zr和V的溶解使得合金结构发生变化；合金的严重粉化及表面致密氧化膜的形成，是导致Ti一V－Cr合金电化学性能的衰减的主要原因。

荣成基底片麻岩原岩岩石成因及其构造意义

Extensive high to ultrahigh pressure metamorphic rocks are outcropped in the the Dabie-Sulu UHP orogenic belt. Disputes still exist about for protolith nature of metamorphic rocks, petrogenesis, tectonic setting, and influence on upper mantle during the Triassic deep subduction. In this study, a combined study of petrology, geochemistry, isotope geochemistry and zircon chronology was accomplished for high-grade gneisses in the basement of the ultrahigh-pressure metamorphic Rongcheng terrane to reveal protolith nature and petrogenesis of the gneisses and to disucss the magmatic succession along the northern margin of the Yangtze block in Neoproterozoic. Gneisses in the Rongcheng terrane are characterized by negative Nb, Ta, P and Ti anomalies, relatively low Sr/Y ratios and relatively high Ba/La, Ba/Nb and Ba/Zr ratios, mostly displaying geochemical affinity to Phanerozoic volcanic arc. Neoproterozoic protolith ages (0.7 ~ 0.8 Ga) and Paleoproterozoic average crustal residence time (1.92 ~ 2.21 Ga) favour a Yangtze affinity. The gneisses mostly display characteristics of enrichment of LREE, flat heavy rare earth elements (REE) patterns, moderately fractionation between LREE and HREE and slight negative or positive Eu anomalies, probably reflecting that melting took place in the middle to low crust (26 ~ 33 km), where amphibole fractionated from the melts and/or inherited from source material as major mineral phases in the source area. Sr-Nd isotopic composition of the gneisses supports this conclusion. According to εNd(t) and εHf(t) values, the gneisses can be divided into three groups. Gneisses of group I have the highest εNd(t) and εHf(t) values, corresponding to the range of -6 ~ -3 and -2.9 ~ 13.4, respectively. This suggests obvious influx of depleted mantle or juvenile crust in the formation of protoliths. Gneisses of group II have medium εNd(t) (-9 ~ -7) and εHf(t) values (-15.8 ~ -1.4), corresponding to relatively high TDM2(Nd) (1.99 ~ 2.31 Ga) and TDM2(Hf) (1.76 ~ 2.67 Ga) , respectively. This suggests these gneisses were formed by partial melting of Paleoproterozoic crust. Gneisses of group III have the lowest εNd(t) (-15 ~ -10) and εHf(t) values (-15.8 ~ -1.4), corresponding to the largest TDM2(Nd) (1.99 ~ 2.31 Ga) and TDM2(Hf) ( 1.76 ~ 2.67 Ga), respectively. This indicates that gneisses of group III were formed by remelting of Archean crustal material and further demonstrates existence of an Archean basement probably of the Yangtze affinity beneath the Rongcheng terrane. Gneisses of three groups have also certain different geochemical characteristics. Contents of REEs and trace elements reduce gradually from group I to group III. Zirconium saturation temperatures also show similar tendency. Compared to gneisses of group II and group III, gneisses of group I display geochemical feature similar to extensional tectonic setting, having relatively little influence by the source area. Therefore, geochemical characteristics for gneisses of group I can indictate that the protoliths of the Rongcheng gneisses formed in an extensional rifting tectonic setting. This conclusion is supported by the results of eclogites and gabbros previously reported in the Dabie-Sulu orogenic belt. Statistical results of the protolith ages of the Rongcheng gneisses show two age peaks around ~728 Ma and ~783 Ma with an about 50 Ma gap. Extensive magatism in abou 750 Ma along the northern margin of the Yangtze block can hardly be observed in the Rongcheng terrane. This phenomenon likely suggests discontinuous Neoproterozoic magmatism along the northern margin of the Yangtze block.

Energy Dissipation In Fracture Of Bulk Metallic Glasses Via Inherent Competition Between Local Softening And Quasi-Cleavage

Compression, tension and high-velocity plate impact experiments were performed on a typical tough Zr41.2Ti13.8Cu10Ni12.5Be22.5 (Vit 1) bulk metallic glass (BMG) over a wide range of strain rates from similar to 10(-4) to 10(6) s(-1). Surprisingly, fine dimples and periodic corrugations on a nanoscale were also observed on dynamic mode I fracture surfaces of this tough Vit 1. Taking a broad overview of the fracture patterning of specimens, we proposed a criterion to assess whether the fracture of BMGs is essentially brittle or plastic. If the curvature radius of the crack tip is greater than the critical wavelength of meniscus instability [F. Spaepen, Acta Metall. 23 615 (1975); A.S. Argon and M. Salama, Mater. Sci. Eng. 23 219 (1976)], microscale vein patterns and nanoscale dimples appear on crack surfaces. However, in the opposite case, the local quasi-cleavage/separation through local atomic clusters with local softening in the background ahead of the crack tip dominates, producing nanoscale periodic corrugations. At the atomic cluster level, energy dissipation in fracture of BMGs is, therefore, determined by two competing elementary processes, viz. conventional shear transformation zones (STZs) and envisioned tension transformation zones (TTZs) ahead of the crack tip. Finally, the mechanism for the formation of nanoscale periodic corrugation is quantitatively discussed by applying the present energy dissipation mechanism.

HfO2的纯度对紫外多层膜反射率的影响

用辉光放电质谱法和二次离子质谱仪测定了两种HfO2材料及它们相应的单层膜中的杂质含量，结果发现，无论是在体材料中还是在用电子束蒸发技术沉积的材料单层薄膜中，ZrO2都是这两种HfO2材料中最主要的杂质。而且，这两种HfO2材料中Zr含量的差别远远大于Ti、Fe含量的差别，这说明Zr含量的差别正是引起两种HfO2膜层光学性能差别的原因。用这两种不同纯度的HfO2材料与同一纯度的SiO2材料组合，沉积形成266nm的紫外反射镜，实验结果表明这两种反射镜的反射率分别在99.85% 和 99.15%左右。这个结果与依据单层膜得出的光学常数所设计的结果符合的很好。

热处理工艺对Mg-RE-Zn-Zr系合金显微组织及力学性能的影响

通过气体保护制备了Mg-RE-Zn-Zr[RE=Ce-40La(wt%)的富铈稀土]合金,并对合金进行了热处理,测试了不同状态下合金的硬度、抗拉强度及伸长率等力学性能,采用光学显微镜、X射线衍射仪及扫描电镜对合金显微组织、拉伸断口进行了分析。结果发现,采用T6热处理工艺后,合金的晶粒尺寸明显细化,硬度、抗拉强度、屈服强度和伸长率显著提高,分别提高了11%,24%,7.3%和102%

SYNTHESIS, PROPERTIES AND MOLECULAR-STRUCTURE OF 5-COORDINATE N,N-DIBENZYLDITHIOCARBAMATE COMPLEXES OF TITANOCENE, ZIRCONOCENE AND HAFNOCENE

The five complexes (RC5H4)2M(S2CNBz2)Cl (R = H, CH3; M = Ti, Zr, Hf; Bz = CH2C6H5) have been prepared by the reaction of (RC5H4)2MCl2 with anhydrous sodium salts of dibenzyldithiocarbamate in refluxing CH2Cl2. These complexes have been characterized by elemental analysis, IR and H-1 NMR. X-ray crystal structure determination of Cp2Zr(S2CNBZ2)Cl shows the molecule has a five-coordinate bent metallocene geometry in which the zirconium atom is attached to two eta-5-C5H5 groups, one bidentate dibenzyldithiocarbamate ligand and one chlorine [Zr-Cl, 2.549(1) angstrom; Zr-S, 2.734(1), 2.667(1); Cl-Zr-S, 137.6(1)-degrees and 73.3(1)-degrees; S-Zr-S, 64.3(1)-degrees]. The catalytic system Cp2Ti (S2CNBZ2)Cl-NaH exhibits high initial catalytic activity of hydrogenation of hexene-1 under mild conditions.

大别山硬玉石英岩带中的水

The Dabie Mountains is a collisional orogenic belt between the North China and Yantze Continental plates. It is the eastern elongation of the Tongbai and Qingling orogen, and is truncated at its east end by the Tan-Lu fault. Jadeite-quartzite belt occurs in the eastern margin of UHPMB from the Dabie Mountains. Geochemical features indicate that the protoliths of the jadeite-quartzite and associated eclogite to be supracrustal rocks. The occurrence of micro-inclusions of coesite in jadeite and garnet confirmed that the continental crust can be subducted to great depth (8 0-100km) and then exhumed rapidly with its UHP mineral signature fairly preserved. Therefore, study of UHP jadeite-quartzite provides important information on subduction of continental crustal rocks and their exhumation histories, as well as the dynamics of plate tectonic processes at convergent margins. The purpose of this paper is to investigate the presence of hydrous component in the jadeite-quartzite belt, significant natural variations in the hydrous component content of UHP minerals and to discuss the role of water in petrology, geochemistry and micro-tectonic. On the basis of our previous studies, some new geological evidences have been found in the jadeite-quartzite belt by researches on petrography, mineralogy, micro-tectonic, hydrous component content of UHP minerals and combined with the study on rheology of materials using microprob, ER, TEM. By research and analysis of these phenomenona, the results obtained are as follows: 1. The existence of fluid during ultra-high pressure metamorphic process. Jadeites, omphacite, garnet, rutile, coesite and quartz from the jadeite-quartzite belt have been investigated by Fourier transform infrared spectrometer and TEM. Results show that all of these minerals contain trace amount of water which occur as hydroxyl and free-water in these minerals. The two-type hydrous components in UHP minerals are indicated stable in the mantle-depth. The results demonstrated that these ultra-high pressure metamorphic minerals, which were derived from continental crust protoliths, they could bring water into the mantle depth during the ultra-high pressure metamorphism. The clusters of water molecules within garnet are very important evidence of the existence of fluid during ultra-high pressure metamorphic process. It indicated that the metamorphic system was not "dry"during the ultra-high pressure stage. 2.The distribution of hydrous component in UHP minerals of jadeite-quartzite. The systematic distribution of hydrous components in UHP minerals are a strong indication that water in these minerals, are controlled by some factors and that the observed variations are not of a random nature. The distribution and concentration of hydrous component is not only correlated with composition of minerals, but also a function of geological environment. Therefore, the hydrous component in the minerals can not only take important part in the UHP metamorphic fluid during subduction of continental crustal rocks, but also their hydroxyl transported water molecules with decreasing pressure during their exhumation. And these water molecules can not only promote the deformation of jadeite through hydrolytic weakening, but also may be the part of the retrograde metamorphic fluid. 3.The role of water in the deformed UHP minerals. The jadeite, omphacite, garnet are strong elongated deformation in the jadeite-quartzite from the Dabie Mountains. They are (1) they are developed strong plastic deformation; (2) developed dislocation loop, dislocation wall; (3) the existence of clusters of water molecular in the garnet; and (4) the evolution of micero-tectonic from clusters of water molecular-dislocation loop in omphacite. That indicated that the water weakening controlled the mechanism of deformed minerals. Because the data presented here are not only the existence of clusters of water molecular in the garnet, but also developed strong elongation, high density of dislocation and high aspect ratios, adding microprobe data demonstrate the studied garnet crystals no compositional zoning. Therefore, this indicates that the diffusion process of the grain boundary mobility did not take place in these garnets. On the basis of above features, we consider that it can only be explained by plastic deformation of the garnets. The clusters of water molecules present in garnet was directly associated with mechanical weakening and inducing in plastic deformation of garnet by glissile dislocations. Investigate of LPO, strain analysis, TEM indicated that these clinopyroxenes developed strong elongation, high aspect ratios, and developed dislocation loop, dislocation wall and free dislocations. These indicated that the deformation mechanism of the clinopyroxenes plastically from the Dabie Mountains is dominant dislocation creep under the condition of the UHP metamorphic conditions. There are some bubbles with dislocation loops attached to them in the omphacite crystal. The bubbles attached to the dislocation loops sometimes form a string of bubble beads and some loops are often connected to one another via a common bubble. The water present in omphacite was directly associated with hydrolitic weakening and inducing in plastic deformation of omphacite by dislocations. The role of water in brittle deformation. Using microscopy, deformation has been identified as plastic deformation and brittle deformation in UHP minerals from the Dabie Mountains. The study of micro-tectonic on these minerals shows that the brittle deformation within UHP minerals was related to local stresses. The brittle deformation is interpreted as being caused by an interaction of high fluid pressure, volume changes. The hydroxyl within UHP minerals transported water molecules with decreasing pressure due to their exhumation. However, under eclogite facies conditions, the litho-static pressure is extreme, but a high fluid pressure will reduce the effective stress and make brittle deformation possible. The role of water in prograde metamorphism. Geochemical research on jadeite-quartzite and associated eclogite show that the protoliths of these rocks are supracrustal rocks. With increasing of temperature and pressure, the chlorite, biotite, muscovite was dehydrous reaction and released hydrous component during the subduction of continental lithosphere. The supracrustal rocks were transformed UHP rocks and formed UHP facies assemblage promotely by water introduction, and was retained in UHP minerals as hydrous component. The water within UHP minerals may be one of the retrograde metamorphic fluids. Petrological research on UHP rocks of jadeite-quartzite belt shows that there was existence of local fluids during early retrograde metamorphism. That are: (1) coronal textures and symplectite around relict UHP minerls crystals formed from UHP minerls by hydration reactions; (2) coronal textures of albite around ruitle; and (3) micro-fractures in jadeite or garnet were filled symplectite of Amp + PI + Mt. That indicated that the reactions of early retrograde metamorphism dependent on fluid introduction. These fluids not only promoted retrograde reaction of UHP minerals, but also were facilitate to diffuse intergranular and promote growth in minerals. Therefore, the hydrous component in the UHP minerals can not only take important part in the UHP metamorphic fluid during subduction of continental crustal rocks, but also their hydroxyl transport water molecules with decreasing pressure and may take part in the retrograde metamorphic fluid during their exhumation. 7. The role of water in geochemistry of UHP jadeite-quartzite. Geochemical research show that there are major, trace and rare earth element geochemical variations in the jadeite-quartzite from the Changpu district of Dabie Mountains, during retrograde metamorphic processes from the jadeite-quartzite--gneiss. The elements such as SiO_2、FeO、Ba、Zr、Ga、La、Ce、PTN Nd% Sm and Eu increase gradually from the jadeite-quartzite to retrograded jadeite-quartzite and to gneiss, whilst TiO_2. Na_2CK Fe2O_3、Rb、Y、Nb、Gd、Tb、Dy、Ho、Er、Tm、Yb decrease gradually. And its fO_2 keep nearly unchanged during early retrograde metamorphism, but decreased obviously during later retrograde metamorphism. These indicate that such changes are not only controlled by element transformation between mineralogical phases, but also closely relative to fluid-rock interaction in the decompression retrograde metamorphic processes.

乌兰图嘎超大型锗矿床含锗煤的矿物学

内蒙古乌兰图嘎锗矿是我国近年来发现的产在煤层中的超大型锗矿床,锗金属储量达1600 t。以乌兰图嘎超大型锗矿床的含锗煤为研究对象,利用X射线衍射(XRD)、带能谱的扫描电镜(SEM-EDX)和电子探针(EPMA)详细研究了乌兰图嘎含锗煤及其同时代的红旗煤矿无矿煤的矿物学特征。分析结果表明,乌兰图嘎含锗煤中的主要矿物包括石英、蒙脱石;次要矿物包括长石、高岭石、伊利石;另含少量三水铝石、角闪石、叶蜡石、石膏、绿泥石、锐钛矿、黄铁矿、方解石、白云石和草酸钙石;微量的锆石、闪锌矿、白钨矿、重晶石、黄铜矿、卤化物、磷酸盐以及含Pb、Bi、Cr、As和Sb矿物。未发现含锗矿物。推测含锗煤中的锗可能主要呈有机结合,而Ba、Zn、Ti、W、Pb、Bi、Cr、Fe、As、Zr、Sb、Cu和REE可能主要与矿物相结合。此外,首次在乌兰图嘎含锗煤及红旗煤矿无矿煤中发现含银颗粒或自然银,推测胜利煤田的褐煤可能有相当规模的Ag矿化。

新疆霍什布拉克铅锌矿床地质、地球化学特征研究

新疆霍什布拉克铅锌矿床的矿体和含矿地层的产状一致,主矿体的矿石具有条带状、纹层状构造,矿石中大量发育霉球状、管状和环带状生物结构,显示出层控、热水沉积成因的特点。含矿地层和矿石样品的主量元素PER图解显示含矿碳酸盐岩以含石膏的灰岩为主,围岩的白云岩化微弱,矿化与硅化关系密切。矿石、含矿碳酸盐岩和页岩、粉砂质灰岩和泥质粉砂岩等碎屑岩具有各自鲜明的微量元素分布特征,上层矿体矿石中较强的富集过渡族元素Ti、V、Cr、Mn、Co、Ni、非活动性元素Zr、Hf及大离子亲石元素Sr和Pb,亏损活动性元素Na、K、Rb、Ba和非活动性元素Nb、Th。其围岩重结晶泥晶灰岩富集Ti、Mn、Ni、Sr和Pb,亏损Na、K、V、Fe、Rb、Ba、Zr、Hf、Nb和Th。下层矿体的围岩页岩和泥质、粉砂质灰岩样品的微量元素分布在平均上地壳线附近,部分样品较明显的富集Ti、V、Cr、Mn、Co、Ni、Rb、Y、Zr和Hf,亏损Na、Fe、Sr、Nb。上层矿体矿石和下层矿体围岩中的部分碎屑岩富集强亲岩浆元素Cr、Co、Ni,且上层矿体矿石的稀土元素分布模式具有强的正Eu异常,部分下层矿体围岩具有较明显的正Eu异常。地质和地球化学特征显示该矿床属于热水沉积矿床中的SEDEX型矿床.

樟村-郑坊黑色岩系钒矿床地质地球化学研究

樟村－郑坊黑色岩系钒矿床产于江南古岛弧外侧的浙赣海底盆地中(即钱塘拗陷西缘)，盆地南面即为著名的绍兴-江山-东乡深断裂，其西段为占华南洋块与江南古岛弧系的碰撞拼接带，东段为江南古岛弧与华夏古陆的对接带。临近矿床的北西方向即北东走向的东乡－德兴－歙县深断裂，为九岭地体与怀玉地晚元古代拼接带。区内发育的构造体系影响了地层的沉积、分布以及岩性，以绍兴-_江山-东乡深断裂为界，以北为江南岛弧区型沉积，以南则为古华南洋(华南褶皱系)型沉积，二者岩性、厚度均有很大的差异；绍兴-江山-东乡深断裂以北，以东乡-德兴－歙县深断裂为界，北西部广泛出露元代双桥山群(九岭群)并零星或呈断块状出露了晚古生代至中生代的地层，南东部地区则除在深断裂边缘狭长地区内分布元古代漆工群外，广泛出露了震旦-奥陶纪的地层，在紧靠绍兴-江山-东乡深断裂的北侧也有晚古生代-中生代的地层展布。矿区出露的地层有震旦系、寒武系、奥陶系和第四系。含矿岩系为下寒武统，矿体主要赋存在荷塘组的下部，即荷塘组上段的第一亚段(_1h~(2-1))。为—套黑色(碳质)硅质岩-细碎屑岩夹少量碎屑碳酸盐建造。反应了含矿岩系形成时缺少陆源粗碎屑和碳酸盐的非补偿性的深水环境，可能属于前弧斜坡、前弧台地或前弧盆地。矿床中的黑色岩系含矿建造主要岩石类型为黑色硅质岩和黑色富(含)长石岩矿物成分主要为石英、长石、粘士(伊利石或绢云母)以及黄铁矿、重品石等。整套岩系富含污染型有机碳。电子探针分析表明，岩石中的长石基本都是钡冰长石，其中Ba的含量最高达18.91％。仅偶见钾长石。因此证实了含矿岩系中发现有大量的钡冰长石存在，富(含)长石岩应为富(含)钡冰长石岩。钡冰长石的产出环境极为有限，黑色岩系中的钡冰长石被认为是热水沉积的标志性矿物，是热水沉积矿床在(早期)成岩作用过程中形成的自生矿物。矿床的容矿岩石是富(含)钡冰长石岩。电子探针研究表明，V主要赋存在一种可能是未定名矿物族的V－Ti氧化物和钾伊利石中。这种V-Ti氧化物的化学通式为V_2O_3·nTiO_2，n = 4-9；对该类矿物微区X-衍射的数据分析表明，该类矿物可能属于三斜晶系。整个含矿岩系富Ba、K、V，缺Na、Mn和Mg、Ca。矿床的地质地球化学研究表明，V与火山或热水沉积来源的元素Ba、Se和亲基性元素Cr、Co、Ni、Ti、Fe等呈明显的正相关，表明它们之间可能的同源关系，也显示了它们不同于正常沉积环境产物的特征，可能代表了热水沉积作用；此外，V与K、Al、Ga也呈明显的正相关，这可能是两方面原因造成的：1．含V岩石中大量存在钡冰长石，且V含量随Ba含量的增高而增高：2．一部分V存在于粘土矿物之中。因此导致了V与Al、K的正相关。至于Ga，由于其离子半径与Al~(3+)相似，因而其地球化学行为受Al~(3+)的控制，所以也与V呈正相关关系。V与LOI、Si等负相关。 REE研究表明，矿床中的硅质岩LREE与HREE强烈分馏，球粒陨石标准化分布模式表现为右倾的没有或有极弱的Ce负异常、有中等的Eu负异常的图形，其NASC分布模式为一右倾的图形，这可能反应了未与海水充分混合的热水快速化学沉积过程。作为容矿岩石的富(含)钡冰长石岩的球粒陨石标准化模式为右倾的有中等Ce负异常和中等Eu负异常的图形，NASC标准化分布模式富集中稀土和重稀土，与现代热水沉积物相似。弱Yb负异常可能反应了玄武岩的REE分配模式。地质和地球化学特征表明了该矿床可能的热水(喷流)沉积成因。硅质岩是典型的热水沉积岩，富(含)钡冰长石岩是陆源物质在同生沉积过程中受到热水流体作用改造形成的热水沉积岩。V、Ti、Ba、Si等元素可能来源于海底火山岩，Al、K则可能来源于陆源物质和海底岩石的海解作用。该矿床可能应属于主要为海底化学沉积系统的海底热水环境。基于对其地质地球化学特征的考察，作者对该矿床的成矿模式作了以下假设：下渗的海水与海底岩石发生反应并在此过程中受到下部热源的加热，使其变为酸性且通过淋滤富含Ba、V、Ti、Co、Cr、Mo、Ni、Si等元素；热水溶液沿温度和压力降低的方向折回海底，透过海底的松散沉积物，并最终溢出海底，由于温压的释放和海水的混合，热水流体迅速达到饱和并以各种方式沉积出流体中的元素：V、Ti、Ba、Si等。在通过海底沉积物时，流体在其中进行了交代。

广西贺县龙水金矿床的同位素地球化学研究及成因探讨

广西贺县龙水金矿位于湘桂稳定区，桂粤交界山脉的北段，博白-茶陵深断裂的西侧，区内广泛发育加里东期到燕山期的花岗岩，出露的基底地层主要为震旦系到寒武系。本文主要研究龙水金矿II号矿化带。该带位于寒武系水口群清溪亚群和大宁花岗闪长岩体的接触带附近，围岩为寒武系的碳质板岩，矿脉为硫化物石英脉，主要有黄铁矿、方铅矿、闪锌矿和石英等矿物。金矿化与硫化物密切相关。主要的金矿物为银金矿，少许自然金。确定金矿床的成矿年龄一直是个比较刺手的问题。本文选择矿脉中信为是成矿期的石英作为Rb-Sr等时年龄测定的对象，是基于其纯净和其中的原生气液包体基本可代表成矿热液的特征。结果表明其Rb-Sr等时年龄为120.5Ma，并认为此年龄代表了成矿年龄。有石英Rb-Sr等时线的~(87)Sr/~(86)Sr初始比为0.732089, 与矿脉中碳酸相加矿物的Sr同位素比值（约为0.7337-0.7402）一起，表明Sr应是来自地壳的富Rb盐矿物的Sr源区。另外，为了与围岩的蚀变年龄对比，测定了近矿围岩的Rb、Sr同位素组成，结果形成两条等时线，年龄分别为245.9 Ma和173.6 Ma，表明成矿以前至少发生了两次地质事件，导致了Sr同位素的均一化。这两次地质事件分别与华南的东吴运动及燕山运动第一幕相对应。矿石Pb同位素的~(206)Pb/~(204)Pb、 ~(207)Pb/~(204)Pb 和~(208)Pb/~(204)Pb 分别在18.4-18.9、15.6-16.1和38.4-39.6的范围内，并在~(207)Pb/~(204)Pb vs ~(206)Pb/~(204)Pb坐标图上呈现出斜率为1左右的线性排布。只有个别数据点要以得出依据Doe模式的模式年龄，约为200 Ma。在Zart,am Pb构造模式中，矿石Pb同位素数据大部分位于上地壳Pb线以上，呈现出富放射性成因Pb的特征。为了解释异常Pb的成因，本文进行了定量计算。结果表明矿石Pb为古老的存留地壳Pb与少地幔源Pb的混合，即矿石Pb同位素经历了这样的演化过程：在39-29.8亿年间由地幔分异出的地壳 Pb，未参与壳幔循环作用，一直到燕山期，与少量幔源Pb混合，并加入成矿。混合μ值为9.85-10.22。矿石的地质情况及矿石Pb同位素的Δα-Δβ-Δγ示踪结果均支持这一结论。本文初次研究了脉石英中的U、Pb同位素组成。脉石英中Ｕ含量很低。Pb同位素组成基本可以划分为两组，一组为与方铅矿数据近似的普通Pb组成，另一组则较富放射性成因Pb，并向围岩的Pb同位素组成漂移，可能是随着热液的演化和大气降水的加入，受围岩Pb的影响所致。矿脉中硫化物样品的S同位素比值（加权平均为0.16‰）和碳酸盐矿物样品的C同位素比值（在-0.1～-4.1‰的范围内），表明其应为内生来源。根据脉石英的气液包体均一温度（180-250 ），计算与脉石英存在0同位素平衡的热液的同位素的同位素组成，结果为1.2～-4.8‰，表明有大气降水的参与。石英气液包体水溶液为弱碱性，其成分分析表明其中K_2O/Na_2和CaO/MgO（分别根据K~+/Na~+和Ca~(2+)/Mg~(2+)的换算）与围岩相差很大。另外，矿石中微量元素主要为Au、A2g、Cu、Pb、Zn、Co、Ni、Mo、Bi、Ga、As、Sb、和Hg，而围岩中微量元素则主要为Cu、Ni、Mn、V、Zr、Ti、Cr和Ba。因此，热液中成矿元素主要不是来自围岩。黄铁矿的Co/Ni、S/Se/的比值可以指示热液化的来源。龙水金矿矿脉中黄铁矿的Co/Ni > 1，S/Se < 15000，均在与岩浆作用有关的热液范围内。因此，热液活动应主要与岩浆岩有关。矿石、围岩和花岗闪长岩的稀土配分模式相似，均呈现向右倾斜的V字型，并且类似于太古代后沉积岩。结合Pb、Sr同位素的研究，推测花岗闪长岩的源岩主要为古老的地壳物质。概括起来，龙水金矿床为约120.5 Ma形成的中低温热液矿床；热液中成矿物质主要来自花岗闪长岩。由于围岩与矿床紧密的空间联系及围岩中的高Au含量，围岩可能提供了一部分Au及其他成矿物质。

基底对光学薄膜弱吸收测量的影响

对表面热透镜技术测量光学薄膜弱吸收低频调制时不同基底对测量的影响进行了理论分析。用Lambda-900分光光度计测量了K9和石英基底的Ti3O5单层膜的吸收值，将该组样品作为定标片；用表面热透镜装置分别测量了BK7和石英空白基底及HfO2，ZnO两组不同基底不同厚度单层膜样品的吸收。通过分析比较同一工艺条件下镀制的不同基底薄膜样品用与其同种和不同种基底定标片定标测量的结果，表明在低频测量时需要用与测量样品同种基底的定标片定标；不同厚度样品的测量结果表明，在不能严格满足热薄条件时，测量结果需引入修正值。

In vitro anti-HIV and -HSV activity and safety of sodium rutin sulfate as a microbicide candidate

Sodium rutin sulfate (SRS) is a sulfated rutin modified from the natural flavonol glycoside rutin. Here, we investigated its in vitro anti-HIV and -HSV activities and its cytotoxic profile. Fifty percent inhibitory concentration (IC50) values of SRS against HIV-1 X4 virus IIIB, HIV-1 R5 isolates Ada-M and Ba-L were 2.3 +/- 0.2, 4.5 +/- 2.0 and 8.5 +/- 3.8 mu M with a selectivity index (SI) of 563, 575 and 329, respectively. Its IC50 against primary R5 HIV-1 isolate from Yunnan province in China was 13.1 +/- 5.5 mu M, with a Sl of 197. In contrast, unsulfated rutin had no activity against any of the HIV-1 isolates tested. Further study indicated that SRS blocked viral entry and virus-cell fusion likely through interacting with the HIV- I envelope glycoprotein. SRS also demonstrated some activity against human herpes simplex virus (HSV) with an IC50 of 88.3 +/- 0.1 mu M and a Sl of 30. The 50% cytotoxicity concentration (CC50) of SRS was >3.0 mM, as determined in human genital ME 180, HeLa and primary human foreskin fibroblast cells. Minimum inhibitory concentration of SRS for vaginal lactobacilli was >3.0 mM. These results collectively indicate that SRS represents a novel candidate for anti-HIV-1/HSV microbicide development. (C) 2007 Elsevier B.V. All rights reserved.