添加纳米TiO2的氯醚树脂的XPS分析

在紫外线老化前后,利用光电子能谱(XPS)研究了分别添加金红石型和锐钛型纳米TiO2的氯醚树脂。研究发现,氯醚树脂中氯、氧元素具有表面富积现象——趋肤效应,而钛和碳元素在内层聚集;添加颜料粒子越小,在表面含量越大;金红石型纳米二氧化钛紫外屏蔽性好,减缓树脂老化;而锐钛型纳米二氧化钛具有显著的光催化活性,加速树脂老化。因此,金红石型纳米二氧化钛将是一种有前途的紫外线吸收剂。     

Li_2S─B_2O_3（─LiBr）玻璃的结构表征

用ＮＭＲ和ＸＰＳ技术研究了Ｌｉ２Ｓ─Ｂ２Ｏ３（─ＬｉＢｒ）体系硫氧化物玻璃的结构，结果指出，４─配位硼分数Ｎ４仅仅由玻璃Ｌｉ２Ｓ／Ｂ２Ｏ３摩尔比决定．而与ＬｉＢｒ含量无关，这表明Ｌｉ２Ｓ作为变形剂参与了玻璃网络形成，而ＬｉＢｒ仅作为参杂剂溶解于玻璃基体中，并进入网络间隙。含ＬｉＢｒ玻璃７ＬｉＮＭＲ谱运动变窄说明Ｌｉ＋离子是移迁离子．Ｓ２ｐ的ＸＰＳ解析谱证实了玻璃中桥硫和非桥硫的存在．Ｌｉｌｓ结合能值显示出Ｌｉ＋离了迁移的化学环境。     

邻二氮杂菲银/蒙脱石复合物的XPS和TG研究

用微波辐射法制备了邻二氮杂菲银/蒙脱石抗菌复合物。以X射线光电子能谱(XPS)及热重分析(TG/DTG)对抗菌复合物及其热处理产物的表面特性及热稳定性进行探讨。结果表明:邻二氮杂菲银络离子插入到蒙脱石层间后,层间水含量减少。样品表面的银以邻二氮杂菲银络合物的状态存在,煅烧温度低于或等于200℃时,邻二氮杂菲银络合物没有发生分解;当煅烧温度到达300℃时,邻二氮杂菲银络合物开始分解产生新的物质Ag2O;当煅烧温度到达400℃时,样品表面开始有银粒子产生,随着温度的增加,银粒子的粒径不断增加。     

Application of Chlorite Geothermometry to Hydrothermal Alteration in Toyoha Geothermal System, Southwestern Hokkaido, Japan

In this study, we applied chemical geothermometers to the estimation of formation temperatures of chlorites from various types of hydrothermally altered rocks in the Toyoha geothermal field, using core samples from six drill holes (TH-2 to TH-7) together with wasted ore samples from Toyoha vein-type ore deposit. Based on the preliminary examination of mineral assemblages by X-ray powder diffraction and optical microscopy, hydrothermal alteration observed through the drill holes was classified into four types of alteration zones: propylitic, mixed-layer minerals, kaolin minerals, and ore mineralized zones. The mineral assemblage of the ore mineralized zone observed through TH-2, TH-4, and TH-6 is similar to those of Toyoha ore veins reported previously. The Fe³⁺/ΣFe ratios of chlorites were determined by X-ray photoelectron spectroscopy (XPS), in addition to the usual microprobe analyses. The ratios ranged from 0.20–0.26 for chlorites from the propylitic alteration zone and from 0.13 to 0.17 for those from the ore mineralized zone associated with sulfide minerals. After correcting the Fe³⁺ contents in the octahedral sites of chlorite structures, we obtained acceptable temperatures of the chlorite formation by application of geothermometers, for instance, a similar range of 150–300°C for chlorites from either the propylitic zone or the ore mineralized zone developed through TH-2, TH-4, and TH-6. Chlorites from the ore mineralized zone proximal to the Toyoha deposit are characterized by high Fe and Mn contents compared to the propylitic chlorites, which is similar to the Toyoha vein-filling chlorites; the formation temperatures were close to both the homogenization temperatures of fluid inclusions and the present subsurface temperatures measured through drill holes. Chlorites from the Toyoha ore veins, however, gave slightly higher formation temperatures (180–350°C) than those of chlorites from the ore mineralized zone in the drill cores. This suggests that several types of hydrothermal alteration occurred at different stages in the Toyoha geothermal field and the composition of product chlorite was controlled not only by the temperature but also the composition of fluid related to the formation. Reliable estimation of temperature for the chlorite formation provides basic information on evaluating correctly other physicochemical conditions prevalent at the formation.     

孔道结构化合物(H3NCH2CH2NH3)3[(VO)4(PO4)2(HPO4)4]的钒氧化态与热稳定性关系研究

热处理脱除有机模板易导致VPO体系孔道结构化合物结构破坏,从而阻碍此类材料的实际应用。以孔道结构化合物(H3NCH2CH2NH3)3[(VO)4 (PO4 )2 (HPO4 )4 ](简称V2P3 en)为研究对象,利用热分析(DSC TG)、动态原位高温X 射线衍射(XRD)及多功能X 射线光电子能谱(XPS)等方法,研究了该化合物在不同气氛热处理过程中模板脱除及结构演化规律,重点探讨了钒氧化态的变化对结构稳定性的影响。结果表明,加热过程中随着有机模板的分解脱除,形成较强的还原环境,骨架中的部分钒被还原(V4+→V3+),使原有的配位环境([VⅣO5]三角双锥、[VⅣO6]畸变八面体)与钒的氧化态不符而导致结构重组。因此,钒氧化态的变化是影响热稳定性的重要因素之一。     

甘肃阳山金矿床含砷黄铁矿及毒砂的XPS研究

阳山金矿是西秦岭地区新发现的超大型金矿.载金矿物中元素的赋存状态是认识成矿机理、评价矿床采选冶过程对环境影响的重要依据.作者运用XPS技术测定了载金矿物含砷黄铁矿和毒砂新鲜断裂面的As3d、Fe2p及S2p的存在形式和相对原子百分含量.结果表明,在含砷黄铁矿表面,超过50%的As以As~(-1)形式存在,约18%～20%的As以As~(3+)形式存在,约30%的As以As~(5+)形式存在.在毒砂表面,超过60%的As以As~(1-)形式存在,约30%的As~(3+)形式存在,其余10%的As主要以As~(3+)形式存在.分析证明As、Fe、S等元素在含砷黄铁矿和毒砂中主要以As`(1-)、Fe~(2+)、S~(1-)形式存在外,As元素可能还以As~(3+)形式存在于含砷黄铁矿及毒砂结构中.     

Interpretation of Ni2p XPS spectra of Ni conductors and Ni insulators

Ni2p_3/2 X-ray photoelectron spectral peak binding energies of Ni metal, NiS, and NiAs (all conductors) span a range of about 0.5 eV and are, consequently, insensitive to formal Ni oxidation state and to the nature of the ligand to which Ni is bonded, relative to other metals (e.g., Fe). Ni2p_3/2 peak structures and binding energies reflect two energetic contributions. The major contribution is that associated with the electrostatic field produced by ejection of the Ni(2p) photoelectron, the minor contribution is the relaxation energy associated with filling unoccupied, conduction band 3d⁹ and 4s Ni metal orbitals. These conduction band orbitals become localized on the Ni photoion (and sometimes filled) in response to the field created by the photoemission event. Because only the core Ni2p electron and nonbonding orbitals of predominantly metallic character are affected, the main peak of all three conductors are affected similarly, leading to similar Ni2p_3/2 main peak binding energies. NiO, Ni(OH)₂, and NiSO₄ are insulators in which Ni is divalent and is bonded to oxygen. Although Ni is bonded to oxide in these phases, Ni2p binding energies differ substantially, and reflect primarily the nature of the ligand (O²⁻, OH⁻, SO₄ ²⁻) to which Ni is bonded. The influence of the ligand is the result of charge (electron) transfer from valence band bonding orbitals of dominantly ligand character, to unoccupied conduction band orbitals localized on Ni photoions. Relaxation energy resulting from charge transfer is acquired by the emitted photoelectron, thus Ni2p_3/2 photopeak binding energies of these insulators reflect the nature of the ligand to which Ni is bonded. The Ni2p main peak binding energy of these conductors and insulators is a poor guide to Ni oxidation states. The Ni2p_3/2 binding energies of insulators reflect, however, the nature of the ligand in the first coordination sphere of Ni. The intensity of the Doniach–Sunjic contribution to Ni2p XPS spectra of NiS and NiAs is dependent on the nature of the ligand. The Doniach–Sunjic contribution to ligand XPS core-level photopeaks (e.g., S2p of NiS and As3d of NiAs) has not been explained and is poorly understood. Received 24 May 1999 / Revised, accepted: 30 June 1999     

铜在坡缕石中的吸附位置和吸附机理研究

对四个吸附铜的坡缕石的解吸附实验研究表明,被解吸附的铜来自于坡缕石的表面和纤维状晶体的网状空隙。吸附铜的坡缕石的X射线光电子能谱（XPS）上出现了932．5eV和933．7eV的光电子峰,表明坡缕石表面的铜以Cu^＋和Cu^2＋的形式存在;傅立叶变换红外吸收光谱（FTIR）上八面体离子的吸收峰出现规律性偏移,其中Mg3OH和Al2□OH吸收峰向高频方向移动了3～5cm^-1,部分铜离子进入到坡缕石的晶体结构的通道中;电子顺磁共振谱上（ESR）出现了g=2．34、2．12、2．08和2．05等4个信号：表明铜离子位于H^＋难以到达的位置。吸附铜的坡缕石的矿物学研究及其解吸附实验的结果均表明铜在坡缕石中以3种形式存在：①以Cu^＋和Cu^2＋的形式吸附在坡缕石纤维的表面,与坡缕石表面的悬空氧成键;②以ECu（H2O）4]^2＋的形式存在于坡缕石的晶体结构的微空腔中（通道）;③以Cu^2＋的形式存在于坡缕石晶体结构中的硅氧四面体六元环的底部或八面体位。     

Synthesis of Pb-Feldspar by Ion Exchange Reaction and Its Implications

Feldspar and Pb（NO3）2 were mixed and reacted at T=380℃ to synthesize Pb-feldspar. In the XRD （X-ray diffraction） pattern of the product, the d values （crystal lattice spacing） of the five peaks are 0.654, 0.342, 0.332, 0.327 and 0.257 nm. The XPS analysis results show that the binding energy of Pb 4f（7/2） in the feldspar was between 137.81-138.03 eV. Pb^2＋ can replace alkali and alkali earth cations in the feldspar structure through ion exchange reaction to form Pb-feldspar.     

基于XML的地质信息共享与交换模型

作者简单介绍了了地质信息资源网络化的意义和发展状况，最近几年地质信息的网络化取得了飞跃的发展，在信息共享和交换方面取得了一定进展，但也暴露出许多不足，作者提出了在信息使用中数据源和客户端使用者之间建立了基于XML－Externsible Markup Language的地质信息共享与交换网络服务层的思路，对网络服务层的概念和优点进行阐述，并通过程序代码和简单注释说明使用XML技术的实现方案和方法。