Zinc doping effect on the optical bands of cr3 in LiNbO3: Zn, Cr crystals

The optical absorption and luminescence of Cr³⁺ ions in ZnO doped LiNbO₃:Cr³⁺ crystals have been studied. It has been found that ZnO produces the same effect as that observed in MgO co-doped samples: A strong reduction in the Cr³⁺ concentration together with a shift in the ⁴A₂ → ⁴T₁ vibronic transition to lower energy. As in the case of MgO co-doped samples a new Cr³⁺ centre is formed in ZnO co-doped samples.     

Electronic properties of metal—amorphous silicon barriers and junctions

The aim of the paper is to review certain aspects of the electronic structure and properties of metal—a-semiconductor barriers which are of relevance to the theme of this Conference. The discussion will be confined to amorphous silicon (a-Si) prepared by the plasma decomposition of silane, which is of much current interest as an electronically controllable model material. A brief survey of preparation and of some electronic properties of a-Si will be given. We then turn to the model of an ideal Schottky barrier and discuss its application to metal—a-Si contacts where the localised state distribution in the a-semiconductor has a important effect on barrier space charge and profile. In a more realistic model interfacial states at a thin oxide—semiconductor interface are taken into account. In this connection we shall discuss recent experimental work using internal photoemission to investigate the height of metal/a-Si barriers as a function of the metal workfunction. Analysis of these and other results suggests that interfacial state densities on a-Si barriers lie between 10¹³ and 10¹⁴ cm⁻² eV⁻¹, remarkably similar to corresponding values for crystalline Si barriers. The final section of the paper deals with the electronic structure of a-Si p⁺ -i-n⁺ junctions. The promising photovoltaic properties of these devices will briefly be considered.     

GAS ABSORPTION IN A HOLLOW FIBER DEVICE

The absorption of S0² and NH³ from air and air/CO ² streams was studied for the first time in a certain novel hollow fiber mass transfer device, for various inlet gas compositions, liquid compositions, gas flow rates, and liquid flow rates. The gas and liquid flows were countercurrent. Analyses of the amounts of S0²and NH³ absorbed demonstrate that the hollow fiber unit has a relatively small membrane resistance and is an effective gas scrubbing device. Additionally, it offers a large interfacial area per unit volume, and avoids flooding problems entirely     

化学交换法分离锂同位素的理论及新技术研究进展

发展核能是我国可持续发展的重要举措,锂作为重要的能源战略金属,锂同位素（⁶Li、⁷Li）分离是核能开发必须解决的关键技术难题,受到国际及国内科学家的广泛关注。⁶Li、⁷Li具有完全相同的电子结构,两者具有几乎相同的化学性质,分离难度极大。本文简要回顾了20世纪60年代以来化学交换法分离锂同位素取得的进展,重点综述了同位素分离的理论研究以及近五年来锂同位素分离的新材料、新介质。针对目前冠醚在分离锂同位素过程中存在的冠醚分子易流失、Li⁺的分配系数低等问题对现有的研究和报道进行了总结,有望为锂同位素分离新材料和新体系的开发提供指导。     

SrFe0.6Co0.4O3催化降解孔雀石绿的研究

具有复杂分子结构的三苯甲烷类染料孔雀石绿是一种典型的较难降解染料,是工业废水处理的难点之一。本文根据Goldschmidt半径容差规则法,设计了用于孔雀石绿降解的ABO₃型SrFe_(1-x)Co_xO₃催化剂,并选择出活性较高的SrFe_0.6Co_0.4O₃催化剂。通过XRD、SEM、BET吸附及XPS分析表明:该催化剂是纯净钙钛矿结构,颗粒形貌为无规则堆叠的“蜂窝”片状;吸附等温线没有明显的回滞环,说明没有“墨水瓶”类孔结构;XPS谱中,B位离子同时存在Fe²⁺/Fe³⁺和Co²⁺/Co³⁺ 4种价态离子,且反应前后,4种离子的分布比例有较大变化。根据实验结果,推测该催化反应机理为:催化剂B位Co³⁺与溶解氧形成活性氧[O₂]⁺和Co²⁺;活性氧[O₂]⁺完成氧化反应后其正电荷转移到B位Fe²⁺上形成Fe³⁺,Fe³⁺的正电荷可再转移到Co²⁺形成Co³⁺,完成催化过程的电荷转移与循环。     

Untersuchung über die anionenadsorption mit hilfe markierter ionen

From previous work, the adsorption of anions is regarded as an essential factor for the different corrosion behaviour of metals in solutions containing different anions. Adsorption is measured by means of ³⁶Cl⁻, ⁸²Br⁻, ¹⁸ F⁻, ³⁶ClO₄⁻, ³⁵O₄²⁻, H³⁵S⁻ and ¹⁴CN⁻ on Pt, Ni and Fe in the form of sheets and evaporated films. Besides the determination of the adsorption after dipping into the solution, a method has been developed for the measurement of adsorption in contact with the solution and for the determination of its kinetics. The method can also be applied to O₂-free metal surfaces produced under vacuum. In this case, however, very rapid adsorption is observed, whereas normally saturation is reached only after many hours. It is concluded that, in general, exchange between oxygen on the metal and the anion takes place rather than simple adsorption.

The distribution of the anions adsorbed on the metal surface has been studied by autoradiography; adsorption takes place preferentially at the grain boundaries and increases when the crystal size decreases.

These results confirm the interpretation of passivation as a competition between various processes: metal dissolution, coverage by a passivating oxide film, and displacement of oxygen by anions.     

Effects of External Loading of Fiber on Fiber/Matrix Interfacial Shear Strength

The effect of external loading of fiber on fiber/resin interfacial adhesion has been studied using the microbond technique. The results show that the applied load on the fiber weakened the fiber/matrix bonding at the interface. The effect of cyclic loading of fiber on fiber/matrix interfacial adhesion was also investigated by loading and unloading the fiber by means of a moving platform oscillating vertically at a specific frequency. After the cyclic loading process, residual bond strengths were measured using the TRI microbond pullout procedure.

Fiber/matrix combinations of Kevlar 49^®/Epon 828^® and Kevlar 49/polycarbonate have been investigated using this technique. Significant bond strength reduction is observed when load is applied and after cyclic loading. In the latter case, most of the loss occurs after relatively few cycles. Possible bond weakening mechanisms are proposed to explain the experimental results.     

Diamond growth by carbon ion implantation of diamond

Medium energy (5–25 keV) ¹³C⁺ ion implantation into diamond (100) to a fluence ranging from 10¹⁶ cm⁻² to 10¹⁸ cm⁻² was performed for the study of diamond growth via the approach of ion beam implantation. The samples were characterized with Rutherford backscattering/channelling spectroscopy, Raman spectroscopy, X-ray photoemission spectroscopy and Auger electron spectroscopy. Extended defects are formed in the cascade collision volume during bombardment at high temperatures. Carbon incorporation indeed induces a volume growth but the diamond (100) samples receiving a fluence of 4 × 10¹⁷ to 2 × 10¹⁸ at. cm⁻² (with a dose rate of 5 × 10¹⁵ at. cm⁻² s⁻¹ at 5 to 25 keV and 800 °C) showed no He-ion channelling. Common to these samples is that the top surface layer of a few nanometers has a substantial amount of graphite which can be removed by chemical etching. The rest of the grown layer is polycrystalline diamond with a very high density of extended defects.     

烟杆废物热解动力学研究

通过热重分析（TGA）方法,采用单步和三平行反应模型分别考察烟杆废物的热解动力学。烟杆废物单步热解的平均活化能为182.4 kJ/mol,最适宜的反应机理函数为14级反应机理f（α）=（1-α）¹⁴。能量补偿效应结果显示烟杆废物的热解可以分为3个阶段α=0~0.32、α=0.32~0.80和α=0.80~1,各阶段的指前因子分别为2.88×10¹⁰、4.33×10¹⁴和9.76×10¹⁶s^-1。单步热解过程中伴有表观活化能的变化以及高级数反应的机理,不能合理地描述烟杆废物的热解机理。采用混合韦伯分布活化能模型考察了三平行反应热解动力学,结果显示：混合韦伯分布活化能模型能很好地拟合烟杆废物热解数据,相关系数R²≥0.997 6;3种伪组分的活化能大小符合E₀（木质素,195.26 kJ/mol）> E₀（纤维素,152.54 kJ/mol）> E₀（半纤维素,121.18 kJ/mol）的顺序;半纤维素的热解机理为一级反应f（α）=1-α,纤维素的热解机理属于成核机理,木质素的机理亦呈现级数反应,级数介于n=3~4之间,木质素的热解机理复杂,可能为多步反应。     

Electrical resistivity of transition metal ion doped Mullite

The electrical resistivity of pure mullite (3Al₂O₃.2SiO₂) varies from 10¹³ ohm-cm at room temperature (r.t.) to 10⁴ ohm-cm at 1400 °C. It was observed that by doping mullite with the 3d-type transition metal ions, e.g. Mn, Fe, Cr and Ti, the resistivity of mullite could be reduced to 10¹¹ ohm-cm, i.e. 1/100 that at r.t. and 1/5 that at 1400 °C. The resistivity of doped and undoped mullite decreased by 6–5 orders at about 500–600 °C but 4–3 orders between this temperature and 1400 °C. The 3d orbital electrons, the oxidation states and the concentration of the transition metal ions as well as the sites of mullite lattice occupied by the ions were found responsible for lowering of resistivity of mullite. Evidence of the presence of Mn²⁺, Mn³⁺, Fe³⁺, Cr³⁺ and Ti⁴⁺ ions in mullite had been obtained which entered the octahedral site. The Ti⁴⁺ ion which substituted Al³⁺ ion in the octahedral site of mullite structure appeared to be the most efficient one to reduce the resistivity. This has been confirmed by the results of activation energy of resistivity/band gap energy, Eg which was the lowest for mullite doped with 1·0 wt% Ti⁴⁺ ion. At 1·0 wt% concentration level, these ions lowered the resistivity of mullite to minimum.     

钛白粉生产工艺优化与设备改进

某公司1.5万t/a硫酸法钛白粉生产工艺存在“三废”排放量大、能耗高、生产成本居高不下等问题。针对以上问题对钛白粉生产工艺进行了优化,对设备进行了改造,主要包括酸解反应过程、煅烧尾气处理过程以及转窑系统等,最大程度地降低了钛白粉的生产成本。实践结果表明：将废酸回用于酸解反应,可将酸解率提高并稳定在95%以上,每吨钛白粉硫酸消耗从4.52 t下降到4.25 t;将偏钛酸二次洗水用作煅烧尾气喷淋水再回用到偏钛酸一次洗水,每年可节约蒸汽5.9×10³ t;改造转窑系统,提高了燃烧效率,每吨钛白粉煤气消耗从780 m³降至533 m³。通过以上工艺优化和设备改进,累计可降低钛白粉生产成本912.8元/t。     

CuSO4对氰化提金贫液中SCN-的沉淀效果以及对共存离子浓度的影响

针对氰化提金贫液循环利用过程SCN^-积累以及外排带来的环境污染问题,以CuSO₄作为沉淀剂处理某高浓度SCN^-贫液,考察了沉淀剂用量、沉淀时间及沉淀温度对SCN^-沉淀效果和对共存离子浓度的影响。结果表明,当在贫液中加入1.6倍化学反应计量的CuSO₄后于室温搅拌60 min,SCN^-的去除率达87.5%以上,体系中T_Cu、S₂O₃ ^2-和SO₃ ^2-浓度也大幅降低,同时得到纯度达97%以上的CuSCN产品。沉SCN^-后的贫液只需石灰中和并沉部分SO₄ ^2-后,其活性得到进一步恢复,可直接返回金精矿浸出工序充分利用其中的CN^-,实现提金贫液的循环利用。     

生物甲烷膜分离提纯系统的设计与优化

以厌氧发酵生物气为原料生产压缩天然气是大规模利用生物质资源的重要途径。首先,在过程模拟软件UniSim Design中基于有限元方法建立了中空纤维膜的离散数值计算模型,适合于模拟渗透切割比非常高的生物甲烷膜分离过程。以单级聚酰亚胺膜分离系统为例研究了关键操作条件--膜的进料压力对处理能力、甲烷收率及压缩天然气生产单耗的影响。目前的评估体系下,提高进料压力有利于提高处理能力和甲烷回收率,而压缩天然气生产单耗在2.70 MPa时最低,为0.46 kW·h·m^-3压缩天然气。通过分析渗透气的甲烷浓度变化趋势,开发了一级二段气体膜分离系统,兼具流程简单、设备投资低、甲烷收率高、产值高的优点。以处理1000 m³·h^-1生物气为例,甲烷收率达95.0%,压缩天然气产量500 m³·h^-1。对应地,装置总投资为3.8×10⁶ CNY,年运行费用及设备折旧为1.5×10⁶ CNY,年经济效益（毛利）超过2.50×10⁶ CNY。     

铁基载氧体辅助无烟煤焦富氧燃烧动力学分析

流化床铁基载氧体辅助富氧燃烧下传统石英砂床料被铁基载氧体替代,铁基载氧体扩展了传统床料的“热载体”的功能,另承担了“氧载体”的角色,为调节炉内氧分布与煤燃烧过程匹配提供了新思路。本文在热重实验平台探究了10%O₂/90%CO₂气氛下分析纯Fe₂O₃、赤铁矿及钢渣三种铁基载氧体辅助无烟煤焦燃烧特性及动力学。结果表明,相较于纯无烟煤焦燃烧,铁基载氧体辅助燃烧下无烟煤焦的燃烧特性得到显著改善,其中燃烧速率提高29%以上,燃尽温度降低65℃以上,综合燃烧指数提升2倍以上,活化能与指前因子同步增加且表现出“补偿效应”。三种铁基载氧体中分析纯Fe₂O₃对无烟煤焦燃烧特性的改善略优于赤铁矿和钢渣,钢渣可作为流化床铁基载氧体辅助富氧燃烧的床料替代石英砂。     

Kinetics of halogen-exchange fluorination of 2,6-dichlorobenzaldehyde

Under the conditions of phase transfer catalysis and nitrobenzene as the solvent, the halogen-exchange fluorination of 2,6-dichlorobenzaldehyde using KF as fluorinating agent was studied. The kinetics was investigated and the reaction rate constants were obtained under the optimum conditions of n(KF):n(2,6-dichlorobenzaldehyde):n(Ph₄PBr):n(acetone-furan crown ether) = 4:1:0.1:0.05 and temperatures of 433 K, 443 K, 453 K and 463 K. The results illustrated the activation energy of the first and the second step is 4.57 × 10⁴ J·mol^-l and 3.53 × 10⁴ J·mol^-1, respectively. The pre-exponential factor is 4.50 × 10⁵ h^-1 and 1.08 × 10⁴ h^-1, respectively. Thus a reliable kinetics data could be obtained for further research.     

碳羟基磷灰石/钾长石复合材料对镍的吸附性能研究

以钾长石为原料,用液相合成法制备碳羟基磷灰石/钾长石吸附剂（CHAK）去除水中的重金属镍,用静态吸附实验考察了CHAK添加量、溶液初始pH、吸附时间、镍初始浓度等因素对镍去除效果的影响,并结合动力学及热力学拟合探究吸附机理。结果表明：随着CHAK量的增加,对Ni ²⁺的去除率增加,但吸附量会降低;溶液pH=6时吸附效果达到最佳;吸附时间为10 h时吸附达到平衡;Ni ²⁺溶液的初始质量浓度为50~4 000 mg/L时,CHAK对Ni ²⁺的吸附量呈先增长后平稳趋势,饱和吸附量与原材料相比增大7.1倍。动力学及热力学拟合结果显示：准二级模型更符合描述该吸附行为。ΔH>0,表明该吸附过程为吸热反应,升温有利于吸附。ΔG<0,表明该反应能自发进行。     

Re: Contact Theory of Adhesion

Recently we have developed a contact theory of adhesion published under the title “Interfacial Contact and Bonding in Autohesion”.¹ The theory was formed for the case of polymers in a highly viscous state, where it is hard to bring them together for bonding. For low viscosity materials coalescence occurs very rapidly and contact is not a problem. However, most cases of adhesion that give us problems belong to the former case where establishment of contact between the two surfaces is the primary requirement. The rate of contact formation is controlled by the shape of the surfaces in contact, the viscous or viscoelastic properties of the material comprising them and the contact pressure. This is handled by extending Hertz' contact theory² by applying Alfrey's and Gurnee's elastic-viscous-viscoelastic analogy. Where-ever contact is established the interfacial bond strength may be obtained from molecular primary or secondary bond forces. This was obtained by using Good's⁴ 6-12 Lennard-Jones potential treatment which is an extension of Hamaker's calculations.⁵ Good has brought in the repulsive component in addition to the attractive forces. In case of polystyrene it is found that the intermolecular van der Waals' forces are sufficient to yield interfacial bond strength values equivalent in magnitude to the tensile strength of the polymer.     

On the possibility of the application of a radiotracer method for the in situ study of the accumulation of ions in corrosion products adhered to the surface of some steels

The sorption of ³⁶Cl labelled Cl⁻ ions into the layer of corrosion products adhered to the surface of corroding powdered steel samples has been studied as a function of the time at 1.8 × 10⁻² NaCl concentration. The effect of CrO²⁻₄ and SO₂₋₄ ions on the sorption process and the mobility of sorbed species was investigated.     

煤制天然气过程全局能量集成优化

我国正在大力发展煤制天然气项目实现清洁能源供给。然而现有煤制天然气示范项目存在能耗大、CO₂排放高、生产成本缺少竞争力的问题。本文从煤制天然气能量系统出发,通过全局能量集成实现煤制天然气项目的节能减排与经济效益的提高。根据煤化工示范项目特点,提出了煤制天然气过程全厂能量系统集成优化策略：建立了煤制天然气各单元过程模型,对全流程的物流和能流展开了详细的模拟计算;利用夹点技术对全厂内各单元过程的能量系统展开了用能分析;利用全局温焓曲线对全厂能量系统进行了分析,揭示出全厂能量利用效率低是由于高品位热量降质利用和低品位余热未得到合理利用引起的。通过装置间热回收集成和增设有机朗肯余热回收装置可有效地提高热回收率。通过全厂能量系统优化集成,燃料煤消耗由现有过程1.26t/kNm³（0℃、101325Pa标准状态）天然气下降到1.07t/kNm³天然气。由于公用工程系统消耗的减少,全厂能量利用效率由原来的57.2%提高到59.6%,同时CO₂排放可以由原来5.02t/kNm³天然气下降到4.66t/kNm³天然气。相比于现有过程,改进过程的总投资仅增加了2%左右,而单位生产成本由1.65CNY/Nm³下降到了1.59CNY/Nm³,对于年产20亿立方米煤制天然气厂每年可节约生产成本1.2亿元。     

NOTE The Application of Surface Analysis Techniques in the Adhesive Bonding of Oily Automotive Steel

There are fewer papers on the adhesive bonding of steel for structural applications than for aluminum and titanium alloys. However, the approach to the adhesive bonding of all three adherends has been similar, that is, the surfaces are pretreated prior to bonding. Trawinski, et al.^1,2,3 reviewed several conversion coatings or etching processes used for steel. Haak and Smith⁴ selected two surface treatments among nineteen based on minimal cost, simplicity and good durability. Smith⁵ has reported work on stainless steel-epoxy bonds under hydrothermal stress. Bischof, et al.⁶ investigated the effect of surface pretreatment of steel on bonding strength obtained with polyvinyl chloride. Ziane, et al.⁷ identified four fracture zones resulting from shear loading of epoxy bonded galvanized steel following four different surface pretreatments. But in some cases, as in the automotive industry, there is a need to bond oily steel directly without surface pretreatment. Rosty, et al.⁸ have reported a study of the role of fillers and cure temperature on the shear strength of oily steel bonded with epoxy. None of the reported research utilizes both microscopic and spectroscopic techniques to analyze the fracture surfaces.