不同Li/Nb摩尔比In∶Fe∶LiNbO_3晶体的生长及其光学性能

在Li NbO3(LN)中掺摩尔分数为1%的In和掺质量分数为0.03%的Fe,用提拉法技术生长具有不同n(Li)/n(Nb)[n(Li)/n(Nb)=0.94,1.05,1.20,1.38]的In∶Fe∶LN晶体。测试不同n(Li)/n(Nb)的In∶Fe∶LN晶体的吸收光谱、抗光致散射能力和指数增益系数,并计算晶体的有效载流子浓度。结果表明晶体样品随着n(Li)/n(Nb)增加,吸收光谱的吸收边发生紫移,抗光致散射能力增加,指数增益系数和有效载流子浓度增大。采用n(Li)/n(Nb)=1.38的In∶Fe∶LN晶体作记录介质,n(Li)/n(Nb)=1.05的In∶Fe∶LN晶体作位相共轭镜进行全息关联存储实验。实验表明存储系统具有实时处理,成像质量好,信噪比高和能反复使用等优点。     

Reaction pathway of benzonitrile formation during toluene ammoxidation on vanadium phosphate catalysts

The reaction pathway of the ammoxidation of toluene on (VO)₂P₂O₇ used as catalyst and the interaction of potential intermediates with the pyrophosphate were studied by spectroscopic techniques (FTIR, EPR), temperature-programmed chemisorptions/ reactions (TPD, TPRS) and transient studies such as the temporal analysis of products (TAP) technique. NH₃ is chemisorbed on the catalyst surface, forming three different species, i.e., NH ₄ ⁺ ions located on BrØnsted sites, coordinatively bound NH₃ on Lewis sites and NH ₂ ^– groups, presumably P-NH₂. Toluene that is probably adsorbed on Lewis sites reacts in a first step to a benzyl radical. A subsequent partial oxidation by interaction of V^IV=O groups generates a V...O=CH-C₆H₅ surface structure. This benzaldehyde-like surface species reacts with adsorbed NH₃ according to a Langmuir-Hinshelwood mechanism. TAP experiments on ammonium-containing vanadium phosphates revealed that NH ₄ ⁺ ions could act as potential N-insertion species. No formation of benzylamine as well as the generation of V=NH surface groups as possible intermediates or N-insertion sites were observed.     

温度对还原增感立方体氯化银乳剂中光电子衰减的影响

利用微波介电检测技术,测得还原增感立方体氯化银乳剂中自由光电子与浅束缚光电子衰减行为随还原增感温度的变化。实验发现还原增感温度变化会引起增感中心陷阱作用的变化:当还原增感温度较低时,增感中心起空穴陷阱作用,延缓光电子衰减;还原增感温度较高时,增感中心起深电子陷阱作用,加速光电子衰减。由此,我们得到了确定最佳增感温度的依据。     

有机溶剂下盐酸环丙沙星的荧光特性研究

本文在几种有机试剂(乙醇，甲醇，丙酮)条件下，对盐酸环丙沙星产生的荧光特性进行了初步的研究，并初步探讨了有机溶剂下温度对其荧光强度的影响。     

二苯二硒的合成和晶体结构

报道了一种新的合成工艺,采用氯化镉为催化剂,利用空气中的氧气直接氧化苯硒酚合成了二苯二硒晶体,表征了其晶体结构和红外光谱性质。晶体属于正交晶系,空间群 P21 21 21,a= 0 5646 (2) nm,b= 0 8288 (3) nm,c=2 4100(9)nm; V=1 1276(7)nm3,Dc=1 839 g·cm-3,Z=4, R=0 0259。     

ESI-MS法对重烷基苯烃基结构的研究

采用多种分析手段,其中以电喷雾质谱为主的方法研究了重烷基苯的烃基结构。首先通过柱色谱法对重烷基苯进行分离,将其分成了六个族组分。通过各族组分的红外、紫外鉴定,确定它们各自的归属,用电喷雾质谱测定Ⅱ～Ⅴ族组分磺酸盐的相对分子量分布,结合红外、紫外测定的结果及每族物质的不饱和度和通式,推算出了烷基芳烃部分的相对分子质量和烷基的碳数分布。重烷基苯中几个主要成分的碳数分布为:其中二烷基苯的碳数分布在10～25之间,单烷基苯的碳数分布在10～25之间,烷基萘的碳数分布在5～20之间,烷基二联苯的碳数分布在4～19之间。     

Study of the sorption and acidic properties of MTW-type zeolite

The acidity of H-MTW-type zeolite has been investigated using infrared spectroscopy of adsorbed pyridine. Pore volume has been measured by nitrogen andn-hexane adsorption. The zeolite exhibits infrared signals at 3612 and 3580 cm^–1 tentatively attributed to bridging hydroxyl groups vibrating in the main channel and in the six-membered rings of the structure, respectively. Both hydroxyl groups possess high acid strength and are readily accessible to pyridine. H-MTW shows an-hexane cracking activity at 350°C comparable to that obtained with MFI and BEA-type materials with a product selectivity between medium and large pore structural types.     

黄腐酸结构、构象和聚集过程的分子模拟研究

自然界中广泛存在着的腐植物质(HS)有多种化学反应能力,诸如矿物质的风化、养分的生物有效利用和污染物的迁移等相关的生物地球化学反应能力。腐植物质的反应性取决于其官能团的化学特性与微观结构,同时又受到周围环境及介质组分的影响。为了更好地了解腐植物质在水、土壤中的结构、构象以及聚集过程,文中描述了以伯明翰东北部庙宇(TNB)的样本,按离子或非离子的黄腐酸分子结构建模研究的过程。该理论研究结果和黄腐酸的溶解度(偶极矩)、电子和振动光谱等一些实验研究的结果能很好的吻合。其中水分子的存在对静电有很大的稳定作用,并且随着离子化程度的增加,这种作用变得更强。在真空中,由于氢键和非键力相互作用增加,未离子化的聚集体比单体更稳定。因此,随着黄腐酸分子的离子化,聚集作用将不再发生。在溶液中,黄腐酸的浓度是聚集的关键因素。若当量浓度太低,含有两个黄腐酸的系统就不可能发生聚集,但是随着当量浓度的提高,系统中聚集体的数量也将上升,情况就发生改变。离子态是聚集的另一个关键因素。离子态的黄腐酸分子有着更高的负电荷,而这会增强能量势垒,阻碍由布朗运动引起的黄腐酸分子的相互接近。     

Heat capacities of polyethylene and linear fluoropolymers

Heat capacities at constant pressure, C_p, and at constant volume C_v, were calculated with the help of normal mode frequency spectra and compared to experimental data for crystalline or semicrystalline polyethylene, poly(vinyl fluoride), poly(vinylidene fluoride), polytrifluooroethylene and poly(tetrafluoroethylene). A calculation scheme using a Tarasov function for 2N skeletal vibrational modes and an approximation of the residual 7N normal modes from known data on polyethylene and polytetrafluoroethylene is developed for all homologous, linear fluoropolymers. N is the number of carbon backbone atoms of the repeating unit. Calculations can be carried out over the whole temperature range 0 K to melting. For the two theta temperatures and the constant A₀ used for C_v to C_p conversion, fluorine-concentration dependent curves are given. The relations are expected to hold also for copolymers and blends of intermediate fluorine contents. Recommended experimental (data bank) heat capacities agree to ±2.5% with the calculations.     

Relationship between chemical degradation and thickness loss of an amine-cured epoxy coating exposed to different UV environments

The relationship between chemical degradation and thickness loss of an unpigmented, non UV-stabilized, crosslinked amine-cured epoxy coating exposed to three UV conditions was investigated. Spin-coated samples having a thickness of approximately 7 μm on an Si substrate were prepared from a stochiometric mixture of a bisphenol A epoxy resin and a tetra-functional amine curing agent. Samples were exposed outdoors and to two accelerated laboratory UV environments. Chemical degradation and thickness loss were measured by transmission Fourier transform infrared spectroscopy (FTIRS) and laser scanning confocal microscopy (LSCM), respectively. In addition, surface roughness and morphological changes were measured by atomic forcemicrosocopy (AFM) and LSCM. Substantial chemical degradation, thickness loss, and morpholocal changes occurred in the exposed films, and the rate of chemical degradation was greater than that due to the thickness loss. This additional chemical loss was attributed to an inhomogeneous degradation process in which nanoscale localized depressions initiate at certain sites on the surface, which then enlarge and deepen with exposure time. The results of this study provide a better understanding of the degradation mechanism and should lead to the development of scientific-based models for predicting the service life of crosslinked amine-cured epoxy coatings. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL