5DXC FTIR宏指令研究聚氨酸化学反应

利用Ｎｉｃｏｌｅｔ ５ＤＸＣ ＦＴＩＲ操作系统听提供的宏编辑程序，论述了自定义宏指令在聚氨酯化学反应动力学及结构分析研究中的应用。表明，运用５ＤＸＣ宏指令，简单易行，测量准确，工作效率高，可以满足数分钟内完成的聚氨酯聚合反应动力学研究的需要。借助宏指令发现聚氨酯聚合反应在一定反应程度范围内服从二级反应动力学，催化剂的性质影响二级反应动力学的适用范围。随着聚合反应的进行，聚氨酯酰胺Ⅱ谱带呈阶跃式由１     

LaH2分子基态（C2V,A1）的势能函数

在ＱＣＩＳＤ水平上基于相对论紧致有效势（ＲＣＥＰ：Ｒｅｌａｔｉｖｉｓｔｉｃ Ｃｏｍｐａｃｔ Ｅｆｆｅｃｔｉｖｅ Ｐｏｔｅｎ－ｔｉａｌ）方法优化出ＬａＨ２分子的基态为Ｃ２ｖ（Ｘ＾２Ａ１）构型,其〈ＨＬａＨ－１２４４°、平衡核间距Ｒｅ＝２．１９４５Ａ和离子解能Ｄｅ＝５．５９９ｅＶ,并计算出谐振频率：ｖ１＝１２１６．５２１ｃｍ＾－１、ｖ２＝１０８７．４１７ｃｍ＾－１和ｖ３＝２１５６．９５７２ｃｍ＾－１。     

CO（a）与CS2和CS传能反应中激发态碎片形成速率

本文利用流动余辉技术研究了亚稳态ＣＯ（ａ）与ＣＳ２和ＣＳ的传能反应，测定了反应产生的激发态碎片ＣＳ（Ａ）和ＣＳ（ａ）的形成速率常数。ＣＯ（ａ）与ＣＳ２传能反应中ＣＳ（Ａ）和ＣＳ（ａ）的形成速率常数分别为３．４６×１０＾－１１ｃｍ＾３·ｍｏｌｅｃ＾－１·ｓｅｃ＾－１和１．１４×１０＾－１０ｃｍ＾３·ｍｏｌｅｃ＾－１·ｓｅｃ＾－１。ＣＯ（ａ）与ＣＳ传能反应中ＣＳ（Ａ）和ＣＳ（ａ）的形成速率常数分别为１     

在Ar和Xe低温基体中Fe（CO）3与CO扩散控制反应研究

本文用２８０ｎｍ脉冲激光光解被Ａｒ和Ｘｅ基体隔离的Ｆｅ（ＣＯ）５以产生配位不饱和的Ｆｅ（ＣＯ）３。用傅里衰变换红外光谱仪实时监察光解停止后Ｆｅ（ＣＯ）３和ＣＤ的复合，并以Ｓｍｏｌｕｃｈｏｗｓｋｉ扩散控制反应动力学理论模型求得Ｆｅ（ＣＯ）３与ＣＯ的反应半径为４．０×１０＾－１０ｍ，ＣＯ在１０Ｋ的Ａｒ和Ｘｅ基体中的扩散系数分别为２．２×１０＾－２３ｍ＾２／ｓ和４．５×±∩＾－２３ｍ＾２／ｓ。     

对Bi-2212超导体中的Raman谱指认

本文对Ｂｉ２－ｘＰｂｘＳｒ２ＣａＣｕ２Ｑδ（ｘ＝０￣０．５）系列样吕以及在真空下不同温度退火的Ｂｉ１．６Ｐｂ０．４Ｓｒ２ＣａＣＵ２Ｏδ样品进行了Ｘ射线衍射和Ｒａｍａｎ谱实验研究。测量表明,随着退火温度的升高,ａ,ｂ,ｃ轴晶格常数增加,与Ｏ（１）ＣｕＢｇ模式相关的２９４ｃｍ＾－１的峰强减少,峰位红移。研究结果进一步表明,４６４ｃｍ＾－１和６３０ｃｍ＾－１峰分别与Ｏ（３）ＢｉＡ１ｇ和Ｏ（２）ＳｒＡ１ｇ     

铜与2-羟基-3-羧基-5-磺酸基苯重氮氨基偶氮苯反应的分光光度法研究及应用

研究了铜与２－羟基－３－羧基－５－磺酸基苯重氮氨基偶氮苯（ＨＣＳＤＡＡ）的显色反应。在Ｔｒｉ－ｔｏｎＮ－１０１存在下和ｐＨ１０．４～１１．５的缓冲介质中，Ｃｕ２＋与ＨＣＳＤＡＡ形成１∶２的红色配合物，其最大吸收波长是５３０ｎｍ，对比度为１０２ｎｍ，表观摩尔吸光系数为１．３１×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。铜在０～０．２４μｇ／ｍＬ范围内服从比尔定律。用于铅锌矿和花生中微量铜的测定，相对误差不大于３．７％，相对标准偏差不大于１．６％（ｎ＝６）。     

析相光度法测定铜（Ⅱ）的研究

本文研究了Ｃｕ－ＰＥＧ－ＤＤＴＣ（铜试剂）（ＮＨ４）２ＳＯ４体系的析相光度法并应用于测定Ｃｕ。最宜酸度为３．６－９．０（ＮａＡｃ－ＨＡｃ，ＮＨ４Ｃｌ－ＮＨ３．Ｈ２Ｏ）缓冲溶液，其络合物的最大吸收位于４５０ｎｍ，表观摩尔吸光系数为９．０５×１０＾３Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，Ｃｕ浓度在０－３０μｇ／Ｌ范围内服从比耳定律，铜与ＤＤＴＣ形成组成为１：２的稳定络合物。该方法用于铝合金中铜的测定，获得了满     

用CRDS技术研究分子光谱和气相反应动力学

介绍了用ＣＲＤＳ技术研究分子光谱和气相反应动力学，把ＣＲＤＳ光谱技术应用于Ｉ２的光谱，利用ＣＲＤＳ方法测量了反射镜的反射率，Ｉ２的蒸汽压为０．１Ｐａ，脉冲激光能量为０．１ｍＪ。     

动态MOCVD法在Ag／Ni复合基体上连续制备YBCO超导带

本报道用ＭＯＣＶＤ方法在以１５ｃｍ／ｈｒ速度连续走带的Ａｇ／Ａｉ复合基体上制备ＹＢＣＯ超导带的结果。所有ＹＢＣＯ超导带的Ｊｃ值为１．３×１０＾４Ａ／ｃｍ＾２；样品主相为ＹＢＣＯ１２３，呈强烈ｃ－轴取向，其衍射峰的摇摆曲线半高宽约为２．８°；另外，还含有少量Ｙ２ＢａＣｕＯ５和ＢａＣｕＯ２杂相，本还用ＳＥＭ和ＥＤＸ对样品沉积层进行了观测分析。     

傅里叶红外光谱研究血清白蛋白构象

用傅里叶红外光谱法研究了ＢＳＡ及其水溶液的红外光谱。通过对其酰胺Ｉ带傅里叶自转积谱分析,为其及部分水溶液中的二级结构构象进行了指认。结果表明,ＢＳＡ水溶液状态与固态时的二级结构是不同的。随着溶液浓度的降低,酰胺Ｉ带二级结构峰存在明显的位移现象,即１６０９．８６ｃｍ＾－１位移到１６０８．２４ｃｍ＾－１,１６３３．８５位移到１６３８．３６ｃｍ＾－１,１６５３．６９ｃｍ＾－１位移到１６５６．１０ｃｍ＾－     

Polyurethane‐Carbon Nanotube Nanocomposites Prepared by In‐Situ Polymerization with Electroactive Shape Memory

In‐situ polymerization was employed to achieve well‐dispersed carbon nanotube‐reinforced polyurethane composites. In‐situ polymerization showed predominant as primarily dispersal of carbon nanotubes in the matrix polymer according to scanning electron microscopy (SEM) observation and atomic force microscopy (AFM) images. Differential scanning calorimetry (DSC) results suggested that the addition of multi walled nanotubes (MWNTs) into polyurethane increased the rate of crystallization, this effect being more significant in polyurethane (PU)‐MWNT composite, which was prepared by an in‐situ polymerization process. The composites obtained by in‐situ polymerization showed enhanced mechanical properties as well as good electroactive shape memory. The original shape of the sample was almost recovered with bending mode when an electric field of 50 V was applied.     

Molecular alignment during gel formation from methyl methacrylate: An excimer fluorescence study

Glass transition during bulk polymerization was studied in free-radical cross-linking copolymerization (FCC) of methyl methacrylate (MMA) using the steady-state fluorescence (SSF) technique. Naphthalene (N) was used as a monomer and excimer forming probe. Changes in the viscosity of the pregel solutions due to gel formation dramatically enhance both monomer and excimer fluorescent yield of N molecules. The reaction time at which the monomer and excimer intensities exhibit a sudden increase corresponds to the reaction time at which the rate of polymerization becomes maximum resulting from the gel effect. This effect was used to study the gelation of MMA, as a function of time, in various N concentrations. The results were interpreted in the view of percolation theory. The gel fraction, β, and weight average degree of polymerization, γ, exponents β?=?0.40?±?0.02 and γ?=?1.70?±?0.07 were found in agreement with percolation results for both monomer and excimer measurements, respectively.     

Studying of the critical exponents around the glass transition in bulk polymerization of ethyl methacrylate by using fluorescence techniques

The glass transition during bulk polymerization was studied in free-radical crosslinking copolymerization (FCC) of ethyl methacrylate (EMA), using both the steady-state fluorescence (SSF) and the fast transient fluorescence (FTRF) techniques. Pyrene (Py) was used as a fluorescence probe. Changes in the viscosity of the pregel solutions due to gel formation dramatically enhance the fluorescent yield of Py molecules. The reaction time at which the Py intensity and lifetime exhibit a sudden increase corresponds to the reaction time at which the rate of polymerization becomes maximum resulting from the gel effect. This effect is used to study the gelation of EMA, as a function of time, at various crosslinker concentrations and different temperatures. The results were interpreted in the view of percolation theory. The gel fraction, β and weight average degree of polymerization, γ exponents β?=?0.37?±?0.01, γ?=?1.71?±?0.04 and β?=?0.36?±?0.002, γ?=?1.687?±?0.01 are found in agreement with percolation results for SSF and FTRF measurements, respectively.     

Regulation of the elastic modulus of polyurethane microarrays and its influence on gecko-inspired dry adhesion

We studied the influence of the elastic modulus on the gecko-inspired dry adhesion by regulating the elastic modulus of bulk polyurethane combined with changing the size of microarrays. Segmented polyurethane (PU) was utilized to fabricate micro arrays by the porous polydimethyl siloxane (PDMS) membrane molding method. The properties of the micro arrays, such as the elastic modulus and adhesion, were investigated by Triboindenter. The study demonstrates that bulk surfaces show the highest elastic modulus, with similar values at around 175 MPa and decreasing the arrays radius causes a significant decrease in E, down to 0.62 MPa. The corresponding adhesion experiments show that decrease of the elastic modulus can enhance the adhesion which is consistent with the recent theoretical models.     

红外光谱原位跟踪活性自由基聚合反应过程研究

使用新型可插入式红外光谱仪原位检测在4－羟基2，2，6，6－四甲基氧化哌啶醇（HTEMPO）存在下苯乙烯稳定自由基活性均聚合反应和苯乙烯／甲基丙烯酸羟丙酯的共聚合反应以及苯乙烯原子转移活性自由基聚合（ATRP）反应三个过程，分别考虑了它们的反应动力学，并给出了可能的聚合反应机理。研究结果表明，对于均相的苯乙烯（St)均聚合反应和苯乙烯（St)/甲基丙烯酸羟丙酯（HPMA）的自由基共聚合反应体系，聚合反应显示一定的诱导期，与反应体系中存在的HTEMPO捕捉自由基有关，而对于St／HPMA共聚合体系，诱导期更长，这是因为HPMA易和HTEMPO自由基发生氢转移反应，导致游离的HTEMPO浓度升高。最后用红外光谱实时跟踪苯乙烯非均相ATRP过程，发现苯乙烯聚合反应动力学接近于表现零级。因为单体分子在由增长自由基、卤化铜和联二吡啶形成的络合物的界面增长，与单体相内St浓度无关。     

POLYMERIZATION,MORPHOLOGY, AND CRYSTAL STRUCTURE OF POLY(p-BENZAMIDE)*

Isothermal polymerization of acetaminobenzoic acid at various temperatures in bulk and solution was monitored by acetic acid evolution. The polymerization took place initially in a homogeneous phase, but it soon changed to heterogeneous as the polymer precipitated from the melt or solution. The reaction course consisted of a short induction period, followed by a fast second-order reaction and a third slow, also second-order, reaction. The different polymerization rates in the second and third stage were due to polymer precipitation. The degree of polymerization of the resulting polymer was generally low, usually less than 5. The polymer was highly crystalline and prone to decarboxylation at temperatures above 300°C. Sample structure and morphology were characterized by various lamellar formations similar to those seen previously in many aromatic polyesters. Epitaxial solution polymerization/crystallization on mica resulted in three different morphologies, the most unique being shish kebab–type structures. Polybenzamide [poly(p-aminobenzoate)] is polymorphic; the most frequently seen hk0 electron diffraction patterns were similar to those from phase I of aromatic polyesters. Phase II of polybenzamide was seen only rarely. Simulation, using Cerius², suggested equal agreement with [001], [100], and fiber electron diffraction (ED) patterns and X-ray powder patterns for two different orthorhombic unit cells (a = 7.71, b = 5.35, c = 12.94 Å, ρ = 1.55 g/cm³); both have a parallel packing of adjacent molecules, but in one, successive phenyl rings along a given chain are parallel, while in the other they are twisted at ±30°. For both unit cells, neighboring molecules were displaced by ±0.14 Å along c to obtain better agreement with the observed patterns. The [010] patterns could distinguish between the two cells, but were not obtainable.

     

Y2BaCuO5粒子对顶部籽晶熔融织构YBCO微结构的影响

本文主要研究了Y211相粒子在顶部籽晶熔融织构YBCO块材中的分布及其对材料超导特性的影响.研究发现,在籽晶正下方,YBCO超导块材中的Y211粒子分布呈不均匀性.样品在近籽晶处Y211粒子非常少,从样品顶部到样品底部Y211相粒子的容积率呈增大趋势.由于Y123粒子和Y211粒子热膨胀系数存在差异,这种不均匀性导致了块材内部产生微裂纹,从而降低了磁悬浮力.     

Co/GaAs(100)界面形成以及Co超薄膜磁性质的研究

利用同步辐射光电发射和铁磁共振(FMR)研究了Co/GaAs(100)界面形成以及Co超薄膜的磁性质.结果表明,在低覆盖度(约为0.2nm)下,Co吸附原子与衬底发生强烈的界面反应,在覆盖度为0.9nm时,形成稳定的界面.从衬底扩散出的Ga原子与Co覆盖层合金化,而部分As原子与Co原子发生反应,形成稳定的键合,这些反应产物都停留在界面处很窄的区域(0.3—0.4nm)内.另一部分As原子偏析在Co覆盖层表面.结合理论模型,详细地讨论了界面结构及Ga，As原子的深度分布.FMR结果表明,生长的Co超薄膜具 关键词：     

低损耗阶跃型塑料光纤(SI-POF)工艺的研究

介绍一种用高分子材料研制低损耗阶跃型塑料光纤(SI-POF)的新型工艺流程,采用甲基丙烯酸甲酯(MMA)与其他高分子材料共聚合成一种阶跃型折射率分布塑料光纤(SI-POF).该光纤采用含氟树脂包层,可以降低损耗.原料的精馏提纯、聚合反应、拉丝等整个工艺过程都处在一个密闭系统中.探讨聚合反应方式对塑料光纤导光性能的影响,从而获得性能优异的塑料光纤,光纤的使用距离为50～100m,其导光性能为:光损耗小于200dB/km;数值孔径为0.35～0.55.     

In situ monitoring of styrene polymerization using Raman spectroscopy. Multi‐scale approach of homogeneous and heterogeneous polymerization processes

Free radical polymerization of styrene was monitored in situ by combining Raman spectroscopy to other experimental techniques (gravimetry and rheology). Three different processes were investigated: bulk, emulsion and miniemulsion polymerization. A complete analysis of the evolution of Raman spectrum during the course of reaction showed that a lot of information about molecular dynamics could be extracted and related to chemical phenomena. In addition, we report for the first time the coupling of Raman spectroscopy to a rheometer in order to monitor styrene bulk polymerization both at the scale of chemical bonds and at the scale of macroscopic phenomena (viscosity variation). Copyright © 2013 John Wiley & Sons, Ltd.