嵌段聚酯型聚脲氨酯弹性体的红外光谱研究

用红外光谱法对基于4,4′－二苯基甲烷二异氰酸酯（MDI）、乙二胺（ED）和聚己二酸丁二醇酯（PBA）（分子量分别为1975和1228）的嵌段聚脲氨酸（PUU）弹性体进行了研究。首先归属了PUU的红外吸收谱带,并对前人已经归属过的1600、1317、1520和1230cm^-1谱带提出了新的看法。氚化和变温技术的使用为上述红外谱带的归属和氢键化研究提供了可靠的理论依据。研究结果表明氢键化主要发生在硬段聚集区中,少量的氢键在软、硬段之间的界面上形成,由此推断PUU材料是相分离的。     

嵌段聚酯型聚脲氨酯硬段微区中氢键化的红外光谱研究

用红外光谱法对基于4,4′二苯基甲烷二异氰酸酯（MDI）、乙二胺（ED）和聚己二酸丁二醇酯（PBA）（分子量分别为1975和1228）的两系列嵌段聚酯型聚脲氨酯（PUU）硬段微区的氢键化进行了研究。发出脲C＝0基随着硬段含量增国出现双峰吸收,提出了PUU不同长度硬段序列中脲C＝0基的两种平面氢键化的模型。认为这些平面氢键可以通过进一步键合来形成硬段微区中的三维氢键。     

对苯二甲酸丁二酯-ε-己内酯多嵌段共聚物中硬链段的受限结晶

用差示扫描量热法（DSC）,广角X射线衍射（WAXD）,傅立叶变换红外光谱（FTIR）等技术研究了对苯二甲酸丁二酸－ε－己内酯多嵌段共聚物中硬链段的受限结晶。结果表明,PBT－PCL共聚酯中软硬链段在非晶区的混容性比较好,不同组成的样品均显示出一个玻璃化转变温度;对硬段含量超过50％的共聚物来说,硬链段可以结晶,而软链段不能结晶;由于硬链段的受限特点,BT硬链段的结晶受软链段的影响和制约,其结晶能力随硬段序列长度的增加而逐渐增大。     

氘氚化锂分解残渣中微量氚的回收

氘作同位素交换气对除氚后的新鲜氘氚化锂残渣[主要成分是硅锂化合物和二氧化硅，渣中含氚约为0．9443mg／g(渣)]中的微量氚进行氚的计量与回收，为氘氚化锂残渣中氚的回收提供技术支持。     

LiAlO_2陶瓷小球的堆外放氚行为

将LiAlO2陶瓷小球置于裂变反应堆中辐照,采用热解吸技术研究该类产氚材料的堆外放氚特性,考察了升温速率、载气组分、催化活性元素和提氚温度对氚释放行为的影响;采用电子自旋磁共振(ESR)实验技术研究了辐照缺陷的顺磁特征。结果表明:LiAlO2中氚的扩散速度慢,热解吸活化能高,氚释放主要分布在750~1000K;表面氢同位素交换反应贡献大,释氚形态受载气条件的影响较大,当氦气中添加H2时,会增大HTO转化成HT的比例;中子辐照会在LiAlO2中诱生F+,O-和O2-等缺陷色心,其退火湮灭行为与氚释放过程存在一定关系。     

FEB—E氚泄漏分析

由于氚本身非常昂贵而且氚的泄漏将造成环境污染,因此氚的控制对D－T加料的聚变堆来说是非常重要的问题。通常规定聚变堆环境周围总的氚泄漏率应＜3．7×10^11Bq·d^-1。在聚变实验增殖堆FEB－E设计中采用高压氦气冷却,液态锂作氚增殖剂,因而氚与增殖材料之间具有强的化学亲合力。在正常工作条件下,即温度低于680℃,由于氚的气相分压强很低,氚渗透泄漏几乎可以忽略不计,所以从包层泄漏极少。但是由于FEB－E氚燃耗率太低（2.08%),因而氚的通过量较大,氚泄漏主要发生在以下过程：从等离子体抽出气体的氚处理系统中（氢同位素低温分馏系统）漏失;氚从第一壁、偏滤器靶板渗透到氦气冷却剂,再由冷却剂工作流质的漏失导致氚的泄漏;氚植入和渗透到第一壁和偏滤器靶板材料及冷却剂管道内,再由这些部件的材料损坏、更换和报废过程中引起的氚漏失;从液态锂中提取氚的过程中氚增殖剂本身的直接损失引起的氚漏失;从等离子体加料系统（弹丸制作过程）的氚漏失。本文运用SWITRIM编码和Sieverts'定律,从氚在液态锂中的浓度以及溶解率常数随温度的变化关系中得到液态锂中氚的分压、再由氚压强的平方根（或一次幂）差定律计算氚向氦冷却剂中的泄漏,再假设一定的工作流失损失率,对FEB－E氚系统的氚泄漏进行分析,为环境安全评估提供必要的数据。在事故状态下的氚泄漏主要考虑当包层温度失控时氚从液态锂中析出向冷却剂渗透,再由于冷却剂工作流质的漏失导致氚的泄漏。     

对苯二甲酸乙二醇酯-ε-己内酯共聚酯中硬链段结晶特性研究

利用广角X射线衍射和傅里叶变换红外光谱研究了对苯二甲酸乙二醇酯-ε-己内酯(TCL)共聚酯中对苯二甲酸乙二醇酯(ET)硬链段的晶区结构和结晶特性。结果表明,在ET硬段含量较高的TCL共聚酯中,ET链段的结晶特性与纯的聚对苯二甲酸乙二醇酯(PET)基本相同。ET硬段晶区的尺寸和结晶度均随链段序列长度的减小而减小。     

含氚废气处理

研究了Pt-Al2O3亲水催化剂和Pt-SDB（聚苯乙烯一二乙烯基苯）疏水催化剂对含氚空气的净化处理。通过Pt-SDB单程催化氧化氢气性能研究和潮湿环境对Pt-SDB催化剂催化氧化性能影响研究（图1）显示，Pt-SDB催化剂在室温下对H2（氚）的催化氧化具有效率高，并且不容易受潮，能在潮湿的环境下保持活性，是一种较好的含氚废气处理催化剂。     

316L不锈钢表面Al2O3镀层中氚的扩散渗透行为

在３１６Ｌ不锈钢表面，用磁控溅射方法镀２－３μｍ的Ａｌ２Ｏ３膜。实验表明，这种膜与基体相容性好，且具有抗氧化、抗热冲击、抗辐照、低活性等特点，氚在其中的渗透率低。在６０４－７７３Ｋ温度下，氚在此种材料中的渗透率比在基体材料中低４－６个数量级。此种材料可用作为氚容器材料，用于氚的生产、分离和净化工艺中，还可以用作聚变 堆氚工艺中氚靶包壳材料。     

“氚坑深度”和“氚坑时间”

裂变堆中的氙-135中毒效应是由于裂变产生的碘-135经由β衰变产生氙。135，后者吸收中子的截面很大，如停堆时剩余反应性不够，就要经过一段“碘坑时间”才能恢复到原来停堆前的反应性后才正常工作起来。与此类似却有所不同的一个全新的概念，“氚坑深度”和“氚坑时间”首次被我们引入到聚变堆研究领域，它表明为了实现“得失相当”，起动一个聚变堆所要求的最少氚储备和运行时间。“氚坑深度”和“氚坑时间”与具体的氚回收方案、提取氚的工艺过程、堆部件材料中的氚扣留量、增殖剂中不可回收的氚份额、泄漏到堆大厅的包容惰性气体氦中的份额以及氚自然衰变等等有关。     

Theoretical analysis of the IR and Raman spectra of acridone taking into account intermolecular hydrogen bonds

The geometric parameters, the force field, and the absolute intensities of the IR and Raman spectra of acridone, the hydrogen-bonded dimer of acridone, and its N-deuterated analogue are calculated quantum mechanically in terms of the density functional theory by the B3LYP/6-31G(d) method. The vibrational bands in the IR and Raman spectra of acridone are assigned and interpreted using the calculational data on acridone dimers and the data on the isotopic shifts of vibrational frequencies upon deuteration. The vibrations of acridone and anthraquinone are comparatively analyzed. Original Russian Text ￠ K.V. Berezin, T.V. Krivokhizhina, V.V. Nechaev, 2006, published in Optika i Spektroskopiya, 2006, Vol. 100, No. 1, pp. 20–27.     

Gel stabilization in chelate sol–gel preparation of Bi-2223 superconductors

A chelating sol–gel method was used for the preparation of the superconducting Bi-2223 phase. We compared pH range of both solution and gel stability in samples with EDTA, TEA and their equimolar mixture addition. A pH range of stability (for precipitation) was extended in EDTA solutions with addition of TEA. IR spectroscopy was used to identify the type of bonding between EDTA and TEA in a stabilized solution. IR bands belonging to polyester bonding were found in the IR spectra of gels prepared at 130 °C. We describe the influence of both gel decomposition and calcinations regime on the evolution of Bi-2223 phase. The optimized temperature treatment was used for the comparison of superconducting transport and of magnetic properties of the prepared samples. Moreover, an extra 800 °C calcination step was tested to enhance the decomposition of unfavorably formed carbonates.     

Fourier‐transform infrared and Raman spectra,vibrational assignment and density functional theory calculations of 1,4,5‐triazanaphthalene

The Fourier‐transform infrared (FT‐IR) (4000–50 cm⁻¹) and Raman spectra (3500–100 cm⁻¹) of 1,4,5‐triazanaphthalene in polycrystalline state were measured. Comparison between the spectra by two techniques, a series of density functional theory (DFT) calculations and the spectral behaviour upon deuteration were used for the assignment of the vibrational spectra of the title compound. The calculated vibrational wavenumbers by the B3LYP density functionals are generally consistent with the observed spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

FTIR研究热处理对RIM PUU的形态及力学性能的影响

将PUU(聚氨酯脲)样品薄膜放入FTIR恒温池内进行原位扫描。FTIR红外谱图的结果表明,在一定温度下,随着热处理时间的延长,氢键化的脲键的吸收逐渐增加,达到一定时间后,吸收变化甚微。在热处理过程中,有序氢键化脲键基团吸收的变化率(反映微相分离动力学)随着温度的提高而增加。PUU材料在热处理之前,羰基振动区内游离的氨酯键、无序氢键化的氨酯键、有序氢键化氨酯键、无序的氢键化脲键和有序的氢键化脲键等多种羰基并存,热处理后仅存游离的氨酯键、氢键化的氨酯键及有序的脲键3种吸收谱带。在100℃下,热处理时间(超过8h)越长,力学性能越差。而在相同的热处理时间(8h)内,热处理温度在100℃,PUU弹性体具有较好的综合力学性能。     

Revisited vibrational assignments of imidazolium‐based ionic liquids

Imidazolium‐based ionic liquids (ILs) involving anions of variable coordinating strength have been investigated using infrared (IR) and Raman spectroscopies, density functional theory (DFT) calculations and selective deuteration of the imidazolium CH groups. Particular emphasis has been placed on the vibrational assignments of the anion and cation internal vibrations, a prerequisite before any interpretation of spectral changes due to ion–ion interactions in these unconventional liquids. The vibrations of highly symmetric and weakly coordinating anions, such as PF₆⁻, have unperturbed wavenumbers, but unexpected IR or Raman activity for some modes, showing that the anion is subjected to an anisotropic electric field. The stretching as well as the in‐plane and out‐of‐plane bending modes of the imidazolium CH groups are anharmonic. They give broad bands that reflect a large distribution of interactions with the surrounding anions. All the bending modes are mixed with ring vibrations and the stretching modes are complicated by Fermi resonance interactions with overtones and combination of in‐plane ring modes. However, the stretching vibration of the quasi‐diatomic C₍₂₎ D bond appears to be a good spectroscopic probe of the increasing cation–anion interactions when the coordinating strength of the anion increases. The broad absorption observed in the far IR with weakly coordinating anions remains practically unchanged when the acidic C₍₂₎ H imidazolium bond is methylated and even when the imidazolium cation is substituted by tetra‐alkyl ammonium or pyrrolidinium cations. It is concluded that this absorption is a general feature of any IL, coming from the relative translational and librational motions of the ions without needing to invoke C₍₂₎ H anion hydrogen bonds. Copyright © 2010 John Wiley & Sons, Ltd.     

Spectroscopic Analysis of Organophosphorus Pesticides Using Colorimetric Reactions

The UV-Vis and infrared (IR) absorption spectra of organophosphorus (OP) pesticides have been studied. A correlation in spectra was developed to optimize the OP pesticides in the environments. The spectroscopic (UV-Vis and IR) spectrum of OP pesticides like methyl parathion, malathion and parathion has been interpreted in detail. A complete calculation of the normal frequencies and absolute intensities of UV-Vis and IR absorption bands are interpreted with the help of corresponding experimental data. In the colorimetric reactions, the bands appear at 2 077, 1 637, 1 455, 1 015, 655 cm-1 for malathion; 2 081, 1 639, 1 316, 1 015, 794, 683 cm-1 for parathion; 2 078, 1 632, 1 032, 794 cm-1 for methyl parathion were used for quantitative or qualitative analysis. All these IR spectra were acquired by averaging 100 scans at a resolution of 4 cm-1. It is determined experimentally in the region 200～450 nm for UV-Vis absorption bands and in the region 400～4 000 cm-1 for IR absorption bands. It is concluded that the mainly optically active groups (P—OH, CO, PO, C—O—C, P—O—C, PS, —OH) present in pesticides which are responsible in change in significant data for quantitative and qualitative analysis. The various optical properties like wavelength, band energy, wave number, and frequency, also are calculated.     

TGA-DTA and infrared spectra of potassium nitroprusside dihydrate: K2[Fe(CN)5NO] · 2H2O

The infrared spectra of the polycrystalline compound of the title, both normal and with different degrees of deuteration, at temperatures ranging between ca. 80 K and room temperature, were obtained. As no structural data are currently available for the compound, the assignment of the observed bands was accomplished supposing the existence of two different nitroprusside ions and, consequently, four inequivalent water molecules in the asymmetric unit, as suggested by the two bands found in the NO stretching region and the complexity observed in the water regions. TGA-DTA data are also presented and discussed.     

一种皮革产品的红外无损检验

基于红外光谱法可以对不同形态物质进行结构分析,可对皮革产品进行定性分析。依据红外光谱谱带的数目、位置、形状和强度都随化合物不同而各不相同的特点,将牛皮革、羊皮革和聚氯乙烯（PVC）革的红外谱图进行比对和剖析,并用于皮革产品的检验。通过实验得出,利用红外方法可以快速对皮革产品进行红外无损检验。