聚氨酯脲(PUU)固化过程中形态及力学性能的变化

用透射电镜TEM和“原位”FTIR技术研究了预聚物法聚氨酯脲（PUU）本体聚合反应过程中材料内部的形态变化。FTIR的光谱数据表明：随着反应时间的增加，氢键化的NH基团的谱带吸收愈来愈强且逐渐向低波数移动；反应初期，游离氨基甲酸酯羰基的吸收几乎不变，在高转化率逐渐变小，反应末期变化甚微；随着反应时间的增加，脲羰基谱带的振动位置逐渐向低波数移动，有序氢键化脲羰基谱带的吸收越来越强，归属了聚合反应过程中出现的羰基变带。透射电镜的照片从另一角度证实，随着脲键氢键化程度的增强，相分离程度增强。     

FTIR研究半预聚物法聚氨酯脲密封材料固化过程的表观动力学及氢键化作用

采用原位FTIR技术跟踪了半预聚物法聚醚型聚氯酯脲的固化过程,研究了其固化过程的宏观动力学.原位FTIR的光谱数据表明,随着反应时间的增加.脲键羰基的吸收逐渐增强,脲羰基的波数位置呈阶跃式向低波数方向移动.脲键羰基的氢键化作用逐渐增强.不含催化剂时,硬段优先形成,不利于NCO与OH的反应.氨酯羰基的峰高增加缓慢.脲键的生成对NCO/OH反应生成氨酯键无催化作用.     

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。     

梯度固化聚氨酯脲中氢键的红外光谱分析

聚氨酯脲弹性体中的氢键可以反映其内部的微相分离状态,并对材料的宏观性能有着比较重要的影响。通过梯度固化的方法制得了微相分离程度沿厚度方向梯度渐变的聚氨酯脲弹性体。利用傅里叶变换红外光谱(FTIR)研究了梯度聚氨酯脲弹性体中的氢键,分析了羰基、亚氨基以及醚氧键的氢键,对弹性体的微相分离程度进行了表征。结果表明,羰基区的氢键化程度随固化温度的升高而升高,表明微相分离程度的逐渐升高。醚氧键氢键化程度随固化温度改变有差异,亚氨基的氢键化程度在交联较低的试样中随固化温度的升高而升高,在交联程度较高的试样中则相反。脲羰基形成的三维氢键的强度比醚氧键形成的氢键强。氢键化醚氧键的振动吸收大约位于1076cm-1。     

温度对交联聚氨酯脲弹性体结构与性能的影响

采用“原位”变温ＦＴＩＲ研究了温度对交联聚氨酯脲结构的影响。结果表明：随着温度的升高,氢键化的ＮＨ振动的谱带面积逐渐变小、游离的ＮＨ振动的谱带面积逐渐增加;氢键化的ＮＨ基团的振动吸收位置由低波数逐渐移向高波数,游离的ＮＨ振动的吸收位置保护不变;所有羰基的振动吸收位置均向高波数移动;酰胺Ⅱ谱带及萃环中的大π键的变形振动则移向低波数。聚氨酯脲弹性体的力学性能决定于其;软段区的形态结构。     

红外光谱法研究聚醚型聚脲氨酯内的氢键

本文用红外光谱法较系统地研究了聚醚型聚脲氨酯内的氢键及其性质,表明材料内的NH基团是几乎完全氢键化的。在这些氢键中,NH作为质子的给予体;质子的接受体包括醚氧原子、氨基甲酸酯羰基和脲羰基。氢键对温度十分敏感,随温度上升而逐渐解离,且此解离存在着平衡。从平衡解离温度可知不同类型的氢键的相对稳定性不同。     

有机锡对聚氨酯脲弹性体固化过程的形态及力学性能的影响

采用“原位”傅里叶变换红外技术,研究了半预聚物法聚氨酯脲（ＰＵＵ）本体聚合反应过程中的形态变化。通过对羰基区振动谱带变化的定量研究。详细讨论了催化剂二月桂酸二丁基锡在聚合反应过程中,对聚氨酯酯脲形态结构及力学性能的影响。结果表明：随着有机锡浓度的增大,硬段区氢键化脲键的有序性降低,当－ＮＣＯ／－ＯＨ反应的速率常数和－ＮＣＯ／－ＮＨ２反应的速率常数相近时,材料的力学性能较好。     

氘化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）的嵌段聚酯型聚脲氨酯（PUU）弹性体及其氚化产物进行了研究。结果表明氚化反应对PUU中涉及PUU中涉及氢键化N－H振动红外吸收光谱带的影响较大,受氚化影响较大的那些谱带分别在3332,3190,1600,1539,1317,1257和1230cm^-1附近。另外也发现不同硬段含量和不同聚酯软段分子量的PUU受氚化影响的程度基本相似。     

GeO2-SiO2纳米复合材料的合成及其光学特性研究

运用溶胶-凝胶法合成了GeO2-SiO2纳米复合材料,探索了为pH在2的条件下通过水解Si(OC2H5)4和GeCl4合成GeO2-SiO2干胶的过程.在100～1 200℃下对干胶进行热处理.采用UV光谱法测定了材料的光学性质,观察到随热处理温度的升高,样品光谱的吸收边向长波方向移动.由于温度的影响,晶粒长大,带隙能量减小,纳米微晶的量子尺寸效应显示出来.经X射线衍射分析,观察到了随热处理温度的增高,材料结构从无序到有序的转变过程,直到1 100℃时,有明显的微晶生成,其尺寸为5～10nm.     

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。     

变温红外光谱研究表面双稳态液晶分子的相变过程

运用变温红外和样本-样本相关光谱对40～150℃温度区间内的表面双稳态液晶分子MHOCPOOB的相变过程中的分子构象、排布及相互作用的变化进行研究.结果表明:室温时,分子烷基链中同时存在Zigzag和Gauche两种构象.随温度升高,其中有序的Zigzag构象转化为无序的Gauche构象,链的扭曲程度增加.刚性核部分,羰基与相邻的苯环形成共轭体系,苯环之间相互倾斜排列,在相变过程中羰基与苯环的共平面作用逐渐被打破,且在相变点苯环间的二面角明显增大.由于表面稳定化的作用,使得在液晶盒表面上的一层膜,其结构并不随温度、相结构的变化而变化,因而在液晶盒的光谱中观察到的相变点较少.通过二维光谱作者发现,在122℃时分子出现细微结构调整.     

NEXAFS spectromicroscopy of polymers: overview and quantitative analysis of polyurethane polymers

The successful application of X-ray spectromicroscopy to chemical analysis of polymers is reviewed and a detailed application to quantitative analysis of polyurethanes is presented. Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy is the basis of chemical sensitive X-ray imaging, as well as qualitative and quantitative micro-spectroscopy. These capabilities are demonstrated by a review of recent work, and by presentation of new results outlining a methodology for quantitative speciation of polyurethane polymers. C 1s inner-shell excitation spectra of a series of molecular and polymeric model compounds, recorded by gas phase inelastic electron scattering (ISEELS) and solid phase NEXAFS techniques, are used to understand the spectroscopic basis for chemical analysis of polyurethanes. These model species contain the aromatic urea, aromatic urethane (carbamate) and aliphatic ether functionalities that are the main constituents of polyurethane polymers. Ab initio calculations of several of the model molecular compounds are used to support spectral assignments and give insight into the origin and relative intensities of characteristic spectral features. The model polymer spectra provide reference standards for qualitative identification and quantitative analysis of polyurethane polymers. The chemical compositions of three polyurethane test polymers with systematic variation in urea/urethane content are measured using the spectra of model toluene diisocyanate (TDI) urea, TDI-carbamate, and poly(propylene oxide) polymers as reference standards.     

Nanoscale Structure of Urethane/Urea Elastomeric Films

The nanostructure of urethane/urea elastomeric membranes was investigated by small-angle X-ray scattering (SAXS) in order to establish relationships between their structure and mechanical properties. The networks were made up of polypropylene oxide (PPO) and polybutadiene (PB) segments. The structural differences were investigated in two types of membranes with the same composition but with different thermal treatment after casting. Type I was cured at 70–80 °C and type II at 20 °C. Both membranes showed similar phase separation by TEM, with nanodomains rich in PB or PPO and 25 nm dimensions. The main difference between type I and type II membranes was found by SAXS. The type I membrane spectra showed, besides a broad band at a 27-nm q value (modulus of the scattering vector), an extra band at 6 nm, which was not observed in the type II membrane. The SAXS spectra were interpreted in terms of PPO, PB soft segments, and urethane/urea links, as well as hard moiety segregation in the reaction medium. This additional segregation (q = 7 nm), although subtle, results in diverse mechanical behavior of in both membranes.     

Hydrogen bonding and liquid crystallinity of low molar mass and polymeric mesogens containing benzoic acids: a variable temperature Fourier transform infrared spectroscopic study

The phase behaviour and mesomorphism of poly(4-(6-propenoyloxyhexyloxy)benzoic acid) (PPOHBA) and 4-pentyloxybenzoic acid (POBA) is studied using variable-temperature Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction. PPHOBA exhibits a smectic C phase and POBA, a nematic phase. The temperature dependence of the Fermi resonance bands associated with the hydroxyl groups and of the carbonyl stretching region in the FTIR spectra indicates that there is a dynamic equilibrium between monomers and open and closed dimers formed by hydrogen bonding between benzoic acid moieties. The nematic phase observed for POBA is linked to the anisotropic cyclic dimer, while an abrupt increase in the concentration of monomer drives isotropisation. In PPOHBA, hydrogen-bonded supramesogens promote smectic behaviour, while hydrogen-bonded crosslinks stabilise the lamellae. The increased viscosity arising from this dynamic crosslinking is offset by the flexibility of the acrylate backbone and alkyl spacers.     

Study of optical band gap, carbonaceous clusters and structuring in CR-39 and PET polymers irradiated by 100 MeV O ions

Commercially purchased CR-39 and PET polymers were irradiated by 100 MeV O⁷⁺ ions of varying fluences, ranging from 1×10¹¹ to 1×10¹³ ions/cm². The effects of swift heavy ions (SHI) on the structural, optical and chemical properties of CR-39 and PET polymers were studied using X-ray diffraction (XRD), UV-visible spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The XRD patterns of CR-39 show that the intensity of the peak decreases with increasing ion fluence, which indicates that the semicrystalline structure of polymer changes to amorphous with increasing fluences. The XRD patterns of PET show a slight increase in the intensity of the peaks, indicating an increase in the crystallinity. The UV-visible spectra show the shift in the absorbance edge towards the higher wavelength, indicating the change in band gap. Band gap in PET and CR-39 found to be decrease from 3.87 to 2.91 and 5.3-3.5 eV, respectively. The cluster size also shows a variation in the carbon atoms per cluster that varies from 42 to 96 in CR-39 and from 78 to 139 in PET. The FTIR spectra show an overall reduction in intensity of the typical bands, indicating the degradation of polymers after irradiation.     

Influence of Curing Pressure on the Structure and Properties of Epoxy Adhesive Films

The effects of different curing pressures on the structure and properties of bisphenol A type epoxy adhesive film (METLBOND 1515-4, Cytec Industries Inc. Germany) were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), nano-indentation analysis, and tensile testing. When the curing pressure was increased from 0?MPa to 0.5?MPa FTIR showed that more rigid carbonyl groups were found in the polymers. In addition, the microscopic and macroscopic mechanical properties of the cured adhesive films were improved. Nano-indentation analysis showed that the elastic modulus of the cured product increased significantly, from 2.92?GPa to 3.49?GPa. However, the tensile tests showed that the breaking-elongation increased only slightly, from 3.10% to 3.73%, when the curing pressure was increased from 0?MPa to 0.5?MPa. DMA results showed that the crosslinking densities of the cured epoxy films were improved by the increased curing pressure. These results indicated that a higher modulus of the cured product could be gained by increasing the curing pressure appropriately.