用偏振红外光谱表征经单轴和双轴拉伸的PET薄膜

用偏振红外光谱方法研究了拉伸速率和不同拉伸方式,包括单轴拉伸、双轴同时拉伸和双轴依次拉伸等,对PET薄膜取向的影响。对由不同拉伸方式制得的反式结构含量和密度均基本相同的试样进行比较得出:单轴拉伸试样中分子链相对拉伸方向的轴取向程度最高,分子链在薄膜平面内的取向分布亦最不均匀;双轴拉伸试样中分子平面(苯环面)相对薄膜平面有明显的平面取向,而单轴拉伸试样中分子平面和薄膜平面基本上无共平面趋势。在所用的实验条件下,拉伸速率对取向程度几乎没有影响。     

不同结晶速率的PET薄膜在拉伸过程中的结晶与取向

用多种方法对两个结晶速率不同的PET样品在拉伸过程中的结晶和取向进行了研究。结果表明在同样的拉伸条件下,结晶速率较快的样品的结晶度和取向程度均比另一样品要高得多,这种结构变化上的差别说明把拉伸行为的差别归因于结晶速率的不同是合理的。     

快压法制备非晶聚醚醚酮的应变诱导结晶行为

利用快速增压和淬火2种方法分别制备了非晶聚醚醚酮(PEEK), 并利用二维广角X射线衍射(WAXD)研究了2种非晶样品在不同拉伸温度(T_d)和不同应变速率(v)条件下的结晶行为. 结果表明, 在相同拉伸温度及应变速率条件下, 快压样品的临界结晶应变明显低于淬火样品; 随着拉伸温度和应变速率的升高, 2种样品的临界结晶应变均逐渐降低; 在相同应变条件下, 拉伸温度对PEEK材料结晶度的影响很大, 而应变速率对其影响较小.     

单向和双向拉伸聚酯(PET)薄膜取向的光学评价

<正> 通常人们采用X-射线法和红外二向色性法等获得有关高聚物材料的晶区取向和分子链上某些特定基团的取向状况,但存在着设备要求高且操作复杂的弊端。Schael和Samuels等发展了利用改装型阿贝折射仪,可以方便地同时获得高聚物薄膜样品(聚烯烃和羟基丙基纤维素等)三个轴向上的折射率。有关聚酯(PET)的报道则不多见。本工作主要研究了不同拉伸条件(拉伸方式和拉伸速率等)对PET薄膜取向状况(折射率和     

用U核裂变碎片径迹法研究PET薄膜的高分子聚集态结构

<正> 高聚物薄膜如聚对苯二甲酸乙二酯(PET),聚碳酸酯,硝酸纤维素等经铀核裂变碎片轰击后,再用化学试剂蚀刻,可以显示核裂片在高聚物薄膜内的经迹,这已在核物理研究中得到很好的应用。本文应用核经迹法对PET不同取向和结晶程度的试样进行了观察,认为该方法对于研究高分子聚集态结构是有深入探讨意义的。     

聚对苯二甲酸乙二酯非晶态膜片单轴热——拉伸中的结晶与松弛

用动态力学损耗温度谱作为测试手段,研究了非晶态PET膜片在78—112℃温度范围内的单轴拉伸。实验结果说明,在较低温度下所得结晶的拉伸试样,完全由于应变诱发结晶,发生在应力-应变曲线的屈服后应力开始上升的阶段。在较高温度下(90℃或更高)拉伸可得非晶态而且光学各向同性的试样,是由于分子链的小尺度取向在拉伸过程中已完全热松弛所致,而分子链的大尺度取向要通过高弹态流动而松弛,其速率较慢,用拉伸后试样两端固定时的应力松弛进行了观察。在较低温度下应力松弛后仍为非晶态,在较高温度下应力松弛到起始应力的1O％下才开始结晶。FTIR研究表明在这种状态下的结晶有一结晶诱导期,其时间尺度与应力松弛阶段相当。     

溶液成膜的温度对聚对苯二甲酸乙二酯结晶度的影响

<正> 用溶液成膜是制备聚合物薄膜的常用方法之一。但是溶液成膜的条件,如成膜温度,溶液浓度等对半结晶聚合物结晶度的影响研究报道较少。制备聚对苯二甲酸乙二酯(PET)非晶态薄膜通常使用熔融热压其后淬火的方法。由于PET在熔点附近易于降解,在薄膜中产生气泡,因而很难制备较大面积的均一厚度的薄膜,如在拉伸试验中所需     

拉伸对β晶型聚丙烯结构的影响

用DSC法研究了不同拉伸条件对β晶型聚丙烯(β-PP)结构的影响,结合X-射线衍射法探讨了拉伸比,拉伸温度和拉伸速率等对β→α转变及其结晶结构的变化所起的作用。 结果表明提高拉伸温度和拉仲比有利于β→α转变及结晶度的提高。并讨论了拉伸过程中β→α转变机理及影响结晶结构的因素。     

结晶及拉伸取向对聚对苯二甲酸乙二酯纤维分子运动的影响

用声频共振法在 100—430°K温度范围内研究了结晶及拉伸取向对 PET纤维分子运动的影响。在研究的温度范围内PET出现两个转变,243°K(β_c),354—383°K(α_a)。拉 伸使α_a转变显著移向高温,而β_c转变基本上不随拉伸比改变,这说明PET纤维的拉伸主要改变了非晶区分子链间的相互作用。 根据高柳的力学模型及建议的方法从α_a及β_c转变的损耗模量峯值计算了PET的“结晶度”,说明用密度法测得的结晶度反映了晶区与晶区缺陷部分的总和。     

应变调控单层氧化锌能带结构的第一性原理研究

采用基于密度泛函理论的第一性原理计算对单层ZnO薄膜能带结构的应变调控进行了研究.计算结果表明:沿着之字形方向的压缩应变和扶椅形方向的拉伸应变对薄膜带隙的调控都是线性的,而且带隙调控的范围最大;相反地,在沿着之字形方向的拉伸应变和扶椅形方向的压缩应变的调控下,带隙则呈现出非线性的变化.对于双轴应变的拉伸与压缩,带隙的变化都是非线性的.这种通过不同的应变加载方式来实现对带隙不同程度的调控,对ZnO薄膜在光学和催化等领域的应用具有重要的指导意义.     

聚醚氨酯的红外酰胺Ⅰ.谱带分析

通过对聚醚氨酯红外光谱酰胺-Ⅰ谱带的二级微商及傅里埃自解卷积处理,发现了位于1715cm~(-1)的新组分并可归属于无序的相间界面。应用差减光谱及曲线拟合对热处理试样的光谱谱带进行分析表明聚醚氨酯的加热/冷却过程是与可逆的无序/有序化过程及微相混合/分离过程有关的。新发现的1715cm(-1)组分强度的变化与无序/有序化过程是一致的。     

Conformation orientation of syndiotactic polypropylene induced by deformation at different temperatures

Two syndiotactic polypropylene (sPP) sample films (S0 and S90) with different initial structures were prepared in this paper by isothermal crystallization from the melt at 0 and 90 degrees C, respectively. The polymorphic transitions of the two samples induced by deformation at different temperatures (20, 40, and 60 degrees C) were investigated by rheo-optical FTIR spectroscopy. The results indicated that stretching leads to the transition from the helical to trans-planar conformation and improves the orientation of both helical and trans-planar conformations for the sPP films. With increasing stretching temperature, the conformational transitions for the two sPP samples are all suppressed, and the orientation behavior of the two samples appears completely different. The orientation degree of S0 decreases with increasing stretching temperature, while that of S90 increases. These results suggest that the stretching temperature and initial structure have great influence on the conformation transition and orientation behavior of the sPP sample. On the basis of the experimental results, the schematic illustration of the conformation transition and orientation behavior of sPP during stretching has been proposed.     

IR-laser induced interconversions of hydrogen-bonded dimers in cryogenic matrices

IR-laser induced interconversions of hydrogen-bonded alcohol dimers have been studied in cryogenic matrices by means of FTIR spectroscopy and a tunable F-center laser as photolysis source. Four different conformational forms of the open chain methanol dimer have been identified in solid nitrogen matrices. These conformations have been interconverted by selective vibrational excitation into the OH stretching absorption bands.     

Infrared spectroscopic and density functional theory study on the reactions of lanthanum atoms with carbon dioxide in rare-gas matrices

Reactions of laser-ablated La atoms with CO2 molecules in solid argon and neon have been investigated using matrix-isolation infrared spectroscopy. On the basis of isotopic shifts, mixed isotopic splitting patterns, and CCl4-doping experiments, absorptions at 1839.9 and 753.6 cm-1 in argon and 1855.9 and 771.3 cm-1 in neon are assigned to the C-O and La-O stretching vibrations of the OLaCO molecule, respectively. Ultraviolet-visible photoinduced isomerization of OLaCO to La-(eta2-OC)O and OLa-(eta2-CO) have been observed under different wavelength photolyses in the solid matrix. The neon matrix experiments give the C-O and La-O stretching vibrations of the OLaCO- anion at 1769.5 and 779.3 cm-1, respectively. Density functional theory calculations have been performed on these products, which support the experimental assignments of the infrared spectra. The present study reveals that the C-O stretching vibrational frequencies of OMCO decrease from Sc to La, which indicates an increase in metal d orbital --> CO pi* back-donation in this series.     

高聚物声发射的一些观察

对高聚物的声发射做了进一步的实验观察。玻璃态高聚物在拉伸屈服以前的声发射有Kaiser效应,但在高弹态则不然。非晶态高聚物从玻璃态到高弹态的转变,玻璃态拉伸时在屈服附近出现声发射,高弹态时声发射要少而弱得多,只在高弹拉伸的断裂前出现声发射。非晶态、晶态高聚物或共混高聚物在突然升温到100℃时有声发射,但在突然降温到-60℃时却不出现声发射,这可能也说明声发射与高聚物试样内形成空洞有关。一种聚丙烯树脂在不同注射成形工艺条件下所得试件,在拉伸时的声发射行为可反映加工成形的好坏,成形好的声发射少得多。     

T dependence of vibrational dynamics of water in ion-exchanged zeolites A: a detailed Fourier transform infrared attenuated total reflection study

In order to explore the influence of cation substitution on the vibrational dynamics of water molecules in zeolites, the evolution of structural properties of the O-H stretching band of water in fully hydrated Na-A and Mg-exchanged A zeolites has been studied, for different percentages of induced ion exchange, by Fourier transform infrared attenuated total reflection spectroscopy as a function of temperature. The differences revealed in the O-H stretching band shapes have been accounted by fitting the spectra as a sum of four components, corresponding to water molecules exhibiting different types of hydrogen bonding. The dependencies of the relative intensities, peak wave numbers, and bandwidths of the resolved components on temperature and Mg2+ content have been discussed. Evidence of the "structure-maker" role played by a zeolitic surface on physisorbed water, systematically enhanced by increasing the percentage of induced ion exchange, is given in the whole explored temperature range.     

聚醚氨酯的红外酰胺Ⅰ.谱带分析

 通过对聚醚氨酯红外光谱酰胺-Ⅰ谱带的二级微商及傅里埃自解卷积处理,发现了位于1715cm^-1的新组分并可归属于无序的相间界面。应用差减光谱及曲线拟合对热处理试样的光谱谱带进行分析表明聚醚氨酯的加热/冷却过程是与可逆的无序/有序化过程及微相混合/分离过程有关的。新发现的1715cm^-1组分强度的变化与无序/有序化过程是一致的。     

Vibrational spectroscopy of the basic copper phosphate minerals: pseudomalachite,ludjibaite and reichenbachite

The vibrational spectra of pseudomalachite, reichenbachite and ludjibaite have been obtained at 298 K using a combination of FTIR and Raman microscopy. The vibrational spectra of the minerals are different, in line with differences in crystal structure and composition. Some similarity in the Raman spectra of the three polymorphs pseudomalachite, reichenbachite and ludjibaite exists, particularly in the OH stretching region, but characteristic differences in the OH deformation regions are observed. Differences are also observed in the phosphate stretching and deformation regions.     

Studies of the characteristic frequencies of vapor-phase infrared spectra: II. The characteristic frequencies of ketones and aldehydes

Vapor-phase infrared characteristic frequencies of ketones and aldehydes have been studied. The CO stretching vibrations in vapor phase have higher frequencies than those in condensed phase. The shifts are about 20 cm⁻¹ for ketones and about 10 cm⁻¹ for aldehydes. Both ketone and aldehyde have an absorption band at the range 1300–1100 cm⁻¹, although their intensities are very different. This band was assigned to the CC stretching vibration of C(CO)unit.