具有分子取向的拉伸高聚物(PET)中~(13)C—NMR化学位移值的估算

本文从已知的聚对苯二甲酸乙二醇酯(PET)的X-射线原子坐标和化学位移张量主值出发,计算了拉伸的PET样品,相对于外磁场不同放置方位下的~(13)C-NMR谱峰的化学位移值,很好地解释了实验结果,并得到了拉伸条件下,高聚物中分于取向的信息。     

伽马射线辐射原位强化增韧含三羟甲基丙烷三丙烯酸酯的PET/弹性体合金

在少量的交联剂三羟甲基丙烷三丙烯酸酯存在下,研究了高能伽马射线辐射对PET/弹性体（ST2000）合金的原位强化增韧效应.在PET合金熔融共混的高温下,TMPTA可与PET和ST2000的分子链发生反应,使PET和ST2000发生分子内和分子间的交联,增强界面相互作用,使得PET合金的冲击性能提高,但拉伸强度有所下降.PET合金经过高吸收剂量的伽马射线辐照后,可以原位增加体系内部弹性相和界面相的化学交联程度,进一步提升PET合金的综合力学性能.当吸收剂量为100 kGy时,样条在冲击测试条件下未发生断裂,同时拉伸强度几乎保持不变.     

基于数字图像相关技术的风电叶片静态特性试验研究

进行了风电叶片双轴静载试验,全程采用数字图像相关技术监测其全场三维变形。结果表明,在各工况荷载作用下,风电叶片的三维位移分布具有良好规律,而应变分布则无明显规律。3个方向位移中,平面外位移远大于平面内位移。双轴荷载作用下,风电叶片挥舞方向位移与摆振方向位移均随加载等级增大而增大。在风电叶片全场范围内,挥舞方向位移沿叶片展向逐渐增大,直至叶尖达到最大值。叶片各点的摆振方向位移均为负位移,负位移最大值出现在叶片中部。在叶根至41%叶长(55 cm)区域内,叶片各工况下的展向位移几乎接近于0;而在41%叶长至叶尖区域,当荷载较小时,叶片迎风面纤维的受拉伸长量大于平面外弯曲的展向位移分量而产生正位移;随着荷载增大,叶片平面外弯曲变形的展向位移分量大于迎风面纤维的受拉伸长量而产生负位移。     

基于位移光栅尺的拉伸法弹性模量测量

基于光栅光学原理,利用位移光栅尺测量了弹性模量,建立了位移光栅尺拉伸法测量系统,通过实验获得金属丝在拉伸过程中的微小形变量数据,再利用拉伸法测量弹性模量与微小形变量之间的关系,最终实现弹性模量的测量.     

外标法NMR实验中化学位移的校正

推导了 NMR实验中任意条件下柱状介质所感受到的有效磁场和固有化学位移的公式 ,概括了通过单谱仪、双谱仪和魔角实验校正化学位移的方法 ,阐述了平行场和垂直场中的介质磁化率效应。     

质子化学位移各向异性的测量

测量质子化学位移各向异性（CSA）有助于表征分子结构与其动力学,但由于¹H-¹H同核偶极耦合相互作用很强及质子各向异性化学位移较小,测量质子化学位移各向异性仍具有巨大挑战,特别是对含有多种质子的生物大分子,如蛋白质.本文简要综述了测量质子化学位移各向异性的方法,包括同核去耦慢速魔角旋转方法、超快魔角旋转方法、对称重耦（RN_n^v）方法、xCSA方法以及量子化学计算方法.我们重点介绍了在高速魔角旋转条件下蛋白质氨基质子化学位移各向异性的测量及它们与氢键长度、蛋白质二级结构之间的关系.     

大气压低温空气刷型微等离子体在生物医学应用

在这项研究中,自行研制在大气压下能够实现稳定刷型空气放电便携式等离子体装置并应用PET聚合物表面改性和生物医学中,在室温下整齐稳定的刷型微等离子体形成于Al_2O_3陶瓷腔底端微孔中空光纤管的末端附近,这种等离子体可以均匀大面积改性PET聚合物.等离子体可以有效地防止热敏聚合物被损坏,并且很明显的改善被处理的聚合物表面的特性,例如表面的化学成分、疏水性和生物相容性.通过对比未经等离子体处理的PET表面吸附大量的血小板和经等离子体处理后的PET表面几乎没有吸附血小板,这可归功于PET表面功能特性的改变.为了找出影响生物相容性关键因素,进一步分析了等离子体的发射光谱及PET聚合物表面化学成份.     

环丁酮衍生物的2D-NMR研究

本文用¹H-NMR,¹³C-NMR,同核化学位移相关2D、异核化学位移相关2D技术,测定了两种环丁酮的衍生物,求出其优势构象并归属了化合物中所有氢及碳的化学位移。     

19F NMR化学位移经验公式的影响因素

化学位移是核磁共振技术的重要参数,目前对¹H NMR、¹³C NMR已提出一系列估算化学位移的经验公式,但¹⁹F NMR化学位移规律研究报道则较少,以δ=B+∑△i+C化学位移通式为基础,分析屏蔽常数对化学位移的作用,并针对¹⁹F原子,分析了氟的电子云密度、立体效应、溶剂效应、氢键、标准、浓度和温度等影响因素,对¹⁹F NMR化学位移经验公式的提出提供理论依据。     

AT1受体拮抗剂缬沙坦化学位移的量子化学计算研究

核磁共振波谱实验能够通过谱峰化学位移归属确定化合物分子结构,同时理论计算预测化学位移有助于核磁共振对化合物的谱峰归属. 该文基于李芳等人的核磁共振实验以及分子动力学模拟结果,采用量子化学方法预测了缬沙坦（Valsartan）在SDS胶束中2种构象的化学位移. 通过比较不同量子化学方法和基组的计算结果,特别是采用了ONIOM模型考虑了胶束环境对药物分子化学位移的影响,表明Valsartan在SDS胶束溶液中所存在的2种构象可以通过理论计算加以区分,且这2种构象的化学位移理论预测值与NMR实验值吻合得很好. 本工作表明在计算复杂体系化合物的化学位移时,理论模型应该考虑环境效应的影响.     

Epitaxial crystallization of crystalline polymers on the surface of drawn polytetrafluoroethylene

Crystallization of crystalline polymers on the surface of drawn polytetrafluoroethylene (PTFE) was studied. Further, cold-drawn polyethylene (PE) was heat treated in contact with drawn PTFE, holding their drawing axes at right angles to each other, and then the morphological change of PE at the interface was studied. Molecular orientation in the surface layer of the PE was examined by observing the molecular orientation of polycaprolactone (PCLn) crystallized on the PE surface.

It was found that PE, PCLn, and nascent nylon 6 crystallize epitaxially on drawn PTFE, which is well known as a polymer having a low energy surface. Intermolecular interaction between PTFE and the overgrown crystalline polymers was explained on the basis of their crystal structures. The molecular orientation of PE in the interfacial region changes from the drawing direction of PE to the drawing direction of PTFE during annealing. It is proposed that PE partially melts during annealing, and nuclei of PE with their c-axis parallel to the molecular axis of PTFE are formed at the interface. Consequently, PE lamellar crystals with their c-axis perpendicular to the original drawing direction grow in the interfacial region between PE and PTFE.     

A proton magnetic resonance investigation of some weak interactions in solution

The proton chemical shifts of cyclohexane, methyl iodide and iodoform are measured in a number of solvents. A complete calculation of the contribution to the solute proton chemical shift arising from the magnetic anisotropy of cylindrically symmetric solvents is given. Although the formula predicts the direction of the observed shifts, the observed values for non-polar solutes are always much larger than the calculated values. Some possible reasons for this are given and discussed.

The variation of the proton chemical shifts of the polar solutes methyl iodide and iodoform in aliphatic solvents are shown to agree with present theories of these effects. However, in aromatic solvents considerable deviations from the theoretical line are found and these are postulated to arise from solute solvent complexes in which the dipole axis of the solute lies along the hexagonal axis of symmetry of the benzene ring with the protons towards the ring. From the variation of the proton chemical shifts of methyl iodide and iodoform in toluene solution with temperature the following parameters were obtained. For the methyl iodide toluene complex the energy and entropy of formation are 1·3 ± 0·5 kcals/mole and 4·9 ± 0·4 e.u. respectively. For the iodoform toluene complex the corresponding values are 1·6 ± 0·2 kcals/mole and 6·4 ± 0·2 e.u.     

Biaxial Orientation Mechanism of Drawn Natural Rubber. I. Appearance of the Biaxial Orientation

Triple centrifuged natural rubber (NR) film was crystallized at room temperature by uniaxial drawing at draw ratio (λ) 6.0. Morphologies of the induced crystals were studied by wide angle X‐ray diffraction (WAXD). Using a special drawing apparatus for shifting the X‐ray beam positions, crystalline orientation was surveyed all over the drawn sample. WAXD results show the biaxial orientation (BO) with the c‐axis being parallel to the draw direction and the a‐axis parallel to the film surface. By means of the WAXD pattern with the incident beam perpendicular to the film, the drawn NR film was separated into three regions: (200+120) region indicating a low degree of BO, (200) region having a high degree of BO, and the intermediate region in between the above two regions. The degree of BO is enhanced from center to the clamping end depending on the increment of the sample width. At lower draw ratios (4.0<λ<6.0), BO was developed with increasing draw ratio. In the intermediate region, BO increases sharply with a small increment of the width. The degree of BO is lowered at the periphery of the film.     

Thermal optics distortion of face pump slab lasers with two pump arrangements

Two pump arrangements, which are the slow axis and the fast axis of LD stacks parallel to the length direction of the slab, are simulated. From the results the optical intensity along the width of the slab is Gaussian and super-Gaussian distribution, respectively. Then based on heat conduction equation and conductively cooling boundary condition, the calculation of the distribution of absorbed pump power, temperature and thermal stress with the tool of finite element analyses is performed. From these results we numerically calculate the thermal focusing in zigzag and perpendicular zigzag planes using the ray tracing method running at low and high repetition rates. It is found that the temperature distribution along width has a significant impact on the thermal stress and thermal optics distortion, especially running at high repetition rate or high average power. Finally, the conclusion was that the pump arrangement with the fast axis of LD stacks parallel to the length direction of the slab is superior to the slow axis of LD stacks parallel to the length direction of the slab in decreasing thermal lens effect and obtaining high beam quality.     

Temperature dependence of the elastic modulus of crystalline regions of Poly(ethylene terephthalate)

The temperature dependence of the elastic modulus E₁ of crystalline regions of poly(ethylene terephthalate) (PET) in the direction parallel to the chain axis has been investigated by x-ray diffraction. The axial chain contraction coefficient is constant from 25°C to 200°C, and correspondingly the value of E₁ (108 GPa) remain unchanged up to 215°C. This is in contrast with the temperature dependence of E₁ values of various polymers previously reported. It is considered for PET that the axial thermal molecular motions which cause the decrement of E₁ do not take place in the crystalline regions, and that the force constant of bond stretching and that of bond angle bending are constant over both the temperature and the stress range studied. It is reasonable to conclude that the mechanical structure of drawn PET is composed of the series model.     

Detecting and avoiding the necking deformation along polypropylene fibre axis using the fringe pattern analysis of multiple-beam microinterferometry

A fibre-drawing device attached with the system for producing multiple-beam Fizeau fringes in transmission is used to optimize the optical properties during the cold drawing of polypropylene (PP) fibres. This system is automated for interference pattern analysis. Two drawing processes for the PP fibres are applied and investigated. The first one is fast drawing in which the necking deformation is predicted and the other is the slow (step) drawing in which the necking can be avoided. The refractive index profiles (n and n) of PP fibres are determined at different positions along the fibre axis during the fast and slow drawing processes. The fibre interference patterns are automatically digitized and stored in a computer storage media. The slow drawing technique for PP fibres is recommended to overcome the deformation difficulties along the fibre axis due to necking during the drawing processes. Microinterferograms in case of light vibrating parallel and perpendicular to the fibre axis are given for illustration.     

光斜入射时偏振器作用的表述

对偏振器特性的分析表明,当光斜入射时,振动方向与偏振器透光轴不平行的光也能通过偏振器,只要该方向与系统光轴与透光轴构成的平面平行。提出了透光平面的概念。利用欧拉角表示光波坐标系和偏振器坐标系之间的变换,得到透过偏振器后偏振光的振动方向及其大小的数学表述,给出了简化表达式及其使用条件。表达式具有一般性,可以直接使用。     

Mapping misoriented fibers using X-ray dark field tomography

X-ray grating interferometers produce three distinct signals; an absorption signal, a differential phase signal and a dark field signal. Until now a method for successfully creating dark field tomograms of nonisotropic samples has not been demonstrated. In this paper we test a method for creating such tomograms on a highly nonisotropic sample, i.e. a five layer “sandwich” of oriented carbon fibers. The fibers are parallel within the individual sandwich layers, but perpendicular to the fibers in the adjacent layers. We show that by choosing a rotation axis parallel to the grating stepping direction (i.e. a horizontal rotation axis in most setup configurations) it is possible to produce a darkfield tomogram where fibers parallel to the probed scattering direction appear to have no dark field signal. The method produces a tomogram in the form of a scalar field of dark field scattering values.     

三层材料纳米颗粒形状对消光特性的影响

通过高分辨率电子束光刻方法制备了不同形状的三层复合材料纳米颗粒,研究了这种纳米颗粒的形状变化对消光特性的影响。测试结果表明,当入射波偏振方向平行于短轴时,随着长宽比的增大,共振峰位置发生蓝移;当光源偏振方向平行于长轴时,随着长宽比的增大,共振峰位置发生红移。还用时域有限差分算法以及表面等离波子的Lorentz模型对纳米颗粒的消光特性进行数值计算,所得的消光频谱曲线、共振峰位置变化趋势与实验基本一致。此外,还研究了主体材料层厚度对消光特性的影响,发现其厚度在20～90nm变化时,共振峰发生3～115nm的蓝移。