X射线小角散射法研究聚乙烯的熔融辐照交联结晶

使用荷兰菲利浦公司提供的PW-1700自动粉末衍射仪及其Kratky小角散射体系附件,进行熔融辐照交联结晶聚乙烯的研究,从而得到了长周期随辐照剂量变化的关系,发现其熔融结晶是以Fischer固化模型为主.     

聚乙烯片晶辐照破坏的X射线散射研究

聚乙烯片晶辐照破坏的Ｘ射线散射研究王国英，姜炳政（中国科学院长春应用化学研究所长春１３００２２）关键词辐照聚乙烯，广角Ｘ射线衍射，小角Ｘ射线散射有关聚乙烯辐照破坏和交联问题，Ｈｏｓｅｍａｎ等［１］从Ｘ射线衍射的研究指出，辐照交联和破坏在晶区内部发生；...     

γ—射线辐照对聚乙烯单晶结构的影响

采用混合晶红外光谱、X-射线衍射及小角散射、差示扫描量热法研究γ-射线辐照对溶液生长聚乙烯单晶的影响,表明γ-射线辐照在单晶的规则折叠区也引起了不可忽视的结构缺陷或畸变。     

聚乙烯片晶辐照破坏机理的电子显微镜研究

用透射电子显微镜观察了高密度辐照聚乙烯的形态结构,并通过统计方法定量地分析了其结构与辐照剂量的关系。发现室温辐照聚乙烯的片晶形态不随辐照剂量而变化。若将室温辐照聚乙烯重新熔融,然后再于125℃下等温结晶4h后,其片晶厚度则随辐照剂量的增加而变薄,长周期亦随之变短。小角X射线散射的测试结果与上述结果符合得很好。室温辐照聚乙烯及其125℃重结晶试样的电子显微镜数据从又一直观角度验证了辐照聚乙烯“片晶内部破坏机理”的正确性。     

交联聚乙烯熔体结晶的晶胞结构及微晶尺寸

用X -衍射方法研究了熔融辐照交联结晶聚乙烯的晶胞结构变化规律 ,并得到了垂直( 110 )晶面方向微晶尺寸随辐射照剂量变化的关系。结果表明晶格尺寸和缺陷随交联度增加而增长。     

超高分子量聚乙烯凝胶膜超高取向过程的几个不同阶段

通过Ｘ射线衍射、平板照相、扫描电镜等方法观测超高分子量聚乙烯凝胶／结晶膜取向过程中的结构形态变化，并根据ＰＥ片晶分子动力学模拟结果，提出ＵＨＭＷＰＥ凝胶膜在热拉伸取向过程中明显存在３个不同阶段，即：初期片晶转动或滑移，ｂ轴优先垂直于拉伸方向取向；随着拉伸比增大，片晶的ｃ轴平等于伸方向，同时，分子链的解折叠开始，部分非晶链也进入伸直链区取向，当拉伸比达到极限倍率时，分子链已经接近完全伸展成为比较刚直     

茂金属支化聚乙烯的结构、形态与熔融行为

综述了茂金属支化聚乙烯的形态，结构和熔融行为，详细讨论了支链大小和含量以及分子量对其物理性质的影响。     

短链支化对低分子量聚乙烯结晶及熔融行为的影响

研究了金属茂催化的低分子量支化聚乙烯和线性聚乙烯的结晶及熔融行为 ,发现支化聚乙烯的结构与线性聚乙烯相同为正交结构 ,但晶格略有膨胀 .支链的存在对熔融行为影响不大 ,两种聚乙烯的熔点均随结晶温度的升高而非线性增加 ,表现出低分子量样品的共同特征 .但支链的存在对结晶行为却有很大的影响 ,主要是由于支链的存在降低了晶体的结晶速率从而影响结晶过程 ,使得低分子量的支化聚乙烯的结晶行为与高分子量线性聚乙烯的结晶行为相似而与低分子量的线性聚乙烯不同 .动力学分析表明 ,低分子量的支化聚乙烯的结晶生长方式的转变温度比同等分子量的线性聚乙烯降低了约 2 0℃     

辐照聚乙烯单晶的退火研究

用红外光谱、ＤＳＣ、ＳＡＸＳ和ＷＡＸＤ等方法考察了辐照５ＭＧｙ后的聚乙烯单晶在退火前后的结构变化，对比未辐照样品在同样条件下的变化，提出在９０℃以下和１０５℃聚乙烯有不同的退火机理，辐照引起的交联和晶区结构损伤，限制了退火对晶体结构的改善程度．     

The Isothermal Melting Kinetics of Ultra-High Molecular Weight Polyethylene Crystals

The isothermal melting behaviors of ultra-high molecular weight polyethylene (UHMWPE) with different entangled states (i.e., nascent and melt-crystallized samples) are studied. For two kinds of UHMWPE samples, the result shows that the relative content of survived crystals (X_s) exponentially decreases with time and reaches a constant value. It is suggested that such a melting behavior is related to the observed nonlinear growth of crystals induced by the kinetically rejected entanglements accumulated at the growth front. Additionally, the exponential decay of X_s with time provides a characteristic melting time (τ) for the melting process. Compared to the melt-crystallized UHMWPE, the τ value of nascent UHMWPE is generally longer even in a higher temperature range, which is mainly because the former has a larger entanglement density difference. Furthermore, these observations demonstrate that UHMWPEs with different entangled states have an analogous melting mechanism since they exhibit a similar melting activation energy (≈1300 kJ mol⁻¹).     

BPDA/PPD/OTOL聚酰亚胺纤维的力学性能、形貌和结构

在3,3’,4,4’-联苯四酸二酐(BPDA)和对苯二胺(PPD)体系中引入3,3’-二甲基联苯胺(OTOL),显著改善了纤维的力学性能。当n(PPD)∶n(OTOL)=70∶30时,纤维的拉伸强度可达到改性前的2倍,其拉伸强度和拉伸模量分别为1.50和80 GPa。SEM照片显示了纤维的断面为圆形且没有孔穴,也没有明显的"皮芯"结构和原纤结构。WAXD和SAXS分析表明,纤维的轴向堆积和分子链取向在热牵伸过程中得到改善。     

Domain structure and interphase dimensions in poly(urethaneurea) elastomers using DSC and SAXS

Small‐angle X‐ray scattering (SAXS) and differential scattering calorimetry (DSC) were used to demonstrate distinct differences in domain size, phase separation, and hydrogen bonding in a series of segmented urethaneurea elastomers prepared from isocyanate‐terminated prepolymers and aromatic diamine chain extenders. Two types of prepolymers were studied. The first contained a broadly polydisperse high molecular mass oligomer with relatively high levels of free isocyanate monomer. The second type of prepolymer contained low levels of high molecular mass oligomers with mass fractions greater than 90% of the two‐to‐one adduct of toluene diisocyanate (TDI) to polytetramethylene glycol (PTMEG). The mass fraction of the residual unreacted diisocyanate was less than 0.1% in the second type. Two chain extenders, 4,4′‐methylene bis‐(2‐chloroaniline)(Mboca) and 4,4′‐methylene bis‐(3‐chloro‐2,6‐diethylaniline) (MCDEA), were used to convert the prepolymers to poly(urethaneurea) elastomers. Materials prepared from the prepolymers with low oligomer polydispersity exhibited smaller hard segment domains with more ordered morphology, greater phase separation, and more hydrogen bonding than those prepared from prepolymers with high oligomer polydispersity. These tendencies were enhanced in those elastomers prepared by chain extension with MCDEA compared to those made with Mboca. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2586–2600, 1999     

Effect of Stereoregular Polyelectrolyte on Protein Thermal Stability

Myoglobin was used as a model protein to study the effect of polyelectrolyte on protein thermal stability for solutions. Stereoregular polystyrene sulfonate was used to investigate the effect of chain properties on protein polyion binding affinity. Turbidity measurement indicate stronger binding to protein of atactic polystyrene sulfonate than isotactic polystyrene sulfonate, an effect that might be due to the higher chain flexibility of the atactic form. Differential scanning calorimetry (DSC) and small angle x-ray (SAXS) scattering indicate the presence of the polyelectrolyte has a destabilizing effect on the protein. The results showed that, although the presence of polyelectrolytes has no effect on myoglobin structure at room temperature at pH 7.4, myoglobin stability is reduced as the temperature is elevated. This effect is linked to the binding of the protein to the polylectrolyte. This binding is probably driven by a combination of electrostatic and hydrophobic interactions, the latter of which are enhanced at higher temperatures.     

Radiation Damage of Crystal Polyesters

The change of crystal structures in polyethylene terephthalate (PET) and polyhexa methylene terephthalate (PHT) irradiated by γ-ray were investigated by using the methods of WAXD and SAXS. It was found that irradiation caused the crystal parameters of PET and PHT to lengthen, and the cell to expand; and at the same time, the long period and the thickness of lamellae were unchanged. These results indicate that the radiation damage of crystal polyesters causes the increase of lacunaries within the crystal polyester.     

Micro-Macro Scale Relationship in Creep Deformation of Ultra High Molecular Weight Polyethylene

Macroscopic and microscale creep deformations of UHMWPE were investigated by using in situ SAXS.A methodology for the measurement of the local creep deformation of inter-lamellar amorphous phase has been proposed.The local strain of inter-lamellar amorphous phase (εa) and macroscopic strain (εmacro) were evaluated and they were compared to study the relationship between macroscopic and microscale creep deformation of UHMWPE.Both of them exhibit two deformation regions against creep time.The entanglements show a strong impact on both the macroscopic and local inter-lamellar amorphous phase creep behavior and they can be well correlated to the molecular weight between two entanglements estimated from strain-hardening modulus.Compared to the macroscopic creep deformation,local inter-lamellar amorphous layers have a smaller creep deformation.From the local creep measurement,the apparent modulus of inter-lamellar amorphous phase can also be estimated (200 ＜ Ma ＜ 500 MPa).These values are much higher than the Young's modulus of bulk amorphous PE,which can be well explained by the confinement of the lamellar stacks and the enhancement of the amorphous phase with the relatively high concentration of entanglements.This study provides a useful means and quantitative data for achieving the scale transition between the micro and the macro structural levels for the study of viscos-elastic deformation.     

Cellulose-polyamide 66 blends. I. Processing and characterization

Each homopolymer, cellulose and polyamide 66 (PA66), was separately dissolved in a mixture of N-methyl morpholine N-oxide and phenol (80/20 w/w). Then, the two solutions were mixed together. This step leads to the crystallization of PA66 in small aggregates (about 1 μ) regularly dispersed in the cellulose solution. It appeared that this morphology remains independent of further processing such as spinning or casting. Finally, fibers or films were precipitated in methanol. The entire preparation technique used here results mainly in two-phase systems in which PA66 domains are embedded in an amorphous cellulose matrix. The specimens obtained were at first characterized by differential scanning calorimetry, scanning electron microscopy, and wide angle x-ray scattering. © 1994 John Wiley & Sons, Inc.