尼龙1010球晶的转化

本文利用偏光显微镜研究了尼龙1010球晶的转化。发现在降温过程中放射状球晶多转变成相同光性的环状球晶。升温时正环状转化为正放射状球晶;正、混合放射球晶部分转化为负放射状球晶;黄蓝两瓣球晶在一定温度范围内可与负放射球晶相互转变。多种球晶共存时,混合放射球晶可转变成两瓣、不对称四瓣和六瓣形放射球晶;正、混合坏状分别转变成不对称四瓣和六瓣形环状球晶;最后都以环状球晶熔化。     

尼龙1010等温结晶球晶形态与生成条件研究

 本文利用偏光显微镜研究了等温结晶时尼龙1010球晶的形态与生成条件,发现在原始样品熔点附近或高于原始熔点以上温度结晶,主要生成暗、亮与带正环的负光性放射状球晶;熔点以下至195℃主要生成正放射状球晶;在较宽的温度范围内可生成混合光性放射状球晶,与少量的六瓣、两瓣、不对称四瓣形三种异常光性球晶;181℃以下主要生成正环状球晶.     

尼龙1010等温结晶球晶形态与生成条件研究

本文利用偏光显微镜研究了等温结晶时尼龙1010球晶的形态与生成条件,发现在原始样品熔点附近或高于原始熔点以上温度结晶,主要生成暗、亮与带正环的负光性放射状球晶;熔点以下至195℃主要生成正放射状球晶;在较宽的温度范围内可生成混合光性放射状球晶,与少量的六瓣、两瓣、不对称四瓣形三种异常光性球晶;181℃以下主要生成正环状球晶.     

尼龙1010球晶的熔融

本文利用偏光显微镜研究了尼龙1010等温结晶所生成的几类球晶的熔融现象,测得正环状球晶的熔点(T_m)为182℃,正放射球晶T_m=203℃;混合放射球晶T_m=202～205℃;暗负放射球晶T_m=204～210℃;亮负放射球晶T_m=205～210℃。利用Hoffman T_m-T_ε外推法测得其平衡熔点T_m~0=215℃。     

间规聚苯乙烯晶体结构的研究——等温结晶球晶形态及生成条件研究

用偏光显微镜研究了 2 0 0℃～Tm 等温熔体结晶间规聚苯乙烯 (s PS)的球晶形态及其生成条件 ,发现s PS共可生成八类球晶 .在较低温度 (Tc<2 40℃ )下 ,生成大量晶片排列疏散的羽毛状球晶 ;而Tc>2 40℃时 ,生成大量晶片堆砌紧密的八瓣球晶及少量四瓣球晶 ;此外 ,2 30℃附近还有带螺旋消光环的正球晶和串晶生成     

聚氧乙烯球晶上彩色环状条纹的形成

用自然白光代替偏振光在显微镜下观察聚氧乙烯球晶的生长过程, 可以更清晰地看到彩色环形条纹的形成. 当成长中的二维球晶相互碰撞后, 被挤出的熔体改变球晶的原有结晶方向, 流向饼形球晶中央而在其表面上逆向结晶, 由于被挤出的熔体数量有限, 晶层的厚度逐渐减小, 在盖玻片下方形成一个盘状的楔形真空间隙. 此间隙导致彩色环状干涉条纹的形成. 实验用肉眼直接观察到二维球晶在生长过程中结晶方式的变化, 为二次结晶理论的发展提供了实验依据.     

聚对苯二甲酸乙二酯形态结构的光散射研究

在不同结晶条件下,聚对苯二甲酸乙二酯样品出现了三种不同的光散射图形(正常球晶、异常球晶和混合球晶散射图形)。并假定正常球晶的光轴方向与半径垂直;异常球晶的光轴方向与半径夹+45°角或-45°角;混合球晶则是正常球晶与异常球晶叠加的结果。基于这些假定,按照Clough的计算公式,用二维球晶模型分别对具有上述各种光轴取向的球晶进行了计算。结果表明,计算出的H_v、V_v散射图形与实验所得的散射图形符合得很好。偏光显微镜的观察结果也进一步证实了这些模型的假定。     

含柔性间隔基的热致液晶性共聚酯的结晶形态

采用偏光显微镜、扫描和透射电镜从不同层次的结构水平上研究了含柔性间隔基热致液晶性共聚酯的结晶形态。在偏光显微镜下观察到典型的负光性球晶形态,透射电镜揭示了球晶是由厚度为10nm并沿着径向生长的片晶结构所组成,分子链沿晶片厚度方向取向排列。并研究了分子链的刚性程度对热致聚芳酯结晶性质的影响。结果表明,分子链刚性越大其结晶性和球晶的完善性越高。     

表面富含羧基的单分散交联聚合物微球的快速自组装制备胶体晶的研究

在20～70℃范围内,用垂直沉积的方法可使表面富含羧基的单分散交联聚合物微球在不同的基底上快速自组装成三维有序的胶体晶.不同粒径的微球形成的胶体晶其光禁带峰位不同,因此可调控不同波长的光在胶体晶中的传播.利用紫外-可见光谱研究了胶体晶的光禁带峰位与组成其微球粒径之间的关系.结果表明,随着构成胶体晶微球粒径的增大,胶体晶光禁带峰位发生了红移,而随着入射光角度的增大,胶体晶的光禁带峰位发生了蓝移.利用原子力显微镜和扫描电子显微镜研究了其它条件对聚合物微球有序排列的影响,发现聚合物微球在pH值为3.0～13.0范围内可以形成三维有序自组装胶体晶.这是由于在不同的pH值下,聚合物微球表面发生羧基化及去羧基化反应,导致在自组装过程中微球之间和微球与介质之间作用力的变化     

基于量子级联激光器的Pump-Probe光路球晶雕刻实验

利用2台中红外量子级联激光器(QCL)组成的泵浦探测(pump-probe)光路通过红外共振吸收对高分子球晶进行选择性熔融进而实现球晶雕刻.当QCL激光频率和分子基团振动频率相同时,会发生共振吸收,产生强烈的热效应,诱导样品快速熔融;QCL激光具有高偏振性,优先诱导振动方向和红外激光偏振方向一致的基团发生共振吸收,因此可以实现选择性熔融;高分子球晶中有沿着各个方向的分子链并且取向方向确定,可以通过pump球晶不同部位来验证球晶雕刻的可行性.一台激光器(pump)对应分子链中基团的强吸收峰,共振加热诱导晶体熔融;另一台激光器(probe)对应分子特征基团(构象)的吸收峰,追踪结构变化;pump光可以选择性定点熔融,pump和probe 2束光均能在线追踪样品熔融程度,是该检测方法的突出优点.选用聚丁烯-1(iPB-1)为研究对象,实验结果显示,球晶熔融程度随基团振动方向与pump光偏振方向夹角的增大而减弱,证明了利用QCL在球晶尺度上进行雕刻是可行的,为原位在线研究快速熔融过程提供了新的研究途径,为定点调控晶型转变及晶体聚集态结构形态提供了思路.     

Lyotropic mesophase of cellulose in ammonia/ammonium thiocyanate solution

Solutions of cellulose in a mixture of 27:73 (w/w) of liquid ammonia and ammonium thiocyanate become liquid crystalline at room temperature above a certain critical concentration which depends on the degree of polymerization of the dissolved cellulose. The high optical rotations of the solution suggest that the cellulose mesophase is cholesteric in nature. In the two-phase region, the cellulose solutions exhibit negatively birefringent spherulites that possess both ringed and nonringed internal structures. The anisotropic solutions can be oriented by shear, indicating high potential for spinning them into useful fibers.     

尼龙1010结晶与熔融行为的研究

用DSC研究了降温速率R对尼龙10 10结晶与熔融的影响,以及室温(RT)和液氮(LN)骤冷退火样品的熔融.降温时结晶温度随R增大线性降低;T_g以上可完成结晶时结晶度相同;结晶起始温度>181℃生成的晶体有三个熔融峰,对应于环状和放射状球晶的转化与熔融;在181℃和T_g间结晶,无放射球晶转化峰;T_g下有结晶放热峰样品加热时有冷结晶发生.RT未退火样品三个熔融峰,退火温度T_α≥180℃样品两个峰,结晶度C∝T_a;LN未退火样品单一熔融峰,T_a>160℃双峰,T_a≤160℃三峰,低温峰温与C均∝T.     

Isothermal crystallization kinetics and spherulitic morphology of poly(4‐hydroxybutyric acid‐alt‐glycolic acid)

Isothermal crystallization behavior of a new regular polyester constituted by glycolic acid and 4‐hydroxybutyric acid units is studied by means of differential scanning calorimetry and hot‐stage optical microscopy. A wide range of crystallization conditions were experimentally accessible, allowing various morphological features to be observed and accurate estimates made of characteristic growth parameters, including radial growth and nucleation rates. Three‐dimensional spherulitic growth from heterogeneous nuclei is deduced from the Avrami analysis, whereas optical micrographs reveal two different spherulitic textures that agree with the existence of two crystallization regimes. These can be well distinguished from the breaks observed in the Lauritzen and Hoffman plots when the linear crystal growth rate or the overall crystallization rate is considered. Ringed and nonringed spherulites with negative and positive birefringence, respectively, can be obtained depending on crystallization conditions and regimes. The studied polyester shows rather complex melting behavior which is interpreted in terms of a recrystallization process involving the two different kinds of spherulites. This study allows polymorphism to be discounted. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2640–2653, 2007     

Correlation between melting behavior and ringed spherulites in poly(trimethylene terephthalate)

The lamellar types as revealed by the multiple melting peaks and possible mechanisms of ringed spherulites in poly(trimethylene terephthalate) (PTT) were analyzed with differential scanning calorimetry (DSC), optical microscopy, and scanning electron microscopy. Several interesting correlations were found. If PTT is melt‐crystallized in a certain temperature range, it shows multiple melting peaks and rings in PTT. Once rings are formed in the original melt‐crystallized PTT, they do not disappear but persist and become even more apparent upon postcrystallization annealing at higher temperatures. Furthermore, for PTT that is capable of exhibiting ringed spherulites, a temperature range exists where rings do not form. This behavior can be interpreted in relation with the demonstrated thermal behavior in PTT. Reorganization took place upon postcrystallization scanning or annealing to or at higher temperatures. A postulation was proposed and rigorously tested with evidence to correlate the ringed spherulites and melting behavior. Rings in PTT may be related to multiple lamellae in the spherulites. Consequently, if a temperature of crystallization is selected so that there is only one type of lamella in the spherulites, then there should be no rings. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 80–93, 2002     

尼龙1010异常光性球晶的旋转观察

通过在偏光显微镜下对尼龙１０１０三类异常光性球晶的旋转观察，发现其消光图案和加一级红补色器时的颜色分布，均随观察角度不同而呈周期性变化，表明其结构单元并并非是沿任一半径均等效排列，而可能是半径不等效的．     

MULTIPLE MELTING AND CRYSTALLIZATION BEHAVIOR OF NYLON 1212

The wide-angle X-ray diffraction (WAXD) patterns of isothermally crystallized Nylon 1212 show that γ-form crystals form below 90℃ and the α-form crystals can exist above 140℃. In the temperature range of 90-140℃, the α-form and γ-form crystals coexist. Variable-temperature WAXD exhibits that the nylon 1212 γ-form does not show crystal transition on heating, while α-form isothermally crystallized at 160℃ exhibits Brill transition at a little higher than 180℃ on heating. The multiple melting behaviors of Nylon 1212 isothermally crystallized from melt come from a complex mechanism of different crystal structures, dual lamellar population and melting-recrystallization. In polarized optical microscope (POM) observations, Nylon 1212 isothermally crystallized at 175℃ shows the ringed banded spherulites. However, at temperatures below 160℃ the ringed banded image disappears, and cross-extinct spherulites are formed.     

Formation of ringed spherulites in polyethylenes

The effects of molecular weight, molecular weight distribution, crystallization temperature, quenching medium, and sample preparation on the formation of ringed spherulites in linear polyethylenes were studied by polarized light microscopy and small-angle light scattering. When the samples were crystallized at a predetermined temperature, ringed spherulites were formed over a narrow range of temperature and molecular weight with both fractionated and unfractionated polymer samples. Quenching the samples in air at room temperature considerably extended the range of molecular weights for the formation of ringed spherulites. Minor modification of an airquench method further extended the range and yielded better-defined structures. The results are interpreted in terms of the anisotropy of the melt, the thermal conductivity of the quenching medium, and the shear stress applied during the crystallization process. That highly specific conditions are necessary for spherulite formation, of both the conventional and ringed type, is a major conclusion of this study.     

聚己内酯和乙基纤维素共混体系的环带球晶及液晶形态

聚己内酯（ＰＣＬ）中加入与其有一定混溶性的非晶组分乙基纤维素（ＥＣ）,可明显影响其长环带球晶的行为．表明具有低混溶性及某种分子间相互作用的二元共混体系ＰＣＬ／ＥＣ仍能在一定温度范围内形成环带球晶;良好的混溶性,强的分子间相互作用并非是二元共混体系中ＰＣＬ长环带球晶不可缺少的因素．通过偏光显微镜发现ＰＣＬ的加入有利于乙基纤维素／二氯乙酸溶液中液晶相的形成,用Ｆｌｏｒｙ关于棒状分子无规线团溶剂三元体系的理论对其进行了讨论．