THE HIGH-PRESSURE CRYSTALLIZATION AND ANNEALING BEHAVIORS OF POLYETHYLENE TEREPHTHALATE OLIGOMER

Polyethylene terephthalate (PET) oligomer samples crystallized and annealed at high pressure were investigated with differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The results showed that better crystals were obtained through high-pressure crystallization from the melt than annealing under the same conditions. The difference of the effects of crystallization and annealing on the morphology of crystals reduced with the increase of crystallization time. The melting temperature was determined by the lamellar thickness when it was shorter than the length of the molecular chains, while the main factor governing the melting temperature changed from lamellar thickness to density of chain-end defects when the lamellar thickness was much longer than the molecular length. PET oligomer extended-chain crystals with thickness up 100 μm were obtained.     

ON MORPHOLOGY AND MULTIPLE MELTING IN POLYPROPYLENE

A series of polypropylenes, including two modern high crystallinity materials (HCPP) were subjected to a stepwise crystallization procedure as a guide to their properties. The results were complicated by the development of double melting endotherms at the highest crystallization temperature. Both HCPP, when grown at the temperature of 145°C, give a double melting peak, but the proportions of the two peaks varied according to the density of nucleation. By partially melting a specimen between the two peaks, it was possible to assign the higher peak to radial dominant lamellae and the lower peak to mostly tangential subsidiary lamellae filling the space in between. Uniformly cross-hatched lamellae at the center of spherulites melt along with the lower melting population in the outer regions of the spherulites. Even if differences in crystallization temperature are eliminated, the properties of nucleated as opposed to nonnucleated PP may therefore be influenced by differences between the center and periphery of spherulites, with “central” properties much more in evidence in nucleated material. The development of these double endotherms is related to morphological constraint, rather than molecular fractionation. Their form is strongly influenced by cross-hatching, but the phenomenon is still found at 160°C where cross-hatching does not form.     

ABSENCE OF ISOTHERMAL LAMELLAR THICKENING IN A LINEAR POLYETHYLENE BLEND

Melting and lamellar morphology of a polyethylene blend were studied. Two linear polyethylene (LPE) samples were used. A commercial LPE and a low molecular weight LPE fraction (M _n ≈ 2015) were solution blended. The pure LPE and a blend (30% commercial LPE content) were held in the melt at 126° C for up to 48 h, above the equilibrium melting point of the fraction, but below the crystallization temperature of the commercial LPE. The melting behavior of both materials as a function of storage time was studied using differential scanning calorimetry (DSC), in addition to transmission electron microscopy (TEM) of chlorosulfonated samples. Results showed that, although the LPE lamellae grew at the same temperature, those in the pure LPE were thicker than in the blend. Correspondingly, isothermally grown lamellae in pure LPE melt at higher temperatures.     

聚乙烯与水反应的高温高压实验及热力学探讨

 在金刚石压腔设备中进行聚乙烯的高温高压裂解实验研究。实验分含水和不含水两种情况。在显微镜下观察反应过程中的变化并显微照相记录有关现象,在高压下就位测定反应过程中荧光的变化。用气相色谱方法测定气相产物组成。含水实验中CH₄占烃类气体产物的92%并有CO₂生成,固体残余物非常少,表明水直接参与了化学反应,为烃类气体的形成提供氢源,为CO₂的形成提供氧源。不含水实验中烃类气体的产率相对较低并有较多的固相残余物存在。用热力学理论探讨了实验中有关反应的机制。根据聚乙烯与干酪根结构的可比性,推测在水参与条件下有利于提高有机质裂解成烃的产率。     

MICROMECHANICAL BEHAVIOR OF BRANCHED POLYSTYRENE AS REVEALED BY IN SITU TRANSMISSION ELECTRON MICROSCOPY AND MICROHARDNESS*

The internal structure and failure of crazes in linear and long-chain branched poly(styrene) (PS) were investigated by means of in situ transmission electron microscopy (TEM). It was found that long-chain branched PS presents more finely fibrillated up to homogeneous crazes at room temperature instead of the typical fibrillated ones for linear PS. The failure of homogeneous crazes in long-chain branched PS indicates a more ductile behavior than the fibrillated ones. The microhardness of these materials was measured, and it was seen that the hardness value increased with increasing amount of long branches in the PS. In addition, the rate of creep under the indenter (creep constant) for these materials was investigated. The lowest value for the creep constant corresponded to the PS sample with the largest amount of long branches.

     

线胀系数的视频在线光干涉法测量研究

实验室测量金属的线胀系数普遍采用的是光杠杆法,经实验证明光杠杆法存在偶然误差大、测量精度低、占地空间大等问题,通过利用劈尖的等厚干涉法能够很好地解决光杠杆法存在的问题.新方法具有温升范围小、加热功率低、测量精度高、操作简单直观、占地空间小等优点,便于实际教学中教师的讲解、示教和演示,有利于学生综合应用知识,提高综合设计实验的能力.     

数值模拟颗粒旋转对流化床内气固两相流动特性的影响

流化床内颗粒自旋转将影响颗粒相的流动特性.本文运用基于颗粒动理学理论的欧拉-欧拉气固多相流模型,考虑颗粒自旋转流动对颗粒碰撞能量交换和耗散的影响,数值模拟流化床内气体颗粒两相流动特性.计算结果表明颗粒的自旋转使得床内更容易形成气泡,颗粒浓度分布变化增大.颗粒自旋转运动将导致床内非均匀结构更明显.     

元素钾、硅和铝在PM10的形态与分布研究

通过对平顶山烟煤在沉降炉内的燃烧试验,结合热力学平衡计算分析,研究了三种选定的矿物质成灰元素钾、硅和铝在可吸入颗粒物中的形态与分布.燃烧试验条件为煤粉粒径小于63 μm,燃烧温度在1400℃,炉内燃烧气氛为空气气氛.试验采用低压撞击器(LPI)按不同粒径大小从0.03～10 μm共分为13级,分别采集燃烧后的可吸入颗粒物.并采用热力学平衡计算分析方法研究了氧化性气氛中元素钾、硅和铝的化学形态和物理相.试验和计算结果显示钾元素主要以K单质的形式气化,大部分以K2SO4、KCl、K2HPO4的形式存在于亚微米颗粒中,极少量以KAlSi2O6相存在于PM1.0-10中;极少量Si和Al元素分别以SiO和OAlOH及A1OH的形式气化,以固相SiO2和Al2O3存在于亚微米颗粒中,而大部分则以SiO2和A16Si2O13的形式存在于PM1.0-10中.     

孔隙射流位置对直扩压叶栅壁面静压及流谱影响

对带有孔隙射流的某大折转角直扩压叶栅性能进行了实验研究,分析了不同位置孔隙射流对壁面静压及极限流线的影响.结果表明,孔隙射流能够改善角区流动,同时降低叶片中部损失;最佳开孔位置位于25%相对叶高处,总压损失系数相对无孔隙射流叶栅降低4.9%;孔隙位置对端壁静压的影响不大.