Zi‐Xiu Du  Jun‐Ting Xu  Yong Yang  Zhi‐Qiang Fan 《应用聚合物科学杂志》2007,105(2):771-776

A series of poly(?‐caprolactone)‐b‐poly(ethylene glycol) (PCL‐b‐PEG) block copolymers with different molecular weights were synthesized with a salicylaldimine‐aluminum complex in the presence of monomethoxy poly(ethylene glycol). The block copolymers were characterized by ¹H NMR, GPC, WAXD, and DSC. The ¹H NMR and GPC results verify the block structure and narrow molecular weight distribution of the block copolymers. WAXD and DSC results show that crystallization behavior of the block copolymers varies with the composition. When the PCL block is extremely short, only the PEG block is crystallizable. With further increase in the length of the PCL block, both blocks can crystallize. The PCL crystallizes prior to the PEG block and has a stronger suppression effect on crystallization of the PEG block, while the PEG block only exerts a relatively weak adverse effect on crystallization of the PCL block. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

    

Sang‐Young Lee  Soon‐Yong Park  Heon‐Sik Song 《应用聚合物科学杂志》2007,103(5):3326-3333

The row‐nucleated lamellar crystalline structure of high‐density polyethylene (HDPE) films was prepared by applying elongation stress to HDPE melt during T‐die cast film extrusion and subsequently annealing the extruded films. This unusual crystalline structure was analyzed in terms of lamellar crystalline orientation, long‐period lamellar spacing, crystallite size, and degree of crystallinity. The contribution of melt‐extension represented by draw‐down‐ratio (DDR) to the overall orientation was found to be most noticeable than other processing variables. Meanwhile, the long‐period lamellar spacing, the crystallite size, and the degree of crystallinity were influenced predominantly by the annealing temperature. Finally, the processing (melt extension and annealing temperature) – structure (lamellar crystalline structure) – property (hard elasticity) relationship of HDPE films was investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3326–3333, 2007  相似文献   

    

N. M. Ghasem  S. A. Sata  M. A. Hussain 《化学工程与技术》2007,30(9):1193-1202

Batch polymerization reactors commonly use optimal temperature control as the strategic operation parameter. This strategy allows for better operability and a more economic process. The main objective of the batch polymerization reactor control is to obtain acceptable product quality. Direct measurement of polymer quality is rarely achievable, which makes the online control of the reactor difficult. Temperature is the most controllable operational variable in the polymer reactor, which is seen to have a direct effect on the polymer properties. Temperature is chosen as the set point by using either the isothermal temperature or optimal temperature trajectory. Online control of the optimal temperature profile of a bench‐scale batch polymerization reactor was experimentally investigated in this study. The temperature trajectory was used as the target for controllers to follow. The time‐profile temperature was obtained with the objective of obtaining the desired conversion and number‐average chain length within the minimum time. Two advanced controls of fuzzy logic control and generic model control were applied to the polymer reactor. A comparison of the controllers reveals that both performed better than conventional controllers.  相似文献   

    

Xianfeng Li  Xiaolong Lu 《应用聚合物科学杂志》2007,103(2):935-941

Polyvinylidene fluoride hollow fibers were prepared by melt‐spinning technique under three spinning temperatures. The effects of annealing treatment on the structure and properties of hollow fiber were studied by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), tensile test, and scanning electron microscopy (SEM) measurements. DSC and WAXD results indicated that the annealing not only produced secondary crystallization but also perfected primary crystallization, and spinning and annealing temperature influenced the crystallinity of hollow fiber: the crystallinity decreased with the increase of spinning temperature; 140°C annealing increased the crystallinity, and hardly influenced the orientation of hollow fiber; above 150°C annealing increased the crystallinity as well, and furthermore had a comparative effect on the orientation. The tensile tests showed that the annealed samples, which did not present the obvious yield point, exhibited characteristics of hard elasticity, and all the hollow fiber had no neck phenomenon. Compared with the annealed sample, the precursor presented a clear yield point. In addition, the annealed samples had a higher break strength and initial modulus by contrast with the precursor, and the 140°C annealed sample showed the smallest break elongation. SEM demonstrated the micro‐fiber structure appeared in surface of drawn sample. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 935–941, 2007  相似文献   

    

Jiali Cai  Ying Han 《应用聚合物科学杂志》2007,103(2):1311-1324

Nonisothermal cold‐ and melt‐crystallization of syndiotactic polystyrene (sPS) were carefully carried out by Perkin–Elmer Diamond differential scanning calorimetry, polarized optical microcopy (POM), and wide angle X‐ray diffraction. The experimental data subjected to the two types of processing were thoroughly analyzed on the basis of Avrami, Tobin, Ziabicki, and combination of Avrami and Ozawa models. Avrami, Tobin, and Ziabicki analyses indicate that nonisothermal cold‐crystallization (A) characterizes smaller Avami and Tobin exponent and larger Ziabicki kinetic crystallizability index G than those obtained from nonisothermal melt‐crystallization (B) possibly due to the existence of partially ordered structures in the quenched samples. Kissinger and the differential isoconversional method (DICM) of Friedman's were utilized to obtain effective energy barrier of A, in good agreement with that obtained by using Arrhenius equation to analyze the isothermal cold‐crystallization, indicating that Kissinger and Friedman equations can be applied to obtain activation energy from A of sPS. X‐ray diffraction analysis indicates that cold‐crystallization mainly produces α‐type crystal but for melt‐crystallization the contents of α‐type and β‐type crystals depend on the cooling rates. The POM also indicates the difference of end morphology of the sample between A and B. At the same time, the DICM of Friedman's was applied to analyze experimental data of B, which were divided into two groups with 20 K/min as the threshold, and it was found that the formation of β‐type crystal possesses larger absolute value of effective activation barrier than the formation of α‐type crystal. © 2006Wiley Periodicals, Inc. J Appl Polym Sci 103: 1311–1324, 2007  相似文献   

    

Ying Gao  Honglai Liu 《应用聚合物科学杂志》2007,106(4):2718-2723

The crystallization behavior of semicrystalline PEO homopolymer/triblock PS‐PEO‐PS copolymer blend system, which exhibited “Dry‐Brush” in the melt. A symmetric polystyrene–poly(ethylene oxide)–polystyrene triblock copolymer was blended with PEO homopolymer (h‐PEO) having the same molecular weight as that of the PEO block in the copolymer. Considering the composition of the blend (W_ps ≥ 0.8), PEO spheres were formed in the blend. Because of the dry‐brush phase behavior of this blend, h‐PEO added was localized in the PEO microdomains, which increases the domain size without changing the microdomain morphology. The crystallization of PEO block was confined within the microdomains and the crystallization temperature was about 60°C lower than normal. Self‐seeding tests were performed to clarify the nucleation mechanism of the blend. Because the droplets size varies greatly, multicrystallization peaks were witnessed in the self‐seeding process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

    

Sungho Lee  Myung‐Soo Kim  Amod A. Ogale 《应用聚合物科学杂志》2007,106(4):2605-2614

Crystallization behavior of LLDPE nanocomposites is reported in the presence of three types of carbon nanofibers (CNFs) (MJ, PR‐19, and PR‐24). During nonisothermal crystallization studies, all three crystalline melting peaks for LLDPE matrix were observed in the presence of PR‐19 nanofibers (up to 15 wt % content), but only the high‐ and low‐temperature peaks were observed in the presence MJ nanofibers. The broad melting peak at low‐temperature became bigger, suggesting an increase in the relative content of thinner lamellae in the presence of MJ nanofibers. TEM results of nanocomposites revealed transcrystallinity of LLDPE on the surface of CNFs, and a slightly broader distribution of lamellar thickness. STEM studies revealed a rougher surface morphology of the MJ nanofibers relative to that of PR nanofibers. Also, BET studies confirmed a larger specific surface area of MJ nanofibers relative to that of PR nanofibers, suggesting that the larger and the rougher surface of MJ nanofibers contributes toward the different crystallization behavior of MJ/LLDPE nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

    

C. T. Love  G. Xian  V. M. Karbhari 《应用聚合物科学杂志》2007,104(1):331-338

Blends of high‐density polyethylene (HDPE) and a reactive ethylene terpolymer (RET) were developed as a protective coating material for steel. A morphological study with scanning electron microscopy (SEM) indicated that blends of HDPE and RET are immiscible, while high interaction between these two phases was found. Crystallization and thermomechanical behavior of the blends were investigated using differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The crystallinity of HDPE decreased with the incorporation of RET slightly due to the disturbance of the highly viscous RET melt during crystallization. Tensile tests indicated that the addition of RET reduced both strength and modulus but increased the strain‐to‐break. Adhesion to steel substrates was improved with the incorporation of the RET component. An optimum composition of RET loading was detected to be in the range of 25–33 wt %, leading to the best adhesive performance, high tensile strength, and strain‐to‐failure of the blend material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 331–338, 2007  相似文献   

    

S. A. Pande  D. S. Kelkar  D. R. Peshwe 《应用聚合物科学杂志》2007,103(5):3094-3098

Nylon 11 samples were filled with metal (Zn) fillers of two different concentrations (1 and 5% w/w) each. The samples in the form of disc were obtained by using hot press molder. The structural properties have been investigated using density measurement and wide angle X‐ray diffraction (WAXD) technique. The morphology of pure and Zn‐filled samples has been studied using scanning electron microscopy. Glass transition (T_g) temperature was determined using dynamic mechanical thermal analyzer (DMTA). The result shows that there is slight crystal modification due to the addition of metal fillers (Zn), and the crystallinity has improved. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3094–3098, 2007  相似文献   

    

Mingtao Run  Aijun Song  Yingjin Wang  Chenguang Yao 《应用聚合物科学杂志》2007,104(5):3459-3468

The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (T_g) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t_1/2 and the parameters Z_c showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献