管道防腐用高密度聚乙烯的非等温结晶行为

采用差示扫描量热法考察了管道防腐专用高密度聚乙烯(SHDPE)专用料的非等温结晶行为,并结合Ozawa、莫志深等方程对非等温结晶动力学过程进行研究,并与专用料的基础树脂(BHDPE)进行了对比.结果表明:随着降温速率增加,SHDPE,BHDPE的结晶起始温度和结晶峰温度均向低温方向移动,且达到相同相对结晶度的时间减少,SHDPE的结晶能力低于BHDPE,但SHDPE的晶体完善程度高于BHDPE;Ozawa方程不适于描述冷却速率较低时(5℃/min)的SHDPE,BHDPE的非等温结晶过程,而莫志深方程能很好地描述该过程.     

茂金属线形低密度聚乙烯／普通聚乙烯共混体系非等温结晶行为的研究

用DSC和X-射线衍射法研究了茂金属线形低密度聚乙烯(m-PE-LLD)与高密度聚乙烯(PE-HD)、低密度聚乙烯(PE-LD)、线形低密度聚乙烯(PE-LLD)共混时PE-HD、PE-LD、PE-LLD不同加入量对m-PE-LLD非等温结晶行为和结晶动力学的影响。研究结果表明：PE-HD与m-PE-LLD共混使样品结晶峰变窄，结晶度和结晶速率有所提高，说明两者有较好的相容性与共结晶行为；PE-LD的加入使共混物结晶峰变宽，说明PE-LD与m-PE-LLD共结晶行为较差，存在部分相分离，但在PE-LD含为20％时有最大结晶度，结晶速率有所提高；PE-LLD的加入对m-PE-LLD非等温结晶和动力学影响较小。X-射线衍射结果证明共混使球晶粒径减小。     

结晶分级技术表征PE100级与耐热级管材树脂结构的差异性

通过逐步等温结晶分级技术(SIS)、升温淋洗分级技术(TREF)和连续自成核退火分级技术(SSA)表征了聚乙烯(PE) 100级管材树脂GC100S和耐热级管材树脂4731B结构的差异性.结果表明,4731B和GC100S树脂的熔融温度、结晶温度、结晶度、片晶厚度及共聚单体在主链中的分布状况基本相同,主要区别在于含有共聚单体的聚乙烯分子链的相对含量不同,4731B不含或含有少量共聚单体的聚乙烯分子链的含量比GC100S多.     

聚乙烯/纳米蒙脱土复合材料的非等温结晶行为

原位聚合法制备了不同蒙脱土含量的聚乙烯(PE)/纳米蒙脱土(MMT)复合材料.用透射电镜分析了MMT在PE基体中的分散情况,结果表明:随着MMT含量的增加,复合材料的结构从剥离型转变为剥离型和插层型混合结构.用DSC分析了PE/纳米MMT复合材料的非等温结晶行为,结果表明:复合材料的非等温结晶行为符合Avramin方程,随着MMT含量的增加,Avramin方程指数(n)减小,结晶时间(t1/2)增加.     

管材专用PPR的等温结晶动力学

研究了管材专用无规共聚聚丙烯(PPR)的结晶温度和等温结晶行为,利用Avrami方程对等温结晶过程和动力学进行了分析。结果表明:北欧化工公司的PPR1具有更高的结晶温度、结晶度以及更快的结晶速率。同一结晶温度条件下,国产PPR3的结晶度达到一半的时间略高于其他PPR。利用Hoffman-Lauritzen结晶动力学理论计算得到了PPR的成核常数和结晶生长时大分子在垂直于分子链方向的折叠表面自由能(σ_e),与其他试样相比,PPR1的σ_e最低,PPR3的σ_e最高,结晶速率最慢。通过偏光显微镜照片可以发现,PPR1的球晶尺寸最小,PPR3和PPR4的球晶较大,球晶尺寸比较接近。     

HDPE/空心玻璃微珠复合材料非等温结晶研究

采用熔融共混挤出的方法,制备了高密度聚乙烯/空心玻璃微珠(HDPE/HGB)复合材料,用差示扫描量热法研究了HDPE和HDPE/HGB的非等温结晶过程,通过Jeziorny法研究了非等温结晶动力学.结果表明,随降温速率的增大,HDPE和HDPE/HGB试样的结晶峰温和结晶度降低,结晶速率增大;HGB的加入使结晶度增大,但对HDPE的结晶速率影响较小.     

聚乙烯管材专用料的现状及发展展望

详细分析了近年来国内外聚乙烯管材专用料的发展状况。重点论述PEl00材料的优越性能，并将它与PE80进行了比较。介绍了聚乙烯管材专用料的发展方向，提出了发展聚乙烯管材专用料的一些建议。     

mLLDPE非等温结晶动力学研究

利用差示扫描量热仪(DSC)研究了茂金属线性低密度聚乙烯(mLLDPE)和传统线性低密度聚乙烯(LLDPE)的非等温结晶行为。采用Jeziorny法和莫志深法对所得的数据进行了分析。结果表明,采用莫志深法处理数据可得到较好的线性关系,且mLLDPE在相同的相对结晶度下的结晶速率低于LLDPE。     

YGH041T管材专用料的突破

采用北欧化工“北星双峰”技术生产的牌号为YGH041T的高密度聚乙烯黑色管材专用料，经瑞典国家测试和鉴定研究院按ISO9080标准，用SEM(标准外推法)评价，通过了PE100等级认证。     

独山子石化公司铬系聚乙烯管材料获国家PE80等级认证

独山子石化公司自行开发生产的铬系聚乙烯管材专用料取得国家化学建材测度中心颁发的PE80等级认证书。独山子石化公司研发生产的铬系聚乙烯管材专用料在国家化学建材测试中心通过了10000h的PE80级长期寿命评价认证测试,随后测试中心通过近3个月的数据处理与分析,产品各项性能指标符合燃气管、城市给水等高标准管材专用料要求,认证通过,产品将可以应用于燃气管、城市给水等特殊要求管材的生产。独山子石化公司开发的铬系聚乙烯管材专用料属于国内第一家中密度聚乙烯,相比较其它化工企业生产的高密度管材料聚乙烯,有着降低下游生产企业成本…     

On the nonisothermal melt crystallization kinetics of industrial batch crosslinked polyethylene

The chemical modification of commodity polymers such as polyethylene (PE) is a versatile synthetic approach for preparing materials that cannot be manufactured cost-effectively using conventional polymerization techniques. Aiming to improve PE character low contents of dicumyl peroxide (DCP), from 0% to 1.5% was added as crosslinker to an industrial batch (PEs mixture and additives). From tensile testing crosslinking provided higher elastic modulus most due to the restrained microstructure where XPEs macromolecular chains are interconnected also providing lower strain at break. Crosslinking effects on the nonisothermal melt crystallization rate (Cmax) and degree of crystallinity (Xc) were evaluated; Cmax increased with the cooling rates, whereas Xc increased upon DCP addition. The melt crystallization kinetics were thoroughly investigated applying Pseudo-Avrami, Ozawa, and Mo models. Ozawa failed to describe the crystallization most due to ignore the secondary crystallization and spherulites impingement at the end of crystallization while Pseudo-Avrami and Mo provided quite good fits. The activation energy was computed using Arrhenius' approach, crosslinked compounds presented higher energy consumption, whereas exception was verified for 0.5XPE which displayed the lowest energy and overall the best mechanical performance this is the most proper compound for industrial applications, such as packaging, and disposables as well as general goods.     

PE/PE‐g‐MAH/Org‐MMT nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of high‐density polyethylene (HDPE) and polyethylene (PE)/PE‐grafted maleic anhydride (PE‐g‐MAH)/organic‐montmorillonite (Org‐MMT) nanocomposite were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny, Ozawa analysis, and a method developed by Liu well described the nonisothermal crystallization process of these samples. The difference in the exponent n, m, and a between HDPE and the nanocomposite indicated that nucleation mechanism and dimension of spherulite growth of the nanocomposite were different from that of HDPE to some extent. The values of half‐time (t_1/2), K(T), and F(T) showed that the crystallization rate increased with the increase of cooling rates for HDPE and composite, but the crystallization rate of composite was faster than that of HDPE at a given cooling rate. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. It was 223.7 kJ/mol for composite, which was much smaller than that for HDPE (304.6 kJ/mol). Overall, the results indicated that the addition of Org‐MMT and PE‐g‐MAH could accelerate the overall nonisothermal crystallization process of PE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3054–3059, 2004     

山梨醇衍生物对聚乙烯结晶行为的影响

分别以山梨醇与对甲基苯甲醛、对乙基苯甲醛、3,4-二甲基苯甲醛为原料,利用缩醛反应机理,合成出3种不同的山梨醇衍生物——1,3-2,4-二亚(对甲基)苄基山梨醇(MDBS)、1,3-2,4-二亚(对乙基)苄基山梨醇(EDBS)、二(3,4-二甲基二苄叉)山梨醇(DMDBS)。使用溶液沉淀法制备含DMDBS、EDBS、MDBS质量分数分别为0.3%的3种粉末聚乙烯(PE)样品;采用X衍射仪、红外光谱仪、偏光显微镜、差示扫描量热仪对其进行了结晶结构及性质考察;用Avrami模型、Kissinger方程计算了各PE样品的结晶动力学参数。结果表明,山梨醇衍生物没有改变PE的晶体结构,保持了PE晶体的稳定性,提高了成核密度,使PE球晶尺寸由65μm平均降至53μm。动力学数据表明,山梨醇衍生物能提高PE的结晶速率,降低结晶活化能,PE的Avrami指数由4减小至3~3.6。在添加量相同的条件下,DMDBS、EDBS和MDBS可分别令PE结晶度提高4.83%、4.42%、1.25%。DMDBS对PE的改性效果最明显,EDBS次之,MDBS最小。     

Effect of the ionic liquid [bmim]PF6 on the nonisothermal crystallization kinetics behavior of poly(ether‐b‐amide)

Blending ionic liquid with crystalline polymer permits the design of new high‐performance composite materials. The final properties of these materials are critically depended on the degree of crystallinity and the nature of crystalline morphology. In this work, nonisothermal crystallization behavior of poly(ether‐b‐amide) (Pebax®1657)/room temperature ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate, [bmim]PF₆) was investigated by differential scanning calorimetry. The presence of [bmim]PF₆ can retard the nucleation of Pebax®1657 and lead to the crystallization depression of the PA block and the crystalline disappearance of the PEO block. However, the dilution effect of the IL results in a higher growth rate of crystallization of PA block. The influence of [bmim]PF₆ content and cooling rate on crystallization mechanism and spherulitc structures was determined by the Avrami equation modified by Jeziorny and Mo's methods, whereas the Ozawa's approach fails to describe the nonisothermal crystallization behavior of Pebax®1657/[bmim]PF₆ blends. In the modified Avrami analysis, the Avrami exponent of PA blocks, n > 3, for pure Pebax®1657, while 3 > n > 2 for Pebax®1657/[bmim]PF₆ blends testifies the transformation of crystallization growth pattern induced by [bmim]PF₆ from three‐dimensional growth of spherulites to a combination of two‐ and three‐dimensional spherulitic growth. Further, lower activation energy for the nonisothermal crystallization of PA blocks of Pebax®1657 can be observed with the increase of [bmim]PF₆ content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42137.     

Molecular fractionation in melt-crystallized polyethylene: 1. Differential scanning calorimetry

This is the first paper in a series in which molecular fractionation (segregation) in melt-crystallized polyethylene (PE) has been studied by differential scanning calorimetry (d.s.c.). A number of PE's (both high- and medium-density materials) have been given a variety of thermal treatments, including isothermal crystallization from the melt and annealing. The melting of the samples as registered by d.s.c. has been extensively analysed and information regarding the crystallization, particularly in relation to molecular fractionation, is presented.     

Comparison of crystallization kinetics in various nanoconfined geometries

Phase morphological effect on crystallization kinetics in various nanoconfined spaces in a polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer with a PEO volume fraction of 37 vol% was investigated. The phase morphology was characterized by small-angle X-ray scattering and transmission electron microscopy techniques. When the sample was cast from chloroform solution and annealed at 150 °C, a double gyroid (DG) phase was obtained. After it was subjected to a large-amplitude reciprocating shear, the sample transformed to an oriented hexagonal cylinder (Hex) phase. To obtain a lamellar confined geometry, lamellar single crystals were grown from dilute solutions. The crystallization in the lamellar (Lam) phase was one-dimensionally (1D) confined, while it was two-dimensionally (2D) confined in the DG and Hex phases, although they had different structures. Differential scanning calorimetry (DSC) was employed to study the crystallization kinetics using the Avrami analysis for these three nanoconfined geometries. Heterogeneous nucleation was found in all three samples in the crystallization temperature (T_c) regions studied. DSC results indicated that the crystallization kinetics in the Lam phase was the fastest, and the PEO crystals possessed higher thermodynamic stability than in the DG and Hex phases. For the crystallization kinetics in two 2D-confined phases, at low T_c (<35 °C) the PEO crystallization rates in the DG and Hex phases were similar, while at high T_c (>35 °C) the PEO crystallization was slower in the DG phase than in the Hex phase. The Avrami exponent n-values for the DG and the Hex samples were similar (∼1.8), yet the values of lnK in the DG phase were smaller than those in the Hex phase. This suggested that the linear growth rate was slower in the DG phase than in the Hex phase due to continuous curved channels in the DG phase.     

低密度聚乙烯/石墨烯纳米复合材料非等温结晶动力学

采用差示扫描量热仪研究了不同石墨烯(GP)含量的低密度聚乙烯(PE–LD)纳米复合材料在不同降温速率下的非等温结晶行为。结果表明,不同含量GP填料的加入均导致PE–LD结晶温度提高,表明GP填料对PE–LD基体起到异相成核作用;莫志深法能很好地描述纳米复合材料的动态结晶行为。动力学数据显示,当GP质量分数为0.5%和2%时,PE–LD复合材料的整体结晶速率、活化能、成核常数和生长晶面的表面自由能均比纯PE–LD低,而含量为5%时其值均比纯PE–LD高,因此适量的GP有利于PE–LD的结晶。由成核常数、表面自由能值可看出低含量GP促进PE–LD晶粒的二次成核、生长,而高含量GP则抑制晶粒二次成核、生长。     

基于不同材料特性的水辅注塑模拟

基于广义非牛顿流体本构方程,采用有限体积法,对不同类型材料(结晶型材料PE和非结晶型材料HIPS、ABS)的短射法水辅注塑成型进行了数值模拟研究。研究发现,结晶型材料PE因结晶导致的体积收缩性,使其水辅注塑制件的水穿透长度比其它两种非结晶材料更长。当冷却时间过长时,结晶型材料PE因结晶导致的内应力增加,使其水辅注塑制件的水穿透长度比其他两种非结晶材料更短。这3种材料在注水延迟时间或注射量增加的情况下,均不利于水穿透长度的增加。另外,结晶型材料PE比非结晶型材料HIPS和ABS更容易发生二次穿透现象,且当熔体经过一定时间冷却,黏度提高时,更容易发生该现象。     

Influence of branching on the thermal behavior of poly(butylene isophthalate)

The thermal behavior of linear and randomly branched poly(butylene isophthalate) samples was investigated by thermogravimetric analysis and differential scanning calorimetry. As to the thermal stability, it was found to be good and similar for all the samples. The thermal analysis carried out using DSC technique showed that the melting temperature of the polymers decreased with increasing branching unit content, although the glass‐transition temperature was practically not affected by ramifications. The multiple endotherms typical of linear PBI were also observed in branched samples and were found to be influenced both by temperature and degree of branching. By applying the Hoffman‐Weeks' method, the equilibrium melting temperatures of the polymers were obtained. The presence of a crystal‐amorphous interphase was evidenced only for the branched samples and the interphase amount was found to increase as the branching unit content was increased. Isothermal melt crystallization kinetics was analyzed according to Avrami's treatment. The introduction of branching points was found to decrease the overall crystallization rate of poly(butylene isophthalate). Values of Avrami's exponent n close to 3 were obtained for all the samples, in agreement with a crystallization process originating from predetermined nuclei and characterized by three dimensional spherulitic growth. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2001–2010, 2002; DOI 10.1002/app.10517     

成核剂对PET非等温结晶动力学的影响

利用差示扫描量热仪(DSC)研究了滑石粉、苯甲酸钠和离子聚合物Surlyn对聚对苯二甲酸乙二醇酯(PET)非等温结晶行为的影响,并用Ozawa模型计算了非等温结晶动力学参数。结果表明:三种成核剂均是PET的良成核剂,其中苯甲酸钠的成核效果最为显著。与纯PET相比,三种成核剂的加入均使PET的结晶峰温度Tmc向高温偏移,过冷度(Tm-Tmc)明显降低,结晶速率常数K明显增大。纯PET和PET/成核剂共混体系的Ozawa指数n值介于1-4之间,均不为整数,且PET/成核剂共混体系的Ozawa指数n值小于纯PET的n值。