Effects of the structural components on slow crack growth process in polyethylene blends. Composition intervals prediction for pipe applications

A linear low density polyethylene (LLDPE) obtained from a metallocene based catalyst, was blended in an extruder with a high density polyethylene (HDPE) homopolymer synthesized with an iron based catalyst. The bimodal polyethylenes, made with blends from 0 to 100 wt % of copolymer were characterized by SEC, DSC, ESEM, SEC‐FTIR, and TREF, while their resistance to the slow crack growth (SCG) was evaluated through the PENT test. Results provide that polymer blends with copolymer contents between 47.5 and 72.5 wt % are suitable for pipe applications. Furthermore, a method based on the intercrystalline tie chains calculus is proposed as suitable and attractive, because of its simplicity and novelty, to forecast long term performance and to predict capabilities. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚乙烯管材SCG性能评价及寿命预测论述

管材的慢速裂纹萌生和扩展至管材破坏的时间是评价管材使用性能的一项重要指标。随着原材料性能的提高,聚乙烯(PE)管材抗裂纹萌生和耐慢速裂纹扩展的能力大幅提高。优异的PE100 RC管材在FNCT、PENT等实验评价方法下,测评时间均超过15000 h。PE管慢速裂纹评价方法普遍存在实验条件复杂、重复性差等问题,严重制约了PE管材的开发进程。对此,国外学者提出了更简洁快速的评价方法——循环载荷缺口圆棒(CRB)法。文章着重论述了,循环载荷CRB法对管材SCG性能及管材寿命预测的评价,同时,论述了几种管材性能评价方法的相关性。最后,指出了循环载荷CRB方法后续用作其他塑料管评价的研究方向。     

A sensitive mechanical test for slow crack growth in polyethylene

Slow crack growth (SCG) in a wide variety of polyethylenes has been investigated by a constant tensile load test (the PENT test) for a single edge notched specimen. The PENT test is very sensitive to the changes in molecular structure and morphology of polyethylene. The resistance to SCG depends on the density of the tie molecules and the strength of the crystals.     

聚乙烯管材慢速裂纹增长性能及其评价方法

简要概述了聚乙烯(PE)管材的慢速裂纹增长性能,全面介绍了评价慢速裂纹增长性能的各种试验方法。详细分析了聚乙烯给水管和燃气管的国家标准与国际标准对慢速裂纹增长性能的要求及其差异;同时还分析了PE100+协会、国内G5+质量控制小组以及最新的PAS 1075标准对聚乙烯管道产品的慢速裂纹增长性能要求的区别。最后就聚乙烯慢速裂纹增长性能评价方法的发展方向及其应用进行了分析与展望。     

High-density polyethylene pipe with high resistance to slow crack growth prepared via rotation extrusion

Slow crack growth (SCG) is one failure principal mode in polyethylene (PE) pressure pipe applications. In the conventional extrusion process, the molecular chains in the plastic pipes are oriented along the axial direction, which are disadvantageous to their resistance to SCG. In order to change the orientation direction of molecules in the plastic pipe, a new rotation extrusion processing system was designed to extrude high-density polyethylene (HDPE) pipes, and a thorough research was done on the effect of the rotation speed on its microstructure and resistance to SCG during the rotation extrusion. The experimental results showed that when the die rotated during the extrusion process of PE pipes, the hoop stress exerted on the polymer melt could make the molecular orientation deviate from the axial direction, and therefore the consequent multi-axial orientation of molecular chains could be obtained. As a result, the PE pipe with better resistance to SCG was prepared. Compared to the PE pipe produced by the conventional extrusion, the crack initiation time of the PE pipe manufactured by the novel method increased from 27 to 57 h.     

Fracture prediction in tough polyethylene pipes using measured craze strength

In this study, an empirical model is developed that predicts the time to failure for PE pipes under combined pressure and deflection loads. The time‐dependent craze strength of different PE materials is measured using the circumferentially deep‐notched tensile (CDNT) test. In agreement with previous research, results indicate that bimodal materials with comonomer side‐chain densities biased toward high‐molecular‐weight PE molecules exhibit significantly higher long‐term craze strengths. A comparison of currently available PE materials with CDNT samples taken from a PE pipe that failed by slow crack growth in service clearly indicates the superior performance of new‐generation materials. Using measured craze strength data from the CDNT test, a simplified model for predicting failure in buried PE pipes is developed. Extending previous research, the reference stress concept is used to calculate an equivalent craze stress for a pipe subjected to combined internal pressure and deflection loads. Good agreement is obtained between the model predictions and observed failure times in an experimental test‐bed study of pipes under in‐service loading conditions. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Slow crack growth resistance in resin blends of chromium and metallocene catalyzed ethylene‐hexene copolymers for pipe applications

A bimodal system has been developed by blending a high density and linear medium density ethylene‐hexene copolymers synthesized with chromium and metallocene catalysts, respectively. The resistance to slow crack growth examined by the Pennsylvania Edge‐Notch Tensile test (PENT test‐ASTM F1473) and the crack opening displacement was determined at 80°C and 2.4 MPa. The effects of molecular and morphological structure on the slow crack growth (SCG) resistance were evaluated, the molecular weight and lamellar thickness being the most critical parameters for this system. The great importance of the short chain branching content and distribution was determined and discussed by SEC‐FTIR. Therefore, two main factors were found determinant in the SCG resistance. On the one hand, the increase of tie molecule density and therefore the continuity in the network formed by crystals and tie molecules and, on the other hand, the short chain branching density increase as the linear medium density ethylene‐hexene copolymer fraction does so. In addition, a morphological analysis of the fracture surface was performed in order to analyze the fracture mechanisms that took place. Differences observed in the fracture surface morphology were related to the molecular and morphological structure. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

聚乙烯管材应变硬化模量与裂纹扩展速率相关性研究

采用应变硬化试验和锥体试验分别得到不同聚乙烯100（PE100）管材试样的应变硬化模量和裂纹扩展速率,并对它们之间的相关性进行研究,以期验证应变硬化试验法评价PE管材耐慢速裂纹扩展性能的正确性。结果表明,锥体试验中PE管材试样的裂纹扩展程度随着试验时间的增加而增大;应变硬化试验和锥体试验对不同PE管材试样的耐慢速裂纹扩展性能评价结果完全相同,应变硬化试验法评价PE管材耐慢速裂纹扩展性能的正确性得到验证;应变硬化试验不仅误差较小,而且可以区分不同牌号PE100管材耐慢速裂纹扩展性能的细微差异,评价结果相对于锥体试验要更加可靠。     

管材专用高密度聚乙烯的研究进展

综述了国内高密度聚乙烯(HDPE)的生产装置及工艺。采用双峰聚合工艺使短支链更多地分布在高相对分子质量部分是HDPE管材从PE80级升至PE100级的主要原因。管材的耐环境应力开裂性能随HDPE相对分子质量减小而下降,提高短支链含量可提高管材的耐环境应力开裂性能。HDPE的相对分子质量越高,管材抗裂纹扩展性能越好,将短支链分布在高相对分子质量端可提高抗裂纹扩展性能。     

HDPE与PPR全切痕拉伸断裂过程银纹性能测试

通过对高密度聚乙烯(HDPE)和无规共聚聚丙烯(PPR)进行不同拉伸速率的全切痕拉伸测试,考察了两种材料在近似于平面应变条件的拉伸断裂性能。对其全切痕拉伸过程应力-位移曲线、位移-屈服应力曲线分析:HDPE和PPR的屈服应力均随着拉伸速率的增加而增大;在较高拉伸速率时,HDPE全切痕拉伸断裂可认为是由常临界位移控制的银纹断裂,PPR的全切痕拉伸断裂过程几乎无恒定的常拉伸位移。通过显微镜显示的断裂形貌观察揭示了沿拉伸方向上HDPE有微纤空穴产生;在全切痕拉伸断裂过程中,PPR的银纹化易于发生在非晶区的片晶间,银纹微纤可产生在任意方向上。     

The Use of Ethylene/Propylene Copolymers as Compatibilizers for Recycled Polyolefin Blends

Compatibilizing effects of ethylene/propylene (EPR) diblock copolymers on the morphology and mechanical properties of immiscible blends produced from recycled low‐density polyethylene (PE‐LD) and high‐density polyethylene (PE‐HD) with 20 wt.‐% of recycled poly(propylene) (PP) were investigated. Two different EPR block copolymers which differ in ethylene monomer unit content were applied to act as interfacial agents. The morphology of the studied blends was observed by scanning‐ (SEM) and transmission electron microscopy (TEM). It was found that both EPR copolymers were efficient in reducing the size of the dispersed phase and improving adhesion between PE and PP phases. Addition of 10 wt.‐% of EPR caused the formation of the interfacial layer surrounding dispersed PP particles with the occurrence of PE‐LD lamellae interpenetration into the layer. Tensile properties (elongation at yield, yield stress, elongation at break, Young's modulus) and notched impact strength were measured as a function of blend composition and chemical structure of EPR. It was found that the EPR with a higher content of ethylene monomer units was a more efficient compatibilizer, especially for the modification of PE‐LD/PP 80/20 blend. Notched impact strength and ductility were greatly improved due to the morphological changes and increased interfacial adhesion as a result of the EPR localization between the phases. No significant improvements of mechanical properties for recycled PE‐HD/PP 80/20 blend were observed by the addition of selected block copolymers.     

聚乙烯管材热熔对接接头抵抗慢速裂纹扩展性能评价

采用应变硬化试验(SH)对不同焊接工艺下的聚乙烯管材热熔对接接头抵抗慢速裂纹扩展（SCG）性能进行评价。通过建立焊接温度梯度（190~250 ℃）、焊接压力梯度（0.6~1.4 MPa）和吸热时间梯度（40~140 s）试验,分析在不同焊接工艺参数条件下,不同聚乙烯管材热熔对接接头耐SCG性能的变化规律,探索冷焊及过焊2种典型缺陷对管材接头耐SCG性能的影响。结果表明,焊接温度、焊接压力和吸热时间都是影响管材热熔对接接头耐SCG性能的重要工艺参数,试验测得PE100, d_n110, SDR11型管材的最佳焊接参数为焊接温度230 ℃,焊接压力1 MPa及吸热时间100 s,当焊接参数选取过高或过低时,会造成管材接头出现过焊或冷焊缺陷,降低管材接头的耐SCG性能。     

基于循环载荷法评价聚乙烯管材性能的可靠性研究

为研究循环载荷法对加速表征聚乙烯（PE）管材耐慢速裂纹扩展（SCG）性能的可靠性,对5种不同等级的PE管材采用循环载荷缺口圆棒（CRB）试验和全切口拉伸蠕变（FNCT）试验的方法对其耐慢速裂纹扩展性能进行评估,同时对其试验结果进行相关性分析。此外,通过测量PE管材的分子量及其分布、结晶度和片晶厚度等高分子材料参数进一步佐证所选PE管材耐慢速裂纹扩展性能的优劣,进而验证CRB试验方法的可靠性。结果表明,循环载荷CRB试验方法不仅能可靠有效评估PE管材的耐SCG性能,且相比FNCT试验方法,其试验所需时长更短及试验条件要更贴近实际使用工况。     

聚乙烯原料对高密度聚乙烯土工膜性能的影响

本实验采用吹塑成型工艺,以不同牌号的聚乙烯(PE)树脂为原料生产2 mm厚度双光面高密度聚乙烯(HDPE)土工膜,研究PE原料对HDPE土工膜性能的影响。结果表明:中密度聚乙烯(MDPE)土工膜综合性能优异,主要是由其特有的分子结构(如分子量分布双峰性、α烯烃长支链)所决定的;不同PE原料氧化诱导时间不同,可通过调节含抗氧剂色母料(或抗氧剂)的含量,使HDPE土工膜氧化诱导时间达到要求;HDPE土工膜在焊接时应根据PE材质的不同而选择不同的焊接条件。     

Intrinsic lifetime of polyethylene pipelines

An equation was developed for calculating the time to failure by slow crack growth (SCG) failure in any polyethylene structure. The equation requires the following experimental inputs: (1) the resistance to SCG as measured by the PENT test (ASTM F1473), (2) the stress intensity of the defect from which failure originates, and (3) the temperature. A simple experiment for determining the stress intensity is presented. The equation was applied to SCG failures that are associated with the inherent random defects that occur in the wall of all pipes. The size of the inherent random defect that exists in commercial gas pipes was found to be 0.14 mm. POLYM. ENG. SCI., 47:477–480, 2007. © 2007 Society of Plastics Engineers.     

Crystallization kinetics modeling of high density and linear low density polyethylene resins

This paper describes isothermal and nonisothermal crystallization kinetics of a Ziegler‐Natta catalyzed high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) resins. Standard techniques such as differential scanning calorimetry (DSC) and light depolarization microscopy (LDM) techniques were used to measure isothermal kinetics at low supercoolings. DSC was also used to measure nonisothermal crystallization kinetics at low cooling rates. Extrapolation of isothermal crystallization half‐times of Z‐N catalyzed LLDPE resin using the isothermal half‐time analysis led to erroneous predictions, possibly due to Z‐N LLDPE consisting of a mixture of molecules having different amounts of short chain branching (comonomer). However, predicted reciprocal half‐times at high supercoolings, using isothermal half‐time analysis and using nonlinear regression of nonisothermal crystallization kinetics measured at low cooling rates using the differential Nakamura model, of the HDPE were similar to measured reciprocal half times at high supercoolings of a similar HDPE by Patki and Phillips. It is also shown that the differential Nakamura model can be effectively used to model nonisothermal crystallization kinetics of HDPE resins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

温度梯度对聚乙烯耐慢速开裂性能的影响

通过调控温度梯度得到含取向球晶的聚乙烯(PE)试样,研究取向球晶结构对PE耐慢速开裂性能的影响。结果表明:在温度梯度作用下,PE球晶呈椭圆形,片晶沿温度梯度方向取向生长。当温度梯度下制备的试样受到轴向应力作用,取向晶片垂直于受力方向,易发生晶片层间破坏,导致其耐慢速裂纹开裂性能降低。随温度梯度增加,取向球晶增多,耐慢速开裂性能下降更明显。     

台塑公司高密度聚乙烯专用树脂的开发策略

介绍了台湾塑胶工业股份有限公司高密度聚乙烯(HDPE)树脂的生产装置、工艺技术、生产能力、树脂牌号及新产品开发现状,同时阐述了HDPE专用树脂的开发策略。目前,台塑公司HDPE商品牌号台塑烯的产品包括薄膜专用树脂、中空吹塑专用树脂、挤出专用树脂和注塑等用树脂等,并且产品具有单峰、双峰甚至宽峰相对分子质量分布的特性。2006年,台塑公司将调整台塑烯专用树脂的生产比例,强化产品结构而维持一定的营利水平。     

Thermoplastic elastomers based on epoxidized natural rubber and high‐density polyethylene blends: Effect of blend compatibilizers on the mechanical and morphological properties

Epoxidized natural rubber (ENR) with a level of epoxide groups of 20 mol % was prepared via the performic epoxidation method. It was then used to blend with high‐density polyethylene (HDPE) at various blend ratios. Three types of blend compatibilizers were prepared. These included a graft copolymer of HDPE and maleic anhydride (MA; i.e., HDPE‐g‐MA) and two types of phenolic modified HDPEs using phenolic resins SP‐1045 and HRJ‐10518 (i.e., PhSP‐PE and PhHRJ‐PE), respectively. We found that the blend with compatibilizer exhibited superior tensile strength, hardness, and set properties to that of the blend without compatibilizer. The ENR and HDPE interaction via the link of compatibilizer molecules was the polar functional groups of the compatibilizer with the oxirane groups in the ENR molecules. Also, another end of the compatibilizer molecules (i.e., HDPE segments) was compatibilizing with the HDPE molecules in the blend components. The blend with compatibilizer also showed smaller phase morphology than the blend without compatibilizer. Among the three types of the blend compatibilizer, HDPE‐g‐MA provided the blend with the greatest strength and hardness properties but the lowest set properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008