FDM用PETG系列耗材的改性研究

对市售聚对苯二甲酸乙二醇酯-1，4-环己烷二甲醇酯（PETG）丝材及原材料进行研究，选用PETG 2012作为制备熔融堆积成型技术（FDM）用PETG丝材的基体树脂。选用聚碳酸酯（PC）对基体PETG进行增韧增强改性，并制成3D打印高分子丝材进行打印测试，探讨了PC含量对PETG耗材及制件性能的影响。结果表明，在低PC含量下，PETG与PC的相容性较好，PETG与PC制件未出现明显的分层，分布比较均匀；共混物的流动性随着PC含量的增加而降低，且打印件的维卡软化温度和热变形温度随着PC用量的增加而增加；此外，PC材料的加入使得PETG打印件的力学性能得到较大改善：打印件的拉伸强度随着PC用量的增加而增大，缺口冲击强度却随着PC用量的增加呈现先增加后减小的趋势； PETG/PC的配比为1∶1时，可制得力学性能优异的3D打印耗材。     

导热绝缘PE-LD/PE-g-MAH/h-BN泡沫塑料的制备及性能研究

采用熔融共混法制备了一系列导热绝缘的低密度聚乙烯/马来酸酐接枝聚乙烯/六方氮化硼(PE-LD/PE-g-MAH/h-BN新型泡沫塑料，研究了相容剂PE-g-MAH的加入、h-BN含量对PE-LD/PE-g-MAH/h-BN泡沫体系导热性能、绝缘性能、力学性能及热稳定性的影响。结果表明，PE-g-MAH有利于增加PE?LD与h?BN的界面黏结，增强泡沫体系拉伸强度和断裂伸长率，显著提高其热导性能；当h-BN含量为30 %时， PE-LD/PE-g-MAH/h-BN泡沫体系的导热率为0.256 W/(m·K)，相对于PE-LD/h-BN泡沫体系的0.217 W/(m·K) 和纯PE-LD泡沫体系的0.039 W/(m·K)，热导率分别提高1.18和6.57倍，同时保持较好的绝缘性和热稳性。     

Measurement of solubility and diffusion coefficients of ethylene in solid and molten low-density polyethylene with different melt indices

The diffusion behavior of ethylene in polyethylene is of great importance for the polymerization and degassing of polyethylene (PE) industry. Based on the gravimetric sorption and desorption measurement approach, an intelligent gravimetric analyzer is applied to obtain the solubility and diffusion coefficients of ethylene in solid low-density PE (LDPE) with different melt indices at 30°C to 70°C, 0 to 4 atm and in molten LDPE at 160°C to 230°C, 0 to 4 atm, respectively. Results indicate that both the solubility and diffusion coefficients of ethylene in solid LDPE are smaller than those in molten LDPE, while the dissolution enthalpy and diffusion activation energy of ethylene in solid LDPE are higher. In addition, one- and two-dimensional diffusion models are built and the effects of particle size, polymer properties, and operation conditions are systematically investigated on the diffusion behaviors of ethylene in solid and molten LDPE.     

钛酸酯偶联剂对磷石膏/HDPE性能的影响

采用3种钛酸酯偶联剂改性超细磷石膏(UPG),将改性后的UPG添加到高密度聚乙烯(HDPE)中,研究了钛酸酯偶联剂结构对UPG/HDPE复合材料力学性能的影响。结果表明,钛酸酯偶联剂改性的UPG接触角增大,吸油值降低,201-UPG改性效果最佳,接触角和吸油值分别为106.25°和0.23。与UPG/HDPE复合材料相比,101-UPG/HDPE、201-PG/HDPE、311-UPG/HDPE复合材料的拉伸性能、弯曲性能和冲击性能得到了一定的提高,在101-UPG/HDPE复合材料中的效果最佳,分别提高了42.41%、64.04%、174.65%。SEM测试表明,加入了钛酸酯改性剂的UPG在HDPE中的分散效果较佳;流变测试显示,101-UPG/HDPE复合材料的黏度比HDPE明显提高。     

核电厂聚乙烯管道设计方法及标准简介

随着聚乙烯管道在三门核电厂、大亚湾核电厂中的试应用成功，大量的新建核电厂及核电厂改造项目均将聚乙烯管道作为海水冷却水管道系统的首选管材，自主研制核电厂聚乙烯管技术标准迫在眉睫。本文介绍了核电聚乙烯管道的发展历史和应用现状，对比了核安全3级聚乙烯管道和非核安全相关聚乙烯管道、城市燃气与给水聚乙烯管道技术标准的设计方法及适用范围，探讨了中国目前聚乙烯管技术标准与核3级聚乙烯管道技术标准的差异与差距，为核电厂聚乙烯管道的设计制造与标准研制提供参考。     

醇脱氢酶在聚乙烯膜表面的固定化研究

以聚丙烯酸（PAA）改性的聚乙烯（PE）膜为载体，研究了醇脱氢酶（ADH）的两种固定化路线，并以甲醛为底物考察了固定化酶的催化性能。路线1用聚乙烯亚胺（PEI）进一步改性，使用戊二醛（GA）固定化ADH。最优固定化pH为6.0，温度为5～15℃，酶浓度为1.0 mg/ml，GA浓度为0.01%(质量)；固定化酶的最适反应pH为6.5，温度为15～30℃，反应速率最高为9.6 μmol/(L·min)；重复利用10次后可保持47.3%的活性。路线2以PAA-PE为载体，用1-(3-二甲氨基丙基)-2-乙基碳二亚胺盐酸盐（EDC）和N-羟基琥珀酰亚胺（NHS）为活化剂，固定化ADH。EDC和NHS最优摩尔比为1∶0.5，固定化时间为24 h；固定化酶的最适反应pH为6.5，温度为20～37℃，反应速率为15.58 μmol/(L·min)；重复利用10次后可保持53.8%的活性。     

Polarity Effect and Electromagnetic Radiation of Partial Discharge Accompanying Growth of Electrical Tree

We have investigated the characteristics of radiated electromagnetic (EM) waves from positive and negative partial discharges (PD) in epoxy resin and cross‐linked polyethylene. We found that there is a correlation among the EM level from PD, the positive PD current, and electrical trees. Therefore, the growth of an electrical tree produces a lot of positive PD. We have also investigated the characteristics of the frequency region of EM waves from PD in air, insulating oil, and liquid epoxy in addition to the above insulators. EM waves were detected in the frequency region of 40 MHz to 300 MHz from positive and negative PD in epoxy resin and cross‐linked polyethylene. EM waves were also detected in the frequency region of 40 MHz to 150 MHz from positive and negative PD in air. In the case of insulating oil and liquid epoxy, EM waves were detected in the frequency regions of 40 MHz to 150 MHz from positive PD, and 40 MHz to 250 MHz from negative PD. The frequency region differed depending on the material and the discharge polarity. Our investigation indicates that the cause is differences in electric field strength at the time of PD occurrence.     

Numerical study of polyethylene burning in counterflow: Effect of pyrolysis kinetics and composition of pyrolysis products

The burning behavior of polyethylene in the counterflow of oxidizing air has been studied numerically with a coupled model describing feedback heat and mass transfer between gas‐phase flame and polymeric solid fuel. A 2‐dimensional elliptic equation in axisymmetric formulation (revealing the cylindrical shape of the polymer sample used in the experiment) has been employed to simulate heat transfer in solid fuel, and a set of 1‐dimensional hyperbolic equations has been used to determine the solid‐to‐gas conversion degree of the pyrolysis reaction. Four sets of products compositions and two modifications for the kinetic parameters of solid fuel pyrolysis reaction have been taken into account. Gas‐phase formulation is presented by set of 1‐dimensional conservation equations for multi‐component flow with detailed kinetic mechanism of combustion. The profiles of temperature and species concentrations in the flame zone have been calculated and compared with the results of experimental study of combustion of ultrahigh molecular weight polyethylene. Higher hydrocarbon composition (dodecane) has been found to show the best agreement between the temperature and species concentration profiles with the measurements, especially for the low‐level mass fractions of the by‐product components—propylene, butadiene, and benzene.     

Bi-supported Ziegler–Natta TiCl4/MCM-41/MgCl2 (ethoxide type) catalyst preparation and comprehensive investigations of produced polyethylene characteristics

Bi-supported Ziegler–Natta catalysts (TiCl₄/MCM-41/MgCl₂ (ethoxide type)) were synthesized to improve the morphology and the properties of polyethylene. The morphology control is a crucial issue in polymerization process, while tailoring the properties of polymers is needed for specific applications. The catalysts were synthesized in different ratios of two supports with impregnation method. The polymerization process was carried out in atmospheric slurry reactor. The catalysts were characterized with scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM–EDX), inductively coupled plasma, Fourier transform infrared spectrometry (FTIR), and Brunauer-Emmett-Teller (BET) methods. The polymers were analyzed with scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry, FTIR, and tensile-strength analyses. Ubbelohde viscometer and frequency sweep measurements showed that the synthesized polymers are ultra-high-molecular-weight polyethylene. Mechanical properties of polymers showed higher Young's modulus in samples containing MCM-41, having higher thermal stability supported by TGA analysis. SEM images of bi-supported catalyst showed a controlled spherical morphology with uniform size distribution. SEM analysis support that the polymers replicate their morphology from catalyst, improving their morphology comparing to MgCl₂-supported catalyst. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48553.     

使用不同催化剂转产过程中淤浆法HDPE脱气仓结块原因分析

在英力士淤浆环管工艺高密度聚乙烯(HDPE)装置上,由采用钛系催化剂生产PE100级管材专用HDPE转换成用铬系催化剂生产的过程中,使用钛系催化剂的停车期间以及使用铬系催化剂的开车期间,粉料输送至低压闪蒸脱气仓都会产生块状的聚乙烯,严重影响装置的正常运行;通过对块状聚乙烯进行密度与凝胶渗透色谱分析,发现结块的聚乙烯主要为低相对分子质量、低密度的聚乙烯粉料黏结物。停车期间,将第一反应器氢气进料量降低50%,提前终止1-己烯进料,从而完全消除结块的形成。