近年来特种工程塑料的研究开发及其应用

特种工程塑料包括聚苯硫醚(PPS)、聚酰亚胺(PI)、聚醚砜(PES)、聚醚醚酮(PEEK)、聚砜(PSF)、聚芳酯(PAR)、液晶聚合物(LCP)和工程塑料合金等。它们具有高强度、耐辐射、耐化学品、耐高温等特点。由于特种工程塑料新产品的不断开发,为近代工业和尖端技术领域提供了较为理想的材料。 当前,特种工程塑料的技术和市场都有了很大的发展。销售量较大的是工程塑料合金、液     

液晶聚合物的注射成型技术

叙述了特种工程塑料液晶聚合物的结构、性能特点及应用；介绍了液晶聚合物制品和模具的设计应考虑的因素；重点阐述了液晶聚合物制品的注射成型工艺，包括原料干燥、料筒温度、注射压力和速度、嵌件预热模具温度、成型周期和注意事项。     

高端微结构塑料制品的成型加工技术与装备研发

随着我国塑料加工产业的快速发展,带有微型化结构的塑料制品越来越多地应用在生物医学、能源环保、电子信息、航空航天和国防军工等领域。本文从微通道塑料制品、微注塑制品和特种工程塑料3D打印制品三个方面,对高端微结构塑料制品成型加工技术及装备研发展开介绍,分析微通道的成型加工过程、微注塑成型的工艺设备以及特种工程塑料应用于3D打印的途径,为微结构塑料制品加工工艺及设备产业化应用提供参考。     

聚醚醚酮的成型加工（上）

聚醚醚酮树脂（Polyether Ether Ketone，简称PEEK树脂）是一种高性能特种工程塑料，被称为塑料工业的金字塔尖，已在航天航空、电子信息、石油化工等领域广泛应用，并成为不可或缺的关键材料。目前，除我国外，全世界仅有英国Victrex公司一家能够生产，并垄断了全世界的经营市场。虽然PEEK树脂在我国已经实现了批量生产，但与国外公司相比，我国在应用开发上还存在一些问题。为此，本刊特别邀请中国首位工程塑料成型加工应用技术专家，美国通用电气公司（GE）上海工程塑料技术服务部经理、市场发展资深专家。美国尖端材料与加工工程学会会员。香港毅兴行工程塑料公司市场部高级经理、技术顾问陶国源先生撰写了“聚醚醚酮的成型加工（上、下）”“聚醚醚酮应用实例（上、下）”从2006年第一期开始分四期连续刊发，敬请关注。     

聚醚砜的耐辐射特性

1 前言聚醚砜(PES)是一种性能优异的特种工程塑料。由于其特殊的化学结构,使得PES具有优异的机械性能、电性能、化学性能、耐磨性和耐辐射性,并可采用通常的塑料成型机械生产制品,因而得到越来越多的应用。自1972年英国ICI公司成功地开发PES以来,它已被广泛应用于电气、电子、汽车、航空航天等许多工业领域。     

新型特种工程塑料PEEK超细纤维成型过程的难点分析

新型特种工程塑料PEEK纤维在国防及民用上有很高的应用价值,通过机理研究分析高强度、耐高温特种工程塑料熔体挤出超细纤维过程的难点,为挤出特种塑料超细纤维成型工艺及设备的制定提供理论依据.     

聚醚醚酮共混改性研究进展

综述了聚醚醚酮（PEEK）、聚醚酰亚胺（PEI）、聚四氟乙烯（PTFE）、热致液晶（TLCP）和聚醚砜（PES）等高性能工程塑料的共混改性研究进展,详细探讨了各种PEEK共混物的相容性、结晶行为、微观结构、热行为和力学性能等性能特征。PEEK与PEI在熔融和无定形状态下完全相容,常用于PEEK的结晶行为和微观结构的基础研究;与PTFE、TLCP、PES共混分别是提高PEEK的摩擦磨损性能、加工性能和热稳定性的有效手段。各种共混物的相容性好坏对其结晶行为和微观结构有重要影响,从而影响了共混物的力学性能。在此基础上,对PEEK共混改性领域进一步的研究方向和内容进行了讨论。     

新型特工程塑料PEEK超细纤维成型过程的难点分析

新型特种工程塑料PEEK纤维在国防及民用上有很高的应用价值,通过机理研究分析高强度、耐高温特种工程塑料熔体挤出超细纤维过程的难点,为挤出特种塑料超细纤维成型工艺及设备的制定提供理论依据.     

PEEK特种工程塑料耐磨改性研究进展及其应用展望

介绍了聚醚醚酮（PEEK）特种工程塑料耐磨增强改性方法的研究现状;总结了PEEK工程塑料常见的摩擦磨损类型以及特定工况下PEEK工程塑料摩擦学机理的研究进展;最后对PEEK工程塑料的应用进行了展望。     

DR在聚醚醚酮注射制品缺陷检测中的应用

介绍了X射线数字成像检测(DR)技术及其特点,对热塑性工程塑料聚醚醚酮(PEEK)注射成型制品进行了DR检测,给出了PEEK注射制品内部典型缺陷气泡和夹杂的DR图像特征,并采用计算机断层扫描技术(CT)对检测结果进行了验证。研究表明,DR技术能够快速、准确、清晰地检测出PEEK注射制品内部缺陷;分析产生缺陷的原因,结合实际情况提出了避免缺陷产生的改进措施。     

Crystallization and melting behavior of poly(ether ether ketone)/poly(aryl ether sulfone) blends

The crystallization and melting behavior of poly(ether ether ketone) (PEEK) in blends with poly(aryl ether sulfone) (PES) prepared by melt mixing are investigated by differential scanning calorimetry (DSC) and wide‐angle X‐ray scattering (WAXS). The presence of PES is found to have a notable influence on the crystallization behavior of PEEK, especially when present in low concentrations in the PEEK/PES blends. The PEEK crystallization kinetics is retarded in the presence of PES from the melt and in the rubbery state. An analysis of the melt crystallization exotherm shows a slower rate of nucleation and a wider crystallite size distribution of PEEK in the presence of PES, except at low concentrations of PES, where, because of higher miscibility and the tendency of PES to form ordered structures under suitable conditions, a significantly opposite result is observed. The cold crystallization temperature of the blends at low PES concentration is higher then that of pure PEEK, whereas at a higher PES concentration little change is observed. In addition, the decrease in heat of cold crystallization and melting, which is more prevalent in PEEK‐rich compositions than in pure PEEK, shows the reduction in the degree of crystallinity because of the dilution effect of PES. Isothermal cold crystallization studies show that the cold crystallization from the amorphous glass occurs in two stages, corresponding to the mobilization of the PEEK‐rich and PES‐rich phases. The slower rate of crystallization of the PEEK‐rich phase, even in compositions where a pure PEEK phase is observed, indicates that the presence of the immobile PES‐rich phase has a constraining influence on the crystallization of the PEEK‐rich phase, possibly because of the distribution of individual PEEK chains across the two phases. The various crystallization parameters obtained from WAXS analysis show that the basic crystal structure of PEEK remains unaffected in the blend. Further, the slight melting point depression of PEEK at low concentrations of PES, apart from several other morphological reasons, may be due to some specific interactions between the component homopolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2906–2918, 2003     

Thermal,crystalline, and tribological properties of PEEK/PEI/PES plastics alloys

PEEK/PEI/PES plastics alloys in weight ratios of 70/30/0, 70/25/5, 65/30/5, 60/30/10, 60/35/5, and the three kinds of single high performance engineering plastics 100/0/0, 0/100/0, 0/0/100 were prepared by twin‐screw extrusion molding. A single glass‐transition temperature (T_g) of each alloy in the former five kinds of the plastics alloys could be measured by DSC and always rose to higher one than that of the pure PEEK by about 20°C. The crystalline degrees of these alloys could also ascended to more than 35.81% higher than that of the pure PEEK, especially for the alloy of the ratio 60/30/10 reached the maximum crystalline degree 37.76%. Adding PEI or PEI and PES, the crystalline temperatures of the PEEK alloys were decreased. The wear resistances of the alloys under dry sliding condition were considerably improved compared with pure PEI or PES, and the specific wear rate of the pure PEI or PES were four to six times as large as that of the alloys. However, the specific wear rates of the alloys were six to eight times larger than that of the pure PEEK, and the friction coefficients of the alloys were higher than that of the pure PEEK for 0.2–0.3. The polymeric transferred film on the steel ring surface against the alloys could be found, but no film on that against pure PES or PEI was found. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of dihydroxydiphenyl ether on poly(ether ether ketone)

A series of modified poly(ether ether ketone) (PEEK) polymers were synthesized by introduction of addition ether groups from dihydroxydiphenyl ether (DHDE) into the PEEK structure. The inherent viscosity of the DHDE-modified PEEK increased with reaction time at 320 °C. DSC thermograms showed the melting points of the obtained PEEK decreased with the increase of the DHDE content in the backbone. The degradation temperature (T_d) was slightly decreased by the introduction of DHDE. The crystallinity as measured via the X-ray diffraction (XRD) increases with the introduction of DHDE into the modified PEEK. The crystalline structure was identified as an orthorhombic structure with lattice constants a = 7.72 Å, b = 5.86 Å, and c = 10.24 Å. Due to the glass transition temperature (T_g) and the melting temperature (T_m) decreasing with the increase of the DHDE content in the reaction system. the processability of the resultant PEEK could be improved through this DHDE modification.     

Spherulitic growth kinetics in miscible blends of poly(ether ether ketone) and poly(ether imide)

Growths of poly(ether ether ketone) (PEEK) spherulites from both pure melt and its miscible blends with poly(ether imide) (PEI) have been studied by polarized optical microscopy. The nucleation density of PEEK spherulites was depressed upon blending with PEI, which can be attributed to the reduction in degree of supercooling arising from equilibrium melting point depression. A modified Lauritzen-Hoffman (L-H) theory was adopted to analyze the growth kinetics. Regime III-II transition was observed with the transition temperature decreasing with increasing PEI composition. Assuming free rotations of the virtual bonds in PEEK molecule, the side surface free energy of 12.0 erg/cm² was calculated from the characteristic ratio. The fold surface free energy of 188 erg/cm² and work of chain folding of 12.3 kcal/mol were then obtained from the modified L-H analysis.     

Poly(ether ether ketone)/poly(aryl ether sulfone) blends: Relationships between morphology and mechanical properties

Mechanical properties such as the tensile modulus, yield (break) strength, and elongation to break (or yield) are measured for multiphase poly(ether ether ketone) (PEEK)/poly(aryl ether sulfone) (PES) blends. Specimens with three different levels of thermal histories (quenched, as‐molded, and annealed) are prepared in order to study their effects on the mechanical properties of PEEK/PES blends. Synergistic behavior is observed in the tensile modulus and tensile strength of the blends in almost the whole range of compositions. The ductility of quenched blends measured as the elongation to break (yield) shows an unexpected synergistic behavior in the blend containing 90 wt % PEEK, although a negative deviation from additive behavior is observed in the rest of the compositions. A ductile–brittle transition is observed between 50 and 75 wt % PEEK in the blend. The ductile–brittle transition in as‐molded blends shifts to 75–90 wt % PEEK. Annealed blends show predominantly brittle behavior in the whole composition range. The experimental data are further correlated with the theoretically predicted results based on various composite models. Although the prediction based on these equations fails to fit the experimental data in the whole composition range, the simplex equations that are normally used for blends showing synergistic behavior produced a reasonable fit to the experimental data. The mechanical properties obtained for different blend compositions are further correlated with their morphology as observed by scanning electron microscopy. Morphological observation shows a two‐phase morphology in PES‐rich blends, which is an interlocked morphology in which the disperse phase is not clearly visible in PEEK‐rich blends, and a cocontinuous type of morphology for a 50/50 composition. Considerable permanent deformation of both the disperse and matrix phase, especially in the case of quenched tensile specimens, demonstrates the remarkable adhesion present between the two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2887–2905, 2003     

复合成盐剂对聚醚醚酮合成与性能的影响

采用4,4′-二氟二苯甲酮、对苯二酚为原料,以不同比例的碳酸钾和碳酸钠为复合成盐剂,二甲苯为脱水剂,二苯砜为溶剂成功制备了一系列聚醚醚酮(PEEK)树脂。通过傅里叶红外光谱和X射线衍射对PEEK树脂结构进行了表征,证明合成的样品是对苯二酚型PEEK树脂。其次,对所制样品分别进行力学性能、特性黏度、热性能测试,详细地探讨不同钾/钠比例的复合成盐剂对PEEK性能的影响。结果表明,所有样品均展示了优异的力学性能和热性能,其熔点和初始分解温度分别大于330℃和520℃,拉伸强度介于77~101 MPa。此外,当碳酸钾和碳酸钠的物质的量比为7∶3时,PEEK树脂的综合性能达到最优。     

聚醚醚酮表面接枝O-羧甲基壳聚糖及其血液相容性研究

采用紫外自引发光接枝在聚醚醚酮表面接枝聚丙烯酸,并进而以此为反应位点,通过共价键结合引入O羧甲基壳聚糖(O-CMC)。采用接触角测定仪、扫描电子显微镜、X射线光电子能谱和血小板粘附实验等对改性聚醚醚酮进行了表征。结果表明,改性聚醚醚酮表面浸润性得到提高,具有抗凝血性能。     

Fine poly(ether ether ketone) powders

The physical form of polymers is often important for carrying out subsequent processing operations. For example, fine powders are desirable for molding and sintering compounds because they consolidate to produce void free components. The objective of this work is to prepare fine polymeric particulates suitable for processing into fiber reinforced polymer matrix composites. Micron size particles of poly(ether ether ketone) (PEEK) were prepared by rapidly quenching solutions of these materials. PEEK pellets were dissolved at temperatures near the PEEK melting point in a mixture of terphenyls and quaterphenyls; then the solution was quenched to a temperature between the T_g and T_m (≈ 225°C) by adding a room temperature eutectic mixture of diphenyl ether and biphenyl. A supersaturated, metastable solution of PEEK resulted, causing rapid nucleation. Fine PEEK particles rapidly crystallized from this solution. The average particle size was measured using transmission electron microscopy, atomic force microscopy, and by light scattering of aqueous suspensions which had been fractionated by centrifugation. The average particle diameter was about 0.6 μm. Three dimensional photomicrographs obtained via atomic force microscopy showed some aggregates in the suspensions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1571–1578, 1997     

Mechanical and Thermal Properties of Poly(Phthalazinone Ether Sulfone)/Poly(Ether Sulfone) Blends

The mechanical and thermal properties of poly(phthalazinone ether sulfone) (PPES)/poly(aryl ether sulfone) (PES) blends prepared by melt-mixing were investigated by dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). The dynamic mechanical thermal analysis results show that the incorporated PES has a large influence on the heat stability of PPES. The DMTA results display that the blends with a single glass transition temperature, which increases with increasing PPES content, indicates that PPES and PES are completely miscible over the studied composition range. The thermodegradative behavior of PPES/PES blends was used to analyze their thermal stability. The Friedman technique was used to determine the kinetic parameters (i.e., the apparent activation energy and order of reaction of the degradation process). The results indicate that the presence of the PES component influences the thermal stability of the PPES. On the basis of the kinetic data derived from Friedman' approach, the lifetime estimates for pure PPES, pure PES, and the blends generated from the weight loss of 5% were constructed.