Influence of microstructure on elastic and viscoelastic properties of polyether ether ketone

Dynamic, creep and static tests were conducted to characterize experimentally the linear elastic and viscoelastic properties of polyether ether ketone (PEEK) as a function of the degree of crystallinity. The semicrystalline polymer was modeled as a two-phase composite material. Values for crystalline modulus and effective crystalline aspect ratios have been extracted from the model. These values together with experimental creep compliance values for amorphous PEEK have been used to predict the creep response for intermediate levels of crystallinity, which compare well with the experimental data. Time-temperature shifting parameters obtained from dynamic mechanical studies compare well with those from creep experiments. At temperatures below 140°C, the shifting parameters were found to be approximately equal for all levels of crystallinity. Prediction for long-term creep has been made from these tests by properly accounting for physical aging phenomenon.     

Phase behaviour and mechanical properties of poly(ether ether ketone)-poly(ether sulphone) blends

The phase behaviour and the mechanical properties of binary blends composed of poly(ether ether ketone) and poly(ether sulphone) have been studied both in the amorphous state and after crystallization of poly(ether ether ketone).Differential scanning calorimetry and dynamical mechanical analysis clearly show the existence of phase separation in the blends. Density measurements confirm the absence of strong interactions between the blend components, as well as the slight effect of PES on the crystallization of PEEK.The mechanical properties of the quenched, amorphous blends remain surprisingly good in spite of the observed immiscibility, however, slowly cooled, crystalline blends appear as brittle materials.     

碳纤维-AlN/聚醚醚酮复合材料的制备与性能

以聚醚醚酮(PEEK)为基体树脂、碳纤维(CF)和氮化铝(AlN)为填料,通过模压成型的方法制备了抗静电耐热型CF-AlN/PEEK复合材料。采用高阻计、导热系数测定仪、热失重、差示扫描量热仪和SEM研究了CF-AlN/PEEK复合材料的抗静电性能、热性能、力学性能以及降温速率对复合材料性能的影响,并探讨了后期热处理对力学性能的影响。结果表明:当CF和AlN的质量分数均为10%时,CF-AlN/PEEK复合材料的性能较优,其表面电阻率达到108 Ω,比PEEK的表面电阻率提高了6个数量级;导热系数为0.418 W·(m·K)-1,初始分解温度高达573℃;拉伸强度提高了40.4%;降温速率越低,复合材料的熔点越高;后期热处理会影响CF-AlN/PEEK复合材料的力学性能,在270℃下热处理2 h,其拉伸强度可达146 MPa,表明在生产过程中,加工温度是影响复合材料性能的因素之一。      

Effect of carbon nanotubes on the mechanical properties and crystallization behavior of poly(ether ether ketone)

Pristine carbon nanotubes (CNTs) and noncovalently functionalized carbon nanotubes (f-CNTs) were used to prepare poly(ether ether ketone) (PEEK) composites (CNTs/PEEK and f-CNTs/PEEK) via melt blending. Noncovalently functionalized multiwalled nanotubes were synthesized using hydrogen-bonding interactions between sulfonic groups of sulfonated poly(ether ether ketone) (SPEEK) and carboxylic groups of nanotubes treated by acid (CNTs–COOH). The effects of these two kinds of nanotubes on the mechanical properties and crystallization behavior of PEEK were investigated. CNTs improved mechanical properties and promoted the crystallization rate of PEEK as a result of heterogeneous nucleation. Better enhancement of mechanical properties appeared in the f-CNTs/PEEK composites, which is ascribed to the good interaction between f-CNTs and PEEK. However, the strong interaction of f-CNTs and PEEK chains decreased the crystallization rate of PEEK for high content of f-CNTs.     

The influence of thermal history on the mechanical properties of poly(ether ether ketone) matrix composite materials

The purpose of this study is to provide insight into the microstructural factors that affect the flexural fatigue performance of carbon-fibre-reinforced poly(ether ehter ketone) (PEEK) composites. Specifically, the effect of the degree of crystallinity on the mechanical properties is examined at two crystallinity levels of the as-received composites (35%) and of quenched composites (10%). Higher static flexural strength and modulus as well as longer fatigue life are observed for the higher crystallinity level. By varying the loading angle with respect to the fibre direction it is shown that the crystallinity effect is not matrix dependent alone. Rather, a strong effect is evident in the fibre direction, which is attributed to the influence of the transcrystalline layer formed on the fibre surface in the high-crystallinity material. As a result, the longitudinal fatigue life at 1·7GPa of the 35% crystallinity material is three orders of magnitude higher than that of the 10% crystallinity composite.     

聚醚醚酮增韧改性环氧树脂

采用共混法用聚醚醚酮(PEEK)改性环氧树脂(EP),借助差示扫描量热分析(DSC)确定了环氧树脂的固化工艺,测试了共混体系的工艺性能,研究了聚醚醚酮含量对环氧树脂力学性能的影响.借助扫描电子显微镜(SEM)对材料断裂面的形态结构进行了分析,探讨了体系的形态结构与冲击性能之间的关系.结果表明,在改性材料的韧性有所提高的同时,压缩强度、马丁耐热都没有降低.从断裂面的形态来看,是属于韧性断裂.当PEEK的加入量为6%时,韧性最好,达到19.1 kJ/m2,比纯的环氧树脂增加了107.6%.     

聚醚醚酮增韧改性环氧树脂

采用共混法用聚醚醚酮(PEEK)改性环氧树脂(EP),借助差示扫描量热分析(DSC)确定了环氧树脂的固化工艺,测试了共混体系的工艺性能,研究了聚醚醚酮含量对环氧树脂力学性能的影响。借助扫描电子显微镜(SEM)对材料断裂面的形态结构进行了分析,探讨了体系的形态结构与冲击性能之间的关系。结果表明,在改性材料的韧性有所提高的同时,压缩强度、马丁耐热都没有降低。从断裂面的形态来看,是属于韧性断裂。当PEEK的加入量为6%时,韧性最好,达到19．1kJ/m~2,比纯的环氧树脂增加了107．6%。     

The mechanical properties of insert-molded poly (ether imide) (PEI)/C fiber poly (ether ether ketone)(PEEK) composites

The mechanical properties of insert-molded poly(ether imide) (PEI)/carbon fiber poly(etheretherketone) (CF PEEK) have been examined. Bimaterial composite specimens were constructed by injecting CF PEEK into a mold containing one-half of a PEI tensile specimen. These PEI/CF PEEK composites retained much of their strength and dimensional integrity at temperatures as high as 200°C. Variations in test speed had little affect on breaking strains or stiffness. For two grades of PEI examined, properties were independent of the molecular weight of the PEI. Ultimate properties and fracture surfaces suggested good adhesion between the PEI and CF PEEK, possibly aided by miscibility between the two materials. The PEI/CF PEEK bimaterial composites behaved similarly to PC/CF PEEK specimens, but exhibited higher breaking stresses and moduli, both at room and elevated temperatures.     

聚醚醚酮改性研究进展

聚醚醚酮(PEEK)作为一种新型高性能热塑性工程塑料,在许多工程领域有着广泛的应用.采用不同手段增强PEEK,改善其加工性能和力学性能、热性能、摩擦学性能,有利于降低材料成本和进一步拓展应用范围.本文从纤维增强PEEK、颗粒填充PEEK、PEEK表面改性、与聚合物共混等方面综述了PEEK改性研究的进展情况.     

Thin film and bulk deformation behaviour of poly(ether ether ketone)/poly(ether imide) blends

The deformation behaviour of amorphous thin films of poly(ether ether ketone) (PEEK)/poly(ether imide) (PEI) blends was investigated over a wide temperature range by optical and transmission electron microscopy. All the materials showed localized shear deformation at temperatures well below Tg. In pure PEI and in blends with up to 60 wt% PEEK content, a transition from shear deformation to disentanglement crazing occurred as the temperature was raised. However, this transition was absent in PEEK, which deformed by shear over the whole temperature range, and similar behaviour was found for PEI/80 wt% PEEK. It is argued that at high PEEK content disentanglement crazing is suppressed by strain-induced crystallization and some evidence for crystalline order in deformed regions of initially amorphous PEEK thin films was obtained by electron diffraction. The thin film deformation behaviour of the blends was also shown to be consistent with their bulk deformation behaviour, a high temperature ductile–brittle transition being observed at low PEEK content in tensile tests. This revised version was published online in November 2006 with corrections to the Cover Date.     

Design and preparation of graphene/poly(ether ether ketone) composites with excellent electrical conductivity

Graphene/poly(ether ether ketone) (m-TRG/PEEK) composites with excellent electrical conductivity were fabricated by hot pressing technique with thermally reduced graphene nanosheets (m-TRG) which were modified by poly(ether sulfone). Moreover, the conductive, thermal, and mechanical properties of PEEK/m-TRG composites were investigated by the precision impedance analyzer, thermal gravimetric analyzer, differential scanning calorimetry, and universal tester, respectively. The electrical conductivity of m-TRG/PEEK composites was greatly improved by incorporating graphene, resulting in a sharp transition from electrical insulator to semiconductor with a low percolation threshold of 0.76 vol.%. A high electrical conductivity of 0.18 S m^?1 was achieved with 3.84 vol.% of m-TRG. The data were compared with those of composites reduced chemically, and the results showed that thermal reduction was an effective method to acquire higher electrical conductive composites. The excellent electrical property should be attributed to the large specific surface area of m-TRG, well dispersion of m-TRG in PEEK matrix, and good compatibility of m-TRG with PEEK matrix, as proven by scanning electron microscope. Besides, m-TRG/PEEK composites also exhibited relatively good thermal and mechanical properties.     

Molecular interaction and properties of poly(ether ether ketone)/liquid crystalline polymer blends incorporated with functionalized carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were functionalized with a carboxyl group (-COOH) to achieve better interfacial adhesions with both phases of the poly(ether ether ketone) (PEEK) and liquid crystalline polymer (LCP) in their blend. These strong interfacial interactions among the functionalized MWCNTs, PEEK and LCP improved the mechanical properties of the polymer blend. Three different weight percentages (0.6%, 1.2% and 1.8%) of acid modified CNTs were used with PEEK-LCP blend, for the preparation of nanocomposites. In PEEK-LCP blend, the ratio of PEEK and LCP was maintained as 10:6 respectively. The tensile strength and modulus of the composites were improved by 51% and 73% respectively with the incorporation of only 1.2% of MWCNT-COOH as compared to the unfilled PEEK/LCP blend. Moreover, careful studies of the molecular interaction, morphological, dynamic mechanical and thermal properties confirmed that a better miscibility between PEEK and LCP had been constituted in the presence of MWCNT-COOH. Therefore, it was found that the functionalized MWCNTs not only played the traditional role as reinforcing filler, but also performed a novel role as a compatibilizer for the PEEK/LCP blends.     

High-performance conductive materials based on the selective location of carbon black in poly(ether ether ketone)/polyimide matrix

A novel high performance conductive material with excellent comprehensive properties was prepared by melt-blending, and its performances were adjusted by controlling the selective location of carbon black (CB) in poly(ether ether ketone) (PEEK)/thermoplastic polyimide (TPI) matrix. With increasing the CB loadings, the morphology of PEEK/TPI blends changed from sea-island to co-continuous structure, which was owing to the selective location of CB in TPI phase. Notably, with the selective location of CB in the induced co-continuous PEEK/TPI matrix, the electrical percolation threshold was reduced to 5 wt%, which was significantly lower than that of binary PEEK/CB (9 wt%) and TPI/CB (10 wt%) composites. And the electrical conductivity of ternary PEEK/TPI/CB composites was 10⁴ to 10⁶ times higher than that of binary composites at identical 7.5 wt% CB loading, which was attributed to the double percolation effect. Moreover, the incorporation of CB could improve the thermal and mechanical properties effectively.     

Cooling rate influences in carbon fibre/PEEK composites. Part 1. Crystallinity and interface adhesion

The effect of cooling rate on the fibre–matrix interface adhesion for a carbon fibre/semicrystalline polyetheretherketone (PEEK) composite was characterised based on the fibre fragmentation, fibre pullout and short beam shear tests. The interface adhesion was correlated to the degree of crystallinity and the crystalline morphology, as well as the bulk mechanical properties of neat PEEK resin, all of which were in turn controlled by cooling rate. It was shown that the interface bond strength decreased with increasing cooling rate; the tensile strength and elastic modulus of PEEK resin decreased, while the ductility increased with increasing cooling rate through its dominant effect on crystallinity and spherullite size. The improvement of crystalline perfection and flattened lamella chains with high crystallinity at the interphase region were mainly responsible for the strong interface bond in composites processed at a low cooling rate. The interphase failure was characterised by brittle debonding in slow-cooled composites, whereas the amorphous PEEK-rich interphase introduced in fast cooled specimens failed in a ductile manner with extensive plastic yielding.     

热致液晶聚酯/聚醚醚酮复合纤维的制备与表征

将热致液晶聚酯(VA)与聚醚醚酮(PEEK)共混后,通过熔融纺丝制备了热致液晶聚酯/聚醚醚酮复合纤维,并对复合纤维的热性能、聚集态结构、相态结构和力学性能进行了研究。结果表明,VA的加入能够降低PEEK纤维的玻璃化温度和冷结晶温度,同时PEEK的结晶温度也随着VA的加入而升高;VA的加入有利于提高PEEK的结晶性能,使得PEEK晶粒尺寸变大,晶面间距变小,晶体更加完善,晶区取向增强;随着VA添加量的增大,VA相逐渐由球状或椭球状向微纤状变化;随着喷丝头拉伸比的增大,VA相的长径比呈现先增大后减小的趋势;添加1%和2%的VA后,复合纤维的断裂强度有少许下降,而当VA的添加量增大到4%后,复合纤维的总拉伸倍数提高,并且断裂强度有一定的提升。     

聚醚醚酮和烯丙基化合物改性双马来酰亚胺复合材料微观结构及力学性能

采用浓H₂SO₄氧化聚醚醚酮（PEEK）得到磺化聚醚醚酮（SPEEK）,以3,3'-二烯丙基双酚A （BBA）、双酚A双烯丙基醚（BBE）为活性稀释剂、SPEEK为改性剂、双马来酰亚胺（BMI）树脂为基体,浇注成型制备SPEEK/BBA-BBE-BMI复合材料,同时研究了SPEEK的改性效果及复合材料微观形貌与力学性能。结果表明：SPEEK改性效果较好,在FTIR中存在明显的磺酸基团特征峰,SEM和能谱分析表明,SPEEK微观形貌变化明显,硫元素含量较高;SPEEK/BBA-BBE-BMI复合材料的微观形貌显示,SPEEK在基体中呈现直径为2 μm左右的多孔状两相结构,且分散均匀,此多孔结构改善了复合材料的断裂形貌,由脆性断裂转变为韧性断裂,当断裂纹遇到SPEEK组分时受阻而出现不规则发散,此变化会赋予复合材料更加优异的性能。力学性能测试结果显示,当SPEEK含量为5wt%时,SPEEK/BBA-BBE-BMI复合材料的弯曲强度和冲击强度达到最佳,分别为147.93 MPa和15.74 kJ/mm²,分别比基体提高了49.47%和66.21%。     

Influence of the crystallinity on the transport properties of polyethylene

Transport properties of dichloromethane were analysed in high- and low-density polyethylene films, obtained with different thermal treatments, in order to correlate sorption and diffusion with the crystallinity of the samples. The crystalline fraction of all the analysed samples was evaluated from density and X-ray data; it ranged from 40%–85%. From the X-ray diffractograms the reciprocal of the width at half-height for the strongest reflection was derived for all the samples; it was considered as an order parameter. It was found that the sorption depends only on the fraction of amorphous phase; in fact, the specific sorption, normalized for the crystallinity of the sample, is constant for all the samples. However, the zero concentration diffusion coefficient,D ₀, varies with the sample crystallinity, but there is no simple correlation between these two parameters; rather a transition seems to separate two ranges in which the diffusion coefficient decreases with the crystallinity. At variance, a linear decrease of the diffusion parameter with the order parameter, derived from the X-ray diffractograms, was found in the whole range of crystallinity.     

聚醚醚酮及其共混物的研究EI

综述了高性能树脂聚醚醚酮及其共混物的研究现状，讨论了聚醚醚酮的形态结构、结晶和熔融双峰行为及力学性能的研究，指出了共混物的分子结构对相容性、形态结构及力学性能的影响，说明共混使所得高分子材料的性能更多样化。     

Annealing study of poly(etheretherketone)

Annealing of poly(etheretherketone), PEEK, has been studied for two materials cold crystallized from the rubbery amorphous state. The first material is a low molecular weight PEEK synthesized in our laboratory; the second is commercially available neat resin. Differential scanning calorimetry was used to monitor the melting behaviour of annealed samples. The effect of thermal history on melting behaviour is very complex and depends upon annealing temperature, residence time at the annealing temperature, and subsequent scanning rate. Thermal stability of both materials is improved by annealing, and for an annealing temperature near the melting point, the polymer can be stabilized against reorganization during the scan. Variations of density, degree of crystallinity, and X-ray long period were studied as a function of annealing temperature for the commercial material. Wide angle X-ray scattering was used to study the structure of annealed PEEK. An additional scattering peak was observed at higher d-spacing when annealed samples were cooled quickly.     

Solvent induced crystallization in poly(aryl-ether-ether-ketone)

Sorptions of methylene chloride and methylene chloride/n-heptane liquid solutions in poly(aryl-ether-ether-ketone) (PEEK) are analysed and interpreted assuming multiple transport mechanisms. The presence of the highly interacting methylene chloride is responsible for anomalous sorption behaviours. PEEK films immersed in methylene chloride poor n-heptane solutions sorb by non-ideal Fickian diffusion, while limiting Case II and diffusion controlled swelling accompany equilibration in progressively richer methylene chloride solutions. The optical microscopy observation of cryogenically fractured samples conditioned in pure liquid methylene chloride at 5, 20 and 36 ° C for different times, revealed the presence of a sharp moving front. Differential scanning calorimetry (DSC) indicates that the glass transition temperature of the penetrated shells was always lower than the treatment temperature. The high levels of solvent swelling and plasticization were probably responsible for the crystallinity detected in DSC thermograms and wide angle X-ray scattering (WAXS) diffractograms of the solvent treated and initially amorphous samples. The differences of WAXS diffractograms of samples crystallized by immersion in methylene chloride at 5 and 36 ° C for various times and by thermal treatment are discussed. Increasing levels of crystallinity were induced in the samples equilibrated in progressively richer methylene chloride solutions.