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.     

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 effects of solvent sorption on the properties of poly(ether ether ketone)

A study has been carried out on the sorption of ortho-dichlorobenzene, N,N-dimethylformamide and water by poly(ether ether ketone) (PEEK). Two types of PEEK samples have been analysed; the first in the amorphous state and the second with a high crystallinity level. The sorption and desorption curves have been determined and the effect of the solvent presence on the mechanical properties has been analysed by means of the tensile test. PEEK is affected to a different extent by the solvents studied and also by the crystallinity of the polymer. Sorption takes place only in the case of amorphous PEEK. Its effect on the mechanical properties of PEEK is explained on the basis of the two concomitant processes that are the consequence of sorption, these are: plasticization and induced crystallization.     

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。     

Carbon-nanofibre-reinforced poly(ether ether ketone) fibres

Nano-reinforced fibres were spun from a semicrystalline high-performance poly(ether ether ketone) containing up to 10 wt% vapour-grown carbon nanofibres using conventional polymer processing equipment. Mechanical tensile testing revealed increases in nanocomposite stiffness, yield stress, and fracture strength for both as-spun and heat-treated fibres. X-ray and differential scanning calorimetry analyses were performed in order to investigate both the orientation of nanofibres within the polymer matrix and the matrix morphology. The carbon nanofibres were found to be well aligned with the direction of flow during processing. Significantly, the degree of crystallinity of the poly(ether ether ketone) matrix was found to increase with the initial addition of nanofibres although the crystal structure was not affected. The measured increase in composite tensile modulus is compared to injection-moulded nanocomposite samples made from the same blends. The results highlight the need to characterise the matrix morphology when evaluating nanocomposite performance and hence deducing the intrinsic properties of the nanoscale reinforcement.     

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%。     

Poly(ether ether ketone) with pendent methyl groups as a toughening agent for amine cured DGEBA epoxy resin

A diglycidyl ether of bisphenol-A (DGEBA) epoxy resin was modified with poly(ether ether ketone) with pendent methyl groups (PEEKM). PEEKM was synthesised from methyl hydroquinone and 4,4′-difluorobenzophenone and characterised. Blends of epoxy resin and PEEKM were prepared by melt blending. The blends were transparent in the uncured state and gave single composition dependent T _g. The T _g-composition behaviour of the uncured blends has been studied using Gordon–Taylor, Kelley–Bueche and Fox equations. The scanning electron micrographs of extracted fracture surfaces revealed that reaction induced phase separation occurred in the blends. Cocontinuous morphology was obtained in blends containing 15 phr PEEKM. Two glass transition peaks corresponding to epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum of the blends. The crosslink density of the blends calculated from dynamic mechanical analysis was less than that of unmodified epoxy resin. The tensile strength, flexural strength and modulus were comparable to that of the unmodified epoxy resin. It was found from fracture toughness measurements that PEEKM is an effective toughener for DDS cured epoxy resin. Fifteen phr PEEKM having cocontinuous morphology exhibited maximum increase in fracture toughness. The increase in fracture toughness was due to crack path deflection, crack pinning, crack bridging by dispersed PEEKM and local plastic deformation of the matrix. The exceptional increase in fracture toughness of 15 phr blend was attributed to the cocontinuous morphology of the blend. Finally it was observed that the thermal stability of epoxy resin was not affected by the addition of PEEKM.     

Miscibility, Thermal Stability, Rheological and Mechanical Properties of Blends Derived from Polysulfone Oligomer and Poly (phthalazinone ether sulfone ketone)

Poly (phthalazinone ether sulfone ketone) (PPESK) was melt blended with bisphenol-A polysulfone oligomer (O-PSF) to produce a thermoplastic polymer blends. The miscibility, thermal stability, rheological and mechanical properties of the blends were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and capillary rheometry. The blends showed single Tg over the composition range and possess homogeneous microstructure. The addition of O-PSF slightly affected the thermal properties of the blends. PSF oligomer, as a processing aid, could markedly improve the processability of the PPESK. In addition, the mechanical properties of the blends were increased, to some degree, by adding O-PSF.     

Synthesis and characterization of poly(ether sulfone ether ketone ketone) grafted poly(sulfopropyl methacrylate) for proton exchange membranes via atom transfer radical polymerization

A series of copolymers of poly(ether sulfone ether ketone ketone) grafted poly(sulfopropyl methacrylate) (PESEKK-g-PSPMA) were successfully synthesized by atom transfer radical polymerization (ATRP) of sulfopropyl methacrylate (SPMA) after chloromethylation of poly(ether sulfone ether ketone ketone) (PESEKK) backbone. The structure of the chloromethyl PESEKK and the copolymers were carefully investigated. Variation of the polymerization time leads to the formation of copolymers with different degree of sulfonation (DS). The properties of the proton exchange membranes such as water uptake, ion exchange capacity, proton conductivity, and methanol permeability are studied with compared to those of Nafion 117 membranes and could be modulated simply by control of the ATRP time. The copolymers exhibited much lower methanol permeability and higher proton conductivity as compared with Nafion 117.     

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%。     

新型杂萘联苯聚芳醚腈(酮)耐高温绝缘漆的研制

系统地研究了杂萘联苯PPEN（K）聚合物在绝缘漆领域的应用,考察了PPENK中腈、酮含量对绝缘漆性能的影响,发现当N／K=1／1时,绝缘漆具有优异的机械性能;对比了PPENK、PPENKK、PPEN和PPEN—BPA几种聚合物所制备的绝缘漆的性能,认为以PPENK树脂为主要成膜物制得的绝缘漆综合性能最优;在此基础上,选择适当的涂线工艺,成功地研制出了新型PPENK漆包线,其机械性能、电性能和热性能都远远高于220级聚酰亚胺漆包线国家标准要求。     

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.     

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.     

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.     

Structure and properties of injection molded blends of poly(ether imide) and a thermotropic copolyester

The phase structure and mechanical properties of blends composed of poly(ether imide) and a thermotropic liquid-crystalline copolyester, Rodrun LC-5000, processed by injection molding were studied in the PEI-rich region. The addition of Rodrun to PEI produces fully immiscible blends and strongly improves the processability of PEI. Injection molding gave rise in very poor LCP blends to fine dispersed phases; in the rest of compositions it gave rise to coarse structures. This was probably due to the very large viscosity difference between the components of the blends. An increase in the melt temperature led to a smaller viscosity difference and as a consequence dispersed phase dispersion improved. The Young's modulus clearly increased with the Rodrun content. The tensile strength was maintained up to a LCP content of 5% but decreased at higher contents because of the coarse morphologies obtained. The overall mechanical behavior was a main consequence of the lack of fibrillation and of the LCP dispersion level in the matrix.     

Preparation and characterization of poly(ether ether ketone)/poly(ether imide) [PEEK/PEI] blends for fused filament fabrication

Journal of Materials Science - The present study focuses on the preparation and characterization of a poly(ether ether ketone)/poly(ether imide) [PEEK/PEI] blend for application in additive...     

Preparation of nanosilver particles into sulfonated poly(ether ether ketone) (S-PEEK) nanostructures by electrospinning

By using the interaction between the sulfonated groups and silver ions, nanosilver particles were successfully introduced into S-PEEK nanostructures (nanospheres and nanofibers) by electrospinning. The nanoparticles were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectra (XPS), UV/vis, etc. The size of the spheres increases with the weight concentration of silver exchanged sulfonated poly(ether ether ketone) (S-PEEK-Ag) increasing. The size of the silver particles can be controlled by adjusting the sulfonated degree (number of sulfonate groups per repeating unit) of sulfonated poly(ether ether ketone) (S-PEEK) and the weight ratio of the S-PEEK solutions. This paper provides a new method for the preparation of nanometal particles into nanostructures.     

Carbon-nanofibre-reinforced poly(ether ether ketone) composites

Poly(ether ether ketone) nanocomposites containing vapour-grown carbon nanofibres (CNF) were produced using standard polymer processing techniques. Evaluation of the mechanical composite properties revealed a linear increase in tensile stiffness and strength with nanofibre loading fractions up to 15 wt% while matrix ductility was maintained up to 10 wt%. Electron microscopy confirmed the homogeneous dispersion and alignment of nanofibres. An interpretation of the composite performance by short-fibre theory resulted in rather low intrinsic stiffness properties of the vapour-grown CNF. Differential scanning calorimetry showed that an interaction between matrix and the nanoscale filler could occur during processing. Such changes in polymer morphology due to the presence of a nanoscale filler need to be considered when evaluating the mechanical properties of such nanocomposites.