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。     

PEEK/CF复合材料中PEEK结晶行为研究进展

对聚醚醚酮（PEEK）/碳纤维（CF）复合材料界面结晶研究现状进行综述,分析PEEK在复合过程中的结晶形态演变,总结影响PEEK在CF表面形成横晶结构的关键因素。PEEK横晶结构的生成与CF和PEEK的微观结构匹配性、导热性能匹配性,以及复合材料的热处理条件密切相关。诱导PEEK在CF表面形成横晶结构有助于提高二者的界面结合强度,进而提升复合材料的拉伸强度和杨氏模量。     

碳纤维和纳米氮化硼增强聚醚醚酮/聚四氟乙烯复合材料的摩擦学性能研究

以碳纤维（CF）为增强相，添加不同含量的纳米氮化硼（h-BN），通过注塑成型的方式，制备了聚醚醚酮/聚四氟乙烯（PEEK/PTFE）复合材料样条，使用力学试验机进行拉伸试验，利用摩擦试验机进行表面摩擦试验，并利用白光仪对磨痕数据和三维形貌进行观测，使用SEM对磨痕进行观测与分析。结果表明：随着h-BN含量的增加，PEEK/PTFE复合材料样条最大应力先增加后减小；当h-BN含量分别为3%、6%时，PEEK/PTFE复合材料样条的最大应力分别为174 MPa、165 MPa。与PEEK/PTFE相比，单独添加CF的样品摩擦系数降至0.23。同时添加CF、h-BN时，复合材料样条的摩擦系数均降低；h-BN含量分别为3%、6%时，复合材料样条的摩擦系数分别为0.06、0.09。随着h-BN含量的升高，PEEK/PTFE/CF/h-BN复合材料的磨损率先降低后升高。h-BN含量为3%时，复合材料样条的磨损率最低。     

CF增强PEEK/Cu复合材料的制备与性能

采用模压法制备碳纤维(CF)增强聚醚醚酮(PEEK)/Cu复合材料,研究了CF等离子处理时间、CF用量和热处理工艺对PEEK/Cu/CF复合材料力学性能的影响。结果表明:随着未处理CF用量增加,PEEK/Cu/CF复合材料的力学性能逐渐下降;当CF等离子处理时间小于等于4 min时,PEEK/Cu/CF复合材料的拉伸强度和冲击强度随处理时间增加而提高;等离子处理4 min,随CF用量的增加,PEEK/Cu/CF复合材料的拉伸强度提高,但其冲击强度下降。与未处理的复合材料相比,热处理Ⅱ和Ⅲ这2种处理工艺的复合材料结晶度和熔点均提高,且热处理Ⅲ的提高幅度大于热处理Ⅱ的。     

聚醚醚酮及其复合材料的特性与应用研究进展

介绍聚醚醚酮（PEEK）的发展概况，综述PEEK及其复合材料的物理力学性能、改性技术和成型工艺，着重评述PEEK的摩擦学特性及其耐磨机理，展望PEEK及其复合材料在机械、石油、化工等领域的应用前景。     

TLCP/GF混杂增强聚醚砜酮复合材料的研究

用热致性液晶聚合物(TLCP)和玻璃纤维(GF)对二氮杂萘酮联苯结构聚醚砜酮(PPESK)进行混杂增强改性,用双螺杆挤出机通过熔融共混的方式制备了改性PPESK复合材料。研究了PPESK/TLCP、PPESK/TLCP/GF复合材料的加工性能和力学性能,并对复合材料的拉伸断面形貌进行观察。结果表明,随着TLCP用量的增加,熔体的粘度逐渐降低,加工流动性得到改善;TLCP/GF的混杂增强使PPESK复合材料的拉伸强度得到一定提高,冲击强度有所降低;TLCP用量小于10份时,TLCP以球状粒子或棒状形式存在,当TLCP用量为20份时,TLCP在材料中形成直径为亚微米数量级的高长径比微纤。     

UP/GF/TLCP原位混杂复合材料的性能研究

采用自行合成的双键液晶聚合物（TLCP），通过原位复合的方法制备了不饱和聚酯（UP）／玻璃纤维（GF）／TLCP原位混杂复合材料。研究了TLCP用量对UP／GF／TLCP复合材料的磨损性能、流变性能和材料表面电阻和体积电阻的影响。结果表明，TLCP用量对材料的流变性能、磨损性能和吸水性能有较大影响，当加入质量分数为5％的TLCP时，材料的流动性能最好，熔体体积流动速率达到0．097cm^3／s；当TLCP质量分数为7．5％时，材料的磨损量比未加TLCP的材料减少50％；随着TLCP用量的增加，材料的吸水性降低；TLCP用量对材料电性能影响不大。     

碳纤维增强聚醚醚酮的非等温结晶行为与力学性能

利用聚酰亚胺(PI)作为碳纤维(CF)界面改性剂,制备了界面改性碳纤维增强聚醚醚酮(MCF/PEEK)复合材料。采用差示扫描量热仪(DSC)讨论了CF及其界面改性对PEEK非等温结晶行为的影响机制与作用规律,并基于莫志深法研究了MCF/PEEK的非等温结晶动力学;借助DSC和小角X射线散射仪(SAXS)表征不同降温速率下PEEK基体的结晶结构,采用万能试验机评价了MCF/PEEK的力学性能。结果发现:CF对PEEK的结晶有较为明显的异相成核促进作用,经过PI界面改性之后成核作用有所下降,但结晶行为仍较纯PEEK更容易发生,整体结晶速率更快;随冷却速率的增大,基体结晶度、片晶厚度与长周期均减小,MCF/PEEK的拉伸强度与模量也显著减小,层间断裂韧性提高。     

CF表面改性对CF/LDPE复合材料电磁屏蔽性的影响

将碳纤维（CF）用马弗炉煅烧后,用硝酸对其进行酸化氧化,再用硅烷偶联剂KH550对其进行偶联处理,然后用熔融混合法将偶联后的CF与LDPE复合,制备出CF／LDPE复合材料。研究了CF的表面改性对CF／LDPE复合材料电磁屏蔽性能的影响。用SEM和FTIR分析了复合材料的内部微观结构,用四电极法测量了复合材料的体积电阻率（ρv）,用法兰同轴法测定了复合材料的电磁屏蔽效能（SE）。研究发现三种CF／LDPE复合材料的ρv随CF质量分数（p）的增加出现“渗滤现象”,在相同CF质量分数时,经表面处理的复合材料的渗滤阈值最低;当CF质量分数为10％时,SE值最高,能达到45dB。     

激光原位铺放CF增强PEEK基复合材料工艺研究

通过激光原位铺放制备了CF增强PEEK基(CF/PEEK)复合材料,采用差示扫描量热法(DSC)与热重分析法(TGA)对CF/PEEK热性能进行了分析,利用扫描电子显微镜(SEM)表征CF/PEEK微观形貌,并研究了不同温度与铺放压力下CF/PEEK的力学性能。结果表明,激光原位铺放温度在400℃到420℃、铺放压力在220 N左右时,PEEK基体的流动性较好,CF/PEEK粘接牢固,成型的复合材料具有优异的力学性能。     

Application of raman microscopy to the analysis of high modulus polymer fibres and composites

Raman microscopy has been used to study the deformation of carbon fibres and an experimental grade carbon-fibre/PEEK composite prepreg. It has been found that the peak position of the Raman-active bands in the fibres are sensitive to the level of applied strain. Examination of the peak positions from the carbon fibres near the surface of the prepreg shows that the fibres are subjected to a residual compressive strain. The application of a tensile stress to the composite causes the fibre strain to become tensile although significant scatter is found in the measurements. The scatter is thought to be due to variations in the local carbon-fibre strain at the 1 μm level. It is demonstrated that residual compressive strain is expected from differential shrinkage between the fibres and matrix on cooling the composite from the processing temperature to room temperature.     

The effect of titanium surface treatment on the interfacial strength of titanium – Thermoplastic composite joints

Co-consolidated titanium – carbon fibre reinforced thermoplastic composite hybrid joints show potential for application in aerospace structures. The strength of the interface between the titanium and the thermoplastic composite is crucial for the strength of the entire hybrid joint. Application of a surface treatment on the titanium is an effective way to improve this interfacial strength. This paper evaluates the effect of several titanium surface treatments on the interfacial strength between titanium and carbon fibre reinforced polyetheretherketone (PEEK) or polyetherketoneketone (PEKK). Furthermore, the underlying bonding mechanisms, activated by these surface treatments, are studied. The research result shows that the grit blasted titanium – carbon fibre reinforced PEKK interface outperforms the other interfaces.     

The improved interface performance between carbon fiber and poly(ether-ether-ketone) by sulfonated polyether sulfone (s-PSF) sizing agent with different sulfonation degree

The effects of sulfonated polyether sulfone (s-PSF) with different sulfonation degrees on the interfacial properties of carbon fiber (CF)/poly(ether-ether-ketone) (PEEK) composites were investigated systematically. The performance of the modified CF and the corresponding CF/PEEK composites and was tested and characterized. Test results show that the CF surface polarity increases, the surface contact angle decreases, and the surface free energy increases with the increase in the s-PSF sulfonation degree. Scanning electron microscopy analysis shows that the increase in the sulfonation degree of s-PSF is beneficial to improve the interface between CF and PEEK. This condition can be ascribed to the hydrogen bonding force between the s-PSF sulfonic acid group and the polar functional group on the surface of the modified CF and the compatibility between s-PSF and PEEK. In terms of physical properties, the thermal and mechanical properties of CF/PEEK composite are improved with the increase in s-PSF sulfonation degree. The interlaminar shear strength, flexural strength, and modulus of CF/PEEK composites increase by 60.16%, 30.27%, and 19.30%, respectively.     

Improvement of carbon fiber/PEEK hybrid fabric composites using plasma treatment

A carbon fiber (CF)/polyetheretherketone (PEEK) composite was manufactured using hybrid fabrics composed of CF and PEEK fiber. The fiber/matrix interface was modified by low temperature oxygen plasma treatment. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Fourier transform attenuated total reflection infrared spectroscopy (FTIR-ATR) were used to relate the roughness and the functionality of the CF surface with the interfacial adhesion strength of the CF/PEEK composite. Scanning electron micrographs showed that plasma treatment increased the roughness of the CF surface up to 3 min of plasma treatment time; and prolonged treatment resulted in overall smoothing. XPS results confirmed that increasing treatment time marginally increased surface functionality: treatment for more than 5 min decreased the surface functionality by removing the active site of the CF surface. In addition, flexural strength and interlaminarshear strength (ILSS) of the CF/PEEK composite were measured. Their maximum values were observed at 3 min of plasma treatment time as a result of surface roughening by plasma etching. The SEM results were correlated with mechanical properties of the CF/PEEK composite.     

Instrumented thermoforming of advanced thermoplastic composites. III: Relative performance of various prepregs in forming double curvature parts

Thermoforming of a double curvature hemispherical cap-shaped part from different continuous carbon fiber-reinforced thermoplastic composite prepregs has been investigated. A novel three-piece matched die mold was used for shaping the prepregs directly from 16-ply unconsolidated lay-ups. For poly(ether ether ketone) (PEEK)-based prepregs, PEEK/graphite fiber unidirectional tapes and commingled knitted three-dimensional fabric yielded parts that possessed good shape conformity and were free of any major delamination. Encouraging results were also obtained for modified polysulfone (PXM-8505) based unidirectional fabric as well as PEEK/graphite knitted bidirectional fabrics. Several other prepregs performed rather poorly in forming acceptable quality parts. Fiber alignment was found to be better for fabric prepregs than unidirectional tapes. Both stretching and “draw in” of the material occur during deformation, even though the relative contribution depends strongly on the prepreg form. Our thermoforming studies suggest a cycle time of 10 min or less to form good quality parts, which is an attractive feature, considering that cycle times are typically several hours for conventional thermosetting resins.     

Preparation,properties and in vitro cellular response of multi-walled carbon nanotubes/bioactive glass/poly(etheretherketone) biocomposite for bone tissue engineering

Desired bone repair biomaterial must have good biocompatibility and suitable mechanical properties that are equivalent to those of human bones. In this study, multi-walled carbon nanotubes (MWCNTS) was designed to incorporate into bioactive glass/poly(etheretherketone) to fabricate a composite of multi-walled carbon nanotubes/bioactive glass/poly(etheretherketone) (MWCNTS/BG/PEEK) through a compounding and injection-molding process. The microstructures, mechanical properties, thermal stability and bioactivity of the ternary biocomposite, as well as preliminary cell responses of MC3T3-E1 osteoblast cells to this biomaterial, were investigated. The mechanical performance of ternary MWCNTS/BG/PEEK composite was vastly superior to binary BG/PEEK composite. More importantly, cell culture tests showed that cell adhesion, viability and differentiation of MC3T3-E1 cells were significantly promoted on the MWCNTS/BG/PEEK composite. Moreover, it was found that MWCNTS in composite further promoted cell metabolic vitality and osteogenic differentiation of osteoblast cells. Hence, this MWCNTS/BG/PEEK biomaterial may be used as a promising bone graft scaffold in dental and orthopedic applications.     

碳纤维增强PEEK复合材料的摩擦学性能研究

用磨损试验机对碳纤维增强聚醚醚酮（PEEK）复合材料进行室温干滑动磨损试验。考察了碳纤维的含量，石墨润滑剂，对靡时间及载荷对材料靡损量及摩擦系数的影响，并用电子显微镜对其磨损表面进行了观察与分析，同时对材料的磨损机理进行了探讨，研究结果表明，随着载荷的升高和对磨时间的延长，材料的摩擦系数逐渐降低并趋于稳定，磨损量呈上升趋势，加入碳纤维可以明显地降低材料的摩擦系数和磨损量，当碳纤维含量为5％－10％时复合材料的摩擦系数和磨损量最低；加入适量固体石墨可进一步降低复合材料的摩擦系数和磨损量。     

Low temperature growth of carbon nanotubes on carbon fibre to create a highly networked fuzzy fibre reinforced composite with superior electrical conductivity

We report a method for the growth of carbon nanotubes on carbon fibre using a low temperature growth technique which is infused using a standard industrial process, to create a fuzzy fibre composite with enhanced electrical characteristics. Conductivity tests reveal improvements of 510% in the out-of-plane and 330% in the in-plane direction for the nanocomposite compared to the reference composite. Further analysis of current–voltage (I–V) curves confirm a transformation in the electron transport mechanism from charge – hopping in the conventional material, to an Ohmic diffusive mechanism for the carbon nanotube modified composite. Single fibre tensile tests reveal a tensile performance decrease of only 9.7% after subjecting it to our low temperature carbon nanotube growth process, which is significantly smaller than previous reports. Our low-temperature growth process uses substrate water-cooling to maintain the bulk of the fibre material at lower temperatures, whilst the catalyst on the surface of the carbon fibre is at optimally higher temperatures required for carbon nanotube growth. The process is large-area production compatible with bulk-manufacturing of carbon fibre polymer composites.     

葡糖氧化酶修饰碳纤维电极

研究了碳纤维电极经预处理后与葡糖酶的偶联行为，电化学氧化处理碳纤维的最佳时间是２ｍｉｎ，此法制得的碳纤维葡糖酶修饰电极活性期可达２个月以上。