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.     

Fe3O4-碳纳米管/聚偏氟乙烯复合材料的制备与性能

通过在碳纳米管（CNTs）表面进行功能化修饰,改善CNTs与聚偏氟乙烯（Polyvinylidene Fluoride,PVDF）的分散性及界面结合程度,从而获得优异的力学性能和电学性能,提高其在传感器、致动器和储能方面的应用性能。采用原位水热合成法,在CNTs表面修饰磁性Fe₃O₄纳米粒子,然后将Fe₃O₄-CNTs加入PVDF中,采用流延工艺制备出Fe₃O₄-CNTs/PVDF复合薄膜。采用SEM、TEM、XRD和DSC研究了Fe₃O₄-CNTs/PVDF复合薄膜的结构和结晶行为,采用动态力学分析（DMA）、宽带介电谱测试系统和交流击穿场强测试系统研究了Fe₃O₄-CNTs对复合材料力学性能、介电性能及击穿场强的影响。结果表明：Fe₃O₄-CNTs的引入促使PVDF形成了β晶相,同时抑制了Fe₃O₄-CNTs/PVDF复合材料结晶度的下降;提高了弹性模量,抑制了阻尼特性下降;提高了介电常数和击穿场强,抑制了介电损耗升高。     

The influence of heat treatment and finishing on the mechanical and dielectric properties of glass fabric-epoxy resin laminar composites

The aim of this investigation was to define the optimum conditions of obtaining glass fabric-epoxy resin laminar composites with mechanical and dielectric properties that satisfy the quality needed for production of printed circuit boards for microelectronics. Commercial materials: glass woven fabric, different types of silane finish and epoxy resin were the starting materials in obtaining composites. The conditions needed for the thermal removal of the original size from glass fabric were investigated. The optimal heat treatment should be performed at temperatures less than 550 °C, while cooling rates should be as low as possible. In this manner, the fabric has less than 0.1% of residual size, and the mechanical properties remain satisfactory. Different types of adhesion promoters based on silanes were applied on heat-treated glass fabric as finishes. The quality of the composite material made of thermally and chemically treated glass fabric and epoxy resin was controled by measuring the tensile and dielectric strength of the composite. Depending on which properties of composite are of primary concern, mechanical or dielectric, a finish with an amino functional group and lower heat-treatment temperature or epoxy-modified coatings and higher heat-treatment temperature should be used for obtaining glass-fabric epoxy resin laminar composites.     

Date palm wood flour/glass fibre reinforced hybrid composites of recycled polypropylene: Mechanical and thermal properties

Recycled polypropylene (RPP) based hybrid composites of date palm wood flour/glass fibre were prepared by different weight ratios of the two reinforcements. Mixing process was carried out in an extruder and samples were prepared by injection molding machine. Recycled PP properties were improved by reinforcing it by wood flour. The tensile strength and Young’s modulus of wood flour reinforced RPP increased further by adding glass fibre. Glass fibre reinforced composites showed higher hardness than other composites. Morphological studies indicated that glass fiber has good adhesion with recycled PP supporting the improvement of the mechanical properties of hybrid composites with glass fiber addition. Addition of as little 5 wt% glass fibre to wood flour reinforced RPP increases the tensile strength by about 18% relative to the wood flour reinforcement alone. An increase in wood particle content in the PP resulted in a decrease in the degree of crystallinity of the polymer. The tensile strength of the composites increased with an increase in the percentage of crystallinity when adding the glass fibre. The improvement in the mechanical properties with the increase in crystallinity percentage (and with the decrease of the lamellar thicknesses) can be attributed to the constrained region between the lamellae because the agglomeration is absent in this case.     

Fabrication and mechanical properties of glass fibre reinforced thermoplastic elastomer composite

The paper investigates the effects of fabrication conditions on mechanical properties of glass fibre reinforced thermoplastic elastomer composites. The impregnation time was varied between 5 and 30 min and the cooling conditions were rapid and gradual cooling. Tensile testing was carried out on samples with different fibre orientations. Double Cantilever Beam (DCB) tests were carried out to evaluate the fracture toughness of the composites. The degree of crystallinity and morphology of the composite were studied by using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Impregnation of matrix resin into glass fibre was found to be complete before 30 min and tensile properties increased with increasing impregnation time. SEM micrographs of fractured surfaces revealed poor adhesion between the matrix and the reinforcing agent. Due to the flexible nature of the composite, the fracture toughness (G_IC) could not be determined because of the formation of ridges on the surface.     

玻璃纤维增强HDPE的性能及界面研究

通过扫描电镜观察、红外光谱分析及材料力学性能试验等方法考察了不同界面粘结形式下玻璃纤维增强HDPE的力学性能及其与界面粘结性的关系。结果表明,复合过程中加入的界面反应性试剂及其与HDPE接枝而形成的接枝物可与玻纤表面及其硅烷发生化学作用或交(?),从而显著提高复合材料的界面粘结强度及其力学性能。     

玻璃纤维增强PP性能、界面及基体晶态研究

本文通过扫描电镜、红外光谱、偏光显微、DSC分析和材料力学性能试验等方法考察了PP/玻纤的界面粘结性与其材料性能及基体结晶的关系.结果表明:在材料复合过程中加入的界面反应性试剂及其与PP接枝而形成的接枝物可与玻纤表面及其硅烷发生化学作用,促使玻纤表面树脂包覆层的形成,从而显着提高复合材料的界面粘结强度及其力学性能;复合材料试样成型过程中,因树脂冷却收缩而产生的界面应力可应变诱导玻纤周围基体树脂的结晶,促使其结晶形态和结晶度产生显着变化;而复合材料的界面粘结强度则是产生应变诱导作用和控制异相结晶的关键.     

SiO2/聚（3-羟基丁酸酯-co-4-羟基丁酸酯）薄膜研究

目的研究纳米SiO2对可生物降解聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P34HB)包装膜结晶行为和力学性能的影响。方法采用溶液浇铸法制备SiO_2/P34HB纳米复合薄膜,利用红外光谱仪(FTIR)、扫描电镜(SEM)、正置热台显微镜(POM)、差示扫描量热仪(DSC)和万能力学试验机等研究纳米SiO_2对P34HB结构、结晶性和力学性能等的影响。结果纳米SiO_2在P34HB中起到异相成核的作用,SiO2/P34HB复合膜的结晶速率和结晶度得到明显改善。相比P34HB包装膜,当纳米SiO_2质量分数为2%时,SiO_2/P34HB复合膜的弹性模量和拉伸强度分别提高了72.7%和60.9%。结论获得了纳米SiO2改善可生物降解聚(3-羟基丁酸酯-co-4-羟基丁酸酯)包装膜结晶度和力学性能的最佳掺杂比例参数。     

Oxygen-ion-assisted deposition of thin gold films

Thin gold films have been deposited on glass and silicon substrates using ion-assisted deposition techniques. The adhesion of the films to the substrates is assessed by a scratch test. Deposition assisted by 100 eV-1 keV oxygen ions yields highly adhesive films that can only be removed by damaging the substrate. Argon and hydrogen ions produce films with relatively poor adhesion. The results show that the reflectance of oxygen-assisted films is reduced by trapping of the oxygen in the gold but no bulk chemical or structural changes are detected. It is proposed that a thin stable layer of gold oxide is formed during film growth and diffuses into the substrate, providing a strong bond for subsequent film deposition. Highly adhesive films with bulk optical properties are deposited on glass and silicon using oxygen-ion assistance only to the point of continuous film formation.     

Abrasion of thin films deposited onto glass by the Taber test

The mechanism of abrasion of sputtered metal nitride thin films on glass by the Taber abrasion test and the effects of mechanical and tribological properties of thin films on Taber abrasion were investigated. The abrasion occurred in a peeling mode: the film was peeled off the substrate and the peeled area increased with increasing number of Taber abrading cycles. The peel rate per Taber cycle, a quantitative measure to represent the abrasion resistance of the thin films, was small in the film with greater adhesion strength, higher hardness and lower frictional resistance of the surface. The effect of these properties on the peel rate was represented with a mathematical equation of exponential form. The peel rate was found to vary most sensitively with the hardness.     

Mechanical properties of SiNxCx ceramic films prepared by plasma CVD

The mechanical properties of Si₃N₄-SiC, SiN_x and SiC_y films prepared at a low temperature of 400 °C by plasma chemical vapour deposition are reported. Microhardness, internal stress of the film and adhesive strength between the film and glass or stainless steel substrate were evaluated as principal mechanical properties. Microhardness was measured to be about 10 to 20 G Pa dependent on the film composition in each system. Internal stress of the films on borosilicate glass substrates extensively varied from tensile to compressive with the film composition change from Si₃N₄ to SiC. Adhesive strength, as ascertained by the scratch test, was about 580 to 800 MPa for crown glass substrates, and about 210 to 310 M Pa for 316 stainless steel substrates. It is pointed out that tensile stress in these films brought about more abrupt decreases of the adhesive strength than did compressive stress.     

Interface enhancement of glass fiber reinforced vinyl ester composites with flame-synthesized carbon nanotubes and its enhancing mechanism

Interface enhancement with carbon nanotubes (CNTs) provides a promising approach for improving shock strength and toughness of glass fiber reinforced plastic (GFRP) composites. The effects of incorporating flame-synthesized CNTs (F-CNTs) into GFRP were studied, including on hand lay-up preparation, microstructural characterization, mechanical properties, fracture morphologies, and theoretical calculation. The experimental results showed that: (1) the impact strength of the GFRP modified by F-CNTs increased by more than 15% over that of the GFRP modified by CNTs from chemical vapor deposition; and (2) with the F-CNT enhancement, no interfacial debonding was observed at the interface between the fiber and resin matrix on the GFRP fracture surface, which indicated strong adhesive strength between them. The theoretical calculation revealed that the intrinsic characteristics of the F-CNTs, including lower crystallinity with a large number of defects and chemical functional groups on the surface, promoted their surface activity and dispersibility at the interface, which improved the interfacial bond strength of GFRP.     

Cooling rate influences in carbon fibre/PEEK composites. Part II: interlaminar fracture toughness

A study has been made of the effect of cooling rate on interlaminar fracture toughness of unidirectional carbon fibre–polyetheretherketone (PEEK) matrix composites. It is shown that the propagation values of both mode I and II propagation interlaminar fracture toughness increased with increasing cooling rate towards a saturation level for the range of cooling rate studied. The cooling rate dependency of the composite interlaminar fracture toughness is the result of complex interactions between two important properties, namely the matrix ductility and fibre–matrix interface bond strength. These two properties varied totally in an opposite manner against cooling rate through its effect on crystallinity: matrix ductility varied directly proportional to cooling rate while the converse is true for interface bond strength. The extent of plastic deformation of PEEK matrix contributed a predominant part to composite toughness, while an adequate interface bond is required to allow matrix deformation to take place to a full degree. A practical implication is that these two properties need to be optimised using an appropriate cooling rate to produce composites possessing high interlaminar fracture resistance.     

Preparation and dielectric properties of surface modified TiO2/PEN composite films with high thermal stability and flexibility

A series of surface modified titanium dioxide (TiO₂)/polyarylene ether nitriles (PEN) composite films with different modified TiO₂ contents were prepared by solution casting method combined with ultrasonic dispersion technology. TiO₂ particles were successfully surface modified by PEN–COOH polymer previously, which was confirmed by transmission electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. Besides, SEM images of composite films revealed that the interfacial adhesion between surface modified TiO₂ particles and the PEN matrix was effectively improved because of their common cyano groups and similar structure units. Furthermore, thermal, mechanical and dielectric characterizations showed that the composite films possess excellent thermal properties and flexibility as well as good dielectric properties, their glass transition temperatures were as high as 223?°C and the initial decomposition temperatures were all above 480?°C. In addition, it was found that the tensile strength of modified TiO₂/PEN composites was better than raw TiO₂/PEN composites. More importantly, the dielectric constant of composite films increases linearly with increment of the surface modified TiO₂ particles content. When the mass fraction of modified TiO₂ particles reached 40?%, the dielectric constant of the composite film increased to 7.9 (1?kHz), while the dielectric loss is just 0.028 (1?kHz).     

Molecular dynamics study of adhesion strength and diffusion at interfaces between interconnect materials and underlay materials

A molecular-dynamics technique for determining the adhesion strength and analyzing diffusion at interfaces between different materials has been developed. The adhesion strength is determined by calculating the adhesive fracture energy defined as the difference between the total potential energy of the material-connected state and that of the material-separated state. This technique is used to determine the adhesion strength and analyze diffusion at the interfaces between Cu films and high-melting-point materials that are used as underlay materials for Cu interconnects in ULSIs. The adhesive fracture energy shows that the adhesion strength of the Cu/Ru and Cu/Ir interfaces is much higher than that of the Cu/W, Cu/TiN, and Cu/Ta interfaces. Because the diffusion of Cu atoms at the Cu/Ru and Cu/Ir interfaces is suppressed, the surface smoothness of Cu films on Ru and Ir is much better than that on W, TiN, and Ta. It is also found that adhesion strength and smoothness increase with decreasing lattice mismatch between Cu and the underlay material. These results are confirmed by SEM (scanning electron microscope) and scratch testing. Received 27 October 1999     

新型聚乙烯防滑包装材料的制备及其性能研究

以聚乙烯包装薄膜为基材、乙烯-醋酸乙烯酯(EVA)热熔胶为防滑涂层,经热喷涂和后期热处理,制备得到EVA喷涂PE防滑包装材料(E-S-PE)与热处理后EVA喷涂PE防滑包装材料(HE-S-PE)。通过扫描电镜、摩擦因数/剥离实验仪、智能电子拉力试验机进行表征,研究了喷涂定量和后续热处理工艺对材料防滑性能、黏结强度和力学性能的影响,并确定其最优喷涂定量。结果表明:E-S-PE与HE-S-PE的摩擦因数均随EVA喷涂定量的增加先增大后稳定,喷涂定量分别为40 g/m~2和70 g/m~2时,其摩擦因数较大,但其力学性能均随喷涂定量增大而整体下降,且HE-SPE的力学性能较E-S-PE的下降更明显。因此,确定该防滑材料EVA的最优喷涂定量为40 g/m~2。     

冷却方式对MMT/LDPE介电性能的影响

采用熔融插层法制备了蒙脱土/低密度聚乙烯(MMT/LDPE)纳米复合材料, 探讨空气自然冷却、空气快速冷却、水冷却和油冷却四种制备工艺对复合材料介电性能的影响。利用XRD、FTIR、AFM、PLM、DSC和TSC等分别对复合材料和纳米MMT粒子的微观形态、复合材料的电导、击穿、介电频谱和空间电荷特性进行表征。结果表明, 经表面修饰的纳米MMT粒子在基体聚合物中已经剥离并均匀分散; 不同冷却方式对复合材料的结晶度有一定的影响, 其中油冷却试样结晶速率最高, 结晶尺寸最小; 纳米MMT的加入使复合材料内部陷阱密度和深度均有所增加, 且试样的介电性能有不同程度的改善。油冷却试样抑制空间电荷的作用比较明显, 在20和40 kV/mm的场强下, 试样中正电荷的峰值与空气自然冷却试样相比分别下降了63.57%和51.39%; 且油冷却试样的电导率最小, 击穿场强值最大; 在1~10⁵ Hz的测试频率范围内, 与空气自然冷却试样相比, 其他三种试样的介电常数和介质损耗角正切值都有不同程度的降低。     

Effect of molecular weight and testing rate on adhesion property of pressure-sensitive adhesives prepared from epoxidized natural rubber

The dependence of peel strength and shear strength of epoxidized natural rubber (ENR 25)-based pressure-sensitive adhesive on molecular weight and rate of testing was investigated using coumarone-indene as the tackifying resin. Toluene and polyethylene terephthalate (PET) were used as the solvent and substrate respectively throughout the study. A SHEEN hand coater was used to coat the adhesive on the substrate at a coating thickness of 120 μm. All the adhesion properties were determined by a Llyod Adhesion Tester operating at different rates of testing. Result shows that peel strength and shear strength increases up to an optimum molecular weight of 6.5 × 10⁴ of ENR 25. For peel strength, the observation is attributed to the combined effects of wettability and mechanical strength of rubber at the optimum molecular weight, whereas for the shear strength, it is ascribed to the increasing amount of adhesive present in the coating layer which enhances the shear resistance of the adhesive. Peel strength and shear strength also increases with increase in rate of testing, an observation which is associated to the viscoeslastic response of the adhesive. Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) study confirms the miscibility of tackifier and the ENR 25.     

航空用Al-Li合金阳极氧化对粘接性能的影响

为研究Al-Li合金不同粘接工艺对粘接性能的影响,对其进行了磷酸阳极化处理,并选用不同的胶黏剂来考察Al-Li合金粘接副的拉剪强度。结果表明,阳极化处理使Al-Li合金试片表面产生了微观粗糙的多孔膜,实现了粘接界面上良好的机械啮合。经阳极化处理后,Al-Li合金粘接性能显著提高,当粘接副采用Lord 320/322胶粘接时拉剪强度提高了49%,当粘接副采用FM94胶粘接时拉剪强度提高了167%,破坏模式多为内聚破坏。     

Physical properties of low-<Emphasis Type="Italic">k</Emphasis> films based on the co-condensation of methyltrimethoxysilane with a bridged silsesquioxane

Though spin-on organosilicates are considered as the promising candidates of low dielectric constant materials, it is necessary for a successful integration to improve mechanical strength such as modulus and fracture toughness. In this study, five sets of MTMS–BTMSE copolymers were synthesized and characterized while the monomer content of BTMSE (bis(trimethoxysilyl)ethane) was varied from 9.1 to 47.3 mol% vs. MTMS (methyltrimethoxysilane). In parallel with the measurement of dielectric constant, four different tests were carried out to evaluate mechanical properties of the MTMS–BTMSE copolymers. Modulus was measured by the nanoindentation technique and the modified edge lift-off test (MELT) was employed to extract adhesive fracture toughness quantitatively. In addition, residual stress was calculated by sensing the change in radius of curvature of the substrate. The chemical structure of the copolymers was also analyzed with FTIR and NMR. Network formation was enhanced as the amount of BTMSE increased, which led to improvement of modulus and the increase in refractive index and dielectric constant. However, an increasing rate of fracture toughness by the MELT was not proportional to the increase in the amount of BTMSE, which implied that it was necessary to optimize the composition of the copolymers since adhesion strength was conjectured the most critical factor for a successful integration.