Surface Modification of Para-Aramid Fiber by Direct Fluorination and its Effect on the Interface of Aramid/Epoxy Composites

Surface modification of a para-aramid fiber (DAFIII) was performed by direct fluorination. The properties of treated and untreated fibers were characterized and compared in detail by mechanical testing, Fourier transform infrared (FTIR) spectroscopy characterization, X-ray photoelectron spectroscopy (XPS) analysis and static contact angle measurements. The results showed that little damage of the fiber occurred after direct fluorine treatment, and the content of polar groups on the fibers surfaces were increased significantly, which resulted in a lower value of contact angle. The interlaminar shear strength (ILSS) of DAFIII fiber/epoxy composites and the tensile strength of NOL-ring specimens increased by 33% and 12%, increasing to 56.2 MPa and 2340 MPa, respectively, which indicated that the interfacial adhesion between the matrix and the aramid fiber was improved significantly by the fluorination treatment. Further tests showed that the durability of the direct fluorination treatment on the aramid fiber was also satisfactory.     

Interfacial characterisation and mechanical properties of heat treated non-woven kenaf fibre and its reinforced composites

This paper reports on the comprehensive characterisation of heat treated kenaf fibre (KF) and its composites. The kenaf fibres were modified by heating for 2.5–12.5 h inside a drying oven. Heat treatment produces an increase in the crystallinity index and fibre strength of KF. The highest value of KF strength was recorded by applying heat treatment of 10 h on KF. The heat treatment results in the partial removal of impurities/extractives on the KF surface which is detected by scanning electron microscopy and X-ray photoelectron spectroscopy. Atomic force microscopy results signify the decrease of roughness, the increase in peak area density and the increase of the adhesion force on the surface area of heat treated KF. The effect of the heat treatment in enhancing the interface bonding characteristics between the KF and unsaturated polyester matrix can be reflected by the interlaminar shear strength (ILSS) and dynamic mechanical analysis value of the composites. The flexural properties of the composites showed a similar trend to ILSS. However, the fracture toughness revealed contrasting results. Water absorption induced a drastic loss of the mechanical properties of the composites albeit better retention of properties was observed in the case of heat-treated KF composites.     

Improvement of aramid fiber III reinforced bismaleimide composite interfacial adhesion by oxygen plasma treatment

Domestic Aramid Fiber III (DAF III) was modified by oxygen plasma treatment. The effects of oxygen plasma treatment power on fiber surface and DAF III reinforced bismaleimides (BMI) composite interfacial properties were investigated, respectively. The fiber surface characteristics were analyzed by X-ray photoelectron spectroscopy, Scanning Electron Microscopy, Atomic Force Microscopy and Dynamic Contact Angles Analysis, respectively. The results showed that oxygen plasma treatment introduced new oxygen containing groups such as C=O and –COO on to the fiber surfaces, changed the fiber surface morphologies and enhanced surface roughness by oxidative reactions and plasma etching. Finally, the fiber surface wettability was effectively improved. The total free energy increased from 49.8 to 71.7 mJ/m2 at maximum with 300 W oxygen plasma treatment. The composite interlaminar shear strength (ILSS) was evaluated by short beam shear measurement. The ILSS value increased from 49.3 to 59.8 MPa (by 21.3%) within 300 W plasma treatment.     

等离子体处理的聚丙烯和聚乙烯的粘合体

采用射频辉光放电等离子体和介质阻挡放电等离子体对聚丙烯（PP）和聚乙烯（PE）进行处理后,使用聚氨酯进行粘接,并测试了混合粘合体的剪切强度。介质阻挡放电功率是100 W时,等离子体处理对混合粘合体的剪切强度无影响。介质阻挡放电的功率为200 W、处理时间20 s时,等离子体处理效果最佳,剪切强度为1.58 MPa,是未处理的混合粘合体的14.36倍。介质阻挡放电的功率是300 W时,样品在10 s内就被击穿。射频辉光放电等离子体中,使用空气处理后最大剪切强度为1.60 MPa（100 W,3 min）,使用氮气处理后的最大剪切强度为1.57 MPa（200 W,3 min）。通过扫描电镜（SEM）对等离子体处理前后的PP表面形貌观察,发现未处理样品的表面比较平滑,而经等离子体放电处理后的样品表面变得疏松,出现了大量泡状物质,表面粗糙程度提高。     

Effects of surface treatment and weave structure on interlaminar fracture behaviour of plain glass woven fabric composites: Part II. Report of the 2nd round robin test results

This paper reports the second part of the results from the round robin test program proposed by the Society of Interfacial Materials Science (SIMS) to characterise the interlaminar fracture behaviour of E-glass woven fabric reinforced vinylester composites. Special emphasis was placed on the study of loading direction (i.e. weft and warp directions) effect on interlaminar shear strength and fracture toughness. Ten laboratories worldwide participated in this test (Table 1). Each laboratory was supplied with composite laminates and conducted the tests according to its own procedure. The results showed that although there were large variations in absolute magnitude between laboratories, a general trend was established with higher interlaminar fracture resistance in the weft direction than in the warp direction for a given silane agent. The larger number of strands running in the warp direction with rougher, more undulating areas perpendicular to the direction of crack propagation was mainly responsible for this result. The results also confirmed the previous finding that the mode I interlaminar fracture toughness increased with increasing silane agent concentration.     

Enhanced surface free energy of polyimide fibers by alkali treatment and its interfacial adhesion behavior to epoxy resins

In this article, polyimide (PI) fibers were modified by alkali treatment, and PI fiber-reinforced epoxy composites were fabricated. The effects of different alkali treatment times on the surface properties of the PI fibers and the adhesion behaviors of PI fiber/epoxy composites were studied. The surface morphologies, chemical compositions, mechanical properties, and surface free energy of the PI fibers were characterized by atomic force microscopy, X-ray photoelectron spectroscopy, single-fiber tensile strength analysis, and dynamic contact angle analysis, respectively. The results show that alkali treatment plays an important role in the improvement of the surface free energy and the wettability of PI fibers. We also found that, after the 3 min, 30 °C, 20 wt% NaOH solution treatment, the fibers possessed good mechanical properties and surface activities, and the interlaminar shear strength of the composites increased to 64.52 MPa, indicating good interfacial adhesion properties.     

Improving the adhesion between a aqueous PU and a polyamide fibre with silane

Glycidoxypropyltrimethoxysilane (GPS) and γ-aminopropyltrimethoxysilane (APS) were used to modify the surface chemistry of polyamide fibre. The surface chemistry was characterised using X-ray photoelectron spectroscopy. The silanol functional group was designed to be introduced on the surface of polyamide fibre to increase its chemical activity by N-alkylation of GPS and hydrolysis of APS, and to improve the poor interfacial adhesion between a polyamide 66 fibre and an aqueous polyurethane polymer adhesive. The microbond test was used to measure the interfacial shear strength between the waterborne PU adhesive and the polyamide fibre. It has been found that APS hydrolysis and GPS-alkylated fibre surface can be used to improve the interfacial adhesion of polyamide fibre to PU. The IFSS can be improved by N-alkylation of GPS from 5.0 to 8.4?MPa. After water immersion at 50?°C for 48?h, then drying, the IFSS increased to 8.8?MPa due to the plasticisation of PU in water. Better interfacial adhesion was also observed by the hydrolysis of APS, but not significantly improved by this method due to the relatively weak hydrogen bond at the interface between APS and polyamide fibre.     

Effects of argon plasma treatment on the interfacial adhesion of PBO fiber/bismaleimide composite and aging behaviors

This paper is concerned with the influence of argon plasma on the interfacial adhesion of PBO fiber/bismaleimide composites and aging behaviors. The interlaminar shear strength (ILSS) was greatly increased to 62.3 MPa with an increase of 39.7% after treatment for 7 min at 80 Pa, 200 W. A small amount of O and N atoms was incorporated onto the fiber surface, but the plasma caused C-O bonds to break and generated OC-N groups. The fiber surface roughness increased, contributing much to the wettability. However, long-time treatment excessively destroyed the inherent and newly created structures. The SEM images suggested that the fracture shifted from the interface to the matrix. The modification effects degraded with storage time in the air and the ILSS decreased to approximately 54.0 MPa after 10-30 days. The composite had low water absorption of 2.0 wt% and a high retention of 90% in the ILSS at moisture conditions.     

Influence of carbon fiber’s surface state on interlaminar shear properties of CFRP laminate

In order to investigate the influence of carbon fiber’s surface state on the interlaminar shear properties of carbon fiber-reinforced plastic (CFRP) laminate, the carbon fiber’s surface state was modified by thermal treatment at elevated temperatures. The interlaminar shear strength (ILSS) of CFRP laminates reinforced with treated fibers was measured by means of short-beam shear test, and the surface state of fiber was characterized by Electron Spectroscopy for Chemical Analysis (ESCA) analysis to reveal the dominate factor for controlling the ILSS. Combining the ILSS measurement with the ESCA analysis, the results indicated that: (1) the ILSS is strongly dependent on the oxygen-containing functional groups on the surface of carbon fiber; (2) the fiber treated at 600?°C has the highest oxygen-containing functional groups that lead to the highest ILSS of CFRP; and (3) at temperatures beyond 600?°C, the oxygen-containing functional groups decrease with increasing the heat treatment temperature, resulting in a low ILSS of CFRP laminates. Furthermore, from the microstructure observation, it was found that the CFRP mainly failed in the mode of multi-interlaminar shear. The multi-interlaminar shear failure in the CFRP laminates with low ILSS is more severe due to a weak fiber-matrix interface.     

Weibull analysis of microbond shear strength at sisal fibre–polyester resin interfaces

An analysis has been made of the tensile strength of sisal fibres and the interfacial adhesion between fibres and polyester resin droplets. Density and microscopy methods were used to determine the cross-sectional area of the sisal fibres. The average tensile strength of treated sisal fibres decreased by a modest amount following treatment with 0.06 M NaOH. However, this treatment resulted in a substantial increase in the interfacial shear strength at the sisal fibre to polyester resin interface. Weibull analysis has been used successfully to analyse variability in tensile strengths and interfacial shear strength using probability of failure plots. Scanning electron microscopy has revealed the shape of resin droplets on the surface of treated and untreated sisal fibres and contact angles are much lower for droplets on treated fibres. Damage to the surface of fibres has been examined following shear testing. Weibull analysis is an effective tool for characterising highly variable fibre properties and evaluating the level of adhesion between polymer resin and the fibre surface.     

Effect of Processing Parameters on the Interlaminar Shear Strength of Carbon Fiber/Epoxy Composites

The objective of this work was to improve the interlaminar shear strength of carbon fiber/epoxy composites by determining the effect on it of the processing parameters of the cured composites system, i.e., temperature, content of curing agent, and heating rate. Taguchi methodology and analysis of variance were applied for optimizing and statistically determining the significant factors that influenced the mechanical properties of the composites. It was found that the temperature and content of curing agent were equally the primary significant factors in controlling the interlaminar shear strength of the composites. Also, the correlation between water absorption and mechanical properties of the composites was investigated.     

Influence of γ-ray radiation grafting on interfacial properties of aramid fibers and epoxy resin composites

This research used Co⁶⁰ γ-ray radiation to modify Armos fibers in 1,2-epoxy-3-chloropropane. After the treatment, the interlaminar shear strength (ILSS) values of aramid/epoxy composites were improved by about 20%. Surface elements of Armos fibers were determined by XPS analysis, which indicated that the oxygen/carbon ratio was increased. The surface of the fibers treated was rougher than that of the untreated fibers when examined by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Fourier transform infrared (FT-IR) spectra confirmed that the epoxy group was grafted onto the fibers. The wettability of the fibers' surface was also enhanced by the treatment. Nanoindentation technique analysis showed that the nanohardnesses of the various phases (the fiber, the interface and the matrix) in the composite, whose fibers were treated, were correspondingly higher than those in the composite, whose fibers were untreated. The results indicate that γ-ray irradiation grafting technique, which is a suitable batch process for industrialization, can modify the physicochemical properties of Armos fibers and improve the interfacial adhesion of its composite.     

Ultrasonic treatment of aramid fiber surface and its effect on the interface of aramid/epoxy composites

Aramid fiber/epoxy composites have been treated by ultrasound during the winding process to enhance the adhesion. According to the ultrasonic treatment interlaminar shear strength (ILSS) of composites has been greatly improved. Dynamic wetting method, XPS and AFM are used to examine the microscopic properties of resultant composites. The enhanced ILSS is attributed to the ultrasonic cavitation, which improves the wetting between aramid fibers and resins.     

The influence of surface treatment of stitch threads and stitching on interlaminar properties of unidirectional laminates

An experimental investigation was carried out to study the influence of graft treatment for Kevlar stitch threads on the interlaminar properties of stitched unidirectional laminates. The surfaces of Kevlar stitch threads were immersed in a solution of Dimethyl sulfoxide mixed with NaH for some time, and then alkoxysilane was grafted onto the surface of modified Kevlar threads. The corresponding physical and chemical changes in the surface of Kevlar threads were carefully evaluated using XPS, SEM, water absorption, and tensile measurement. Results show that the treated Kevlar threads have much rougher surface morphologies, its tensile strength is slightly improved, and their wettability are greatly improved. The stitched carbon /epoxy composite using surface-treated Kevlar threads has excellent hydrothermal property. The resins can better wet the surface treatment of Kevlar stitch threads, and the sizes of rich resin can be reduced. The moisture uptake of stitched composites decreases by 53.3% and its residue ratio of interlaminar shear strength in a wet state improves by 13.1%.     

Void content and interfacial properties of composite laminates under different autoclave cure pressure

With an identical temperature profile, various cure pressures were applied to determine the effect of cure pressure on void distribution and interlaminar shear strength (ILSS) of [0]₁₀ T800/X850 composite laminate. Void shape, distribution, and void content within the composite laminates were characterized using optical microscope. The ILSS was evaluated using short-beam three-point bending tests and their interface debonding failure and fracture surfaces were determined using scanning electron microscope. The experimental results indicated that long strips voids are generated in the low-pressure curing stage. The voids mainly exist in the two forms of rod-like shape and spherical shape, and their number and size decrease as the cure pressure increases. The influence of cure pressure on the void content and ILSS shows a different trend in two stages: when the cure pressure is lower than 0.4 MPa, the ILSS decrease by 5.21% with 1% increase in void content, and their relationship is inversely linear. However, when the cure pressure is higher than 0.4 MPa, the void content is less than 1% and ILSS increase slightly by 1.69% when the cure pressure goes from 0.4 to 0.6 MPa, the influence of cure pressure on void content and ILSS is clearly presented.     

Shear and distensile fracture behaviour of Ti-based composites with ductile dendrites

The room-temperature deformation and fracture behaviour of Ti-based composites with ductile dendrites, prepared by copper mold casting and arc-melting techniques, was investigated. Under compressive loading, the Ti-based composites display high fracture strength (about 2000?MPa) and good ductility (about 4 or 10%). The yield strength of the Ti-based composites is relatively low (about 565–923?MPa). However, they have a large strain-hardening ability before failure, due to the interactions between shear bands and dendrites. For the arc-melted Ti-based composites, fracture often occurs in a shear mode with a high plasticity (about 10%). In contrast, the cast Ti-based composites break or split into several parts with a compressive plasticity of 4%, rather than failing in a shear mode. A new fracture mechanism, i.e. distensile fracture, is proposed for the first time to elucidate the failure of the as-cast Ti-based composites. Based on the difference in the fracture modes of the differently prepared composites, the relationships between shear and distensile fracture mechanisms and the corresponding fracture criteria are discussed.     

Effects of plasma surface modification on the mechanical properties of carbon fiber and carbon fiber/epoxy composite

_The effect of surface treatment on mechanical properties of carbon fibers has been investigated by application of plasma polymerization of selected monomers in the vapor phase. The role of the fiber-matrix interface on carbon fiber-reinforced epoxy resin composites has also been studied. Composites have been prepared separately by the use of plasma-modified and unmodified carbon fibers in the epoxy resin matrix. The mechanical properties of carbon fibers (Hercules and Grafil) as well as of fiber/epoxy composites were examined by using single filament and three-point bending tests, respectively. It was observed that plasma polymerization treatment at selected plasma conditions led to significant improvement of interlaminar shear and flexural strength values of composites.     

Influence of Grafting Density of Diblock Copolymers on Interfacial Assembly Behavior and Interfacial Shear Strength of Glass Fiber/Polystyrene Composites

To investigate the influence of the grafting density and the molecular structure of block copolymers on the interfacial assembly behavior and interfacial shear strength, macromolecular coupling agents, hydroxyl-terminated poly(n-butyl acrylate-b-styrene) (HO-P(BA-b-S)) were synthesized by atom transfer radical polymerization, and then chemically anchored on the glass fiber surfaces to form a well-defined monolayer. The phase separation and 'hemispherical' domain morphologies of diblock copolymer brushes at the polystyrene/glass fiber interface were observed. The interfacial assembly morphology differs with changes in the grafting density of diblock copolymers. When the grafting density is greatest, the highest height difference of the hemispherical domain and the largest surface roughness are achieved, as well as the best interface shear strength. It was also found that the copolymer brush with a PBA block of the polymerization degree (Xn) about 77 is the optimal option for the interfacial adhesion of PS/GF composites. Thus, the grafting density and molecular structure of diblock copolymers determines the interfacial assembly behavior of copolymer brushes, and therefore the interfacial shear strength.     

Energy release rate and stress field calculation for debonding crack extension at the fibre-matrix interface during single-fibre pull-out

For the micromechanical modelling of the macroscopic failure of fibre-reinforced composites the formulation of a critical parameter for initiation and extension of debonding cracks at the fibre-matrix interface is essential. This point is discussed for the 'fibre pull-out' specimen, a test commonly used to measure the adhesion quality of fibre-matrix systems. Some of the simplifying assumptions fundamental to shear lag theory-based models of the fibre pull-out test are compared with results from a detailed finite element (FE) model to examine their validity. The FE model strongly contradicts assumptions made with the shear lag theory that the axial stress gradient in the matrix can be neglected from the equilibrium equation. A critical interface shear strength is commonly used as a measure of adhesion quality. But for elastic materials the nature of the stress concentrations at the fibre end and interface crack-tip are singular. Therefore a fracture mechanic approach is better suited for a debonding criterion than a simple finite shear strength. The energy release rate shows a minimum for short crack lengths and may stabilize the moving crack.     

Experimental study of transcrystallinity in UHMWPE/LLDPE composites

This study deals with the effect of a transcrystalline LLDPE (linear low-density polyethylene) layer grown on Spectra 1000 UHMWPE (ultrahigh molecular weight polyethylene) fibres. Chemical similarity between the fibre and the surrounding melt does not promote transcrystallinity as no transcrystalline microstructure appears from the surface of as-received Spectra 1000 UHMWPE fibres. However, oxygen plasma treatment of the UHMWPE fibres yields a degree of surface roughness that appears to promote easy nucleation and growth of LLDPE transcrystallinity. The kinetics of transcrystalline growth were investigated quantitatively. The growth rate increased by a factor of about 12 for a 10°C increase in supercooling, and at 105°C the maximum observed thickness of the transcrystalline layer was about one fibre diameter. The induction time was found to decrease as the crystallization isotherm increased. We discuss the possibility of using surface energy parameters to define a better criterion for the nucleation of transcrystallinity from the UHMWPE fibre substrate. Preliminary data were generated for the interfacial mechanical shear strength by means of the microbond test. It is conjectured that the combined effects of a thermal treatment and the presence/absence of a transcrystalline layer might produce significant changes in the interfacial shear strength, as illustrated here by a 43% increase observed with specimens subjected to different thermal treatments.