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.     

Quantitative evaluation of interfacial adhesion between fiber and resin in carbon fiber/epoxy composite cured by semiconductor microwave device

Interfacial adhesion between carbon fiber (CF) and epoxy resin in carbon fiber-reinforced epoxy composite, which was prepared by different heating process such as semiconductor microwave (MW) device and conventional electric oven, has been evaluated quantitatively. The interfacial shear strength (IFSS) between CF and epoxy resin, which was an indicator of adhesion on the interface, was measured by a single fiber fragmentation test. The single fiber fragmentation test showed that the IFSSs of the prepared specimens were different by heating methods. In the case of MW process, the curing reaction of epoxy resin on the CF interface would be progressed preferentially due to the selective heating of CF, resulting that the IFSSs of specimens prepared by MW irradiation were increased by enhancing the output power of MW. However, the IFSSs of the specimens were decreased by excessively high output power because the matrix resin on the CF interface was thermally degraded. As results, by optimizing the MW conditions of output power and irradiation time, the IFSS of the sample cured by MW was increased by 21% as compared to oven-heated one. It was found that the interfacial adhesion between CF and epoxy resin would be improved by the MW-assisted curing reaction on the surface of CF.     

Carbon fiber/epoxy composite materials cured thermally and with microwave irradiation

In this paper, composite materials of short carbon fibers (CFs) and a thermosetting epoxy were prepared in three different ways: without curing, thermal curing, and thermal curing followed by microwave irradiation. Mechanical properties of the three kinds of CF reinforced plastic (CFRP) composites were studied to explore the effect of microwave irradiation. Microscopic study with the aid of a scanning electron microscope (SEM) was performed on fractured composite surfaces to identify the principle features of failure. Degree of polymerization of the epoxy resin in the three CFRP composites was evaluated by infrared (IR) spectroscopy. The microwave irradiated CFRP exhibited mechanically ductile behavior even though its highest degree of polymerization. Use of microwaves and resultant stronger physico-chemical linkage at the interface between CF and epoxy resin are the main feature of this study.     

Effect of processing temperature on the micro- and macro-interfacial properties of carbon fiber/epoxy composites

Three different temperature schemes were applied on carbon fiber/epoxy composite to elucidate the effect on interfacial shear strength (IFSS) and inter-laminar shear strength (ILSS). It showed that carbon fiber/epoxy IFSS was significantly influenced by the processing temperature, while ILSS was only slightly changed. Moreover, the mechanical properties revealed no necessary relationship between the micro- and macro-interfacial strengths with the properties of epoxy matrix. Among all the temperature schemes, Pro2 (the one-platform curing scheme with relatively rapid heating rate) produced highest IFSS and ILSS. Fourier transform infrared spectroscopy analysis demonstrated that the sizing agent can chemically react itself and also react with epoxy resin at temperature 180?°C. The resin rheological data showed that different temperature schemes can considerably impact diffusion behavior of the resin molecules. Hence, the highest interfacial strengths for Pro2 scheme were ascribed to large extent of chemical reactions and good inter-diffusion between components, at the interface region.     

Effect of a Novel Polymeric Coupling Agent on the Water Uptake Property and Warp Stability of Poly(vinyl chloride)/Bamboo Flour Composite

Water uptake property and warp stability of poly(vinyl chloride) (PVC)/bamboo flour composite were investigated employing a novel polymeric coupling agent, poly(styrene-co-maleic anhydride)-block-poly(styrene-co-acrylonitrile) {P[(SMA)-b-(SAN)]}. P[(SMA)-b-(SAN)] was synthesized through controlled/'living' radical polymerization (CRP) technique in an one-pot reaction and incorporated into the composite to improve the interfacial adhesion between PVC and bamboo flour. The structure of P[(SMA)-b-(SAN)] was confirmed by ¹H-NMR, FT-IR and GPC. PVC/bamboo flour composite sheets were then prepared from a single screw extruder and two-roll mill in the presence of P[(SMA)-b-(SAN)] coupling agent. As the content of the coupling agent increased, improved interfacial bonding between PVC and bamboo flour filler was observed. Water uptake property and warp stability were also improved in the presence of the coupling agent. These results suggest that the block copolymer successfully acted as a coupling agent in PVC/bamboo flour composites.     

Novel Route to Control Interfacial Properties of Glass Fiber-Reinforced Polystyrene Composites via a Photo-Cross-Linkable Block Copolymer Coupling Agent

A diblock copolymer of polystyrene–block–poly(2-hydroxyethyl acrylate) (PS-b-PHEA) was synthesized via atom transfer radical polymerization (ATRP) and reacted with cinnamoyl chloride in triethylamine to yield PS-b-(PCEA-co-PHEA) copolymer with photo-cross-linkable poly(2-cinnamoylethyl acrylate) (PCEA) moieties. Then the triblock copolymer of polystyrene–block–poly(2-cinnamoylethyl acrylate-co-2-hydroxyethyl acrylate)–block–poly(γ-methacryloxypropyltrimethoxysilane) (PS-b-(PCEA-co-PHEA)-b-PMPS) was synthesized viaATRP from PS-b-(PCEA-co-PHEA) copolymer. Using as-prepared triblock copolymer as a macromolecular coupling agent to modify glass fibers, via microbond tests, the interfacial bond strength between pretreated glass fiber and polystyrene was compared before and after copolymer photo-crosslinking. The partially crosslinked block copolymer coupling agent greatly improved the interfacial adhesion of glass fiber-reinforced polystyrene.     

The effect of interphase modification on carbon fiber/polyarylacetylene resin composites

Interfacial modification for carbon fiber (CF) reinforced polyarylacetylene (PAA) resin, a kind of non-polar, was investigated. The high carbon phenolic resin was used as coating to treat the surface of CF after oxidation. Atomic force microscopy (AFM) with force modulation mode was used to analyze the interphase of composite. The interlaminar shear strength (ILSS) and mechanical properties of CF/PAA composites were also measured. It was found that the CF/PAA composites treated with oxidation and coating after oxidation had transition area between carbon fiber and PAA resin. The existence of transition area led to the improvement of interfacial performance of composites. Specially, the thickness and stiffness of interphase of composite treated with coating after oxidation were more suitable for CF/PAA composites. Thus, the composite treated with coating after oxidation had the highest value of ILSS and the best mechanical properties.     

The Effect of Triethylene-Tetramine Treatment of Carbon Fibers on Performance of Composites

Amino groups can be introduced to the surface of carbon fibers (CF) by triethylene-tetramine (TETA) treatment. Carbon fibers coated with triethylene-tetramine (TETA) were treated at 400°C for 30 s in an oxidizing furnace. Differential scanning calorimetry studies showed that the surface functional groups of CF reacted with TETA. The changes of the surface composition and structure of CF were tested by X-ray photoelectron spectrometry (XPS). The interfacial interaction between the resulting CF and an epoxy matrix was also characterized by scanning electron microscopy (SEM) and three-point short-beam shear testing. The XPS results indicate that the number of amino groups on the surface of the CF was significantly increased after being treated with TETA. The interlaminar shear strength (ILSS) of TETA-treated CF-reinforced resin composites (CFRP) was increased by 30% compared with untreated ones, and in the treated CF fracture sections, CFRP pores and carbon fiber pullout were seldom observed. The failure of composites reinforced by treated CF shows a cohesive failure effect in the interface layer.     

General approach for fabricating nanoparticle arrays via patterned block copolymer nanoreactors

A general approach to fabricate nanoparticle arrays of different kinds of materials is demonstrated in this paper. It was found that the center-to-center distance of the nanoparticles or the nanoclusters can be controlled using patterned block copolymer nanoreactors by adding polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer thin film. The number of the nanoparticles formed in the P4VP nanodomains can also be adjusted by addition of polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer. In fabrication of Au nanoparticle arrays, HAuCl₄ precursor was directly loaded into P4VP nanodomains of the diblock copolymer thin film by using a methanol solvent, which is a good solvent for P4VP but non-solvent for PS. The Au nanoparticle arrays were then obtained by reducing HAuCl₄ with sodium citrate dihydrate, and then in situ transferred to silicon substrate by a two-step calcination method. ZnO and Fe _x O _y nanoparticle arrays were also synthesized by this approach with thermal decomposition and double decomposition reactions, respectively. Additionally, the advantage of using two-step calcination method over the air plasma method was discussed.     

Effect of the surface roughness on interfacial properties of carbon fibers reinforced epoxy resin composites

The effect of the surface roughness on interfacial properties of carbon fibers (CFs) reinforced epoxy (EP) resin composite is studied. Aqueous ammonia was applied to modify the surfaces of CFs. The morphologies and chemical compositions of original CFs and treated CFs (a-CFs) were characterized by Atomic Force Microscopy (AFM), and X-ray Photoelectron Spectroscopy (XPS). Compared with the smooth surface of original CF, the surface of a-CF has bigger roughness; moreover, the roughness increases with the increase of the treating time. On the other hand, no obvious change in chemical composition takes place, indicating that the treating mechanism of CFs by aqueous ammonia is to physically change the morphologies rather than chemical compositions. In order to investigate the effect of surface roughness on the interfacial properties of CF/EP composites, the wettability and Interfacial Shear Strength (IFSS) were measured. Results show that with the increase of the roughness, the wettabilities of CFs against both water and ethylene glycol improves; in addition, the IFSS value of composites also increases. These attractive phenomena prove that the surface roughness of CFs can effectively overcome the poor interfacial adhesions between CFs and organic matrix, and thus make it possible to fabricate advanced composites based on CFs.     

Temperature dependence of the stress transfer for thermal resistance polymer composites by X-ray diffraction

Temperature dependence of the stress transfer from the matrix resin to the incorporated fiber has been measured for poly(p-phenylene benzobisoxazole) (PBO) fiber/bismaleimide (BMI) resin composite by a novel X-ray diffraction method. At 120°C, stress transfer and tensile strength of the PBO/BMI composite are superior to that of the PBO/epoxy composite, due to the excellent thermal resistance and good mechanical property of BMI resins. The PBO/BMI composite possesses good adhesion and excellent mechanical properties at high temperature, which are suitable for thermal resistance applications.     

In situ observation of interfacial debonding process induced by matrix crack propagation in two-dimensional unidirectional model composites

Interfacial debonding behavior is studied for unidirectional fiber reinforced composites from both experimental and analytical viewpoints. A new type of two-dimensional unidirectional model composite is prepared using 10 boron fibers and transparent epoxy resin with two levels of interfacial strength. In situ observation of the internal mesoscopic fracture process is carried out using the single edge notched specimen under static loading. The matrix crack propagation, the interfacial debonding growth and the interaction between them are directly observed in detail. As a result, the interfacial debonding is clearly accelerated in specimens with weakly bonded fibers in comparison with those with strongly bonded fibers. Secondary, three-dimensional finite element analysis is carried out in order to reproduce the interfacial debonding behavior. The experimentally observed relation between the mesoscopic fracture process and the applied load is given as the boundary condition. We successfully evaluate the mode II interfacial debonding toughness and the effect of interfacial frictional shear stress on the apparent mode II energy release rate separately by employing the present model composite in combination with the finite element analysis. The true mode II interfacial debonding toughness for weaker interface is about 0.4 times as high as that for a stronger interface. The effect of the interfacial frictional shear stress on the apparent mode II energy release rate for the weak interface is about 0.07 times as high as that for the strong interface. The interfacial frictional shear stress and the coefficient of friction for weak interface are calculated as 0.25 and 0.4 times as high as those for strong interface, respectively.     

Interface Stability of Microencapsulated-Paraffin Filled Epoxy Composites: Effect of Methylation on Melamine–Formaldehyde Shell Material

Microcapsules containing phase change materials (microPCMs) can be filled in polymeric matrix forming smart temperature-controlling composites. The aim of this study was to investigate the composite interface stability of microPCMs/epoxy composites. Paraffin was applied as the phase change materials. Methanol–melamine–formaldehyde (MMF) and melamine–formaldehyde (MF) were both used to form the shell of microPCM by in-situ polymerization. The investigation focused on studying the effect of methylation and interface stability. The MF- and MMF-prepolymers were both successfully used to fabricate microcapsules with globe shapes and smooth surface. Thermal stability tests proved that the MMF-shell microPCMs/epoxy composites had a better interface stability than MF-shell microPCMs/epoxy composites. Mechanical properties also indicated that the MMF-shell microPCMs/epoxy composites had less tensile strength destruction after the thermal treatment. These results mean the MMF-resin enhanced the interface bonding stability though improving the interface molecule entanglement. As the MMF molecular has relative flexible ability and can adjust its conformation under change in environmental conditions, the interface will decrease the microstructure defects such as cracks, gaps and debonding.     

Anisotropic orientation of the carbon fiber/liquid crystalline epoxy resin composites

Anisotropic orientation of carbon fiber (CF)/liquid crystalline epoxy (LCE) resin composite was readily induced during curing on a CF surface along a long molecular axis of CF. Orientation of LCE was confirmed with polarized optical microscope (POM) and wide angle X-ray diffractometer (WAXD). In addition, anisotropic ordering of LCE was correlated with curing rate, dynamic mechanical properties and thermal expansion behaviors of CF/LCE composite. Curing of LCE was accelerated in the presence of CF and the rubbery modulus of the CF/LCE composites cured at low temperature was enhanced by long-range, long axis orientational ordering of the LCE resin along a CF surface. Fully cured CF/LCE composite showed a negative coefficient of thermal expansion in the fiber direction. These results obtained in this study are interpreted in terms of structural changes occurring during curing.     

Nanostructured Thermosetting Blends of Phenolic Thermosets and Poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) Triblock Copolymer

The amphiphilic triblock copolymer, poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) (PEO‐b‐PPO‐b‐PEO) was incorporated into novolac resin to prepare thermosetting blends. The morphology of the thermosetting blends was investigated by means of atomic force microscopy (AFM) and small‐angle x‐ray scattering (SAXS) and the nanostructures were obtained. It was identified that the reaction‐induced phase separation occurred in the blends of phenolic thermosets with the model poly(propylene oxide) (PPO), whereas poly(ethylene oxide) (PEO) was miscible with novolac resin after and before the curing reaction. In terms of miscibility and phase behavior of the subchains of the triblock copolymer with novolac resin, it was demonstrated that the formation of nanostructures in the thermosets followed a mechanism of reaction‐induced microphase separation.     

Thermal and Mechanical Properties of Epoxy/Carbon Fiber Composites Reinforced with Multi-walled Carbon Nanotubes

Multi-scale hybrid composite laminates of epoxy/carbon fiber (CF) reinforced with multi-walled carbon nanotubes (MWCNTs) were fabricated in an autoclave. For laminate fabrication, 0.5 wt% of pristine MWCNTs or silane-functionalized MWNCTs (f-MWCNTs) were dispersed into a diglycidyl ether of bisphenol-A epoxy system and applied on the woven carbon fabric. The neat epoxy/CF composite and the MWCNTs-reinforced epoxy/CF hybrid composites were characterized by thermogravimetric analysis (TGA), thermomechanical analysis (TMA), tensile testing, and field emission scanning electron microscopy (FE-SEM). A significant improvement in initial decomposition temperature and glass transition temperature of epoxy/CF composite was observed when reinforced with 0.5 wt% of f-MWCNTs. The coefficient of thermal expansion (CTE), measured by TMA, diminished by 22% compared to the epoxy/CF composite, indicating an improvement in dimensional stability of the hybrid composite. No significant improvement in tensile properties of either MWCNTs/epoxy/CF composites was observed compared to those of the neat epoxy/CF composite.     

Interfacial reinforcement in composites with PPT aramid fiber modified by network-intercalation method

—A novel surface treatment for poly(p-phenylene telephthalamide) (PPTA) fiber is performed with silanes and urethane binder that are usually used as sizes for glass fiber treatment. The PPTA used for the surface treatment is modified by a spinning process to make the gaps between PPTA crystallites open. In this treatment, supercritical carbon dioxide fluid method is used to impregnate the sizing molecules into open gaps in PPTA fiber. After the impregnation, the fiber is heated at 100–170°C to make the gaps close and turn open-gapped fiber to the normal type of PPTA modified with sizes. The interfacial shear strength of fiber to epoxy resin is measured by microdroplet method. The modified PPTA improves the interfacial shear strength by ca. 67% to the interfacial shear strength given by normal PPTA without treatment. Those improvements are 33% without heating, 18% with only silanes, and 12% with only urethane instead of the mixture of silane and urethane. In addition, the fiber strength shows no remarkable decrease after the treatment.     

Interfacial mechanical properties of carbon nanotube-deposited carbon fiber epoxy matrix hierarchical composites

Functionalized multiwalled carbon nanotubes were successfully deposited on carbon fibers using four different techniques including dip coating, hand layup, spray up and electrophoretic deposition (EPD). A uniform coating of nanotubes was achieved from EPD in comparison to other coating techniques. Later nanotube-coated fibers by EPD were introduced in epoxy resin to investigate interfacial mechanical properties of the developed hierarchical composites by vacuum bagging technique. The increases in flexural and interlaminar shear properties up to 15% and 18% were observed in composites containing nanotube-coated carbon fibers than composites with virgin carbon fibers, respectively. Microscopic observation revealed the proper impregnation of multiscale reinforcements, i.e., carbon fibers and carbon nanotubes, in resin along with the modification of fiber/matrix interface due to the presence of nanotubes at interface. Finally, the mechanisms for improved mechanical properties were identified along with the presentation of a schematic model for better understanding of the improved performance of hierarchical composite after depositing uniformly dispersed nanotubes on carbon fibers.     

Crystallization Behavior of PEO in Nano‐Structured PEO‐b‐PS/PPO Blends

Blends of poly (ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer and poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) homopolymer were obtained by solution blending, and the morphologies of PEO dispersed nanoparticles in PPO/PS matrix were observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The isothermal crystallization kinetics was studied using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Nonisothermal crystallization kinetics was studied using DSC. The results showed that PEO segments were easier to crystallize in the blend than in the copolymer probably due to the interfaces of PPO acting as nucleation sites to promote the crystallization of PEO. The crystallization of PEO blocks destroyed the pre‐existing microdomain structure even though the glass transition temperature of the matrix was much higher than the crystallization temperature.     

Molecular mobility of confined phases in model mesoporous (MCM-41) and microporous (AlPO4-5 zeolite) host materials

This paper discusses the self-assembly of block copolymers into vesicular morphology. After a brief state of art of the field, a system based on an amphiphilic poly(butadiene)-b-poly(-L-glutamic acid) (PB-b-PGA) diblock copolymer in aqueous solution is discussed in detail. The aggregation behavior of this block copolymer has been investigated by means of fluorescence spectroscopy, dynamic (DLS) and static (SLS) light scattering as well as transmission electron microscopy (TEM). The diblock copolymer was found to form well-defined vesicles in water. The size of these so-called polymersomes or peptosomes could be reversibly manipulated as a function of both pH and ion strength. Depending on the pH of the aqueous solution, the hydrodynamic radii of these vesicles were found to vary from 100 nm to 150 nm. By cross-linking the 1,2-vinyl double bonds present in the polybutadiene block, the ability to transform a transient supramolecular self-organized aggregate into a permanent “shape-persistent stimuli-responsive nanoparticle” has been demonstrated. Received 25 June 2002 and Received in final form 22 October 2002 Published online: 11 March 2003