Determination of Water Diffusion Coefficients and Dynamics in Adhesive/Carbon Fiber Reinforced Epoxy Resin Composite Joints

To determinate the water diffusion coefficients and dynamics in adhesive/carbon fiber reinforced epoxy resin composite joints,energy dispersive X-ray spectroscopy analysis(EDX)is used to establish the content change of oxygen in the adhesive in adhesive/carbon fiber reinforced epoxy resin composite joints.As water is made up of oxygen and hydrogen,the water diffusion coefficients and dynamics in adhesive/carbon fiber reinforced epoxy resin composite joints can be obtained from the change in the content of oxygen in the adhesive during humidity aging,via EDX analysis.The authors have calculated the water diffusion coefficients and dynamics in the adhesive/carbon fiber reinforced epoxy resin composite joints with the aid of both energy dispersive X-ray spectroscopy and elemental analysis.The determined results with EDX analysis are almost the same as those determined with elemental analysis and the results also show that the durability of the adhesive/carbon fiber reinforced epoxy resin composite joints subjected to silane coupling agent treatment is better than those subjected to sand paper burnishing treatment and chemical oxidation treatment.     

EFFECTS OF COUPLING AGENTS ON THE CRYSTALLIZATION BEHAVIOR OF PP/T-ZnOw COMPOSITES

The objectives of this paper are to understand the crystallization behavior of polypropylene(PP)composites with surface modified tetra-needle-shaped zinc oxide whisker(T-ZnOw).T-ZnOw was surface modified with different coupling agents,such as silane coupling agents(KH-550,KH-560)and titanate coupling agent(NDZ-105),in order to improve the compatibility between PP and T-ZnOw.DSC and POM were used to characterize the melt and crystallization behavior and the crystalline structures of the composites,respectively.The results show that the surface modified T-ZnOw acts as a nucleating agent of PP crystallization,depending on the coupling agent used for modification.KH-550 and KH-560 have more apparent role in improving the interfacial interaction than NDZ-105 and induce PP crystallization at higher temperature and with smaller spherulites size.The results also suggest that the crystallization behavior depends on not only the content of coupling agent,but also the content of the surface modified T-ZnOw used in the composites.     

RHEOLOGICAL BEHAVIOR OF KAOLIN TOUGHENED POLYPROPYLENE COMPOSITES

The relation between the rheological behavior and various interfacial properties ofKaolin rigid particle toughened polypropylene (PP / Kaolin) composites were studied bymeans of parallel-plate rheometer, melt flow rate apparatus, scanning electron microscopy(SEM) and other testing methods. The results show that addition of interfacial modffier toPP/Kaolin composites is advantageous to homogeneous dispersion of filler in PP matrix,formation of flexible interlayer between Kaolin particles and PP matrix and Amprovementof the melt processibility of the composites.     

A Triple Crosslinking Design toward Epoxy Vitrimers and Carbon Fiber Composites of High Performance and Multi-shape Memory

It remains a challenge to use a simple approach to fabricate a multi-shape memory material with high mechanical performances. Here,we report a triple crosslinking design to construct a multi-shape memory epoxy vitrimer(MSMEV), which exhibits high mechanical properties,multi-shape memory property and malleability. The triple crosslinking network is formed by reacting diglycidyl ether of bisphenol F(DGEBF) with4-aminophenyl disulfide, γ-aminopropyltriethoxysilane(APTS) and poly(propylene glycol) bis(2-aminopropyl ether)(D2000). The triple crosslinking manifests triple functions: the disulfide bonds and the silyl ether linkages enable malleability of the epoxy network; the silyl ether linkages impart the network with high heterogeneity and broaden the glass transition region, leading to multi-shape memory property; a small amount of D2000 increases the modulus difference between the glassy and rubbery states, thereby improving the shape fixity ratio. Meanwhile,the high crosslinking density and rigid structure provide the MSMEV with high tensile strength and Young's modulus. Moreover, integrating carbon fibers and MSMEV results in shape memory composites. The superior mechanical properties of the composites and the recyclability of carbon fiber derived from the dissolvability of MSMEV make the composites hold great promise as structural materials in varied applications.     

STUDY ON THE EPOXY RESIN TOUGHENED BY HYDROXY-TERMINATED BUTADIENE-ACRYLONITRILE COPOLYMER

Toughened epoxy resin with excellent properties was obtained by adding organic acid anhydride curing agent and hydroxy-terminated butadiene-acrylonitrile copolymer (HTBN), which is cheaper than CTBN. The anhydride reacts with both epoxy groups on epoxy resin and hydroxyl groups on HTBN. As a result the soft long chains of HTBN and the rigid chain of epoxy resin form one network, giving the resin toughness. Two-phase structure of the toughened resin was observed by SEM and TEM.     

Carbon Fibers Decorated by Polyelectrolyte Complexes Toward Their Epoxy Resin Composites with High Fire Safety

The achievement of both robust fire-safety and mechanical properties is of vital requirement for carbon fiber(CF) composites.To this end, a facile interfacial strategy for fabricating flame-retardant carbon fibers decorated by bio-based polyelectrolyte complexes(PEC) consisting of chitosan(CH) and ammonium polyphosphate(APP) was developed, and its corresponding fire-retarded epoxy resin composites(EP/(PEC@CF)) without any other additional flame retardants were prepared. The decorated CFs were characterized by SEMEDX, XPS and XRD, indicating that the flame-retardant PEC coating was successfully constructed on the surface of CF. Thanks to the nitrogen-and phosphorous-containing PEC, the resulting composites exhibited excellent flame retardancy as the limiting oxygen index(LOI) increased from 31.0% of EP/CF to 40.5% and UL-94 V-0 rating was achieved with only 8.1 wt% PEC. EP/(PEC8.1@CF) also performed well in cone calorimetry with the decrease of peak-heat release rate(PHRR) and smoke production rate(SPR) by 50.0% and30.4%, respectively, and the value of fire growth rate(FIGRA) was also reduced to 3.41 kW·m~(-2)·s~(-1) from 4.84 kW·m~(-2)·s~(-1), suggesting a considerably enhanced fire safety. Furthermore, SEM images of the burning residues revealed that the PEC coating exhibited the dominant flame-retardant activity in condensed phase via the formation of compact phosphorus-rich char. In addition, the impact strength of the composite was improved, together with no obvious deterioration of flexural properties and glass transition temperature. Taking advantage of the features, the PEC-decorated carbon fibers and the relevant composites fabricated by the cost-effective and facile strategy would bring more chances for widespread applications.     

SPATIAL HIERARCHY AND INTERFACIAL STRUCTURE IN INJECTIONMOLDED BARS OF POLYPROPYLENE-BASED BLENDS AND COMPOSITES

The hierarchical structure and interfacial morphology of injection-molded bars of polypropylene （PP） based blends and composites have been investigated in detail from the skin to the core. For preparation of injection-molded bars with high-level orientation and good interfacial adhesion, a dynamic packing injection molding technology was applied to exert oscillatory shear on the melts during solidification stage. Depending on incorporated component, interfacial adhesion and processing conditions, various oriented structure and morphology could be obtained. First, we will elucidate the epitaxial behavior between PP and high-density polyethylene occurring in practical molded processing. Then, the shear-induced transcrystalline structure will be the main focus for PP/fiber composites. At last, various oriented clay structures have been ascertained unambiguously in PP/organoclay nanocomposites along the thickness of molded bars.     

Effects of different compatibilizing agents on the interfacial adhesion properties of polypropylene/magnesium oxysulfate whisker composites

The effects of maleic anhydride-grafted polypropylene(PP-g-MAH) and maleic anhydride-grafted polyolefin elastomer(POE-g-MAH) on interfacial adhesion properties of the polypropylene/magnesium oxysulfate whiskers(PP/MOSw) composites were investigated via mechanical, thermal, ATR-FTIR and rheological tests. Although significant increases in yield strength and Young's modulus were observed in PP-g-MAH treated composites, a sharp decline in these properties was observed in POE-g-MAH treated composites. ATR-FTIR results indicated that esterification occurred between the hydroxyl groups of MOSw and the carbonyls of anhydrides of both compatibilizers but POE-g-MAH was still incompatible with the PP matrix, as verified by the presence of shoulder peaks in DTG curves and numerous voids in SEM micrographs. On the other hand, PP-g-MAH was highly compatible with the PP matrix, as evidenced by the peaks in DTG curves and vague interfaces with wrapped melts on the surface of MOSw. Rheological behaviors also confirmed that introducing PP-g-MAH resulted in a transition from liquid-like to solid-like, which was attributed to the stronger interfacial adhesion between MOSw and the PP matrix. POE-g-MAH treated composites, in contrast to PP-g-MAH, maintained liquidlike rheological behaviors as typical molten polymers. There is likely a MOSw network formed in the PP/15PP-gMAH/15 MOSw composite as suggested by the significant deviation of G′ versus G″ plots and the two crossover frequencies observed in plots of tan? versus frequency.     

Rheological Behavior for Mica-filled Polypropylene Composite Melts

The study on rheological properties of a series of mica-filled polypropylene (PP) composites was carried out. The influence of surface-treatment of mica particles on dynamic rheological behavior of the composites were dealt with. The viscosity (η) and dynamic modulus ( G‘ ) of the composite melts were higher than those of PP matrix, especially those for systems treated with silane, which was attributed to the interfacial adhesion enhancement. However, surface-treatment of mica by titanate resulted in lower η and G‘, as compared with the treatment by silane. The reason for this is believed to be the formation of the mono-molecular layer on the mica surface.     

Poly(methyl methacrylate)-induced Microstructure and Hydrolysis Behavior Changes of Poly(L-lactic acid)/Carbon Nanotubes Composites

Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of the service life of the articles.In this work,a small quantity of poly(methyl methacrylate)(PMMA)(2 wt%-10 wt%)was incorporated into the PLLA/carbon nanotubes(CNTs)composites.The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated.The results showed that PMMA promoted the dispersion of CNTs in the composites.Amorphous PLLA was obtained in all the composites.Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA,especially at relatively high PMMA content.Incorporating 10 wt%PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19%/h of the PLLA/CNT composite sample to 0.059%/h of the PLLA/PMMA-10/CNT composite sample.The microstructure evolution of the composites was also detected,and the results showed that no crystallization occurred in the PLLA matrix.Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs,which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs.This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.     

EFFECTS OF COMPATIBILIZERS ON THE MECHANICAL PROPERTIES OF LOW DENSITY POLYETHYLENE/LIGNIN BLENDS

Low density polyethylene(LDPE)/lignin blends were prepared using melt blending.Two kinds of compatibilizers, ethylene-vinylacetate(EVA) which is softer than LDPE and polyethylene grafted with maleic anhydride(PE-g-MA) which is harder than LDPE were used to improve the interfacial adhesion.Scanning electron microscope(SEM) was used to investigate the dispersion of lignin in LDPE matrix.The results showed that both of the compatibilizers could improve the interaction between the low density polyethylene an...     

Preparation and Characterization of Microcapsules for Self-healing Materials

The urea-formaldehyde(UF) capsules filled with a healing agent, a mixture of epoxy resins(epoxy 711 and E-51) as core material, were produced by means of one step in-situ polymerization. The characteristics of these microcapsules were studied via scanning electron microscopy(SEM), particle size analysis, FTIR and DSC/TGA. The results show that the dispersed and integrated microcapsules of 5 μm in shell thickness were synthesized successfully. The capsules were produced with diameters ranging from 10 to 250 μm via controlling agitation rate. Young’s modulus of the capsule was a little lower than those of the epoxy resins, but the microcapsules having such a shell thickness were robust enough to survive handling during manufacturing self-healing composites. When damage occurred in the epoxy matrix, the crack could rupture the microcapsule to make the repairing agent release.     

Thermo-reversible MWCNTs/epoxy polymer for use in self-healing and recyclable epoxy adhesive

A self-healing and recyclable carbon tube/epoxy adhesive was prepared by epoxy monomer with Diels-Alder(DA) bonds, diethylenetriamine and polyethyleneimine modified multi-wall carbon nanotubes(MWCNTs). The self-healing and recyclable ability was attained by thermally reversible Diels-Alder reaction between furan and maleimide in the epoxy monomer. By controlling the molar ratio of furfuryl glycidyl ether and 4,4′-methylenebis(N-phenylmaleimide), the glass transition temperature and mechanical properties of MWCNTs/epoxy adhesives were varied. The self-healing properties of MWCNTs/epoxy polymers were evaluated by lap shear experiment and the results showed that the MWCNTs/epoxy adhesives exhibited enhanced mechanical properties and excellent self-healing ability under heat stimulus. The healing efficiency was related to the molecule mobility and the conversion of DA reaction between furan and maleimide. The MWCNTs/epoxy adhesives also displayed excellent recyclable ability by transforming into soluble polymer under heating. These materials offer a wide range of possibilities to produce materials with healing and recyclable ability and have the potential to bring great benefits to our daily lives by enhancing the safety, performance, and lifetime of products.     

PREPARATION AND PROPERTIES OF CHITOSAN/LIGNIN COMPOSITE FILMS

Biodegradable composite films based on chitosan and lignin with various composition were prepared via the solution-casting technique.FT-IR results indicate the existence of hydrogen bonding between chitosan and lignin,and SEM images show that lignin could be well dispersed in chitosan when the content of lignin is below 20 wt%due to the strong interfacial interaction.As a result of strong interaction and good dispersion,the tensile strength,storage modulus,thermal degradation temperature and glass transi...     

ELECTRODEPOSITION OF POLYMERS ON CARBON FIBERS

Styrene-co-maleic anhydride, vinyl acetate-co-maleic anhydride, methyl methacrylate-co-maleic anhydride copolymers were deposited on the surface of carbon fibers by an electrodcposition technique. The anion-free radical mechanism of this process and the physical adhesion to the surface were preliminarily confirmed. The adhesion at fiber-resin matrix interface in carbon fiber reinforced plastics was improved by the electrodeposited polymer interlayer and the shear failure occurred mainly in the matrix. Interlaminar shear strength of the unidirectional carbon fiber reinforced epoxy composite is increased from about 600 kg/cm~2 to 1000 kg/cm~2 by electrodeposition of polymers and the strength loss of the composite which has been immersed in boiling water for 100 hrs is decreased.     

Preparation and Characterization of DGEBA/EPN Epoxy Blends with Improved Fracture Toughness

The physical and mechanical properties of blends composed of two kinds of epoxy resins of different numbers of functional groups and chemical structure were studied.One of the resins was a bifunctional epoxy resin based on diglycidyl ether ofbisphenol A and the other resin was a multifunctional epoxy novolac resin.Attempt was made to establish a correlation between the structure and the final properties of cured epoxy samples.The blend samples containing high fraction of multifunctional epoxy resin showed higher solvent resistance and lower flexural modulus compared with the blends containing high fraction of bifunctional epoxy resin.The epoxy blends showed significantly higher ductility under bending test than the neat epoxy samples.The compressive modulus and strength increased with increasing of multifunctional epoxy in the samples,probably due to enhanced cross-link density and molecular weight.Morphological analysis revealed the presence of inhomogeneous sub-micrometer structures in all samples.The epoxy blends exhibited significantly higher fracture toughness (by 23％ at most) compared with the neat samples.The improvement of the fracture toughness was attributed to the stick-slip mechanism for crack growth and activation of shear yielding and plastic deformation around the crack growth trajectories for samples with higher content of bifunctional epoxy resin as evidenced by fractography study.     

Fiber-reinforced three-dimensional graphene aerogels for electrically conductive epoxy composites with enhanced mechanical properties

To enhance the mechanical properties of three-dimensional graphene aerogels with aramid fibers,graphene/organic fiber aerogels are prepared by chemical reduction of graphene oxide in the presence of organic fibers of poly(p-phenylene terephthalamide)(PPTA) and followed by freeze-drying. Thermal annealing of the composite aerogels at 1300 ° C is adopted not only to restore the conductivity of the reduced graphene oxide component but also to convert the insulating PPTA organic fibers to conductive carbon fibers by the carbonization. The resultant graphene/carbon fiber aerogels(GCFAs) exhibit high electrical conductivities and enhanced compressive properties, which are highly efficient in improving both mechanical and electrical performances of epoxy composites. Compared to those of neat epoxy, the compressive modulus, compressive strength and energy absorption of the electrically conductive GCFA/epoxy composite are significantly increased by 60%, 59% and 131%, respectively.     

Preparation and Properties of HBS Lignin from Masson Pine

In order to establish a new method for making cellulose and lignin from Masson pine, a high boiling solvent (HBS) pulping process with an aqueous solvent of 1,4-butanediol was investigated. Masson pine chips were pulped with a 70%--90% aqueous solution of 1,4-butanediol containing a small amount of a catalyst at 200--220℃ for 60--180 min. HBS Masson pine cellulose is suitable for making paper. Water-insoluble HBS lignin was separated from the liquor reaction mixture by water precipitation. The recovered high boiling solvent (RHBS) is able to be recycled as a pulping solvent, indicating that the HBS method is a pulping process of Masson pine which is energy saving, resources saving and pollution free. HBS lignin has a better chemical reactivity and a lower ash content than lignin sulfonate.     

STUDIES ON THE INTERFACIAL ADHESION BETWEEN FUNCTIONALIZED POLYPROPYLENE AND POLYAMIDE 1010*

The interface behavior of polyamide 1010 (PA1010) and polypropylene (PP) was studied. In orderto improve their interfacial adhesion, functional PP was prepared by means of grafting glycidyl methacrylate(GMA) on PP main chains and used instead of plain PP. Several technological characterizations wereperformed here on their interfaces. ESCA was used to confirm that some kind of reaction occurred betweenend groups of PA1010 and epoxy species of PP-g-GMA. The peel test was adopted to measure interfacialadhesion. It was found that the fracture energy of interfaces between PA1010 and PP-g-GMA wasdramatically increased with the content of GMA. Their interfaces were observed as being blurred by usingSEM and TEM and a crack that could be seen in the case of the interfaces of the PA1010 and the plain PPdisappeared.     

Synergistic Optimization of Toughness and EMI Shielding Properties in Rigid Polyurethane Composites by Designing Ring Structures on the Surface of Carbon Fibers

How to achieve both toughness and enhanced electromagnetic interference shielding effectiveness(EMI SE) of carbon fibers(CFs)reinforced rigid polyurethane(RPU) composites is a significative challenge at present. In this work, a ring-shaped zinc coating was deposited on the short CFs by electrodeposition technique. It is expected to improve the interfacial properties between the fibers and the resin matrix as well as enhance the EMI shielding properties of the composites by changing the surface m...