Mechanical,thermal, and viscoelastic response of novel in situ CTBN/POSS/epoxy hybrid composite system

The present study focuses on the preparation of a novel hybrid epoxy nanocomposite with glycidyl polyhedral oligomeric silsesquioxane (POSS) as nanofiller, carboxyl terminated poly(acrylonitrile‐co‐butadiene) (CTBN) as modifying agent and diglycidyl ether of bisphenol A (DGEBA) as matrix polymer. The reaction between DGEBA, CTBN, and glycidyl POSS was carefully monitored and interpreted by using Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC). An exclusive mechanism of the reaction between the modifier, nanofiller, and the matrix is proposed herein, which attempts to explains the chemistry behind the formation of an intricate network between POSS, CTBN, and DGEBA. The mechanical properties, such as tensile strength, and fracture toughness, were also carefully examined. The fracture toughness increases for epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems with respect to neat epoxy, but for hybrid composites toughening capability of soft rubber particles is lost by the presence of POSS. Field emission scanning electron micrographs (FESEM) of fractured surfaces were examined to understand the toughening mechanism. The viscoelastic properties of epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems were analyzed using dynamic mechanical thermal analysis (DMTA). The storage modulus shows a complex behavior for the epoxy/POSS composites due to the existence of lower and higher crosslink density sites. However, the storage modulus of the epoxy phase decreases with the addition of soft CTBN phase. The T_g corresponding to epoxy‐rich phase was evident from the dynamic mechanical spectrum. For hybrid systems, the T_g is intermediate between the epoxy/rubber and epoxy/POSS systems. Finally, TGA (thermo gravimetric analysis) studies were employed to evaluate the thermal stability of prepared blends and composites. POLYM. COMPOS., 37:2109–2120, 2016. © 2015 Society of Plastics Engineers     

Mechanical and electret properties of polypropylene unwoven fabrics reinforced with POSS for electret filter materials

A novel polypropylene/Polyhedral oligomeric silsesquioxanes (PP/POSS) composite unwoven fabric with permanent electret was prepared through melt-blown process with corona charging. Field-emission scanning electron microscope (FESEM) and wide-angle X-ray diffraction (WAXRD) were employed to investigate the morphology of the composite fibers and the distribution of POSS nanoparticles on the surface of the fibers, respectively. POSS acted as nucleating agent and accelerated the crystallization process during nonisothermal cooling. The utmost stable charge density of PP/POSS melt-blown unwoven fabric was improved by 78.4% compared with the neat PP unwoven fabric. The maximum value of collection efficiency measured by monodisperse polystyrene aerosol (PSL) (particle size: 0.3 μm) collection could reach 97.36% for PP/POSS composite melt-blown unwoven fabric, which improved by 9% compared with neat PP melt-blown unwoven fabric. Moreover, both stress and elongation at break of the PP/POSS melt-blown unwoven fabrics were improved compared with PP unwoven fabric.     

Catalytic and reinforcing effects of polyhedral oligomeric silsesquioxane (POSS)-imidazolium modified clay in an anhydride-cured epoxy

In this article, we report novel epoxy-based hybrids prepared via incorporating 1,2-dimethyl-3-(benzyl-heptaisobutyl-POSS) imidazolium chloride (POSS-IMC) and POSS-IMC-modified clay (POSS-MMT) into the resin based on 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ECHM) and hexahydrophthalic anhydride (HHPA). We demonstrate that both POSS-IMC and POSS-MMT can reduce the cure temperature of the epoxy/anhydride system, and the catalyzing effect involves chemical reactions between POSS-IMC and ECHM/HHPA, which may lead to the attachment of POSS cages at chain ends. The incorporation of the POSS-IMC, free and ionically bonded in clay, gives rise to dissimilar morphologies that affect the thermo-mechanical properties of the hybrids. The ECHM/HHPA/POSS-IMC resin exhibits a slight improvement in glassy modulus as compared with the neat ECHM/HHPA resin, which is attributed to the formation of sub-micron and nano-sized POSS domains that act as physical cross-link points hindering polymer chain motions. The much enhanced reinforcing effect of POSS-MMT is ascribed to the effective stress transfer between the matrix and clay layers that may originate from the strong interactions between the pendent POSS in the network and POSS attached to the clay surfaces. Reduction in coefficient of thermal expansion (CTE) was also found for the hybrids.     

Nanotailoring of Nanocomposite Hydrogels Containing POSS

The development and commercialization of nanoparticles such as nanoclays, carbon nanotubes and polyhedral-oligomeric-sil-sesquioxanes (POSS) offer new possibilities to tailor hydrogels in the nanometer scale range. Due to the large surface area of the nanosize particles, only small amounts are needed to cause significant changes in hydrogels properties. Properties affected include swelling behavior and thermo-mechanical properties. Experimental results showed that only small amounts of POSS (<5 wt%) were needed to enhance the storage modulus and the swelling ability compared with that of the pure Poly(N-vinyl-2-pyrrolidone itaconic acid) hydrogel. In the case of epoxy functionalized POSS incorporated into the hydrogel, the weight swelling increased by more than 120% while the volumetric swelling by 350%. In addition the storage modulus increased by 300% compared to the neat hydrogel. The results led to the conclusion that the incorporation of functionalized POSS particles in hydrogels could improve the hydrogel properties.     

Fabrication and characterization of functionally graded nanoclay/glass fiber/epoxy hybrid nanocomposite laminates

In this work, hardness, tensile, impact, bearing strength and water absorption tests were performed to study the mechanical properties of stepwise graded and non-graded hybrid nanocomposites. Three different stepwise graded nanocomposites and one non-graded (homogeneous) nanocomposite with the same geometry and total nanoclay content of 10 wt% were designed and prepared. Moreover, one neat glass fiber laminate was manufactured. The results of the tests indicated that addition of the graded and non-graded nanoclay improves hardness over neat glass fiber reinforcement. The maximum increase in hardness of about 53% over neat specimen is obtained for specimens that have the highest weight percentage (2 wt%) of the clay nanoparticles on its surface (S-specimen and the side of F-specimen that reinforced with 2 wt% nanoclay). The gradation process results in an increase in hardness of about 11% compared with non-graded (homogeneous) specimen. In addition, an improvement of 11.9% in strain-to-failure is achieved with specimen having greatest amount of nanoclay in the middle over neat glass fiber/epoxy composite. The other nanoclay-filled glass fiber composites have strain-to-failure close to neat glass fiber/epoxy. The addition of nanoclay reinforcement has insignificant effect on ultimate tensile strength, tensile modulus, water absorption, bearing strength and impact strength compared with neat glass fiber/epoxy.     

Synthesis of EP‐POSS mixture and the properties of EP‐POSS/epoxy,SiO2/epoxy,and SiO2/EP‐POSS/epoxy nanocomposite

The hybrid material of EP‐POSS mixture was synthesized by the hydrolysis and condensation of (γ‐glycidoxypropyl) trimethoxysilane. A series of binary systems of EP‐POSS/epoxy blends, epoxy resin modified by silica nanoparticles (SiO₂/epoxy), and ternary system of SiO₂/EP‐POSS/epoxy nanocomposite were prepared. The dispersion of SiO₂ in the matrices was evidenced by transmission electron micrograph, and the mechanical properties, that is, flexural strength, flexural modulus, and impact strength were examined for EP‐POSS/epoxy blends, SiO₂/epoxy, and SiO₂/EP‐POSS/epoxy, respectively. The fractured surface of the impact samples was observed by scanning electron micrograph. Thermogravimetry analysis were applied to investigate the different thermal stabilities of the binary system and ternary system by introducing EP‐POSS and SiO₂ to epoxy resin. The results showed that the impact strength, flexural strength, and modulus of the SiO₂/EP‐POSS/epoxy system increased around by 57.9, 14.1, and 44.0% compared with the pure epoxy resin, T_i, T_max and the residues of the ternary system were 387°C, 426°C, and 25.2%, increased remarkably by 20°C, 11°C and 101.6% in contrast to the pure epoxy resin, which was also higher than the binary systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 810‐819, 2013     

Surface functionalization of HMPBO fibers with MSA/KH550/GlycidylEthyl POSS and improved interfacial adhesion

A novel “three‐step approach” of methanesulfonic acid/γ‐aminopropyl triethoxy silane/GlycidylEthyl polyhedral oligomeric silsesquioxane (MSA/KH550/POSS) was proposed to functionalize the surface of high modulus poly (p‐phenylene‐2,6‐benzobisoxazole) (HMPBO) fibers. Results indicated that GlycidylEthyl POSS was successfully grafted on the surface of HMPBO fibers and the surface roughness of HMPBO fibers was increased obviously. The single fiber pull‐out strength of POSS‐g‐HMPBO/epoxy resin microcomposite was improved to 1.19 MPa, better than that of native HMPBO/epoxy resin microcomposite. POLYM. COMPOS., 35:611–616, 2014. © 2013 Society of Plastics Engineers     

Thermal conductivity and dynamic mechanical property of glycidyl methacrylate‐grafted multiwalled carbon nanotube/epoxy composites

The well dispersed multiwalled carbon nanotube (MWCNT)/epoxy composites were prepared by functionalization of the MWCNT surfaces with glycidyl methacrylate (GMA). The morphology and thermal properties of the epoxy nanocomposites were investigated and compared with the surface characteristics of MWCNTs. GMA‐grafted MWCNTs improved the dispersion and interfacial adhesion in epoxy resin, and enhanced the network structure. The storage modulus of 3 phr GMA‐MWCNTs/epoxy composites at 50°C increased from 0.32 GPa to 2.87 GPa (enhanced by 799%) and the increased tanδ from 50.5°C to 61.7°C (increased by 11.2°C) comparing with neat epoxy resin, respectively. Furthermore, the thermal conductivity of 3 phr GMA‐MWCNTs/epoxy composite is increased by 183%, from 0.2042 W/mK (neat epoxy) to 0.5781 W/mK. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties of graphene nanoplatelet/epoxy composites

Because of their high‐specific stiffness, carbon‐filled epoxy composites can be used in structural components in fixed‐wing aircraft. Graphene nanoplatelets (GNPs) are short stacks of individual layers of graphite that are a newly developed, lower cost material that often increases the composite tensile modulus. In this work, researchers fabricated neat epoxy (EPON 862 with Curing Agent W) and 1–6 wt % GNP in epoxy composites. The cure cycle used for this aerospace epoxy resin was 2 h at 121°C followed by 2 h at 177°C. These materials were tested for tensile properties using typical macroscopic measurements. Nanoindentation was also used to determine modulus and creep compliance. These macroscopic results showed that the tensile modulus increased from 2.72 GPa for the neat epoxy to 3.36 GPa for 6 wt % (3.7 vol %) GNP in epoxy composite. The modulus results from nanoindentation followed this same trend. For loadings from 10 to 45 mN, the creep compliance for the neat epoxy and GNP/epoxy composites was similar. The GNP aspect ratio in the composite samples was confirmed to be similar to that of the as‐received material by using the percolation threshold measured from electrical resistivity measurements. Using this GNP aspect ratio, the two‐dimensional randomly oriented filler Halpin–Tsai model adjusted for platelet filler shape predicts the tensile modulus well for the GNP/epoxy composites. Per the authors' knowledge, mechanical properties and modeling for this GNP/epoxy system have never been reported in the open literature. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Kinetic studies of POSS–DGEBA precursors derived from monoamine functional POSS using dynamic dielectric sensing and nuclear magnetic resonance

Incorporation of pre‐reacted monofunctional polyhedral oligomeric silsesquioxane (POSS)–epoxy adducts dramatically improves dispersion of POSS in epoxy–amine networks. The relationship between reaction kinetics and mechanism for formation of POSS–epoxy adducts versus reaction temperature was investigated. Reactivities of epoxy–monoamine functional POSS molecules were determined using in situ reaction monitoring by dynamic dielectric sensing and ²⁹Si NMR spectroscopy. The amine‐functional POSS–epoxy isothermal reaction showed reduced reactivity due to reduced molecular mobility, that is, diffusion limitations. Kinetic parameters were determined by fitting ²⁹Si NMR data to the model of Kamal that was extended to include diffusion. Fitting of this model to experimental data showed very good agreement over the entire conversion range for pre‐reaction between amine‐functionalized POSS and epoxy. An autocatalytic mechanism, the same as that for the neat epoxy–amine systems, was indicated. Gel permeation chromatography, scanning electron microscopy and transmission electron microscopy were used to investigate molecular weight evolution and morphology of final networks cured by 4,4′ diaminodiphenyl sulfone using pre‐reacted POSS–epoxy adducts. POSS aggregate size decreased with increased pre‐reaction temperature; more homogenous POSS dispersion was observed with higher pre‐reaction temperature. Dynamic mechanical analysis demonstrated that T_g of composites decreased slightly compared to that of the neat matrix and there appeared to be little change in microstructural heterogeneity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45994.     

微脱黏法在碳纤维/环氧树脂界面性能评价中的应用

利用微脱黏法测定碳纤维/环氧树脂复合材料的界面剪切强度,并分析了造成测试结果分散的影响因素.结果表明:在脱黏过程中,最大脱黏力随碳纤维埋人环氧树脂内长度的增加而线性递增,当埋人长度超过一定值后最大脱黏力趋于稳定:碳纤维与环氧树脂间的接触角对复合材料界面剪切强度有一定影响,接触角越大,界面剪切强度越高;测试结果的分散性与树脂微球的半月板区域、钳口区等因素有关;未经表面处理的碳纤维增强环氧树脂复合材料的界面剪切强度仪为39.4 MPa,低于处理后的复合材料(60.6 MPa).     

Formation of a carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube hybrid reinforcement and its effect on the interfacial properties of carbon fiber/epoxy composites

A carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube (CF–POSS–CNT) hybrid reinforcement was prepared by grafting CNTs onto the carbon fiber surface using octaglycidyldimethylsilyl POSS as the linkage in an attempt to improve the interfacial properties between carbon fibers and an epoxy matrix. X-ray photoelectron spectroscopy, scanning electron microscopy, dynamic contact angle analysis and single fiber tensile testing were performed to characterize the hybrid reinforcements. Interlaminar shear strength (ILSS), impact toughness, dynamic mechanical analysis and force modulation atomic force microscopy were carried out to investigate the interfacial properties of the composites. Experimental results show that POSS and CNTs are grafted uniformly on the fiber surface and significantly increase the fiber surface roughness. The polar functional groups and surface energy of carbon fibers are obviously increased after the modification. Single fiber tensile testing results demonstrate that the functionalization does not lead to any discernable decrease in the fiber tensile strength. Mechanical property test results indicate the ILSS and impact toughness are enhanced. The storage modulus and service temperature increase by 11 GPa and 17 °C, respectively. POSS and CNTs effectively enhance the interfacial adhesion of the composites by improving resin wettability, increasing chemical bonding and mechanical interlocking.     

Thermal pressure coefficient of a polyhedral oligomeric silsesquioxane (POSS)‐reinforced epoxy resin

The thermal pressure coefficients of a neat, unfilled, epoxy resin and a 10 wt % POSS (polyhedral oligomeric silsesquioxane)‐filled epoxy nanocomposite have been measured using a thick‐walled tube method. It is found that just below the glass transition temperature the thermal pressure coefficient is ～ 20% smaller for the polymer composite containing 10% POSS than for the neat, unfilled resin. The thermal expansion coefficient and thermal pressure coefficient of the uncured POSS itself are also reported. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Role of core‐shell rubber particle cavitation resistance on toughenability of epoxy resins

The role of rubber particle cavitation resistance on toughening of epoxy resins is still unresolved. In this research, the role of rubber particle cavitation resistance was exclusively studied. Two types of core‐shell rubber (CSR) particles with different cavitation resistances were utilized for modifying epoxy resin. Matrix crosslink density (XLD) was varied by using nonstoichiometric amounts of hardener. Fracture toughness values of neat and CSR‐modified epoxy samples decreased with lowering of XLD via deviation from stoichiometric point. It was resulted by higher modulus and lower elongation at break of the nonstoichiometric samples, and also antiplasticization of epoxy networks resulted from suppression of β‐transition relaxation motions. In all XLDs, the CSR particles with higher core T_g and modulus yielded higher fracture energy. Results showed that core properties such as T_g and modulus of CSR particles had a significant effect on toughening of the epoxy networks. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Study of epoxy toughened by in situ formed rubber nanoparticles

The effect of rubber nanoparticles on mechanical properties and fracture toughness was investigated. Rubber nanoparticles of 2–3 nm were in situ synthesized in epoxy taking advantage of the reaction of an oligomer diamine with epoxy. The chemical reaction was verified by gel permeation chromatography (GPC) and ¹HNMR, and the microstructure was characterized by transmission electron microscope. The rubber nanoparticles caused much less Young's modulus deterioration but toughened epoxy to a similar degree in comparison with their peer liquid rubber that formed microscale particles during curing. Fifteen wt % of rubber nanoparticles increased fracture energy from 140 to 840 J/m² with Young's modulus loss from 2.85 to 2.49 GPa. The toughening mechanism might be the stress relaxation of the matrix epoxy leading to larger plastic work absorbed at the crack tip; there is no particle cavitation or deformation; neither crack deflection nor particle bridging were observed. The compound containing rubber nanoparticles demonstrates Newtonian liquid behavior with increasing shear rate; it shows lower initial viscosity at low shear rate than neat epoxy; this provides supplementary evidence to NMR and GPC result. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Adhesion Characteristics of Carbon Black Embedded Glass/Epoxy Composite

The surface of glass/epoxy composite material was embedded with carbon black which was dispersed in methyl ethyl ketone (MEK) during the curing process to enhance the adhesion strength of the glass/epoxy composite structure. The morphological effect of the carbon black on the surface of composite was observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Quantitative chemical bonding analysis with X-ray photoelectron spectroscopy (XPS) was also performed to observe chemical bonding states on the surface. The lap shear strength of the glass/epoxy composite adhesive joints where composite adherends were embedded with carbon black was investigated with respect to the type and amount of embedment. Also, the tensile properties of the carbon black embedded glass/epoxy composites were measured to observe the mechanical degradation of the composite due to the MEK. The surface free energies of carbon black embedded composites were determined from the van Oss–Chaudhury–Good equation to correlate the lap shear strength of the adhesive joints with the surface free energies of composite adherends. From the experimental results, it was found that the carbon black embedment of the composite adherend improved much the bond strength due to the increased surface roughness on nano-scale as well as increased surface free energy.     

Crystallization,morphology, and mechanical properties of poly(butylene succinate)/poly(ethylene oxide)‐polyhedral oligomeric silsesquioxane nanocomposites

The biodegradable poly(butylene succinate) (PBS)/poly(ethylene oxide)‐polyhedral oligomeric silsesquioxane (PEO‐POSS) nanocomposites were prepared by the solution blending and melt‐injection methods. The effect of PEO‐POSS on the non‐isothermal and isothermal crystallization, morphology, as well as mechanical properties of PBS was carefully investigated. The PEO‐POSS nanoparticles dispersed well in the PBS matrix, with the diameters around 30 nm. From isothermal crystallization analysis, the incorporation of PEO‐POSS enhanced the crystallization of PBS due to the heterogeneous nucleation effect while the crystal structure of PBS remained. PBS/PEO‐POSS nanocomposites showed of higher glass transition temperatures than that of neat PBS, attributing to the existence of PEO‐POSS decreasing the flexibility of PBS chains. The elongation at break of the PBS/PEO‐POSS nanocomposites reached the maximum value with PEO‐POSS content of 5 wt%. However, the elastic modulus of PBS decreased after the incorporation of PEO‐POSS. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Polyhedral oligomeric silsesquioxane trisilanols as dispersants for titanium oxide nanopowder

Trisilanol isobutyl polyhedral oligomeric silsesquioxane (POSS) was used to disperse nanosized titanium dioxide (TiO₂) particles in polypropylene (PP). The silanol groups of the POSS cage were bound to the surface of the TiO₂ particles, creating a layer of isobutyl POSS that improved compatibility with the PP matrix. POSS was an effective dispersant both when applied in a chemical pretreatment of TiO₂ and when simply added to the blend during melt compounding. The average particle size of TiO₂ was reduced from 70 nm for neat TiO₂ to 50 nm for the POSS/TiO₂ blend to 33 nm for TiO₂ chemically treated with POSS. Additionally, the POSS coating improved the color of the material and reduced the catalytic effect of TiO₂ on thermooxidative degradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Epoxy/acrylonitrile-butadiene-styrene copolymer/clay ternary nanocomposite as impact toughened epoxy

Epoxy resins have low impact strength and poor resistance to crack propagation, which limit their many end use applications. The main objective of this work is to incorporate both acrylonitrile-butadiene-styrene copolymer (ABS) and organically modified clay (Cloisite 30B) into epoxy matrix with the aim of obtaining improved material with the impact strength higher than neat epoxy, epoxy/clay and epoxy/ABS hybrids without compromising the other desired mechanical properties such as tensile strength and modulus. Impact and tensile properties of binary and ternary systems were investigated. Tensile strength, elongation at break and impact strength were increased significantly with incorporation of only 4 phr ABS to epoxy matrix. For epoxy/clay nanocomposite with 2.5% clay content, tensile modulus and strength, and impact strength were improved compared to neat epoxy. With incorporation of 2.5% clay and 4 phr ABS into epoxy matrix, 133% increase was observed for impact strength. Ternary nanocomposite had impact and tensile strengths greater than values of the binary systems. Morphological properties of epoxy/ABS, epoxy/clay and epoxy/ABS/clay ternary nanocomposite were studied using atomic force microscopy (AFM) phase imaging, scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). New morphologies were achieved for epoxy/ABS and epoxy/ABS/clay hybrid materials. Exfoliated clay structure was obtained for epoxy/clay and epoxy/ABS/clay nanocomposite.     

Epoxy nanocomposites containing mercaptopropyl polyhedral oligomeric silsesquioxane: Morphology,thermal properties,and toughening mechanism

A novel polyhedral oligomeric silsesquioxane (POSS) containing a mercaptopropyl group [mercaptopropyl polyhedral oligomeric silsesquioxane (MPOSS)] was synthesized via the hydrolytic condensation of γ-mercaptopropyl triethoxysilane in an ethanol solution catalyzed by concentrated hydrochloric acid and was used to modify epoxy–amine networks by a cocuring reaction with diglycidyl ether of bisphenol A (DGEBA). The structure, morphology, and thermal and mechanical properties of these MPOSS/DGEBA epoxy nanocomposites were studied and investigated with thermogravimetric analysis/differential thermal analysis (TGA–DTA), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). From SEM analysis, we observed that the miscibility between epoxy and POSS occurred at a relatively high POSS content, which characterized this mixture as a polymer nanocomposite system. The impact test showed that MPOSS reinforced the epoxy effectively, and the SEM study of the impact fracture surface showed that the fibrous yielding phenomenon observed was an indication of the transition of the brittle stage to a ductile stage and correlated well with the large increases in the impact strength; this was in agreement with the in situ reinforcing and toughening mechanism. The TGA–DTA analysis indicated that the MPOSS/DGEBA epoxy hybrids exhibited lower thermostability at a lower temperature but higher thermostability and higher efficiency in char formation at an elevated temperature. Differential scanning calorimetry showed that the glass transition temperature (T_g) of the MPOSS/epoxy hybrids were lower than that of the neat epoxy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008