Preparation and properties of TiO2‐filled poly(acrylonitrile‐butadiene‐styrene)/epoxy hybrid composites

Poly (acrylonitrile‐butadiene‐styrene) (ABS) was used to modify diglycidyl ether of bisphenol‐A type of epoxy resin, and the modified epoxy resin was used as the matrix for making TiO₂ reinforced nanocomposites and were cured with diaminodiphenyl sulfone for superior mechanical and thermal properties. The hybrid nanocomposites were characterized by using thermogravimetric analyzer (TGA), dynamic mechanical analyzer (DMA), universal testing machine (UTM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The bulk morphology was carefully analyzed by SEM and TEM and was supported by other techniques. DMA studies revealed that the DDS‐cured epoxy/ABS/TiO₂ hybrid composites systems have two T_gs corresponding to epoxy and ABS rich phases and have better load bearing capacity with the addition of TiO₂ particles. The addition of TiO₂ induces a significant increase in tensile properties, impact strength, and fracture toughness with respect to neat blend matrix. Tensile toughness reveals a twofold increase with the addition of 0.7 wt % TiO₂ filler in the blend matrix with respect to neat blend. SEM micrographs of fractured surfaces establish a synergetic effect of both ABS and TiO₂ components in the epoxy matrix. The phenomenon such us cavitation, crack path deflection, crack pinning, ductile tearing of the thermoplastic, and local plastic deformation of the matrix with some minor agglomerates of TiO₂ are observed. However, between these agglomerates, the particles are separated well and are distributed homogeneously within the polymer matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improving thermal conductivity and shear strength of carbon nanotubes/epoxy composites via thiol‐ene click reaction

This study investigates the effect of the thiol‐ene click reaction on thermal conductivity and shear strength of the epoxy composites reinforced by various silane‐functionalized hybrids of sulfhydryl‐grafted multi‐walled carbon nanotubes (SH‐MWCNTs) and vinyl‐grafted MWCNTs (CC‐MWCNTs). The results of Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermal gravimetric analysis (TGA), and transmission electron microscopy (TEM) show that the sulfhydryl groups and vinyl groups are successfully grafted onto the surface of MWCNTs, after treatment of MWCNT with triethoxyvinylsilane and 3‐mercaptopropyltrimethoxysilane, respectively. Scanning electron microscopy (SEM), HotDisk thermal constant analyzer (HotDisk), optical microscope, and differential scanning calorimetry (DSC) are used to characterize the resultant composites. It is demonstrated that the hybrid of 75 wt % SH‐MWCNTs and 25 wt % CC‐MWCNTs has better dispersion and stability in epoxy matrix, and shows a stronger synergistic effect in improving the thermal conductivity of epoxy composite via the thiol‐ene click reaction with 2,2′‐azobis(2‐methylpropionitrile) as thermal initiator. Furthermore, the tensile shear strength results of MWCNT/epoxy composites and the optical microscopy photographs of shear failure section indicate that the composite with the hybrid MWCNTs has higher shear strength than that with raw MWCNTs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44579.     

Preparation and properties of multiwalled carbon nanotube/epoxy‐amine composites

Different amounts of multiwalled carbon tubes (MWCNTs) were incorporated into an epoxy resin based on diglycidyl ether of bisphenol A and both epoxy precursor and composite were cured with 4,4′‐diamino diphenyl sulfone. Transmission and scanning electron microscopy demonstrated that the carbon nanotubes are dispersed well in the epoxy matrix. Differential scanning calorimetry measurements confirmed the decrease in overall cure by the addition of MWCNTs. A decrease in volume shrinkage of the epoxy matrix caused by the addition of MWCNTs was observed by pressure–volume–temperature measurements. Thermomechanical and dynamic mechanical analysis were performed for the MWCNT/epoxy composites, showing that the T_g was slightly affected, whereas the dimensional stability and stiffness are improved by the addition of MWCNTs. Electrical conductivity measurements of the composite samples showed that an insulator to conductor transition takes place between 0.019 and 0.037 wt % MWCNTs. The addition of MWCNTs induces an increase in both impact strength (18%) and fracture toughness (38%) of the epoxy matrix with very low filler content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical properties of poly(styrene‐co‐acrylonitrile)‐modified epoxy resin/glass fiber composites

Poly(styrene‐co‐acylonitrile) was used to modify diglycedyl ether of bisphenol‐A type epoxy resin cured with diamino diphenyl sulfone and the modified epoxy resin was used as the matrix for fiber‐reinforced composites (FRPs) to get improved mechanical properties. E‐glass fiber was used as fiber reinforcement. The tensile, flexural, and impact properties of the blends and composites were investigated. The blends exhibited considerable improvement in mechanical properties. The scanning electron micrographs of the fractured surfaces of the blends and tensile fractured surfaces of the composites were also analyzed. The micrographs showed the influence of morphology on the properties of blends. Results showed that the mechanical properties of glass FRPs increased gradually upon fiber loading. Predictive models were applied using various equations to compare the mechanical data obtained theoretically and experimentally. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of amino‐functionalization of multi‐walled carbon nanotubes on the dispersion with epoxy resin matrix

Amino‐functionalization of multiwalled carbon nanotubes (MWCNTs) was carried out by grafting triethylenetetramine (TETA) on the surfaces of MWCNTs through the acid–thionyl chloride way. The amino‐functionalized MWCNTs show improved compatibility with epoxy resin and, as a result, more homogenous dispersion in the matrix. The mechanical, optical, and thermal properties of the amino‐functionalized MWCNT/epoxy composites were also investigated. It was found that introducing the amino‐functionalized MWCNTs into epoxy resin greatly increased the charpy impact strength, glass transition temperature, and initial decomposing temperature of cured epoxy resin. In addition, introducing unfunctionalized MWCNTs into epoxy resin was found greatly depressing the light transmission properties, which would affirmatively confine the application of the MWCNTs/epoxy composites in the future, while much higher light transmittance than that of unfunctionalized MWCNTs/epoxy composites was found for amino‐functionalized MWCNTs/epoxy composites. SEM of the impact cross section and TEM of ultrathin film of the amino‐functionalized MWCNTs/epoxy composites showed that the amino‐functionalized MWCNTs were wetted well by epoxy matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 97–104, 2006     

Acid‐Based Surfactant‐Aided Dispersion of Multi‐Walled Carbon Nanotubes in Epoxy‐Based Nanocomposites

In this study, the dispersion of multi‐walled carbon nanotubes (MWCNTs) in epoxy was facilitated by an anionic surfactant, linear alkyl benzene sulfonic acid. Different types of composites were prepared using a fixed amount of MWCNTs (0.5 wt%), in absence of solvent/surfactant, in presence of solvent and solvent/surfactant. The composites were characterized using Fourier transform infrared spectrophotometer, thermogravimetric analyzer (TGA), differential scanning calorimeter (DSC), universal testing machine, pendulum impact system, X‐ray diffraction, and scanning electron microscope. The epoxy/MWCNTs nanocomposite exhibited significantly higher mechanical properties due to the better dispersion in the presence of the surfactant. The tensile strength and flexural strength were increased by 75% and 108%, respectively. The thermal, structural, and morphological analyses were also excellent as a result of the better dispersion. In addition, the solvent‐surfactant behavior was hypothesized for the epoxy/MWCNTs system. POLYM. ENG. SCI., 59:E80–E87, 2019. © 2018 Society of Plastics Engineers     

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     

环氧树脂/ABS复合材料的制备及性能表征

以环氧树脂为基体,苯乙烯-丙烯腈-丁二烯（ABS）树脂为增韧剂,制备了环氧树脂/ABS复合材料,讨论了增韧剂对复合材料的热性能和机械性能的影响。结果表明,ABS的添加可提高复合材料的断裂韧性。扫描电镜结果显示,基体的剪切屈服和橡胶颗粒的微孔洞是ABS增韧环氧树脂的主要增韧机理。     

Toughening of cycloaliphatic epoxy resin by multiwalled carbon nanotubes

The toughness of cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate (ERL‐4221) has been improved by using multiwalled carbon nanotubes (MWCNTs) treated by mixed acids. The MWCNT/ERL‐4221 composites were characterized by Raman spectroscopy and their mechanical properties were investigated. A significant increase in the tensile strength of the composite from 31.9 to 55.9 MPa was obtained by adding only 0.05 wt % of MWCNTs. And a loading of 0.5 wt % MWCNTs resulted in an optimum tensile strength and cracking energy, 62.0 MPa and 490 N cm, respectively. Investigation on the morphology of fracture surface of the composites by field emission scanning electron microscopy demonstrated the crack pinning‐front bowing and bridging mechanisms of toughening. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A comparative study on the properties of the different amino‐functionalized multiwall carbon nanotubes reinforced epoxy resin composites

Multiwall carbon nanotubes (MWCNTs) were amino‐functionalized by 1,2‐ethylenediamine (EDA)' triethylenetetramine (TETA), and dodecylamine (DDA), and investigated by fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and thermogravimetric analysis (TGA). The dispersion of the DDA functionalized MWCNT in DMF is better than that of the MWCNT functionalized by the EDA and the TETA. Carbon nanotubes reinforced epoxy resin composites were prepared, and the effect of the amino‐functionalization on the properties of the composites was investigated by differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), and TGA. The composites reinforced by the MWCNTs demonstrate improvement in various mechanical properties. The increase of T_g of the composites with the addition of amino‐functionalized MWCNT compared to the T_g of the composites with the addition of unfunctionalized MWCNT was due to the chemical combination and the physical entanglements between amino group from modified MWNTs and epoxy group from the epoxy resin. The interfacial bonding between the epoxy and the amino group of the EDA and the TETA‐modified MWCNT is more important than the well dispersion of DDA‐modified MWCNT in the composites for the improvement of the mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rheological properties and fracture toughness of epoxy resin/multi‐walled carbon nanotube composites

Multi‐walled carbon nanotubes (MWCNTs), surface‐treated via chemical functionalization, i.e., oxidation and amidation, were used to reinforce diglycidylether of bisphenol F (DGEBF) epoxy resin. The effects of the functionalization on the dispersion stability, rheological properties, and fracture toughness of DGEBF/MWCNT composites were investigated. The dispersion homogeneity of the MWCNTs in the epoxy matrix improved after functionalization. In addition, isothermal rheology measurements revealed that the DGEBF/dodecyl amine‐functionalized MWCNT (D‐MWCNT) composite had a longer gel time and higher activation energy of cross‐linking than the DGEBF/acid‐treated MWCNT (A‐MWCNT) composite. The fracture toughness of the former was also significantly higher than that of the latter; this resulted from the relatively high dispersion stability of the D‐MWCNTs in the epoxy matrix, owing to the presence of alkyl groups on the D‐MWCNT surface. POLYM. ENG. SCI., 55:2676–2682, 2015. © 2015 Society of Plastics Engineers     

Effect of multi‐walled carbon nanotubes dispersity on the light transmittancy of multi‐walled carbon nanotubes/epoxy composites

Two types of multi‐walled carbon nanotubes (MWCNTs), chemically modified and unmodified, were dispersed in epoxy resin with ultrasonication. The light transmittance characteristics of epoxy composites with different ratios of MWCNTs to epoxy resin were measured at wavelengths ranging from 200 to 1100 nm. Results showed that composites with modified MWCNTs had a much higher light transmittance than those with unmodified MWCNTs. This was presumably due to a more uniform dispersion of modified MWCNTs in the epoxy matrix, as indicated by both transmission electron microscopy and optic microscopy. The wavelength dependency of light transmittance of the composites was expressed empirically as a function of weight fraction (f_w) of MWCNTs and the light wavelength (λ). POLYM. ENG. SCI. 46:635–642, 2006. © 2006 Society of Plastics Engineers.     

Epoxy‐tert‐butyl poly(cyanoarylene ether) blends: Phase morphology,fracture toughness,and mechanical properties

Tert‐butyl hydroquinone–based poly(cyanoarylene ether) (PENT) was synthesized by the nucleophilic aromatic substitution reaction of 2,6‐dichlorobenzonitrile with tert‐butyl hydroquinone using N‐methyl‐2‐pyrrolidone (NMP) as solvent in the presence of anhydrous potassium carbonate in a nitrogen atmosphere at 200°C. PENT‐toughened diglycidyl ether of bisphenol A epoxy resin (DGEBA) was developed using 4,4′‐diaminodiphenyl sulfone (DDS) as the curing agent. Scanning electron micrographs revealed that all blends had a two‐phase morphology. The morphology changed from dispersed PENT to a cocontinuous structure with an increase in PENT content in the blends from 5 to 15 phr. The viscoelastic properties of the blends were investigated using dynamic mechanical thermal analysis. The storage modulus of the blends was less than that of the unmodified resin, whereas the loss modulus of the blends was higher than that of the neat epoxy. The tensile strength of the blends improved slightly, whereas flexural strength remained the same as that of the unmodified resin. Fracture toughness was found to increase with an increase in PENT content in the blends. Toughening mechanisms like local plastic deformation of the matrix, crack path deflection, crack pinning, ductile tearing of thermoplastic, and particle bridging were evident from the scanning electron micrographs of failed specimens from the fracture toughness measurements. The thermal stability of the blends were comparable to that of the neat resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3536–3544, 2006     

Toughening of an epoxy resin with hydroxy‐terminated poly(arylene ether nitrile) with pendent tertiary butyl groups

Hydroxy‐terminated poly(arylene ether nitrile) oligomers with pendent tert‐butyl groups (PENTOH) were synthesized by the nucleophilic aromatic substitution reaction of 2,6‐dichlorobenzonitrile with tert‐butyl hydroquinone in N‐methyl‐2‐pyrrolidone medium with anhydrous potassium carbonate as a catalyst at 200°C in a nitrogen atmosphere. The PENTOH oligomers were blended with diglycidyl ether of bisphenol A epoxy resin and cured with 4,4′‐diaminodiphenyl sulfone. The curing reaction was monitored with infrared spectroscopy and differential scanning calorimetry. The morphology, fracture toughness, and thermomechanical properties of the blends were investigated. The scanning electron micrographs revealed a two‐phase morphology with a particulate structure of the PENTOH phase dispersed in the epoxy matrix, except for the epoxy resin modified with PENTOH with a number‐average molecular weight of approximately 4000. The storage modulus of the blends was higher than that of the neat epoxy resin. The crosslink density calculated from the storage modulus in the rubbery plateau region decreased with an increase in PENTOH in the blends. The fracture toughness increased more than twofold with the addition of PENTOH oligomers. The tensile strength of the blends increased marginally, whereas the flexural strength decreased marginally. The dispersed PENTOH initiated several toughening mechanisms, which improved the fracture toughness of the blends. The thermal stability of the epoxy resin was not affected by the addition of PENTOH to the epoxy resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

FTIR and SEM analysis of polyester‐ and epoxy‐based composites manufactured by VARTM process

Polyester‐ and epoxy‐based composites containing glass and carbon fibers were manufactured using a vacuum‐assisted resin transfer molding (VARTM) process. Fourier transform infrared (FTIR) spectroscopy analyses were conducted to determine the interaction between fibers and matrix material. The results indicate that strong interaction was observed between carbon fiber and epoxy resin. However, weak interactions between remaining fiber‐matrix occur. Scanning electron microscopy (SEM) analysis was also performed to take some information about strength of interaction between fibers and matrix material. From SEM micrographs, it is concluded that the findings in SEM analysis support to that obtained in FTIR analysis. Another aim of the present work was to investigate the influence of matrix on composite properties. Hence, the strengths of composites having same reinforcement but different matrix systems in axial tension and transverse tension were compared. Short beam shear test has been conducted to characterize the interfacial strength in the composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Temperature effect on graphene‐filled interface between glass–carbon hybrid fibers and epoxy resin characterized by fiber‐bundle pull‐out test

The overall mechanical performance of glass–carbon hybrid fibers reinforced epoxy composites depends heavily upon fiber–matrix interfacial properties and the service temperatures. Fiber‐bundle pull‐out tests of glass (GF) and/or carbon fiber (CF) reinforced epoxy composites were carried out at room and elevated temperatures. Graphene nanoplatelets were added in the interfacial region to investigate their influence on the interfacial shear strength (IFSS). Results show that IFSS of specimens with fiber‐bundle number ratio of GF:CF = 1:2 is the largest among the hybrid composites, and a positive hybridization effect is found at elevated temperatures. IFSS of all the specimens decreases with the increasing of test temperatures, while the toughness shows a contrary tendency. As verified by scanning electron microscopy observations, graphene nanoplatelets on fiber surface could enhance the IFSS of pure glass/carbon and hybrid fibers reinforced epoxy composites at higher temperatures significantly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46263.     

Mode II interlaminar fracture behavior of carbon bead‐filled epoxy/glass fiber hybrid composite

To investigate the effect of including carbon beads on the mechanical properties of epoxy resin, the fracture toughness of carbon bead‐filled epoxy was earlier evaluated using a CT (compact tension) specimens and Mode I fracture toughness was observed. Based on those results, in this study, the Mode II interlaminar fracture toughness of carbon bead filled epoxy/glass fiber hybrid composites was evaluated using end notch flexure (ENF) specimens. The hybrid composites showed increased Mode II interlaminar fracture toughness. The optimal bead volume fraction was around 15%.     

Multiscale fiber‐reinforced composites prepared by vacuum‐assisted resin transfer molding

Carbon nanotube (CNT)/aramid fiber epoxy composites were produced using a new manufacturing method proposed in this study. The rheological and morphological experiments of the CNT/PEO nanocomposites indicates that the PEO nanocomposites have a good dispersion state of the CNTs. The flexural mechanical properties of the aramid fiber/CNT epoxy composites were measured. The CNTs dispersed in the epoxy resin between the aramid fibers were observed using field emission scanning electron miscroscope (FESEM). It was found that the flexural properties of the multiscale fiber‐reinforced composites were higher than those of aramid fiber/epoxy composites. POLYM. COMPOS., 28:458–461, 2007. © 2007 Society of Plastics Engineers.     

Curing and toughening of a styrene‐modified epoxy resin

A commercially available epoxy resin (E907) formulated with a viscosity‐reducing styrene monomer and several additives was subjected to thermal cure studies and mechanical property measurements. Thermoplastic poly(arylene ether sulfone) (PES) and poly(arylene ether phosphine oxide) (PEPO) with reactive amine or hydroxyl end groups were utilized to toughen and co‐cure with the system. The cure cycle was optimized and the networks were analyzed via differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analyzer, scanning electron microscopy, sol–gel extractions, and fracture toughness. A model epoxy resin was prepared from a tetrafunctional epoxy, e.g., MY722, difunctional EPON828, styrene monomer, and benzoyl peroxide initiator (BPO), and was evaluated as a control to assess the possible role of the styrene monomer. The optimized cure cycle for E907 was 6 h at 93°C, followed by a postcure of 2 h at 204°C. The fracture toughness of E907 was increased only marginally with PES and PEPO. In contrast, the model epoxy resin demonstrated a positive effect due to the styrene monomer and BPO and exhibited significantly increased fracture toughness with PES modification. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1504–1513, 2001     

Preparation and thermo‐mechanical properties of heat‐resistant epoxy/silica hybrid materials

Diglycidyl ether of bisphenol‐A (DGEBA) based epoxy/silica hybrid materials filled with various amounts of 3‐glycidoxypropyltrimethoxysilane (GPTMS) and silica nanoparticles were prepared, using 4,4′‐diaminodiphenyl sulfone (DDS) as curing agent. The obtained hybrid materials were analyzed by means of Fourier‐transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results indicated that the introduction of GPTMS and silica nanoparticles had synergistic effect. The addition of GPTMS not only ameliorated the compatibility between silica and the epoxy matrix but also increased the crosslinking density of the epoxy system; meanwhile the nano‐silica further reinforced the inorganic network of the hybrid system. Consequently, the hybrid materials showed much improved heat‐resistant properties. The storage modulus of the hybrid systems showed no obvious decrement in the glass transition region and kept at a high value even in the temperature region up to 300°C. The integral thermal stability of the resulting hybrid materials was also improved compared with the corresponding pure epoxy resin. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.