Fracture toughness of bisphenol A‐type epoxy resin

The relationship between the postcuring conditions and the fracture toughness of a bisphenol A‐type epoxy resin cured with acid anhydride was investigated. The glass transition temperature and fragility parameter, derived from the thermo‐viscoelasticity, were used to characterize the epoxy resin postcured under various conditions. Relationship between these two parameters and the fracture toughness was then investigated, based on the fractography results of a microscopic roughness examination of a fractured surface. The values of the glass transition temperature and fragility greatly depended on the postcuring conditions. The glass transition temperature was approximately 400 K when the crosslinking reaction was saturated. The fragility was independent of the saturation of the reaction and varied between 50 and 180. The results of the fracture test and fractography examination showed that there was no direct correlation between the glass transition temperature, the fracture toughness, and the roughness. On the other hand, there was a correlation between the fragility, fracture toughness, and roughness when the glass transition temperature saturated (at 400 K). As the fragility decreased from 180 to 50, the fracture toughness increased from 0.6 to 1.1 MPa · m^1/2 at the same glass transition temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 10: 2266–2271, 2002     

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%.     

Thermally stimulated creep (TSCr) study of viscoelastic behavior and physical aging of a polymeric matrix composite for spacecraft structures

Thermally Stimulated Creep (TSCr) mechanical spectroscopy has been used to analyze molecular movements in KMU‐4lcarbon/epoxy composite material around the glass transition temperature. This technique is powerful to characterize the microstructure and micromechanical properties of the epoxy matrix and their evolution upon thermal aging. Three cooperative submodes have been distinguished by resolving the fine structure of the material complex α‐retardation mode. The elementary processes constituting this mode possess activation enthalpies and preexponential factors that strongly depend on the thermal history of the sample. The activation parameters of the composite are subject to perceptible evolution due to postcuring degradation. The α‐mode associated complex spectrum shifts towards higher temperatures by 27°C as a consequence of a series of quenching in the temperature range 260 to 0°C; the material shows a rise in the fragility and a deterioration in the crack‐growth resistance qualities. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 342–350, 2002     

Fracture and toughening behavior of aramid fiber/epoxy composites

The effect of short Aramid fibers on the fracture and toughening behavior of epoxy with high glass transition temperature has been studied. Fine dispersion of the fibers throughout the matrix is evidenced by optical microscopy. Compared with neat epoxy resin, the fracture toughness (K_IC) of the composites steadily increases with increasing fiber loading, indicating that addition of Aramid fibers has an effective toughening effect to the intrinsically brittle epoxy matrix. Scanning electron microscopy (SEM) indicates that formation of numerous step structures for fiber‐filled epoxy systems is responsible for the significant toughness improvement. SEM and transmitted optical microscopy show that fiber pullout and fiber breakage are the main toughening mechanisms for the Aramid fiber/epoxy composites. POLYM. COMPOS. 26:333–342, 2005. © 2005 Society of Plastics Engineers.     

Micro‐mechanical deformation mechanisms in the fracture of hybrid‐particulate composites based on glass beads,rubber and epoxies

Two tougheners, glass beads and carboxyl terminated butadiene acrylonitrile copolymer (CTBN), are used to toughen and stiffen an epoxy thermoset. Rubber‐encapsulated glass beads are used and the hybrid particulate composites containing them are compared with those containing non‐encapsulated glass beads. Within a certain range of composition, the rubber encapsulation is found to change the interactions between glass beads and CTBN particles, resulting in an increase in fracture toughness. The toughening effect is explained by the fact that the cavities of CTBN particles are larger in encapsulation systems than in non‐encapsulation systems. As more CTBN particles are incorporated into glass bead filled epoxies, the cavitation/shear yielding mechanism of CTBN particles replaces the micro‐shear banding mechanism of glass beads as the major micro‐mechanical deformation. Rubber encapsulation seems to enable this transition of major micro‐mechanical deformation to occur at a lower volume fraction of CTBN.     

Novel polymer composites based on a mixture of preformed nanosilica‐filled poly(methyl methacrylate) particles and a diepoxy/diamine thermoset system

In this work, a new material based on an epoxy thermoset modified with a thermoplastic filled with silica nanoparticles was investigated. When thermoplastic particles are filled with nanoparticles with unique properties such as high efficiency for absorbing ultraviolet light, electric or magnetic shielding, high electrical conductivity, and high dielectric constants, more than an enhancement of the mechanical properties is expected to be achieved for modified epoxy‐based thermosets. Particles of poly(methyl methacrylate) (PMMA) filled with silica nanoparticles were used to modify a thermoset based on a full reaction between diglycidyl ether of bisphenol A and 3‐(aminomethyl)benzylamine. When the preformed thermoplastic particles were mixed with the reactive constituents of the epoxy system under certain curing conditions in which total miscibility was avoided, uniform particle dispersions could be obtained. The relationships between the composition, morphology (nanoscale and microscale), glass‐transition temperature, mechanical properties, and fracture toughness were considered. Four main results were obtained for consideration of the potential of silica‐filled PMMA as an important modifier of brittle epoxy thermoset systems: (1) a good dispersion of the silica nanoparticles in the PMMA domains, (2) a good dispersion of the silica‐filled PMMA microparticles in the epoxy matrix, (3) the possibility of partial dissolution of the PMMA‐rich domains into the epoxy system, and (4) a slight increase in properties such as the hardness, indentation modulus, and fracture toughness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal and toughness property studies on a polybenzimidazole‐modified epoxy resin system

The effect of polybenzimidazole (PBI) on a silica‐filled epoxy resin matrix has been investigated. Polybenzimidazole (PBI) was incorporated into a difunctional epoxy resin matrix to the extent of 10 %, before being cured with an anhydride hardener. The effects of PBI on the curing reaction and glass transition temperature (T_g) and on the toughness of the cured epoxy matrix have been studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and a universal testing machine (Instron). The results indicate that the PBI modifier enhanced not only the glass transition temperature of the difunctional epoxy matrix but also its toughness, by its catalytic action. Further investigations have been carried out on the fractured specimens, using scanning electron microscopy (SEM) to support the enhanced toughness property of the epoxy matrix. © 2000 Society of Chemical Industry     

Enhancement of interlaminar fracture toughness of carbon fiber–epoxy composites using polyamide‐6,6 electrospun nanofibers

In this study, carbon fiber–epoxy composites are interleaved with electrospun polyamide‐6,6 (PA 66) nanofibers to improve their Mode‐I fracture toughness. These nanofibers are directly deposited onto carbon fabrics before composite manufacturing via vacuum infusion. Three‐point bending, tensile, compression, interlaminar shear strength, Charpy impact, and double cantilever beam tests are performed on the reference and PA 66 interleaved specimens to evaluate the effects of PA 66 nanofibers on the mechanical properties of composites. To investigate the effect of nanofiber areal weight density (AWD), nanointerlayers with various AWD are prepared by changing the electrospinning duration. It is found that the electrospun PA 66 nanofibers are very effective in improving Mode‐I toughness and impact resistance, compressive strength, flexural modulus, and strength of the composites. However, these nanofibers cause a decrease in the tensile strength of the composites. The glass‐transition temperature of the composites is not affected by the addition of PA 66 nanofibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45244.     

Mechanical properties and fracture behaviors of epoxy composites with phase‐separation formed liquid rubber and preformed powdered rubber nanoparticles: A comparative study

Epoxy composites filled with phase‐separation formed submicron liquid rubber (LR) and preformed nanoscale powdered rubber (PR) particles were prepared at different filler loading levels. The effect of filler loading and type on the rheological properties of liquid epoxy resin suspensions and the thermal and mechanical properties of the cured composites as well as the relative fracture behaviors are systematically investigated. Almost unchanged tensile yield strength of the cured epoxy/PR composites is observed in the tensile test compared with that of the neat epoxy; while the strength of the cured epoxy/LR composites shows a maximum value at ∼4.5 wt% and significantly decreases with increasing LR content. The glass transition temperature (T_g) of the cured PR/epoxy has shifted to the higher temperature in the dynamic mechanical thermal analysis compared with that of the cured pure epoxy and epoxy/LR composites. Furthermore, the presence of LR results in highly improved critical stress intensity factor (K_IC) of epoxy resin compared with the corresponding PR nanoparticles. In particular, the PR and LR particles at 9.2 wt% loading produce about 69 and 118% improvement in K_IC of the epoxy composites, respectively. The fracture surface and damage zone analysis demonstrate that these two types of rubber particles induce different degrees of local plastic deformation of matrix initiated by their debonding/cavitation, which was also quantified and correlated with the fracture toughness of the two epoxy/rubber systems. POLYM. COMPOS., 36:785–799, 2015. © 2014 Society of Plastics Engineers     

Dynamic mechanical properties and hysteresis loss of epoxidized natural rubber chemically bonded to the silica surface

High‐temperature (180°C) molding of epoxidized natural rubber (ENR) filled with precipitated silica leads to chemical bond formation between epoxy groups of ENR and silanol groups of silica. The extent of chemical bond formation is further enhanced in the presence of the silane coupling agent N‐3‐N‐(vinyl benzyl amino)ethyl‐γ‐amino‐propyl trimethoxy silane mono hydrogen chloride (trade name Z‐6032). The results of hysteresis loss measurements show that hysteresis loss increases with increase in coupling agent loading as a result of the higher modulus of the compounds compared to that of the ENR–silica mix. The dynamic mechanical property measurements show that the addition of coupling agent increases the glass‐transition temperature. Whereas strain‐dependent dynamic mechanical properties show that filler structure breakdown increases with increasing loading of coupling agent. Sulfur‐cured systems show higher filler structure breakdown compared to that of nonsulfur systems. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2171–2177, 2002     

Effect of resin modifiers on the structural properties of epoxy resins

Thermomechanical, mechanical and fracture mechanical properties of modified epoxy resins with two different modifiers are investigated. Carboxyl‐terminated butadiene‐acrylonitrile (CTBN) is used as toughening agent and hexanediole diglycidyl ether (HDDGE) as reactive diluent. Both modifiers are admixed in contents from 0 up to 100 phr (parts per hundred resin) and exhibit flexibilizing and toughening qualities. The glass transition temperature is strongly depressed by the admixed reactive diluent, whereas the tensile modulus exhibits greater dependency on the toughening agent contents. The tensile strength and strain at break values are higher for the formulations with diluent compared to resins with toughening agent. Up to a content of 45 phr both modified systems exhibit comparable fracture toughness values. Only the toughened systems comprise increasing values for modifier amounts higher than 45 phr. For the formulation with both modifiers (toughening agent and diluent) a significantly higher toughness but a reduced glass transition temperature was obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45348.     

Highly dispersed nanosilica-epoxy resins with enhanced mechanical properties

Epoxy-nanocomposite resins filled with 12-nm spherical silica particles were investigated for their thermal and mechanical properties as a function of silica loading. The nanoparticles were easily dispersed with minimal aggregation for loadings up to 25 wt% as determined using transmission electron microscopy (TEM) and ultra-small-angle X-ray scattering (USAXS). A proportional decrease in cure temperatures and glass transition temperature (for loadings of 10 wt% and above) was observed with increased silica loading. The morphology determined by USAXS is consistent with a zone around the silica particles from which neighboring particles are excluded. The “exclusion zone” extends to 10× the particle diameter. For samples with loadings less than 10 wt%, increases of 25% in tensile modulus and 30% in fracture toughness were obtained. More highly loaded samples continued to increase in modulus, but decreased in strength and fracture toughness. Overall, the addition of nanosilica is shown as a promising method for property enhancement of aerospace epoxy composite resins.     

Effect of organosilane coupling agents on microstructure and properties of nanosilica/epoxy composites

Three types of silane coupling agents, γ‐aminopropyltriethoxysilane, γ‐glycidoxypropyltrimethoxysilane, and γ‐methacryloxypropyltrimethoxysilane, were used as modifiers to modify the surface of the nanosilica, respectively, and the nanocomposites of the epoxy resin filled with nano‐sized silica modified by three silane coupling agents were prepared by physical blending. The properties of the modified silica nanoparticles were characterized by Fourier transform infrared spectrum and particle‐size analyzer. The microstructure, mechanical behavior, and heat resistant properties of the nanocomposites were investigated by transmission electron microscopy, scanning electron microscopy, thermo gravimetric analyses, differential thermal gravity, differential scanning calorimetry, and flexural tests. The results showed that these modifiers are combined to the surfaces of nanosilica by the covalent bonds, and they change the surface properties of nanosilica. The different structures of coupling agents have different effects on the dispersibility and stability of modified particles in the epoxy matrix. In comparison, the silica nanoparticles modified by γ‐glycidoxypropyltrimethoxysilane exhibit a good dispersivity. The nanocomposites with 4 wt% weight fraction nanosilica modified by γ‐glycidoxypropyltrimethoxysilane have higher thermal decomposing temperature and glass transition temperature than those of the other two composites with the same nanosilica contents, and they are raised by 43.8 and 8°C relative to the unmodified composites, respectively. The modified silica nanoparticles have good reinforcing and toughening effect on the epoxy matrix. The ultimate flexural strengths of the composites with 4 wt% nanoparticles modified by γ‐aminopropyltriethoxysilane, γ‐glycidoxypropyltrimethoxysilane, and γ‐methacryloxypropyltrimethoxysilane are increased by 10, 30, and 8% relative to the unmodified composites, respectively. The flexural fracture surfaces of modified composites present ductile fracture features. POLYM. COMPOS. 2012. © 2012 Society of Plastics Engineers     

Enhancement in the thermal and dynamic mechanical properties of high performance liquid crystalline epoxy composites through uniaxial orientation of mesogenic on carbon fiber

In this work, a high performance liquid crystalline epoxy composite was prepared and the effect of the alignment of LCE with long lateral substituent on the carbon fiber surface curing at low temperature on fracture toughness, dynamic mechanical, and thermal properties of liquid crystalline epoxy with lateral substituent (LCE6) was investigated by polarized optical microscopy (POM), wide angle X‐ray diffraction measurements (WAXS), dynamic mechanical analysis (DMA), thermogravimetric (TGA), and scanning electron microscopy (SEM). Curing degree of the composite was observed by FTIR. The experimental results indicate that the fracture toughness, glass transition temperature (T_g), thermal stability, degradation kinetics are associated with the alignment of LCE6 along long axis of carbon fiber. The alignment of LCE6 on carbon fiber surface can increase mesogen network density, which leads to higher fracture toughness, higher thermal stability, increase of the activation energies and higher T_g of the composite. The dynamic mechanical analysis shows that the compoaite possesses extremely higher dynamic storage moduli, which indicates that this LCE6/DDM/CF composite can be a high performance composite. Thus, the compoaite can be a potential candidate for advanced composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40363.     

Time–temperature dependency of mode II fracture toughness for bisphenol A type epoxy resin

We investigated the mode II fracture toughness (K_IIc) with time and temperature dependence of the bisphenol A type of epoxy resin. We performed an asymmetric four‐point bending test under various conditions of temperature and displacement rate. We found that K_IIc strongly depended on the displacement rate and the temperature, even at room temperature. Moreover, it was governed by the time–temperature equivalence principle in regard to the fracture time. The time–temperature dependency of K_IIc was similar to that of the loss modulus (E″), and the transition of brittle to ductile fractures occurred nearly simultaneously when E″ peaked. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 51–55, 2005     

Thermophysical properties of anhydride‐cured epoxy/nano‐clay composites

Polymer nano‐composites made with a matrix of anhydride‐cured diglycidyl ether of bisphenol A (DGEBA) and reinforced with organo‐montmorillonite clay were investigated. A sonication technique was used to process the epoxy/clay nano‐composites. The thermal properties of the nano‐composites were measured with dynamic mechanical analysis (DMA). The glass transition temperature T_g of the anhydride‐cured epoxy was higher than the room temperature (RT). For samples with 6.25 wt% (4.0 vol%) of clay, the storage modulus at 30°C and at (T_g + 15)°C was observed to increase 43% and 230%, respectively, relative to the value of unfilled epoxy. The clay reinforcing effect was evaluated using the Tandon‐Weng model for randomly oriented particulate filled composites. Transmission electron microscopy (TEM) examination of the nano‐composites prepared by sonication of clays in acetone showed well‐dispersed platelets in the nano‐composites. The clay nano‐platelets were observed to be well‐intercalated/expanded in the anhydride‐cured epoxy resin system. POLYM. COMPOS., 26:42–51, 2005. © 2004 Society of Plastics Engineers.     

Flexural and Charpy impact behaviour of epoxy/glass fabric treated by nano-SiO2 and silane blend

A sizing formulation, containing compatible and incompatible silane coupling agents with epoxy resin in conjunction with nanoscale colloidal silica, was used to modify the surface of glass fabric. The modified glass fabric/epoxy resin composite panels were fabricated and characterised by flexural test, Charpy impact test and scanning electron microscope (SEM). By combining nano silica with silane blend in the fabric sizing, more energy was consumed under bending and impacting, which resulted in an improvement of the toughness in composites. The flexural strength, bending stain and Charpy impact strength of the epoxy composite/glass fabric treated with 1?wt-% nano silica and silane blend were ～42, ～22 and 35%, respectively, higher than those of silane blend coated glass fabric-reinforced composites (without nano silica). Furthermore, the change of the brittle fracture of the composite into ductile fracture was investigated by SEM micrographs. A possible toughening mechanism was also proposed.     

Preparation and characterization of bismaleimide (N,N′‐bismaleimido‐4,4′‐diphenyl methane)–unsaturated polyester modified epoxy intercrosslinked matrices

An intercrosslinked network of unsaturated polyester–bismaleimide modified epoxy matrix systems was developed. Epoxy systems modified with 10, 20, and 30% (by weight) of unsaturated polyester were made by using epoxy resin and unsaturated polyester with benzoyl peroxide and diaminodiphenylmethane as curing agents. The reaction between unsaturated polyester and epoxy resin was confirmed by IR spectral studies. The unsaturated polyester toughened epoxy systems were further modified with 5, 10, and 15% (by weightt) of bismaleimide (BMI). The matrices, in the form of castings, were characterized for their mechanical properties. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) of the matrix samples were performed to determine the glass transition temperature (T_g) and thermal degradation temperature of the systems, respectively. Mechanical properties, viz: tensile strength, flexural strength, and plain strain fracture toughness of intercrosslinked epoxy systems, were studied by ASTM methods. Data obtained from mechanical and thermal studies indicated that the introduction of unsaturated polyester into epoxy resin improves toughness but with a reduction in glass transition, whereas the incorporation of bismaleimide into epoxy resin improved both mechanical strength and thermal behavior of epoxy resin. The introduction of bismaleimide into unsaturated polyester‐modified epoxy resin altered thermomechanical properties according to their percentage concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2853–2861, 2002     

Mechanical properties of epoxy‐based hybrid composites containing glass beads and α,ω‐oligo(butylmethacrylate)diol

A novel phase‐separating liquid rubber based on oligo(alkylmethacrylate) in combination with microglass beads was used to toughen an anhydride‐cured epoxy resin. The resulting hybrid composites, containing 5 or 10 wt % of oligomeric liquid rubber and between 10 and 60 wt % glass beads as well as composites containing corresponding amounts of glass beads but no liquid rubber, were characterized mechanically. The experimental data show that modification with glass beads results in increased stiffness and toughness compared to the neat resin but reduces tensile strength. Compared to the glass bead–filled composites, additional modification with methacrylic rubber leads to a further increase in toughness and also to an increase in strength but does not alter stiffness and glass‐transition temperature. This synergistic behavior is explained by the fact that the rubber separates preferably on the surface of the glass bead, forming a core–shell morphology during curing. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1040–1048, 2003     

The effect of silica nanoparticles and carbon nanotubes on the toughness of a thermosetting epoxy polymer

Silica nanoparticles and multiwalled carbon nanotubes (MWCNTs) have been incorporated into an anhydride‐cured epoxy resin to form “hybrid” nanocomposites. A good dispersion of the silica nanoparticles was found to occur, even at relatively high concentrations of the nanoparticles. However, in contrast, the MWCNTs were not so well dispersed but relatively agglomerated. The glass transition temperature of the epoxy polymer was 145°C and was not significantly affected by the addition of the silica nanoparticles or the MWCNTs. The Young's modulus was increased by the addition of the silica nanoparticles, but the addition of up to 0.18 wt % MWCNTs had no further significant effect. The addition of both MWCNTs and silica nanoparticles led to a significant improvement in the fracture toughness of these polymeric nanocomposites. For example, the fracture toughness was increased from 0.69 MPam^1/2 for the unmodified epoxy polymer to 1.03 MPam^1/2 for the hybrid nanocomposite containing both 0.18 wt % MWCNTs and 6.0 wt % silica nanoparticles; the fracture energy was also increased from 133 to 204 J/m². The mechanisms responsible for the enhancements in the measured toughness were identified by observing the fracture surfaces using field‐emission gun scanning electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011