Morphology control in polysulfone‐modified epoxy resins by demixing behavior

Polysulfone (PSu) was used as a modifier of epoxy/aromatic diamine formulations. Two epoxy monomers, based on diglycidyl ether of bisphenol A (DGEBA), were used. The cure agent was 4,4′‐diaminodiphenylsulfone. PSu was miscible with DGEBA, as shown by the existence of a single glass‐transition temperature within the whole composition range. The effect of PSu addition on the cure kinetics was investigated. The reaction rate of the epoxy–amine species was slightly lower in the presence of PSu. The morphology was analyzed by optical and scanning electron microscopy. A range of microstructures were obtained by control over the cure temperature, the amount of PSu incorporated, and the molecular weights of the epoxy resins. The variations in the morphology resulted from the different stages of demixing, which were arrested because of the different developments of the viscosity of the system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 405–412, 2003     

Polymerization‐induced bimodal phase separation in a rubber‐modified epoxy system

The bimodal phase separation process of a rubber‐modified epoxy system, consisting of diglycidyl ether of bisphenol A (DGEBA), and a hydroxyl‐terminated butadiene–acrylonitrile random copolymer (HTBN), during curing with tetrahydro‐phthalic anhydride was studied by time‐resolved small‐angle light scattering (TRSALS), differential scanning calorimetry (DSC), and digital image analysis (DIA). The HTBN/DGEBA mixture reveals an upper critical solution temperature (UCST). At higher curing temperatures, double‐peak structure from the matrix was investigated by TRSALS and confirmed by DIA. The special two characteristic size distribution behavior was explained qualitatively by nucleation growth coupled with spinodal decomposition (NGCSD) and the competition between phase separation and polymerization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 59–67, 1999     

Morphology of rubber‐modified vinyl ester resins cured at different temperatures

The morphologies of styrene (St) crosslinked divinylester resins (DVER) modified with elastomers were analyzed. The primary focus of this study was on the effect of the molecular weight of the resins, the reactivity of the elastomeric modifiers, and the temperature of curing. All of these variables have a strong influence on both the miscibility and the viscosity of the system, affecting the phase‐separation process that takes place in the unreacted and the reacting mixture. The selected liquid rubbers were carboxyl‐terminated poly(butadiene‐co‐acrylonitrile) (CTBN), a common toughening agent for epoxy resins, and an almost unreactive rubber with the DVER; and St comonomers and vinyl‐terminated poly(butadiene‐co‐acrylonitrile (VTBN), a reactive rubber. Different morphologies potentially appear in these systems: structures formed by DVER–St nodules surrounded by elastomer and spanning the whole sample; dual cocontinuous micron‐size domains formed by elastomer‐rich or resin‐rich domains; and a continuous DVER–St‐rich phase with included complex nodular domains. These microstructures can be varied by just changing the nature and concentration of the elastomer, the molecular weight of the resin, or the curing temperature. The appearance of these morphologies is discussed as a function of the above variables. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 274–283, 2003     

Thermomechanical behavior of epoxy resins modified with epoxidized vegetable oils

Biobased epoxy materials were prepared from diglycidyl ether of bisphenol A (DGEBA) and epoxidized vegetable oils (EVOs) (epoxidized soybean oil and epoxidized castor oil) with a thermally latent initiator. The effects of EVO content on the thermomechanical properties of the EVO‐modified DGEBA epoxy resins were investigated using several techniques. Differential scanning calorimetry indicated that the cure reaction of the DGEBA/EVO systems proceeded via two different reaction mechanisms. Single and composition‐dependent glass transition temperature (T_g) mechanisms were observed for the systems after curing. The experimental values of T_g could be explained by the Gordon–Taylor equation [Gordon M and Taylor JS, J Appl Chem 2 :493 (1952)]. The thermal stability of the systems decreased as the EVO content increased, due to the lower crosslinking density of the DGEBA/EVO systems. The coefficient of thermal expansion of the systems was found to increase linearly with increasing EVO content. This could be attributed to the fact that the degrees of freedom available for motions of the segments of the macromolecules in the network structure were enhanced by the addition of EVO. Copyright © 2008 Society of Chemical Industry     

Effect of molecular weight between crosslinks on the fracture behavior of rubber‐toughened epoxy adhesives

The effect of molecular weight between crosslinks, M_c, on the fracture behavior of rubber‐toughened epoxy adhesives was investigated and compared with the behavior of the bulk resins. In the liquid rubber‐toughened bulk system, fracture energy increased with increasing M_c. However, in the liquid rubber‐toughened adhesive system, with increasing M_c, the locus of joint fracture had a transition from cohesive failure, break in the bond layer, to interfacial failure, rupture of the bond layer from the surface of the substrate. Specimens fractured by cohesive failure exhibited larger fracture energies than those by interfacial failure. The occurrence of transition from cohesive to interfacial failure seemed to be caused by the increase in the ductility of matrix, the mismatch of elastic constant, and the agglomeration of rubber particles at the metal/epoxy interface. When core‐shell rubber, which did not agglomerate at the interface, was used as a toughening agent, fracture energy increased with M_c. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 38–48, 2001     

Thermooxidative aging mechanism of crumb‐rubber‐modified asphalt

We investigated the thermooxidative aging mechanism of crumb‐rubber‐modified asphalts (CRMAs) by tracing the evolution of the chemical structure and physical properties of CRMA during aging. The chemical structural evolution of crumb rubber (CR) in various aged CRMAs was characterized by measurement of the crosslink structure and composition of extracted CR. The residual asphalt of the aged CRMA was investigated by IR spectroscopy. The physical properties of CRMA were characterized by conventional testing before and after aging. We found that the change in the physical properties of CRMA correlated well with both the evolution of the rubber network and the oxidation of asphalt. The thermooxidative aging resistance of CRMA was improved with increasing CR dosage; this further illustrated that aging promoted the dissolution of CR into asphalt. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43323.     

Fracture behavior of core‐shell rubber–modified clay‐epoxy nanocomposites

Morphology and fracture mechanisms in two nanoclay‐filled epoxy systems were investigated using both microscopy and spectroscopy tools. Clay exfoliation was achieved using a series of sample preparation steps, and confirmed using wide angle X‐ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. Significant improvement in modulus was obtained when clay exfoliation was achieved. Incorporation of core‐shell rubber (CSR) in both caly‐filled epoxy systems leads to greatly enhanced fracture toughness. Optical microscopy and TEM observations of the CSR‐modified nanocomposites suggest that CSR cavitation. shear yielding of the matrix, clay layer delamination. CSR bridging, crack bifurcation. and crack deflection are among the operative toughening mechanisms observed, depending on the nature of the epoxy matrix utilized.     

Oil‐absorption function of physical crosslinking in the high‐oil‐absorption resins

The concept of physical crosslinking was introduced into the research field of oil‐absorption resins, which were traditionally synthesized only by chemical crosslinking. Specifically, the partially physical crosslinking acrylic series for high‐oil‐absorption resins were prepared in the suspension process, and the swelling behavior of the samples was observed and recorded online. This demonstrated that a kind of relaxing three‐dimensional network was indeed formed by the introduction of polybutadiene (PB). The effects of monomer feed ratios, crosslinking agent concentration and type, particle size, and temperature on the oil absorbency and oil‐absorption speed were investigated. The results indicated that there were an optimum monomer feed ratio and an optimum amount of ethylene glycol dimethacrylate or PB. In addition, the particle size and temperature had a serious influence on the oil‐absorption speed in comparison with the monomer feed ratio and the crosslinking agent concentration and type. The results also showed that particle size affected oil absorbency to a great degree and that the effect of temperature on oil absorbency was complex. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3945–3950, 2003     

Thermoplastic‐modified epoxy resins cured with different functionalities amine mixtures: Morphology,thermal behavior,and mechanical properties

Epoxy matrices inherent brittleness and poor crack resistance make necessary some form of toughening. In this work, to improve their fracture toughness and ductility epoxy matrices were modified by changing its architecture and by the addition of a third component. The matrices architecture were modified by stoichiometrically reacting a bifunctional epoxy resin with different functionalities amine mixtures, one of which being a monoamine that plays the role of chain extender. In the modification by the addition of a third component, poly(methyl methacrylate) (PMMA) was selected as modifier. PMMA is initially miscible with epoxy/amine systems but can phase separate during curing. The kinetics and miscibility of these systems were studied previously. At constant curing conditions, materials from completely opaque (phase separated) to transparent (miscible) can be obtained with the increase in monoamine content. In this work, the effects of the modifier content and of the monoamine : diamine ratio in stoichiometric epoxy/amine mixtures on the resultant morphologies as well as on their thermal and mechanical properties was studied.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Castor-oil-modified epoxy resins as model systems of rubber-modified thermosets. 1: Thermodynamic analysis of the phase separation

Castor oil (CO) was used to replace polydisperse commercial rubbers (carboxy- or epoxy-terminated butadiene-acrylonitrile random copolymers, CTBN or ETBN) in model systems developed to analyse the origin of the phase separation process in rubber-modified thermosets. Mixtures of CO with an epoxy resin based on the diglycidyl ether of bisphenol A (DGEBA) showed a higher miscibility than a typical CTBN (18% acrylonitrile)-DGEBA system. Thermodynamic factors accounting for this behaviour are discussed using the Flory-Huggins lattice model. Addition of a stoichiometric amount of ethylenediamine (EDA) to a DGEBA-CO solution increased the miscibility. A pseudo-binary approach was used to fit the cloud point curve up to 30% volume fraction of CO. Percentage conversions at the cloud point during the DGEBA-EDA polymerization were experimentally determined and compared with theoretical predictions using the pseudo-binary approach in the framework of the Flory-Huggins lattice model. Reasonable agreement was found, giving direct evidence of the fact that phase separation results from the decrease in the entropic contribution to the free energy of mixing during polymerization.     

Thermal stability and kinetics analysis of rubber‐modified epoxy resin by high‐resolution thermogravimetric analysis

A dynamic heating rate mode of high‐resolution thermogravimetric analysis was used to study the thermal and thermal‐oxidative stability, as well as kinetics analyses, of a model liquid rubber‐modified epoxy resin, Ep/CTBN, made up of bisphenol A diglycidyl ether‐based epoxy and carboxyl‐terminated butadiene acrylonitrile rubber (CTBN). Results show that the thermal degradation of Ep/CTBN resin in nitrogen and air consists of two and three independent steps, respectively. Moreover, Ep/CTBN has a higher initial degradation temperature and higher activation energy than those of pure epoxy resin in both gases, indicating that the addition of CTBN to epoxy can improve the thermal and thermal‐oxidative stability of pristine epoxy resin. Kinetic parameters such as activation energy, reaction order, and preexponential factor of each degradation step of both Ep/CTBN and pure epoxy resins in air and nitrogen were calculated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3594–3600, 2003     

Evaluation and modeling of the mechanical behavior of carbon nanoparticle/rubber‐modified polyethylene nanocomposites

Recently, the production of polymers loaded with inorganic nanomaterials has been one of the most economical techniques playing a special role in improving the physical and mechanical properties of nanocomposites. Rubbers loaded with different concentrations of carbon nanoparticles (CNPs) were synthesized. The mechanical properties were tested according to standard methods. It was found that the properties of the investigated nanocomposites were improved, depending on the concentration of CNPs in the investigated composite. The optimum concentration was found to be 1.3 vol %. Affine deformation based on the Mooney–Rivilin model was used to visualize the effect of CNPs on the rubber. When polyethylene (PE) was added to rubber/CNPs at the optimum concentration (12.4 vol %), the modulus, tear resistance, and fatigue life were increased, whereas the tensile strength decreased, and the strain at rupture remained almost same. A crosslink model was used to explain the influence of PE on the rubber/CNP nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Relationship between gelation and morphology of rubber-modified epoxy resins

The addition of both a solid and a liquid rubber to an epoxy resin has been shown to strongly increase the toughness of the material. Moreover, it is well known that toughening depends on the morphology of the system, which, in turn, depends on the cure conditions. In the present work the morphologies of epoxy resins modified with mixtures of solid and liquid rubbers have been studied through transmission electron microscopy. An investigation of the influence of the elastomers and of the gel time on the morphology of the hardened material was carried out. Gel times were evaluated, through rheological measurements, at different cure temperatures.     

Fracture and adhesion behaviors of epoxy resins modified with poly(amine‐quinone)

An amine‐quinone monomer, i.e. 2,5‐bis(4,4′‐methylenedianiline)‐1,4‐benzoquinone (BB), was synthesized by the Michael addition of 4,4′‐diaminodiphenyl methane with 1,4‐benzoquinone. To evaluate the effect of BB content on the glass transition temperature (T_g) and crosslinking density (ρ) of cured diglycidyl ether of bisphenol A (DGEBA)/BB systems, storage modulus and loss factor measurements were obtained using dynamic mechanical analysis. The mechanical properties of the systems were determined in terms of the fracture toughness, impact strength, and adhesion strength. As a result, the ρ values of the systems were found to decrease systematically as the BB content increased. The fracture toughness and adhesion strength of the systems increased with increasing BB content. These results indicate that the addition of BB into epoxy resins increases the free volume of the epoxy network and absorbs the deformation energy, resulting in an improvement of the mechanical properties of the DGEBA/BB systems. Copyright © 2006 Society of Chemical Industry     

Influence of two-step process and of different stoichiometric ratios on morphologies generated in castor oil epoxy resins

Phase separation during polymerization was studied in a model system consisting of a diepoxide based on diglycidyl ether of bisphenol A (DGEBA), variable amounts of ethylenediamine (EDA) and the mass of castor oil (CO) necessary to obtain a mass fraction equal to 0-15 in a final system where the stoichiometric ratio of amine to epoxy equivalents, r, was equal to 1. A two-step polymerization process was performed by curing first a system with r = 0-5, during variable times before phase separation, and then carrying the system to r = 1. Thermodynamic analysis of samples with different r values led to a linear relationship between the Flory-Huggins interaction parameter and r. The concentration (P) and average size (D?) of dispersed-phase particles followed opposite trends, i.e. P increased while D? decreased, when either r was increased or the time of curing in the first step of a two-step process was decreased. This was explained by assuming that the competition between nucleation and growth was determined by the viscosity at the cloud point, η_cp. Low values of η_cp favoured growth over nucleation and led to fewer but larger particles.     

无机纳米粒子填充改性环氧树脂研究进展

介绍了无机纳米粒子的结构,复合机理,用其填充改性环氧树脂复合材料的制备方法,作用机理及研究进展。     

Effects of in situ esterification on the performance of carboxyl functionalized rubber‐modified epoxy film adhesives

Epoxy‐based film adhesive formulations were developed with 10 wt % solid carboxyl functional rubber. Due to the high rubber content and resulting viscosity restrictions, the rubber could not be prereacted with the epoxy before hot‐melt filming. Therefore, an esterification catalyst was used to perform this reaction in situ before the epoxy curing reactions. The performance of this adhesive system is compared to that of one without the esterification catalyst. A significant difference in the flow characteristics was observed with incorporation of the esterification catalyst, but only small variations in mechanical performance were found. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 728–734, 2000     

Effects of amino‐functionalized carbon nanotubes on the properties of amine‐terminated butadiene–acrylonitrile rubber‐toughened epoxy resins

Amino‐functionalized multiwalled carbon nanotubes (MWCNT‐NH₂s) as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA) toughened with amine‐terminated butadiene–acrylonitrile (ATBN). The curing kinetics, glass‐transition temperature (T_g), thermal stability, mechanical properties, and morphology of DGEBA/ATBN/MWCNT‐NH₂ nanocomposites were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis, a universal test machine, and scanning electron microscopy. DSC dynamic kinetic studies showed that the addition of MWCNT‐NH₂s accelerated the curing reaction of the ATBN‐toughened epoxy resin. DSC results revealed that the T_g of the rubber‐toughened epoxy nanocomposites decreased nearly 10°C with 2 wt % MWCNT‐NH₂s. The thermogravimetric results show that the addition of MWCNT‐NH₂s enhanced the thermal stability of the ATBN‐toughened epoxy resin. The tensile strength, flexural strength, and flexural modulus of the DGEBA/ATBN/MWCNT‐NH₂ nanocomposites increased increasing MWCNT‐NH₂ contents, whereas the addition of the MWCNT‐NH₂s slightly decreased the elongation at break of the rubber‐toughened epoxy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40472.     

Carboxyl‐terminated butadiene acrylonitrile rubber/epoxy polymer alloys as damping adhesives and energy absorbable resins

Carboxyl‐terminated butadiene acrylonitrile (CTBN) liquid rubber/epoxy (diglycidyl ether of bisphenol‐A: DGEBA) / diamino diphenyl methane (DDM) resins, in which CTBN was 60 wt % as the major component, were formulated to evaluate the damping and adhesive properties. In cases where acrylonitrile (AN) was 10～18 mol % as copolymerization ratio in CTBN, the blend resins showed micro‐phase separated morphologies with rubber‐rich continuous phases and epoxy‐rich dispersed phases. The composite loss factors (η) for steel laminates, which consisted of two steel plates with a resin layer in between, depended highly on the environmental temperature and the resonant frequencies. On the other hand, in the case where AN was 26 mol % in CTBN, the cured resin did not show clear micro‐phase separation, which means the components achieve good compatibility in nano‐scale. This polymer alloy had a broad glass‐transition temperature range, which resulted in the high loss factor (η > 0.1) for the steel laminates and excellent energy absorbability as the bulk resin in a broad temperature range. Also the resin indicated high adhesive strengths to aluminum substrates under both shear and peel stress modes. The high adhesive strengths of the CTBN/epoxy polymer alloy originated in the high strength and the high strain energy to failure of the bulk resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fluorescence labels to monitor water absorption in epoxy resins

Water uptake phenomena was studied in a group of commercial epoxy based thermosets using gravimetric and fluorimetric analysis. The different epoxy formulations were labeled with two dansyl derivatives differing in the spacer length between the chain and the fluorophore moiety. The fluorimetric method consisted of monitoring the changes in the first moment of the dansyl emission band as a function of water immersion time. Using the fluorescence, it was possible to obtain the parameters that govern the water diffusion process and there was a good concordance with gravimetric results. Furthermore, the fluorescence response of the dansyl moieties was used to study the effect of the molecular structure of the polymers in the water absorption process.