Epoxy Blends Research Articles

Confocal microscopy study of phase morphology evolution in epoxy/polysiloxane thermosets

The morphology of stoichiometric initially immiscible reactive blends of DGEBA epoxy resin and poly(3-aminopropylmethylsiloxane) has been characterized by laser scanning confocal microscopy. Observations were done on samples cured isothermally at different curing temperatures in the range 20–120 °C as well as in situ and in real time at 60 °C. Three different processes were revealed: coalescence, which occurs primarily at very low conversion, diffusion of DGEBA through polysiloxane-rich domains and chemical reaction, which occurs at the interphase between both phases. The interphase-thickness and compositional gradients were characterized by laser scanning confocal microscopy (LSCM). Results show that as curing temperature increases within the studied range, the material becomes more homogeneous although the interphase thickness remains almost constant.

Mobility, Miscibility, and Microdomain Structure in Nanostructured Thermoset Blends of Epoxy Resin and Amphiphilic Poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) Triblock Copolymers Characterized by Solid-State NMR

Solid-state NMR methods were used to characterize the heterogeneous dynamics, miscibility, and microdomain structure in nanostructured thermoset blends of epoxy resin (ER) and amphiphilic poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) triblock copolymers (PEO−PPO−PEO). NMR experiments show that there is a distinct dynamic difference between the block copolymer (both PEO and PPO) and cured-ER matrix indicating the presence of phase separation, which also confirms the existence of the interphase region including a considerable amount of immobilized PEO and mobilized partially cured ER. An improved method based on spin-diffusion experiments enabled a quantitative determination of the interphase thickness. It is shown that a large percentage of PEO were intimately mixed with ER in the interphase region of the blends, while the rest mobile PEO and all PPO segregated from the ER network. It is observed that the domain size and long period depend strongly on the PEO fraction in the c...

Influence of intramolecular specific interactions on phase behavior of epoxy resin and poly(ε-caprolactone) blends cured with aromatic amines

Two aromatic amines were used as the curing agents to prepare the thermosetting blends of epoxy and poly(ε-caprolactone) (PCL). When cured with 4,4′-methylenebis(2-chloroaniline) (MOCA), the thermosetting blends are miscible in the amorphous state in the entire composition, which was evidenced by the behavior of single, and composition-dependent glass transition temperatures ( T g's) in terms of thermal analysis. Fourier transform infrared spectroscopy (FTIR) showed that there are the intermolecular specific interactions (viz. hydrogen bonding) between the component polymers. However, the 4,4′-diaminodiphenylsulfone (DDS)-cured epoxy forms the immiscible blends with PCL. The blends displayed a typical reaction-induced phase separation morphology. The phase behavior seems to be more than the expected since it was ever proposed that there would be the intermolecular specific interactions between amine-cured epoxy and PCL, which would fulfill the miscibility of the systems. To interpret the phase behavior, we investigated that the miscibility and intermolecular specific interactions in the blends of model compounds and linear homologues of epoxy with PCL. It was observed that in MOCA-cured blends there were much stronger intermolecular specific interactions than in DDS-cured counterparts. The weaker intermolecular specific interactions between DDS-cured epoxy and PCL resulted from the formation of the intramolecular hydrogen bonding interactions within DDS-crosslinked epoxy, which were involved with the sulfonyl groups and the secondary hydroxyls. The intramolecular association could suppress the formation of the strong intermolecular hydrogen bonding interactions between carbonyls and hydroxyls of amine-cured epoxy, which are sufficient to fulfill the homogenization of the system during the in situ polymerization. Therefore, the presence of the intramolecular specific interactions between sulfonyl and hydroxyl groups was taken as the origin of phase-separated morphology for DDS-cured blends of epoxy with PCL.

Compatibilization of Poly(Trimethylene Terephthalate)/Polycarbonate Blends by Epoxy. Part 2. Melting Behavior and Spherulite Morphology

The melting behaviors of poly(trimethylene terephthalate)/polycarbonate (PTT/PC) blends, compatibilized by epoxy, and PTT spherulite morphology in the blends were investigated. When epoxy was present during blending, the melting behaviors of PTT/PC blends changed substantially; glass transition temperatures (Tg's) and cold crystallization temperature (Tcc's) of the PTT‐rich phase shifted to higher temperatures, while Tm's shifted slightly to lower temperatures, indicating that epoxy suppressed considerably all processes of dynamic movements pertinent to molecular (or segmental) movements. The cold crystallization process responded sensitively to thermal history. Changes of Tcc's with composition suggested that the epoxy's compatibilization effect was pronounced when PTT and PC were in near equal content. Recrystallization or reorganization exotherms appeared before melting for isothermally crystallized PTT/PC and PTT/PC epoxy (E) blends. A wide angle X‐ray diffraction (WAXD) analysis showed that, although the perfection of PTT crystallites was influenced either by PC content and the presence of compatibilizer or by the crystallization temperature and crystallization time, PTT's crystal structure was independent of these variables. The polarized light microscopy (PLM) observations showed that PTT spherulite morphology was very sensitive to blend composition. Epoxy addition interfered severely with the growth of PTT spherulites, causing them to be much less developed. When the spherulites grew under a condition of varied composition, they would exhibit diversified spherulite morphology, though in one spherulite.

Ternary Thermosetting Blends of Epoxy Resin, Poly(ethylene oxide) and Poly(ε‐caprolactone)

AbstractSummary: The ternary thermosetting blends composed of epoxy resin, poly(ethylene oxide) (PEO) and poly(ε‐caprolactone) (PCL) were prepared via in situ polymerization of epoxy monomers in the presence of the two crystalline polymers, PEO and PCL. DSC results showed that the binary blends of epoxy with PEO (and/or PCL) are fully miscible in the entire composition in the amorphous state. FTIR indicates that there were interchain specific interactions between the crosslinked epoxy and the linear polymers in the binary blends and the hydrogen bonding interactions between epoxy and PCL are much weaker than those between epoxy and PEO. The difference in the strength of interchain specific interactions gives rise to the competitive hydrogen bonding interactions in the ternary blends of epoxy, PEO and PCL, which were evidenced by the results of FTIR. The results of optical microscopy and DSC showed that in the ternary blends PCL component separated out with inclusion of PEO. The formation of the specific phase structures is ascribed to the competitive interchain specific interactions among the crosslinked epoxy, PEO and PCL.Phase boundary diagram of epoxy, PEO and PCL ternary blends.imagePhase boundary diagram of epoxy, PEO and PCL ternary blends.

Morphological Studies of Epoxy/Polyaniline Blends

AbstractSummary: Polyaniline‐dodecybenzenesulfonic acid (PANI‐DBSA)/epoxy resin (EP) blends were prepared by a solution‐in‐toluene process and direct mixing of PANI‐DBSA with EP. The dispersion quality of PANI‐DBSA proved to be strongly related to the final electrical properties of the cured blends. The solution processed blends showed enhanced electrical properties with small PANI‐DBSA contents (percolation threshold determined was around 2.3 wt.‐% PANI‐DBSA). The morphologies of these blends were investigated by atomic force (AFM), scanning electron (SEM) and transmission electron (TEM) microscopy. The existence of a translucent PANI‐DBSA network exists within the EP matrix. The microscopy investigations were in agreement with the results from differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA).SEM image of the PANI‐DBSA‐rich regions (indicated by arrows) surrounded by the conductive EP/PANI‐DBSA matrix (5 wt.‐% PANI‐DBSA).magnified imageSEM image of the PANI‐DBSA‐rich regions (indicated by arrows) surrounded by the conductive EP/PANI‐DBSA matrix (5 wt.‐% PANI‐DBSA).

The use of bimodal blends of vinyl ester monomers to improve resin processing and toughen polymer properties

Vinyl ester (VE) monomers with bimodal molecular weight distributions were prepared by reacting methacrylic acid with blends of monodisperse epoxy resins ranging in molecular weight from 350–7000 g/mol. Monodisperse vinyl ester monomers were prepared from epoxy resins of a single molecular weight. The extent of vinyl ester formation was found to be near complete and side reactions, such as etherification, did not occur to a significant extent. The viscosities of these vinyl ester resins were measured as a function of styrene content. It was found that resin viscosity, η, increased exponentially and predictably as both the styrene content (S) decreased and as the number average molecular weight ( M n) of the vinyl ester monomers increased: η∼exp( M n)/exp(S). Cure kinetics studies showed that the vinyl ester reactivity ratio decreased to 0.1 from 0.6 for bimodal blends relative to monodisperse resins while the styrene reactivity ratio increased from 0.4 to 0.6. Thus, the microgels in bimodal blends were smaller than in monodisperse resins. Emissions studies proved that decreasing the styrene content reduced the VOC emission rate and total emissions. Higher VE molecular weights decreased the overall emissions due to a reduction in monomer mobility. T g decreased from 143 to 125 °C as M n of the VE monomers increased from 540 to 920 g/mol; yet, T g of these bimodal blends were still equal to or greater than that of commercial VE resins (∼125 °C). The fracture toughness of bimodal blends increased from ∼100 to ∼330 J/m 2 as VE M n increased from 540 to 920 g/mol because of matrix toughening. The fracture properties did not improve as the styrene content increased from 35 to 45 wt% because of corresponding changes in the morphology. Yet, there were numerous low VOC bimodal formulations with fracture properties in excess of the low VOC Dow Derakane 441–400 (110 J/m 2) and even the industry standard Derakane 411–350 (240 J/m 2).

Preparation and Characteristics of Reactive Blends of Phosphate-containing Maleimide and Epoxy

Abstract Three kinds of phosphate-containing maleimide(PMI) monomers, namely diethyl (4-(N-maleimido) phenyl) phosphate (4P) diphenyl (4-(N-maleimido) phenyl) phosphate (PP) and diethyl (2,6-dibromo-4-(N-maleimido)phenyl) phosphate (BrP), were synthesized and blended with a phenol-novolac type of epoxy so as to study their potential as reactive flame retardants. Thermal reaction of these blending systems had been discussed. Mechanical and thermal properties of blends had also been analysed. It was expected that with an increase in the PMI content in the blending system, the Michael-addition reaction would take place more and easily. Increasing the PMI contents reduced the storage modulus, the Tg and the tensile strength, however good thermal stability was maintained. The flame retardancy of all the phosphate-containing epoxy systems was promoted significantly by increasing the PMI content. Besides, the PMI with halogen atom may combine the flame retarding mechanism of gas-phase and solid-phase to promote their flame retardancy.

Reactive blends of epoxy resin (DGEBA) crosslinked by anionically polymerized polycaprolactam. II. Mechanical and electrical properties

AbstractVarious reactive blends of diglycidyl ether of bisphenol A (DGEBA)/polycaprolactam were synthesized by anionic polymerization at 140°C, conducted by sodium hydride catalyst, a strong base, along with N‐acetyl caprolactam as a cocatalyst. The experiments were performed to study the effect of composition on the mechanical and electrical properties of the reactive blends, such as tensile properties, flexural properties, Izod impact strength, Rockwell hardness, and volume resistivity. It was observed that the DGEBA was crosslinked by the polycaprolactam through the rapid reaction of the oxirane group with amide nitrogen. The heat of reaction and heat‐deflection temperature of the reactive blends increased with increasing DGEBA content from 50 to 80 wt %, and increased dramatically above 70 wt % DGEBA content. The mechanical and electrical properties of the reactive blends increased with increasing DGEBA content from 50 to 80 wt %. Substantial increases in these properties were observed above 70 wt % DGEBA content in the reactive blends. SEM studies revealed that the reactive blends show a multiphase system with an increase in the DGEBA content from 50 to 80 wt % as the mixing of the two phases increased. The reactive blend Ep80Ca20, with 80 wt % DGEBA content, resembles a single‐phase system because of better mixing of the two phases; as a result, this reactive blend showed the highest mechanical and electrical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 537–549, 2005

Experimental modeling of the cure behavior of a formulated blend of DGEBA epoxy and C12-C14 glycidyl ether as a reactive diluent

Microwave curing of polymer matrix composites has been suggested as an attractive substitute for conventional thermal curing. Formulations of epoxy and reactive diluents have the advantage of better wettability and uniform fiber impregnation. However, higher peak exotherms in large masses, and thus thermal overshoot, presents a challenge for cure cycle optimization. Therefore, building a reliable curing model will not only predict the behavior of these materials during actual processing, but also facilitate numerical modeling of the process and comparison of other resin formulations. In this study the effect of the reactive diluent on the isothermal cure kinetics of low viscosity epoxy was investigated using differential scanning calorimetry (DSC). A formulated blend of diglycidyl ether of bisphenol A (DGEBA) and C12–C14 aliphatic glycidyl was cured using diethylene triamine as the curing agent. Using a standardized procedure, ISO 113571-5, the epoxy formulation was isothermally cured at several temperatures and the heat flow monitored and recorded. Using the heat flow data from DSC, the rate of cure was determined experimentally and a proper autocatalytic model with a total order of about 2.3 was fit to describe the process. Least-square regression and isoconversion methods were used to find the model parameters and the activation energy, respectively. The accuracy of the model shows fine correlation with experimental data. By comparison to other epoxy resin without diluents, the analysis of the data shows that the reactive diluent increased the curing rate, while the values of activation energy and process parameters remained within the typical values of epoxy formulations. Based on these data, the future use of these types of resins in nonthermal curing of epoxy matrix composites is discussed. POLYM. COMPOS., 26:593–603, 2005. © 2005 Society of Plastics Engineers

Cure Kinetics and Mechanical Properties of New Polyetherimide Toughened Epoxy Resin

The cure kinetics of blends of epoxy resin (4,4′-tetraglycidyl diaminodiphenyl methane; TGDDM)/curing agent (diaminodiphenyl sulfone; DDS) with ATPEI-CTBN-ATPEI triblock copolymer (ABA type) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction parameters such as activation energy and reaction constants. By increasing the amount of ABA in the blends, the final cure conversion was decreased. Lower values of the final cure conversions in the epoxy/ABA blends indicated that ABA hinders the cure reaction between the epoxy and the curing agent. The value of the reaction order m for the initial autocatalytic reaction was not affected by blending ABA with epoxy resin, i.e., the value was approximately 1.0. The value of n for the n-th order component in the autocatalytic analysis was increased from 2.0 to 3.4 by increasing the amount of ABA in the blends. A diffusion controlled reaction was observed as the cure conversion increased and the curing reaction was successfully analyzed by incorporating the diffusion control term in the rate equation for the epoxy/DDS/ABA blends. The glass transition temperature of the cured blend was improved from 187 to 205°C and the value of the fracture toughness was also improved by about 400% compared to that of the unmodified resin at 30 wt% of ABA triblock copolymer. This is attributed to the formation of co-continuous morphology between the epoxy phase and ABA triblock copolymer phase. By increasing the amount of ABA, compressive strain, tensile stress and strain of the cured blends were increased, but the compressive stress was reduced due to the presence of CTBN rubbery phases.

Curing behaviour of syndiotactic polystyrene–epoxy blends: 1. Kinetics of curing and phase separation process

AbstractThe modification of the curing behaviour and the phase separation process for an epoxy resin blended with a crystalline thermoplastic was investigated in the case of the diglycidylether of bisphenol‐A (DGEBA)/4,4′‐methylene bis(3‐chloro‐2,6‐diethylaniline) (MCDEA) blended with syndiotactic polystyrene (sPS) and cured at 220 °C. Phase separation taking place during curing of the blend was investigated by differential scanning calorimetry (DSC) and optical microscopy in order to get a better understanding of the complex interactions between cure kinetics of epoxy matrix and crystallisation of sPS, both influenced by blend composition. Results suggested that phase separation and crystallisation of sPS occurred at almost similar times, with phase separation just being ahead of crystallisation. DSC and near‐infrared measurements were used for the determination of the cure kinetics. Slow delays on the cure reactions were observed during the first minutes for the sPS‐containing blends compared with the neat DGEBA/MCDEA system but, after some time, the reaction rate became faster for the blends than for the neat matrix. Phase separation occurring in the mixtures may explain this particular phenomenon. Copyright © 2004 Society of Chemical Industry

Curing kinetics and reaction‐induced homogeneity in networks of poly(4‐vinyl phenol) and diglycidylether epoxide cured with amine

AbstractMixtures of diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin with poly(4‐vinyl phenol) (PVPh) of various compositions were examined with a differential scanning calorimeter (DSC), using the curing agent 4,4′‐diaminodiphenylsulfone (DDS). The phase morphology of the cured epoxy blends and their curing mechanisms depended on the reactive additive, PVPh. Cured epoxy/PVPh blends exhibited network homogeneity based on a single glass transition temperature (Tg) over the whole composition range. Additionally, the morphology of these cured PVPh/epoxy blends exhibited a homogeneous network when observed by optical microscopy. Furthermore, the DDS‐cure of the epoxy blends with PVPh exhibited an autocatalytic mechanism. This was similar to the neat epoxy system, but the reaction rate of the epoxy/polymer blends exceeded that of neat epoxy. These results are mainly attributable to the chemical reactions between the epoxy and PVPh, and the regular reactions between DDS and epoxy. Polym. Eng. Sci. 45:1–10, 2005. © 2004 Society of Plastics Engineers.

Effect of Biodegradable Epoxidized Castor Oil on Physicochemical and Mechanical Properties of Epoxy Resins

AbstractSummary: Biobased epoxy materials were prepared from diglycidyl ether of bisphenol A (DGEBA) and epoxidized castor oil (ECO) initiated by a latent thermal catalyst. The physicochemical and mechanical interfacial properties of the DGEBA/ECO blends were investigated. As a result, the thermal stability of the cured epoxy blends showed a maximum value in the presence of 10 wt.‐% ECO content, which was attributed to the excellent network structure in the DGEBA/ECO blends. The storage modulus and glass transition temperature of the blends were lower than those of neat epoxy resins. The mechanical interfacial properties of the cured specimens were significantly increased with increasing the ECO content. This could be interpreted in terms of the addition of larger soft segments of ECO into the epoxy resins and thus reducing the crosslinking density of the epoxy network, which results in increasing toughness in the blends.KIC values of the DGEBA/ECO blends as a function of ECO content.magnified imageKIC values of the DGEBA/ECO blends as a function of ECO content.

Synthesis and Characterization of 1,1-bis(3-Methyl-4-Cyanatophenyl) Cyclohexane-Epoxy-Bismaleimide Matrices

A new cyanate ester monomer, 1,1-bis(3-methyl-4-cyanatophenyl) cyclohexane has been synthesized and characterized. Epoxy modified with 4, 8 and 12% (by wt) of cyanate ester were made using epoxy resin and 1,1-bis(3-methyl-4-cyanatophenyl) cyclohexane and cured by using diaminodiphenyl-methane. The cyanate ester modified epoxy matrix systems were further modified with 4, 8 and 12% (by wt) of bismaleimide ( N,N′-bismaleimido-4,4′-diphenyl methane). The formation of oxazolidinone and isocyanurate during cure reaction of epoxy and cyanate ester blend was confirmed by IR spectral studies. Bismaleimide-cyanate ester-epoxy matrices were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterized for their mechanical properties; namely tensile strength, flexural strength and unnotched Izod impact test as per ASTM methods. Mechanical studies indicate that the introduction of cyanate ester (CE) into epoxy resin improves the toughness and flexural strength with reduction in tensile strength and glass transition temperature, whereas the incorporation of bismaleimide (BMI) into epoxy resin enhances the mechanical and thermal properties according to its percentage content. However, the introduction of both CE and BMI enhances the values of thermo-mechanical properties according to their percentage content. DSC thermogram of cyanate ester modified epoxy and BMI-modified epoxy show an unimodal reaction exotherms. The thermal degradation temperature and heat distortion temperature of the cured BMI-modified epoxy and CE-epoxy systems were increased with increasing BMI content. The morphology of the BMI modified epoxy and CE-epoxy systems were also studied by scanning electron microscope.

Effects of epoxy content on dynamic mechanical behaviour of PEI‐toughened dicyanate–novolac epoxy blends

AbstractBy varying the cyanate/epoxy ratio, three polyetherimide(PEI)‐modified bisphenol A dicyanate–novolac epoxy resin blends with different epoxy contents were prepared. The effects of epoxy content on the dynamic mechanical behaviour of those blends were investigated by dynamic mechanical thermal analysis. The results showed that the glass transition temperature of the cyanate–epoxy network (Tg1) in the modified blend decreases with epoxy content. When the epoxy content increases, both the width of the glass transition of the cyanate–epoxy network and its peak density are depressed substantially. Although the tangent delta peak value of PEI is basically independent of epoxy content, the Tg of PEI (Tg2) decreases with epoxy content. Tg1 is independent of the PEI loading. When Tg1 is lower than Tg2, however, the Tg1 in the blend with revised phase structure is substantially lower than other blends. Copyright © 2004 Society of Chemical Industry

Effect of crosslinking on intermolecular interactions in thermosetting blends of epoxy resin with poly(ethylene oxide)

AbstractThe miscibility and intermolecular‐specific interactions in thermosetting blends of epoxy resin (ER) with poly(ethylene oxide) (PEO) cured with various amounts of 1,3,5‐tridroxybenzene (THB) were investigated by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The glass‐transition behavior indicated that all the blends were miscible and had homogeneous amorphous phases; FTIR showed that there were the intermolecular hydrogen‐bonding interactions between crosslinked ER and PEO. However, both the glass‐transition behavior and infrared spectroscopy also indicated that the intermolecular interactions were significantly reduced by the formation of crosslinked structures, which was shown by comparing the experimental results of poly(hydroxyether of bisphenol A) (PH)/PEO and ER/PEO blends cured with various amounts of the curing agent. In ER/PEO blends the intermolecular hydrogen‐bonding interactions were much weaker than the self‐association of hydroxyls of ER, which was in marked contrast to the interactions in PH/PEO blends. In ER/PEO blends with various amounts of the curing agent, the intermolecular interactions between epoxy polymers and PEO were reduced with an increasing degree of crosslinking. The results were interpreted in terms of the effect of crosslinking on the intermolecular interactions, such as steric shielding, the screening effect, and chain connectivity resulting from the formation of the three‐dimensional crosslinked network, which could reduce the intermolecular hydrogen‐bonding interactions among hydroxyls of ER versus ether oxygen atoms of PEO. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2567–2575, 2004

Influence of carboxyl‐terminated (butadiene‐co‐acrylonitrile) loading on the mechanical and thermal properties of cured epoxy blends

AbstractA mixture of epoxy with liquid nitrile rubber, carboxyl‐terminated (butadiene‐co‐acrylonitrile) (CTBN) was cured under various temperatures. The cured resin was a two‐phase system, where spherical rubber domains were dispersed in the matrix of epoxy. The morphology development during cure was investigated by scanning electron microscope (SEM). There was slight reduction in the glass transition temperature of the epoxy matrix (Tg) on the addition of CTBN. It was observed that, for a particular CTBN content, Tg was found to be unaffected by the cure temperature. Bimodal distribution of particles was noted by SEM analysis. The increase in the size of rubber domains with CTBN content is due probably to the coalescence of the rubber particles. The mechanical properties of the cured resin were thoroughly investigated. Although there was a slight reduction in tensile strength and young's modulus, appreciable improvements in impact strength, fracture energy, and fracture toughness were observed. Addition of nitrile rubber above 20 parts per hundred parts of resin (phr) made the epoxy network more flexible. The volume fraction of dispersed rubbery phase and interfacial area were increased with the addition of more CTBN. A two‐phase morphology was further established by dynamic mechanical analysis (DMA). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2531–2544, 2004

Elastomer‐modified epoxy/amine systems in a resin transfer moulding process

AbstractThe effect of the elastomer structure on toughening highly crosslinked epoxy systems in a resin transfer moulding process (RTM) was investigated. Two kinds of elastomers containing carboxyl functionalized groups were used: (1) a reactive liquid elastomer based on carboxyl‐terminated butadiene‐acrylonitrile copolymer (CTBN), (2) a preformed core‐shell rubber (CSR). The introduction of CTBN rubber caused the modification in the glass transition temperature due to the miscibility in the epoxy matrix, whereas CSR particles did not. During cure, these elastomers affected the morphological, rheological and dielectric behaviour of epoxy/amine systems. A blend of 5% CTBN and 5% CSR exhibited a bimodal distribution of rubber particle sizes (analyzed by transmission electron microscopy) whereas scanning electron microscopy showed the glass fibre‐matrix cohesion in fracture surfaces. A semi‐empirical model was used (developed by Castro‐Macosko for describing chemorheological behaviour of epoxy/amine systems for the RTM process). The increase in viscosity and the reduction in ion conductivity were the two key parameters to monitor the cure process. The presence of rubber affected the rheological behaviour involving initial viscosity and gel point. The investigation of temperatures, pressures and ionic conductivities in various glass fibre layers was conducted to control the front flow filling and the cure reaction. The introduction of rubber modified the inflexion area of the cured rubber–epoxy blends by changing the cure rate. Copyright © 2004 Society of Chemical Industry

Phosphonate‐containing bismaleimide resins. II. Preparation and characteristics of reactive blends of phosphonate‐containing bismaleimide and epoxy

AbstractTwo kinds of phosphonate‐containing bismaleimide (BMI) monomers, phenyl‐(4,4′‐bismaleimidophenyl) phosphonate and ethyl‐(4,4′‐bismaleimido‐phenyl) phosphonate, were synthesized and added through blending to two epoxy systems for the study of their applications as reactive flame retardants. The thermal behaviors of the BMI monomers in both kinds of epoxy systems, bisphenol and phenol–novolac, were similar. An increase in the BMI contents increased the storage modulus and glass‐transition temperature but slightly reduced the mechanical strength of the epoxy blends. The pyrolysis models of both BMI blends in the two epoxy systems were quite alike. Although the initial pyrolysis temperatures of all the blending systems gradually decreased as the phosphorous content increased, the flame retardancy of all the phosphonate‐containing epoxy systems was promoted significantly by increasing contents of BMI. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2375–2386, 2004