Toughening of vinylester–urethane hybrid resins through functionalized polymers

Liquid nitrile rubber, hyperbranched polyester, and core/shell rubber particles of various functionality, namely, vinyl, carboxyl, and epoxy, were added up to 20 wt % to a bisphenol‐A‐based vinylester–urethane hybrid (VEUH) resin to improve its toughness. The toughness was characterized by the fracture toughness (K_c) and energy (G_c) determined on compact tensile (CT) specimens at ambient temperature. Toughness improvement in VEUH was mostly achieved when the modifiers reacted with the secondary hydroxyl groups of the bismethacryloxy vinyl ester resin and with the isocyanate of the polyisocyanate compound, instead of participating in the free‐radical crosslinking via styrene copolymerization. Thus, incorporation of carboxyl‐terminated liquid nitrile rubber (CTBN) yielded the highest toughness upgrade with at least a 20 wt % modifier content. It was, however, accompanied by a reduction in both the stiffness and glass transition temperature (T_g) of the VEUH resin. Albeit functionalized (epoxy and vinyl, respectively) hyperbranched polymers were less efficient toughness modifiers than was CTBN, they showed no adverse effect on the stiffness and T_g. Use of core/shell modifiers did not result in toughness improvement. The above changes in the toughness response were traced to the morphology assessed by dynamic mechanical thermal analysis (DMTA) and fractographic inspection of the fracture surface of broken CT specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 672–680, 2002; DOI 10.1002/app.10392     

Toughening of cyanate ester resin by N‐phenylmaleimide–N‐(p‐hydroxy)phenyl‐maleimide–styrene terpolymers and their hybrid modifiers

N‐Phenylmaleimide–N‐(p‐hydroxy)phenylmaleimide–styrene terpolymer (HPMS), carrying reactive p‐hydroxyphenyl groups, was prepared and used to improve the toughness of cyanate ester resins. Hybrid modifiers composed of N‐phenylmaleimide–styrene copolymer (PMS) and HPMS were also examined for further improvement in toughness. Balanced properties of the modified resins were obtained by using the hybrid modifiers. The morphology of the modified resins depends on HPMS structure, molecular weight and content, and hybrid modifier compositions. The most effective modification of the cyanate ester resin was attained because of the co‐continuous phase structure of the modified resin. Inclusion of the modifier composed of 10 wt% PMS (M_w 136 000 g mol^?1) and 2.5 wt% HPMS (hydroxyphenyl unit 3 mol%, M_w 15 500 g mol^?1) led to 135% increase in the fracture toughness (K_IC) for the modified resin with a slight loss of flexural strength and retention of flexural modulus and glass transition temperature, compared with the values for the unmodified resin. Furthermore, the effect of the curing conditions on the mechanical and thermal properties of the modified resins was examined. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviour of the modified cyanate ester resin system. © 2001 Society of Chemical Industry     

Effect of hybridization on the mode II fracture toughness properties of flax/vinyl ester composites

In this study, flax fiber reinforced and flax/basalt hybridized vinyl ester composites were produced and their interlaminar fracture toughness (mode II) behavior was investigated using the three‐point bend end‐notched flexural (3ENF) testing. From the results, the average of the maximum values for each group of specimen obtained for critical strain energy release rate G _IIC and stress intensity factor K _II for flax/vinyl ester specimens were 1,940 J/m² and 134 kPam^0.5. Similarly, G _IIC and K _II values recorded for hybridized specimens were 2,173 J/m² and 178 kPam^0.5, respectively. The results for the flax/basalt hybridized composites exhibited an improved fracture toughness behavior compared to flax/vinyl ester composites without hybridization. The cohesive zone modeling (CZM) was also used to predict the delamination crack propagation in mode‐II in laminated composite structures. After the experimental study, the 3ENF specimens were modeled and simulated using ANSYS. The CZM/FEA results were in reasonable agreement with the experimental results. POLYM. COMPOS., 38:1732–1740, 2017. © 2015 Society of Plastics Engineers     

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/m² 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/m²) and even the industry standard Derakane 411-350 (240 J/m²).     

Blending and white spirit permeation properties of the blends of modified polyamide and ethylene vinyl alcohol with varying vinyl alcohol contents

The blending and white spirit permeation properties of the MPAEVOH blends of modified polyamide (MPA) and ethylene vinyl alcohol copolymer (EVOH) were systematically investigated in this study. Three types of EVOHs with varying vinyl alcohol contents were used to prepare the MPAEVOH resins by melt blending them with the MPA resin, respectively. The peak melting temperatures and percentage crystallinity (W_c) values of the EVOH specimens increase significantly as their vinyl alcohol contents increase. The X‐ray diffraction patterns of the melt‐crystallized EVOH crystals transform from monoclinic to orthorhombic lattice as their vinyl alcohol contents are equal to or less than 56 wt %. After blending EVOH in MPA resins, the main melting endotherms and characteristic X‐ray diffraction patterns of both monoclinic and orthorhombic lattices of EVOH crystals originally present in MPAEVOH specimens almost disappear completely, when the weight ratios of MPA to EVOH are equal to or greater than 4. The free‐volume properties and white spirit permeation rates of the EVOH specimens reduce significantly as their vinyl alcohol contents increase. A noticeable “negative deviation” was found on the plots of white spirit permeation rates, annihilation intensity (I₃), and/or fractional free‐volume (F_v) versus MPA contents as the MPA contents of each MPAEVOH sample series reach about 80 wt %. Possible reasons accounting for these interesting blending and barrier properties of MPAEVOH specimens are discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1224–1233, 2006     

Use of hygrothermal decomposed polyester–urethane waste for the impact modification of epoxy resins

Hygrothermally decomposed polyurethane (HD‐PUR) of a polyester type was used as an impact modifier in tri‐ and tetrafunctional epoxy (EP) resins. Between 5 and 80 wt % of the PUR modifier was added to the EP prior to its crosslinking with a diamine compound (diaminodiphenyl sulfone, DDS). The mean molecular weight between crosslinks (M_c ) was determined from the rubbery plateau modulus of the dynamic mechanical thermal analysis (DMTA) spectra. The fracture toughness (K_c) and energy (G_c) of the modified resins were determined on static‐loaded compact tension (CT) specimens at ambient temperature. The change in the K_c and G_c as a function of M_c followed the prediction of the rubber elasticity theory. The efficiency of the HD‐PUR modifier was compared with that of a carboxyl‐terminated liquid nitrile rubber (CTBN). Attempts were also made to improve the functionality of the modifier by hygrothermal decomposition of PUR in the presence of glycine and ε‐caprolactam, respectively. DMTA and fractographic results showed that HD‐PUR functions as an active diluent and a phase‐separating additive at the same time. As HD‐PUR can be regarded as an amine‐functionalized rubber, it was used as the hardener (by replacing DDS) in some EP formulations. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1139–1151, 2000     

Methacrylate/acrylate terminated derivatives of diglycidyl hexahydrophthalate: Synthesis,structural, and thermal characterization

Mono‐ or di(meth)acrylate‐terminated derivatives of diglycidyl hexahydrophthalate (ER) were prepared by reacting 1 : 1 or 1 : 2M ratio of ER and methacrylic acid or acrylic acid. These vinyl ester (VE) resins were characterized by determining epoxy equivalent weight, acid number, and molecular weight by gel permeation chromatography. Structural characterization was done by FTIR and ¹H NMR spectroscopy. In the ¹H NMR spectra of acrylate‐terminated VE resins, three proton resonance signals were observed in the region 5.8–6.4 ppm due to vinyl group while in methacrylate‐terminated VE resins only two proton resonance signals due to vinylidene protons were observed at 5.6–6.1 ppm. The Brookfield viscosity (room temperature (25 ± 2)°C) of these resins diluted with varying amounts of MMA was determined at 20 rpm. Curing behavior was monitored by determination of gel time and differential scanning calorimetry. An exothermic transition was observed in the DSC scans in the temperature range of (81–150)°C. Isothermal curing of MMA‐diluted VE resins containing AIBN as an initiator was done at 60°C for 2 h in N₂ atmosphere, and then heating for another 2 h in static air atmosphere. Thermal stability of isothermally cured resins in N₂ atmosphere was evaluated by thermogravimetric analysis. All cured resins decomposed above 310°C in single step. Thermal stability of the cured resins having acrylate end caps was marginally higher than the resins having methacrylate end groups. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Epoxy modification with poly(vinyl acetate) and poly(vinyl butyral). I. Structure,thermal, and mechanical characteristics

Efficiency of the application of high strength heat resistant thermoplastics for improving fracture toughness and impact properties of epoxy resins motivated authors to try large‐scale production thermoplastics for the same purpose. Epoxy/anhydride systems were modified by up to 8 wt % poly(vinyl acetate) (PVAc) and up to 6 wt % poly(vinyl butyral) (PVB). In epoxy–PVAc blends it was possible to obtain morphologies with continuous thermoplastic phase. However, only sea‐island morphologies with a very small size of PVB‐rich phase were observed in epoxy–PVB matrices. The former type of morphology allowed a notable 2.4‐fold increase in the fracture toughness of epoxy resin and simultaneous up to 30% decrease in its' impact strength. The latter type of morphology caused a notably lower (45%) enhancement of the epoxy fracture toughness combined with a 50% increase in its' impact strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44081.     

Modification of bismaleimide resin by soluble poly(ester imide) containing trimellitimide moieties

Poly(ester imide)s containing trimellitimide moieties have been used to reduce the brittleness of the bismaleimide resin composed of 4,4′‐bismaleimidediphenyl methane and o,o′‐diallyl bisphenol A. The poly(ester imide)s include poly[ethylene phthalate‐co‐ethylene N‐(1,4‐phenylene)trimellitimide dicarboxylate]s containing 20–40 mol% trimellitimide (TI) unit, and poly[trimethylene phthalate‐co‐trimethylene N‐(1,4‐phenylene)trimellitimide dicarboxylate]s (PESIP) containing 20 mol% TI unit. The poly(ester imide)s are effective modifiers for reducing the brittleness of the bismaleimide resin. For example, when using 30 wt% of PESIP (20 mol% TI unit, M_w 13 500 g mol^?1), the fracture toughness (K_IC) for the modified resin is increased by 80% with retention in flexural properties and a slight loss of the glass transition temperature, compared with the values of the unmodified cured bismaleimide resin. Microstructures of the modified resins have been examined by scanning electron microscopy and dynamic viscoelastic analysis. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviour of the modified bismaleimide resin system. © 2004 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     

Determination of fracture toughness of epoxy using fractography

Fracture toughness of epoxy was determined by quantitative fractography, one of the techniques for brittle materials based on fracture mechanics. Two different epoxy systems, an anhydride‐cured and an amine‐cured epoxy based upon diglycidyl ether of bisphenol A (DGEBA) were studied. Epoxies with different average molar mass between crosslinks (M_c) or crosslink density were prepared by varying the cure profiles. The materials were characterized using differential scanning calorimetry (DSC), dynamic mechanical spectroscopy (DMS), and density measurements. Optical microscopy was used to measure the dimensions of the different regions on the fracture surfaces of unnotched samples that were tested to failure under tension. The fracture toughness values were calculated from the relationship between the measured sizes and fracture stress. Epoxies with lower M_c values or higher crosslink densities have lower fracture toughness values. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 257–268, 1999     

Toughness response of vinylester/epoxy‐based thermosets of interpenetrating network structure as a function of the epoxy resin formulation: Effects of the cyclohexylene linkage

Vinylester/epoxy (VE/EP)‐based thermosets of interpenetrating network (IPN) structures were produced by using a VE resin (bismethacryloxy derivative of a bisphenol A–type EP resin) with aliphatic (Al‐EP) and cycloaliphatic (Cal‐EP) EP resins. Curing of the EP resins occurred either with an aliphatic (Al‐Am) or cycloaliphatic diamine compound (Cal‐Am). Dynamic mechanical thermal analysis (DMTA) and atomic force microscopy (AFM) suggested the presence of an interpenetrating network (IPN) in the resulting thermosets. Fracture toughness (K_c) and fracture energy (G_c) were used as the toughness characterization parameters of the linear elastic fracture mechanics. Unexpectedly high K_c and G_c data were found for the systems containing cyclohexylene units in the EP network, such as VE/Al‐EP+Cal‐Am and VE/Cal‐EP+Al‐Am. This was attributed to the beneficial effects of the conformational changes of the cyclohexylene linkages (chair/boat), which were closely analogous to those in some thermoplastic copolyesters. The failure mode of the VE/EP thermoset combinations was studied in scanning electron microscopy (SEM) and discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2124–2131, 2003     

Characterization of the fracture toughness property (G1c) of composite laminates using the double cantilever beam specimen

The results of a study on the interlaminar fracture toughness properties (G_1c) of four unidirectional carbon fiber epoxy materials are presented. The selected materials included Narmco 5245C, Hexcel F584, and American Cyanamid 1806 resins reinforced with Hercules IM6 fibers and for a baseline material Narmco 5208 reinforced with T300 fibers. The G_1c values determined on Double Cantilever Beam specimens were found to range from 93 to 370 J/m². The higher values may partly result from fiber bridging during fracture. This paper discusses specimen configuration, test procedure, and the Scanning Electron Microscope results.     

Toughening of cyanate ester resin by N‐phenylmaleimide–styrene copolymers

The N‐phenylmaleimide–styrene copolymer (PMS) was prepared and used to improve the brittleness of the cyanate ester resin. PMS was an effective modifier for improving the brittleness of the resin. The morphologies of the modified resins depended on PMS molecular weight and content. The most effective modification of the cyanate ester resin was attained because of the cocontinuous phase structure of the modified resin. Inclusion of 10 wt % PMS (M_w 133,000) led to an 160% increase in the fracture toughness (K_IC) for the modified resin with a slight loss of flexural strength and retention of flexural modulus and the glass transition temperature, compared to the values for the unmodified resin. Low water absorptivity of the parent‐cured resin was not deteriorated by modification. The toughening mechanism was discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified cyanate ester resin system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2931–2939, 1999     

Rheology of silicon carbide/vinyl ester nanocomposites

Silicon carbide (SiC) nanoparticles with no surface treatment raise the viscosity of a vinyl ester resin much more intensely than micrometer‐size SiC particles. An effective dispersant generally causes a reduction in the resin viscosity attributed to its surface‐active properties and thereby increases the maximum fraction of particles that can be introduced. This article assesses the rheological behavior of SiC‐nanoparticle‐filled vinyl ester resin systems with the Bingham, power‐law, Herschel–Bulkley, and Casson models. The maximum particle loading corresponding to infinite viscosity has been determined to be a 0.1 volume fraction with the (1 ? η_r^?1/2)–? dependence (where η_r is the relative viscosity and ? is the particle volume fraction). The optimum fractional weight percentage of the dispersants (wt % dispersant/wt % SiC) is around 40% for 30‐nm SiC nanoparticles, which is much higher than 1–3% for micrometer‐size particles. SiC nanoparticles at a concentration of 9.2 wt % (0.03 volume fraction) cause a fourfold increase in the resin viscosity. The addition of a dispersant at the optimum dosage lowers the viscosity of SiC/vinyl ester suspensions by 50%. The reduction in the viscosity is substantial to improve the processability of SiC/vinyl ester nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4365–4371, 2006     

Mechanical behavior and structure of rubber modified vinyl ester resins

Vinyl esters are used widely as thermoset matrix materials for reinforced composites; however, they suffer from low‐impact resistance. Substantial enhancement of the toughness of brittle polymers may be achieved by dispersing elastomeric inclusions or rubber particles in the polymer matrix, inducing multiple crazing and shear yielding of the matrix. The main objectives of this work are morphological characterization of vinyl ester/reactive rubber systems and investigation of the mechanical and fracture behavior of these systems. Additional studies focused on rubber endcapped vinyl ester in the absence and presence of added reactive rubber. The initial compatibility of the liquid rubber with the liquid resin was studied. This is a key factor, along with cure conditions, in determination of the possible morphologies, namely, the degree of phase separation and particle size. The initial rubber/resin compatibility was found poor and all attempts to improve it by means of surfactants or ultrasonic treatment have not been successful. The flexure mechanical and fracture behavior of the cured resin/rubber systems was investigated. Three basic types of crack propagation behavior, stable, unstable, and stick‐slip, were observed. Fracture toughness of various resin/rubber systems was evaluated and was found to increase with increased content of rubbery second‐phase material. However, there is some payoff in stiffness and flexural strength of the cured resins. The addition of rubber does not affect the resin toughness at impact conditions. Analysis and interpretation of fractures morphology show that both multiple crazing and external cavitation play an important role in the fracture mechanism of the rubber modified specimens. No shear yielding is evident. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 647–657, 1999     

Mechanical and dynamic mechanical studies of resol/vinyl acetate‐2‐ethylhexylacrylate/ hexamethoxymethylmelamine interpenetrating network systems

Resol was solution blended with vinyl acetate–2‐ethylhexylacrylate (VAc–EHA) resin in aqueous medium, in varying weight fractions, with hexamethoxymethylmelamine (HMMM) as crosslinker, and data was compared with a control. The present work was aimed at getting an optimum combination of tensile strength, dynamic mechanical strength, impact strength, and toughness by synthesis of an interpenetrating network (IPN) of the resins. The control gave a semi‐IPN system, in which the resol crosslinked, while the acrylic did not, whereas the blend, where HMMM was the crosslinker, gave a full IPN system. Full IPNs of the resol/VAc–EHA system had higher moduli and ultimate tensile strength than the semi‐IPNs. Dynamic mechanical study showed that full IPN systems have higher T_g values than semi‐IPN systems. The impact strength increases with increasing proportions of VAc–EHA copolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1765–1771, 2003     

Synthesis of reactive hyperbranched and star-like polyethers and their use for toughening of vinylester-urethane hybrid resins

A vinylester-urethane hybrid resin (VEUH) was toughened by adding various vinyl-functionalized branched polyethers in 10 and 20 wt%. Two sets of hyperbranched polymers (HBPs) with different branching density were compared with a set of six-arm star polymers. Besides the architecture, the polymers also varied in their characteristics (molecular mass and mass distribution, vinyl/hydroxy ratio). The morphology of the modified VEUH was studied by dynamic-mechanical thermal analysis (DMTA), transmission (TEM) and scanning electron microscopy (SEM). The toughness was characterized by the fracture energy (G_c) determined on compact tension specimens at room temperature. It was established that the architecture and vinyl/hydroxy ratio of the HBPs are those parameters which control the morphology and thus the related linear elastic fracture mechanical response. Less compact star-like polymers with long, flexible arms and with high vinyl functionality produced the largest toughness improvement in VEUH.     

Synthesis,characterization, and properties of thermosets based on the cocuring of an acetylene‐terminated liquid‐crystal and silicon‐containing arylacetylene oligomer

A thermotropic acetylene‐terminated liquid‐crystal monomer, 2‐methyl‐1,4‐phenylene bis(4‐ethynylbenzoate) (MPBE), was prepared and used as a modification composition to react and cocure with a silicon‐containing arylacetylene (PSA) oligomer for improving PSA resin. The curing behavior of the PSA–MPBE resins were characterized by differential scanning calorimetry and Fourier transform infrared spectroscopy. The microstructure and morphology of the PSA–MPBE resins were investigated by scanning electron microscopy (SEM) and transmission electron microscopy. Their dynamic mechanical properties and thermostability were measured by dynamic mechanical analysis (DMA) and thermogravimetric analysis. The results indicate that the thermotropic acetylene‐terminated liquid‐crystal monomer melted into a schlieren texture. MPBE and PSA could copolymerize to fix the mesogenic domain in the crosslinked network and form a homogeneous‐phase sea‐island structure, which improved the rigidity and toughness of the materials. DMA showed that the storage modulus of the PSA–MPBE resins increased by about 400 MPa compared to the those of the pure components. The SEM experiments showed a noticeable change in the morphology, from a typical brittle fracture for the pure PSA to microplastic deformation behavior for the PSA–MPBE resins. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45141.     

Toughening of vinylester–urethane hybrid resins by functional liquid nitrile rubbers and hyperbranched polymers

Liquid nitrile rubbers with vinyl (VTBN), carboxyl (CTBN) and epoxy (ETBN) and hyperbranched polyesters with vinyl (VHBP) and epoxy (EHBP) functionalities were added in 10 wt% to a bisphenol-A based vinylester–urethane hybrid resin (VEUH) for its toughening. The fracture energy (G_c) was determined on compact tensile specimens at ambient temperature. High toughness improvement was achieved by adding ETBN and CTBN to VEUH. It was established that a change in the initial stoichiometry of OH/NCO may affect G_c.The combination of CTBN with other additives in 1:1 ratio yielded a synergistic effect with respect to G_c. Changes in G_c were explained by differences in the fracture mode based on fractographic inspection of the fracture surface of the specimens. It was shown the same G_c may be derived from completely different failure scenarios.