Epoxidized natural rubber/epoxy blends: Phase morphology and thermomechanical properties

Epoxidized natural rubbers (ENRs) were prepared. ENRs with different concentrations of up to 20 wt % were used as modifiers for epoxy resin. The epoxy monomer was cured with nadic methyl anhydride as a hardener in the presence of N,N‐dimethyl benzyl amine as an accelerator. The addition of ENR to an anhydride hardener/epoxy monomer mixture gave rise to the formation of a phase‐separated structure consisting of rubber domains dispersed in the epoxy‐rich phase. The particle size increased with increasing ENR content. The phase separation was investigated by scanning electron microscopy and dynamic mechanical analysis. The viscoelastic behavior of the liquid‐rubber‐modified epoxy resin was also evaluated with dynamic mechanical analysis. The storage moduli, loss moduli, and tan δ values were determined for the blends of the epoxy resin with ENR. The effect of the addition of rubber on the glass‐transition temperature of the epoxy matrix was followed. The thermal stability of the ENR‐modified epoxy resin was studied with thermogravimetric analysis. Parameters such as the onset of degradation, maximum degradation temperature, and final degradation were not affected by the addition of ENR. The mechanical properties of the liquid‐natural‐rubber‐modified epoxy resin were measured in terms of the fracture toughness and impact strength. The maximum impact strength and fracture toughness were observed with 10 wt % ENR modified epoxy blends. Various toughening mechanisms responsible for the enhancement in toughness of the diglycidyl ether of the bisphenol A/ENR blends were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39906.     

Functionalized liquid natural rubber and liquid epoxidized natural rubber: A promising green toughening agent for polyester

Toughened unsaturated polyester resins (UPRs) were prepared using two different reactive rubbers, namely, liquid natural rubber (LNR) and liquid epoxidized natural rubber (LENR). The effect of varying amounts of LNR and LENR on the morphology, thermal, and mechanical properties of UPR were evaluated. Fourier Transform Infrared spectroscopy was used to investigate the probable crosslinking reaction and changes in the functional groups on crosslinking. Field emission scanning electron microscopy and infinite focus microscopy were used to study the morphology of fracture surfaces. Tensile test showed that both the rubber‐modified resins (1.5 wt %) improved tensile strength. The viscoelastic properties and thermal stability of the toughened polyesters were evaluated using dynamic mechanical thermal analysis and thermogravimetric analysis, respectively. A slight reduction in the glass transition temperature (T_g) of the polyester was reported on the addition of both the rubbers. An increment in impact strength and fracture toughness was observed at 1.5 wt % for LNR and 4.5 wt % for LENR‐modified UPR. The results showed that both the liquid rubbers improved the mechanical properties of UPR. However, LENR‐modified UPR exhibited a more significant improvement in the mechanical properties compared to LNR‐modified UPR. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41292.     

Effects of rubber‐rich domains and the rubber‐plasticized matrix on the fracture behavior of liquid rubber‐modified araldite‐F epoxies

The fracture behavior of a bisphenol A diglycidylether (DGEBA) epoxy, Araldite F, modified using carboxyl‐terminated copolymer of butadiene and acrylonitrile (CTBN) rubber up to 30 wt%, is studied at various crosshead rates. Fracture toughness, K_IC, measured using compact tension (CT) specimens, is significantly improved by adding rubber to the pure epoxy. Dynamic mechanical analysis (DMA) was applied to analyze dissolution behavior of the epoxy resin and rubber, and their effects on the fracture toughness and toughening mechanisms of the modified epoxies were investigated. Scanning electron microscopy (SEM) observation and DMA results show that epoxy resides in rubber‐rich domains and the structure of the rubber‐rich domains changes with variation of the rubber content. Existence of an optimum rubber content for toughening the epoxy resin is ascribed to coherent contributions from the epoxy‐residing dispersed rubber phase and the rubber‐dissolved epoxy continuous phase. No rubber cavitation in the fracture process is found, the absence of which is explained as a result of dissolution of the epoxy resin into the rubber phase domains, which has a negative effect on the improvement of fracture toughness of the materials. Plastic deformation banding at the front of precrack tip, formed as a result of stable crack propagation, is identified as the major toughening process.     

Structure-property relationships in rubber-toughened epoxies

Epoxies toughened with two reactive liquid rubbers, an epoxy-terminated butadiene acrylonitrile rubber (ETBN) and an amino-terminated butadiene acrylonitrile rubber (ATBN), were prepared and studied in terms of their structure property relationships. A two-phase structure was formed, consisting of spherical rubber particles dispersed in an epoxy matrix. A broad distribution of rubber particles was observed in all the materials with most of the particles ranging in size from 1 to 4 μm, but some particles exceeding 20 μm were also found. Impact strength, plane strain fracture toughness (K_IC), and fracture energy (G_IC) were increased, while Young's modulus and yield strength decreased slightly with increasing rubber content and volume fraction of the dispersed phase. Both G_IC and K_IC were found to increase with increasing apparent molecular weight between crosslinks and decreasing yield strength. The increased size of the plastic zone at the crack tip associated with decreasing yield strength could be the cause of the increased toughness. An ATBN-toughened system containing the greatest amount of epoxy sub-inclusion in the rubbery phase demonstrated the best fracture toughness in this series. In the present systems, rubber-enhanced shear deformation of the matrix is considered to be the major toughening mechanism. Curing conditions and the miscibility between the liquid rubber and the epoxy resin determine the phase morphology of the resulting two-phase systems. Kerner's equation successfully describes the modulus dependence on volume fraction for the two-phase epoxy materials.     

Preparation of binary and hybrid epoxy nanocomposites containing graphene oxide and rubber nanoparticles: Fracture toughness and mechanical properties

Binary and hybrid epoxy nanocomposites modified with graphene oxide (GO) and core–shell rubbers (CSR) were synthesized via the solvent-exchange method. X-ray diffraction analysis and scanning electron microscopy of the samples showed a homogeneous dispersion of GO and CSR in the epoxy matrix. The tensile modulus and tensile strength of the samples modified with CSR decreased continuously with increasing CSR content; however, with the addition of only 0.05 phr GO to the neat epoxy and rubber-modified epoxy, these properties significantly increased. The use of GO and CSR individually improved the fracture toughness, but the impact of GO was greater. The simultaneous use of GO and CSR improved both the fracture toughness and the mechanical properties. Our investigation of the toughening mechanism indicated that crack deflection–bifurcation, crack pinning, and particle debonding–pullout in the presence of GO nanosheets and limited rubber particle cavitation contributed to fracture toughness improvement in the hybrid systems. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46988.     

Fracture of an epoxy polymer containing recycled elastomeric particles

The fracture behavior of elastomer-modified epoxy was investigated using compact-tension geometry. The elastomeric modifiers included a liquid carboxyl-terminated butadiene acrylonitrile and solid rubber particles of different sizes which were obtained from recycled automobile tires. When used with solid rubber alone, no significant improvement in the fracture toughness was observed. However, when used in combination with the liquid rubber modifier, it was observed that the fracture toughness of these hybrid epoxies was higher than that of those toughened with liquid rubber alone. This synergistic effect is explained in terms of crack deflection and localized shear yielding. Furthermore, we observed a slight improvement in the fracture toughness as the size of the solid rubber particles increased. Although using a combination of both reactive rubber liquids and solid rubber particles as toughening agents had been investigated previously, in this study, the solid rubber particles used were from recycled rubber tires. Therefore, we have clearly demonstrated an application of producing high-quality engineering epoxy systems using toughening modifiers that are relatively low in cost and created higher-value products for recycled solid rubber. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 271–277, 1997     

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     

Modification of epoxy resins with acrylic rubbers containing a pendant epoxy group

New acrylic rubbers with a pendant epoxy group were prepared by copolymerization of butyl acrylate (BA) with vinylbenzyl glycidyl ether (VBGE). The modification of an epoxy system (bisphenol-A diglycidyl ether/p,p′-diaminodiphenyl sulfone) with the acrylic rubbers was carried out in order to increase the toughness of the cured epoxy resin. The addition of 20 wt.-% of the copolymer containing 74% of BA and 26% of VBGE units resulted in a 30% increase in the fracture toughness (K_IC) of the cured resin at minimal expenses of strength and modulus of the resin. The modified epoxy resin had two-phase morphology in which the rubber particles with average diameter of 2 μm are dispersed in the epoxy matrix. The copolymer without the pendant epoxy group, prepared from BA and vinylbenzyl methoxyethyl ether, was ineffective as a modifier, indicating that the reaction of the pendant epoxide with the epoxy matrix resulted in good interfacial adhesion between the rubber particles and the matrix, and in the increased toughness. The epoxide-containing copolymers with 55 or 86% of BA units were also insufficient modifiers. The addition of the former yielded cured resins with homogeneous structure, whereas that of the latter resulted in macroscopic phase separation between the rubber and the epoxy resin.     

Toughening of aromatic diamine-cured epoxy resins by modification with hybrid modifiers composed of N-phenylmaleimide–styrene copolymers and N-phenylmaleimide–styrene–p-hydroxystyrene terpolymers

Hybrid modifiers composed of N-phenylmaleimide–styrene copolymers (PMS), and N-phenylmaleimide–styrene–p-hydroxystyrene terpolymers (PMSH) containing pendent p-hydroxyphenyl groups as functionalities, were used to improve the toughness of bisphenol-A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulphone. The hybrid modifiers were effective in toughening the epoxy resin. When using the modifier composed of 10 wt% PMS (M?_w 313000) and 2.5 wt% PMSH (2.5 mol% p-hydroxystyrene units, M?_w 316000), the fracture toughness (K_IC) for the modified resins increased 100% with no deterioration in the flexural properties and the glass transition temperature. The improvement in toughness of the epoxy resins was attained because of the co-continuous phase structure and the improvement in interfacial adhesion. The toughening mechanism is discussed in terms of the morphological characteristics of the modified epoxy resin systems.     

Investigation of readily processable thermoplastic-toughened thermosets. II. Epoxy toughened using a reactive solvent approach

The fracture toughness of epoxy thermosets was increased by up to 220% using very low-molecular-weight (∼ 1000 g/mol) imide thermoplastic. The objective was to produce a low-viscosity prepolymer that could be easily autoclave-processed to give a tough thermoset. Here, an homogenous epoxy prepolymer was prepared by first synthesizing very low-molecular-weight linear aromatic imide (∼ 1000 g/mol) directly in a liquid allyl phenol reactive solvent, followed by dissolution of the epoxy (Epon® 825) and the cure agent (DDS) directly in the thermoplastic solution. The allyl phenol both cures into the epoxy network, through phenol functional groups, and accelerates the cure. The viscosity of the pure epoxy was 1.4 Pa · S at 30°C. The prepolymer formulations ranged from ∼ 5–33 Pa · S at 30°C, but all reduced to less than 1 Pa · S at 90°C. The onset of cure is well above 90°C so the prepolymer viscosity is within the range for autoclave processing. The cured resin plaques were not transparent, but phase-separated domains were not found by scanning electron microscopy, indicating that the domain size is below the detection limit of the instrument. The reactive solvent causes a decrease in both the T_g and the high temperature modulus of the thermoset. Introduction of the thermoplastic results in partial recovery of the T_g and modulus. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 935–942, 1998     

Acrylate‐based liquid rubber as impact modifier for epoxy resin

Carboxyl‐terminated poly(2‐ethyl hexyl acrylate) (CTPEHA) having various molecular weights were synthesized by bulk polymerization in the form of liquid rubber. The liquid rubbers (LR‐1 to LR‐4) were characterized by ¹³C‐NMR spectroscopic analysis, nonaqueous titration, and vapor‐pressure osmometry (VPO). The liquid rubber having the lowest molecular weight (M?_n = 3600) was prereacted with the epoxy resin and the modified epoxy networks were made by curing with an ambient temperature curing agent. The modified epoxy networks containing different concentrations of CTPEHA were evaluated with respect to their thermal and impact properties. The optimum properties were obtained at about 10–15 phr of CTPEHA concentration (phr stands for parts per hundred parts of epoxy resin). Fracture surface analysis by scanning electron microscopy (SEM) indicated the presence of a two‐phase microstructure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1792–1801, 2001     

High performance HTLNR/epoxy blend—Phase morphology and thermo-mechanical properties

An attempt was made to toughen diglycidyl ether of bisphenol A (DGEBA) type epoxy resin with liquid natural rubber possessing hydroxyl functionality (HTLNR). Epon 250 epoxy monomer is cured using nadic methyl anhydride as hardener in presence of N, N dimethyl benzyl amine as accelerator. HTLNR of different concentrations up to 20 wt % is used as modifier for epoxy resin. The addition HTLNR to an anhydride hardener/epoxy monomer mixture has given rise to the formation of phase-separated structure, consisting of small spherical liquid natural rubber particles bonded to the surrounding epoxy matrix. The particle size increased with increase in rubber content. The viscoelastic properties of the blends were analyzed using dynamic mechanical thermal analysis. The T_g corresponding to epoxy rich phase was evident from the dynamic mechanical spectrum, while the T_g of the rubber phase was overlapped by the β relaxation of epoxy phase. Glass transition of the epoxy phase decreased linearly as a function of the amount of rubber. The mechanical properties such as impact and fracture toughness were also carefully examined. The impact and fracture toughness increase with HTLNR content. A threefold increase in impact strength was observed with 15 wt % HTLNR/epoxy blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study of impact properties and morphology of 4,4′‐diaminodiphenyl methane cured epoxy resin toughened with acrylate‐based liquid rubbers

Randomized carboxyl poly(2‐ethylhexyl acrylate) (A‐1) and randomized epoxy poly(2‐ethylhexyl acrylate) (B‐1) rubbers were synthesized in the form of liquid rubber by a solution polymerization technique. The liquid rubbers A‐1 and B‐1 were characterized by ¹H NMR and IR spectroscopic analysis, non‐aqueous titration, viscosity measurements and gel permeation chromatography. The liquid rubbers A‐1 (M?_n = 3900 g mol^?1), B‐1 (M?_n = 4100 g mol^?1) and a (1:1) mixture of A‐1 and B‐1 were pre‐reacted with epoxy resin separately and the modified epoxy networks were made by curing with high temperature curing agent. The modified epoxy networks were evaluated by unnotched Izod impact testing. The morphology and toughening behaviour were analysed by scanning electron microscopy. Optimum properties were obtained with the mixture of A‐1 and B‐1. Copyright © 2003 Society of Chemical Industry     

Mechanical and morphological properties of epoxy resins modified by poly(phthalazinone ether sulfone ketone)

A series of blends have been prepared by adding a novel thermoplastic poly(phthalazinone ether sulfone ketone) (PPESK) in varying proportions to diglycidyl ether of bisphenol A epoxy resin (DGEBA) cured with p‐diaminodiphenylsulfone (DDS). All the blends showed two‐phase structures characterized by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Addition of the PPESK resulted in great enhancement of glass transition temperatures (T_g) both in the epoxy‐rich phase and in the PPESK‐rich phase by reason of the special structure of PPESK. There was moderate increase in the fracture toughness as estimated by impact strength. Fracture mechanisms such as crack deflection and branches, ductile microcracks, ductile tearing of the thermoplastic, and local plastic deformation of the matrix were responsible for the increase in the fracture toughness of the blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Adhesive properties of epoxy resin modified by end‐functionalized liquid polybutadiene

Adhesive properties of epoxy resin networks modified with different functionalized liquid polybutadiene were evaluated by using aluminum adherent. The end‐functionalized polybutadiene rubbers were hydroxyl‐ (HTPB), carboxyl‐ (CTPB), and isocyanate‐terminated polybutadiene (NCOTPB). The adhesive properties depend upon the morphology and the degree of interaction between the rubber–epoxy system. The most effective adhesive for Al–Al joint in both butt and single‐lap shear testing was epoxy resin–NCOTPB system. This system presents stronger rubber–epoxy interactions and a higher degree of rubber particle dispersion with particle size diameter in the nanoscale range. These characteristics were not important for improving the toughness of the bulk network but are fundamental for the improvement of adhesive strength. The effect of the pretreatment of the aluminum surface on the roughness was also evaluated by using profilometry analysis. The type of failure was also investigated by analyzing the adhered surfaces after fracture by scanning electron microscopy and profilometry. A proportion of cohesion failure higher than 90% was observed in all systems. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2370–2378, 2004     

Effect of rubber/matrix interfacial modifications on the properties of a rubber-toughened epoxy resin

The interface of a rubber-toughened epoxy resin was modified by using epoxide end-capped carboxyl-terminated butadiene and acrylonitrile random copolymer (CTBN). The end-capping epoxides were formulated with different ratios of flexible diglycidyl ether of propylene glycol (DER732) and rigid diglycidyl ether of bisphenol-A (Epon 828). The microstructure and the fracture behavior of these rubber-modified epoxy resins were studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. The thermal and mechanical properties were also investigated. With an increase in the amount of end-capping DER732, the interfacial zone of an undeformed rubber particle and the degree of cavitation of the rubber cavity on the fracture surface were greatly increased. At the maximal addition of DER732, fracture energy (GIc) for this toughened epoxy resin containing 10phr CTBN rubber increases up to 2.4 fold compared to that of a conventional CTBN-toughened epoxy resin, but the thermal and the mechanical properties remained quite unaffected. The modification on the interfacial property provides a new technique in the improvement of fracture toughness of a rubber-toughened epoxy resin.     

环氧树脂的增韧

添加一种分相的橡胶粒子到环氧树脂中可增加其破坏韧性。已知的这些改性剂有 Ｃ Ｔ Ｂ Ｎ、微凝胶和核壳粒子等。这些橡胶增韧环氧树脂体系形成海岛结构,增韧的原因是橡胶粒子的撕裂并诱发母体的塑性变形。另一类替代反应性橡胶用于改性环氧的是多种强韧的热塑性塑料,环氧树脂变韧是形成了双连接相结构。综合讨论了改性剂和母体的性质对环氧树脂共混物韧性的影响以及增韧机理。     

A novel reactive liquid rubber with maleimide end groups for the toughening of unsaturated polyester resins

An amino-terminated butadiene–acrylonitrile copolymer was chemically modified into a maleim-ido-terminated rubber and was used as a toughening agent for an unsaturated polyester resin. The reactive rubber was characterized by Fourier transform infrared spectroscopy. The mechanical and fracture properties of the blends containing the unmodified and the modified rubbers were investigated. Furthermore, a morphological analysis was carried out by scanning and transmission electron microscopy. A substantial enhancement of toughness was found when the modified rubber was used in place of the plain copolymer. © 1996 John Wiley & Sons, Inc.     

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     

Rubber-modified epoxy resins containing high functionality acrylic elastomers

The effect of the functionality of n-butylacrylate/acrylic acid copolymers upon the impact resistance of epoxy resins modified with these rubbery copolymers as a second phase was investigated using a high speed tensile test and scanning electron microscopy. It was found that an optimum functionality of copolymer existed for maximum impact resistance. This optimum value was the result of the competition between the amount of rubber–matrix reaction, an increases in which tended to increase toughness, and solubility of the rubber in the epoxy matrix, which eventually decreased toughness.