Toughening of dicyandiamide-cured DGEBA-based epoxy resins by CTBN liquid rubber

Toughening of a diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin with liquid carboxyl-terminated butadiene acrylonitrile (CTBN) copolymer has been investigated. For this purpose six blend samples were prepared by mixing DGEBA with different concentrations of CTBN from 0 to 25 phr with an increment of 5 phr. The samples were cured with dicyandiamide curing agent accelerated by Monuron. The reactions between oxirane groups of DGEBA and carboxyl groups of CTBN were followed by Fourier-transform infrared (FTIR) spectroscopy. Tensile, impact, fracture toughness and dynamic mechanical analysis of neat as well as the modified epoxies have been studied to observe the effect of CTBN modification. The tensile strength of the blend systems increased by 26 % when 5 phr CTBN was added, and it remained almost unchanged up to 15 phr of CTBN. The elongation-at-break and Izod notched impact strength increased significantly, whereas tensile modulus decreased gradually upon the addition of CTBN. The maximum toughness of the prepared samples was achieved at optimum concentration of 15 phr of CTBN, whereas the fracture toughness (K _IC) remained stable for all blend compositions of more than 10 phr of CTBN. The glass transition temperature (T _g) of the epoxy resin significantly increased (11.3 °C) upon the inclusion of 25 phr of CTBN. Fractured surfaces of tensile test samples have been studied by scanning electron microscopic analysis. This latter test showed a two-phase morphology where the rubber particles were distributed in the epoxy resin with a tendency towards co-continuous phase upon the inclusion of 25 phr of CTBN.     

Effect of resin modifiers on the structural properties of epoxy resins

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

Tertiary-amine-terminated polybutadiene and butadiene acrylonitrile: Synthesis and application in the modification of epoxy resins

Two tertiary-amine-terminated liquid rubbers (TATPB and TATBN) containing polybutadiene and butadiene acrylonitrile are successfully synthesized and used in the modification of epoxy networks. By taking advantage of the flexibility of rubbers, the toughness of epoxy resin has been significantly improved. The addition of 60 phr TATPB and TATBN increased the impact strength of epoxy resins from 12.2 to 59.8 and 92.0 KJ/m², respectively. Meanwhile, due to the dual role of tertiary amine of TATPB and TATBN in catalysis and curing for epoxies, their T_g values shifted from 87.7 to 102.0 and 95.7°C, respectively. TATPB with a smaller polarity improves the toughness of the epoxy resin slightly less than TATBN with a larger polarity, but the former is more effective in increasing the T_g values. This study demonstrates a novel strategy to enhance the toughness of epoxy composites as well as improve the high temperature resistance by designing the end-structure of toughening agents.     

Synergistic Toughening in Ternary Silica/Hollow Glass Spheres/Epoxy Nanocomposites

Herein, the fracture toughness of ternary epoxy systems containing nanosilica and hollow glass microspheres (HGMS) is investigated. The experimental measurements reveal synergistic fracture toughness in some hybrid compositions: The incorporation of 10 phr of HGMS and nanosilica alone modify the fracture toughness of epoxy by 39% and 91%, respectively. However, use of 10 phr hybrid modifier can enhance the fracture toughness of the resin up to 120%. Observations reveal different toughening mechanisms for the blends i.e., plastic deformation for silica nanoparticles and crack bifurcation for HGMS. Both of these toughening mechanisms additively contribute to the synergism in ternary epoxies.     

Laser confocal microscopical characterization of toughened epoxy resins: Correlations between structural features and mechanical properties

Laser confocal microscopy is used to analyze the morphology of an epoxy resin (DGEBA) modified with different amounts of toughening agent carboxyl terminated butadiene acrylonitrile (CTBN). The size and phase volume of the distributed spherical toughening particles is ranging from 0.7 to 1.6 µm and 5 to 40 vol %, respectively. These morphological parameters and particles/µm² reveal a nonlinear relationship with the amount of toughening agent. With increasing particle size and number the glass transition temperature and the tensile modulus are decreasing, whereas the fracture toughness increases. Particles larger than 1.3 µm and a value of particles/µm² higher than 0.15 exhibit a more significant impact on the resin properties. Linear correlations between the rubber phase volume and the glass transition temperatures as well as the mechanical properties, i.e., tensile modulus and fracture toughness are ascertained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46094.     

Room temperature and low temperature toughness improvement in SAN/ASA blends by blending with CPE,HNBR, and BR

Styrene‐acrylonitrile copolymer (SAN)/acrylonitrile‐styrene‐acrylate terpolymer (ASA) blends (75/25, wt/wt) was toughened by blending with impact modifiers including chlorinated polyethylene (CPE), hydrogenated nitrile butadiene rubber (HNBR), and butadiene rubber (BR) and the impact property was tested at four temperatures (–30, ?15, 0, and 25 °C). The combination of CPE and HNBR was imported to toughen the SAN/ASA blends, indicating that CPE and HNBR had similar toughening effect at room temperature but HNBR exhibited a better performance at low temperature. When a little HNBR was substituted by BR, the impact strength improved dramatically with the total content of impact modifiers keeping at 30 phr. After 15 phr CPE, 10 phr HNBR and 5 phr BR were employed into blends together, the impact strength reached to a peak of 14 kJ/m² at ?30 °C while the impact strength of the blends individually toughened by 30 phr CPE or 30 phr HNBR was 5 or 12 kJ/m², respectively. The toughening mechanism showed that the low glass‐transition temperature (–108 °C) of BR and the compatibilization between BR and matrix accounted for the improvement of toughness. Simultaneously, scanning electron microscopy, dynamic mechanical analysis, flexural and tensile properties, heat distortion temperature, and Fourier transform infrared spectroscopy were measured. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45364.     

Enhanced fracture toughness of epoxy resins with novel amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) triblock copolymers

Amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) (PES‐CTBN‐PES) triblock copolymers with controlled molecular weights of 15,000 (15K) or 20,000 (20K) g/mol were synthesized from amine‐terminated PES oligomer and commercial CTBN rubber (CTBN 1300x13). The copolymers were utilized to modify a diglycidyl ether of bisphenol A epoxy resin by varying the loading from 5 to 40 wt %. The epoxy resins were cured with 4,4′‐diaminodiphenylsulfone and subjected to tests for thermal properties, plane strain fracture toughness (K_IC), flexural properties, and solvent resistance measurements. The fracture surfaces were analyzed with SEM to elucidate the toughening mechanism. The properties of copolymer‐toughened epoxy resins were compared to those of samples modified by PES/CTBN blends, PES oligomer, or CTBN. The PES‐CTBN‐PES copolymer (20K) showed a K_IC of 2.33 MPa m^0.5 at 40 wt % loading while maintaining good flexural properties and chemical resistance. However, the epoxy resin modified with a CTBN/8K PES blend (2:1) exhibited lower K_IC (1.82 MPa m^0.5), lower flexural properties, and poorer thermal properties and solvent resistance compared to the 20K PES‐CTBN‐PES copolymer‐toughened samples. The high fracture toughness with the PES‐CTBN‐PES copolymer is believed to be due to the ductile fracture of the continuous PES‐rich phases, as well as the cavitation of the rubber‐rich phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1556–1565, 2002; DOI 10.1002/app.10390     

Fatigue crack propagation of rubber-toughened epoxies

Epoxies containing epoxy-terminated butadiene acrylonitrile rubber (ETBN) or amino-terminated butadiene acrylonitrile rubber (ATBN) were prepared and studied in terms of fatigue crack propagation (FCP) resistance and toughening mechanisms. Rubber incorporation improves both impact and FCP resistance, but results in slightly lower Young's modulus and T_g As T_g increases, the degree of toughening decreases. Rubber-induced shear yielding of the epoxy matrix is believed to be the dominant toughening mechanism. Decreasing fatigue resistance with increasing cyclic frequency is observed for both neat and rubber-toughened epoxies. This result may be explained by the inability of these materials to undergo possible beneficial effects of hysteretic heating. FCP resistance is linearly proportional to M_c^1/2, where M_c is the apparent molecular weight between crosslinks determined on the rubber-toughened material. FCP resistance also increases with increasing static fracture toughness K_IC. ATBN-toughened epoxies demonstrated better fatigue resistance than ETBN-toughened systems.     

Fracture toughness of a hybrid-rubber-modified epoxy. I. Synergistic toughening

The fracture behavior of a hybrid-rubber-modified epoxy system was investigated. The modified epoxy included amine-terminated butadiene acrylonitrile (ATBN) rubber and recycled tire particles as fine and coarse modifiers, respectively. The results of the fracture toughness (K_IC) measurement of the blends revealed synergistic toughening in the hybrid system when 7.5-phr small particles (ATBN) and 2.5-phr large particles (recycled tire) were incorporated. Transmission optical micrographs showed different toughening mechanisms for the blends; fine ATBN particles increased the toughness by increasing the size of the damage zone and respective plastic deformation in the vicinity of the crack tip. However, in the case of hybrid resin, coarse recycled rubber particles acted as large stress concentrators and resulted in the branching of the original crack tip. Mode mixity at the branch tips led to synergistic K_IC in the hybrid system. It seemed that the ductility of the matrix played an effective role in the nature of the crack-tip damage zone in the hybrid epoxies. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of fluorinated poly(etherimide)s toughening for carbon fiber‐reinforced epoxy composites

Novel‐fluorinated poly(etherimide)s (FPEIs) with controlled molecular weights were synthesized and characterized, which were used to toughen epoxy resins (EP/FPEI) and carbon fiber‐reinforced epoxy composites (CF/EP/FPEI). Experimental results indicated that the FPEIs possessed outstanding solubility, thermal, and mechanical properties. The thermally cured EP/FPEI resin showed obviously improved toughness with impact strength of 21.1 kJ/m² and elongation at break of 4.6%, respectively. The EP/FPEI resin also showed outstanding mechanical strength with tensile strength of 91.5 MPa and flexural strength of 141.5 MPa, respectively. The mechanical moduli and thermal property of epoxy resins were not affected by blending with FPEIs. Furthermore, CF/EP/FPEI composite exhibited significantly improved toughness with Mode I interlaminar fracture toughness (G_IC) of 899.4 J/m² and Mode II interlaminar fracture toughness (G_IIC) of 1017.8 J/m², respectively. Flexural properties and interlaminar shear strength of the composite were slightly increased after toughening. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Study of ionic polymer toughening epoxy resin

In this study, PEL [copolymer of poly(propylene) oxide (PPO) and poly(ethylene oxide) (PEO)] toughening epoxy resin with ionic charge was used to produce an interpenetrating action between the cross‐linking network structure of the epoxy resin and the PEL additive. Fourier transform infrared (FTIR) analysis of the toughening epoxy resin revealed that ? NCO disappeared at 2400 cm^?1, ? NH appeared at 3300 cm^?1, and ? C?O appeared at 1750 cm^?1. These results indicate that a urethane bond was produced. Dynamic mechanical analysis (DMA) and mechanical testing results indicated that as the level of PEL increased, the compatibility between the epoxy resin and PEL also increased. In addition, the compatibility was improved because the addition of cornate hardener produced a graft phenomenon. The tensile property, impact strength, and fracture toughness of PEL toughening epoxy resin all had a tendency to improve. The tensile strength, impact strength, and fracture toughness (K_IC value) were most improved when 30 phr cornate was added. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3740–3751, 2002     

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.     

Fracture toughness of a hybrid rubber modified epoxy. II. Effect of loading rate

Effect of loading rate on toughness characteristics of hybrid rubber-modified epoxy was investigated. Epoxy was modified by amine-terminated butadiene acrylonitrile (ATBN) and recycled tire. Samples were tested at various loading rates of 1–1000 mm/min. Fracture toughness measurements revealed synergistic toughening in hybrid system at low loading rates (1–10 mm/min); hybrid system exhibited higher fracture toughness value in comparison with the ATBN-modified resin with same modifier content. However, synergistic toughening was eliminated by increasing the loading rate. At higher loading rates (10–1000), the fracture toughness of hybrid system decreased gradually to the level lower than that of ATBN-modified epoxy. Fractography of the damage zones showed the toughening mechanisms of ATBN-modified system was less affected by increasing the loading rate compared to that of hybrid system. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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 and properties of MWCNTs/poly(acrylonitrile‐ styrene‐butadiene)/epoxy hybrid composites

Poly(acrylonitrile‐styrene‐butadiene) (ABS) was used to modify diglycidyl ether of bisphenol‐A (DGEBA) type epoxy resin, and the modified epoxy resin was used as the matrix for making multiwaled carbon tubes (MWCNTs) reinforced composites and were cured with diamino diphenyl sulfone (DDS) for better mechanical and thermal properties. The samples were characterized by using infrared spectroscopy, pressure volume temperature analyzer (PVT), thermogravimetric analyzer (TGA), dynamic mechanical analyzer (DMA), thermo mechanical analyzer (TMA), universal testing machine (UTM), and scanning electron microscopy (SEM). Infrared spectroscopy was employed to follow the curing progress in epoxy blend and hybrid composites by determining the decrease of the band intensity due to the epoxide groups. Thermal and dimensional stability was not much affected by the addition of MWCNTs. The hybrid composite induces a significant increase in both impact strength (45%) and fracture toughness (56%) of the epoxy matrix. Field emission scanning electron micrographs (FESEM) of fractured surfaces were examined to understand the toughening mechanism. FESEM micrographs reveal a synergetic effect of both ABS and MWCNTs on the toughness of brittle epoxy matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characterization and mechanical properties of Cf/ZrB2-SiC composites fabricated by a hybrid technique based on slurry impregnation,polymer infiltration and pyrolysis and low-temperature hot pressing

The continuous carbon fiber reinforced ZrB₂-SiC composite was fabricated successfully via a hybrid technique based on nano ceramic slurry impregnation, polymer infiltration and pyrolysis and low-temperature hot pressing. The C_f/ZrB₂-SiC composites exhibited non-brittle fracture modes and the chemical interaction at the fiber/matrix interfaces was effectively inhibited owing to the low sintering temperature. The S2-C_f/ZrB₂-SiC composite presented the highest mechanical properties with fracture toughness of 4.47?±?0.15?MPa?m^1/2 and the work of fracture of 877?J/m², which was attributed to the multiple length-scale toughening mechanisms including the macroscopic toughening mechanisms of crack deflection and crack branching, the micro toughening mechanisms of fiber bridging and fiber pull-out. This work presented a novel and effective method to fabricate high-performance continuous carbon fiber reinforced ceramic matrix composites.     

Effects of Rubber Addition to an Epoxy Resin and Its Fiber Glass‐Reinforced Composite

Epoxy resins are considered as one of the most important class of thermosetting polymers and find extensive use in various fields. However, these materials are characterized by a relatively low toughness. In this respect, many efforts have been made to improve the toughness of cured epoxy resins. In this work, samples of epoxy resin diglycidyl ether of bisphenol‐A and fiber glass‐reinforced composite of this polymer with and without liquid carboxyl‐terminated butadiene acrylonitrile (CTBN) copolymer were prepared to assess the effect of CTBN rubber on the properties of polymeric and composite laminate specimens. The addition of CTBN into the polymeric specimens led to a decrease in the glass transition temperature, fracture stress (from 70.39 to 56.34 MPa), and tensile elasticity modulus (from about 3.51 to 2.65 GPa), accompanied by an increase in elongation (from 2.47 to 5.64%). However, the degradation temperature of the polymeric system was not modified. Infrared analysis evidenced the occurrence of chemical reaction between the two components, and scanning electron microscopy results suggested rubber particles deformation as the prevailing toughening mechanism. The rubber addition in the composite specimens, promoted an increase simultaneous in fracture stress and in elongation at fracture. The elasticity tensile modulus has not changed. This probably results from the increased deformation capacity of the matrix, which prevents its premature cracking, and better adhesion between fibers and matrix observed in the CTBN‐modified composite laminates. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Influence of whisker-aspect-ratio on densification,microstructure and mechanical properties of Al2O3 whiskers-reinforced CeO2-stabilized ZrO2 composites

A novel composite of 12 mol% CeO₂-stablized tetragonal ZrO₂ reinforced with Al₂O₃ whiskers (designated as Ce-TZP/A_w) has been prepared and studied in this work. The objective of this investigation was to systematically study the influence of whisker-aspect-ratio on the densification behaviors, microstructure evolution, and mechanical properties of Ce-TZP/A_w composite. Results showed that the sintered density of composite increased and the grain growth tended to diminish with the decrease in whisker aspect radio. Both the fracture toughness and flexural strength reached maximum values of 475 ± 12 MPa and 11.4 ± 0.2 MPa m^1/2, respectively at a whisker aspect ratio of about 12. It was also observed that the fracture toughness, flexural strength and tetragonal to monoclinic ZrO₂ transformation of the dual-phase composite exhibited similar variation trend as a function of the whisker-aspect-ratio, which suggested that the stress-induced phase transformation should be the main toughening and strengthening mechanism in the Ce-TZP/A_w composite.     

Studies on conductivity of acrylonitrile‐butadiene rubber/LiClO4 composite and its modification by adding epoxy resin

Solid polymer electrolytes based on acrylonitrile‐butadiene rubber (NBR) and LiClO₄ were prepared and their conductivity was evaluated. The effect of nitrile group ? CN/LiClO₄ mole ratio on the conductivity was investigated. The maximum conductivity of 1.21 × 10^?4 S cm^?1 (20°C) was achieved in the NBR/LiClO₄ composite at the ? CN/LiClO₄ mole ratio of 1/2.5, which was in accordance with the strongest coordination between ? CN and Li⁺ indicated by Fourier transform infrared spectrometry measurement. The conductivity was further increased by two to three times when 30 phr epoxy resin was introduced into NBR, and the conductivity could retain around the maximum value with the ? CN/LiClO₄ mole ratio ranged from 1/2.5 to 1/3.5, while the conductivity of NBR/LiClO₄ composite existed a decrease in the same range. Field emission scanning electron microscopy and atomic force microscopy characterization showed that epoxy resin significantly improved the dispersion of LiClO₄, leading to better surface smoothness of NBR/epoxy resin/LiClO₄ composite film and contributing to the increase of ionic conductivity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improved thermosets obtained from diglycidyl ether of bisphenol A/4,4′‐diaminodiphenylsulfone based on a new epoxy‐terminated hyperbranched polymer

A new hyperbranched polymer (HBP) with a flexible aromatic skeleton and terminal epoxy groups was synthesized to improve the toughness of diglycidyl ether of bisphenol A. The HBP was characterized using nuclear magnetic resonance, Fourier transfer infrared spectroscopy and gel permeation chromatography. The effect of HBP on the thermomechanical and mechanical properties of modified epoxy systems was studied. For evaluating the efficiency of the modified epoxy systems, composite samples using glass fiber cloth were molded and tested. Using dynamic mechanical analysis, a slight reduction in glass transition temperature (T_g) with increasing HBP content was observed. Analysis of fracture surfaces revealed a possible effect of HBP as a toughener and showed no phase separation in the modified resin systems. The results showed that the addition of 15 phr HBP maximized the toughness of the modified resin systems with 215 and 40% increases in impact and flexural strengths, respectively. T_g and heat resistance of cured modified resin systems decreased slightly with an increase in HBP content and, at 15 phr HBP, only a 2.6% decrease in thermomechanical properties was observed. Meanwhile, a molded composite with HBP showed improved mechanical properties and retention rate at 150 °C as compared to that made with neat resin. © 2015 Society of Chemical Industry