端羧基丁腈橡胶改性环氧树脂的结构与性能

用液体端羧基丁腈橡胶(CTBN)对环氧树脂(EP)进行改性,合成了CTBN/EP预聚物,FT-IR分析表明,在反应中EP的环氧基开环后与CTBN的羧基反应生成了酯键。研究了CTBN/EP/聚醚胺(PEA)体系的力学性能,结果表明,随着CTBN含量的增大,其弯曲强度、拉伸强度降低,冲击强度、断裂伸长率增大,说明CTBN通过化学预聚改性的EP具有良好的韧性。SEM分析表明,固化过程中析出了橡胶相并均匀分散在环氧树脂基体中。     

CTBN改性双酚A型氰酸酯树脂的性能

为改善氰酸酯树脂的冲击韧性,在双酚A型二氰酸酯(BADCy)树脂中混入了不同含量的端羧基丁腈橡胶(CTBN).用差示扫描量热法(DSC)及红外光谱法(FTIR)对CTNB/BADCy共混体系的反应性研究发现,CTBN能促进BADCy低温下的三嗪环反应,但是使BADCy的后处理温度提高.SEM分析表明,当CTBN的含量(质量分数)大于15%后,有CTBN颗粒从BADCy中析出,形成两相结构,且随着CTBN含量的增大,分散相的粒径增大,在断口处产生的银纹和剪切带使BADCy/CTBN共混体系的韧性提高.当CTBN的含量为25%时体系的冲击强度提高了2.3倍.     

Effect of hybridization of liquid rubber and nanosilica particles on the morphology, mechanical properties, and fracture toughness of epoxy composites

A liquid carboxyl-terminated butadiene–acrylonitrile copolymer (CTBN) and SiO₂ particles in nanosize were used to modify epoxy, and binary CTBN/epoxy composites and ternary CTBN/SiO₂/epoxy composites were prepared using piperidine as curing agent. The morphologies of the composites were observed by scanning electron microscope (SEM) and transmission electron microscope (TEM), and it is indicated that the size of CTBN particles increases with CTBN content in the binary composites, however, the CTBN particle size decreases with the content of nanosilica in the ternary composites. The effects of CTBN and nanosilica particles on the mechanical and fracture toughness of the composites were also investigated, it is shown that the tensile mechanical properties of the binary CTBN-modified epoxy composites can be further improved by addition of nanosilica particles, moreover, obvious improvement in fracture toughness of epoxy can be achieved by hybridization of liquid CTBN rubber and nanosilica particles. The morphologies of the fractured surface of the composites in compact tension tests were explored attentively by field emission SEM (FE-SEM), it is found that different zones (pre-crack, stable crack propagation, and fast crack zones) on the fractured surface can be obviously discriminated, and the toughening mechanism is mainly related to the stable crack propagation zone. The cavitation of the rubber particles and subsequent void growth by matrix shear deformation are the main toughening mechanisms in both binary and ternary composites.     

端羧基液体丁腈橡胶改性海因环氧树脂性能研究

目的 采用端羧基液体丁腈橡胶(CTBN)对海因环氧树脂进行增韧改性。方法 通过热熔法将不同份数的CTBN添加到海因环氧树脂中，以4,4''–二氨基二苯甲烷为固化剂制备了改性环氧树脂，通过固化动力学研究确定了其固化工艺，考察CTBN用量对改性树脂体系的反应活性、力学性能、热性能以及断面微观形貌的影响。结果 随着CTBN的加入，改性树脂的固化放热峰向高温方向偏移。CTBN可显著提高树脂体系的断裂伸长率和冲击强度，其热性能基本保持不变。改性树脂的断面呈现两相“海岛”结构。结论 CTBN对海因环氧树脂有明显的增韧作用，制备的改性树脂体系可用于金属防腐涂料和胶黏剂等材料。     

Role of rigid nanoparticles and CTBN rubber in the toughening of epoxies with different cross-linking densities

Experimental investigations were conducted to characterize the fracture behaviours of Bisphenol A diglycidyl ether (DGEBA) epoxies modified with rigid nanoparticles (nanosilica or halloysite) and a reactive liquid carboxylterminated butadiene–acrylonitrile (CTBN) liquid rubber to identify toughening mechanisms and toughenability in the cured epoxies with different cross-linking densities. The epoxy was cured using three different hardeners, a heterocyclic amine (piperidine), a cycloaliphatic polyamine (Aradur 2954) and an aromatic amine [4,4′-Diaminodiphenyl sulfone (DDS)] to form nanocomposites with different cross-linking densities. It was found that both the hybrid particles, nanosilica with CTBN rubber and halloysite with CTBN rubber, were effective additives that clearly increased the fracture toughness of the three epoxy composites. In particular, the use of halloysite nanoparticles as additives for the epoxies showed greater potential than nanosilica to increase strength and modulus due to the reinforcing effect of the halloysite nanotubes (HNTs). The epoxy systems cured with the hardeners (Aradur 2954 and DDS), which generated relatively high cross-linking densities, evidenced inferior toughenability of the hybrid particles, compared with the epoxy systems cured using the hardener (piperidine), which produced lower cross-linking densities. The CTBN rubber formed dissimilar domains in different epoxy systems, features which were attributed to the different toughenability of the hybrid particles in the systems due to variations in the dominant toughening mechanisms involved.     

Toughened carbon/epoxy composites made by using core/shell particles

Toughened epoxy resin composites have been prepared by resin-transfer moulding by using a range of toughening agents. Two types of epoxy-functional preformed toughening particles were investigated and have a three-layer morphology in which the inner core is crosslinked poly(methyl methacrylate), the intermediate layer is crosslinked poly(butyl acrylate) rubber and the outer layer is a poly[(methyl methacrylate)-co-(ethyl acrylate)-co-(glycidyl methacrylate)]. The presence of glycidyl groups in the outer layer facilitates chemical reaction with the matrix epoxy resin during curing. Comparisons were made with acrylic toughening particles that have a similar structure, but which do not have the epoxy functionality in the outer shell, and with a conventional carboxy-terminated butadiene acrylonitrile (CTBN) liquid rubber toughening agent. The composites were characterised by using tensile, compression and impact testing. The fracture surfaces and sections through the moulded composites were examined by means of optical and scanning electron microscopy. Short-beam shear tests and fragmentation tests were used to investigate the interfacial properties of the composites. In general, use of the epoxy-functionalised toughening particles gave rise to superior properties compared with both the non-functionalised acrylic toughening particles and CTBN.     

Enhancement of fracture toughness,mechanical and thermal properties of rubber/epoxy composites by incorporation of graphene nanoplatelets

Carboxyl terminated butadiene acrylonitrile (CTBN) was added to epoxy resins to improve the fracture toughness, and then two different lateral dimensions of graphene nanoplatelets (GnPs), nominally <1 μm (GnP-C750) and 5 μm (GnP-5) in diameter, were individually incorporated into the CTBN/epoxy to fabricate multi-phase composites. The study showed that GnP-5 is more favorable for enhancing the properties of CTBN/epoxy. GnPs/CTBN/epoxy ternary composites with significant toughness and thermal conductivity enhancements combined with comparable stiffness to that of the neat resin were successfully achieved by incorporating 3 wt.% GnP-5 into 10 wt.% CTBN modified epoxy resins. According to the SEM investigations, GnP-5 debonding from the matrix is suppressed due to the presence of CTBN. Nevertheless, apart from rubber cavitation and matrix shear banding, additional active toughening mechanisms induced by GnP-5, such as crack deflection, layer breakage and separation/delamination of GnP-5 layers contributed to the enhanced fracture toughness of the hybrid composites.     

Studies on the blends of modified epoxy resin and carboxyl-terminated polybutadiene (CTPB)—II: thermal and mechanical characteristics

Blend samples were prepared by physical mixing of resole–epoxy blend with carboxyl-terminated polybutadiene (CTPB) liquid rubber ranging between 0 and 25 wt% in the interval of 5 wt%. Resoles were synthesized with phenol and various alkyl phenols. The blends were cured with 40 wt% polyamide. The structural changes during the curing were investigated by infra-red spectroscopic analysis. The presence of CTPB in resole-epoxy blends did not affected the values of cure times and ΔH whereas the gel time decreased up to 15 wt% addition of CTPB in the blends. The blend systems containing p-cresolic resole, epoxy and CTPB showed minimum gel time amongst all other blend samples. A clear-cut two-step mass loss in thermogravimetric (TG) trace of unmodified and CTPB-modified systems was observed. The mechanical properties of the blend samples were found to be affected by the CTPB addition. The plane strain fracture toughness (K _IC) values of CTPB-modified matrix resins were greater that that for the unmodified resole/epoxy blends. This was further verified by scanning electron microscopic (SEM) analysis.     

Rubber-toughened epoxy loaded with carbon nanotubes: structure–property relationships

The paper reports on the preparation, structure and properties of ternary thermosetting blends, based on DGEBA epoxy, cured with 3,3′-DDS and modified by the addition of CTBN reactive liquid rubber and/or 0.3 wt% of commercial multi-walled carbon nanotubes. The toughening effect of the phase-separated rubber particles is enhanced by the presence of the nanotubes, through a change in the morphology. In the absence of the rubber, the nanotubes alone produce a minimal effect upon the thermo-mechanical characteristics of the resin. However, the electrical conductivity of the cured resin samples is found to increase by five orders of magnitude, up to 3.6 × 10⁻³ S/m in the ternary blend.     

Effect of nanoclay and carboxyl-terminated (butadiene-co-acrylonitrile) (CTBN) rubber on the reaction induced phase separation and cure kinetics of an epoxy/cyclic anhydride system

The effects of nano clay, carboxyl-terminated (butadiene-co-acrylonitrile) (CTBN) liquid rubber and the combination of both on the cure kinetics of diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin/nadic methyl anhydride were studied. Cure kinetics studies were carried out by performing dynamic and isothermal differential scanning calorimetric (DSC) experiments. The dynamic DSC experiments were carried out at four different heating rates. Dynamic kinetic modeling was performed using Kissinger and Ozawa approaches. Since these methods are based exclusively on the maximum rate of cure, which occurs approximately at the beginning of the cure reaction, the activation energy calculated using these methods is valid only for the initial stage of the cure. The clay (3 phr) filled epoxy system has an activation energy 24 % lower than the unfilled system. The role of the surfactant chemistry on the initial stage of the cure reaction was also studied. A plausible reaction mechanism which involves the effect of the nanoclay surfactant as an accelerator of the cure reaction was proposed. The phase separated CTBN rubber hindered the cure reaction and has 3 % higher activation energy for epoxy/CTBN system than the unfilled system. In the ternary epoxy/3 phr clay/15 phr CTBN system, the accelerating effect of clay on cure was highlighted. The cure activation observed in the presence of clay overshadows the hindrance created by the phase separated CTBN. Isothermal DSC scans were carried out at five different temperatures. The experimental datas showed an autocatalytic behavior of the reaction, and the isothermal modeling was carried out by Kamal autocatalytic model. The results showed a very good agreement within the whole conversion range for the unfilled and all the filled systems. The evolution of the morphology and phase separation was also studied using optical and scanning electron microscope. Faster cure reaction resulted in smaller phase-separated CTBN particles in epoxy/clay/CTBN ternary system as compared with those observed in epoxy/CTBN binary blend.     

环氧树脂复合材料的制备及力学性能

通过配方设计,以硅烷偶联剂改性的空心玻璃微珠(HGB)为填料,端羧基液体丁腈橡胶(CTBN)为增稠剂和增韧剂,环氧树脂(EP)为基体,经变温分段固化技术制备环氧树脂/端羧基丁腈橡胶/空心玻璃微珠(EP/CTBN/HGB)三元泡沫复合材料并研究其力学和流变性能。结果表明,CTBN使得复合材料由脆性断裂变为韧性断裂;CTBN劣化了复合材料模量而HGB弥补了复合材料模量;当CTBN、HGB含量分别为12%(质量分数)和30%(体积分数)时,三元复合材料的冲击、弯曲、拉伸强度及弯曲模量均优于纯EP。另外,纯环氧树脂和EP/CTBN共混物的黏度呈现出牛顿流体的流变行为,而三元共混物的黏度表现出明显的剪切变稀现象。     

Toughening of epoxy using core–shell particles

An epoxy resin, cured using an anhydride hardener, has been modified by the addition of preformed core–shell rubber (CSR) particles which were approximately 100 or 300 nm in diameter. The glass transition temperature, T _g, of the cured epoxy polymer was 145 °C. Microscopy showed that the CSR particles were well dispersed through the epoxy matrix. The Young’s modulus and tensile strength were reduced, and the glass transition temperature of the epoxy was unchanged by the addition of the CSR particles. The fracture energy increased from 77 J/m² for the unmodified epoxy to 840 J/m² for the epoxy with 15 wt% of 100-nm diameter CSR particles. The measured fracture energies were compared to those using a similar amount of carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber. The CTBN particles provided a larger toughening effect when compared to CSR particles, but reduced the glass transition temperature of the epoxy. For the CSR-modified epoxies, the toughening mechanisms were identified using scanning electron microscopy of the fracture surfaces. Debonding of the cores of the CSR particles from the shells was observed, accompanied by plastic void growth of the epoxy and shell. The observed mechanisms of shear band yielding and plastic void growth were modelled using the Hsieh et al. approach (J Mater Sci 45:1193–1210). Excellent agreement between the experimental and the predicted fracture energies was found. This analysis showed that the major toughening mechanism, responsible for 80–90% of the increase in fracture energy, was the plastic void growth.     

Mechanical properties and failure characteristics of a recycled CFRP under tensile and cyclic loading

An examination has been made of the mechanical and failure properties of a recycled short carbon fiber reinforced plastic (rCFRP). The rCFRP samples were fabricated by the following process: the CFRP, consisting of epoxy resin with carbon fiber, is ground before mixing with acrylonitrile butadiene styrene resin with different weight fractions of CFRP. The tensile strength (σ_UTS) increased with increasing CFRP content, but dropped considerably for the sample with higher fiber content. From in situ measurement of localized failure in rCFRP, it appeared that material failure occurs even if a low tensile stress of 30% σ_UTS is applied. The localized damage was related to the pull-out (or debonding) of the fibers from the matrix. The fatigue strength increased with increasing the content of the recycled carbon fiber even for the samples with low tensile strength. This was attributed to the low crack driving force arising from severe crack closure. Details of the crack growth behavior were discussed using various crack growth models proposed in previous studies.     

Structural-mechanical relationship of epoxy compatibilized polyamide 6/polycarbonate blends

Polyamide 6 (PA6)/polycarbonate (PC) blends compatibilized with solid epoxy resin (bisphenol type-A) were prepared by extrusion followed by injection molding. The effects of epoxy resin on the microstructure, tensile, impact and compatibility of the PA6/PC blends were investigated. The results showed that both the tensile modulus and elongation at break of PA6/PC blends were inferior as compared to their parent polymers. This resulted from incompatibility between the PA6 and PC phases. SEM observation revealed that the introduction of 0.5 part per hundred (phr) epoxy resin into the PA6/PC75/25 blend yields a finer dispersion of PC phase in PA6 matrix. The boundaries between the PC domains and PA6 matrix became obscure with the incorporation of 1 phr epoxy resin. Such an improvement in compatibility was suggested to be resulted from the formation of in situ epoxy bridged PA6-PC block copolymer in the blend during compounding. Consequently, the tensile modulus, yield strength and impact strength of the PA6/PC 75/25 blend improved considerably with increasing epoxy content.     

Low-temperature behaviour of epoxy-rubber particulate composites

Toughness and mechanical property data are presented for a carboxyl-terminated acrylonitrile butadiene (CTBN) rubber-modified epoxy resin in the temperature range 20 to – 110° C. A toughening model based on ultimate strain capability and tear energy dissipation of the rubber, present as dispersed microscopic particles in an epoxy matrix, is used to explain the suppression of composite toughness (G _Ic ) below – 20° C. The toughness loss is attributed to a glass transition in the rubber particles, and to a secondary transition in the epoxy resin, both occurring in the range – 40 to – 80° C. Strain-tofailure and modulus measurements on bulk rubber-epoxy compounds, formulated to simulate rubber particle compositions, confirm a decrease in rubber ductility coincident with the onset of composite toughness loss. An increase in rubber tear energy associated with its transition to a rigid state can explain the observation that even at low temperatures composite toughness generally remains significantly higher than that of pure epoxy. Although the low-temperature epoxy transition reduces molecular mobility in the matrix phase, residual ductility in, and energy dissipation by, the rubber particles determine the extent of composite toughness suppression. The low-temperature data bear out the particle stretching-tearing model for toughening.     

Poly(ether ether ketone) with pendent methyl groups as a toughening agent for amine cured DGEBA epoxy resin

A diglycidyl ether of bisphenol-A (DGEBA) epoxy resin was modified with poly(ether ether ketone) with pendent methyl groups (PEEKM). PEEKM was synthesised from methyl hydroquinone and 4,4′-difluorobenzophenone and characterised. Blends of epoxy resin and PEEKM were prepared by melt blending. The blends were transparent in the uncured state and gave single composition dependent T _g. The T _g-composition behaviour of the uncured blends has been studied using Gordon–Taylor, Kelley–Bueche and Fox equations. The scanning electron micrographs of extracted fracture surfaces revealed that reaction induced phase separation occurred in the blends. Cocontinuous morphology was obtained in blends containing 15 phr PEEKM. Two glass transition peaks corresponding to epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum of the blends. The crosslink density of the blends calculated from dynamic mechanical analysis was less than that of unmodified epoxy resin. The tensile strength, flexural strength and modulus were comparable to that of the unmodified epoxy resin. It was found from fracture toughness measurements that PEEKM is an effective toughener for DDS cured epoxy resin. Fifteen phr PEEKM having cocontinuous morphology exhibited maximum increase in fracture toughness. The increase in fracture toughness was due to crack path deflection, crack pinning, crack bridging by dispersed PEEKM and local plastic deformation of the matrix. The exceptional increase in fracture toughness of 15 phr blend was attributed to the cocontinuous morphology of the blend. Finally it was observed that the thermal stability of epoxy resin was not affected by the addition of PEEKM.     

Interfacial adhesion improvement of plain woven carbon fiber reinforced epoxy filled with micro-fibrillated cellulose by addition liquid rubber

In certain application of fiber reinforced polymer composites fracture resistance is required. The aim of this study was to improve the interfacial adhesion between plain woven carbon fiber (CF) and epoxy matrix filled with microfibrillated cellulose (MFC) modified with carboxyl-terminated butadiene acrylonitrile (CTBN) as liquid rubber. CF/Epoxy/MFC/CTBN composite was characterized by different techniques, namely, tensile, bending, fracture toughness (mode I) test, and scanning electron microscope (SEM). The results reveal that at a fiber content 1% of MFC and 10% CTBN, initiation and propagation interlaminar fracture toughness in mode I improved significantly by 96 and 127%, respectively, which could be attribute to strong adhesion between filled epoxy, CF, and rubber. This can be explained by SEM at given weight as well; SEM images showed that in front of the tip, fiber breakage during initiation delimination as well as the extensive matrix deformation between fibers accounting for increase fracture toughness.     

Toughening mechanism for a rubber-toughened epoxy resin with rubber/matrix interfacial modification

For a rubber-toughened piperidine-DGEBA epoxy resin, the interface between the rubber particle and the epoxy resin matrix was modified by an epoxide end-capped carboxyl terminated butadiene and acrylonitrile random copolymer (CTBN). The end-capping epoxides used were a rigid diglycidyl ether of bisphenol-A (Epon 828), a short-chain flexible diglycidyl ether of propylene glycol (DER 736), and a long-chain flexible diglycidyl ether of propylene glycol (DER 732). The microstructures and the fracture behaviour of these rubber-modified epoxy resins were studied by transmission electron microscopy and scanning electron microscopy. Their thermal and mechanical properties were also investigated. In the rubber-modified epoxy resins, if the added CTBNs were end-capped by a flexible diglycidyl ether of propylene glycol (DER 732 or DER 736) before curing, the interfacial zone of the undeformed rubber particle, the degree of cavitation of the cavitated rubber particle on the fracture surface and the fracture energy of the toughened epoxy resin were all significantly increased. The toughening mechanism based on cavitation and localized shear yielding was considered and a mechanism for the interaction between cavitation and localized shear yielding that accounts for all the observed characteristics is proposed.     

Studies on blends of cycloaliphatic epoxy resin with varying concentrations of carboxyl terminated butadiene acrylonitrile copolymer I: Thermal and morphological properties

Differential scanning calorimetric (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) of the blends of cycloaliphatic epoxy (CAE) resin toughened with liquid elastomer such as carboxyl terminated butadiene acrylonitrile copolymer (CTBN) have been carried out. Exothermal heat of reaction due to cross linking of the resin in the presence of diamino diphenyl sulphone (DDS, an amine hardener) showed a decreasing trend with increasing rubber concentration. Enhancement of thermal stability as well as lower mass loss of the epoxy-rubber blends with increasing rubber concentration have been observed in thermogravimetric analysis (TGA). Dynamic mechanical properties reflected a monotonic decrease in the storage modulus (E′) with increasing rubber concentration. The loss modulus (E″) and the loss tangent (tan δ) values, however, showed an increasing trend with rise of temperature up to a maximum (peak) followed by a gradual fall in both cases.     

Shear ductility and toughenability study of highly cross-linked epoxy/polyethersulphone

The objective of the present study was to determine whether the ductility and toughenability of a highly cross-linked epoxy resin, which has a high glass transition temperature, T _g, can be enhanced by the incorporation of a ductile thermoplastic resin. Diglycidyl ether of bisphenol-A (DGEBA) cured by diamino diphenyl sulphone (DDS) was used as the base resin. Polyethersulphone (PES) was used as the thermoplastic modifier. Fracture toughness and shear ductility tests were performed to characterize the materials. The fracture toughness of the DDS-cured epoxy was not enhanced by simply adding PES. However, in the presence of rubber particles as a third component, the toughness of the PES–rubber-modified epoxy was found to improve with increasing PES content. The toughening mechanisms were determined to be rubber cavitation, followed by plastic deformation of the matrix resin. It was also determined, through uniaxial compression tests, that the shear ductility of the DDS-cured epoxy was enhanced by the incorporation of PES. These results imply that the intrinsic ductility, which had been enhanced by the PES addition, was only activated under the stress state change due to the cavitation of the rubber particles. The availability of increasing matrix ductility seems to be responsible for the increase in toughness. This revised version was published online in November 2006 with corrections to the Cover Date.