丁腈橡胶增韧环氧树脂研究进展

综述了近年来丁腈类橡胶增韧环氧树脂的研究进展,其中包括固体丁腈橡胶,液体丁腈橡胶(丁腈-40液体橡胶,无规端羧基液体丁腈橡胶(CRBN),端羧基液体丁腈橡胶(CTBN),改性端羟基丁腈橡胶(HTBN),改性端氨基液体丁腈橡胶(ATBN))以及改性液体丁腈橡胶与纳米SiO2共同增韧环氧树脂。     

Interaction of toughening mechanisms in a hybrid epoxy system

Interaction between different toughening mechanisms is studied using a heat treated hybrid system, consisting of carboxyl‐terminated butadiene acrylonitrile (CTBN) rubber and EXPANCEL (expandable hollow microspheres) as modifiers for an epoxy resin. It was found that the fracture toughness of the hybrid system is higher than that of either individually EXPANCEL‐ or CTBN‐modified system for a given content of modifier, although the maximum toughness was not substantially high compared with maxima of single modifier systems. Microscopic examination revealed that damage zone due to CTBN particles ahead of the crack reduces due to the presence of EXPANCEL particles and nevertheless its fracture toughness increased. A possibility was deduced that the cavitation due to CTBN assists with promoting compressive stresses around EXPANCEL particles ahead of the crack tip, resulting in increase in fracture toughness. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4470–4475, 2006     

Fracture behavior of epoxy polymers modified with core-shell rubber particles

Physical and thermomechanical properties of BDMA-catalyzed DGEBA/Dicy epoxy toughened with core-shell particles were studied. Relationships between these properties and the level of toughening are reported. The blends have been made in well-defined processing conditions. In fact, the resulting properties depend on the state of dispersion of the particles in the prepolymer matrix before crosslinking and on the cure schedule. The considered core-shell particles were of two types: i) poly(butadiene-co-styrene) core/carboxy-functionalized poly(methyl methacrylate-co-styrene) shell. Such core-shell particles have been dispersed in the epoxy matrix at different volume fractions (from 9.5 to 24%); ii) poly(butyl acrylate) core/carboxy functionalized poly(methyl methacrylate-co-styrene) shell. These particles have been dispersed at a volume fraction of 24%. Static mechanical tests were performed in tension and compression modes on these core-shell polyepoxy blends. A slight decrease of Young's modulus and an increase of the ability to plastic deformation were noticed as the volume fraction of the core-shell particles increased. Using linear fracture mechanics (LEFM), an improvement of the fracture properties (K_IC) was measured. Fatigue crack-growth studied for blends demonstrates that the Paris's law can be used to describe the behavior of the materials. Increasing the volume fraction of core-shell particles leads to an improvement of the resistance to fatigue crack-propagation. The same trend is noted on the impact behavior studied by means of high-speed tests performed in a large range of temperatures. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2419–2431, 1997     

On hybrid toughened DGEBA epoxy resins

Considerable improvements in the fracture resistance of epoxy resins have recently been achieved by adding either rubbery or rigid second phase dispersions, or both, to an epoxy matrix. These multiphase epoxy systems are particularly useful as high performance adhesives and as matrix materials in advanced composites. This paper describes the development of new toughened epoxy hybrids, which contain both rubbery and rigid dispersions. The latter dispersions were either zirconia particles, short alumina fibres or glassy-metal ribbons. Micromechanisms of toughening and failure processes in these new materials are identified and discussed in the light of microstructures.     

橡胶增韧环氧树脂低温韧性的研究

以低分子量聚酰胺(PA300)为固化剂,以液体端羧基丁腈橡胶(CTBN)为增韧剂增韧改性双酚A型环氧树脂,考察了橡胶增韧剂、固化剂、稀释剂和无机填料对环氧树脂低温韧性的影响。通过对增韧体系应力应变特性和动态力学性能的研究表明,该体系具有优异的低温韧性。     

橡胶弹性体增韧环氧树脂的研究进展

综述了环氧树脂增韧改性的研究现状,详细介绍了丁晴橡胶、丙烯酸酯橡胶和聚氨酯弹性体增韧环氧树脂的研究进展,展望了橡胶弹性体增韧环氧树脂的前号。     

Failure behavior of adhesively bonded joints with a rubber modified epoxy adhesive under tensile-shear combined cyclic loading

Rubber-modified epoxy adhesives are used widely as structural adhesive owing to their properties of high fracture toughness. In many cases, these adhesively bonded joints are exposed to cyclic loading. Generally, the rubber modification decreases the static and fatigue strength of bulk adhesive without flaw. Hence, it is necessary to investigate the effect of rubber-modification on the fatigue strength of adhesively bonded joints, where industrial adhesively bonded joints usually have combined stress condition of normal and shear stresses in the adhesive layer. Therefore, it is necessary to investigate the effect of rubber-modification on the fatigue strength under combined cyclic stress conditions. Adhesively bonded butt and scarf joints provide considerably uniform normal and shear stresses in the adhesive layer except in the vicinity of the free end, where normal to shear stress ratio of these joints can cover the stress combination ratio in the adhesive layers of most adhesively bonded joints in industrial applications.

In this study, to investigate the effect of rubber modification on fatigue strength with various combined stress conditions in the adhesive layers, fatigue tests were conducted for adhesively bonded butt and scarf joints bonded with rubber modified and unmodified epoxy adhesives, wherein damage evolution in the adhesive layer was evaluated by monitoring strain the adhesive layer and the stress triaxiality parameter was used for evaluating combined stress conditions in the adhesive layer. The main experimental results are as follows: S–N characteristics of these joints showed that the maximum principal stress at the endurance limit indicated nearly constant values independent of combined stress conditions, furthermore the maximum principal stress at the endurance limit for the unmodified adhesive were nearly equal to that for the rubber modified adhesive. From the damage evolution behavior, it was observed that the initiation of the damage evolution shifted to early stage of the fatigue life with decreasing stress triaxiality in the adhesive layer, and the rubber modification accelerated the damage evolution under low stress triaxiality conditions in the adhesive layer.     

Toughening mechanisms in core-shell rubber modified polycarbonate

We have conducted a study of toughening mechanisms in rubber modified polycarbonate systems in order to evaluate the sequence of deformation events which improve fracture toughness. We conclude that cavitation of the rubber particles occurs first, followed by massive shear yielding of the matrix material. The size and shape of the deformation zone created in front of the crack is governed by the mechanical properties of the rubber particles and the stress state at the crack tip. The importance of using a variety of analytical techniques to characterize deformation mechanism is also illustrated.     

橡胶增韧环氧灌封料的研究

以液体羧基丁腈橡胶、液体聚硫橡胶为增韧剂制成环氧树脂灌封料,通过冲击强度、弯曲强度和拉伸剪切强度评价增韧环氧树脂灌封料的效果。实验结果表明,加入增韧剂的灌封料韧性与对照组相比均有不同程度的提高;液体聚硫橡胶增韧的环氧树脂灌封料表现出较好的抗冲击性能和抗弯曲性能;液体羧基丁腈橡胶增韧的环氧树脂灌封料表现出较好的拉伸剪切性能。     

Effect of high loading rate and low temperature on mode I fracture toughness of ductile polyurethane adhesive

The mode I fracture toughness of an adhesive at low temperatures under high loading rates are studied experimentally. Typical R-curves of the polyurethane adhesive under different loading rates (0.5?mm/min, 50?mm/min, 500?mm/min) at different temperatures (room temperature, ?20?°C, ?40?°C) respectively are obtained. From the experimental results, the mode I fracture toughness of this adhesive is extremely sensitive to the high loading rates and low temperatures. With the increase of the loading rate and decrease of temperature, the mode I fracture toughness of this adhesive decreases significantly. Under the loading rate of 500?mm/min at ?40?°C, the mode I fracture toughness of adhesive is 15% of the value at room temperature (RT) under quasi-static conditions. Through the experiment, the relationship between mode I fracture toughness of this adhesive, nominal strain rate and temperature is obtained.     

纳米丁腈橡胶改性环氧树脂的性能及其应用

简述了纳米硫化丁腈橡胶改性环氧树脂的性能特点;介绍了一种耐低温环氧电子灌封胶和一种常温固化耐高温胶的配方、性能及其应用.     

电子模块灌封用柔性阻燃型改性环氧树脂研究

选用柔性环氧树脂、活性增韧剂、磷系列阻燃剂FR-P和复合阻燃剂FR-A对环氧树脂CYD128进行改性,提高环氧树脂的柔韧和阻燃等性能,取得良好的改性效果,成功制备出柔性阻燃环氧电子灌封材料, 有利于解决环氧树脂在电子工程应用过程中的问题。     

丙烯酸酯液体橡胶的合成及其增韧环氧树脂的研究进展

综述了反应性丙烯酸酯液体橡胶的合成方法及其用丙烯酸酯液体橡胶增韧环氧树脂的研究进展。其合成方法以溶液聚合为好,聚合产物以三元共聚物为好。增韧效果与体系的相态结构、化学键合和环氧基体的延展性有关。     

Structure and properties of epoxy resins modified with acrylic particles

The morphology and material properties of dicyandiamide (DICY)‐cured epoxy resins modified with acrylic particles consisting of a PBA (polybutyl acrylate) core and a PMMA (polymethyl methacrylate) shell and epoxy resins modified with acrylic rubber (PBA) particles alone were studied. It was found that the epoxy system modified with core/shell acrylic particles showed higher fracture toughness, indicating that the modification had a larger effect on improving the material properties of the epoxy resin. A characteristic shown by the core/shell acrylic particles is that they swell along with the epoxy resin under exposure to heat and gel before the latter cures. In this process, the epoxy resin penetrates the surface of the shell layer and a bond is formed between the epoxy matrix and the core/shell acrylic particles. This suggests that the epoxy matrix around the core/shell acrylic particles has the effect of increasing the level of energy absorption due to plastic deformation of the matrix. This is thought to explain why the epoxy resin modified with core/shell acrylic particles showed higher fracture toughness. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2955–2962, 1999     

聚芳醚酮增韧环氧体系相结构的冲击韧性及模拟计算研究

采用SEM观察了热塑性聚芳醚酮(PAEK)共混增韧环氧树脂的浇注体脆断断口相形貌,统计分析了浇注体断口粒子相尺寸与PAEK含量间的关系,测试了浇铸体的冲击韧性(ak)。结果表明:随着PAEK的质量分数从23.1%增加到33.3%,热固性颗粒的粒径由1.59μm减小到0.99μm;树脂浇铸体的ak值在PAEK的质量分数为28.6%时增加到28.06 kJ/m2,然后再减小。在上述结果的基础上,通过有限元分析软件重构了该体系的三维相结构,预测了树脂体系的冲击强度并与实验结果进行了对比,二者相符性较好。     

环氧树脂增韧改性的研究进展

环氧树脂(EP)具有优异的综合性能,在许多领域中都得到广泛应用。综述了EP的增韧改性研究(包括橡胶、热塑性树脂、热致液晶、互穿聚合物网络以及纳米粒子等增韧改性方法),并指出了EP增韧的主要发展趋势。     

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     

聚硫橡胶对环氧树脂固化动力学及力学强度的影响

用红外光谱分析了在环氧树脂中加入聚硫橡胶的固化及增韧过程,通过差示扫描量热法研究了增韧体系的反应动力学,探讨了聚硫橡胶用量对固化产物力学强度的影响,并对试样断口形貌进行了扫描电镜观察。结果表明,聚硫橡胶的加入降低了环氧树脂的表观活化能而没有改变反应级数,使得固化反应的总放热量减少、放热过程更加平均。聚硫橡胶对环氧树脂的增韧效果明显,二者通过化学键结合,韧性撕裂的冲击断面形貌验证了这种活性增韧。当聚硫橡胶用量为30份(质量)时,环氧树脂固化物的冲击强度可达到未增韧者的896%。     

Thermal and mechanical properties of epoxidized natural rubber modified epoxy matrices

Two sets (A and B) of bisphenol A–diglycidyl ether (DGEBA) based epoxy resin formulations were modified with epoxidized natural rubber (ENR 50) and its liquid version (LENR 50), and cured with amino propoxylate initiator/accelerator at ambient temperatures. The ENR 50 loading range was 1.6–5.9 wt%. Both sets could be loaded up to 12 wt% with LENR 50. Significant improvements in tensile toughness and impact toughness could only be observed for set A formulations. At the maximum LENR 50 loading achieved, the improvement in tensile toughness is 250% in comparison with that of the neat formulation; that for impact toughness is 125%. Differential scanning calorimetry reveals multiple transitions, characteristic of these systems. Scanning electron micrographs of fractured surfaces show uniform rubber dispersions in the submicrometre size range. At the loading levels used, LENR 50 particle dispersions fall within the range of 0.33–0.47 µm in size; those of ENR 50 are 0.48–0.67 µm in average size. Improvements in toughness are similar for both versions of epoxidized natural rubber. For both LENR 50 and ENR 50 modified epoxy systems, the extremes of 0.80 (set A) and 1.95 (set B) in glycidyl ether/reactive hydrogen molar ratios considered show distinct failure mechanisms, that of ductile failure with yielding in the former and brittle failure in the latter, irrespective of reactive diluent content. © 1999 Society of Chemical Industry     

Studies on isotactic poly(phenyl glycidyl ether)‐modified epoxy resins. II. Toughening of epoxy resins

A semicrystalline polymer, isotactic poly(phenyl glycidyl ether) (i‐PPGE) was used as a modifier for epoxy resin; 1,8‐Diamino‐p‐methane (MNDA) and 4,4′‐Diamino diphenyl sulfone (DDS) were used as curing agents. In the MNDA‐cured resins, the dispersed phase were spherical particles with diameters in the range of 0.5–1.0 μm when the resin was blended with 5 phr i‐PPGE. In the DDS‐cured resins, the particle size distribution of the dispersed phase was much wider. The difference was traced back to the reactivity of the curing agent and the different regimes used for curing. Through dynamic mechanical analysis, it was found that in the MNDA‐cured systems, i‐PPGE had a lower crystallinity than in the DDS‐cured system. In spite of the remarkable difference in the morphology and microstructure of the modified resins cured with these two curing agents, the toughening effects of i‐PPGE were similar for these resins. The critical stress intensity factor (K_IC) was increased by 54% and 53%, respectively, for the resins cured by DDS and by MNDA, blending with 5 phr of the toughner. i‐PPGE was comparable with the classical toughners carboxyl‐terminated butadiene‐acrylonitrile copolymers in effectiveness of toughening the epoxy resin. An advantage of i‐PPGE was that the modulus and the glass‐transition temperature of the resin were less affected. However, this modifier caused the flexural strength to decrease somewhat. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1223–1232, 2002; DOI 10.1002/app.10445