Role of blend morphology in rubber-toughened polymers

The influence of blend morphology on mechanical behaviour of rubber-toughened polymers was investigated. Diglycidyl ether of bisphenol A epoxies toughnened by core-shell rubber particles were employed as the model systems. The blend morphology was varied by changing the composition of the shell of particles, the curing agent, and the extent of agitation prior to casting. It is shown that the most uniform dispersion of particles is obtained when the shell of the modifiers contains reactive groups. In the absence of the reactive groups and when a slow curing agent is employed, however, a highly connected microstructure is obtained. It was found that a blend with a connected microstructure provides significantly higher fracture toughness compared to a similar blend containing uniformly dispersed particles. The reason for this observation is that the connected morphology enables the shear bands to grow further from the crack tip and thus consume more energy before fracture occurs. Also, the yield strength in uniaxial tensile testing is significantly lower in the blend with the connected morphology. Therefore, it should contribute to a larger plastic zone size.     

Fracture behaviours of epoxy nanocomposites with nano-silica at low and elevated temperatures

An investigation was conducted to characterize fracture behaviours of nano-silica modified epoxies at low and elevated temperatures. A nano-silica dispersed epoxy (Nanopox XP 22/0516, Hanse-Chemie, Germany) with 40 wt% silica nano-particles was used as modifier to toughen an epoxy resin, Araldite F (Bisphenol A based, Ciba-Geigy). Fracture toughness and other mechanical properties were measured using standard compact tension (CT), tensile and flexural specimens to elaborate the effects of nano-silica particles on fracture behaviours of epoxy nanocomposites at different temperatures, −50, 0, 23, 50 and 70 °C. Dynamic mechanical analysis (DMA) was utilized to define the glass transition temperature (T _g) upon the addition of different amounts of nano-silica particles. Fracture toughness of the nano-silica modified epoxies was clearly increased at 23 °C and 50 °C, but the role of nano-silica particles in enhancing the fracture toughness became less pronounced at 0 °C and −50 °C and disappeared at 70 °C.     

Improvement of toughness and electrical properties of epoxy composites with carbon nanotubes prepared by industrially relevant processes

The addition of carbon nanotubes (CNTs) to polymeric matrices or master batches has the potential to provide composites with novel properties. However, composites with a uniform dispersion of CNTs have proved to be difficult to manufacture, especially at an industrial scale. This paper reports on processing methods that overcome problems related to the control and reproducibility of dispersions. By using a high pressure homogenizer and a three-roll calendaring mill in combination, CNT reinforced epoxies were fabricated by mould casting with a well dispersed nanofiller content from 0.1 to 2 wt%. The influence of the nano-carbon reinforcements on toughness and electrical properties of the CNT/epoxies was studied. A substantial increase of all mechanical properties already appeared at the lowest CNT content of 0.1 wt%, but further raising the nanofiller concentration only led to moderate further changes. The most significant enhancement was obtained for fracture toughness, reaching up to 82%. The low percolation thresholds were confirmed by electrical conductivity measurements on the same composites yielding a threshold value of only about 0.01 wt%. As corroborated by a thorough microscopic analysis of the composites, mechanical and electrical enhancement points to the formation of an interconnected network of agglomerated CNTs.     

Interlaminar fracture toughness and associated fracture behaviour of bead-filled epoxy/glass fibre hybrid composites

To investigate enhancement of matrix-dominated properties (such as interlaminar fracture toughness) of a composite laminate, two different bead-filled epoxies were used as matrices for the bead-filled epoxy/glass fibre hybrid composites. The plane strain fracture toughness of two different bead-filled epoxies have been measured using compact tension specimens. Significant increases in toughness were observed. Based on these results the interlaminar fracture toughness and fracture behaviour of hybrid composites, fabricated using bead-filled epoxy matrices, have been investigated using double cantilever beam and end notch flexure specimens for Mode I and Mode II tests, respectively. The hybrid composites based on carbon bead-filled matrix shows an increase in both G _IC initiation and G _IIC values as compared to a glass fibre reinforced plastic laminate with unmodified epoxy matrix. The optimum bead volume fraction for the hybrid composite is between 15% and 20%. However, the unmodified epoxy glass-fibre composite shows a higher G _IC propagation value than that of hybrid composites, due to fibre bridging, which is less pronounced in the hybrids as the presence of the beads results in a matrix-rich interply region.     

The phase transformation toughening and synergism in poly(butylene terephthalate)/poly(tetramethyleneglycol) copolymer-modified epoxies

The toughening of epoxy modified with poly(butylene terephthalate)/poly(tetra-methylene glycol) (PBT–PTMG) copolymers of various chemical composition was investigated. The fracture toughness of the brittle epoxy was highly enhanced by the inclusion of PBT–PTMG copolymer without loss of other intrinsic mechanical properties, such as modulus and yield stress. These modified epoxies also exhibited synergism in toughening. The remarkable enhancement and the synergism in fracture toughness of PBT/PTMG-modified epoxies is possibly due to the enhancement of the degree of phase transformation toughening, which is a result of the enhancement of the degree of perfectness of PBT spherulites in the presence of PTMG segments. The changes in micro-morphology of PBT/PTMG phases induced by the different chemical composition of copolymer is the most important cause of the dependency of the fracture energy on the processing variables, such as the relative PBT/PTMG composition and total amount of modifiers. Other toughening mechanisms, such as crack bifurcation, ductile fracture of PBT/PTMG phases, main crack-path alteration, and crack bridging, also contributed to toughness enhancement of the modified epoxies. © 1998 Chapman & Hall     

Toughening mechanisms in elastomer-modified epoxies

The role Of matrix ductility on the toughenability and toughening mechanism of elastomer-modified, diglycidyl ether of bisphenol A (DGEBA)-based epoxies is investigated. Matrix ductility is varied by using epoxide resins of varying epoxide monomer molecular weights. These epoxide resins are cured using 4,4 diaminodiphenyl sulphone (DDS) and, in some cases, modified with 10 vol% carboxyl-terminated copolymer of butadiene and acrylonitrile (CTBN). Fracture toughness values for the neat epoxies are found to be almost independent of the monomer molecular weight of the epoxide resin used. However, the fracture toughness of the elastomer-modified epoxies is found to be very dependent upon the epoxide monomer molecular weight. Tensile dilatometry indicates that the toughening mechanism, when present, is similar to the mechanism found for piperidine cured, elastomer-modified epoxies studied previously. Scanning electron microscopy and optical microscopy techniques corroborate this finding.     

Fracture behaviour of unmodified and rubber-modified epoxies under hydrostatic pressure

The fracture toughness and uniaxial tensile yield strengths of unmodified and CTBN-rubber-modified epoxies were measured under hydrostatic pressure. The purpose of these experiments was to learn how suppressing cavitation in rubber particles affects the deformation mechanisms and the fracture toughness of rubber-modified epoxy. It was found that the cavitation of CTBN-rubber could be suppressed at a relatively low pressure (between 30 and 38 M Pa). With cavitation suppressed, the rubber particles are unable to induce massive shearyielding in the epoxy matrix, and the fracture toughness of the rubber-modified epoxy is no higher than that of the unmodified epoxy in the pressure range studied. Unmodified epoxy shows a brittle-to-ductile transition in fracture toughness test. The reason for this transition is the postponement of the cracking process by applied pressure.Work performed while on a sabbatical leave at the University of Michigan.     

环氧网络结构设计与复合材料增韧的研究

本文以自由体积理论,对BF₃MEA固化环氧网络结构与T_g的关系进行了研究,并分析了组分对网络T_g的贡献,为确定固化剂的影响,对BF₃MEA及DDS固化环氧网络的断裂韧性进行了测试。结果表明,DDS固化体系的韧性要比BF₃MEA固化的相应的环氧网络的高。根据理论分析及实验结果,对复合材料基体的网络结构进行了重新设计,在提高复合材料层间韧性的同时保证其耐热性不会下降。实验结果验证了这一设想。     

Crack propagation in polymeric composites

The velocities of rapidly moving cracks in polymethylmethacrylate, an epoxy resin, a rubber modified epoxy resin, coupled and decoupled glass bead filled epoxies and randomly oriented glass fiber reinforced epoxies were measured with a crack propagation gage that was electrolissecally plated on the surfaces of the materials.

When fracture was initiated from a natural crack it was found that the velocity conformed to Mott's equation , while fracture initiated from a blunted notch resulted in a velocity that conformed to Dulany and Brace's equation . A general energy balance was used to show how one could develop these two equations as bounds to the velocity of catastrophic crack propagation.

The terminal crack velocity in the unfilled materials and the glass bead filled materials was , where E/ρ was the modulus to density ratio of the matrix phase at the macroscopic strain rate of the fracture test. The proportionality constant of 0.28 was independent of matrix type, temperature and degree of adhesion. Cracks in the rubber reinforced epoxies always tended to become blunt, resulting in breaking loads that were higher than that expected for materials possessing a natural crack. In addition, the average terminal velocity was less than 0.28√E/ρ, indicating the retardation effects of the rubber particles. These facts were used to explain the higher fracture toughness of these composites.

Fracture surface roughness was primarily a function of crack extension and breaking stress and was less sensitive to crack velocity. An empirical modification of the Mott energy balance was used to qualitatively explain this behavior.     

Non-stoichiometric curing effect on fracture toughness of nanosilica particulate-reinforced epoxy composites

Non-stoichiometric curing effects on the fracture toughness behaviors of nanosilica particulate-reinforced epoxy composites were experimentally investigated in this study by comparing them with bending strengths to take into consideration the effect of interaction between nanoparticles and network structures in matrix resins. The matrixes were prepared by curing them with an excess mixture of diglycidyl ether of bisphenol A-type epoxy resin as the curing agent for the stoichiometric condition. The volume fractions of the silica particles with a median diameter of 240 nm were constantly 0.2 for all composites. The neat epoxy resins and the composites were cured non-stoichiometrically to change the crosslinking densities of the neat epoxy resins and the matrix resins of the composites within 2740–490 mol/m³. The fracture toughnesses and bending strengths of the composites and the neat epoxy resins strongly depended on the crosslinking densities in the resins. Although the fracture toughness decreased monotonously from that of the stoichiometrically cured resins as the crosslinking density decreased, the fracture toughnesses of composites were largest at a slightly lower crosslinking density of approximately 2490 mol/m³ from the stoichiometric condition of 2740 mol/m³. The fracture toughness and the bending strength were improved for crosslinking densities higher than 2000 mol/m³ by adding particles. At crosslinking density lower than 2000 mol/m³, the particles worked against the mechanical properties as defects in matrix resins.     

固化剂混掺对高温下CFRP板-钢板界面黏结性能的影响

针对单一固化剂难以兼顾耐热性和韧性的不足,研究了耐热性能较好的缩胺105和韧性较好的聚醚胺D230两种固化剂混掺对纳米SiO₂环氧胶黏剂玻璃转变温度及高温下基本力学性能的影响。按一定固化条件制作了30个胶黏剂拉伸试件、21个碳纤维增强树脂复合材料(CFRP)板-钢板双搭接试件,进行了高温及常温下的准静态拉伸试验、拉伸剪切试验,测试了相应胶黏剂的动态热机械性能,并与常用商品胶的耐热性能与力学性能进行比较,得到以下结论:随混掺固化剂中聚醚胺D230比重的增加,胶黏剂高温下的拉伸强度及弹性模量逐渐降低,断裂伸长率及应变能先增加后减小,缩胺105与聚醚胺D230两种固化剂混掺的推荐比例为1∶2。随固化温度的升高,具有固化剂混掺较佳比例的胶黏剂的玻璃转变温度有所提升,综合技术与经济因素,推荐(较佳)固化条件为90℃、2 h。推荐比例与推荐固化条件的纳米SiO₂环氧胶黏剂在环境温度20~70℃之间的拉伸强度及韧性均大大优于常用商品胶黏剂。基于推荐比例与推荐固化工艺的纳米SiO₂胶黏剂粘结的CFRP板-钢板搭接接头,在70℃服役温度下的荷载-位移曲线存在屈服段,承载能力(较采用单一缩胺105和单一聚醚胺D230固化剂的搭接试件分别提升了104.03%、64.43%)和延性(为采用单一缩胺105固化剂的搭接试件的2.5倍以上)均大幅提升。高温和常温下的黏结-滑移本构均为三线性四边形。胶黏剂在满足耐热性的同时,需尽可能提升其韧性,才能有效提升CFRP-钢搭接界面的力学性能。相比于常用商品胶黏剂,研制的推荐胶黏剂粘结的CFRP板-钢板搭接接头具有优越得多的承载能力和界面断裂能。      

Toughening performance of glass fibre composites with core–shell rubber and silica nanoparticle modified matrices

The fracture energies of glass fibre composites with an anhydride-cured epoxy matrix modified using core–shell rubber (CSR) particles and silica nanoparticles were investigated. The quasi-isotropic laminates with a central 0°/0° ply interface were produced using resin infusion. Mode I fracture tests were performed, and scanning electron microscopy of the fracture surfaces was used to identify the toughening mechanisms.The composite toughness at initiation increased approximately linearly with increasing particle concentration, from 328 J/m² for the control to 842 J/m² with 15 wt% of CSR particles. All of the CSR particles cavitated, giving increased toughness by plastic void growth and shear yielding. However, the toughness of the silica-modified epoxies is lower as the literature shows that only 14% of the silica nanoparticles undergo debonding and void growth. The size of CSR particles had no influence on the composite toughness. The propagation toughness was dominated by the fibre toughening mechanisms, but the composites achieved full toughness transfer from the bulk.     

Rate and temperature effects on crack blunting mechanisms in pure and modified epoxies

The failure mechanisms of several epoxy polymers (including pure, rubber- and particulatemodified, as well as rubber/particulate hybrid epoxies) were investigated over a wide range of strain rates (10^–6 to 10² sec^–1) and temperatures (–80 to 60° C). A substantial variation in fracture toughness, G_Ic, with rate was observed at both very high and very low strain rates. Under impact testing conditions, G_Ic for both pure and rubber-modified epoxies displayed peaks at about 23 and –80° C which appeared to correlate with the corresponding size of the crack tip plastic zone. In order to explain these rate and temperature-dependent G_Ic results, two separate crack blunting mechanisms were proposed: thermal blunting due to crack tip adiabatic heating and plastic blunting associated with shear yield/flow processes. Thermal blunting was found to occur in the pure- and rubber-modified epoxies under all impact testing conditions and temperatures above 0° C. For temperatures below –20° C under impact conditions, the fracture toughness is dependent on viscoelastic loss processes and not thermal blunting. Plastic blunting was predominant at very slow strain rates less than 10^–2 sec^–1 for the pure- and rubber-modified epoxies and at impact strain rates for the fibre and hybrid epoxies. Microstructural studies of fracture surfaces provided some essential support for the two proposed crack blunting mechanisms.     

PA和PSPA与1,3-二缩水甘油-5,5-二甲基海因的反应动力学及体系的热性能与力学性能

分别使用邻苯二甲酸酐(PA)和聚葵二酸酐(PSPA)与1,3-二缩水甘油-5,5-二甲基海因(DGDH)进行固化反应。固化反应动力学和热稳定性分别使用DSC和TGA进行表征。考察了使用PSPA改性的DGDH/PA体系的力学性能、热变形温度和冲击断面形貌。动力学结果表明,DGDH/PSPA的反应活化能为75.94 kJ/mol,DGDH/PA的反应活化能仅为56.25 kJ/mol。DGDH/PA体系的热稳定性劣于DGDH/PSPA体系,在DGDH/PA体系中加入质量分数为34%的PSPA时,体系的冲击强度从2.16 kJ/m2提高到6.45 kJ/m2,但相应的热变形温度从132.2℃降低到51.8℃。与DGDH/PA体系断裂形成的光滑断面相比,使用PSPA改性的体系具有不规则的裂纹增长轨迹,从而提高了冲击韧性。     

酚酞基聚醚酮/环氧树脂/氰酸酯半互穿聚合物的制备及性能

采用热熔法制备环氧树脂(EP)/氰酸酯树脂(CE)/酚酞基聚醚酮(PEK-C)半互穿网络聚合物。利用三点弯曲法测定了固化物的力学性能,通过动态力学分析(DMA)研究了固化物玻璃化转变温度(Tg)及储存模量变化规律;用扫描电镜(SEM)对断面进行了观察。结果表明,在Tg和弯曲性能基本保持不变的情况下,PEK-C能有效地改善固化物的韧性。当PEK-C的加入量为15%(质量分数,下同)时,断裂韧性KIC和GIC值可分别提高20%和50%,归功于此时固化物形成双连续相结构。但是随着PEK-C含量的增加,固化物初始分解温度略微下降,这可能与交联密度的少量降低有关。     

Fracture toughness of sub-zero-chilled cast iron

A series of fracture toughness experiments were carried out involving sub-zero-chilled (using liquid nitrogen) cast iron containing 1.5% Cu, and chromium contents ranging from 0.0%–0.2%. By using copper chills of different thicknesses, the effect on fracture toughness of varying the chill rate was also examined. The fracture toughness tests were carried out using three-point bend specimens, each with a chevron notch, as per ASTM E 399-1974 standards. It was found that fracture toughness is highly dependent on the location on the casting from where the test specimens are taken and also on the chromium content of the material. Chill thickness, however, does not significantly affect the fracture toughness of the material. There was found to be an approximately linear relationship between fracture toughness and pearlite content, in which fracture toughness increases as pearlite content decreases and vice versa.     

Improving interlaminar fracture toughness of carbon fibre/epoxy laminates by incorporation of nano-particles

Double-cantilever-beam tests were applied to investigate the mode I interlaminar fracture toughness of carbon fibre/epoxy laminates, in which the epoxy matrices were incorporated with rubber and silica nano-particles, either singly or jointly. It is shown that the toughness is improved owing to the presence of these nano-particles although nano-rubber is more effective than nano-silica. Further, by keeping the total particle weight percentage constant in epoxies (e.g., at 8 and 12 wt.%) filled with equal amount of nano-silica and nano-rubber, the interlaminar toughness values of the hybrid laminates are always higher than those with nano-silica filled epoxies but lower than those with nano-rubber filled matrices. Scanning electron microscopy examination of the delaminated surfaces of composite laminates filled with nano-particles revealed that cavitation of nano-rubber particles/void growth and debonding of nano-silica from epoxy matrix are responsible for the improved interlaminar toughness observed. It is also shown that the bulk toughness of nano-particle filled epoxies cannot be fully transferred to the interlaminar toughness of composite laminates, being limited by the constraint effect imposed by the carbon fibres. Finally, the role of fibre-bridging on the delaminated crack and hence delamination toughness is discussed.     

Influence of adsorption behaviour of a silane coupling agent on interlaminar fracture in glass fibre fabric-reinforced unsaturated polyester laminates

The relationship between the interphase consisting of physisorbed and chemisorbed silane on glass fibres and the resultant composite Mode I delamination fracture toughness in glass fibre fabric laminate, was studied. The Mode I interlaminar fracture toughness of the laminate specimen was obtained by using a double cantilever beam (DCB) specimen. The delamination resistance of the laminate specimen finished with two silane concentrations and washed in methanol solvent, is discussed on the basis of the interlaminar fracture toughness. In order to determine the amount of physisorbed and chemisorbed silane on the glass fibre, the amount of total carbon was determined using an analysis instrument. The physisorbed silane migrated into the resin matrix and influenced the mechanical properties and interlaminar fracture of the laminate specimen. The amount of unsaturated polyester resin blended with a silane coupling agent was measured using dynamic mechanical spectroscopy, and a DCB specimen for mechanical properties and fracture toughness.     

Interfacial evaluation and self-sensing on residual stress and microfailure of toughened carbon fiber/epoxy-amine terminated (AT)-polyetherimide (PEI) composites

Interfacial evaluation and self-sensing of tensile loading/subsequent unloading and microfailure detection of the carbon fiber/epoxy-amine terminated (AT)-polyetherimide (PEI) composites were investigated using micromechanical test and electrical resistance measurement with an aid of acoustic emission (AE). As AT-PEI content increased, both fracture toughness of epoxy-AT-PEI matrix and interfacial shear strength (IFSS) increased due to the optimized matrix modulus for energy absorption. With increasing curing temperature and time, the IFSS increased and then decreased. During curing process, the change in electrical resistance, ΔR increased gradually with adding AT-PEI contents because of different thermal and curing shrinkage of epoxy matrices. Moisture adsorption under durability test could cause to the change in matrix modulus and thus resulted in the change in electrical resistivity correspondently. Under changeable cyclic loading/subsequent unloading, apparent modulus and electrical resistivity during curing process were consistent well with the fracture toughness of epoxy modified with AT-PEI. In compressive test, the electrical resistivity decreased gradually initially and then increased rapidly during subsequent progress of microfailure including fiber fracture showing the buckling pattern.     

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.