Cyclic Olefin Copolymer Interleaves for Thermally Mendable Carbon/Epoxy Laminates

Thin cyclic olefin copolymer (COC) foils were used as intrinsic thermoplastic healing agents in carbon fiber (CF)-reinforced epoxy laminates. COC films were produced by hot pressing and were interleaved in the interlaminar regions between each EP/CF lamina, during the hand layup fabrication of the laminates. Three samples were produced, i.e., the neat EP/CF laminate without COC, and two laminates containing COC layers with a thickness of 44 μm and 77 μm, respectively. It was observed that the fiber volume fraction decreased, and the porosity increased with the introduction of COC layers, and this effect was more evident when thick films were used. These two effects, combined with the sub-optimal adhesion between COC and EP, caused a decrease in the mechanical properties (i.e., the elastic modulus, flexural strength, interlaminar shear strength and interlaminar fracture toughness) of the laminates. Specimens subjected to mode I interlaminar fracture toughness test were then thermally mended under pressure by resistive heating, through the Joule effect of conductive CFs. A temperature of approximately 190 °C was reached during the healing treatment. The healing efficiency was evaluated as the ratio of critical strain energy release rate (G_IC) of the healed and virgin specimens. Healed specimens containing COC layers of 44 μm and 77 μm exhibited a healing efficiency of 164% and 100%, respectively. As expected, the healing treatment was not beneficial for the neat EP/CF laminate without COC, which experienced a healing efficiency of only 2%. This result proved the efficacy of COC layers as a healing agent for EP/CF laminates, and the effectiveness of resistive heating as a way to activate the intrinsic healing mechanism.     

Dynamic 4 ENF test for a strain rate dependent mode II interlaminar fracture toughness characterization of unidirectional carbon fibre epoxy composites

A dynamic 4ENF testing procedure has been proposed to characterize the influence of loading rate on mode II fracture interlaminar toughness of a unidirectional composite material. The stable crack growth accomplished by the proposed dynamic 4ENF procedure allows achievement of the R-curves and the in-situ compliance calibration of each specimen. This enables performance of a monotonic dynamic test and presents a great advantage for the dynamic interlaminar characterization of the composite material. The dynamic G_IIC-s values obtained are similar to those determined by quasi-static loading conditions, which suggests that the proposed testing procedure is able to determine accurately the dynamic G_IIC of a composite material. However, for the tested material and within the analysed loading rate range, both the determined R-curves and G_IIC values do not show any clear sign of loading rate dependence.     

Fracture behavior of core-shell rubber-modified crosslinkable epoxy thermoplastics

The fracture behavior of a core-shell rubber (CSR) modified cross-linkable epoxy thermoplastic (CET) system, which exhibits high rigidity, highT _g, and low crosslink density characteristics, is examined. The toughening mechanisms in this modified CET system are found to be cavitation of the CSR particles, followed by formation of extended shear banding around the advancing crack. With an addition of only 5 wt.% CSR, the modified CET possesses a greater than five-fold increase in fracture toughness (G _IC) as well as greatly improved fatigue crack propagation resistance properties, with respect to those of the neat resin equivalents. The fracture mechanisms observed under static loading and under fatigue cyclic loading are compared and discussed.     

Accelerated ageing due to moisture absorption of thermally cured epoxy resin/polyethersulphone blends. Thermal, mechanical and morphological behaviour

A model epoxy resin/anhydride system, modified with a polyethersulfone (PES) engineering thermoplastic toughening agent, has been studied under hydrothermal ageing in order to investigate the modification of the thermal, morphological and mechanical behaviour through dynamical mechanical thermal analysis, SEM microscopy and fracture toughness test respectively. Two different concentrations of the toughening agent were used in the blends and two ageing conditions have been considered, consisting of the immersion of the samples in distilled water at constant temperature of 70 °C for 1 week and for 1 month. Dynamical mechanical thermal analysis results on hydrothermally aged materials indicated the occurrence of progressive segregation effects with the formation of regions with different cross-linking degrees.Fracture toughness tests showed an increase of the K_IC value with the increase of the toughening agent concentration, revealing both a dramatic decrease of the same parameter after 1 week ageing for all the materials and the tendency to reach an almost constant value after 1 month ageing for all the formulations, with a slight increase with respect to 1 week ageing. These results have been interpreted on the basis of the SEM analysis, showing the presence of a well defined micrometric PES particles distribution in the epoxy/anhydride matrix, and discussed in the light of different water absorption mechanisms at short and long ageing times.     

Finite element modelling of mode I delamination specimens by means of implicit and explicit solvers

The simulation of delamination using the Finite Element Method (FEM) is a useful tool to analyse fracture mechanics. In this paper, simulations are performed by means of two different fracture mechanics models: Two Step Extension (TSEM) and Cohesive Zone (CZM) methods, using implicit and explicit solvers, respectively.TSEM is an efficient method to determine the energy release rate components G_Ic, G_IIc and G_IIIc using the experimental critical load (P_c) as input, while CZM is the most widely used method to predict crack propagation (P_c) using the critical energy release rate as input.The two methods were compared in terms of convergence performance and accuracy to represent the material behaviour and in order to investigate their validity to predict mode I interlaminar fracture failure in unidirectional AS4/8552 carbon fibre composite laminates.The influence of increasing the loading speed and using mass scaling was studied in order to decrease computing time in CZ models.Finally, numerical simulations were compared with experimental results performed by means of Double Cantilever Beam specimens (DCB).Results showed a good agreement between both FEM models and experimental results.     

Development and characterization of thermosetting-thermoplastic polymer blends for applications in damage-tolerant composites

Compatibility or miscibility of polyethersulfones (ICI: Victrex 100P and 300P) and a tetrafunctional epoxy (Ciba-Geigy: MY-720), cured with an aromatic anhydride, has been studied using scanning electron microscopy, x-ray microanalysis, and dynamic mechanical spectroscopy. Fracture toughness of epoxy and blends of an epoxy and polyethersulfones has been measured using three-point bend tests (ASTM: E-399–81), and the energy release rate (G_IC) for the three materials has been compared as a function of test temperature. Fracture surfaces were examined by x-ray microanalysis for detecting concentration of sulfur, present in polyethersulfones, in the matrix and precipitated phase. The influence of morphology of epoxy/polyethersulfone blends on its fracture toughness and toughening mechanism has been studied. A toughening criterion is proposed.     

Interlaminar Fracture Toughness of Carbon Fiber/Epoxy Composites using Short Kevlar Fiber and/or Nylon-6 Powder Reinforcement

Mode I (G_IC) and Mode II (G_IIC) interlaminar fracture toughness of carbon-fiber/epoxy composites have been investigated as a function of the amount of short Kevlar-29 fiber (SKF) and/or Nylon-6 powder (N6P) between continuous fiber layers. G_IIC increased with increasing crack length as a consequence of the presence of SKFs bridging in the wake of propagating crack. G_IIC of SKF alone could reach the maximum at an intermediate amount of SKF. G_IIC of SKF and N6P was lower than that of SKF alone because N6P prevented the orientation of SKF to out-of-plane. The extent of SKF's bridging phenomenon may be influenced by the amount and orientation of SKF. G_IC showed no significant effect with SKF and uniform irrespective of crack length. Scanning electron microscopy after G_IIC test showed that new surfaces were created by extensive fiber bridging, pull-out and fracture of SKF in random direction without any fixed pattern. © 1997 John Wiley & Sons, Ltd.     

Functionalized reduced graphene oxide/epoxy composites with enhanced mechanical properties and thermal stability

One-pot hydrothermal reduction of graphene oxide (GO) in N-methyl-2-pyrrolidone (NMP) suspension was performed, wherein GO surface were functionalized by free radicals generated from NMP molecules. The NMP functionalized reduced GO (NMPG) nanosheets were then incorporated into epoxy matrix to prepare epoxy composites. The significant improvement of 100 and 240% in fracture toughness (critical intensity factor, K_IC) and fracture energy (critical strain energy release rate, G_IC) achieved from single edge notched bending (SENB) test revealed the excellent toughening ability of NMPG. The improved compatibility and interfacial interaction between the epoxy matrix and NMPG yielded∼28, 19 and 51% improvement in tensile strength, Young's and storage modulus, respectively. Thermal stability of pure epoxy and its composites was determined at 5, 10 and 50% weight loss, which showed 30, 27.5 and 29 °C improvement with 0.2 wt% NMPG loading. The work provides a simple method to prepare graphene-based epoxy composites with improved performance.     

Interlaminar fracture toughness of unidirectional DCB specimens: A novel theoretical approach

A novel theoretical approach is presented to calculate the mode I interlaminar fracture toughness (G_Ic) of double cantilever beam (DCB) specimens with low ratio of initial crack length-to-thickness (a₀/2h). This method is based on a sixth-order beam theory, namely Reddy-Bickford beam (RB), on Winkler elastic foundation (WEF) to account for both transverse shear deformation of the beam and local effects at the delamination front (root rotation). RB with only two generalized displacements w and ?; and three boundary conditions at ends and loading points of a shear deformable beam gives more accurate results than the fourth-order Timoshenko beam theory. The accuracy of the proposed method in prediction of initiation G_Ic values is evaluated together with other available models considering the experimental fracture toughness for moderately thick unidirectional E-glass/epoxy DCB specimens with small initial delamination lengths.     

Filled PMMA: mechanical properties and fracture behaviour

The aim of this work is to study the influence of the filler fraction and that of the filler/matrix interfacial adhesion on the mechanical properties and on the fracture behaviour of a poly(methyl methacrylate) PMMA (for injection moulding). The variation of the tensile and flexural mechanical properties with the filler volume fraction was determined. The changes in the fracture behaviour produced by the fillers were studied by evaluating the K_IC and G_IC parameters of the LEFM (Linear Elastic Fracture Mechanics) by carrying out tests with SENB geometry at room temperature and low strain rates. After fracture surfaces examination by SEM (Scanning Electron Microscopy), it was found that the surface treatment had been rather effective and that the fracture toughening mechanism was multiple crazing.     

POLYESTERIMIDE-MODIFIED BISMALEIMIDE RESINS. I. EFFECT OF POLYESTERIMI DE CONTENT

ABSTRACT

A novel polyesterimide (PEsI-M) was used to improve toughness of bismaleimide (BMI) resin composed of bis(4-maleimidediphenyl) methane (BDM) and O,O′-diallyl bisphenol A (DBA). Morphologies of modified resins changed from spherical particles to inverted phase structures, depending on PEsI-M's content based on the observation of scanning electronic microscopy (SEM). PEsI-M was an effective morphology modifier so that loading of 12 pbw resulted in a diverted phase structure. Dynamic mechanical analysis (DMA), rheometrics mechanical spectroscopy (RMS) and differential scanning calorimetry (DSC) were respectively used to investigate the dynamic mechanical behavior, and the gelation time and the curing extent of unmodified and modified BMI resins. The fairly uniform morphology in 15 pbw PEsI-M modified system cured at 180°C suggests that the phase separation might take place via a spinodal decomposition mechanism. The fracture energy (G _IC ) increased with the increase of PEsI-M content in the modified system. G _IC of 15 pbw PEsI-M modified system was 0.63 times larger than that of the unmodified BMI resin.     

Use of maleic anhydride compatibilization to improve toughness and other properties of polylactide blended with thermoplastic elastomers

Polylactide (PLA) being a very brittle biopolymer could be toughened by blending with thermoplastic elastomers such as thermoplastic polyurethane elastomer (TPU) and thermoplastic polyester elastomer (TPE); unfortunately, these blends are immiscible forming round domains in the PLA matrix. Therefore, the purpose of this study was to investigate the effects of using maleic anhydride (MA) compatibilization on the toughness and other properties of PLA blended with TPU and TPE. MA grafting on the PLA backbone (PLA‐g‐MA) was prepared separately by reactive extrusion and added during melt blending of PLA/thermoplastic elastomers. IR spectroscopy revealed that MA graft might interact with the functional groups present in the hard segments of TPU and TPE domains via primary chemical reactions, so that higher level of compatibilization could be obtained. SEM studies indicated that PLA‐g‐MA compatibilization also decreased the size of elastomeric domains leading to higher level of surface area for more interfacial interactions. Toughness tests revealed that Charpy impact toughness and fracture toughness (K_IC and G_IC) of inherently brittle PLA increased enormously when the blends were compatibilized with PLA‐g‐MA. For instance, G_IC fracture toughness of PLA increased as much as 166%. It was also observed that PLA‐g‐MA compatibilization resulted in no detrimental effects on the other mechanical and thermal properties of PLA blends. Copyright © 2014 John Wiley & Sons, Ltd.     

Epoxies toughened with triblock copolymers

Three different commercial triblock copolymers from Arkema were evaluated as potential toughening agents for two different lightly crosslinked epoxies. It was found that the plane strain fracture toughness, K_IC, was on the order of 3.0 MPa√m for 10 parts per hundred resin (phr) of NanoStrength™ E20 resin (a styrene–butadiene–methylacrylate, SBM, type triblock copolymer) in epoxies cured with either aminoethylpiperazine or piperidine. In contrast, 10 phr NanoStrength E40 resin (also an SBM type triblock copolymer) was ineffective in toughening such epoxies. The difference in toughening effectiveness was attributed to the smaller amount of polybutadiene present in the E40 resin. The third toughening agent from Arkema was NanoStrength M22 resin, which is a symmetric triblock copolymer consisting of side blocks of PMMA surrounding a center block of poly(butyl acrylate) and is designated as MAM. At 10 phr MAM both lightly crosslinked epoxies exhibited improvements in toughness. Morphologies were characterized using TEM and toughening mechanisms revealed using SEM and TOM. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1470–1481, 2007     

Mode-I interlaminar fracture behaviour of nanoparticle modified epoxy/basalt fibre-reinforced laminates

The effect of nano-reinforcements on fracture behaviour of bulk epoxy nanocomposites and mode-I interlaminar fracture toughness of filament-wound basalt fibre-reinforced laminates was studied. Fracture energy of the bulk epoxy nanocomposites significantly increased with acrylic tri-block-copolymer addition but remained unchanged with incorporation of nanoclay. Delamination fracture toughness was not influenced by the presence of nanoparticles in the matrix. Decreasing fibre volume fraction, on the other hand, significantly improved interlaminar fracture energy. Rigid fibres in these composites constrict the stress field ahead of the crack-tip. Hence, increasing resin content enhanced composite delamination energy by increasing the capacity for matrix deformation. Interlaminar crack propagation through the composite was observed to occur mainly by interfacial failure and matrix cracking.     

Effect of phase change microcapsules on the thermo-mechanical,fracture and heat storage properties of unidirectional carbon/epoxy laminates

This work aims at producing and characterizing unidirectional carbon/epoxy composites containing different fractions of paraffin microcapsules (MC) for thermal management applications. The viscosity of the epoxy/MC mixtures increases with the MC content, thereby increasing the final matrix weight and volume fraction and reducing that of the fibers. This is at the basis of the decrease in mechanical properties of the laminates with high MC concentration (the elastic modulus decreases up to 53% and the flexural strength up to 67%), but the application of theoretical models shows that this decrease is only due to the lower fiber volume fraction, and not to a change in the properties of the constituents or the fiber/matrix interaction. The MC phase is preferentially distributed in the interlaminar zone, which leads to a thickening of this region and a decrease in matrix-related properties, such as the interlaminar shear strength, which decreases of up to 70%. However, a modest MC fraction causes an increase in the mode I interlaminar fracture toughness of 48%, due to the introduction of new toughening mechanisms. On the other hand, an excessive MC content lets the crack propagating through the matrix and not at the fiber/matrix interface, thereby reducing the toughening mechanism provided by fiber bridging. For the thermal properties, the phase change enthalpy increases with the MC fraction up to 48.7 J/g, and this is reflected in better thermal management performance, as proven by thermal imaging tests. These results are promising for the development of multifunctional polymer composites with thermal energy storage and thermal management properties, and future works will be focused on a deeper study of the micromechanical properties of PCM microcapsules and on the improvement of the capsule/matrix adhesion.     

Modification of epoxy resin using reactive liquid (ATBN) rubber

Epoxy resins are widely utilised as high performance thermosetting resins for many industrial applications but unfortunately some are characterised by a relatively low toughness. In this respect, many efforts have been made to improve the toughness of cured epoxy resins by the introduction of rigid particles, reactive rubbers, interpenetrating polymer networks and engineering thermoplastics within the matrix.In the present work liquid amine-terminated butadiene acrylonitrile (ATBN) copolymers containing 16% acrylonitrile is added at different contents to improve the toughness of diglycidyl ether of bisphenol A epoxy resin using polyaminoimidazoline as a curing agent. The chemical reactions suspected to take place during the modification of the epoxy resin were monitored and evidenced using a Fourier transform infrared. The glass transition temperature (T_g) was measured using a differential scanning calorimeter. The mechanical behaviour of the modified epoxy resin was evaluated in terms of Izod impact strength (IS), critical stress intensity factor, and tensile properties at different modifier contents. A scanning electron microscope (SEM) was used to elucidate the mechanisms of deformation and toughening in addition to other morphological features. Finally, the adhesive properties of the modified epoxy resin were measured in terms of tensile shear strength (TSS).When modifying epoxy resin with liquid rubber (ATBN), all reactivity characteristics (gel time and temperature, cure time and exotherm peak) decreased. The infrared analysis evidenced the occurrence of a chemical reaction between the two components. Addition of ATBN led to a decrease in either the glass transition temperature and stress at break accompanied with an increase in elongation at break and the appearance of some yielding. As expected, the tensile modulus decreased slightly from 1.85 to about 1.34 GPa with increasing ATBN content; whereas a 3-fold increase in Izod IS was obtained by just adding 12.5 phr ATBN compared to the unfilled resin. It is obvious that upon addition of ATBN, the Izod IS increased drastically from 0.85 to 2.86 kJ/m² and from 4.19 to 14.26 kJ/m² for notched and unnotched specimens respectively while K_IC varies from 0.91 to 1.49 MPa m^1/2 (1.5-fold increase). Concerning the adhesive properties, the TSS increased from 9.14 to 15.96 MPa just by adding 5 phr ATBN. Finally SEM analysis results suggest rubber particles cavitation and localised plastic shear yielding induced by the presence of the dispersed rubber particles within the epoxy matrix as the prevailing toughening mechanism.     

Polypropylene filled with flame retardant fillers: mechanical and fracture properties

Two grades of isotactic polypropylene (homopolymer and block copolymer) were filled with magnesium and aluminium hydroxides, and studied focusing the mechanical and fracture characteristics of the composites. As expected, dispersion of such fillers in PP resulted in improved stiffness and reduced tensile yield strength. By one hand, the composites fracture resistance was characterised at low strain rate applying the J‐integral concept; the resistance to crack growth initiation (J_IC) was found decreasing as the Mg(OH)₂ concentration was raised in the copolymer PP matrix. By the other hand, the linear‐elastic fracture mechanics (LEFM) parameters were determined by means of instrumented impact tests at 1 m/s on the homopolymer PP filled with uncoated Al(OH)₃ particles. The higher the Al(OH)₃ mean particle size, the lower the composite fracture energy (G_IC). In the opposite, with commercial surface‐coated filler grades it was not possible to achieve LEFM conditions to characterise the fracture toughness of filled PP at 1 m/s, because the Mg(OH)₂ surface coating, which is applied in practice to improve the melt processing, acts increasing the composite plasticity and reducing the tensile yield strength.     

Mechanical and morphological investigations of reactive polysulfone toughened epoxy networks

The diglycidyl ether of bisphenol-A (DGEBA) epoxy resin was toughened by aminophenyl functional reactive polyethersulfones (R-PES) or by t-butyl terminated non-reactive polyethersulfones (T-PES). The molecular weights of PES were controlled to afford 5,000 to 20,000 g/mole and loadings were also varied from 5 to 30 wt.%. Epoxy networks cured with 4, 4'-diaminodiphenylsulfone (DDS) were subjected to Tg determinations, plane strain fracture toughness (K_1C) measurements, chemical resistance tests and morphological studies by SEM. Very significantly improved K_1C fracture toughness was obtained with reactive PES toughening without loss of chemical resistance, while non-reactive PES blended epoxy resins exhibited only slightly improved fracture toughness but poor chemical resistance. It was possible to load up to 30 wt.% of PES without utilizing solvent and the maximum K_1C fracture toughness with R-PES was around 2.2 MPa-m 0.5, which was equivalent to the neat thermoplastic resin. Ductile fracture of the PES phase is suggested as a major toughening mechanism and this is highly dependent of the excellent adhesion developed between the PES and epoxy phases due to the chemical bonds. The systems demonstrated that chemical resistance of thermosets can be combined with the tough characteristics of thermoplastics.     

Fracture toughness of nylon‐6 blends with maleated rubbers

The fracture toughness of blends of nylon‐6 with maleated ethylene–propylene rubber and maleated styrene/hydrogenated butadiene/styrene triblock copolymer was investigated with a single‐edge‐notched three‐point‐bending instrumented Dynatup test. The blends for which the rubber particle size was less than 0.7 μm fractured in a ductile manner over the whole range of ligament lengths, whereas the blends with particles larger than 0.7 μm showed a ductile‐to‐brittle transition with the ligament length. In this regime, ductile fracture was observed for specimens with short ligaments, whereas brittle fracture was seen for those with long ligaments. The ductile fracture behavior was analyzed with the essential‐work‐of‐fracture model, whereas linear elastic fracture mechanics techniques were used to analyze the brittle fracture behavior. The fact that the ductile fracture energy was larger for the blends with the styrene/hydrogenated butadiene/styrene triblock copolymer than for those with ethylene–propylene rubber was due to the larger dissipative energy density of the blends based on the styrene/hydrogenated butadiene/styrene triblock copolymer. Both the critical strain energy release rate (G_IC) and the plane‐strain critical stress intensity factor (K_IC) increased as the rubber particle size decreased for both blend systems. The G_IC and K_IC parameters had similar values, regardless of the rubber type, when the rubber particle size was fixed. The transition ligament length was near the size criterion for plane‐strain conditions for both blend systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1739–1758, 2004     

Preparation and characterization of graphite nano-platelet (GNP)/epoxy nano-composite: Mechanical,electrical and thermal properties

Epoxy based polymer nano-composite was prepared by dispersing graphite nano-platelets (GNPs) using two different techniques: three-roll mill (3RM) and sonication combined with high speed shear mixing (Soni_hsm). The influence of addition of GNPs on the electrical and thermal conductivity, fracture toughness and storage modulus of the nano-composite was investigated. The GNP/epoxy prepared by 3RM technique showed a maximum electrical conductivity of 1.8 × 10⁻⁰³ S/m for 1.0 wt% which is 3 orders of magnitude higher than those prepared by Soni_hsm. The percentage of increase in thermal conductivity was only 11% for 1.0 wt% and 14% for 2.0 wt% filler loading. Dynamic mechanical analysis results showed 16% increase in storage modulus for 0.5 wt%, although the Tg did not show any significant increase. Single edge notch bending (SENB) fracture toughens (K_IC) measurements were carried out for different weight percentage of the filler content. The toughening effect of GNP was most significant at 1.0 wt% loading, where a 43% increase in K_IC was observed. Among the two different dispersion techniques, 3RM process gives the optimum dispersion where both electrical and mechanical properties are better.