Poly[ethylene‐co‐(methacrylic acid)] Healing Agents for Mendable Carbon Fiber Laminates

The first reported use of two‐dimensional mesh thermoplastic fibers in an epoxy matrix for mendable composites is presented, yielding 100% restoration of G_IC, failure energy, and peak loads over repeated damage‐healing cycles. SEM imaging and EDS mapping showed different surface structures between CFRP_p and CFRP_f and confirmed strength recoveries were attained by delivery of EMAA to the fracture plane which enabled the fractured surfaces to rebind after heating to 150 °C for 30 min.

     

Thermoplastic Healing in Epoxy Networks: Exploring Performance and Mechanism of Alternative Healing Agents

This paper investigates thermally activated healing in an epoxy amine network using six thermoplastic modifiers; ethylene vinyl acetate (EVA), poly (ethylene‐co‐glycidyl)‐methacrylate (PEGMA), poly(vinyl‐butyral) (PVB), styrene‐ethylene‐butadiene copolymer (SEBS), acrylonitrile‐butadiene‐styrene (ABS) and polyethylene‐co‐methacrylic acid (EMAA). They all exhibit healing but varied in efficiency, repeatability and mechanism. EMAA, PEGMA and EVA display superior healing or load recovery compared with ABS, SEBS and PVB with increasing healing events. For EMAA and PEGMA this is attributed to a pressure delivery mechanism, while for EVA, it is attributed to increased viscous flow and a highly elastomeric response to damage. Adhesive binding of the fracture surfaces is also critical in restoring load.

     

Supertoughness in Polysulfone/Poly(ethylene‐octene) Blends

Summary: Poly(sulfone of Bisphenol A) (PSU) based blends were obtained by melt blending PSU with up to 15 wt.‐% poly(ethylene‐octene) either modified with maleic anhydride (mPEO) or not (PEO). The dispersed particle size was small and similar in blends with PEO or mPEO. These facts indicated respectively that the interfacial tension was low and the lack of compatibilizing effect of mPEO. Some preferential presence of PEO in the outer surface of the specimens was observed, and was attributed to the large viscosity difference between the two components of the blends. This had no effect on the modulus of elasticity, but speeded up both the yield stress and ductility decreases at rubber contents above 3.25 wt.‐%. However, despite the immiscibility of the components, and thanks to the small particle size of the blends, super‐toughness was attained in the unmodified PSU/PEO blends. This was at PEO contents (3.25 wt.‐%) at which the modulus, yield stress and ductility of the blends were almost as good as those of pure PSU. It appeared that a change of the chemical nature of the rubber did not influence by itself super‐toughness, unless it was accompanied by either a morphological or adhesion change.

Impact strength of PSU‐based blends vs. PEO (○) or mPEO (?) content.     

Fracture properties of epoxy/poly(styrene‐co‐allylalcohol) blends

The epoxy/polystyrene system is characterized by a poor adhesion between the constituent phases, which determines its mechanical properties. The adhesion can be improved via blends based on epoxy resin and random copolymers, poly(styrene‐co‐allylalcohol) (PS‐co‐PA). In this work, the influence of PS‐co‐PA content and the good adhesion between the phases on the tensile properties and the fracture toughness achieved through instrumented Charpy tests have been investigated. The tensile strength and the deformation at break showed an increase in the PS‐co‐PA content while the Young's modulus remained the same. The tensile fracture surfaces revealed that the improvement of these magnitudes was mainly due to a crack deflection mechanism. Also, the fracture toughness of the blends was superior to that of the pure epoxy resin. The main operating toughening mechanism was crack deflection. The fractographic analysis showed that ～ 80% of the particles were broken, and the crack tended to divert from its original path through the broken PS‐co‐PA particles. The remaining particles were detached from the epoxy resin, and the holes left suffered plastic deformation. Analytical models were used to predict successfully the toughness due to these mechanisms. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Dynamic Mechanical Properties of Poly(propylene) Blends with Poly[ethylene‐co‐(methyl acrylate)]

Summary: Blends of poly(propylene) (PP) were prepared with poly[ethylene‐co‐(methyl acrylate)] (EMA) having 9.0 and 21.5% methyl acrylate comonomer. A similar series of blends were compatibilized by using maleic anhydride grafted PP. The morphology and mechanical properties of the blends were investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) in tensile mode. The DMA method and conditions were optimized for polymer film specimens and are discussed in the experimental section. The DSC results showed separate melting that is indicative of phase‐separated blends, analogous to other PP‐polyethylene blends but with the added polarity of methyl acrylate pendant side groups that may be beneficial for chemical resistance. Heterogeneous nucleation of PP was decreased in the blends because of migration of nuclei into the more polar EMA phase. The crystallinity and peak‐melting temperature did not vary significantly, although the width of the melting endotherm increased in the blends indicating a change had occurred to the crystals. DMA analysis showed the crystal‐crystal slip transition and glass transition (T_g) for PP as well as a T_g of the EMA copolymer occurring chronologically toward lower temperatures. The storage modulus of PP and the blends was generally greater with annealing at 150 °C compared with isothermal crystallization at 130 °C. The storage modulus of the blends for isothermally crystallized PP increased with 5% EMA, then decreased for higher amounts of EMA. Annealing caused a decrease with increasing copolymer content. The extent of the trend was greater for the compatibilized blends. The T_g of the blends varied over a small range, although this change was less for the compatibilized blends.

Storage modulus for PP and EMA9.0 blends annealed at 150 °C.     

Effects of Blended Reversible Epoxy Domains on Structures and Properties of Self‐Healing/Shape‐Memory Thermoplastic Polyurethane

Few thermoplastic polyurethane (TPU) blending materials are reported to tune shape‐memory capability, self‐healing ability, and recyclability as well as mechanical property due to the different requirement of phase morphologies. This work focuses on how reversible epoxy domains affect the structures and properties of TPUs that contain disulfide bonds in main chains. The blended epoxy oligomers with dangling furan groups are miscible with the TPU. Self‐healing efficiency can be improved by such miscible epoxy oligomers that are also beneficial for shape recovery but harmful for shape fixation. In the presence of bis(4‐maleimidophenyl)methane (BMI), crosslinked epoxy domains phase separate from the TPU matrix to form microscale domains after the Diels–Alder (DA) reaction between furan groups and maleimide groups in BMI. Elastic modulus and tensile strength of TPU are greatly improved in comparison with pristine TPU and TPU/epoxy blends without BMI. The phase‐separated domains deteriorate the self‐healing, and the presence of phase‐separated microdomains facilitates the shape fixation but deteriorates the shape recovery. This work is not only useful to further understand the relation between structures of polymer blends with intelligent features, but also offers a useful approach to adjust the properties and capabilities of TPU in a cost‐effective manner.     

Rate‐dependent self‐healing behavior of an ethylene‐co‐methacrylic acid ionomer under high‐energy impact conditions

In this work, the mechanical and the self‐healing behaviors of an ethylene‐co‐methacrylic acid ionomer were investigated in different testing conditions. The self‐healing capability was explored by ballistic impact tests at low‐velocity, midvelocity, and hypervelocity bullet speed; different experimental conditions such as sample thickness and bullet diameter were examined; in all impact tests, spherical projectiles were used. These experiments, in particular those at low and midspeed, allowed to define a critical ratio between sample thickness and bullet diameter below which full repair was not observed. After ballistic damage, the healing efficiency was evaluated by applying a pressure gradient through tested samples. Subsequently, morphology analysis of the affected areas was made observing all tested samples by scanning electron microscope. This analysis revealed different characteristic features of the damaged zones affected at different projectile speed. Stress–strain curves in uniaxial tension performed at different temperatures and strain rates revealed yield strength and postyield behavior significantly affected by these two parameters. A rise of temperature during high strain rate tests in the viscoplastic deformation region was also detected. This behavior has a strong influence on the self‐repairing mechanism exhibited by the studied material during high‐energy impact tests. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1949–1958, 2013     

Mechanical properties of poly(styrene‐co‐acrylonitrile)‐modified epoxy resin/glass fiber composites

Poly(styrene‐co‐acylonitrile) was used to modify diglycedyl ether of bisphenol‐A type epoxy resin cured with diamino diphenyl sulfone and the modified epoxy resin was used as the matrix for fiber‐reinforced composites (FRPs) to get improved mechanical properties. E‐glass fiber was used as fiber reinforcement. The tensile, flexural, and impact properties of the blends and composites were investigated. The blends exhibited considerable improvement in mechanical properties. The scanning electron micrographs of the fractured surfaces of the blends and tensile fractured surfaces of the composites were also analyzed. The micrographs showed the influence of morphology on the properties of blends. Results showed that the mechanical properties of glass FRPs increased gradually upon fiber loading. Predictive models were applied using various equations to compare the mechanical data obtained theoretically and experimentally. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(ethylene‐co‐vinyl acetate)‐graft‐poly(methyl methacrylate) (EVA‐graft‐PMMA) as a modifier of epoxy resins

Conventional approaches to toughen thermosets are: (1) the polymerization‐induced phase separation of a rubber or a thermoplastic, or (2) the use of a dispersion of preformed particles in the initial formulation. In the present study it is shown that it is possible to combine both techniques by using graft copolymers with one of the blocks being initially immiscible and the other that phase separates during polymerization. This is illustrated by the use of poly(ethylene‐co‐vinyl acetate)‐graft‐poly(methyl methacrylate) (EVA‐graft‐PMMA) as modifier of an epoxy resin. EVA is initially immiscible and PMMA phase separates during polymerization. Blends of an epoxy monomer based on diglycidylether of bisphenol A (DGEBA, 100 parts by weight), piperidine (5 parts by weight), and PMMA (5 parts by weight), showed the typical polymerization‐induced phase separation of PMMA‐rich domains before gelation of the epoxy network. Replacing PMMA by EVA‐graft‐PMMA (5 parts by weight), yielded stable dispersions of EVA blocks, favoured by the initial solubility of PMMA blocks. Phase separation of PMMA blocks in the course of polymerization led to a dispersion of in situ generated biphasic particles (plausibly composed of EVA cores surrounded by PMMA shells), with average diameters varying from 0.3 to 0.6 µm with the cure temperature. This procedure may be used to generate stable dispersions of biphasic particles for toughening purposes. © 2002 Society of Chemical Industry     

Poly(ethylene‐co‐methacrylic acid)–lithium ionomer as a compatibilizer for poly(ethylene terephthalate)/linear low‐density polyethylene blends

Poly(ethylene terephthalate) (PET)/linear low‐density polyethylene (LLDPE) blends (75/25), with contents of poly(ethylene‐co‐methacrylic acid) partially neutralized with lithium (PEMA–Li) that were systematically changed from 0 to 45% relative to the LLDPE, were obtained by direct injection molding in an attempt to (1) ameliorate the performance of the binary blend and (2) find the best compatibilizer content. PEMA–Li did not modify the PET or LLDPE amorphous‐phase compositions or the crystalline content of PET. However, PEMA–Li did lead to a nucleation effect and to the presence of a second smaller and less perfect crystalline structure. PET induced a fractional crystallization in LLDPE that remained in the presence of PEMA–Li and reduced the crystallinity of LLDPE. The ternary blends showed two similar dispersed LLDPE and PEMA–Li phases with small subparticles, probably PET, inside. The compatibilizing effect of PEMA–Li was clearly shown by the impressive increase in the break strain, along with only small decreases in the modulus of elasticity and in the tensile strength. With respect to the recycling possibilities of LLDPE, a ternary blend with the addition of 22.5% PEMA–Li, which led to very slight modulus and yield stress decreases with respect to the binary blend and a break strain increase of 480%, appeared to be the most attractive. However, the highest property improvement appeared with the addition of 37.5% PEMA–Li, which led to elasticity modulus and tensile strength decreases of only 9%, along with a very high break strain increase (760%). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1322–1328, 2003     

Effect of octene content in poly(ethylene‐co‐1‐octene) on the properties of poly(propylene)/poly(ethylene‐co‐1‐octene) blends

Ethylene‐octene random copolymer (EOC) is one of the most commonly employed elastomers for PP, and as such its rubber toughening efficiency has been extensively studied. However, most existing studies employ EOC containing an octene comonomer of about 8 mol %. Therefore, in this study, we investigated the effect of EOC octene comonomer content on the morphology and thermal and mechanical properties of PP‐ethylene random copolymer (PP‐CP)/EOC (80/20 wt %/wt %) blends. It was clearly shown that the properties of the blends are significantly affected by the octene content. The rubber particle size of the blends decreased as the octene content in the EOC was increased, which was a consequence of the reduced interfacial tension between PP‐CP and EOC. Impact strength of the blends as a function of octene content displayed a brittle‐ductile transition. The tensile yield strength and modulus of the PP‐CP/EOC blends were decreased by addition of EOC, owing to incorporation of the soft EOC into the hard PP‐CP. The tensile yield strength and modulus of PP‐CP/EOC blends decreased monotonically with the octene content in the EOC. The melting temperature as well as the crystallinity of the PP‐CP phase were not affected significantly by the addition of EOC whereas a notable shift in melting and crystallization temperatures was observed for the EOC phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1133–1139, 2007     

Super‐Tough and Highly‐Ductile Poly(l‐lactic acid)/Thermoplastic Polyurethane/Epoxide‐Containing Ethylene Copolymer Blends Prepared by Reactive Blending

Ethylene‐methyl acrylate‐glycidyl methacrylate copolymer (E‐MA‐GMA) is employed to improve the impact toughness of poly(l ‐lactic acid) (PLLA)/thermoplastic polyurethane (TPU) blends by reactive melt‐blending. The reaction and miscibility between the components are confirmed by Fourier transform infrared spectroscopy, dynamic mechanical analysis, and differential scanning calorimetry. A super‐tough PLLA/TPU/E‐MA‐GMA multiphase blend (75/10/15) exhibits a significantly improved impact strength of 77.77 kJ m^?2, which is more than 17 times higher than that of PLLA/TPU (90/10) blend. A co‐continuous‐like TPU phase structure involving E‐MA‐GMA phase at the etched cryo‐fractured surface and the high‐orientated matrix deformation at the impact‐fractured surface are observed by scanning electron microscopy. The high‐orientated matrix deformation induced by the co‐continuous TPU phase structure is responsible for the super toughness of PLLA/TPU/E‐MA‐GMA blends.     

Mechanical and fracture behavior of an artificially ultraviolet‐irradiated poly(ethylene‐carbon monoxide) copolymer

In this work, 1 wt % carbon monoxide (CO) poly(ethylene‐carbon monoxide) (ECO) copolymer sheets were artificially exposed to ultraviolet (UV) light with a power density of 3 mW/cm² for up to 130 h. A thorough mechanical characterization of the irradiated material was conducted, in which both the stress–strain data and the values of the quasistatic crack initiation and growth toughness were measured and correlated with companion uniaxial tensile tests and single‐edge‐notched fracture tests. Average values of the elastic modulus, failure strain, and failure stress were determined from the tensile tests. The full‐field optical technique of digital image correlation was used to quantify in‐plane deformation (displacements and displacement gradients) during the fracture experiments and to extract values of the crack initiation and growth fracture toughness. The elastic modulus increased monotonically with UV irradiation for the exposure times used in this investigation. In addition, for low irradiation times of less than 5 h, both the failure strain and failure stress of ECO decreased, and this caused a corresponding decrease in the crack initiation and growth toughness. However, for longer irradiation times, the failure strain remained almost invariable, whereas the failure stress increased by about 25% over that of unirradiated ECO. As a result, for longer irradiation times (>5 h), 1 wt % CO ECO became not only stiffer but also stronger and tougher, as quantified by companion fracture experiments. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 139–148, 2004     

Thermal Characterization of Upper Critical Solution Temperature m‐LLDPE/Poly(ethylene‐ran‐butene) Elastomer Blends

Summary: The phase and thermal characteristics of blends consisting of linear low‐density polyethylene (LLDPE) (0.7 mol‐% hexene copolymer) and poly(ethylene‐ran‐butene) (PEB) (26 mol‐% butene copolymer) have been investigated using optical microscopy (OM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). An upper critical solution temperature of 162 °C was exhibited. The addition of PEB not only slowed the overall crystallization rate of LLDPE but also changed the distribution of lamellar thickness or perfection of LLDPE crystals. The equilibrium melting temperature of LLDPE in the blends was reduced and kept relatively constant in the bi‐phase state. The blends showed a single‐stage degradation and an intermediate thermal stability between those of the individual components. It could be attributed to their homogeneous states at degradation temperatures and the similar decomposing mechanisms of two components. The kinetic analysis of thermal degradation also confirmed the above results.

Phase diagram of LLDPE/PEB blends.     

Post‐Crosslinkable Blends: Reactions Between a Linear Poly(hydroxyl‐amino ether) and a Diepoxy

Summary: A thermoplastic poly(hydroxyl‐amino ether) polymer (BLOX) was blended with a diglycidyl ether of bisphenol A monomer (DGEBA). This system may be used as a crosslinkable thermoplastic. It means that it may be processed in an extruder like a classic thermoplastic, and cured by etherification reactions initiated by tertiary amine groups of the BLOX in a second step, to produce a material with good mechanical properties. In order to understand and quantify the etherification reactions occurring at high temperature (135 °C), between epoxy groups of the diepoxy and hydroxyl groups of the thermoplastic, a model system was studied based on DGEBA in excess and ethanolamine. In the model system the rate of the etherification reaction was well described by a second‐order kinetic equation. The specific rate constants and the epoxy conversion at the gel were related to the polarity of the reactive medium. The polyetherification occurring in the DGEBA‐BLOX system could also be fitted with a second‐order kinetics. A significant increase in the reaction rate was observed when using high BLOX concentrations.

     

Properties of soy protein isolate/poly(ethylene‐co‐ethyl acrylate‐co‐maleic anhydride) blends

Blends of soy protein isolate (SPI) with 10, 20, 30, 40, and 50% poly(ethylene‐co‐ethyl acrylate‐co‐maleic anhydride) (PEEAMA), with or without addition of 2.0 wt % methylene diphenyl diisocyanate (MDI), were prepared by mixing with an intensive mixer at 150°C for 5 min, and then milling through a 1‐mm sieve. Blends were then compression‐molded into a tensile bar at 140°C. Thermal and mechanical properties and water absorption of the blends were studied by differential scanning calorimetry (DSC), dynamical mechanic analysis (DMA), a test of modulus and tensile strength (with an Instron tensile tester), a water absorption test, and scanning electron microscopy (SEM). The blends showed two composition‐dependent glass transition temperatures. Furthermore, as the SPI content increased, the melting temperature of PEEAMA remained constant but the heat of fusion decreased. These results indicate that SPI and PEEAMA were partially miscible. Morphology observations support these results. Increasing the PEEAMA content resulted in decreases in the modulus and tensile strengths and increases in the elongation and toughness of the blends. Water absorption of the blends also decreased with increased PEEAMA content. Incorporating MDI further decreased the water absorption of the blends. The mechanism of water sorption of SPI was relaxation controlled, and that of the blends was diffusion controlled. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 407–413, 2003     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Influence of aliphatic amine epoxy hardener on the adhesive properties of blends of mono‐carboxyl‐terminated poly(2‐ethylhexyl acrylate‐co‐methyl methacrylate) with epoxy resin

The adhesive properties have been investigated in blends of mono‐carboxyl‐terminated poly(2‐ethylhexyl acrylate‐co‐methyl methacrylate) with diglycidyl ether of bisphenol A and three different aliphatic amine epoxy hardener. The adhesives properties are evaluated in steel alloy substrate using single‐lap shear test. The copolymers are initially miscible in the stoichiometric blends of epoxy resin and hardener at room temperature. Phase separation is noted in the course of the polymerization reaction. Different morphologies are obtained according to the amine epoxy hardener. The most effective adhesive for steel–steel joints in single‐lap shear test is the blends using 1‐(2‐aminoethyl)piperazine (AEP) as hardener. This system shows the biggest lap shear strength. However, the modified adhesives show a reduction in the mechanical resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Pyridine‐Modified Polymer as a Non‐Covalent Compatibilizer for Multi‐Walled CNT/Poly[ethylene‐co‐(methacrylic acid)] Composites Fabricated by Direct Melt Mixing

Multi‐wall CNT/poly[ethylene‐co‐(methacrylic acid)] composites were prepared by melt mixing. To improve dispersion and promote polymer/nanotube interactions, a novel non‐covalent compatibilizer is synthesized by reacting the polymer with 4‐(aminomethyl)pyridine. The composite based on the pristine polymer shows electrical and rheological percolation thresholds at nanotube loadings of 1.85 and 1.4 wt%, respectively. When 5 wt% of the pyridine‐modified compatibilizer is added, the corresponding values are reduced to 1.44 and 0.8 wt%, respectively. The electrical resistivity decreases even further as 10 wt% of the novel dispersing agent is used. Microscopy and Raman spectroscopy confirm the improved dispersion and π‐interactions established during melt mixing.