Monitoring abiotic degradation of branched polyethylenes formulated with pro-oxidants through different mechanical tests

The mechanical properties of two linear low density and low density polyethylenes containing a pro-oxidant additive were monitored during accelerated aging (60 °C in a convection oven) and weather exposure. Tearing tests (trouser) were performed for the first time in polyethylenes subjected to oxo-degradation revealing a transition from an extensible to a non-extensible material, at exposure times when standard tensile tests were not able to detect any changes in the materials. The essential work of fracture (EWF) technique was also applied and the results were in agreement with those of trouser tests. The specific essential work of fracture first increased with exposure time until the sample experienced a transition to a less ductile state where EWF was no longer applicable. EWF and trouser tear tests were more sensitive detecting the onset of degradation probably because they employ notched specimens that impose more critical stress concentration conditions than conventional tensile tests.     

Mechanical properties of thermoplastic polyester elastomer controlled by blending with poly(butylene terephthalate)

Thermoplastic polyester elastomer (TPEE) blends with poly(butylene terephthalate) (PBT) were prepared by melt compounding for the phase morphology and mechanical property studies. Although PBT is immiscible with the continuous soft poly(tetramethylene glycol) (PTMEG) phase of TPEE, it is miscible with the discrete hard PBT one of TPEE. Therefore, PBT and TPEE are compatible and their blends reveal very low level of interfacial tension and very small size of discrete domains, as well as good interfacial adhesion between two phases, which provide high possibility to prepare TPEE alloys with controllable properties. Mechanical test results reveal that both the modulus and yield and tensile strengths increase with increasing weight ratios of PBT. The increased system rigidity and decreased system plasticity are further confirmed by the cyclic tensile tests. The main objective of this work is to provide useful information on the structure and property control of TPEE by simple mixing with aromatic polyesters.     

Fracture toughness of gamma irradiated polycarbonate sheet using the essential work of fracture

Polycarbonate (PC), a ductile polymer, has been found by both linear elastic fracture mechanics and impact tests to present a ductile-brittle transition, which depends on notched specimen thickness, test speed and gamma irradiation. Owing to large amounts of plastic deformation, fracture toughness measurements by these test methods are not precise. In the present communication, a better method, the Essential Work of Fracture (EWF), to assess the fracture characteristics in plane state of stress was for the first time used to evaluate the fracture toughness of PC sheets subjected to gamma irradiation dose. Three-points bend tests of sharp pre-cracked specimens with different ligament lengths were 340 kGy gamma irradiated. EWF results showed that the total fracture work increased linearly with length for both non-irradiated and gamma irradiated conditions. A significant decrease in EWF fracture toughness was associated with brittleness promoted by gamma irradiation. This brittleness was also confirmed by macro and microscopy (SEM) evidence.     

Fracture studies of polypropylene/nanoclay composite. Part I: Effect of loading rates on essential work of fracture

Polypropylene (PP)/Montmorillonite (MMT) nanoclay based composite was prepared by melt compounding with maleic anhydride grafted polypropylene (MA-g-PP) as a compatibilizer in a twin-screw extruder, and the test specimens were injection molded. Mechanical properties such as tensile modulus, flexural modulus, yield strength and maximum percent strains were measured for pure PP and PP based nanocomposite to establish the effect of clay platelet reinforcement. The fracture properties were measured by using the essential work of fracture (EWF) method. PP/clay nanocomposite shows 25% improvement in specific EWF compared to pure PP. The variation of EWF parameters with loading rate is discussed, whilst the mechanisms of fracture are considered in a subsequent paper.     

Refined fixture design for effective essential work of fracture toughness characterization of m-LLDPE thin films

Characterization of Mode-I fracture toughness of ductile polymeric thin films is nontrivial. Proper specimen preparation and experimental procedures are required to ensure in-plane tensile loading. In this study, a custom-built double-edge notched tensile test fixture was employed to characterize the Mode-I essential work of fracture (EWF) toughness of metallocene linear low-density polyethylene (m-LLDPE) films. Effects of specimen geometry, strain rate and film orientation on the specific essential work of fracture, w_e, and the specific non-essential work of fracture, w_p, were investigated. Results indicate both EWF parameters are independent of the crosshead speed, gauge length (distance between upper and lower clamps) and specimen width within the ranges tested. w_e is significantly higher for thinner films and for crack propagation perpendicular to the blown film machine direction (MD). The usefulness of EWF for evaluating m-LLDPE fracture toughness is discussed.     

Fracture morphology and mechanical properties of ethylene/vinyl acetate rubber vulcanizates reinforced by in situ prepared sodium methacrylate

Ethylene/vinyl acetate rubber (EVM) was reinforced by sodium methacrylate (NaMAA) that was in situ prepared through the neutralization of sodium hydroxide and methacrylic acid in EVM during mixing. The mechanical properties of EVM vulcanizates with different NaMAA loadings and at different crosslink densities were studied and compared with those of high abrasion furnace carbon black (HAF) filled EVM vulcanizates. The fracture surfaces of gum and filled EVM vulcanizates were observed with scanning electron microscopy. The results showed that NaMAA‐reinforced EVM vulcanizates had better mechanical properties than HAF/EVM vulcanizates. When the NaMAA loading was 50 phr, the tensile strength of the NaMAA/EVM vulcanizate was 30 MPa, the tear strength was 102 kN/m, and the elongation at break was over 400%. Fourier transform infrared analysis confirmed that NaMAA formed in the compounding process and underwent polymerization during vulcanization. Scanning probe microscopy analysis revealed that nanoscale particles dispersed in the NaMAA/EVM vulcanizates. The mechanical properties were correlated with the fracture morphology of all the vulcanizates. The tensile rupture of NaMAA‐filled EVM vulcanizates occurred through tearing from a crack in the bulk of the samples. Tear deviation occurred with the addition of NaMAA and resulted in a rough surface, leading to an improvement in the tear strength of NaMAA‐filled EVM vulcanizates. The micrographs of the tear surfaces of the vulcanizates indicated that the different fracture modes depended on the NaMAA loading and the crosslink density. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1715–1724, 2004     

Microstructure and fracture behavior of semicrystalline polymer–clay nanocomposites

The relationships between the microstructure and the fracture behavior of three polymer/clay nanocomposites were studied. Two different polymer matrices were chosen, namely polyamide‐6 and polyethylene (compatibilized with PE‐g‐MA or PE‐g‐PEo), to reach very different clay dispersion states. The microstructure was characterized in terms of polymer crystallinity, orientation of the polymer crystalline lamellae, clay dispersion state, and orientation of the clay tactoids. The mechanical behavior was characterized by tensile tests. The essential work of fracture (EWF) concept was used to determine the fracture behavior of the nanocomposites. Both tensile and EWF tests were performed in two perpendicular directions, namely longitudinal and transversal. It is shown that the fracture behaviors of the matrices mainly depend on the polymer crystalline lamellae orientation. For the nanocomposites, the relationships between the matrix orientation, the clay dispersion states, the values of the EWF parameters (w_e and βw_p), and their anisotropy are discussed. The results show that the lower the average clay tactoid thickness, the lower is the decrease of fracture performance for the nanocomposite and the more consumed energy as longer the path of the crack. Besides, a linear dependence of the anisotropy of the EWF parameters of the nanocomposites on the average clay aspect ratio is found. The more exfoliated the structure is, the less pronounced the anisotropy of the EWF parameters. Interestingly, it is thought that the average clay aspect ratio is the parameter representing the clay dispersion state that governs the fracture anisotropy of the nanocomposites (as the elastic properties determined by tensile tests). © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1820–1836, 2008     

Tearing energy study of “oriented and relaxed” polystyrene in the glassy state

To study the effect of processing history, molecular weight/molecular weight distribution, and thermal history on solid state properties (in particular fracture properties and orientation), carefully characterized polydisperse and monodisperse polystyrene samples were drawn above T_g and the orientation frozen in. The objective was to simulate the incidental orientation of polymer chains after processing, molding, and so forth (e.g., injection or compression, blow molding) as a result of melt flow. A series of polystyrene samples was produced by hot drawing at temperatures of 113 and 148 °C, followed by a relaxation period, and then a quench to below T_g. The level of segmental orientation imposed in the samples was determined by birefringence measurements. The tear energy of the sheets was measured at 20 °C by tearing along the draw direction, ultimately giving a value for the fracture energy, G_3C. Samples of high draw ratio and low segmental orientation were unexpectedly found to have highly anisotropic fracture properties despite the low level of optical anisotropy. The fracture properties also depended significantly on whether the samples were drawn with or without lateral constraint. The results are compared with measurements of isotropic samples and the findings of a previous investigation utilizing SANS and birefringence. Modeling the drawing conditions at the chain level using a recent nonlinear tube theory explains how birefringence alone is an inadequate measure of molecular orientation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 377–394, 2007     

Investigation of degradation mechanisms in mechanical properties of polyimide films exposed to a low earth orbit environment

The degradation of the mechanical properties of polyimide films was evaluated by means of tensile tests after exposure to a low earth orbit (LEO) environment. Polyimide films irradiated with atomic oxygen (AO), ultraviolet (UV) light, and electron beam (EB) rays using ground simulation facilities were also evaluated similarly and compared. In these experiments tensile stress (7.0 MPa or less) was applied to the samples in order to assess its effects on mechanical properties. The mechanical properties of the flight samples decreased concomitantly with increased exposure duration. The fracture surfaces exhibited characteristic radiated patterns initiating from the exposed surfaces which showed a rough texture. In the AO-irradiated samples the mechanical properties degraded and the surface texture developed as the AO fluence increased; similar fracture surfaces appeared in the flight samples. In contrast, UV and EB irradiation had little impact on mechanical properties. Based on these results, the eroded surfaces by AO irradiation served as the starting points of the rupture, resulting in degradation of mechanical properties of polyimide films exposed to a LEO environment. The tensile stress states induced no difference in evaluations.     

Compatible and tearing properties of poly(lactic acid)/poly(ethylene glutaric‐co‐terephthalate) copolyester blends

Fourier transform infrared and nuclear magnetic resonance results suggest that the carboxylic acid groups of poly(lactic acid) (PLA) molecules react with the hydroxyl groups of FePol (FP) molecules during the melt‐blending of PLA_xFP_y specimens. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) experiments of PLA and PLA/FP specimens suggest that only small amounts of poor PLA and/or FP crystals are present in their corresponding melt crystallized specimens. In fact, the percentage crystallinity, peak melting temperature, and onset re‐crystallization temperature values of PLA/FP specimens reduce gradually as their FP contents increase. However, the glass transition temperatures of PLA molecules found by DSC and DMA reduce to a minimum value as the FP contents of PLA_xFP_y specimens reach 6 wt %. Further DMA and morphological analysis of PLA/FP specimens reveal that FP molecules are compatible with PLA molecules at FP contents equal to or less than 6 wt %, as no distinguished phase‐separated FP droplets and tan δ transitions were found on fracture surfaces and tan δ curves of PLA/FP specimens, respectively. In contrast to PLA, the FP specimen exhibits highly deformable and tearing properties. After blending proper amounts of FP in PLA, the inherent brittle deformation and poor tearing behavior of PLA were successfully improved. Possible reasons accounting for these interesting crystallization, compatible and tearing properties of PLA/FP specimens are proposed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 913–920, 2010