Essential Work of Fracture of photo-oxidized LDPE/EVA Films

The Essential Work of Fracture approach (EWF) was used to determine how UV-C irradiation alters the fracture behaviour of LDPE/EVA films. Complementary characterization was performed by FTIR, DSC, TOM, and uniaxial tensile testing. The crosslinking reactions that govern photo-oxidation process at initial stage of exposure stiffened the amorphous phase of the polymer, leading to films with enhanced elastic modulus, yield stress and ultimate strength, but impaired strain at break. In the fracture experiments carried out on films irradiated within 0 and 5 days, EWF methodology requirements were met and the corresponding fracture toughness parameters (w_e and βw_p ) turned out to be sensitive to UV-C irradiation. Longer irradiation time triggered the development of microcracks, which not allowed further stable crack growth and invalidated the application of EWF approach.     

Essential work of fracture and j-integral measurements for ductile polymers

In the ductile tearing of polymers that neck before failure it is shown that the specific essential fracture work (w_e), consisting of the energies dissipated in forming and tearing the neck, is a material property for a given sheet thickness and is independent of specimen geometry. Work of fracture experiments using both double deep-edge notched (DENT) and deep-center notched tension (DCNT) geometries with different ligament lengths yielded almost identical w_e values for a grade of high-density polyethylene. These measurements for w_e are in fairly good agreement with the theoretical values based on the J integral evaluated along a contour surrounding the neck region near the crack tip. Under J-controlled crack growth conditions, it is shown that J_c obtained by extrapolation of the J_R curve to zero crack growth and the slope dJ/da are identical, respectively, to w_e and 4βw_p obtained from the straight line relationship between the specific total work of fracture (w_f) and ligament length (l).     

Relationship between fracture toughness and intrinsic deformation parameters in isotropic and flow‐oriented linear low‐density polyethylene

The fracture toughness of isotropic and flow‐oriented linear low‐density polyethylene (LLDPE) is evaluated by the Essential Work of Fracture (EWF) concept, with a special setup of CCD camera to monitor the process of deformation. Allowing for the molecular orientation, flow‐oriented sample, prepared via melt extrusion drawing, is stretched parallel (oriented‐0°) and perpendicular (oriented‐90°) to its original melt extrusion drawing direction, respectively. The obtained values of specific EFW w_e are 34.6, 10.2, and 4.2 N/mm for the oriented‐0°, isotropic and oriented‐90° sample, respectively. With knowledge of intrinsic deformation parameters deduced from uniaxial tensile tests, moreover, a relationship between specific EFW w_e the ratio of true yield stress to strain hardening modulus σ_ty/G is well established. It means that the fracture toughness of polyethylene is determined by both crystalline and amorphous parts, rather than by one of them. Moreover, the true yield stress seems to be nondecisive factors determining the fracture toughness of polyethylene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2880–2887, 2006     

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.     

Essential work of fracture: An approach to study the fracture behavior of acrylic bone cements modified with comonomers containing amine groups

The fracture behavior of acrylic bone cements modified with comonomers containing amine groups was studied using the essential work of fracture approach. The cements were prepared with either 2-(diethylamino)ethyl-acrylate (DEAEA), 2-(dimethylamino)ethyl-methacrylate (DMAEM) or 2-(diethylamino)ethyl-methacrylate (DEAEM) as comonomer in the liquid phase. Double-Edge-Notched Tensión (DENT) specimens were tested in a universal testing machine at 5 mm/min. The results showed that the essential work (w_e) and nonspecific value of fracture (βw_p) of bone cements modified with all percentages of comonomer were notably increased compared with unmodified bone cement. From Scanning Electron Microscopy (SEM) micrographs, ductile behavior was observed for modified bone cements, i.e. the crack propagation is stable, whereas the unmodified cement exhibited brittle behavior indicating unstable crack propagation. The use of the essential work of fracture approach is suggested to determine the fracture behavior of cements that do not exhibit a linear stress-strain relationship.     

Influences of molecular weight and crystalline structure on fracture behavior of controlled-rheology-polypropylene prepared by reactive extrusion

The molecular weight of ethylene-block-co-polypropylene (co-PP) was adjusted by reactive extrusion with the incorporation of dicumyl peroxide (DCP), and the effect of molecular weight on the crystallization behavior, crystal morphology, and fracture behavior was investigated. It was found that, with increasing DCP content, the molecular weight (MW) decreased and the polydispersity (M_w/M_n) slightly decreased. After modification, the number of spherulites with obscure boundaries increased, and the size of the spherulites was more even due to increasing amount of grafting and micro-cross-linking structures, generated in co-PP degradation, which were acting as nucleating agents. Evaluated by essential work of fracture method, the specific essential work of fracture, w_e, was found to be strongly dependent on the molecular weight, especially, on the number average molecular weight (M_n) linearly, while the specific non-essential work of fracture, βw_p, was enhanced with decreasing z-average molecular weight (M_z), probably owing to the reduction of ultra-high molecular weight component in degraded co-PP.     

Effect of β-phase on the fracture behavior of dynamically vulcanized PP/EPDM blends studied by the essential work of fracture approach

The effect of β phase polypropylene (PP), induced by β-nucleating agent (β-NA), on the fracture behavior in dynamically vulcanized thermoplastic elastomers (TPVs) based on dynamically vulcanized PP/ethylene-propylene-diene rubber (EPDM) blend was studied. Differential Scanning Calorimetry (DSC) and Wide-angle X-ray diffraction (WAXD) were employed to study the melting behavior and crystalline structures, and the results indicated that the β-NA induced β phase of PP effectively in TPVs. With the increasing dosage of the β-NA incorporated in, the content of β phase increased while the total crystallinity of the blend kept constant. The fracture behavior of the TPVs with different β phase content was studied with double edge notched tensile loaded specimens (DENT) using the essential work of fracture (EWF) approach. The specific essential work of fracture (w_e) increased with the increasing of β phase content, indicating that the presence of β phase could effectively enhance the fracture toughness of TPVs.     

Chemical composition effects on the fracture of polystyrene-block-poly(methyl methacrylate)block copolymers

The crazing and fracture behaviors of glassy–glassy block copolymers were investigated for polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymers that had similar overall molecular weights but different poly(methyl methacrylate) (PMMA) molar fractions. A liquid chromatography technique was applied to separate as-synthesized PS-b-PMMA [(1) weight-average molecular weight (M_w) = 94,000 g/mol and PMMA molar fraction = 0.35 and (2) M_w = 65,000 g/mol and PMMA molar fraction = 0.28] into three fractions with different chemical compositions. With a copper-grid technique, the fracture behaviors of 0.5-μm-thick PS-b-PMMA films were studied as a function of the applied strain. For the higher M_w PS-b-PMMA samples, the median strains at crazing and fibril breakdown increased with an increase in the PMMA molar fraction from 0.24 to 0.46, corresponding to an increase in the chain entanglements in the PMMA domains. In contrast, for the lower M_w samples, the two values were not significantly changed even when the PMMA molar fraction was varied from 0.16 to 0.35. M_w of the minor component in PS-b-PMMA played a critical role in controlling the fracture behaviors of the block copolymers. Specifically, M_w/M_e of the minor component (where M_e is the molecular weight between entanglements) had to be roughly larger than 2 for the block copolymers to sustain sufficient strains before fracture. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3612–3620, 2006     

Determination and comparison of the plane stress essentialwork of fracture of three polyesters PET, PPT and PBT

The essential work of fracture (EWF) method has been used to study the relationship between molecular structure and thin film fracture toughness for three ductile polyesters at ambient temperature. The fracture toughness of PPT is of particular interest. Successful fracture characterisation of thin film polyesters has been achieved by the EWF method using double edge notched tension (DENT) specimens. The specific essential work of fracture, w _e, for polyethylene terephthalate (PET), polypropylene terephthalate (PPT) and polybutylene terephthalate (PBT) films is found to be 35.54±2.56, 41.03±3.23 and 31.34±8.60 kJ m^–2, respectively. Differential scanning calorimetry (DSC) has been employed to investigate the crystallinity of the polymers concerned and the effect of this on their EWF values.     

Toughening of a High-performance Bis-nadimide Thermoset by Blending with High-Glass Transition Temperature Linear Polyimides

A nadimide end-capped thermosetting oligomer was modified by blending with three homologous soluble linear polyimides containing bulky lateral fluorene groups with the intention of improving its fracture toughness. These linear polyimides were prepared by polycondensation between 4,4′-(9H-fluoren-9-yliden)-bisphenylamine (cardo structure) and three different bis-phthalic anhydride derivatives, containing between the bis-phthalic moities a secondary alcohol function, a carbonyl function or a hexafluoropropylidene group respectively. The thermoset produced upon heating a thermostable polynadimide network having a glass transition temperature (T_g) close to 300° and a critical stress intensity factor equal to 0.9 MPa.m^1/2. The T_gs of the studied linear polyimides were located above 340° in connection with the chain–chain molecular interactions. After dissolving, the precipitated blend powders with different compositions were thermally polymerized under pressure to give bulk specimens. The resulting morphologies were dependent on the chemical structure of the linear polyimide. As shown by the position of heat deflection temperatures, a well-defined two-phase blend was obtained by introducing the hexafluoropropylidene-containing polyimide, when a fully miscible system was formed with the secondary alcohol-containing polyimide. The parallel increase in fracture toughness seemed to be controlled by the degree of phase separation between the blend components. The greater improvement resulted from the partially fluorinated polyimide: the corresponding K_IC reaching 1.23 MPa.m^1/2 with 20 wt% of linear component. Finally, the toughening effect due to the latter polymer was examined in relation to its average molecular weight. Almost no change was observed if the corresponding inherent viscosity in N-methyl pyrrolidone solution was above 0.2 dl/g. In any case, owing to the high T_g of the linear component, the thermomechanical stability of the blend was maintained at the same level as that of the initial polynadimide network. © 1997 John Wiley & Sons, Ltd.     

Determination and comparison of the essentialwork of fracture (EWF) of two polyester blends

The fracture toughness of blends of polypropylene terephthalate (PPT) with polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) were investigated. Binary blends were prepared comprising 10:90, 30:70, 50:50, 70:30 and 90:10 mass/mass%. The fracture toughness was determined for each blend using the essential work of fracture (EWF) method and thin film double edge notched tension (DENT) specimens. The specific essential work of fracture, w _e, values obtained for blends of PET/PPT ranged from 27.33 to 37.38 kJ m^–2 whilst PBT/PPT blends yielded values ranging from 41.78 to 64.23 kJ m^–2. Differential scanning calorimetry (DSC) was employed to assess whether or not crystallinity levels influence the mechanical properties evaluated. The fracture toughness of PPT deteriorated with PET incorporation. However, high we values exceeding that of pure PPT were obtained for PBT/PPT blends across the composition range studied.     

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     

Polyimide–polyformal block copolymers

In an effort to combine and tailor the properties of thermoplastic resins we have investigated the synthesis of polyimide–polyformal block copolymers prepared by the condensation reaction of α,ω-diamino functionalized polyformal oligomers with α,ω-dianhydride terminated polyimide oligomers. Amino functionalized polyformal oligomers were synthesized by displacement condensation reactions of various bisphenols with methylene dihalides in the presence of base and aminophenols. Oligomeric aromatic polyformals having weight average molecular weights (MW_w) of 7500 to 40,000 were obtained. Anhydride terminated polyimide oligomers with molecular weights (MW_w) ranging from 10,000 to 15,000 were obtained by the condensation of bisphenol-A–dianhydride and aromatic amines. Combining the polyimide oligomers with the polyformal oligomers in dipolar aprotic or nonpolar solvents afforded the desired block copolymers. The polyimide–polyformal block copolymers generally display two distinct glass transition temperatures by differential scanning calorimetry. The (AB)_n block copolymers were evaluated by TGA in both air and N₂ for thermal/oxidative stability.     

Molecular weight dependence of mechanical properties of poly(p,p′-oxydiphenylene pyromellitimide) films

The mechanical properties, i.e., Young's modulus, elongation, and tensile stress, were determined as functions of the molecular weight for films of poly(oxydi-p-phenylene pyromellitimide) prepared by thermal cyclization of the precursor poly(amic acid). The molecular weights of the samples were controlled by the monomer stoichiometry employed for the solution condensation of pyromellitic dianhydride and p,p′-oxydianiline. Weight-average molecular weights were determined by light scattering of the precursor poly(amic acid) as well as the fully cyclized polyimide. The elongation-at-break is most sensitive to the molecular weight, undergoing a rapid increase at M _w ? 8000 and reaching a limiting value of about 60% for M _w > 20,000.     

Effect of scale and surface chemistry on the mechanical properties of carbon nanotubes‐based composites

In this article, Multi‐Walled Carbon Nanotubes (MWCNTs) of varying diameters, both untreated and polycarboxylated, were dispersed at constant weight percentage in an epoxy matrix, and resulting fracture toughnesses (K_Ic) were measured in each case. We show that changing the MWCNT diameter has two effects on the composite fracture toughness: (i) a small MWCNT diameter enables larger interfacial surface for adhesion maximization, which increases toughness; (ii) at the same time, it limits the available pull‐out energy and reduces the MWCNT ability to homogeneously disperse in the matrix due to this same large active surface: this decreases toughness. Most commercially available MWCNTs have a length range of several μm, thus an optimal diameter exists which depends on MWCNT wall thickness and surface treatment. Such optimal diameter maximizes pull‐out energy and thus composite fracture toughness. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Crystallization of spodumene-diopside in the las glass ceramics with CaO and MgO addition

Crystallization, morphology and mechanical properties of a spodumene-diopside glass ceramics with adding different amount of CaO and MgO in Li₂O-Al₂O₃-2SiO₂ were investigated. With CaO and MgO addition, the crystallization temperature (T _p) decreased, the value of Avrami constant (n) decreased from 3.2±0.3 to 1.4±0.2, the activation energy (E) increased from 299±3 kJ mol⁻¹ to 537±5 kJ mol⁻¹. The crystalline phases precipitated were h-quartz solid solution, β-spodumene and diopside. The mechanism of crystallization of the glass ceramics changed from bulk crystallization to surface crystallization. The grain sizes and thermal expansion coefficients increased while flexural strength and fracture toughness of the glass-ceramics increased first, and then decreased. The mechanical properties were correlated with crystallization and morphology of glass ceramics.     

Polyimide solution properties

Solution characterization measurements indicate that cylization of the polyamic acid from 2,4-diaminoisopropylbenzene and pyromellitic dianhydride (PMDA) to the polyimide can be effected with small change in number-average degree of polymerization. An increase in weight-average molecular weight on conversion to polyimide is attributed to branching side reactions. Inherent viscosities of polyimides from 4,4′-diaminodiphenyl ether and PMDA decreased slowly with time in concentrated (97%) sulfuric acid, probably as a result of hydrolytic cleavage. The zero-time viscosity intercepts were related to both the precursor and the estimated polyimide molecular weight. The latter gave η_inh (c = 0.5% solids) = 2.76 × 10^?3M?^0.53_w for 60,000 < M_w < 300,000. The exponent is near the lower limit of 0.5 found in theta solvents. The characteristic ratio of the root-mean-square end-to-end distance of a chain to the square root of its molecular weight is 1.1 Å and the steric factor is 1.1; these results suggest that the unperturbed polyimide chain is almost as extended as an equivalent freely rotating chain, a general feature of long-bonded polymers with p-phenylene rings in the chain backbone.     

Polydispersity effects in polymer self-diffusion measured by small-angle neutron scattering

The small-angle neutron scattering (SANS) method for measuring the self-diffusion coefficient D has been analyzed for effects of polydispersity in degree of polymerization for the case of linear polymers diffusing by reptation. Polydispersities corresponding to M_w/M_n = 1.0?10 were considered. It is shown that in all cases a meaningful effective diffusion coefficient D_e can be obtained from the short time recovery of the SANS intensity. This quantity D_e ≤ 1.3 D(M_w), where D(M_w) is the diffusion coefficient of a monodisperse polymer having molecular weight M = M_w. The method relies on SANS intensities extrapolated to zero scattering angle; realistic extrapolation is shown to give rise to quite acceptable errors on the order of 0.05 D_e.     

A theoretical calculation of dissociation rates of molecular hydrogen in electrical discharges

Dissociation rates of molecular hydrogen in electrical discharges have been calculated at different electron (T_e) and gas (T_g) temperatures (10000 T_e 23000 K, 500 T_g 4000 K), at different pressures p (5 p 50 torr) and electron number densities n_e (0 n_e 10¹² cm⁻³).The results have been obtained by solving a system of master equations, including V---T (vibration-translation), V---V (vibration---vibration) and e---V (electron---vibration) microscopic processes.The results obtained at n_e ≠ O show a “laser-type mechanism” in the dissociation of molecular hydrogen in electrical discharges. In particular one notices a strong increase of dissociation rates with decreasing gas temperature and pressure.The results show that this mechanism is as important as the mechanism of direct dissociation by electron impact.     

Rheological studies of thermotropic liquid crystal copolyesters: P-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid

The rheological behavior of the thermotropic liquid crystal copolyesters composed of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid (indicated as HBA/HNA) is investigated for three different compositions: 75:25, 58:42, 30:70 (in mol%). The inherent viscosities are 9.2, 5.1, and 7.8 dl/g, respectively. Yield stress is observed for all three samples. This indicates the existence of crystallites in the melt which may be related to the shear thinning viscosity at low shear stress. Melt fracture, and a die swell ratio which increases with shear rate, are also observed at higher temperatures and at low shear stress for the two copolyesters having compositions 75:25 and 30:70. We have also estimated for 30HBA/70HNA at 335°C the entrance pressure loss, Δp_ent, and ΔP_ent/δ_w, where δ_w is the shear stress at the capillary wall. The large value of ΔP_ent/δ_w suggest that HBA/HNA is a highly elastic polymeric material. It is found that both ΔP_ent and ΔP_ent/δ_w increase with shear rate. However, the high elasticity does not account for the disappearance of melt fracture and contraction of die swell at high shear stress. This abnormal phenomenon is ascribed to the formation of a network of crystallites caused by blocky regions in the copolymer.