Crack Toughness Behaviour of Multiwalled Carbon Nanotube (MWNT)/Polycarbonate Nanocomposites

Summary: The morphology and fracture behaviour of polycarbonate (PC)/multiwalled carbon nanotube (MWNT) composites have been studied by AFM and post‐yield fracture mechanics. The essential work of fracture (EWF) method has been used to distinguish between two terms representing the resistance to crack initiation and crack propagation. A maximum in the non‐essential work of fracture was observed at 2 wt.‐% MWNT, demonstrating enhanced resistance to crack propagation compared to pure PC. At 4 wt.‐% MWNT, a tough‐to‐brittle transition has been observed. The time‐resolved in‐situ strain field analysis revealed that the onset of crack initiation was shifted to a shorter time for nanocomposites with 4 wt.‐% MWNT compared to that with 2 wt.‐%, and thus explained the existence of a tough‐to‐brittle transition in these nanocomposites.

     

Ductile‐to‐Semiductile Transition in PP‐MWNT Nanocomposites

A ductile‐to‐semiductile transition in the crack resistance behaviour of PP/MWNT composites is discussed, using an essential work of fracture approach based on a post yield fracture mechanics concept and its possible interrelation to the structural attributes studied by TEM, SEM, and WAXD. A maximum in the non‐essential work of fracture is observed at 0.5 wt.‐% MWNT content, which demonstrates the enhanced resistance to crack propagation compared to pure PP, followed by a sharp decline with the increase in MWNT content to 1.5 wt.‐%, which reveals a ductile‐to‐semiductile transition. Fracture kinetic studies present a qualitative picture of the nature of such a transition in terms of a) switch over from non‐steady (in pure PP) to steady‐state crack tip opening displacement rate (in nanocomposites), and b) a ductile‐to‐semiductile transition; largely as a result of delayed‐yielding of the nanocomposites.

     

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     

Application of the essential work of fracture concept to nanostructured polymer materials

The first part of the paper deals with a critical discussion of the methodical basis of essential work of fracture (EWF) concept with respect to the specimen geometry (especially the notch depth) and application to polymers. In the second part, an in situ testing device, which combines a tensile testing machine with an optical strain-field measuring system, has successfully demonstrated possibility of characterization of fracture behaviour of polystyrene-polybutadiene block copolymers and block copolymer/homopolymer blends as examples of nanostructured polymer materials. It has been shown that knowledge of the time evolution of the strain field close to the crack tips leads to a simple verification of the basic precondition for the applicability of the EWF concept, the precondition “plastic zone coalescence-before-stable crack propagation”.     

Strain Field Analysis and Kinetics of Crack Propagation of Binary Triblock Copolymer Blends

Summary: The crack toughness behaviour of binary styrene‐butadiene (SB) triblock copolymer blends of a thermoplastic block copolymer (LN3) and a thermoplastic elastomer (LN4) with different molecular architecture was studied using essential work of fracture (EWF) concept and was correlated to the morphological features from transmission electron microscopy (TEM). An increase in the crack toughness behaviour between 60 and 80 wt.‐% LN3 has been observed and is attributed to a change from cylindrical to lamellar morphology. The time‐resolved crack propagation studies have offered new dimensions to understand the kinetic aspects of fracture behaviour while the strain field analysis has explained the time‐dependent deformation behaviour to characterise the time dependence of the strain energy dissipation modes.

Load‐displacement diagrams of non essential work of fracture values of LN3/LN4 blends.     

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 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.     

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.     

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.     

Mechanical and fracture behavior of polypropylene/poly(ethylene-co-vinyl alcohol) blends compatibilized with ionomer Na

In this work the deformation and fracture behavior of PP/EVOH blends compatibilized with ionomer Na⁺ at room and low temperature was studied. Uniaxial tensile tests on dumb-bell samples and fracture tests on single-edge notched bending (SENB) specimens were performed for 10 wt.% and 20 wt.% EVOH blends with different ionomer content at 23 °C and −20 °C. The incorporation of EVOH to PP led to less ductile materials in tension as judged by the lower values of the ultimate tensile strain displayed by all PP/EVOH blends in comparison to neat PP. In contrast, the ionomer Na⁺ addition partially counteracted this effect. The compatibilizing effect of ionomer Na⁺ was also evident in fracture results since higher values of the fracture parameter were obtained for the ternary blends. SEM observations also confirmed this effect. On the other hand, PP/EVOH blends exhibited different fracture behavior with test temperature. All blends showed “pseudo stable” behavior at room temperature characterized by apparently stable crack growth that could not be externally controlled. On the contrary, blends behaved as semi-brittle at −20 °C with some amount of stable crack growth preceding unstable brittle fracture. Finally, irrespectively of the temperature or the ionomer content all PP/EVOH blends exhibited more ductile fracture behavior with a higher tendency to stable crack propagation than neat polypropylene.     

聚丙烯/POE共混组成对材料断裂行为的影响

采用基本断裂功(EWF)方法对聚丙烯(PP)/聚烯烃弹性体(POE)共混物的注射双边缺口拉伸试样的断裂行为进行了研究,比较了不同POE含量对共混物各断裂参数的影响.结果表明,PP和用量为5phr POE的共混物都可完全满足EWF方法的要求,共混物的断裂韧性-比基本断裂功we,较PP有显著提高;POE用量为10phr以上的共混物则出现明显的成颈现象而限制了EWF方法的应用;PP和各种POE用量的共混物都得到了其屈服所需要的比基本断裂功we,y和比塑性功β′wp,y.     

Impact fracture toughness of polyamide‐6/montmorillonite nanocomposites toughened with a maleated styrene/ethylene butylene/styrene elastomer

Polyamide‐6 (PA6)/montmorillonite (MMT) nanocomposites toughened with maleated styrene/ethylene butylene/styrene (SEBS‐g‐MA) were prepared via melt compounding. Before melt intercalation, MMT was treated with an organic surfactant agent. Tensile and impact tests revealed that the PA6/4% MMT nanocomposite fractured in a brittle mode. The effects of SEBS‐g‐MA addition on the static tensile and impact properties of PA6/4% MMT were investigated. The results showed that the SEBS‐g‐MA addition improved the tensile ductility and impact strength of the PA6/4% MMT nanocomposite at the expenses of its tensile strength and stiffness. Accordingly, elastomer toughening represents an attractive route to novel characteristics for brittle clay‐reinforced polymer nanocomposites. The essential work of fracture (EWF) approach under impact drop‐weight conditions was used to evaluate the impact fracture toughness of nanocomposites toughened with an elastomer. Impact EWF measurements indicated that the SEBS‐g‐MA addition increased the fracture toughness of the PA6/4% MMT nanocomposite. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 585–595, 2005     

Fracture toughness assessment of polypropylene random copolymer with multiple stress modes using the essential work of fracture theory

In recent years, the essential work of fracture (EWF) method has been extensively employed for assessing a material's toughness by specific essential fracture work, especially for polymers showing ductile failure. However, most research has studied either the in-plane stress mode or the out-of-plane stress mode. To obtain a more in-depth understanding of the EWF theory, the specific essential and non-essential fracture work of polypropylene random copolymer (PP-R) was investigated in both in-plane stress mode and out-of-plane stress mode. The effects of ligament length, amount of pre-cracking and pre-cracking method on the specific essential and non-essential fracture work were explored. The specific essential fracture work obtained in both stress modes is compared and discussed.     

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.     

Deformation mechanisms of nanoclay‐reinforced maleic anhydride‐modified polypropylene

Fracture properties and deformation mechanisms of nanoclay‐reinforced maleic anhydride‐modified polypropylene (MAPP) were investigated. Elastic–plastic fracture mechanics was employed to characterize the toughness in light of substantial postyield deformation for the reinforced MAPP. Upon introduction of 2.5 wt % clay loading in maleated MAPP, it was observed that tensile strength, modulus, and fracture initiation toughness concomitantly increased substantially. Continued increase in clay loading thereafter only led to stiffening and strengthening effects to the detriment of fracture toughness. A plot of the J‐integral initiation fracture toughness versus the plastic zone size demonstrated that toughening arose from plastic deformation in the reinforced matrix. Careful examination of deformed tensile specimens using small angle X‐ray scattering (SAXS) showed 2.5 wt % clay gave rise to the highest equatorial scattering, which indicates the presence of microvoids in the matrix. The SAXS results were consistent with that shown in subcritically loaded crack‐tip deformation zone using transmission electron microscopy. Thus, both macroscale three‐point bend fracture data and SAXS results led us to consistent findings and conclusions. Further increase in clay loading above 2.5 wt % reduced the scattering the matrix plasticity and thus the fracture toughness. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2759–2768, 2004     

Structural characterization and thermal properties of polyamide 6.6/Mg, Al/adipate-LDH nanocomposites obtained by solid state polymerization

A new nanocomposite was obtained by dispersing an adipate-modified layered double hydroxide (Ad-LDH) with adipic acid and hexamethylene diamine. These samples were polymerized in the solid phase under a nitrogen flow for 200 min at 190 °C. The structural and compositional details of the nanocomposite were determined by powder X-ray diffraction (PXRD), fourier transform infrared (FTIR) spectroscopy, focused ion beam (FIB), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The PXRD patterns and FIB images show a partially intercalated and partially exfoliated dispersion of layered crystalline materials in the polyamide 6.6 matrix. The best dispersion level is achieved in polyamide 6.6/LDH nanocomposites with low LDH loading. Some residual tactoids and particle agglomerates are also evident at high concentration. The best thermal stability of the nanocomposites is shown by the sample with 0.1% LDH content, for which it is higher than that of pure polyamide.     

Synergistic effect of ammonium polyphosphate and layered double hydroxide on flame retardant properties of poly(vinyl alcohol)

A novel flame retardant system of poly(vinyl alcohol) (PVA) is prepared via using ammonium polyphosphate (APP) and layered double hydroxide (LDH). The flammability of PVA composites containing APP-based LDH at a 15 wt.% global percentage showed that the flame retardancy of all PVA/APP/LDH samples increase with the increase of LDH concentration in the range of 0.1-1.0 wt.%, and reach a LOI value of up to 33 and UL-94 V-0 rating for most composites. Thermo-gravimetric analysis reveals that PVA/APP/LDH samples show higher initial decomposition temperature in comparison with PVA/APP composite. The morphology and structures of residues generated during LOI test were investigated by scanning electronic microscopy (SEM). Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used to analyze the composition of the residue formed after thermo-oxidation to support a fundamental analysis for the mechanism of char formation. The test of mechanical properties demonstrated that LDH can enhance tensile strength, Young's modulus and elongation at break of PVA/APP composites.     

Synergistic effects of layered double hydroxide with hyperfine magnesium hydroxide in halogen-free flame retardant EVA/HFMH/LDH nanocomposites

The synergistic effects of layered double hydroxide (LDH) with hyperfine magnesium hydroxide (HFMH) in halogen-free flame retardant ethylene-vinyl acetate (EVA)/HFMH/LDH nanocomposites have been studied by X-ray diffraction (XRD), transmission electron spectroscopy (TEM), thermogravimetric analysis (TGA), limiting oxygen index (LOI), mechanical properties' tests, and dynamic mechanical thermal analysis (DMTA). The XRD results show that the exfoliated EVA/HFMH/LDH can be obtained by controlling the LDH loading. The TEM images give the evidence that the organic-modified LDH (OM-LDH) can act as a disperser and help HFMH particles to disperse homogeneously in the EVA matrix. The TGA data demonstrate that the addition of LDH can raise 5-18 °C thermal degradation temperatures of EVA/HFMH/LDH nanocomposite samples with 5-15 phr OM-LDH compared with that of the control EVA/HFMH sample when 50% weight loss is selected as a point of comparison. The LOI and mechanical tests show that the LDH can act as flame retardant synergist and compatilizer to apparently increase the LOI and elongation at break values of EVA/HFMH/LDH nanocomposites. The DMTA data verify that the T_g value (−10 °C) of the EVA/HFMH/LDH nanocomposite sample with 15 phr LDH is much lower than that (T_g = −2 °C) of the control EVA/HFMH sample without LDH and approximates to the T_g value (−12 °C) of pure EVA, which indicates that the nanocomposites with LDH have more flexibility than that of the EVA/HFMH composites.     

Influence of SEBS-g-MA on morphology, mechanical, and thermal properties of PA6/PP/organoclay nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organically modified clay (organoclay) toughened with maleated styrene-ethylene-butylene-styrene (SEBS-g-MA) were prepared by melt compounding using co-rotating twin-screw extruder followed by injection molding. X-ray diffraction (XRD) and transmission electron microscope (TEM) were used to characterize the structure of the nanocomposites. The mechanical properties of the nanocomposites were determined by tensile, flexural, and notched Izod impact tests. The single edge notch three point bending test was used to evaluate the fracture toughness of SEBS-g-MA toughened PA6/PP nanocomposites. Thermal properties were studied by using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). XRD and TEM results indicated the formation of the exfoliated structure for the PA6/PP/organoclay nanocomposites with and without SEBS-g-MA. With the exception of stiffness and strength, the addition of SEBS-g-MA into the PA6/PP/organoclay nanocomposites increased ductility, impact strength and fracture toughness. The elongation at break and fracture toughness of PA6/PP blends and nanocomposites were increased with increasing the testing speed, whereas tensile strength was decreased. The increase in ductility and fracture toughness at high testing speed could be attributed to the thermal blunting mechanism in front of crack tip. DSC results revealed that the presence of SEBS-g-MA had negligible effect on the melting and crystallization behavior of the PA6/PP/organoclay nanocomposites. TGA results showed that the incorporation of SEBS-g-MA increased the thermal stability of the nanocomposite.     

Elastomer/LDH nanocomposites: Synthesis and studies on nanoparticle dispersion, mechanical properties and interfacial adhesion

Layered double hydroxides (LDHs) based elastomer nanocomposites have been synthesized and characterized in terms of nanoparticle dispersion, mechanical properties and interfacial adhesion. Since LDH has basic hydroxyl groups on its surface, its potential as reinforcing filler in elastomers and in additionally a crosslinking agent in carboxylated elastomers has been investigated in details. For this purpose, two different elastomers having widely different polarities and functional groups (e.g., ethylene propylene diene terpolymer, i.e. EPDM and carboxylated nitrile rubber, i.e. XNBR) have been used as the matrix. The pristine LDH based on Mg and Al was modified with decane sulfonate by the regeneration method. The morphological analysis of the nanocomposites (done by X-ray diffraction analysis and electron microscopy) shows that in both matrices LDH particles are dispersed in three different forms, i.e. as primary particles, as exfoliated layers and as soft clusters formed by both of them. However, their relative proportion differs drastically in the two matrices. We have shown in this study that the LDH can significantly improve the mechanical properties in both the system. In XNBR/LDH nanocomposites containing no conventional metal oxide curative, this improvement is very prominent due to secondary interaction between LDH and XNBR matrix indicating that LDH can crosslink carboxalated elastomers. It is also observed that LDH particle promotes strain-induced crystallization in XNBR/LDH. The fracture surface analysis shows that in XNBR/LDH nanocomposite very stable polymer-filler interface is formed and tensile failure takes place through the matrix rather than through the interface. In case of EPDM/LDH nanocomposites the opposite is observed and the polymer matrix hardly wets the surface of the LDH particle.