The location and extent of exfoliation of clay on the fracture mechanisms in nylon 66-based ternary nanocomposites

The primary focus of this work is to elucidate the location and extent of exfoliation of clay on fracture (under both static and dynamic loading conditions) of melt-compounded nylon 66/clay/SEBS-g-MA ternary nanocomposites fabricated by different blending sequences. Distinct microstructures are obtained depending on the blending protocol employed. The state of exfoliation and dispersion of clay in nylon 66 matrix and SEBS-g-MA phase are quantified and the presence of clay in rubber is shown to have a negative effect on the toughness of the nanocomposites. The level of toughness enhancement of ternary nanocomposites depends on the blending protocol and the capability of different fillers to activate the plastic deformation mechanisms in the matrix. These mechanisms include: cavitation of SEBS-g-MA phase, stretching of voided matrix material, interfacial debonding of SEBS-g-MA particles, debonding of intercalated clay embedded inside the SEBS-g-MA phase, and delamination of intercalated clay platelets. Based on these results, new insights and approaches for the processing of better toughened polymer ternary nanocomposites are discussed.     

Impact fracture behaviour of nylon 6-based ternary nanocomposites

This study focuses on achieving high stiffness/strength and high fracture toughness in nylon 6/organoclay nanocomposites prepared via melt compounding by incorporating a maleic anhydride grafted polyethylene–octene elastomer (POE-g-MA) as a toughening agent. Mechanical test results indicated that the ternary nanocomposites exhibited higher stiffness than nylon 6/POE-g-MA binary blends at any given POE-g-MA content. More importantly, the brittle–ductile transition of nylon 6/POE-g-MA blends was not impaired in the presence of organoclay for the compositions prepared in this study. TEM analysis shows that organoclay layers and elastomer particles were dispersed separately in nylon 6 matrix. In the binary nanocomposite, no noticeable plastic deformation was observed around the crack tip. In the ternary nanocomposites, the presence of organoclay in the matrix provided maximum reinforcement to the polymer, while their absence in the elastomer particles allowed the latter to promote high fracture toughness via particle cavitation and subsequent matrix shear yielding. The partially exfoliated clay layers also delaminated and hence, adding to the total toughness of the nanocomposites.     

Effects of loading rate and temperature on tensile yielding and deformation mechanisms of nylon 6-based nanocomposites

Tensile tests were conducted on nylon 6/organoclay nanocomposites, with and without POE-g-MA rubber particles, over a range of temperatures and strain rates 10⁻⁴–10⁻¹ s⁻¹. It was shown that the 0.2% offset yield strength varied with both temperature and strain rate which could be described by the Eyring equation thus providing results on the activation energy and activation volume for the physical processes involved. In addition, their tensile deformation mechanisms were characterized using the tensile dilatometry technique to differentiate the dilatational processes (e.g., voiding/debonding caused by the organoclay and rubber particles or matrix) and shear yielding (e.g., matrix with zero volume change). Dilatometric responses indicated that the presence of POE-g-MA rubber particles did not alter the shear deformation mode of neat nylon 6. In contrast, the presence of organoclay layers changed the tensile yield deformation behavior of nylon 6 matrix from dominant shear yielding to combined shear yield plus dilatation associated with delaminations of nanoclay platelets. In nylon 6/organoclay/POE-g-MA ternary nanocomposite, the volume strain response indicated that the POE-g-MA rubber particles promoted shear deformation and suppressed delamination of the organoclay layers. Supports for the deformation mechanisms deduced from the tensile dilatometry tests were corroborated by optical microscopy and transmission electron microscopy micrographs of the studied materials.     

Investigation of the nanostructure and mechanical properties of polypropylene/polyamide 6/layered silicate ternary nanocomposites

This work aims to investigate the structure–property relationship in ternary nanocomposites consisting of polypropylene as the matrix, nanoclay as the reinforcement and polyamide 6 as the intermediate phase. In this regard, composites of polypropylene/organoclay, polyamide/organoclay, blends of polypropylene/polyamide, and ternary nanocomposites of polypropylene/polyamide/layered silicate with and without compatibilizer were produced via melt compounding. Nanostructure was investigated by wide-angle X-ray diffraction and transmission electron microscopy. Scanning electron microscopy was employed to study the microstructure. Modulus of elasticity and yield strength were measured by uniaxial tensile test. Results show that silicate layers can only be observed inside polyamide particles. Moreover, polypropylene was unable to intercalate the grade of organoclay used in this study. While polyamide/organoclay system exhibited an exfoliated structure, the nanostructure of ternary nanocomposites was chiefly intercalated, due to the high concentration of silicate layers inside polyamide particles. Incorporation of organoclay into the polypropylene/polyamide system was seen to have a noticeable effect on the shape and size of polyamide particles. In addition, elastic modulus and yield strength were observed to be directly affected by incorporation of nanoclay and compatibilizer into the polypropylene matrix, respectively. The simultaneous presence of the two constituents in the system resulted in samples with superior mechanical properties in the elastic as well as the plastic deformation regime.     

Mechanical and thermal properties of carbon fiber/polypropylene composite filled with nano-clay

The effect of organoclay on the mechanical and thermal properties of woven carbon fiber (CF)/compatibilized polypropylene (PPc) composites is investigated. Polypropylene–organoclay hybrids nanocomposites were prepared using a maleic anhydride-modified PP oligomer (PP-g-MA) as a compatibilizer. Different weight percentages of Nanomer® I-30E nanoclay were dispersed in PP/PP-g-MA (PPc) using a melt mixing method. The PPc/organoclay nanocomposite was then used to manufacture plain woven CF/PPc nanocomposites using molding compression process. CF/PPc/organoclay composites were characterized by different techniques, namely; dynamic mechanical analysis (DMA), fracture toughness and scanning electron microscope. The results revealed that at filler content 3% of organoclay, initiation and propagation interlaminar fracture toughness in mode I were improved significantly by 64% and 67% respectively, which could be explained by SEM at given weight as well; SEM images showed that in front of the tip, fibers pull out during initiation delamination accounting for fracture toughness improvement. Dynamic mechanical analysis showed enhancement in thermomechanical properties. With addition 3 wt.% of organoclay, the glass transition temperature increased by about 6 °C compared to neat CF/PPc composite indicating better heat resistance with addition of organoclay.     

Clay exfoliation and organic modification on wear of nylon 6 nanocomposites processed by different routes

The role of nanoclay on the wear characteristics of nylon 6 nanocomposites processed via different routes is examined in this paper. Pristine clay and organoclay were used in melt-extrusion with the matrix resulting in a largely aggregated and a highly exfoliated morphology, respectively. High exfoliation of pristine clay was also achieved by a water-assist process in melt compounding. Nylon 6/pristine clay composite had the worst wear resistance due to the large aggregated clay particles. For the two nylon 6/exfoliated clay nanocomposites, the one with the organically modified clay outperformed that with the pristine clay exfoliated by water. Detailed study on the wear track and subsurface below of the nylon 6/clay composites using both transmission and scanning electron microscopy provided new insight into the differences in their deformation and damage mechanisms. It was revealed that the interfacial adhesion of clay to matrix, and not the exfoliated morphology of clay, played a critical role in wear. However, exfoliated clay morphology is preferred to aggregate morphology. Hence, the superior wear-performance of nylon 6/organoclay nanocomposite is brought about by a combined effect of fine dispersion of clay platelets in nylon 6, high interfacial interaction between nylon 6 and clay layers, and effective constraint on surrounding nylon 6 material exerted by the clay platelets.     

Mode I interlaminar fracture behavior and mechanical properties of CFRPs with nanoclay-filled epoxy matrix

The mechanical properties and fracture behavior of nanocomposites and carbon fiber composites (CFRPs) containing organoclay in the epoxy matrix have been investigated. Morphological studies using TEM and XRD revealed that the clay particles within the epoxy resin were intercalated or orderly exfoliated. The organoclay brought about a significant improvement in flexural modulus, especially in the first few wt% of loading, and the improvement of flexural modulus was at the expense of a reduction in flexural strength. The quasi-static fracture toughness increased, whereas the impact fracture toughness dropped sharply with increasing the clay content.Flexural properties of CFRPs containing organoclay modified epoxy matrix generally followed the trend similar to the epoxy nanocomposite although the variation was much smaller for the CFRPs. Both the initiation and propagation values of mode I interlaminar fracture toughness of CFRP composites increased with increasing clay concentration. In particular, the propagation fracture toughness almost doubled with 7 wt% clay loading. A strong correlation was established between the fracture toughness of organoclay-modified epoxy matrix and the CFRP composite interlaminar fracture toughness.     

Fracture mechanisms of epoxy-based ternary composites filled with rigid-soft particles

Epoxy composites filled with different amounts of aggregate-free silica nanoparticles and phase-separated submicron rubber particles were fabricated to study the synergistic effect of multi-phase particles on mechanical properties of the composites. Compared with binary composites with single-phase particles, the ternary composites with both rigid and soft particles offer a good balance in stiffness, strength and fracture toughness, showing capacities in tailoring the mechanical properties of modified epoxy resins. It was observed that debonding of silica nanoparticles from matrix in the ternary composites was less pronounced than that in the binary composites. Moreover, the rubber particles became smaller and their shape tends to be irregular, affected by the presence of rigid silica nanoparticles. The toughening mechanisms in the epoxy composites were evaluated, and the enlarged plastic deformation around the crack tip, induced by the combination of rigid and soft particles, seems to be a dominant factor in enhancing fracture toughness of the ternary composites.     

Cyclic fatigue of polymer nanocomposites

This paper presents an experimental study on cyclic fatigue of two polymer nanocomposites in two common failure modes: mechanical failure in epoxy nanocomposites and thermal softening in polyamide (PA, nylon) 6 nanocomposites. For epoxy nanocomposites, the effects of hard (silica) and soft (rubber) nano-particles on un-notched samples under constant cyclic stress amplitude fatigue were studied. Hard particles were shown to increase but soft particles decrease the fatigue life of nanocomposites compared to unmodified epoxy. At the same stress amplitude, the extent of fatigue crack growth prior to fast fracture was largest in rubber nanocomposites and least in pure epoxy, reflecting the differences in their fracture toughness values. Ternary nanocomposites with both hard and soft (silica and rubber) particles were also investigated and their fatigue performances were compared to the binary nanocomposites. Further, the stress (σ_a) versus life (N_r) test data of pure epoxy and its binary and ternary nanocomposites are well described by Basquin’s law.PA6 nanocomposites exhibited fatigue failure due to thermal softening when the maximum local temperature of the specimens subjected to cyclic loading reached the glass transition temperature, T_g, of the material. Critical stress (σ_a) versus frequency (ω) envelopes for design against thermal failure were obtained for PA6/organoclay, PA6/POE-g-MA and PA6/pristine clay. Experimental results compared favorably with theoretical predictions.     

Mechanical Behavior of Nanodiamond/Epoxy Nanocomposites

The mechanical properties of epoxy-based nanocomposites reinforced by nanodiamond (ND) particles were investigated. The results showed that while the addition of 0.1 wt% of ND improved the Young’s modulus and tensile strength compared with those of the pure epoxy, the mode I fracture toughness did not show any improvement. Furthermore, in order to study the effect of shear deformation on fracture properties of nanocomposites, mixed mode fracture resistance of nanocomposites was investigated. It was found that as the share of shear deformation in mixed mode loading increases, the positive effect of ND particles enhances.     

Toughening and reinforcement of poly(vinylidene fluoride) nanocomposites with “bud-branched” nanotubes

Bud-branched nanotubes, fabricated by growing metal particles on the surface of multi-wall carbon nanotubes (MWCNTs), were used to prepare poly(vinylidene fluoride) (PVDF) based nanocomposites. The results of differential scanning calorimetry (DSC) showed that the introduction of the MWCNTs and bud-branched nanotubes both increased the crystallization temperature, while no significant variation of T_m (melting temperature), ΔH_c (melting enthalpy) and ΔH_m (crystallization enthalpy) occurred. The results of wide angle X-ray diffraction (WAXD) tests showed that α-phase was the dominated phase for both pure PVDF and its nanocomposites, indicating the addition of the MWCNTs and bud-branched nanotubes did not alter the crystal structures. Dynamic mechanical analysis (DMA) tests showed that bud-branched nanotubes were much more efficient in increasing storage modulus than the smooth MWCNTs. In addition, no significant variation of the T_g (glass transition temperature) was observed with the addition of MWCNTs and bud-branched nanotubes. Tensile tests showed that the introduction of MWCNTs and bud-branched nanotubes increased the modulus. However, a dramatic decrease in the fracture toughness was observed for PVDF/MWCNTs nanocomposites. For PVDF/bud-branched nanotubes nanocomposites, a significant improvement in the fracture toughness was observed compared with PVDF/MWCNTs nanocomposites.     

尼龙1212/SEBS-g-MA/DIDP/BSBA共混体系的结晶行为

用W AXD、PLM及DSC研究了尼龙1212/SEBS-g-M A/D IDP/BSBA共混体系的结晶行为。W AXD结果显示,增韧剂的加入改变了尼龙1212的晶型。PLM观察表明共混体系中由于M A与尼龙之间的相互作用,增韧剂充当了成核剂,使得尼龙1212球晶向细晶化发展。用修正A vram i方程的Jez iorny法研究共混体系的非等温结晶动力学,发现共混体系的半结晶时间t1/2缩短,增韧剂对尼龙1212有明显的异相成核作用。     

Microstructures and toughening mechanisms of organoclay/polyethersulphone/epoxy hybrid nanocomposites

Hybrid nanocomposites (HNCs) with high fracture toughness were successfully prepared by incorporating polyethersulphone (PES) and organoclay into epoxy resin. Their microstructures were studied. They were composed of homogeneous PES/epoxy matrices and micron-scale organoclay agglomerates. These agglomerates consisted of smaller tactoid-like regions which were comprised of ordered exfoliated nanolayers. The toughening mechanisms of the two tougheners were also studied and then related to their microstructures. For one thing, the PES which was dissolved in the epoxy resin homogeneously improved the ductility of the epoxy resin and made it easier to deform. For another, the organoclay agglomerates induced crack front bowing, crack bridging, crack deflection, crack bifurcation and plastic deformation of the matrices on the micron-scale, respectively. These toughening processes were achieved by the ordered exfoliated nanolayers with various orientations, which debonded from the matrices, bridged the cracks and induced the plastic deformation of the matrices on the nanoscale.     

On fracture toughness of nano-particle modified epoxy

A systematic study on the effects of silica and rubber nano-particles on the fracture toughness behavior of epoxy was conducted. Mode I fracture toughness (G_IC) of binary silica/epoxy, binary rubber/epoxy and ternary silica/rubber/epoxy nanocomposites with different particle weight fractions was obtained by compact tension tests. It is found that G_IC of epoxy can be significantly increased by incorporating either rubber or silica nano-particles. However, hybrid nanocomposites do not display any “synergistic” effect on toughness. Microstructures before and after fracture testing were examined to understand the role of nano-particles on the toughening mechanisms.     

Effect of surfactant treatment on thermal stability and mechanical properties of CNT/polybenzoxazine nanocomposites

The mechanical and thermo-mechanical properties of polybenzoxazine nanocomposites containing multi-walled carbon nanotubes (MWCNTs) functionalized with surfactant are studied. The results are specifically compared with the corresponding properties of epoxy-based nanocomposites. The CNTs bring about significant improvements in flexural strength, flexural modulus, storage modulus and glass transition temperature, T_g, of CNT/polybenzoxazine nanocomposites at the expense of impact fracture toughness. The surfactant treatment has a beneficial effect on the improvement of these properties, except the impact toughness, through enhanced CNT dispersion and interfacial interaction. The former four properties are in general higher for the CNT/polybenzoxazine nanocomposites than the epoxy counterparts, and vice versa for the impact toughness. The addition of CNTs has an ameliorating effect of lowering the coefficient of thermal expansion (CTE) of polybenzoxazine nanocomposites in both the regions below and above T_g, whereas the reverse is true for the epoxy nanocomposites. This observation has a particular implication of exploiting the CNT/polybenzoxazine nanocomposites in applications requiring low shrinkage and accurate dimensional control.     

The effects of phase morphology and adhesion between phases on fracture of ethylene-vinylalcohol copolymer/nylon 6/12 copolymer blends

The effects of phase morphology and the adhesion between phases of ethylene-vinylalcohol copolymer(EVOH)/nylon 6/12 copolymer blends on the fracture properties were estimated. Films of the blends which were obtained by extrusion processing showed different phase morphologies depending on the composition of the nylon 6/12 copolymer. The morphology of the partially miscible blend (EVOH and nylon 6f-nylon121-f where f=0.8) was needle-like in appearance. On the other hand the immiscible blend (EVOH and nylon 6f-nylon121-f where f=0.5) had equiaxed particles of nylon 6/12. The plastic deformation of films of the blends was observed using transmission electron microscopy. Deformation zones were observed for both blends but extensive debonding of particle interfaces was observed in the immiscible blend system. These observations are reinforced by our measurements of the interfacial fracture energy, Gc, between EVOH and nylon 6f-nylon121-f made using a double cantilever beam test. Gc decreases monotonically as 1–f increases. The fracture toughness of the partially miscible blend film measured at low temperature (–80°C) was higher than that of EVOH alone and there was fractographic evidence of a larger crack tip plastic deformation zone. In contrast, the fracture toughness of the immiscible blend was lower than that of EVOH and there was fractographic evidence of extensive debonding of the second phase nylon particles. This result suggests that it is important to have good adhesion between phases to achieve the optimum fracture toughness of these polymer blends. © 1998 Chapman & Hall     

Reinforcement and toughening mechanisms in polymer nanocomposites – Carbon nanotubes and aluminum oxide

The addition of nanoparticles has been reported as an option to increase the fracture toughness of thermosetting polymers without compromising the stiffness. In this paper, alumina or carbon nanotubes (CNTs), in three different concentrations, were dispersed in an epoxy resin. Mechanical properties were measured through tensile test and the results indicate increases for all nanocomposites, with a maximum for the addition of 0.5% of CNTs (17% in elastic modulus and 22% in ultimate stress). Using TEM images, it was possible to identify the nanostructures and mechanisms that lead to improved stiffness. Fracture toughness tests and SEM images showed that cavitation – shear yielding (for epoxy/alumina nanocomposites) and crack bridging – pull-out (for epoxy/CNTs nanocomposites) are the predominant mechanisms.     

尼龙6/橡胶/天然粘土纳米复合材料的制备及其力学性能

采用一种新型的超细全硫化粉末橡胶/蒙脱土复合粉末(UFPRM),可以制备出剥离型的尼龙6/橡胶/天然粘土(尼龙6/UFPRM)纳米复合材料,所用的橡胶是一种具有特殊结构的超细全硫化粉末橡胶(UFPR).微观分析表明,橡胶粒子在尼龙6基体中分散良好,同时天然粘土在橡胶粒子之间的基体中剥离.在一定份数下,复合粉末可以同时提高尼龙6的韧性、刚性及耐热性;随着复合粉末含量的增加,材料的冲击强度进一步增加.而且,复合粉末对高分子量尼龙6的增强、增韧效果好于低分子量尼龙6.进一步研究发现,在适当的剪切速率下,尼龙6/橡胶/天然粘土纳米复合材料可以获得较好的综合力学性能.     

Morphology,rheology and mechanical properties of polypropylene/ethylene–octene copolymer/clay nanocomposites: Effects of the compatibilizer

The objective of this study was to investigate the effects of two compatibilizers, namely maleated polypropylene (PP-g-MA) and maleic anhydride grafted poly (ethylene-co-octene) (EOC-g-MA), on the morphology and thus properties of ternary nanocomposites of polypropylene (PP)/ethylene–octene copolymer (EOC)/clay nanocomposite. In this regard the nanocomposites and their neat polymer blend counterparts were processed twice using a twin screw extruder. X-ray diffraction, transmission electron microscopy, Energy dispersive X-ray spectroscopy, and scanning electron microscopy were utilized to characterize nanostructure and microstructure besides mechanical and rheological behaviors of the nanocomposites. Clay with intercalated structure was observed in EOC phase of the PP/EOC/clay nanocomposite. Better dispersion state of the intercalated clay in EOC phase was observed by adding EOC-g-MA as a compatibilizer. On the other hand, adding PP-g-MA resulted in migration of the intercalated clay from the EOC to the PP and to the interface regions. It was also demonstrated that the elastomer particles became smaller in size where clay was present. The finest and the most uniform morphology was found in the PP/EOC/clay nanocomposite. In addition, the rheological results illustrated a higher complex viscosity and storage modulus for PP/EOC/PP-g-MA/clay nanocomposite in which clay particles were present in the matrix. Mechanical assessments showed improvements in the toughness of the nanocomposites with respect to their neat blends, without significant change in stiffness and tensile strength values. These results highlight a toughening role of clay in the polymer blend nanocomposites studied.     

Effect of processing parameters and clay volume fraction on the mechanical properties of epoxy-clay nanocomposites

The influence of processing parameters and particle volume fraction was experimentally studied for epoxy clay nanocomposites. Nanocomposites were prepared using onium ion surface modified montmorillonite (MMT) layered clay and epoxy resin (DEGBF). Two different techniques were used for dispersing the clay particles in the epoxy matrix, viz. high-speed shear dispersion and ultrasonic disruption. The volume fraction of clay particles was systematically varied from 0.5 to 6%, and mechanical properties, viz. flexural modulus and fracture toughness, were studied as a function of clay volume fraction and the processing technique. The flexural modulus was observed to increase monotonously with increase in volume fraction of clay particles, while, the fracture toughness showed an initial increase on addition of clay particles, but a subsequent decrease at higher clay volume fractions. In general, nanocomposites processed by shear mixing exhibited better mechanical properties as compared to those processed by ultrasonication. Investigation by X-ray diffraction (XRD) revealed exfoliated clay structure in most of the nanocomposites that were fabricated. Morphologies of the fracture surfaces of nanocomposites were studied using a scanning electron microscopy (SEM). Presence of river markings at low clay volume fractions provided evidence of extrinsic toughening taking place in an otherwise brittle epoxy.