Micro- and nano-scale deformation behavior of nylon 66-based binary and ternary nanocomposites

The primary aim of this paper is to provide an insight on the effect of the location of organoclay on the micro- and nano-scale deformation processes in melt-compounded nylon 66/organoclay/SEBS-g-MA ternary nanocomposites prepared by different blending sequences. In addition, the deformation processes of the ternary nanocomposites were compared to the binary nanocomposites (nylon 66/organoclay and nylon 66/SEBS-g-MA) and neat nylon 66. The incorporation of SEBS-g-MA particles toughened nylon 66 markedly; but the flexural modulus and strength were both reduced. Conversely, the use of organoclay increased the modulus but decreased the fracture toughness of nylon 66. Nylon 66/SEBS-g-MA/organoclay ternary nanocomposites exhibited balanced elastic stiffness and toughness. Stress-whitening studies of the fracture surfaces in terms of gray level were also performed and an attempt was made to correlate the optical reflectivity characteristics with fracture toughness. It was concluded that the capability of SEBS-g-MA particles to cavitate was decreased by the presence of organoclay in the SEBS-g-MA phase, resulting in reduced toughening efficiency. The best micro-structure for toughness and other mechanical properties is thus to maximize the amount of exfoliated organoclay in the nylon 66 matrix rather than to have it embedded in the finely dispersed SEBS-g-MA particles.     

Effect of nanoclay and SEBS-g-MA on the morphology and properties of immiscible poly(methyl methacrylate)/polystyrene blend

In recent years, nanoclays are being used as compatibilizer for various immiscible polymer blends. However, little work has been done on the morphology of immiscible polymer blends in presence of both the nanoclay and a reactive compatibilizer. Here, we report the synergistic effect of nanoclay and SEBS-g-MA on the morphology and properties of (70/30 w/w) PMMA/PS blend. Scanning electron microscopy study of the blend with various amount of nanoclay and SEBS-g-MA indicated a reduction in the average domain sizes (D) of dispersed PS phase in PMMA matrix compared to that in the pure blend. Addition of both SEBS-g-MA and nanoclay significantly lowered the D of PS in the blend compared to that with only SEBS-g-MA or clay. X-ray diffraction study and transmission electron microscopy revealed the presence of intercalated clay platelets in PMMA matrix, as well as, at the interface of the (70/30 w/w) PMMA/PS blend-clay nanocomposites. Addition of SEBS-g-MA in the blend-clay nanocomposites promoted the exfoliation of clays in PMMA matrix. Thus, exfoliated clay platelets in PMMA matrix effectively restricted the coalescence of dispersed PS domains while SEBS-g-MA improved the adhesion between the phases at the interface. At certain loading (phr), storage modulus, elongation at break and thermal stability of the blend were greatly improved when both the nanoclay and SEBS-g-MA were present in the blend. The use of reactive compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites.     

Influence of morphology on the dynamic mechanical characteristics of PP-EP/EVA/organoclay nanocomposites

A study on the dynamic mechanical properties of polypropylene copolymer/ethylene–vinyl acetate/organoclay (PP-EP/EVA/C20A) nanocomposites is presented. Nanocomposites were obtained by melt blending. Morphology consisting of intercalated–exfoliated clay nanolayers preferentially located within the EVA phase was observed by transmission electron microscopy (TEM) and wide angle X-ray diffraction (WAXD). Polar groups of vinyl acetate in the EVA facilitated the polymer–clay interactions. Changes in the glass transition temperature (T_g) were correlated with changes in the clay intercalation–exfoliation levels. The highly reinforced with intercalated–exfoliated clay layers EVA phase was considered as the origin of the improvement on mechanical properties of the ternary nanocomposites and is associated with the increase on viscosity, heat deflection temperature (HDT), and storage modulus.     

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.     

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.     

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.     

Polyethylene organo-clay nanocomposites: the role of the interface chemistry on the extent of clay intercalation/exfoliation

High density polyethylene (HDPE)/clay nanocomposites have been prepared using three different functionalized polyethylene compatibilizers: an ethylene/vinyl acetate copolymer, a polyethylene grafted with maleic anhydride functions and a (styrene-b-ethylene/butylene-b-styrene) block copolymer. The nanocomposites were prepared via two different routes: (1) the dispersion in HDPE of a masterbatch prepared from the compatibilizer and the clay or (2) the direct melt blending of the three components. For each compatibilizer, essentially intercalated nanocomposites were formed as determined by X-ray diffraction and transmission electron microscopy. With the ethylene/vinyl acetate copolymer, a significant delamination of the intercalated clay in thin stacks was observed. This dispersion of thin intercalated stacks within the polymer matrix allowed increasing significantly the stiffness and the flame resistance of the nanocomposite. A positive effect of shear rate and blending time has also been put into evidence, especially for the process based on the masterbatch preparation, improving both the formation of thin stacks of intercalated clay and the mechanical properties and the flame resistance of the formed nanocomposites.     

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.     

Structure and mechanical properties of polycarbonate modified clay nanocomposites

Polycarbonate (PC)/modified clay nanocomposites were prepared, in the absence and presence of different amounts of maleic anhydride grafted polypropylene (PP-g-MA), by direct melt blending. Their structures, as well as mechanical, morphological and thermal properties, were characterized by X-ray diffractometry (XRD), tensile testing, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The XRD results of the PC/clay nanocomposites showed that they had intercalated structures, although some exfoliation was visible at low clay contents, that the gallery heights of the PC/clay nanocomposites were almost the same, and that some of the clay layers collapsed as a result of modifier decomposition at the high processing temperature. The XRD patterns of the PC/PP-g-MA/clay nanocomposites clearly show less intercalation and more exfoliation with increasing PP-g-MA content. These results were supported by TEM observations. Both the tensile strength and modulus show substantial improvements with both increasing clay and PP-g-MA contents, while the elongation at break substantially decreases, although the presence of PP-g-MA somewhat improves these values. All the nanocomposites have lower thermal stability than pure PC, but the presence of PP-g-MA seems to improve the thermal stability of these samples.     

PLA/I.34TCN纳米复合材料的制备及其性能研究

将改性纳米黏土I.34TCN与聚乳酸(PLA)经过二次熔融混合制备了PLA/I.34TCN纳米复合材料。TEM表征结果显示,较高的黏土剥离程度提高了黏土在PLA中的分散性,使两相之间的界面作用力增强,同时可以使两相之间具有较大的界面增塑区;DSC表征结果显示,剥离型纳米黏土对纳米复合材料起到了结晶成核剂的作用,提高了纳米复合材料的结晶度。上述两方面的原因综合改善了纳米复合材料的力学性能,当黏土质量分数为2%时,PLA/I.34TCN纳米复合材料中黏土的剥离程度最高,使得该纳米复合材料的断裂伸长率显著提高,最多可提高101.00%,是纯PLA的18倍。TG表征结果发现,纳米复合材料的热稳定性能随I.34TCN含量的增加而逐渐增加。     

Embrittlement Mechanisms of Nylon 66/Organoclay Nanocomposites Prepared by Melt-Compounding Process

Nylon 66 nanocomposites with different smectite clay loadings were prepared by conventional melt compounding process. The fracture toughness decreases with increasing clay content, which is a direct result of reduced plastic zone size at the crack tip region. The fracture mechanisms were studied using double-notched four-point-bending (DN-4PB) technique. A constraining effect from nanoclay fillers on plastic deformation of matrix is revealed by transmission electron microscopy (TEM). Micron-sized and submicron voids could be observed around the clay platelets. The voids coalesce and form premature cracks that promote crack propagation, thus reducing toughness.     

Migration of Aluminum and Silicon from PET/Clay Nanocomposite Bottles into Acidic Food Simulant

Poly(ethylene terephthalate) (PET)/clay nanocomposite samples were prepared by melt blending PET and Cloisite 20A nanoparticles. A stretch blow‐moulding machine was used to produce bottles from neat PET and PET nanocomposite. Tests were performed on the migration of aluminum and silicon from PET nanocomposite bottles into acidic food simulant. The samples were stored at room temperature (about 25°C) and 45°C for time durations ranging from 7 to 90 days. A specific surface of sheets (prepared from PET/clay nanocomposite) immersed in acidic food simulant, and two‐sided migration of Al and Si was investigated. According to X‐ray diffraction analysis, the nanoclays show intercalated structure in the PET matrix. Transmission electron microscopy and atomic force microscopy micrographs displayed both intercalation and exfoliation morphology for PET/clay nanocomposites. Inductively coupled plasma was used to quantify amounts of Al and Si that had migrated into the acidic food simulant. It was observed that the migration process is dependent on storage time and temperature, and the molar ratio of aluminum and silicon in the acidic aqueous solution (Al/Si)_aq to the ratio in the solid phase of prepared nanocomposites (Al/Si)_solid was about 23% higher in the samples stored at 45°C. Copyright © 2013 John Wiley & Sons, Ltd.     

共插层剂改性蒙脱土制备尼龙1010/蒙脱土纳米复合材料

以间甲酚(MC)、尼龙66盐(NS)分别与十六烷基三甲基溴化铵(CTAB)共插层改性蒙脱土，制备了尼龙1010／蒙脱土纳米复合材料。TG和WAXD实验结果表明，采用共插层剂改性的蒙脱土的片层间距显著增大，且热分解温度较高；蒙脱土的引入改善了尼龙1010的拉伸性能、弯曲性能和热变形温度，冲击韧性基本保持；蒙脱土的加入可能改变了尼龙1010的结晶结构，且使尼龙1010的结晶温度升高。共插层剂两组分所起的作用不同，CTAB的插入有利于蒙脱土片层间距的扩开，MC和NS则起到了界面相容剂的作用．有利于基体树脂与蒙脱土片层的复合。     

Preparation and characterization of poly (styrene-acrylonitrile) (SAN)/clay nanocomposites by melt intercalation

Poly (styrene-acrylonitrile) (SAN)/clay nanocomposites have been prepared by melt intercalation method from pristine montmorillonite (MMT), using hexadecyl trimethyl ammonium bromide (C16) and hexadecyl triphenyl phosphonium bromide (P16) as the reactive compatibilizers between polymer and clay. The influence of the reactive compatibilizers proportion relative to the clay on the structure and properties of the SAN/clay nanocomposites is investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM), high-resolution electron microscopy (HREM), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The effects of the two different clays (MMT and organic modified MMT) on the nanocomposites formation, morphology and property are also studied. The results indicate that the SAN cannot intercalate into the interlayers of the MMT and results in microcomposites. In the presence of the reactive compatibilizers, the dispersion of clay in SAN is rather facile and the SAN/clay nanocomposites reveal an intermediate morphology, an intercalated structure with some exfoliation and the presence of small tactoids. The appropriate proportion with 3 wt% reactive compatibilizers to 5 wt% MMT induces well-dispersed morphology and properties in the SAN matrix. The TGA analyses show that the thermal stability properties of the SAN/clay nanocomposites have been improved compared with those of the pristine SAN. The DMA results show that the storage modulus and glass transition temperature (Tg) of the SAN/clay nanocomposites have remarkably enhancements compared with the pristine SAN. At last the intercalation mechanism of the technology is discussed.     

Preparation and properties of nitrile rubber/montmorillonite nanocomposites via latex blending

The nitrile rubber (NBR)/unmodified montmorillonite (Na-MMT) clay nanocomposites were prepared by latex blending method followed by melt mixing of compounding ingredients by using two-roll mill. The X-ray diffraction (XRD) studies showed an increase in the basal spacing and broadening of peak corresponding to crystal structure of Na-MMT indicating the formation of intercalated/exfoliated clay layers in the NBR matrix. Increase in clay content of nanocomposite increased the XRD peak height due to the formation of many of clay tactoids at higher loading. The transmission electron microscopy (TEM) strengthened the XRD finding by showing the presence of intercalated/exfoliated morphology of clay platelets having good dispersion. The modulus and tensile properties of the nanocomposites were improved with addition of Na-MMT which is proportional to clay concentration. The retention of tensile properties of aged nanocomposites, with all clay concentration, was superior to either pure NBR and carbon black filled NBR composite. The dynamic mechanical analysis showed proportional increase in storage modulus analogous to Na-MMT loading at all the temperature ranges due to the confinement of polymer chains between the clay layers. Nanocomposites with different proportions of clay showed a decrease in tan δ_max peak height with a shift towards higher temperature indicating the reduction in the segmental mobility of polymer chain. A linear model was proposed to correlate the influence of Na-MMT content on storage modulus of nanocomposites. Differential scanning calorimetry indicated a linear increase in glass transition of nanocomposites which is proportional to clay loading. Thermogravimetric analysis revealed a small improvement in the thermal stability of nitrile rubber/clay nanocomposites.     

Microstructure and mechanical properties of epoxy hybrid nanocomposites modified with acrylic tri-block-copolymer and layered-silicate nanoclay

In this study, processing, morphology and mechanical properties of acrylic tri-block-copolymer and organophilic layered-silicate nanoclay modified epoxy hybrid nanocomposites were investigated. The acrylic tri-block-copolymer preferentially self-assembled into spherical micelles in the epoxy matrix, and predominantly intercalated and few exfoliated platelets were observed with nanoclay. Three-phase ternary nanocomposites showed coexistence of both intercalated nanoclay and nanostructured block-copolymer in epoxy. Experimental results revealed that the block-copolymer significantly enhanced fracture toughness. Increased toughness of epoxy coincided with a reduction of tensile stiffness and strength. The nanoclay filled nanocomposites exhibited superior stiffness and slight improvement in tensile strength while compromising ductility. Optimum property enhancement was observed in the case of epoxy hybrid nanocomposites. Mechanical properties of the hybrid nanocomposites depend on microstructure, dispersion state and the ratio between organic and inorganic nanofiller contents.     

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。     

Carbon Nanotube Pullout,Interfacial Properties,and Toughening in Ceramic Nanocomposites: Mechanistic Insights from Single Fiber Pullout Analysis

While debonding and subsequent pullout at fiber‐matrix interfaces can improve fracture toughness in ceramic nanocomposites, the magnitudes of these contributions are currently the subject of ongoing debate. To provide quantitative insight into these mechanisms, ceramic matrix nanocomposites were fabricated with a polymer‐derived ceramic matrix, using multiwalled carbon nanotubes (MWCNTs) that exhibit relatively long pullout lengths. In situ micromechanical pullout tests on individual MWCNTs were used to directly measure the strength of the fiber‐matrix interface. Similar pullout lengths were also observed in bulk and thin film composites, where the fracture toughness of the composite films was measured and found to be higher than that of the matrix material. The interfacial properties from the micromechanical test and the pullout lengths from the composite films were then used to estimate the energy release rates for fiber debonding and pullout. Based on the observed MWCNT and composite failure mechanisms, these results are discussed in terms of their relation to previous estimates of toughening in MWCNT‐ceramic nanocomposites, and in terms of design possibilities for further fracture toughness improvements.     

Blends and clay nanocomposites of cellulose acetate and poly(epichlorohydrin)

The aim of this work was to investigate cellulose acetate/poly(epichlorohydrin) (CA/PEPi) blends and cellulose acetate/poly(epichlorohydrin)/organically modified montmorillonite clay nanocomposites (CA/PEPi/MMTO) prepared by melt processing in a twin-screw extruder. The combination of an elastomer and clay in the cellulose acetate matrix was an attempt made to reach a balance between toughness and strength properties. The blend and nanocomposite structure, morphology and thermal properties were investigated by small angle X-ray scattering, transmission electron microscopy and dynamical mechanical analysis. The results showed immiscibility of the polymer components for all the CA/PEPi blend composition range investigated. In the case of the nanocomposites, the results indicated a significant polymer intercalation in the clay gallery as well as the exfoliation of the silicate layers. Moreover, the organoclay was present in the CA phase, but some of the organoclay migrated to the CA/PEPi interface and tended to surround the PEPi phase. The addition of PEPi elastomer to cellulose acetate showed a significant increase in the blend impact resistance. However the combination of PEPi and MMTO did not in fact produce a good stiffness versus toughness balance.     

Morphological, rheological and mechanical characterization of polypropylene nanocomposite blends

In the present work, the effectiveness of styrene/ethylene-butylene/styrene rubbers grafted with maleic anhydride (MA) and a metallocene polyethylene (mPE) as toughening materials in binary and ternary blends with polypropylene and its nanocomposite as continuous phases was evaluated in terms of transmission electron microscopy (TEM), scanning electron microscopy (SEM), oscillatory shear flow and dynamic mechanical thermal analysis (DMA). The flexural modulus and heat distortion temperature values were determined as well. A metallocene polyethylene and a polyamide-6 were used as dispersed phases in these binary and ternary blends produced via melt blending in a corotating twin-screw extruder. Results showed that the compatibilized blends prepared without clay are tougher than those prepared with the nanocomposite of PP as the matrix phase and no significant changes in shear viscosity, melt elasticity, flexural or storage moduli and heat distortion temperature values were observed between them. However, the binary blend with a nanocomposite of PP as matrix and metallocene polyethylene phase exhibited better toughness, lower shear viscosity, flexural modulus, and heat distortion temperature values than that prepared with polyamide-6 as dispersed phase. These results are related to the degree of clay dispersion in the PP and to the type of morphology developed in the different blends.