Investigation on the competing effects of clay dispersion and matrix plasticisation for polypropylene/clay nanocomposites. Part I: morphology and mechanical properties

The key compatibiliser role of maleated polypropylene (MAPP) to improve the clay dispersability has been explicitly addressed in the fabrication process and material characterisation of polypropylene (PP)/clay nanocomposites. However, its matrix plasticiser role, which has been rarely mentioned, could adversely influence the excellent mechanical properties of such nanocomposites, resulting from the homogeneous clay dispersion. PP/clay nanocomposites in the presence of MAPP were prepared by twin screw extrusion and subsequently injection moulded with three typical material formulations in fixed parametric settings: (1) weight ratio (WR) of clay and MAPP, WR = 1:2; (2) MAPP content of 6 wt% and (3) clay content of 5 wt%. The morphological structures and mechanical properties of PP/clay nanocomposites were examined by using X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and universal mechanical testing. The further improvement of mechanical properties was evidently hindered with very inconsiderable alteration of morphological structures in terms of the clay dispersion level. This observation could be ascribed to the change of MAPP role from a compatibiliser to a plasticiser because of its excessive amount used above a certain saturation level, which was found in the range of 3–6 wt% in MAPP contents for the enhancements of tensile and flexural properties of PP/clay nanocomposites.     

Fracture mechanisms of poly(ethylene terephthalate) and blends with styrene-butadiene-styrene elastomers

Poly(ethylene terephthalate) (PET) was blended with 5 wt % of an elastomeric block copolymer. The hydrogenated styrene-butadiene-styrene (SEBS) elastomers were functionalized with 0–4.5 wt % maleic anhydride grafted on the midblock. Notched tensile tests in the temperature range − 40–55 °C differentiated among the blends in terms of their toughness. The least effective elastomer was the unfunctionalized SEBS; all the functionalized SEBS elastomers effectively increased the toughness of PET. Fractographic analysis indicated that PET and the blend with unfunctionalized SEBS fractured through a pre-existing craze. Although adhesion of the unfunctionalized SEBS to the matrix was poor, the elastomer strengthened the craze somewhat, as indicated by an increase in length of the pre-existing craze when final separation occurred. A functionalized SEBS caused the fracture mechanism to change from crazing to ductile yielding. Graft copolymer formed by reaction of PET hydroxyl end groups with the anhydride in situ was thought to act as an emulsifier to decrease particle size and improve adhesion. These factors promoted cavitation, which relieved the triaxiality at the notch root and permitted the matrix to shear yield. This revised version was published online in November 2006 with corrections to the Cover Date.     

Investigation of physical and chemical properties of polypropylene hybrid nanocomposites

Hybrid nanocomposites fabricated based on an optimized physical and chemical properties modified polypropylene (PP)/polypropylene grafted maleic anhydride (PP-g-MA) with varied concentrations (1–7 wt% at a step of 2 wt%) of organoclay, montmorillonite (MMT). The morphology of the nanocomposites was studied by scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). It was found that partly intercalated and partly exfoliated structure (intercalated–exfoliated structures) existed in the system. The degree of exfoliation is a key factor to determine the reinforcement efficiency. The ratio of exfoliation to intercalation plays an important role in determining the properties of PP nanocomposites and only completely exfoliated silicate layers can significantly improve the properties. PP hybrid nanocomposites showed good thermal stability in the thermogravimetric analysis (TGA). Introduction of ∼3% MMT in the nanocomposites increased the onset temperature of degradation by 27.5 °C compared to that of pure PP, while the 5 wt% MMT resulted the maximum hardness in these nanocomposites. The solvent resistance of PP hybrid nanocomposites slightly increased with increasing the clay content.     

Polymer–clay nanocomposites via chemical grafting of polyacrylonitrile onto cloisite 20A

The synthesis and characterization of polyacrylonitrile (PAN) nanocomposites through grafting the polymer onto organophilic montmorillonite have been reported. Cloisite 20A reacted with vinyltrichlorosilane to replace the edge hydroxyl groups of the clay with a vinyl moiety. Because the reaction liberates HCl, it was performed in the presence of sodium hydrogen carbonate to prevent the exchange of quaternary alkylammonium cations with H^?+? ions. Only the silanol groups on the edge of the clay reacted with vinyltrichlorosilane. The radical polymerization of the product with acrylonitrile (AN) as a vinyl monomer leads to chemical grafting of polyacrylonitrile onto montmorillonite surface. The homopolymer formed during polymerization was separated from the grafted organoclay by Soxhlet extraction. Chemical grafting of the polymer onto Cloisite 20A was confirmed by infrared spectroscopy. The prepared nanocomposite materials and grafted nanoparticles were studied by XRD and TEM. Exfoliated nanocomposites were obtained for 0·5–7 wt% clay content. The nanocomposites were studied by thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMTA).     

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.     

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.     

Melt mixed compatibilized polypropylene/clay nanocomposites: Part 1 – the effect of compatibilizers on optical transmittance and mechanical properties

Polypropylene (PP)/clay nanocomposites were prepared via a melt mixing technique. Two types of compatibilizers, polyolefin elastomer grafted maleic anhydride (POE-g-MA), and polypropylene grafted maleic anhydride (PP-g-MA) were incorporated to improve the dispersion of commercial organoclay (20A). With the introduction of PP-g-MA, the optical transmittance of the nanocomposites displayed higher transmittance than those of the POE-g-MA compatibilized case. However, POE-g-MA greatly increased the interlayer spacing of the clay compared with PP-g-MA. This interesting observation is pertinent to the complex morphology of compatibilized nanocomposites. The PP-g-MA compatibilized system conferred higher tensile strength, Young’s modulus, and cutting strength than the POE-g-MA compatibilized case. The high cutting strength of the PP/clay nanocomposites, with or without compatibilizers, signified the importance of crystalline yielding even in the nano-fracture zone of deformation. This finding has not been published in the literature of this field. Clay and its dispersion effect that conventionally claimed to enhance the tensile properties were rather insignificant under this condition of confined deformation of the cutting design. The current results suggest that a high extent of exfoliation may not guarantee high transparency or strength for nanocomposites. The matrix properties and interphase whose variations were caused by the additional compatibilizers to aid the clay dispersion were also crucial factors to the derived properties.     

Polypropylene-blended organoclay nanocomposites – preparation,characterisation and properties

Intercalated/exfoliated nanocomposites of thermoplastic polyolefin (TPO) blended nanoclay (Cloisite 20?A and Cloisite 30B) were fabricated using melt extrusion process. Polypropylene grafted maleic anhydride (PP-g-MA) was used as a compatibiliser to improve the dispersibility of clay. TPO/nanoclay composites were prepared with different percentages of clay loading (3, 5 and 7?wt%) by adding PP-g-MA as a compatibiliser. The nanocomposites having 5?wt%C20A/5?wt% compatibiliser exhibited a remarkable improvement in mechanical (tensile modulus, flexural modulus and impact strength) and thermal (heat distortion temperature, HDT) properties. The thermal measurements have been carried out by differential scanning calorimetry, thermogravimetric analysis and HDT methods. Dynamic mechanical analysis studies indicated that PP macromolecules were intercalated or exfoliated between the interlayer of silicates. The morphology of nanocomposites was characterised by scanning electron microscopy (SEM) and X-ray diffraction (XRD) was used to find out the arrangement of crystals in the nanocomposites. The SEM and XRD clearly demonstrated the progressive break up of particles and results in decreased particle size with the optimised combination.     

马来酸酐接枝聚丙烯的分子结构及反应机理

简要综述了马来酸酐接枝聚丙烯的研究进展,并重点介绍接枝产物的分子结构、反应机理以及存在的问题．     

HDPE-g-MAH-St/SMA-MMT纳米复合材料的制备与表征

采用反应挤出的方式,首先对非极性的高密度聚乙烯进行共接枝改性,得到聚乙烯的接枝物;采用溶液本体聚合法将马来酸酐和苯乙烯在蒙脱土丙酮混合浊液中共聚,制得SM A/MM T核/壳复合改性材料。然后将其与改性后的HDPE熔融插层,得到分散效果良好的纳米复合材料。用FT-IR对接枝物进行了验证,并用XRD,TEM对复合体系的插层效果进行了分析和表征,用DSC对其结晶性能进行了研究。     

Synthesis,characteristic, and flammability of modified carbon nanotube/poly(ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate) nanocomposites containing phosphorus and silicon

A novel flame retardant containing phosphorus–silicon, spirocyclic pentaerythritol bisphosphorate disphosphorylchloride/9,10-dihydro-9-oxa-10-phosphaphanthrene-10-oxide/vinyl methyl dimethoxysilane (SPDV), has been used to modify multiwalled carbon nanotubes (MWNTs) and the m-MWNTs (MWNTs-g-SPDV) was obtained by the covalent grafting of SPDV onto the surfaces of MWNTs. And then the according poly(ethylene-co-vinyl acetate) nanocomposites were prepared via melt blending. Transmission electron microscopy (TEM) results showed that a core–shell nanostructure with MWNTs as the hard core and SPDV as the soft shell was formed, and the resultant m-MWNTs can achieve better dispersion than pristine MWNTs in EVM matrix. Cone calorimeter results showed that better flame retardancy was obtained for EVM/m-MWNTs nanocomposites. Mechanical measurements showed that the Young’s modulus increases due to the presence of MWNTs or m-MWNTs. The flammability and mechanical properties of the nanocomposites are strongly dependent on the dispersion state of nanotubes.     

Structure-property relationship of specialty elastomer-clay nanocomposites

The present work deals with the synthesis of specialty elastomer [fluoroelastomer and poly (styrene-b-ethylene-co-butylene-b-styrene (SEBS)]-clay nanocomposites and their structure-property relationship as elucidated from morphology studies by atomic force microscopy, transmission electron microscopy and X-ray diffraction and physico-mechanical properties. Due to polarity match, hydrophilic unmodified montmorillonite clay showed enhanced properties in resulting fluoroelastomer nanocomposites, while hydrophobic organo-clay showed best results in SEBS nanocomposites.     

Carbon black–clay hybrid nanocomposites based upon EPDM elastomer

The present study explored the effect of nanoclay on the properties of the ethylene–propylene–diene rubber (EPDM)/carbon black (CB) composites. The nanocomposites were prepared with 40 wt% loading of fillers, where the nanoclay percentage was kept constant at 3 wt%. As the modified nanoclay contains the polar groups and the EPDM matrix is nonpolar, a polar rubber oil extended carboxylated styrene butadiene rubber (XSBR), was used during the preparation of nanocomposites to improve the compatibility. Primarily the nanoclay was dispersed in XSBR by solution mixing followed by ultrasonication. After that EPDM-based, CB–clay hybrid nanocomposites, were prepared in a laboratory scale two roll mill. The dispersion of the different nanoclay in the EPDM matrix was observed by wide-angle X-ray diffraction (WAXD) and high resolution transmission electron microscopy. It was found that the mechanical properties of the hybrid nanocomposites were highly influenced by the dispersion and exfoliation of the nanoclays in the EPDM matrix. Thermo gravimetric analysis, scanning electron microscopy and dynamic mechanical thermal analysis was carried out for each nanocomposite. Among all the nanocomposites studied, the thermal and mechanical properties of Cloisite 30B filled EPDM/CB nanocomposite were found to be highest.     

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.     

Preparation and characterization of poly(methyl methacrylate)-clay nanocomposites via melt intercalation: Effect of organoclay on thermal, mechanical and flammability properties

The PMMA nanocomposites were prepared by melt processing method. The influence of organoclay loading on extent of intercalation, thermal, mechanical and flammability properties of poly(methyl methacrylate) (PMMA)-clay nanocomposites were studied. Three different organoclay modifiers with varying hydrophobicity (single tallow vs. ditallow) were investigated. The nanocomposites were characterized by using wide angle X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), and tensile tests. The intercalation of polymer chain within the silicate galleries was confirmed by WAXD and TEM. Mechanical properties such as tensile modulus (E), tensile strength, percentage elongation at break and impact strength were determined for nanocomposites at various clay loadings. Overall thermal stability of nanocomposites increased by 16-17 °C. The enhancement in T_g of nanocomposite is merely by 2-4 °C. The incorporation of maleic anhydride as compatibilizer further enhanced all the properties indicating improved interface between PMMA and clay. The flammability characteristics were studied by determining the rate of burning and LOI.     

Facile synthesis and application of Ag-chemically converted graphene nanocomposite

An in situ chemical synthesis approach has been employed to prepare an Ag-chemically converted graphene (CCG) nanocomposite. The reduction of graphene oxide sheets was accompanied by generation of Ag nanoparticles. The structure and composition of the nanocomposites were confirmed by means of transmission electron microscopy (TEM), atomic force microscopy (AFM) and X-ray diffraction. TEM and AFM results suggest a homogeneous distribution of Ag nanoparticles (5–10 nm in size) on CCG sheets. The intensities of the Raman signals of CCG in such nanocomposites are greatly increased by the attached silver nanoparticles, i.e., there is surface-enhanced Raman scattering activity. In addition, it was found that the antibacterial activity of free Ag nanoparticles is retained in the nanocomposites, which suggests they can be used as graphene-based biomaterials.      

Investigation on the competing effects of clay dispersion and matrix plasticisation for polypropylene/clay nanocomposites. Part II: crystalline structure and thermo-mechanical behaviour

In view of the structure–property relationship, the mechanical property enhancement of polypropylene (PP)/clay nanocomposites can also be associated with the alterations of their crystalline structures and behaviour in addition to the general interpretation of intercalation/exfoliation level and uniform dispersion of more rigid clay platelets with higher aspect ratios in the PP matrix. Wide-angle X-ray diffraction (WAXD) was utilised to evaluate the effects of clay content, maleated PP (MAPP) content (MAPP as the compatibiliser) on PP crystalline structures of nanocomposites. Furthermore, the melting and crystallisation behaviour of PP/clay nanocomposites was also investigated by conducting differential scanning calorimetry (DSC). The thermo-mechanical properties were characterised via dynamic mechanical thermal analysis (DMTA). It is observed that enhancement of mechanical properties are mainly affected by the preferred orientation of PP crystals, the growth of α-PP phase and effective nucleating agent role of additional clay while the excessive amount of MAPP becomes detrimental to these crucial aspects, which is also evidently revealed in DMTA measurements.     

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.     

接枝马来酸酐对聚乙烯板缝隙液体渗流的影响

用马来酸酐对聚乙烯（PE）进行接枝,制得马来酸酐接枝聚乙烯（PE-g-MAH）,进而制备2组PE板缝隙渗流装置和2组PE-g-MAH板缝隙渗流装置。以蒸馏水和丁酸辛酯为流体,计量各缝隙渗流装置的渗流速度,研究接枝马来酸酐对聚乙烯板缝隙的液体渗流的影响。实验表明;当丁酸辛酯渗流时,接枝马采酸酐对PE板缝隙渗流装置的液体渗流的影响不大,而蒸馏水渗流时,由于马来酸酐基团在界面的富集,降低了水和PE的界面张力。接枝马来酸酐明显地提高了PE板渗流装置液体渗流的速度。     

Effect of elastomer interfacial agents on tensile and impact properties of CaCO3 filled HDPE

This work focuses on the modification of the tensile yield strength of CaCO3 filled HDPE brought about by the incorporation of SEBS elastomers. Two types of SEBS elastomers were used, grafted and ungrafted with maleic anhydride functions. The grafted elastomer encapsulates the filler particles in-situ and creates an adhesive interphase. The tensile yield stress was increased with increasing content of grafted elastomer until a maximum value. The influence of the interfacial area and the volume fraction of filler were studied. It was shown that the relative increase in tensile yield stress when increasing amount of interfacial agent was added, both depends on the volume of filler and the interfacial area.