Crystallization behaviour of polyethylene and i-polybutene-1 blends

The mutual influence of the components on the crystallization behaviour of polyblends, namely, isotactic polybutene-1 (PB) with low-density and high-density polyethylene (LDPE and HDPE), has been studied using techniques such as differential scanning calorimetry, infra-red spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy, etc. Each component in the blend is observed to crystallize independently. There is phase separation and incompatibility, as shown from tensile properties and scanning electron microscopic observation of the fracture surface of the blend. For HDPE-PE blends (<30% HDPE), unusual form I′ crystals of PB are observed along with the usual form II.

Low density polyethylene and grafted lignin polyblends using epoxy-functionalized compatibilizer: mechanical and thermal properties

Lignin was graft copolymerized with methyl methacrylate using manganic pyrophosphate as initiator. This modified lignin was then blended (up to 50 wt%) with low density polyethylene (LDPE) using a small quantity of poly[ethylene-co-(glycidyl methacrylate)] (PEGMA) compatibilizer. The mechanical properties of the blend were substantially improved by using modified lignin in contrast to untreated lignin. Differential scanning calorimetry studies showed loss of crystallinity of the LDPE phase owing to the interaction between the blend components. Thermogravimetric analysis showed higher thermal stability of modified lignin in the domain of blend processing. This suggested that there is scope for useful utilization of lignin, which could also lead to the development of eco-friendly products. (c) 2005 Society of Chemical Industry.

Note: Creep behaviour of high density polyethylene

The Ramberg-Osgood type constitutive law for creep suggested by Iyengar2 has been verified on high-density polyethylene. The time functions are evaluated from the experimental data of Scheweiker and Sidebottom3. It is found that the creep behaviour of the above material can be represented by the Ramberg-Osgood type law.

Solution cation-binding properties of segmented polyethylene oxide-A C-13 NMR spectroscopic study

Two segmented polyethylene oxides, SPEO-3 and SPEO-4, were prepared using a novel transetherification methodology. Their structures were confirmed by H-1 and C-13 NMR spectroscopy. The complexation of these SPEO's with alkali-metal ions in solution was investigated by C-13 NMR spectroscopy. The mole-fraction method was used to determine the complexation ratio of SPEO with LIClO4 at 25 degrees C, which showed that these formed 1:1 (polymer repeat unit/salt) complexes. The association constant, K, for the complex formation was calculated from the variation of the chemical shift values with salt concentration, using a standard nonlinear least-square fitting procedure. The maximum change in chemical shift (Delta delta) and the K values suggest that both SPEO-3 and SPEO-4 formed stronger complexes with lithium salts than with sodium salts. Unexpectedly, the K values were found to be different, when the variation of delta of different carbons was used in the fitting procedure. This suggests that several possible complexed species may be in equilibrium with the uncomplexed one. Structurally similar model compounds were also prepared and their complexation studies indicated that all of them also formed 1:1 complexes with Li salts. Interestingly, it was observed that the polymers gave higher K values suggesting the formation of more stable complexes in polymers when compared to the model analogues. (C) 2000 John Wiley & Sons, Inc.

Electron-Beam-Induced Modifications in High-Density Polyethylene

Post-irradiation studies have been carried out to elucidate the effects of electron beam irradiation on the structural, optical, dielectric, and thermal properties of high-density polyethylene (HDPE) films. The experimental results showed that both the optical band gap and activation energy of HDPE films decreases with an increase in the doses of electron radiation. The electrical measurements showed that dielectric constant and the ac conductivity of HDPE increases with an increase in the dose of electron radiation. The thermal analysis carried out using DSC and TGA revealed that the melting temperature, degree of crystallinity, and thermal stability of the HDPE films increased, obviously, due to the predominant cross-linking reaction following high doses of electron irradiation.

Polyethylene stibinite phosphate esters: Novel flame-retardant plasticizers for PVC

A new series of multielement flame-retardant plasticizers containing polyethylene stibinite phosphate esters have been prepared by bulk polymerization from ethylene glycol with various antimony (III) aryloxydichlorides and arylphosphorodichloridates possessing various combinations of substituent [Cl,Br,NO2]. All the polymers are pink-coloured viscous fluids. They were characterized by inherent viscosity, density, IR, H-1, C-13 and P-31 NMR spectroscopy. The thermal behaviour of the polymers was compared by thermogravimetric analysis and correlated with their structures. The flammability studies were carried out by the limiting oxygen index test. The polymers containing P, Sb, N and Pr elements in their backbone show superior thermal-and flame-retardant characteristics than the other polymers. A comparative study was carried out with one of the synthesized polymers as a polymeric flame-retardant additive to plasticized PVC. The results showed improved LOI and mechanical properties to that of the conventional flame-retardant additive composition. (C) 1997 Elsevier Science Ltd.

Solution grafting of maleic anhydride onto polyethylene and compatibilization of polyetylene-nylon blends

Maleic anhydride (MAH) has been grafted onto high density polyethylene (HDPE) with benzoyl peroxide (BOP) initiator in toluene solution. Maximum degree of grafting (12%) without crosslinking has been obtained using MAH/HDPE and BOP/HDPE weight ratios of 1.0 and 0.15 respectively, at 110 degrees C. The HDPE-g-MAH compatibilizer is found to drastically reduce the dispersed phase size and also to produce homogeneous blends for relatively low concentrations of dispersed phase in HDPE/nylon blends. Addition of this compatibilizer results in increase of tensile strength and modulus with increasing nylon content of HDPE/nylon blends, while the opposite is found for the blends without any added compatibilizer.

Electrical treeing in polyethylene: effect of nano fillers on tree inception and growth

Treeing in polyethylene based nanocomposite samples as well as unfilled polyethylene samples were studied using 50Hz ac voltage. The tree inception voltage was observed for different types of samples. The tree initiation time as well as the tree growth patterns at a fixed ac voltage have also been studied. The results show that there is an improvement in tree inception voltage with nano filler loading in polyethylene. Different tree growth patterns for both the unfilled polyethylene and the polyethylene nanocomposites have been observed. A slower tree growth was observed in polyethylene nanocomposites. The partial discharge characteristics of unfilled and nano filled polyethylene samples during the electrical tree growth period was also studied. Decrease in PD magnitude as well as in the number of pd pulses with electrical tree growth duration in polyethylene nanocomposites has also been observed. The possible reasons for the improvement in electrical tree growth and PD resistance with the addition of nano fillers are discussed.

Use of maleic anhydride-grafted polyethylene as compatibilizer for HDPE-tapioca starch blends: Effects on mechanical properties

Tapioca starch in both glycerol-plasticized and in unplasticized states was blended with high-density polyethylene (HDPE) using HDPE-g-maleic anhydride as the compatibilizer. The impact and tensile properties of the blends were measured according to ASTM methods. The results reveal that blends containing plasticized starch have better mechanical properties than those containing unplasticized starch. High values of elongation at break at par with those of virgin HDPE could be obtained for blends, even with high loading of plasticized starch. Morphological studies by SEM microscopy of impact-fractured specimens of such blends revealed a ductile fracture, unlike blends with unplasticized starch at such high loadings, which showed brittle fracture, even with the addition of compatibilizer. In general, blends of HDPE and plasticized starch with added compatibilizer show better mechanical properties than similar blends containing unplasticized starch. (C) 2001 John Wiley & Sons, Inc.

Injection-molded high-density polyethylene-hydroxyapatite-aluminum oxide hybrid composites for hard-tissue replacement: Mechanical, biological, and protein adsorption behavior

In this article, we report the mechanical and biocompatibility properties of injection-molded high-density polyethylene (HDPE) composites reinforced with 40 wt % ceramic filler [hydroxyapatite (HA) and/or Al2O3] and 2 wt % titanate as a coupling agent. The mechanical property measurements revealed that a combination of a maximum tensile strength of 18.7 MPa and a maximum tensile modulus of about 855 MPa could be achieved with the injection-molded HDPE20 wt % HA20 wt % Al2O3 composites. For the same composite composition, the maximum compression strength was determined to be 71.6 MPa and the compression modulus was about 660 MPa. The fractrography study revealed the uniform distribution of ceramic fillers in the semicrystalline HDPE matrix. The cytocompatibility study with osteoblast-like SaOS2 cells confirmed extensive cell adhesion and proliferation on the injection-molded HDPE20 wt % HA20 wt % Al2O3 composites. The cell viability analysis with the 3(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay revealed a statistically significant difference between the injection-molded HDPE20 wt % HA20 wt % Al2O3 composites and sintered HA for various culture durations of upto 7 days. The difference in cytocompatibility properties among the biocomposites is explained in terms of the difference in the protein absorption behavior. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Surface modification and paclitaxel drug delivery of folic acid modified polyethylene glycol functionalized hydroxyapatite nanoparticles

Nanoparticles are used for a number of biomedical applications. In this work we report the synthesis of folic acid (FA) modified polyethylene glycol (PEG) functionalized hydroxyapatite (HAp) nanoparticles. The anticancer drug, paclitaxel, is attached to the folic acid modified polyethylene glycol functionalized hydroxyapatite nanoparticles and the in vitro drug release is analyzed. The surface modification and functionalization is confirmed by Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA) and UV spectroscopy. The importance of the paper is the investigation of the release behavior of paclitaxel conjugated folic acid modified polyethylene glycol functionalized hydroxyapatite nanoparticles. The results show an initial rapid release and then a sustained release. (C) 2012 Elsevier B.V. All rights reserved.

Effect of morphology on electrical treeing in low density polyethylene nanocomposites

Influence of polymer morphology on the inception and the growth of electrical trees in unfilled low density polyethylene (LDPE) as well as LDPE filled with 1, 3 and 5% by weight nanoalumina samples stressed with 50 Hz ac voltage has been studied. It is seen that there is a significant improvement in tree inception voltage with filler loading in LDPE filled with nanoparticles. Tree inception voltage increased with the filler loading up to 3% by weight nanoalumina loading and showed a reduction at 5% by weight loading. Change in tree growth patterns from branch to bush as well as a slower tree growth with increase in filler loading in LDPE alumina nanocomposites were observed. The degree of crystallinity and change in crystalline morphology induced by the presence of alumina nanoparticles in LDPE was studied using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). DSC results show a similar melting behaviour for both unfilled LDPE and LDPE nanocomposites. However, there is a reduction in the degree of crystallinity for LDPE filled with 5% by weight nanoalumina. An increase in lamellae packing with increase in filler loadings and a highly disordered spherulitic structure for LDPE filled with 5% by weight nanoalumina was observed from the SEM images. The slow propagation of tree growth as well as reduction in tree inception voltage with increase in filler loadings were attributed to the morphological changes observed in the LDPE nanocomposites.

In vitro osteogenic cell proliferation, mineralization, and in vivo osseointegration of injection molded high-density polyethylene-based hybrid composites in rabbit animal model

The present work reports the biocompatibility property of injection molded HDPE-HA-Al2O3 hybrid composites. In vitro cytocompatibility results reveal that osteogenic cell viability and bone mineralization are favorably supported in a statistically significant manner on HDPE-20% HA-20% Al2O3 composite, in comparison to HDPE-40 wt.% HA or HDPE-40 wt.% Al2O3. The difference in cytocompatibility property is explained in terms of difference in substrate wettability/surface energy and importantly, both the cell proliferation at 7 days or bone mineralization at 21 days on HDPE-20% HA-20% Al2O3 composite are either comparable or better than sintered HA. The progressive healing of cylindrical femoral bone defects in rabbit animal model was assessed by implantation experiments over 1, 4 and 12 weeks. Based on the histological analysis as well as histomorphometrical evaluation, a better efficacy of HDPE-20% HA-20% Al2O3 over high-density polyethylene (HDPE) for bone regeneration and neobone formation at host bone-implant interface was established. Taken together, the present study unequivocally establishes that despite the presence of 20% Al2O3, HDPE-based hybrid composites are as biocompatible as HA in vitro or better than HDPE in vivo.

Combinatorial effect of rolling and carbonaceous nanoparticles on the evolution of crystallographic texture and structural properties of ultra high molecular weight polyethylene

Ultra high molecular weight polyethylene (PE) is a structural polymer widely used in biomedical implants. The mechanical properties of PE can be improved either by controlled crystalline orientation (texture) or by the addition of reinforcing agents. However, the combinatorial effect has not received much attention. The objective of this study was to characterize the structure and mechanical properties of PE composites incorporating multiwall carbon nanotubes (MWCNT) and reduced graphene oxide (RGO) subjected to hot rolling. The wide angle X-ray diffraction studies revealed that mechanical deformation resulted in a mixture of orthorhombic and monoclinic crystals. Furthermore, the presence of nanoparticles resulted in lower crystallinity in PE with smaller crystallite size, more so in RGO than in MWCNT composites. Rolling strengthened the texture of both orthorhombic and the monoclinic phases in PE. Presence of RGO weakened the texture of both phases of PE after rolling whereas MWCNT only mildly weakened the texture. This resulted in a reduction in the elastic modulus of RGO composites whereas moduli of neat polymer and the MWCNT composite increased after rolling. This study provides new insight into the role of nanoparticles in texture evolution during polymer processing with implications for processing of structural polymer composites.

Polyester derived from recycled poly(ethylene terephthalate) waste for regenerative medicine

Despite advances in regenerative medicine, the cost of such therapies is beyond the reach of many patients globally in part due to the use of expensive biomedical polymers. Large volumes of poly(ethylene terephthalate) (PET) in municipal waste is a potential source of low cost polymers. A novel polyester was prepared by a catalyst-free, melt polycondensation reaction of bis(hydroxyethylene) terephthalate derived from PET post-consumer waste with other multi-functional monomers from renewable sources such as citric acid, sebacic acid and D-mannitol. The mechanical properties and degradation rate of the polyester can be tuned by varying the composition and the post-polymerization time. The polyester was found to be elastomeric, showed excellent cytocompatibility in vitro and elicited minimal immune response in vivo. Three-dimensional porous scaffolds facilitated osteogenic differentiation and mineralization. This class of polyester derived from low cost, recycled waste and renewable sources is a promising candidate for use in regenerative medicine.