Natural weathering of rape straw flour (RSF)/HDPE and nano-SiO2/RSF/HDPE composites

The use of wood polymer composites (WPCs) in industries has been growing, and this is fueled in part by the use of WPCs in the construction industry. Rape straw flour (RSF)/high-density polyethylene (HDPE) composites as WPCs can also be applied in the construction industry. As a result, the durability of RSF/HDPE composites after natural exposure becomes a concern. Fourier transform infrared (FTIR) spectroscopy is used to monitor the development of degradation products, such as carbonyl groups and vinyl groups, and to determine changes in HDPE crystallinity. Differential scanning calorimetry (DSC) is also used to analyze changes in HDPE crystallinity. The results indicate that the carbonyl index was roughly lower for the RSF/HDPE composites than for the nano-SiO₂/RSF/HDPE composites, and the concentration of vinyl groups was generally much larger for the RSF/HDPE composites than for the nano-SiO₂/RSF/HDPE composites. At the same time, carbonyl index and vinyl index decrease with an increasing depth of composites, particularly decreasing strongly from 100 to 200 μm. The crystallinity of the samples increase because of natural aging, and the values of crystallinity derived by DSC are smaller than those derived by FTIR.     

Physico-mechanical properties of chemically treated palm and coir fiber reinforced polypropylene composites

In this work, palm and coir fiber reinforced polypropylene bio-composites were manufactured using a single extruder and injection molding machine. Raw palm and coir were chemically treated with benzene diazonium salt to increase their compatibility with the polypropylene matrix. Both raw and treated palm and coir fiber at five level of fiber loading (15, 20, 25, 30 and 35 wt.%) was utilized during composite manufacturing. Microstructural analysis and mechanical tests were conducted. Comparison has been made between the properties of the palm and coir fiber composites. Treated fiber reinforced specimens yielded better mechanical properties compared to the raw composites, while coir fiber composites had better mechanical properties than palm fiber ones. Based on fiber loading, 30% fiber reinforced composites had the optimum set of mechanical properties.     

Lignin as additive in polypropylene/coir composites: Thermal, mechanical and morphological properties

PP/CF composites were prepared and the effect of lignin incorporation in the presence and absence of compatibilizer (maleic anhydride grafted polypropylene, PP-g-MA) was investigated by means of mechanical, thermal and morphological properties. Lignin added to the composite was obtained by the Acetosolv process. The composites were prepared in a Haake torque rheometer and assessed by means of tensile testing, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The results showed that in the absence of PP-g-MA, incorporation of lignin did not affect tensile strength and in its presence this property was reduced. Thermal analysis revealed that incorporation of lignin in the composites resulted in increase in both the initial thermal decomposition temperatures and oxidation induction times.     

The immobilization of enzymes and cells of Bacillus stearothermophilus onto poly(maleic anhydride/styrene)-Co-polyethylene and poly(maleic anhydride/vinyl acetate)-Co-polyethylene

The graft copolymer, poly(maleic anhydride/styrene)-co-polyethylene was prepared. The copolymer immobilized bovine serum albumin (BSA), but the amount coupled appeared to be effected by the amount of styrene in the graft copolymer, temperature, and pH of the coupling medium. Competition existed between hydrolysis of the grafted anhydride groups and the protein. A graft copolymer with 66% add-on immobilized 4.5 mg/glucose oxidase/g copolymer, 4.6 mg alkaline phosphates/g copolymer and 0.2 mg cell of Bacillus stearothermophilus/g copolymer. A number of copolymers containing poly(maleic anhydride/vinyl acetate)-co-polyethylene were prepared to cover a range of grafting levels. These immobilized larger quantities of BSA, alkaline phosphatase, and cells of B. stearothermophilus than did the styrene graft copolymer. The copolymer was also hydrolyzed to release the hydroxyl group from the poly(vinyl acetate) component of the grafted chains. Using p-benzoquinone as the "activating agent," the copolymer coupled to BSA and to acid phosphatase. Using p-toluene-sulfonyl chloride, the copolymer was very effective in immobilizing trypsin.     

Renewable resource-based green composites from recycled cellulose fiber and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) bioplastic

Novel "green" composites were successfully fabricated from recycled cellulose fibers (RCF) and a bacterial polyester, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) by melt mixing technique. Various weight contents (15%, 30%, and 40%) of the fibers were incorporated in the PHBV matrix. The effect of the fiber weight contents on the thermal, mechanical, and dynamic-mechanical thermal properties of PHBV was investigated and a comparative property analysis was performed with RCF-reinforced polypropylene (PP) composites. The tensile and storage moduli of the PHBV-based composites were improved by 220% and 190%, respectively, by reinforcement with 40 wt % RCF. Halpin-Tsai and Tsai-Pagano's equations were applied for the theoretical modeling of the tensile modulus of PHBV-based composites. The heat deflection temperature (HDT) of the PHBV-based composites was increased from 105 to 131 degrees C, while the coefficient of linear thermal expansion (CLTE) value was reduced by 70% upon reinforcement with 40 wt % RCF. The PHBV-based composites had also shown better tensile and storage moduli and lower CLTE values than PP-based composites. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) were used to study the melting behavior, thermal stability, and morphology of the composite systems, respectively.     

Comparative biodegradation of HDPE and LDPE using an indigenously developed microbial consortium

A variety of bacterial strains were isolated from waste disposal sites of Uttaranchal, India, and some from artificially developed soil beds containing maleic anhydride, glucose, and small pieces of polyethylene. Primary screening of isolates was done based on their ability to utilize high- and low-density polyethylenes (HDPE/LDPE) as a primary carbon source. Thereafter, a consortium was developed using potential strains. Furthermore, a biodegradation assay was carried out in 500-ml flasks containing minimal broth (250 ml) and HDPE/ LDPE at 5 mg/ml concentration. After incubation for two weeks, degraded samples were recovered through filtration and subsequent evaporation. Fourier transform infrared spectroscopy (FTIR) and simultaneous thermogravimetric-differential thermogravimetry-differential thermal analysis TG-DTG-DTA) were used to analyze these samples. Results showed that consortium-treated HDPE (considered to be more inert relative to LDPE) was degraded to a greater extent 22.41% weight loss) in comparison with LDPE (21.70% weight loss), whereas, in the case of untreated samples, weight loss was more for LDPE than HDPE (4.5% and 2.5%, respectively) at 400 degrees . Therefore, this study suggests that polyethylene could be degraded by utilizing microbial consortia in an eco-friendly manner.     

Mixed protein blends composed of gelatin and Bombyx mori silk fibroin: effects of solvent-induced crystallization and composition

Novel protein blends have been prepared by mixing gelatin (G) with Bombyx mori silk fibroin (SF) and using aqueous methanol (MeOH) to post-induce SF crystallization. When co-cast from solution, amorphous blends of these polymers appear homogeneous, as discerned from visual observation, microscopy, and Fourier-transform infrared (FTIR) spectroscopy. Upon subsequent exposure to aqueous MeOH, SF undergoes a conformational change from random coil to beta sheet. This transformation occurs in pure SF, as well as in each of the G/SF blends, according to X-ray diffractometry and thermal calorimetry. The influence of MeOH-induced SF crystallization on structure and property development has been ascertained in terms of preparation history and blend composition. Thermal gravimetric analysis reveals that the presence of beta sheets in SF and G/SF blends improves thermal stability, while extensional rheometry confirms that SF crystallization enhances the tensile properties of the blends. By preserving a support scaffold above the G helix-to-coil transition temperature, the formation of crystalline SF networks in G/SF blends can be used to stabilize G-based hydrogels for biomaterial and pharmaceutical purposes. The present study not only examines the properties of G/SF blends before and after SF crystallization, but also establishes the foundation for future research into thermally responsive G/SF bioconjugates.     

Chelating efficiency and thermal, mechanical and decay resistance performances of chitosan copper complex in wood-polymer composites

Wood–polymer composites (WPC) have been extensively used for building products, outdoor decking, automotive, packaging materials, and other applications. WPC is subject to fungal and termite attacks due to wood components enveloped in the thermoplastic matrix. Much effort has been made to improve decay resistance of WPC using zinc borate and other chemicals. In this study, chitosan copper complex (CCC) compounds were used as a potential preservative for wood–HDPE composites. CCC was formulated by reacting chitosan with copper salts under controlled conditions. Inductively coupled plasma (ICP) analytical results indicated that chitosan had high chelating efficiency with copper cations. CCC-treated wood–HDPE composites had a thermal behavior similar to untreated and zinc borate-treated wood–HDPE composites. Incorporation of CCC in wood–HDPE composites did not significantly influence board density of the resultant composites, but had a negative effect on tensile strength at high CCC concentration. In comparison with solid wood and the untreated wood–HDPE composites, 3% CCC-treated wood–HDPE composites significantly improved the decay resistance against white rot fungus Trametes versicolor and brown rot fungus Gloeophyllum trabeum. Especially, CCC-treated wood–HDPE composites were more effectively against the brown rot than the untreated and chitosan-treated wood–HDPE composites. Moreover, CCC-treated wood–HDPE composites performed well as zinc borate-treated wood–HDPE composites on fungal decay resistance. Accordingly, CCC can be effectively used as a preservative for WPC.     

Hydroxyapatite surface modified by L-lactic acid and its subsequent grafting polymerization of L-lactide

A new method of surface modification of hydroxyapatite nanoparticles (n-HA) by surface grafting reaction of l-lactic acid and ring-opening polymerization of l-lactide (LLA) was developed. Two modified HA nanoparticles were obtained: HA modified by l-lactic acid (l-HA) and HA grafting with poly(l-lactide) (PLLA; p-HA). The modified surface of n-HA was attested by Fourier transformation infrared, (31)P MAS NMR, and thermal gravimetric analysis. The results showed that l-lactic acid could be easily grafted onto the n-HA surface by forming a Ca carboxylate bond and initiated by the hydroxyl group of the grafted l-lactic acid and LLA could be graft-polymerized onto the n-HA surface in the presence of stannous octanoate. The highest grafting amounts of l-lactic acid and PLLA were about 33 and 22 wt %, respectively. The modified HA/PLLA composites showed good mechanical properties and uniform microstructure. The tensile strength and modulus of the p-HA/PLLA composite containing 15 wt % of p-HA were 67 MPa and 2.1 GPa, respectively, while those of the n-HA/PLLA composites were 45 MPa and 1.7 GPa, respectively. The elongation at the break of the l-HA/PLLA composite containing 15 wt % l-HA could reach 44%, in comparison with 6.5% of the n-HA/PLLA composites containing 15 wt % n-HA.     

Effect of fiber treatments on tensile and thermal properties of starch/ethylene vinyl alcohol copolymers/coir biocomposites

Coir fibers received three treatments, namely washing with water, alkali treatment (mercerization) and bleaching. Treated fibers were incorporated in starch/ethylene vinyl alcohol copolymers (EVOH) blends. Mechanical and thermal properties of starch/EVOH/coir biocomposites were evaluated. Fiber morphology and the fiber/matrix interface were further characterized by scanning electron microscopy (SEM). All treatments produced surface modifications and improved the thermal stability of the fibers and consequently of the composites. The best results were obtained for mercerized fibers where the tensile strength was increased by about 53% as compared to the composites with untreated fibers, and about 33.3% as compared to the composites without fibers. The mercerization improved fiber–matrix adhesion, allowing an efficient stress transfer from the matrix to the fibers. The increased adhesion between fiber and matrix was also observed by SEM. Treatment with water also improved values of Young’s modulus which were increased by about 75% as compared to the blends without the fibers. Thus, starch/EVOH blends reinforced with the treated fibers exhibited superior properties than neat starch/EVOH.     

A plant fiber reinforced polymer composite prepared by a twin-screw extruder

Polypropylene (PP) composites reinforced using a novel plant fiber, sunflower hull sanding dust (SHSD), were prepared using a twin-screw extruder. Thermal and mechanical properties of the SHSD/PP composites were characterized and compared to an organically modified clay (organo-clay)/PP composite. Differential scanning calorimetry (DSC) analysis showed that the crystallization temperature and the degree of crystallinity of PP exhibited changes with addition of SHSD and organo-clay. Mechanical properties of the PP were enhanced with the addition of SHSDs. Both the flexural strength and flexural modulus of the PP composites containing 5% (w/w) SHSD were comparable to that of the 5% (w/w) organo-clay reinforced PP. Scanning electron microscope (SEM) observation showed that no obvious agglomeration of SHSD existed in the PP matrix. Compared to the neat PP and organo-clay/PP, the SHSD/PP composites exhibited a relatively decreasing rate of thermal degradation with increase in temperature. Experimental results suggest that SHSD, as a sunflower processing byproduct, may find promising applications in composite materials.     

Microwave-assisted modification of starch for compatibilizing LLDPE/starch blends

Modification of activated cassava starch (S) was performed by using octenyl succinic anhydride (OSA) at different starch/OSA ratios under microwave radiation. FTIR and titration results indicated that, within a reaction time of 7 min, degrees of substitution (DS) of about 0.045 may be achieved with 20% OSA. Subsequently, linear low density polyethylene/starch (LLDPE/S) blends were prepared employing succinylated starches (S-g-OSA) as compatibilizers. The morphology and mechanical properties of LLDPE/S blends with and without compatibilizer were compared. It was observed that the addition of 10% of compatibilizer with respect to the dispersed phase content led to a reduction of the starch phase size and to an improvement of the blends mechanical properties.     

Studies of the fiber to crystal transition of sickle cell hemoglobin in acidic polyethylene glycol

The crystallization of deoxygenated sickle cell hemoglobin in acidic (pH 5.2) polyethylene glycol (10%) has been studied in order to determine if the mechanism of crystal formation under such conditions has features in common with the mechanism of crystal formation at higher pH values in the absence of polyethylene glycol. The existence of a common mechanism of crystallization under different conditions is relevant in validating the use of the known high resolution crystal structure to interpret the fiber structure. Our findings indicate that deoxygenated sickle cell hemoglobin crystallization in acidic polyethylene glycol is initiated by fiber formation. Fibers, in turn, convert to larger structures called macrofibers within several hours (Wellems et al., 1981). Fibers and macrofibers (and their respective optical transforms) formed in acidic polyethylene glycol appear to have the same structure as their counterparts formed at higher pH values in the absence of polyethylene glycol. Early in the transition one can observe macrofibers in the process of alignment and fusion. The structural characterization of the intermediates leaves little doubt that crystallization in acidic polyethylene glycol is mediated by the same mechanism as that occurring under more physiological conditions, and that fibers are a metastable intermediate whose ultimate fate is to crystallize.     

Porous devices derived from co-continuous polymer blends as a route for controlled drug release

In this study we examine the release profile of bovine serum albumin (BSA) from a porous polymer matrix derived from a co-continuous polymer blend. The porosity is generated through the selective extraction of one of the continuous phases. This is the first study to examine the approach of using morphologically tailored co-continuous polymer blends as a template for generating porous polymer materials for use in controlled release. A method for the preparation of polymeric capsules is introduced, and the effect of matrix pore size and surface area on the BSA release profile is investigated. Furthermore, the effect of surface charge on release is examined by surface modification of the porous substrate using layer-by-layer deposition techniques. Synthetic, nonerodible polymer, high-density polyethylene (HDPE), was used as a model substrate prepared by melt blending with two different styrene-ethylene-butylene copolymers. Blends with HDPE allow for the preparation of porous substrates with small pore sizes (300 and 600 nm). A blend of polylactide (PLA) and polystyrene was also used to prepare porous PLA with a larger pore size (1.5 microm). The extents of interconnectivity, surface area, and pore dimension of the prepared porous substrates were examined via gravimetric solvent extraction, BET nitrogen adsorption, mercury porosimetry, and image analysis of scanning electron microscopy micrographs. With a loading protocol into the porous HDPE and PLA involving the alternate application of pressure and vacuum, it is shown that virtually the entire porous network was accessible to BSA loading, and loading efficiencies of between 80% and 96% were obtained depending on the pore size of the carrier and the applied pressure. The release profile of BSA from the microporous structure was monitored by UV spectrophotometry. The influence of pore size, surface area, surface charge, and number of deposited layers is demonstrated. It is shown that an effective closed-cell structure in porous PLA can be prepared, effectively eliminating all short-term BSA release.     

Glutaraldehyde activation of polymer Nylon-6 for lipase immobilization: enzyme characteristics and stability

An extracellular alkaline lipase of a thermo tolerant Bacillus coagulans BTS-3 was immobilized onto glutaraldehyde activated Nylon-6 by covalent binding. Under optimum conditions, the immobilization yielded a protein loading of 228 microg/g of Nylon-6. Immobilized enzyme showed maximum activity at a temperature of 55 degrees C and pH 7.5. The enzyme was stable between pH 7.5-9.5. It retained 88% of its original activity at 55 degrees C for 2h and also retained 85% of its original activity after eight cycles of hydrolysis of p-NPP. Kinetic parameters Km and Vmax were found to be 4mM and 10 micromol/min/ml, respectively. The influence of organic solvents on the catalytic activity of immobilized enzyme was also evaluated. The bound lipase showed enhanced activity when exposed to n-heptane. The substrate specificity of immobilized enzyme revealed more efficient hydrolysis of higher carbon length (C-16) ester than other ones.     

Block copolymers and melt blends of polylactide with Nodax microbial polyesters: preparation and mechanical properties

Completely renewable resource-based, degradable composites of poly(l-lactide) and Nodax [poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)] were prepared by a melt blending procedure. oligoNodax-b-poly(l-lactide) diblock copolymers were synthesized and their use as compatibilizers in these melt blends was investigated. The block copolymers were prepared from microbially produced Nodax polyhydroxyalkanoate by a two-step transesterification and macroinitiator ring opening polymerization method. Addition of Nodax increased the notched Izod impact resistance of the binary blends compared to that of PLLA homopolymer (44+/-6 J m(-1) versus 22+/-2 J m(-1), respectively). Further addition of the oligoNodax-b-poly(l-lactide) block copolymers to form ternary blends resulted in composites with improved dispersion and decreased Nodax particle size, but no additional improvement in the notched Izod impact properties. Significant Nodax degradation during processing coupled with a high Nodax entanglement molecular weight, as well as crystallization and low impact resistance of the Nodax dispersed phase are implicated as major factors impeding further toughening.     

Supra-molecular ecobionanocomposites based on polylactide and cellulosic nanowhiskers: synthesis and properties

Successful filler dispersion and establishment of good interfacial contact with the surrounding matrix are essential for optimized reinforcement in polymeric nanocomposites. In particular, in renewable-based composites this can be challenging, where hydrophilic attractions between nanofillers facilitate aggregation. Here an innovative approach to prepare cellulosic nanowhisker (CNW) reinforced polylactide (PLA) is presented. The lactide ring-opening polymerization is initiated from CNW surface hydroxyl groups after partial acetylation to control the grafting density. Grafting of PLA chains is verified by Fourier transform infrared spectroscopy. The resulting nanocomposites display exceptional properties; a heat distortion temperature of 120 °C is achieved at 10 wt % CNW loading and can be further enhanced to reach 150 °C at 15 wt % CNW. The formation of a percolating network is verified by comparison of modulus data with an established theoretical model. Additionally, nucleation by CNWs reduces the crystallization half-time to 15 s compared with 90 s for PLA. Melt-pressed films retain transparency indicating good filler dispersion.     

Biogenic synthesis and photocatalysis of Pd-PdO nanoclusters reinforced hierarchical TiO2 films with interwoven and tubular conformations

Hierarchical nanocomposite films with Pd-PdO nanoparticles anchored uniformly on the inner surface of TiO2 nanotubes were achieved through a stepwise bioredox/artificial oxygenation approach by using the natural eggshell membrane (ESM) as a template. The Pd content ratio of Pd-PdO loading could be arbitrarily varied from 0 to 53 wt %, and the ESM-morphic nanocomposites Pd-PdO/TiO2 exhibited porous and multiphasic features, facilitating light transport and molecule accessibility to the active site during photocatalytic reactions. The photocatalytic activity of target nanocomposites was determined by the degradation of rhodamine B. The composites with a ratio of 10 wt % TiO2 (5 wt % Pd of Pd-PdO loading) presented a high degradation efficiency of 99.3% and showed good stability with a second run of about 95.3% and a third run of 94.6%. These composites with structural particularity and complexity are expected to find potential applications in various fields, such as photovoltaic devices, gas sensors, antistatic coating, dye-sensitized solar cells, etc.     

Influence of fiber on the phase transformations in the starch-water system

High-sensitivity, temperature-controlled DSC measurements at a low heating rate and creation of differential DSC traces scaled with respect to the reference material (completely dehydrated starch or completely dehydrated fiber, or their respective blends) permitted investigation of the influence of fiber on phase transformations in the wheat-starch-water system in the course of thermal gelatinization. Thermal effects associated with water interactions over the temperature range from 283 to 384 K under atmospheric pressure were determined. These thermal effects and previous structural studies permit us to make the following observations: (1) The main endothermic transition associated with melting of the crystalline part of the starch granule followed by a helix-coil transition in amylopectin occurs over the temperature range 319-333 K independent of the water and fiber contents. Adding fiber causes that transition to disappear both in the native blends and in water suspensions at low water contents. After adding more water and heating, recrystallization is observed and the transition reappears. (2) The fiber content has practically no influence on the slow exothermic transformation, which follows melting and helix-coil transition in amylopectin, proving that the slow transformation has a specific chemical character. In this reaction, the free ends of the unwound helices of amylopectin reassociate with parts of amylopectin molecules other than their original helix duplex partner, forming physical junctions and creating more general amorphous hydrogen bonded associations. (3) The high-temperature transition and small, but reproducible, distortions on the peaks of the main endothermic transition for water contents near 70-80 wt % are associated with smectic and nematic transitions, respectively. These are significantly influenced by the fiber content; higher fiber content causes an almost complete disappearance of these transitions. (4) The slow exothermic effect appearing almost from the very beginning of the heating in the starch-water system, associated with softening and uptake of water in the amorphous growth rings of the starch granule, is significantly hindered by added fiber.     

Mechanical properties and decay resistance of wood-polymer composites prepared from fast growing species in Turkey

Some mechanical properties of wood-polymer composites from maritime pine (Pinus pinaster Ait.) and poplar (Populus x. euramericana cv. I-214) wood were investigated. Three different monomers; styrene (ST), methyl methacrylate (MMA) and styrene/methyl methacrylate (ST/MMA) mixture were used in preparation of wood-polymer composites (WPCs). Full-loading (FL), half-loading (HL) and quarter-loading (QL) were used as polymer content levels. Untreated pine and pine-polymer composite samples were tested in compression strength parallel to grain and static bending strength. WPCs mechanical properties increased compared to untreated wood. The polymer had greater effect on the strengths of the ST/MMA treated pine than on the ST and MMA treated pine samples. Increasing of the mechanical properties should improve the structural competitiveness of WPCs made from fast growing-low density woods. Weight losses due to fungal attack for pine and poplar-polymer composites were also determined. Although polymers at full and half loading levels helped decreasing weight losses due to both fungi for each wood species, weight losses were still found to be higher.