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[en] Biodegradable polyester polyol was synthesized from oleochemical glycerol monostearate (GMS) and glutaric acid under a non-catalyzed and solvent-free polycondensation method. The chemical structure of GMS-derived polyester polyol (GPP) was elucidated by FTIR, 1H and 13C NMR, and molecular weight of GPP was characterized by GPC. The synthesized GPP with acid value of 3.03 mg KOH/g sample, hydroxyl value of 115.72 mg KOH/g sample and Mn of 1345 g/mol was incorporated with polyethylene glycol (PEG) and polycaprolactone diol (PCL diol) to produce a water-blown porous polyurethane system via one-shot foaming method. The polyurethanes were optimized by evaluating glycerol as a crosslinker, silicone surfactant and water blowing agent on tensile properties of polyurethanes. All polyurethanes underwent structural change, and crystalline hard segments of polyurethanes were shifted to higher temperature suggested that hard segments undergone re-ordering process during enzymatic treatment. In terms of biocompatibility, polyurethane scaffold produced by reacting 100% w/w of GPP with isophorone diisocyanate and additives showed the highest cells viability of 3T3 mouse fibroblast (94%, day 1), and MG63 human osteosarcoma (107%, day 1) and better cell adhesion as compared to reference polyurethane produced by only PEG and PCL diol (3T3 cell viability: 8%; MG63 cell viability: 2%). The current work demonstrated GPP synthesized from renewable and environmental friendly resources produced polyurethanes that allows improvement in physico-chemical, mechanical and biocompatibility properties. By blending with increasing content of GPP, the water-blown porous polyurethane scaffold has shown great potential as biomaterial for soft and hard tissue engineering.
[en] Cellulose micro/nanofibrils were successfully extracted from softwood Douglas fir in three distinct stages. Initially raw Douglas fir wood chips were subjected to a hot water extraction (HWE) treatment. Then HWE treated cellulosic fibers underwent a bleaching process followed by a mild ultrasonication. Chemical composition analysis according to ASTM standards confirmed that most of hemicelluloses and nearly all lignin were removed during the first two stages, respectively. Microscopy studies showed formation of nanofibrils during the ultrasonication process, and increasing ultrasonication time led to generation of greater percentage of nanofibrils. With the removal of the matrix materials, the crystallinity of the cellulosic fibers was increased, whereas thermal stability was maintained. HWE opened up the cell wall structure, thereby facilitating the subsequent fractionation into micro/nanofibrils. The obtained cellulose micro/nanofibrils could serve as reinforcing material in composite products or raw material for other applications, such as filtration membrane.
[en] The molecular structure of poly(3-hydroxyalkanoate) (P3HA) with medium-chain length, biosynthesized from Psuedomonas putida (P. putida), was investigated by thermal analysis, X-ray diffraction, and infrared spectrum. Cultivation in a medium of nonanoic acid and a mixed substrate of nonanoic acid and glycerin as carbon sources provided P3HA with monomer units of 7 and 9 carbons (P3HAn) and 5, 6, 7, 8, 9, and 10 carbons (P3HAmix). Since these P3HA has comparatively long side chains, the crystallinity was as low as about 10%. It was suggested that the hydrogen bonding plays an important role in constructing the crystal. The lamellar thickness was 1.20 nm, estimated from the melting temperature depression. This lamellar thickness corresponds to two repeating units. Crystallinity depending on time was observed by the CO stretching mode in the infrared spectrum, and then Avrami’s theory was applied to analyze the crystallization mechanism. The crystallization rate of P3HAn was very low, on the order of a few hours. An Avrami exponent of 1.45 was estimated from the slope of the Avrami plot. This shows that the conformational arrangement is presumably promoted along the chain axis. The slow crystallization is attributed to the long side chain, which prevents aggregation of the polymer chains.
[en] In this study, the hydrolytic degradation of Poly(lactic acid) (PLA) and acetylated PLA (PLA-Ac)–clay nanocomposites were investigated. The organo clay was obtained by ion exchange reaction using cetyl tri methyl ammonium bromide (CTAB). Nanocomposites containing 2, 5 and 8% mass ratio of organo clay (CTAB-O) were prepared. PLA and its organo clay nanocomposites were characterized by scanning electron microscope (SEM), thermo gravimetric analysis (TGA) and X-ray diffraction (XRD) to determine the morphology before and after hydrolytic degradation. Fourier transform infrared (FTIR) analyses of PLA and PLA-Ac were also obtained. The hydrolytic degradation of polymers and their composites were investigated in the phosphate buffered saline solution (PBS). The results showed that controlled hydrolytic degradation was observed in the samples with end group modification of PLA. While weight loss of PLA films was 28%, that of PLA-Ac films was 18% after 60 days degradation time. The weight loss was obtained as 29.5 and 25.5% for PLA-5 wt% organo clay (PLA/5CTAB-O) and PLA-Ac-5 wt% organo clay (PLA-Ac/5CTAB-O) nanocomposites films, respectively. It was also observed that thermal degradation of PLA-Ac was much more than that of PLA. Hydrolytic degradation increased depending on organo clay content. The end group modificated PLA results in controlled hydrolytic degradation. While hydrolytic degradation in polymer films occurred as surface erosion, bulk erosion was observed in composite films.
[en] In this work, the optimum condition for the adsorption of Reactive Blue 19 dye onto Fe3O4 functionalized with hyperbranched polyethylenimine (Fe@HPEI) was determined using response surface methodology. The properties of synthesized magnetic Fe@HPEI nanoparticles were ascertained using FTIR, SEM, TEM, VSM and zeta potential measurement. The experimental adsorption data indicating the positive effect of adsorbent dose and contact time, and the negative effect of pH, initial dye concentration and ionic strength on dye adsorption. At optimal condition; pH 3.4, contact time 25 min, adsorbent dose 0.4 g/L and initial dye concentration 113 mg/L, Fe@HPEI nanoparticles removed dye up to 99.27%. The maximum experimental dye adsorption was near to the predicted value of 100%, which confirmed the reliability of the selected statistical model. The dye adsorption data were fitted well to Langmuir isotherm and pseudo-second-order kinetic, and the maximum adsorption capacity was 500 mg/g. Totally, Fe@HPEI as an effective superadsorbent can be repeatedly utilized for the adsorption of dye from the aqueous environment.
[en] The preparation and characterization of a low-cost solid materials chitosan–graft–poly(2-methylaniline) as anti-coliform present in wastewater are confirmed by FTIR, TGA, XRD and SEM. The preparation is performed using ammonium persulphate as an oxidant. The data reveals that the grafting process enhances the efficiency of both chitosan and homo-poly(2-methylaniline) to remove coliform present in wastewater. The used wastewater contains 1600 colonies on testing total coliform using classical membrane filter techniques. The total coliform present in wastewater becomes zero by using 50 ppm of the graft, 100 ppm of chitosan and 1000 ppm of poly(2-methylaniline).
[en] Poly(vinyl alcohol) (PVA)–ZnO–Al2O3 composite films have been prepared by the addition of different compositions of ZnO and Al2O3 through solvent casting method. Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible spectroscopy (UV–Vis) and photoluminescence spectroscopy (PL) spectra revealed the successful incorporation of ZnO and Al2O3 onto PVA and interactions among ZnO, Al2O3 and PVA molecules. PL data indeed showed the enhanced luminescence property of composite films compared with the PVA. Thermogravimetric analysis (TGA) data showed that thermal stability of PVA–ZnO–Al2O3 composite films could be greatly improved by the incorporation of ZnO and Al2O3 into the system. The glass transition temperature (Tg) were increased for the composite samples using ZnO and Al2O3. Differential scanning calorimetry (DSC) measurements revealed that the melting temperature (Tm) of PVA–ZnO–Al2O3 composite films are significantly higher (~ 12 to 25 °C) than PVA. The photocatalytic measurements exhibited better photocatalytic degradation ability of PVA–ZnO–Al2O3 composites over PVA. Such photocatalytic capacity makes the PVA–ZnO–Al2O3 composite films promising candidates for the removal of organic dyes for water purification.
[en] Biochemical sludge (BS), generated in the waste water treatment of paper mills, was pretreated by enzyme hydrolysis. The effect and action mechanism of the enzymatic treatment on the properties of polyvinyl chloride (PVC) matrix composites with BS were discussed. Results showed that when the filler content was 30 wt%, the tensile strength of the PVC composites filled with BS and its modified products which were pretreated by laccase, cellulase and hemicellulase can be increased by 38.64, 67.4, 63.5 and 66.3% than the PVC composite filled with calcium carbonate. When the dosage of filler was 40 wt%, the elastic modulus of PVC composites filled with BS and its above three modified products decreased by 53.3, 52.3, 50.0 and 46.3%, respectively. Meanwhile, the thermal stability of PVC composites can also be improved at the temperature of over 340 °C. It can be concluded that the enzyme pretreatment can improve the application performance of BS usage in PVC matrix composites.
[en] Avermectin (AVM) is a highly efficient pesticide against a variety of insects and is widely used in agriculture. However, it is susceptible to oxidation and photolysis, resulting in instability under UV irradiation and a short half-life. Herein, sodium carboxymethyl cellulose (CMC) was grafted by styrene (St), Methyl methacrylate (MMA) and butyl acrylate (BA) respectively to prepare grafted polymer nanoparticles in application for AVM sustained released. And the influence of different grafted monomer and the grafted rate on the AVM/grafted polymer nanoparticles performance was discussed. The larger the grafted rate of St was, the larger the particle size of AVM/grafted polymer nanoparticles had with a higher drug loading rate and stronger resistance to ultraviolet light. Besides, the particle size, drug loading rate and the ability of anti-ultraviolet light of grafted CMC emulsion was also influenced by the modifying agent. While the concentration of AVM was kept the same, the acrylic esters (MMA and BA) grafted emulsion have smaller particle sizes with higher drug loading rates and stronger anti-ultraviolet ability comparing to styrene (St) grafted emulsion. The effect of different amount of St and different monomer grafted on the sustained release performance of AVM/grafted polymer was also investigated. As the grafted rate of St increased, the release rate became smaller. The release speed has a sequence of CMC-g-PBA > CMC-g-PS > CMC-g-PMMA when CMC grafted with different monomer. Their sustained release curves can be described by Korsmeyer-Peppas equation. Finally, the insect toxicity test showed that insecticide toxicity against diamondback moth (Plutella xylostella L.) has no apparent difference among the AVM and AVM/grafted polymer nanoparticles indicating that AVM/grafted polymer nanoparticles can reduce the amount of organic solution used for dissolution and prolonged its service life without decreasing its insecticide toxicity.
[en] Zeolites are crystalline aluminosilicates with nanoporous structure, tasteless and non-toxic materials. In this study, silver ion-exchanged zeolite, which was prepared from the natural Ecuadorian zeolites was used as reinforcement material in low-density polyethylene (LDPE) and polypropylene (PP). Polymers were filled with 1, 2 and 3 wt% concentrations of natural zeolite (Z) and silver ion exchanged zeolite (ZA). Zeolites and composites were characterized by X-ray diffractometry, Fourier transform infrared spectroscopy, scanning electron microscope, thermogravimetric analysis and mechanical analysis techniques. Microbiological analysis of silver ion exchanged zeolite showed effective antibacterial property against Escherichia coli bacteria. PP/ZA composites showed better tensile strengths in all mixes comparing to pure PP. ZAPE2 and ZAPP1 showed the best mechanical properties among all the composites based on polyethylene and PP, respectively. The composites prepared are potential candidates to be used in food packaging, and ZA type zeolites can be used as filler for the preparation of various composites.