Maximizing the utility of bio-based diisocyanate and chain extenders in crystalline segmented thermoplastic polyester urethanes: effect of polymerization protocol

High molecular weight semi crystalline thermoplastic poly(ester urethanes), TPEUs, were prepared from a vegetable oil-based diisocyanate, aliphatic diol chain extenders and poly(ethylene adipate) macro diol using one-shot, pre-polymer and multi-stage polyaddition methods. The optimized polymerization reaction achieved ultra-high molecular weight TPEUs (>2 million as determined by GPC) in a short time, indicating a very high HPMDI diol reactivity. TPEUs with very well controlled hard segment (HS) and soft segment (SS) blocks were prepared and characterized with DSC, TGA, tensile analysis, and WAXD in order to reveal structure property relationships. A confinement effect that imparts elastomeric properties to otherwise thermoplastic TPEUs was revealed. The confinement extent was found to vary predictably with structure indicating that one can custom engineer tougher polyurethane elastomers by "tuning" soft segment crystallinity with suitable HS block structure. Generally, the HPMDI-based TPEUs exhibited thermal stability and mechanical properties comparable to entirely petroleum-based TPEUs. (C) 2014 Elsevier Ltd. All rights reserved.

Panels Produced from Thermoplastic Composites Reinforced with Peach Palm Fibers for Use in the Civil Construction and Furniture Industry

In order to cooperate in minimizing the problems of the current and growing volume of waste, this work aim at the production of panels made from industrial waste -thermoplastic (polypropylene; polyethylene and acrylonitrile butadiene styrene) reinforced with agro-industrial waste - peach palm waste (shells and sheaths). The properties of the panels like density, thickness swelling, water absorption and moisture content were evaluated using the ASTM D1037; EN 317; and ANSI A208.1 standards regarding particle boards. Good results were obtained with formulations of 100% plastic waste; 70% waste plastics and 30% peach palm waste; and 60% waste plastics and 40% peach palm waste.

Thermoplastic starch/natural rubber blends

Thermoplastic starch/natural rubber polymer blends were prepared using directly natural latex and cornstarch. The blends were prepared in an intensive batch mixer at 150 degreesC, with natural rubber content varying from 2.5 to 20%. The blends were characterised by mechanical analysis (stress-strain) and by scanning electron microscopy. The results revealed a reduction in the modulus and in tensile strength, becoming the blends less brittle than thermoplastic starch alone. Phase separation was observed in some compositions and was dependent on rubber and on plasticiser content (glycerol). Increasing plasticiser content made possible the addition of higher amounts of rubber. The addition of rubber was, however, limited by phase separation the appearance of which depended on the glycerol content. Scanning electron microscopy showed a good dispersion of the natural rubber in the continuos phase of thermoplastic starch matrix. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

The influence of UV-C irradiation on the properties of thermoplastic starch and polycaprolactone biocomposite with sisal bleached fibers

The effect of UV-C irradiation of the TPS and PCL biocomposites with sisal bleached fibers was investigated. The biocomposite was UV-C irradiated at room temperature under air atmosphere. The structural and morphological changes produced when the films were exposed to UV irradiation for 142 h, were monitored using Scanning Electron Microscopy (SEM), Mechanical Tensile Tests, Differential Scanning Calorimetry (DSC), X-ray diffraction, Thermogravimetric analysis (TGA), and Fourier transform infra-red analysis (FTIR). Addition of 5-10% fibers in composites exhibited improved mechanical and thermal properties attributed to more efficient dispersibility of fiber in the matrix and good compatibility between fibers and the matrix polymer, however, after irradiated, the tensile properties decreased due to chain scission. The samples of irradiated PCL and IFS showed crystallinity increase, whereas the blend and composites showed a decrease in crystallinity. The DSC and X-ray diffraction studies suggested interaction between polymers in the blend via carboxyl groups in thermoplastic starch-PCL and hydroxyl groups in fibers. (C) 2011 Elsevier Ltd. All rights reserved.

Maxillary canine-first premolar transposition - Restoring normal tooth order with segmented mechanics

Tooth transpositions present at a relatively low incidence in the world population and primarily affect maxillary canines and premolars. Treatment of this disturbance should take into account aspects such as facial pattern, age, malocclusion, tooth-size discrepancy, stage of eruption, and magnitude of the transposition. Mechanics for correction should be entirely individualized, reducing the risks and adverse effects. Practitioners often select simpler options, indicating extraction of permanent teeth, which is an irreversible procedure that may bring about damages to the patient. This study presents a case report and treatment of unilateral transposition of maxillary canine and premolar with repositioning of affected teeth to their respective normal positions.

New strategies in the preparation of exfoliated thermoplastic starch-montmorillonite nanocomposites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Morphological, mechanical properties and biodegradability of biocomposite thermoplastic starch and polycaprolactone reinforced with sisal fibers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Maxillary canine - First premolar transposition: Restoring normal tooth order with segmented mechanics

Tooth transpositions present at a relatively low incidence in the world population and primarily affect maxillary canines and premolars. Treatment of this disturbance should take into account aspects such as facial pattern, age, malocclusion, tooth-size discrepancy, stage of eruption, and magnitude of the transposition. Mechanics for correction should be entirely individualized, reducing the risks and adverse effects. Practitioners often select simpler options, indicating extraction of permanent teeth, which is an irreversible procedure that may bring about damages to the patient. This study presents a case report and treatment of unilateral transposition of maxillary canine and premolar with repositioning of affected teeth to their respective normal positions. © 2006 by The EH Angle Education and Research Foundation, Inc.

A simple procedure for the preparation of laponite and thermoplastic starch nanocomposites: Structural, mechanical, and thermal characterizations

The aim of this article is to propose advances for the preparation of hybrid nanocomposites prepared by the combination of intercalation from solution and melt-processing methods. This research investigates the effect of the laponite RDS content on the thermal, structural, and mechanical properties of thermoplastic starch (TPS). X-ray diffraction was performed to investigate the dispersion of the laponite RDS layers into the TPS matrix. The results show good nanodispersion, intercalation, and exfoliation of the clay platelets, indicating that these composites are true nanocomposites. The presence of laponite RDS also improves the thermal stability and mechanical properties of the TPSmatrix due to its reinforcement effect which was optimized by the high degree of exfoliation of the clay. Thus, these results indicate that the exfoliated TPS-laponite nanocomposites have great potential for industrial applications and, more specifically, in the packaging field. © The Author(s) 2011 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Continuous vs. segmented second-dimension system gradients for comprehensive two-dimensional liquid chromatography of sugarcane (Saccharum spp.)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Vegetable Oil Derived Solvent, and Catalyst Free Click Chemistry'' Thermoplastic Polytriazoles

Azide-alkyne Huisgen click chemistry provides new synthetic routes for making thermoplastic polytriazole polymers-without solvent or catalyst. This method was used to polymerize three diester dialkyne monomers with a lipid derived 18 carbon diazide to produce a series of polymers (labelled C18C18, C18C9, and C18C4 based on monomer chain lengths) free of residual solvent and catalyst. Three diester dialkyne monomers were synthesized with ester chain lengths of 4, 9, and 18 carbons from renewable sources. Significant differences in thermal and mechanical properties were observed between C18C9 and the two other polymers. C18C9 presented a lower melting temperature, higher elongation at break, and reduced Young's modulus compared to C18C4 and C18C18. This was due to the odd-even effect induced by the number of carbon atoms in the monomers which resulted in orientation of the ester linkages of C18C9 in the same direction, thereby reducing hydrogen bonding. The thermoplastic polytriazoles presented are novel polymers derived from vegetable oil with favourable mechanical and thermal properties suitable for a large range of applications where no residual solvent or catalyst can be tolerated. Their added potential biocompatibility and biodegradability make them ideal for applications in the medical and pharmaceutical industries.

Mechanical and Thermal Properties of Thermoplastic Random Copolyesters Made from Lipid- Derived Medium and Long Chain Poly (x-hydroxyfatty acid) s

The physical properties of novel thermoplastic random copolyesters [-(CH2)(n)-COO-/-(CH2)(n)-COO-](x) made of long (n=12) and medium (n=8) chain length -hydroxyfatty esters [HO-(CH2)(n)-COOCH3] derived from bio-based vegetable oil feedstock are described. Poly(-hydroxy tridecanoate/-hydroxy nonanoate) P(-Me13-/-Me9-) random copolyesters (M-n=11,000-18,500 g/mol) with varying molar ratios were examined by TGA, DSC, DMA and tensile analysis, and WAXD. For the whole range of P(-Me13-/-Me9-) compositions, the WAXD data indicated an orthorhombic polyethylene-like crystal packing. Their melting characteristics, determined by DSC, varied with composition suggesting an isomorphic cocrystallization behavior. TGA of the P(-Me13-/-Me9-)s indicated improved thermal stability determined by their molar compositions. The glass transition temperature, investigated by DMA, was also found to vary with composition. The crystallinities of P(-Me13-/-Me9-)s however, were unaffected by the composition. The stiffness (Young's modulus) of these materials was found to be related to their degrees of crystallinity. (c) 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40492.

Thermoplastic polyesters and Co-polyesters derived from vegetable oil: synthesis and optimization of melt polycondensation for medium and long chain poly(omega-hydroxyfatty acid)s and their ester derivatives

The synthesis of a series of omega-hydroxyfatty acid (omega-OHFA) monomers and their methyl ester derivatives (Me-omega-OHFA) from mono-unsaturated fatty acids and alcohols via ozonolysis-reduction/crossmetathesis reactions is described. Melt polycondensation of the monomers yielded thermoplastic poly(omega-hydroxyfatty acid)s [-(CH2)(n)-COO-](x) with medium (n = 8 and 12) and long (n = 17) repeating monomer units. The omega-OHFAs and Me-omega-OHFAs were all obtained in good yield (>= 80%) and purity (>= 97%) as established by H-1 NMR, Fourier Transform infra-red spectroscopy (FT-IR), mass spectroscopy (ESI-MS) and high performance liquid chromatography (HPLC) analyses. The average molecular size (M-n) and distribution (PDI) of the poly(omega-hydroxyfatty acid)s (P(omega-OHFA)s) and poly(omega-hydroxyfatty ester) s (P(Me-omega-OHFA) s) as determined by GPC varied with organo-metallic Ti(IV) isopropoxide [Ti(OiPr)(4)] polycondensation catalyst amount, reaction time and temperature. An optimization of the polymerization process provided P(omega-OHFA) s and P(Me-omega-OHFA) s with M-n and PDI values desirable for high end applications. Co-polymerization of the long chain (n = 12) and medium chain (n = 8) Me-omega-OHFAs by melt polycondensation yielded poly(omega-hydroxy tridecanoate/omega-hydroxy nonanoate) random co-polyesters (M-n = 11000- 18500 g mol(-1)) with varying molar compositions.

Environmental effects on viscoelastic behavior of carbon fiber/PEKK thermoplastic composites

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influence of monomeric and polymeric structure on the physical properties of thermoplastic polyesters derived from hydroxy fatty acids

The physical properties of three vegetable oil derived medium and long chain poly(-hydroxy fatty ester)s (P(Me--OHFA)s), namely poly(-hydroxynonanoate) [P(Me--OHC9)], poly(-hydroxytridecanoate) [P(Me--OHC13)] and poly(-hydroxyoctadecanoate) [P(Me--OHC18)] (n = 8, 12 and 17, respectively), of the [-(CH2)(n)-COO-](x) polyester homologous series are presented. The effect of M-n (M-n 10-40 kg mol(-1)) and n on the crystal structure and thermal and mechanical properties of the P(Me--OHFA)s were investigated by wide-angle X-ray diffraction (WAXD), TGA, DSC, dynamic mechanical analysis (DMA) and tensile analysis and are discussed in the context of the [-(CH2)(n)-COO-](x) polyester homologous series, contrasted with linear polyethylene (PE). For all P(Me--OHFA)s the WAXD data indicated an orthorhombic crystal phase reminiscent of linear PE with crystallinity (X-c = 50%-80%) depending strongly on M-n. The glass transition temperature and Young's modulus for P(Me--OHFA)s increased with X-c. The DSC, DMA and TGA studies for P(Me--OHFA)s (n = 8, 12 and 17) indicated strong correlations between the melting, glass transition and thermal degradation behavior and n. The established predictive structure relationships can be used for the custom engineering of polyester materials suitable for specialty and commodity applications. (c) 2014 Society of Chemical Industry