Enhancement of thermal stability, strength and extensibility of lipid-based polyurethanes with cellulose-based nanofibers

Cellulose was extracted from lignocellulosic fibers and nanocrystalline cellulose (NC) prepared by alkali treatment of the fiber, steam explosion of the mercerized fiber, bleaching of the steam exploded fiber and finally acid treatment by 5% oxalic acid followed again by steam explosion. The average length and diameter of the NC were between 200-250 nm and 4-5 nm, respectively, in a monodisperse distribution. Different concentrations of the NC (0.1, 0.5, 1.0, 1.5, 2.0 and 2.5% by weight) were dispersed non-covalently into a completely bio-based thermoplastic polyurethane (TPU) derived entirely from oleic acid. The physical properties of the TPU nanocomposites were assessed by Fourier Transform Infra-Red spectroscopy (FTIR), Thermo-Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), X-Ray Diffraction (XRD), Dynamic Mechanical Analysis (DMA) and Mechanical Properties Analysis. The nanocomposites demonstrated enhanced stress and elongation at break and improved thermal stability compared to the neat TPU. The best results were obtained with 0.5% of NC in the TPU. The elongation at break of this sample was improved from 178% to 269% and its stress at break from 29.3 to 40.5 MPa. In this and all other samples the glass transition temperature, melting temperature and crystallization behavior were essentially unaffected. This finding suggests a potential method of increasing the strength and the elongation at break of typically brittle and weak lipid-based TPUs without alteration of the other physico-chemical properties of the polymer. (C) 2012 Elsevier Ltd. All rights reserved.

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.

Surface modification of siloxane containing polyurethane polymer by dielectric barrier discharge at atmospheric pressure

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

Polyurethane coating with thin polymer films produced by plasma polymerization of diglyme

Aqueous-based polyurethane dispersions have been widely utilized as lubricants in textile, shoes, automotive, biomaterial and many other industries because they are less aggressive to surrounding environment. In this work thin films with different thickness were deposited on biocompatible polyurethane by plasma polymerization process using diethylene glycol dimethyl ether (Diglyme) as monomer. Molecular structure of the films was analyzed by Fourier Transform Infrared spectroscopy. The spectra exhibited absorption bands of O-H (3500-3200cm(-1)), C-H (3000-2900cm(-1)), C=O (1730-1650cm(-1)), C-O and C-O-C bonds at 1200-1600cm(-1). The samples wettability was evaluated by measurements of contact angle using different liquids such as water, glycerol, poly-ethane and CMC. The polyurethane surface showed hydrophilic behavior after diglyme plasma-deposition with contact angle dropping from 85(0) to 22(0). Scanning Electron Microscopy revealed that diglyme films covered uniformly the polyurethane surfaces ensuring to it a biocompatible characteristic.

Cure Kinetic of Castor Oil-Based Polyurethane

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Dynamic mechanical properties for polyurethane elastomers applied in elastomeric mortar

Dynamic mechanical properties of a polyurethane (PU) elastomer and a mortar processed with the same elastomer (modified polytetramethylene ether glycol (PTMEG)) were studied. The results obtained showed that the liquid aromatic amine ETHACURE (R) 300, used as cure agent, can be used to substitute the aromatic amine MOCA (R), which is usually used as cure agent in high performance elastomers. The resulting mortar produced with ETHACURE (R) 300 presents similar dynamic-mechanical thermal properties when compared with MOCA (R). However, dynamic-mechanical thermal analysis studies showed that the mortar developed with ETHACURE (R) 300 presents some advantages such as the low values of tan d, indicating a good capacity of recovery of the strain after retreating an applied force. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Flexural behavior of Sisal/Castor oil-Based Polyurethane and Sisal/Phenolic Composites

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Characterization of castor oil based polyurethane films prepared with N-methyl-2-pyrrolidinone as a solvent

Molecular mobility in castor oil based polyurethane was investigated with thermally stimulated depolarization current (TSDC) measurements and alternating-current (ac) dielectric relaxation spectroscopy. Three peaks could be observed in TSDC thermograms from 173 to 373 K. The relaxation located at 213 K could be attributed to the change in the molecular chain due to the interaction between the isocyanate and the solvent, and it was well fitted with the Vogel-Fulcher-Tammann equation. The other two peaks were located at 274 and 365 K and could be attributed to interfacial polarization and space charge, respectively. (c) 2005 Wiley Periodicals, Inc.

Effect of the doping medium on blends of polyurethane and polyaniline

Flexible and free-standing films from blends of polyurethane, based on castor oil, and polyaniline were obtained with various compositions by casting. Significant increase on conductivity followed by a considerable decrease on doping time was obtained by doping the films in N,N-dimethylformamide (DMF) solution with p-toluene sulphonic acid (TSA) or HCl instead of the conventional doping in aqueous solution. This doping efficiency is proposed to be due to an improved swelling of the blend structure caused by the solvent. The electrical conductivity increases significantly upon polyaniline content increase reaching 10(-2) S/cm for a polyaniline content of about 10% (w/w).

Dielectric relaxation of vegetable-based polyurethane

Vegetable-based polyurethane (PU) was prepared in the thin film form by spin coating. This polymer is synthesised from castor oil, which can be extracted from the seeds of a native plant in Brazil called mamona. This polymer is biocompatible and is being used as material for artificial bone. The PU was characterised by dielectric spectroscopy in a wide range of frequency (10(-5) Hz to 10(5) Hz) and by thermally stimulated discharge current (TSDC) measurements. The glass transition temperature (T-g=39degreesC) was determined and using the initial rise method the activation energy was found to be 1.58 eV. (C) 2003 Kluwer Academic Publishers.

Piezoelectric effect in composite polyurethane - Ferroelectric ceramics

Flexible and free-standing films of piezoelectric composites made up of lead zirconate titanate (PZT) ceramic powder dispersed in a castor oil-based polyurethane (PU) matrix were obtained by spin coating and characterised as materials for sensor applications. The piezoelectric coefficients d(31) and d(33) were measured with the usual technique. The piezoelectric charge constant d(33) yields values up to less than or equal to 24 pC/N, even at lower PZT content (33 vol%). Some desirable properties like piezoelectricity, flexibility and good mechanical resistance show this new material to be a good alternative for use as sensors and actuators.

Electromechanical properties of 0-3 vegetable based polyurethane and lead zirconate titanate composite.

Composite made of Lead Zirconate Titranate (PZT) ceramic powder and castor oil based polyurethane (PU) were prepared in the thin film form with 0-3 connectivity by spin coating. The composite films were obtained in the thickness range of 100 mum to 300 mum using 33-vol.% of ceramic. The samples mechanical resistance. The material was characterised by dielectric spectroscopy, thermally stimulated discharge current (TSDC), hysteresis measurements and laser-intensity-modulation method (LIMM). The pyroelectric coefficient at 343 K was 7x10(-5) C.m(-2) K-1 for the sample poled with 10 MV/m at 373 K for Ih. The results show that this new composite can be used as suitable piezo and pyroelectric sensors.

Dielectric and pyroelectric properties of a composite of ferroelectric ceramic and polyurethane

Flexible piezo- and pyroelectric composite was made in the thin film form by spin coating. Lead Zirconate Titanate (PZT) ceramic powder was dispersed in a castor oil-based polyurethane (PU) matrix, providing a composite with 0-3 connectivity. The dielectric data, measured over a wide range of frequency (10(-5) Hz to 105 Hz), shows a loss peak around 100 Hz related with impurities in the polymer matrix. There is also an evidence of a peak in the range 10(-4) Hz, possibly originating from the glass transition temperature T of the polymer. The pyroelectric coefficient at 34 K is 7.0x10(-5) C(.)m(-2.)K(-1) which is higher than that of P-PVDF (1X10(-5) C(.)m(-2.)K(-1)).