Thermal degradation of a brominated bisphenol a derivative

The thermal degradation of 2,6,2',6'-tetrabromo-4,4-pm-isoproylidene-di phenol (tetrabromobisphenol A) (TBBPA) has been investigated and a mechanism for its thermal degradation is suggested. TBBPA is a comonomer widely used in epoxy and in unsaturated polyester resins to impart fire retardance. These resins find a common use in electric and electronic equipment. The presence of bromine atoms is the key factor in fire retardant activity, while on the other hand it represents an ecological problem when pyrolytic recycling is programmed at the end of the useful life of such items. However, pyrolysis is the more advantageous recycling system for thermosetting resins and thus efforts should be made to control the pyrolysis in order to avoid or minimize the development of toxics. Homolytic scission of the aromatic bromine and condensation of aromatic bromine with phenolic hydroxyl are the main processes occuring in the range 270-340°C. A large amount of charred residue is left as a consequence of condensation reactions. HBr and brominated phenols and bisphenols are the main volatile products formed. Brominated dibenzodioxins structures are included in the charred residue and not evolved in the volatile phases.

Composite materials of thermoplastic starch and fibers from the ethanol-water fractionation of bagasse

The aim of this study was to evaluate the potential of the fibrous material obtained from ethanol-water fractionation of bagasse as reinforcement of thermoplastic starches in order to improve their mechanical properties. The composites were elaborated using matrices of corn and cassava starches plasticized with 30 wt%glycerin. The mixtures (0,5,10 and 15 wt% bagasse fiber) were elaborated in a rheometer at 150 degrees C. The mixtures obtained were pressed on a hot plate press at 155 degrees C. The test specimens were obtained according to ASTM D638. Tensile tests, moisture absorption tests for 24 days (20-23 degrees C and 53% RH, ASTM E104), and dynamic-mechanical analyses (DMA) in tensile mode were carried out. Images by scanning electron microscopy (SEM) and X-ray diffraction were obtained. Fibers (10 wt% bagasse fiber) increased tensile strength by 44% and 47% compared to corn and cassava starches, respectively. The reinforcement (15 wt% bagasse fiber) increased more than fourfold the elastic modulus on starch matrices. The storage modulus at 30 C (E(30 degrees C)`) increased as the bagasse fiber content increased, following the trend of tensile elastic modulus. The results indicate that these fibers have potential applications in the development of biodegradable composite materials. (c) 2011 Elsevier B.V. All rights reserved.

Study of the production of polyesters for polyurethanes at pilot plant scale

Dissertação para obtenção do grau de Mestre em Engenharia Química

Studies on the Toughening of Epoxy Resins

This thesis aims to develop new toughened systems for epoxy resin via physical and chemical modifications. Initially the synthesis of DGEBA was carried out and the properties compared with that of the commercial sample. Subsequently the modifier resins to be employed were synthesized. The synthesized resin were characterized by spectroscopic method (FTIR and H NMR), epoxide equivalent and gel permeation chromatography. Chemical modification involves the incorporation of thermoset resins such a phenolics, epoxy novolacs, cardanol epoxides and unsaturated polyester into the epoxy resin by reactive belnding. The mechanical and thermal properties of the blends were studied. In the physical modification route, elastomers, maleated elastomers and functional elastomers were dispersed as micro-sized rubber phase into the continuous epoxy phase by a solution blending technique as against the conventional mechanical blending technique. The effect of matrix toughening on the properties of glass reinforced composites and the effect of fillers on the properties of commercial epoxy resin were also investigated. The blends were characterized by thermo gravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, scanning electron microscopy and mechanical property measurements. Among the thermoset blends, substantial toughening was observed in the case of epoxy phenolic novolacs especially epoxy para cresol novolac (ECN). In the case of elastomer blending , the toughest blends were obtained in the case of maleic anhydride grafted NBR. Among functional elastomers the best results were obtained with CTBN. Studies on filled and glass reinforced composites employing modified epoxy as matrix revealed an overall improvement in mechanical properties

Modification of Natural Rubber using Thermoset Resins

This thesis presents the findings of a study on incorporating vanous thermoset resins into natural rubber for property improvement. Natural rubber is an important elastomer with the unique attribute of being a renewable agricultural product. The study was undertaken to investigate the extent to which the drawbacks of natural rubber, especially its poor thermal and oil resistance propel1ies could be nullified by blending with common thermoset resins. A thorough and comparative understanding of the perfonnance of different resins from this viewpoint will be beneficial for both natural IUbber processors and consumers. In this study the thennoset resins used were epoxy resin, phenolics, epoxidised phenolics and unsaturated polyester resin.The resins were incorporated into NR during compounding and their effects on the properties of NR were studied after vulcanization. Properties were studied for both gum and filled N R compounds. The important properties studied are cure characteristics, mechanical properties, ageing propel1ies, thermal propel1ies, crosslink density and extractability. Characterization studies were also conducted using FTIR, TGA and DSC.Improvement in mechanical properties was noticed in many cases. The results show that most resins lead to a reduction in the cure time of NR. The perfonnance of epoxy resin is most noticeable in this respect. Mechanical properties of the modified IUbber show maximum improvement in the case of epoxidised novolacs. Most resins are seen to improve the thermal and oil resistance propel1ies of NR. Epoxy novolacs show maximum effect in this respect also. However the presence of tillers is found to moderate the positive effects of the thermoset resins considerably.

Modification of Phenol Formaldehyde Resin for Improved Mechanical Properties

Phenolic resins suffer from the presence of microvoids on curing. This often leads to less than satisfactory properties in the cured resin. This disadvantage has limited the use of phenolic resins to some extent. This study is an attempt to improve the mechanical properties of the phenolic resol resins by chemical modification aimed at reducing the microvoid population. With this end in view various themoset resins synthesised under predetennined conditions have been employed for modifying phenolic resols. Such resins include unsaturated polyester, epoxy and epoxy novolac prepolymers. The results establish the effectiveness of these resins for improving the mechanical properties of phenolics. Experimental and analytical techniques used include FTIR, DMA, TGA, SEM and mechanical property evaluation. While most of the modifier resins employed give positive results the effect of adding UP is found to be surprising as well as impressive.

Utilização de resíduo lignocelulósico na obtenção de chapa de madeira aglomerada homogênea e compósito reforçado com fibra de vidro-E

This research is about the use of the coconut´s endocarp (nucifera linn) and the waste of derivatives of wood and furniture as raw material to technological use. In that sense, the lignocellulosic waste is used for manufacture of homogeneous wood sheet agglomerate (LHWS) and lignocellulosic load which take part of a polymeric composite with fiber glass E (GFRP-WC). In the manufacturing of the homogeneous wood sheet agglomerate (LHWS), it was used mamona´s resin as waste s agglutinating element. The plates were taken up in a hydraulic press engine, heated, with temperature control, where they were manufactured for different percentage of waste wood and coconuts nucífera linn. Physical tests were conducted to determine the absorption of water, density, damp grade (in two hours and twenty-four hours), swelling thickness (in two hours and twenty-four hours), and mechanical tests to evaluate the parallel tensile strength (internal stick) and bending and the static (steady) flexural. The physical test´s results indicate that the LHWS can be classified as bonded wood plate of high-density and with highly water resistant. In the mechanical tests it was possible to establish that LHWS presents different characteristics when submitted to uniaxial tensile and to the static (steady) flexural, since brittle and elasticity module had a variation according to the amount of dry endocarp used to manufacture each trace of LHWS. The GFRP-WC was industrially manufactured by a hand-lay-up process where the fiber glass E was used as reinforcement the lignocellulósic´s waste as load. The matrix was made with ortofitalic unsaturated polyester resin. Physical and mechanical tests were performed in presence of saturated humidity and dry. The results indicated good performance of the GFRP-WC, as traction as in flexion in three points. The presence of water influenced the modules obtained in the flexural and tensile but there were no significant alteration in the properties analyzed. As for the fracture, the analysis showed that the effects are more harmful in the presence of damp, under the action of loading tested, but despite this, the fracture was well defined starting in the external parts and spreading to the internal regions when one when it reaches the hybrid load

Estudo da flamabilidade e resistência à chama de compósito de poliéster insaturado e fibra da folha do abacaxizeiro (PALF)

In the present research work, composites were prepared using pine apple leaf fibres (PALF) as reinforcement with unsaturated polyester resin as matrix, incorporating with fire retardant at different compositions. The PALF was obtained from the decortication of pine apple leaves obtained from Ramada 4 from Ielmo Marinho in the State of Rio Grande do Norte. The unsaturated polyester resin and the catalyzer were bought from the local establishment. The fire retardant, aluminium tri-hydroxide - Al(OH)3 was donated by Alcoa Alumínio S.A and was used in the proportions of 20%, 40% and 60% w/w. Initially the fibres were treated with 2% NaOH for 1 hour, to remove any impurities present on the fibre surface, such as wax, fat, pectin and pectate, in order to have a better adsorption of the fibres with the matrix as well as the flame retardant. The fibre mat was prepared in a mat preparator by immersion, developed in the Textile Engineering Laboratory, at the UFRN. The composites (300x300x3 mm) were prepared by compression molding and the samples (150x25x3 mm) for analysis of the properties were cut randomly using a laser cutter. Some of the cut samples were used to measure the smoke emission and fire resistance using UL94 standard. Mechanical tension-extension and flexural properties were carried in CTGás RN and the Laboratório de Metais e Ensaios Mecânicos Engenharia de Materiais UFRN , as well as SEM studies were carried out at Núcleo de Estudos em Petróleo e Gás Natural - UFRN . From the observed results, it was noted that, there was no marked influence of the fire retardant on the mechanical properties. Also in the water absorption test, the quantity of water absorbed was less in the sample with higher concentration of fire retardant. It was also observed that the increase in the proportion of the fire retardant increased the time of burning, may be due to the compactness of the composite due to the presence of fire retardant as a filling material even though it was meant to reduce the rate of inflammability of the composite

Desenvolvimento e análise de material compósito a base de penas de frango (fibras de queratina-KF) e matriz de poliéster insaturado

Use of natural fibres as a reinforcement material in the manufacture of composites show a series of advantages: availability, biodegradability, low weight and regeneration in relation to synthetic fibres, thus justifying its utilization. In the present research work, composites were developed with chicken feathers (KF), using unsaturated polyester resin as matrix, for diversified applications, mainly in the furniture/timber industry.At present, in Brazil the chicken feathers are used as part of the animal feed, even though this material possesses low aggregated value. The chicken feathers are hollow, light and resistant. After washing with water at room temperature, a part of the chicken feathers were treated with 2% NaOH. Composites were manufactured using treated and untreated chicken feathers with unsaturated orthothalic polyester resin and 1% peroxide as catalyser, obtained in the commerce. Samples with size 150x25x3 mm for mechanical tests were cut by laser in the composite plate. Mechanical analyses were carried out in the Laboratório de Metais e Ensaios Mecânicos UFRN. All the analyses were in accordance with ASTM standards. SEM analyses were also carried out on the samples.In the analyses of the results obtained, it was observed that the composites made with untreated chicken feathers showed better results (Traction 11.406 MPa and 9.107 MPa Bending 34.947 and 20.918 MPa for samples with and without treatment respectively) compared to the composite with treated feathers. Very low values of the water absorption results, evidenced the impermeability characteristic of the feathers. From the SEM images, the structure, fracture and the fibre/matrix adsorption can be evidenced. In the flammability test, it was observed that despite the feathers having sulfur as a constituent, natural inhibitor of flame, no burning support of the composites, because the manufacturing process of the composite

Estudo da incorporação de resíduo industrial polimérico ao CAP

This work presents the incorporation of an industrial polymeric waste into a petroleum asphalt cement with penetration grade 50-60 (CAP 50-60). The main goal of this research is the development of a polymer-modified asphalt, with improvements in its physical properties, in order to obtain a more resistant material to the traffic loads. Furthermore, the use of this polymeric waste will result in economic and environmental benefits. The CAP 50-60 used in this research was kindly supplied by LUBNOR Lubrificantes e Derivados de Petróleo do Nordeste (produced in Fazenda Belém Aracati - Ceará) and the industrial polymeric waste was provided by a button manufacturer industry, located in Rio Grande do Norte state. This polymeric waste represents an environmental problem due to its difficulty in recycling and disposal, being necessary the payment by the industry to a landfill. The difficulty in its reuse is for being this material a termofixed polymer, as a result, the button chips resulting from the molding process cannot be employed for the same purpose. The first step in this research was the characterization of the polymeric waste, using Differential Scanning Calorimetry (DSC) Infrared spectroscopy (IR spectroscopy), and Thermogravimetric analysis (TGA). Based on the results, the material was classified as unsaturated polyester. After, laboratory experiments were accomplished seeking to incorporate the polymeric waste into the asphalt binder according to a 23 experimental factorial design, using as main factors: the polymer content (2%, 7% and 14%), the temperature of the mixture (140 and 180 oC) and the reaction time (20 and 60 minutes). The characterization of the polymer-modified asphalt was accomplished by traditional tests, such as: penetration, ring and ball softening point, viscosity, ductility and flash point temperature. The obtained results demonstrated that the addition of the polymeric waste into the asphalt binder modified some of its physical properties. However, this addition can be considered as a feasible alternative for the use of the polymeric waste, which is a serious environmental and technological problem.

Estudo do comportamento mecânico de um eco-compósito para aplicação como painéis divisórios de ambientes

Esta pesquisa teve como objetivo o estudo do comportamento mecânico de um eco-compósito em estrutura laminada para aplicação como painéis divisórios de ambientes utilizando uma resina comercial poliuretana a base natural de óleo de mamona, uma resina comercial de poliéster insaturada e um tecido de juta como reforço, obtido de sacarias. A fração em massa de produto natural (juta) ou de base natural (poliuretana a base de óleo de mamona) totalizou 44,32%, habilitando sua denominação como eco-compósito. Foram realizados os ensaios de tração, de compressão, de flexão, de impacto Charpy e de impacto por queda de dardo nos materiais constituintes do compósito para verificação da contribuição de cada material para as propriedades do compósito. Os ensaios de tração foram realizados na matriz de poliuretana, na matriz de poliéster, no tecido de juta, na matriz híbrida (resina de poliuretana e resina de poliéster) e no compósito. Os ensaios de compressão foram realizados na matriz de poliuretana, na matriz de poliéster, na matriz híbrida e no compósito. Os ensaio de flexão foram realizados na matriz de poliéster, na matriz híbrida e no compósito. Os ensaios de impacto foram realizados na matriz de poliuretana, na matriz de poliéster, na matriz híbrida e no compósito. Os resultados obtidos mostram que o compósito apresenta bom comportamento quando submetido a impacto e a esforços de tração.

Clay-based polymer nanocomposites: Research and commercial development

This paper reviews the recent research and development of clay-based polymer nanocomposites. Clay minerals, due to their unique layered structure, rich intercalation chemistry and availability at low cost, are promising nanoparticle reinforcements for polymers to manufacture low-cost, lightweight and high performance nanocomposites. We introduce briefly the structure, properties and surface modification of clay minerals, followed by the processing and characterization techniques of polymer nanocomposites. The enhanced and novel properties of such nanocomposites are then discussed, including mechanical, thermal, barrier, electrical conductivity, biodegradability among others. In addition, their available commercial and potential applications in automotive, packaging, coating and pigment, electrical materials, and in particular biomedical fields are highlighted. Finally, the challenges for the future are discussed in terms of processing, characterization and the mechanisms governing the behaviour of these advanced materials.

Phase behavior, crystallization, and nanostructures in thermoset blends of epoxy resin and amphiphilic star-shaped block copolymers

This article reports thermoset blends of bisphenol A-type epoxy resin (ER) and two amphiphilic four-arm star-shaped diblock copolymers based on hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly(propylene oxide) (PPO). 4,4'-Methylenedianiline (MDA) was used as a curing agent. The first star-shaped diblock copolymer with 70 wt% ethylene oxide (EO), denoted as (PPO-PEO)(4), consists of four PPO-PEO diblock arms with PPO blocks attached on an ethylenediamine core; the second one with 40 wt% EO, denoted as (PEO-PPO)(4), contains four PEO-PPO diblock arms with PEO blocks attached on an ethylenediamine core. The phase behavior, crystallization, and nanoscale structures were investigated by differential scanning calorimetry, transmission electron microscopy, and small-angle X-ray scattering. It was found that the MDA-cured ER/(PPO-PEO)(4) blends are not macroscopically phase-separated over the entire blend composition range. There exist, however, two microphases in the ER/(PPO-PEO)(4) blends. The PPO blocks form a separated microphase, whereas the ER and the PEO blocks, which are miscible, form another microphase. The ER/(PPO-PEO)(4) blends show composition-dependent nanostructures on the order of 10-30 nm. The 80/20 ER/(PPO-PEO)(4) blend displays spherical PPO micelles uniformly dispersed in a continuous ER-rich matrix. The 60/40 ER/(PPO-PEO)(4) blend displays a combined morphology of worm-like micelles and spherical micelles with characteristic of a bicontinuous microphase structure. Macroscopic phase separation took place in the MDA-cured ER/(PEO-PPO)(4) blends. The MDA-cured ER/(PEO-PPO)(4) blends with (PEO-PPO)(4) content up to 50 wt% exhibit phase-separated structures on the order of 0.5-1 mu m. This can be considered to be due to the different EO content and block sequence of the (PEO-PPO)(4) copolymer. (c) 2006 Wiley Periodicals, Inc.

Utilização de resíduo lignocelulósico na obtenção de chapa de madeira aglomerada homogênea e compósito reforçado com fibra de vidro-E

This research is about the use of the coconut´s endocarp (nucifera linn) and the waste of derivatives of wood and furniture as raw material to technological use. In that sense, the lignocellulosic waste is used for manufacture of homogeneous wood sheet agglomerate (LHWS) and lignocellulosic load which take part of a polymeric composite with fiber glass E (GFRP-WC). In the manufacturing of the homogeneous wood sheet agglomerate (LHWS), it was used mamona´s resin as waste s agglutinating element. The plates were taken up in a hydraulic press engine, heated, with temperature control, where they were manufactured for different percentage of waste wood and coconuts nucífera linn. Physical tests were conducted to determine the absorption of water, density, damp grade (in two hours and twenty-four hours), swelling thickness (in two hours and twenty-four hours), and mechanical tests to evaluate the parallel tensile strength (internal stick) and bending and the static (steady) flexural. The physical test´s results indicate that the LHWS can be classified as bonded wood plate of high-density and with highly water resistant. In the mechanical tests it was possible to establish that LHWS presents different characteristics when submitted to uniaxial tensile and to the static (steady) flexural, since brittle and elasticity module had a variation according to the amount of dry endocarp used to manufacture each trace of LHWS. The GFRP-WC was industrially manufactured by a hand-lay-up process where the fiber glass E was used as reinforcement the lignocellulósic´s waste as load. The matrix was made with ortofitalic unsaturated polyester resin. Physical and mechanical tests were performed in presence of saturated humidity and dry. The results indicated good performance of the GFRP-WC, as traction as in flexion in three points. The presence of water influenced the modules obtained in the flexural and tensile but there were no significant alteration in the properties analyzed. As for the fracture, the analysis showed that the effects are more harmful in the presence of damp, under the action of loading tested, but despite this, the fracture was well defined starting in the external parts and spreading to the internal regions when one when it reaches the hybrid load

Experimental study on polyester based concretes filled with glass fibre reinforced plastic recyclates – a contribution to composite materials sustainability

The development and applications of thermoset polymeric composites, namely fibre reinforced plastics (FRP), have shifted in the last decades more and more into the mass market [1]. Despite of all advantages associated to FRP based products, the increasing production and consume also lead to an increasing amount of FRP wastes, either end-of-lifecycle products, or scrap and by-products generated by the manufacturing process itself. Whereas thermoplastic FRPs can be easily recycled, by remelting and remoulding, recyclability of thermosetting FRPs constitutes a more difficult task due to cross-linked nature of resin matrix. To date, most of the thermoset based FRP waste is being incinerated or landfilled, leading to negative environmental impacts and supplementary added costs to FRP producers and suppliers. This actual framework is putting increasing pressure on the industry to address the options available for FRP waste management, being an important driver for applied research undertaken cost efficient recycling methods. [1-2]. In spite of this, research on recycling solutions for thermoset composites is still at an elementary stage. Thermal and/or chemical recycling processes, with partial fibre recovering, have been investigated mostly for carbon fibre reinforced plastics (CFRP) due to inherent value of carbon fibre reinforcement; whereas for glass fibre reinforced plastics (GFRP), mechanical recycling, by means of milling and grinding processes, has been considered a more viable recycling method [1-2]. Though, at the moment, few solutions in the reuse of mechanically-recycled GFRP composites into valueadded products are being explored. Aiming filling this gap, in this study, a new waste management solution for thermoset GFRP based products was assessed. The mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the potential added value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. The use of a cementless concrete as host material for GFRP recyclates, instead of a conventional Portland cement based concrete, presents an important asset in avoiding the eventual incompatibility problems arisen from alkalis silica reaction between glass fibres and cementious binder matrix. Additionally, due to hermetic nature of resin binder, polymer based concretes present greater ability for incorporating recycled waste products [3]. Under this scope, different GFRP waste admixed polymer mortar (PM) formulations were analyzed varying the size grading and content of GFRP powder and fibre mix waste. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacities of modified mortars with regard to waste-free polymer mortars.