MORPHOLOGY AND DYNAMIC MECHANICAL-PROPERTIES OF AB CROSS-LINKED POLYMERS BASED ON POLYURETHANES

Polyoxypropylene glycol (PPG) (or castor oil) and toluene diisocyanate (TDI) were mixed, and the prepolymer polyurethane (PU) (I) was formed. Vinyl-terminated polyurethane (II) was prepared from (I), and hydroxyethyl acrylate, AB crosslinked polymers (ABCPs) were synthesized from (II) and vinyl monomers such as styrene, methyl methacrylate, vinyl acetate, etc. The dynamic mechanical properties and morphology of ABCPs were measured. The ABCPs based on PPG have double glass transition temperatures (T(g)) on the sigma-vs. temperature curves. They display a two-phase morphology with plastic components forming the continous phase and PU-rich domains forming the separated phase on the electron micrographs. Irregular shapes and a highly polydisperse distribution of PU-rich domain sizes were observed. The crosslink density of ABCPs has a notable effect on the morphology and properties. The average diameter of the PU-rich domains depends on the molecular weight of prepolymer PPG. The highly crosslinked structures will produce large numbers of very small domains. ABCPs based on castor oil show a single T(g) relaxation on the dynamic mechanical spectra. The compatibility between the two components is much better in ABCPs based on castor oil than in those based on PPG, because there is a high crosslink density in the former. Comparison of the dynamic mechanical spectra of ABCP and interpenetrating networks (IPN) based on castor oil with similar crosslink density and composition imply that the two components in ABCP are compatible whereas microphase separation occurs in IPN. An improvement in the compatibility is achieved by the crosslinking between the two networks.

11-ketotestosterone inhibits the alternative mating tactic in sneaker males of the peacock blenny, Salaria pavo

In the peacock blenny, Salaria pavo, a species with courtship sex-role reversal, smaller, younger males mimic the courtship behavior and the nuptial coloration of females in order to get access to nests during spawning and to parasitize egg fertilization from nest-holder males. Later in their life, sneakers transform both morphologically and behaviorally into nest-holder males. In the present paper we investigate the activational role of 11-ketotestosterone (KT), the most potent androgen in most teleost species, to promote the switch between tactics in sneaker males of S. pavo. Sneakers were implanted either with KT or with control (i.e. castor oil) silastic implants. A week after implantation they were subjected to a set of behavioral tests and morphometric measurements. KT treatment promoted the differentiation of secondary sex characters, such as the anal glands, and inhibited the expression of female courtship behavior. KT-treated sneakers also showed a trend toward less frequent display of female nuptial coloration. There was no effect of KT treatment on the expression of typical nest-holder male behavior. Finally, there was no effect of KT treatment on the number or soma size of arginine vasotocin neurons in the preoptic area, which are often associated with the expression of vertebrate sexual behavior. Thus, KT seems to play a key role in mating tactic switching by inhibiting the expression of female courtship behavior and by promoting the development of male displaying traits (e.g. anal glands). The lack of a KT effect on behavior typical of nest-holding males and vasotocinergic preoptic neurons suggests that a longer time frame or other endocrine/social signals are needed for the initiation of these traits in males that are switching tactics.

Modification of Unsaturated Polyester Resin by Polyurethane Prepolymers

Unsaturated polyester resins (UPRs) are extensively used by the fiber-reinforced plastic (FRPs) industry. These resins have the disadvantages of brittleness and poor resistance to crack propagation. In this study, UPRs were chemically modified by reactive blending with polyurethane prepolymers having terminal isocyanate groups. Hybrid networks were formed by copolymerisation of unsaturated polyesters with styrene and simultaneous reaction between terminal hydroxyl groups of unsaturated polyester and isocyanate groups of polyurethane prepolymer. The prepolymers were based on toluene diisocyanate (TDI) and each of hydroxy-terminated natural rubber (HTNR), hydroxy- terminated polybutadiene (HTPB), polyethylene glycol (PEG), and castor oil. Properties like tensile strength, toughness, impact resistance, and elongation-at-break of the modified UPRs show considerable improvement by this modification. The thermal stability of the copolymer is also marginally better

The effect of vessel diameter on time dependent gas hold-up variations in highly viscous impeller agitated liquids

Time dependent gas hold-up generated in the 0.3 and 0.6 m diameter vessels using high viscosity castor oil and carboxy methyl cellulose (CMC) solution was compared on the basis of impeller speed (N) and gas velocity (V-G). Two types of hold-up were distinguished-the hold-up due to tiny bubbles (epsilon(ft)) and total hold-up (epsilon(f)), which included large and tiny bubbles. It was noted that vessel diameter (i.e. the scale of operation) significantly influences (i) the trends and the values of epsilon(f) and epsilon(ft), and (ii) the values of tau (a constant reflecting the time dependency of hold-up). The results showed that a scale independent correlation for gas hold-up of the form epsilon(f) or epsilon(ft) = A(N or P-G/V)(a) (V-G)(b), where "a" and "b" are positive constants is not appropriate for viscous liquids. This warrants further investigations into the effect of vessel diameter on gas hold-up in impeller agitated high viscosity liquids (mu or mu(a) > 0.4 Pa s). (C) 2003 Elsevier B.V. All rights reserved.

Resonance response of electrorheological fluids in vertical oscillation squeeze flow

The resonance effect of microcrystalline cellulose/castor oil electrorheological (ER) suspensions was studied in a compressed oscillatory squeeze flow under external electric fields. The resonance frequency first increases linearly with increasing external held, and then shift to high-field plateau. The amplitudes of resonance peak increase sharply with the applied fields in the range of 0.17-1.67kV/mm. The phase difference of the reduced displacement relative to the excitation force inverses in the case of resonance. A viscoelasticity model of the ER suspensions, which offers both the equivalent stiffness and the viscous damping, should be responsible for the appearance of resonance. The influence of the electric field on the resonance frequency and the resonance hump is consistent qualitatively with the interpretation of our proposed model. Storage modulus G' was presented for the purpose of investigating this influence.

Squeeze flow viscoelasticity of electrorheological fluids based on microcrystalline cellulose

Dynamic viscoelasticity of electrorheological fluids based on microcrystalline cellulose/castor oil suspensions was experimentally investigated in squeeze flow. The dependence of storage modulus G' and loss modulus G" parallel to external electric field on electric fields and strain amplitudes is presented. The experiments show that, when external electric field is higher than the critical field, the viscoelasticity of the ER fluids converts from linear to nonlinear, and the ER fluids transfer from solid-like state to fluid state with the growth of strain amplitude. The influences of strain amplitude and oscillatory frequency on the nonlinearity of viscoelasticity were also studied.

Structural Investigation of MFe(2)O(4) (M = Fe, Co) Magnetic Fluids

Ferrites of the type M(II)Fe(2)O(4) (M = Fe and Co) have been prepared by the traditional coprecipitation method. These ferrites were modified by the adsorption of fatty acids derived from soybean and castor oil and were then dispersed in cyclohexane, providing very stable magnetic fluids, readily usable in nonpolar media. The structural properties of the ferrites and modified ferrites as well as the magnetic fluids were characterized by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), DRIFTS (diffusion reflectance infrared Fourier transform spectroscopy), FTMR (Fourier transform near-infrared), UV-vis, normal Raman spectroscopy, and surface-enhanced Raman scattering (SERS). XRD and TEM analysis have shown that the magnetic nanoparticles (nonmodified and modified) present diameters in the range of 10-15 nm. DRIFTS measurements have shown that the carboxylate groups of soybean and castor oil fatty acids adsorb on the ferrite surface, forming three different structures: a bridging bidentate, a bridging monodentate, and a bidentate chelate structure. The FTIR and Raman spectra of nonmodified Fe(3)O(4) and CoFe(2)O(4) nanoparticles have shown that the number of observed phonons is not compatible with the expected O(h)(7) symmetry, since IR-only active phonons were observed. in the Raman spectra and vice versa. SERS measurements of a CoFe(2)O(4) thin film on a SERS-active gold electrode at different applied potentials made possible the assignment of the signals near 550 and 630 cm(-1) to Co-O motions and the signals near 470 and 680 cm(-1) to Fe-O motions.

Effect of polyol excess on the electrical property of vegetable-polyurethane film

Freestanding castor oil-based polyurethane (PU) film was obtained using spin-coating method. The effect of polyol content was analysed by means of thermally stimulated depolarisation current and AC dielectric measurements techniques. Two relaxation peaks were observed in the temperature range of -40 to 60 degrees C for PU with different polyol contents. The presence of polyol excess provides a shift to lower temperature of the a relaxation and the decrease in the activation energy of the transition in this region might be attributed to the plasticising effect of the polyol. The peak at higher temperature is due to the Maxwell-Wagner-Sillars relaxation, which also shifts in the low temperature direction as the polyol content is increased.

Desenvolvimento de redes de polímeros interpenetrantes (IPN) para a aplicação como eletrólito polimérico

Uma nova rede de polímeros interpenetrantes (IPN) baseada em poliuretana de óleo de mamona e poli(etileno glicol) e poli(metacrilato de metila) foi preparada para ser utilizada como eletrólito polimérico. Os seguintes parâmetros de polimerização foram avaliados: massa molecular do poli(etileno glicol) (PEG), concentração de PEG e concentração de metacrilato de metila. As membranas de IPN foram caracterizadas por calorimetria diferencial de varredura (DSC) e espectroscopia de infravermelho por transformada de Fourier (FT-IR). Os eletrólitos de redes de polímeros interpenetrantes (IPNE) foram preparados a partir da dopagem com sal de lítio através do inchamento numa solução de 10% em massa de LiClO4 na mistura de carbonato de etileno e carbonato de propileno na razão mássica de 50:50. As IPNEs foram caracterizadas por espectroscopia de impedância eletroquímica e Raman. As IPNEs foram testadas como eletrólito polimérico em supercapacitores. As células capacitivas foram preparadas utilizando eletrodos de polipirrol (PPy). Os valores de capacitância e eficiência foram calculados por impedância eletroquímica, voltametria cíclica e ciclos galvonostáticos de carga e descarga. Os valores de capacitância obtidos foram em torno de 90 F.g-1 e eficiência variou no intervalo de 88 a 99%. Os valores de densidade de potência foram superiores a 250 W.kg-1 enquanto que a densidade de energia variou de 10 a 33 W.h.kg-1, dependendo da composição da IPNE. As características eletroquímicas do eletrólito formado pela IPN-LiClO4 (IPNE) foram comparadas aos eletrólitos poliméricos convencionais, tais como poli(difluoreto de vinilideno)-(hexafluorpropileno) ((PVDF-HFP/LiClO4) e poliuretana comercial (Bayer desmopan 385) (PU385/LiClO4). As condutividades na temperatura ambiente foram da ordem de 10-3 S.cm-1. A capacitância da célula utilizando eletrodos de PPy com eletrólito de PVDFHFP foi de 115 F.g-1 (30 mF.cm-2) e 110 F.g-1 (25 mF.cm-2) para a célula com PU385 comparadas a 90 F.g-1 (20 mF.cm-2) para a IPNE. Os capacitores preparados com eletrólito de IPNE apresentaram valores de capacitância inferior aos demais, entretanto provaram ser mais estáveis e mais resistentes aos ciclos de carga/descarga. A interpenetração de duas redes poliméricas, PU e PMMA produziu um eletrólito com boa estabilidade mecânica e elétrica. Um protótipo de supercapacitor de estado sólido foi produzindo utilizando eletrodos impressos de carbono ativado (PCE) e o eletrólito polimérico de IPNE. A técnica de impressão de carbono possui várias vantagens em relação aos outros métodos de manufatura de eletrodos de carbono, pois a área do eletrodo, espessura e composição são variáveis que podem ser controladas experimentalmente. As células apresentaram uma larga janela eletroquímica (4V) e valores da capacitância da ordem de 113 mF.cm-2 (16 F.g-1). Métodos alternativos de preparação do PCE investigados incluem o uso de IPNE como polímero de ligação ao carbono ativado, estes eletrodos apresentaram valores de capacitância similares aos produzidos com PVDF. A influência do número de camadas de carbono usadas na produção do PCE também foi alvo de estudo. Em relação ao eletrólito polimérico, o plastificante e o sal de lítio foram adicionados durante a síntese, formando a IPNGel. As células apresentaram alta capacitância e boa estabilidade após 4000 ciclos de carga e descarga. As membranas de IPN foram testadas também como reservatório de medicamento em sistemas de transporte transdérmico por iontoforese. Os filmes, mecanicamente estáveis, formaram géis quando inchado em soluções saturadas de lidocaina.HCl, anestésico local, em propileno glicol (PG), poli(etileno glicol) (PEG400) e suas misturas. O grau de inchamento em PG foi de 15% e 35% em PEG400. Agentes químicos de penetração foram utilizados para diminuir a resistência da barreira causada pela pele, dentre eles o próprio PG, a 2-pirrolidinona (E1) e a 1-dodecil-2-pirrolidinona (E2). Os géis foram caracterizados por espectroscopia de impedância eletroquímica e transporte passivo e por iontoforese através de uma membrana artificial (celofane). O sistema IPN/ lidocaina.HCl apresentou uma correlação linear entre medicamento liberado e a corrente aplicada. Os melhores resultados de transporte de medicamento foram obtidos utilizando o PG como solvente.

Obtenção de álcool alílico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de óleo de mamona

In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ° C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (υ C = C) 1470 -1600 cm -1 and (υ CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals

Desenvolvimento de metodologias analíticas alternativas por cromatografia gasosa para análise de biodiesel

Since the beginning of the National Program for Production and Use of Biodiesel in Brazil, in 2004, different raw materials were evaluated for biodiesel production, trying to combine the agricultural diversity of the country to the desire to reduce production coasts. To determine the chemical composition of biodiesel produced from common vegetables oils, international methods have been used widely in Brazil. However, for analyzing biodiesel samples produced from some alternative raw materials analytical problems have been detected. That was the case of biodiesel from castor oil. Due the need to overcome these problems, new methodologies were developed using different chromatographic columns, standards and quantitative methods. The priority was simplifying the equipment configuration, realizing faster analyses, reducing the costs and facilitating the routine of biodiesel research and production laboratories. For quantifying free glycerin, the ethylene glycol was used in instead of 1,2,4-butanetriol, without loss of quality results. The ethylene glycol is a cheaper and easier standard. For methanol analyses the headspace was not used and the cost of the equipment used was lower. A detailed determination of the esters helped the deeper knowledge of the biodiesel composition. The report of the experiments and conclusions of the research that resulted in the development of alternative methods for quality control of the composition of the biodiesel produced in Brazil, a country with considerable variability of species in agriculture, are the goals of this thesis and are reported in the following pages

Análise macroscópica e histológica do emprego da poliuretana derivada do óleo de mamona (Ricinus communis) aplicada na tíbia de cães em fase de crescimento

OBJETIVO: Estudar o efeito da poliuretana de mamona aplicada ao osso de cães em crescimento. MÉTODOS: Foram utilizados 12 cães subdivididos aleatoriamente em 3 grupos, os quais receberam o implante de mamona na face medial proximal da tíbia, com análise macroscópica e histopatológica aos 30 (GIII), 60 (GII) e 90 (GI) dias. RESULTADOS: A poliuretana foi recoberta por uma cápsula conjuntiva fibrosa, não ocorrendo proliferação óssea ao seu redor. CONCLUSÃO: A poliuretana é biocompatível, comportando-se como espaçador biológico em cães. Nesta espécie não ocorre a osteointegração.

Compósito de poliuretano de mamona e vermiculita para isolação térmica

They are in this study the experimental results of the analysis of thermal performance of composite material made from a plant matrix of polyurethane derived from castor oil of kernel of mamona (COF) and loading of clay-mineral called vermiculite expanded. Bodies of evidence in the proportions in weight of 10%, 15% and 20% were made to determine the thermal properties: conductivity (k), diffusivity (ά) and heat capacity (C), for purposes of comparison, the measurements were also performed the properties of polyurethane of castor without charge and also the oil polyurethane (PU), both already used in thermal insulation. Plates of 0.25 meters of material analyzed were manufactured for use as insulation material in a chamber performance thermal coverage. Thermocouples were distributed on the surface of the cover, and inside the material inside the test chamber and this in turn was subjected to artificial heating, consisting of a bank of incandescent lamps of 3000 w. The results obtained with the composite materials were compared with data from similar tests conducted with the camera alone with: (a) of oil PU, (b) of COF (c) glass wool, (d ) of rock wool. The heat resistance tests were performed with these composites, obtaining temperature limits for use in the range of 100 º C to 130 º C. Based on the analysis of the results of performance and thermal properties, it was possible to conclude that the COF composites with load of expanded vermiculite present behavior very close to those exhibited by commercial insulation material

Desenvolvimento de um compósito de espuma rígida de poliuretana de mamona e fibras de sisal para isolação térmica

The search for sustainable technologies that can contribute to reduce energy consumption is a great challenge in the field of insulation materials. In this context, composites manufactured from vegetal sources are an alternative technology. The principal objectives of this work are the development and characterization of a composite composed by the rigid polyurethane foam derived from castor oil (commercially available as RESPAN D40) and sisal fibers. The manufacture of the composite was done with expansion controlled inside a closed mold. The sisal fibers where used in the form of needlepunched nonwoven with a mean density of 1150 g/m2 and 1350 g/m2. The composite characterization was performed through the following tests: thermal conductivity, thermal behavior, thermo gravimetric analysis (TG/DTG), mechanical strength in compression and flexural, apparent density, water absorption in percentile, and the samples morphology was analyzed in a MEV. The density and humidity percentage of the sisal fiber were also determined. The thermal conductivity of the composites was higher than the pure polyurethane foam, the addition of nonwoven sisal fibers will become in a higher level of compact foam, reducing empty spaces (cells) of polyurethane, inducing an increase in k value. The apparent density of the composites was higher than pure polyurethane foam. In the results of water absorption tests, was seen a higher absorption percent of the composites, what is related to the presence of sisal fibers which are hygroscopic. From TG/DTG results, with the addition of sisal fibers reduced the strength to thermal degradation of the composites, a higher loss of mass was observed in the temperature band between 200 and 340 °C, related to urethane bonds decomposition and cellulose degradation and its derivatives. About mechanical behavior in compression and flexural, composites presented a better mechanical behavior than the rigid polyurethane foam. An increase in the amount of sisal fibers induces a higher rigidity of the composites. At the thermal behavior tests, the composites were more mechanically and thermally resistant than some materials commonly used for thermal insulation, they present the same or better results. The density of nonwoven sisal fiber had influence over the insulation grade; this means that, an increaser in sisal fiber density helped to retain the heat

Estudo das propriedades termofísicas com variação da expansibilidade de compósito desenvolvido com matriz PUR-NOP e carga funcional de argilomineral

In this study were conducted experimental procedures for determination of variation of the expandability of rigid polyurethane foam (PUR) from a natural oil polyol (NOP), specifically the Castor oil plant, Ricinus communis, pure and additions of the vermiculite in phase dispersed in different percentage within a range from 0% to 20%, mass replacement. From the information acquired, were defined the parameters for production of bodies of test, plates obtained through controlled expansion, with the final volume fixed. Initially, the plates were subjected to thermal performance tests and evaluated the temperature profiles, to later be extracted samples duly prepared in accordance with the conditions required for each test. Was proceeded then the measurement of the coefficient of thermal conductivity, volumetric capacity heat and thermal diffusivity. The findings values were compared with the results obtained in the tests of thermal performance, contributing to validation of the same. Ultimately, it was investigated the influence that changes in physical-chemical structure of the material had exerted on the variation of thermophysical quantities through gas pycnometry, scanning electron microscopy (SEM) combined with energy dispersive X-ray fluorescence spectroscopy (EDXRF), infrared spectroscopy using Fourier transform (FTIR), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). Based on the results obtained was possible to demonstrate that all load percentage analyzed promoted an increase in the potential expansion (PE) of the resin. In production of the plates, the composites with density near at the free expansion presented high contraction during the cure, being the of higher density adopted as definitive standard. In the thermal performance tests, the heating and cooling curves of the different composites had presented symmetry and values very close for lines of the temperature. The results obtained for the thermophysical properties of composites, showed little difference in respect of pure foam. The percentage of open pores and irregularities in the morphology of the composites were proportionate to the increment of vermiculite. In the interaction between the matrix and dispersed phase, there were no chemical transformations in the region of interface and new compounds were not generated. The composites of PUR-NOP and vermiculite presented thermal insulating properties near the foam pure and percentage significantly less plastic in its composition, to the formulation with 10% of load