Application of Nonisothermal Cure Kinetics to the Interaction of Poly(ethylene terephthalate) with Alkyd Resin Varnish

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Non-isothermal decomposition kinetics of the interaction of poly(ethylene terephthalate) with alkyd varnish

The recycling of soft drink bottles poly(ethylene terephthalate) (PET) has been used as an additive in varnish containing alkyd resin. The PET, called to recycled PET (PET-R), was added to the varnish in increasing amounts. Samples of varnish containing PET-R (VPET-R) were used as a film onto slides and its thermal properties were evaluated using thermogravimetry (TG). Throughout the visual analysis and thermal behavior of VPET-R it is possible to identify that the maximum amount of PET-R added to the varnish without changing in the film properties was 2%.The kinetic parameters, such as activation energy (E) and the pre-exponential factor (A) were calculated by the isoconversional Flynn-Wall-Ozawa method for the samples containing 0.5 to 2.0% PET-R. A decrease in the values of E was verified for lower amounts of PET-R for the thermal decomposition reaction. A kinetic compensation effect (KCE) represented by the lnA=-13.42+0.23E equation was observed for all samples. The most suitable kinetic model to describe this decomposition process is the autocatalytic Sestak-Berggren, being the model applied to heterogeneous systems.

Kinetic studies of urban solid residues and leachate from sanitary landfill

Urban solid residues are constituted of food remaining, grass leaves, fruit peelings, paper, cardboard, rubber, plastic, etc. The organic fraction formed represents about 50% during the decomposition yields biogas and leachate, which are sources of pollution. Residue samples were collected from the landfill in different and cells from several ages and the corresponding leachate, both after treatments, were submitted to thermal analysis. Kinetic parameters were determined using Flynn-Wall-Ozawa method. The linear relation between the two kinetic parameters (ln A and E) was verified for organic residue urban's samples, but not for leachate's sample. The occurred difference can be attributed to the constituents present in leachate.

Effect of the catalyst MCM-41 on the kinetic of the thermal decomposition of poly(ethylene terephthalate)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Dehydration and volatilization non isothermic kinetic of the solid state aluminium 8-hydroxyquinolinate

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

Non-isothermal kinetic for lyophilized leachate from sanitary landfill and composting usine

Leachate samples from a sanitary landfill of Araraquara city and composting usine of Vila Leopoldina, São Paulo, Brazil were lyophilized to remove the water content. TG/DTG curves at different heating rates were recorded. The second step of the thermal decomposition of leachate from the Araraquara landfill (CB1), from the composting usine from Vila Leopoldina (CB2) from the organic phase extracted (FO) and aqueous phase (FA) were all kinetically evaluated using the non-isothermal method.By Flynn-Wall isoconversional method the following values were obtained: E=234 +/- 3.65 kJ mol(-1) and logA=29.7 +/- 0.58 min(-1) for CB1; E=129 +/- 1.66 kJ mol(-1) and logA=11.8 +/- 0.10 min(-1) for CB2; E=51.6 +/- 1.35 kJ mol(-1) and logA=6.09 +/- 0.09 min(-1) for FO and E=76.91 +/- 6.33 kJ mol(-1) and logA=8.88 +/- 0.7 min(-1) for FA with 95% confidence level. Applying the procedures of Malek and Koga, SB kinetic model (Sestak-Berggren) is the most appropriate to describe the decomposition of CB1, CB2, FO and FA.

Non-isothermal kinetic applied to thermal decomposition of commercial alkyd varnish

Samples of commercial alkyd resin varnish were spread in a film form on slides, dried at room temperature and exposed to solar radiation from one day up to seven months.Thermogravimetric measurements have been done. Based on the TG data, the Flynn-Wall isoconversional method was applied. The activation energy varied between 176-154 kJ mol(-1) and logA was between 15.5-12.9 min(-1) for A, B and C samples at 95% confidence level.

Kinetic of thermal decomposition of residues from different kinds of composting

Non-isothermal kinetic parameters regarding to the thermal decomposition of the ligninocellulosic fraction present in compost from urban solid residues (USR) obtained through stack covered (SC) with composted material, comes from the usine in composing of Araraquara city, São Paulo state, Brazil, and from stack containing academic restaurant organic solid residues (SAR). The samples were periodically revolved round 132 days of composting.Results from TG, DTG and DSC curves obtained on inert atmosphere indicated that the lignocellulosic fraction present, despite the slow degradation during the composting process, is thermally less stable than other substances originated during that process. The lignocellulosic fraction decomposition, between 200 and 400degreesC, were kinetically evaluated through non-isothermal methods of analysis.By using the Flynn-Wall and Ozawa isoconversional method, the medium activation energy, E-a, and pre-exponential factor, IgA, were 283.0+/-4.6, 257.6+/-1.3 U mol(-1) and 25.4+/-0.8, 23.2+/-0.2 min(-1),to the SC and SAR, respectively, at 95% confidence level.From E-a, and IgA values and DSC curves, Malek procedure could be applied, Suggesting that the SB (Sestik-Berggren) kinetic model is suitable for the first thermal decomposition step.

TG studies of a composite solid rocket propellant based on HTPB-binder

Thermal decomposition kinetics of solid rocket propellants based on hydroxyl-terminated polybutadiene-HTPB binder was studied by applying the Arrhenius and Flynn-Wall-Ozawa's methods. The thermal decomposition data of the propellant samples were analyzed by thermogravimetric analysis (TG/DTG) at different heating rates in the temperature range of 300-1200 K. TG curves showed that the thermal degradation occurred in three main stages regardless of the plasticizer (DOA) raw material, the partial HTPB/IPDI binder and the total ammonium perchlorate decompositions. The kinetic parameters E-a (activation energy) and A (pre-exponential factor) and the compensation parameter (S-p) were determined. The apparent activation energies obtained from different methods showed a very good agreement.

Application of non-isothermal cure kinetics on the interaction of poly(ethylene terephthalate) - Alkyd resin paints

Samples of paint (P), reused PET (PET-R) and paint/PET-R mixtures (PPET-R) were evaluated using DSC to verify their physical-chemical properties and thermal behavior. Films from paints and PPET-R are visually similar. It was possible to establish that the maximum amount of PET-R that can be added to paint without significantly altering its filming properties is 2%. The cure process (80-203°C) was identified through DSC curves. The kinetic parameters, activation energy (E a) and Arrhenius parameters (A) for the samples containing 0.5 to 1% of PET-R, were calculated using the Flynn-Wall-Ozawa isoconversional method. It was observed that for greater amounts of PET-R added, there is a decrease in the E a values for the cure process. A Kinetic compensation effect (KCE), represented by the equation InA=-2.70+0.31E a was observed for all the samples. The most suitable kinetic model to describe this cure process is the autocatalytic Šesták-Berggreen, model applied to heterogeneous systems. © 2007 Springer Science+Business Media, LLC.

Estudo de degradação térmica e caracterização de lodos provenientes de diferentes sistemas de tratamento de esgotos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização espectroscópica e estudo do comportamento térmico dos resíduos provenientes da cana-de-açúcar

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização físico-química e avaliação toxicológica preliminar do copolímero sulfato de condroitina-co-N-isopropilacrilamida para uso farmacêutico

A Indústria Farmacêutica utiliza polímeros em forma de nanopartículas em formulações de liberação controlada e vetorizada por possuírem baixo custo em relação a demais métodos de preparações de formas farmacêuticas, aparentemente não serem reconhecidos pelo sistema de defesa do organismo, proporcionar melhora da eficácia, diminuição da toxicidade e da dose de fármaco administrado. O sulfato de condroitina-co-Nisopropilacrilamida (SCM + NIPAAm) é um copolímero proposto para este fim, a partir da reação de um polímero sintético, o poli N-isopropilacrilamida (PNIPAAm), com características termossensíveis, com um natural, o Sulfato de Condroitina (SC), com características bioadesivas. Assim, a copolimerização pode ser capaz de somar estas propriedades e aperfeiçoar o seu uso como um veículo para liberação controlada. Este trabalho objetivou, portanto, realizar a caracterização fisico-quimica das partículas de sulfato de condroitina e Nisopropilacrilamida e do copolímero SCM+NIPAAm (2,5 % e 5%) e do SCM+PNIPAAm 2,5% e uma avaliação toxicológica parcial de um destes copolímeros que apresentar as melhores propriedades de um eficiente carreador de fármacos, selecionado a partir dos ensaios de caracterização físico-química. Para determinar a estrutura química dos sistemas particulados e analisar os seus componentes químicos, foi realizada a Espectroscopia de Ressonância Magnética Nuclear (RMN) e Espectroscopia do Infravermelho com Transformada de Fourrier (FTIR); Para analisar a morfologia das partículas, foi usado a Microscopia Eletrônica de Varredura (MEV); A Termogravimetria/ Termogravimetria Derivada e Análise Térmica Diferencial (TG/DTG) foi usada para avaliar o comportamento térmico dos sistemas particulados, bem como auxiliar na análise de Cinética de Degradação (CD, método de Flynn-Wall-Ozawa); Foi ainda realizado a técnica de degradação in vitro e a determinação carga superficial e tamanho de partículas (análise do Potencial Zeta, PZ). Para avaliar a toxicidade, foi realizado o bioensaio em microcrustáceo Artemia salina (24 e 48 h), viabilidade celular (citotoxicidade) em células PC-12 (método do MTT) e também a toxicidade aguda oral em camundongos. As análises de RMN, FTIR e MEV demonstraram semelhança quanto ao aspecto estrutural e morfológico entre os copolímeros estudados. As análises de TG demonstraram que o SCM+NIPAAm 5% apresentou maior estabilidade térmica em relação aos demais copolímeros avaliados, uma vez que sua decomposição polimérica ocorre em temperaturas superiores, em torno de 233ºC. O DTA demonstrou valores de temperaturas concordantes com os eventos térmicos de decomposição apresentados pelas curvas das análises TG. Sua estabilidade foi confirmada através da CD e estudo de degradação in vitro, apresentando, respectivamente, Ea > 100 kJ mol^-1 e perda de 48% da sua massa inicial após três meses. Além disso, SCM+NIPAAm 5% apresentou diâmetro de partícula inferior a 200 nm e índice de polidispersão de 0,35, além do PZ > -30mV, caracteristicas de um promissor candidato a carreador de fármacos. Em relação às avaliações toxicológicas, o SCM+NIPAAm 5% não apresentou toxicidade no bioensaio de A. salina (CL₅₀ > 1000) e no modelo celular avaliado, dentro das concentrações e circunstâncias de exposição estudadas. O SCM+NIPAAm 5%, na dose oral de 2000 mg/kg, não apresentou nenhum sinal evidente de toxicidade em camundongos, o que foi corroborado pela ausência de alterações anatomo-histopatológicas. A copolimerização do Sulfato de Condroitina e N-isopropilacrilamida na concentração estudada, dada suas características físico-químicas e toxicológicas preliminares, apresenta propriedades que contribuem para a proposta de um sistema que constitui uma nova forma de liberação controlada, especialmente de fármacos.

Caracterização e estudo do comportamento térmico de ligninas extraídas de bagaço de cana-de-açúcar e resíduos sólidos urbanos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo termoanalítico de blendas de poli(tereftalato de etileno) e poli(3-hidroxibutirato)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)