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.

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.

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.

Lightly branched comb polyesters: application in fast drying solvent-borne coating formulations

Novel oxazoline-based comb-polymers possessing linoleyl or oleic side chains have been synthesized and used to produce low viscosity coatings. Inclusion of the polymers in model paint formulations results in coatings that exhibit faster drying times than commercially available alkyd resin formulations. The comb polymers were produced from diol substituted oxazoline monomers that were synthesized through a scalable, solvent free protocol and purified by simple recrystallisation. Co-polymerisation of the oxazolines with adipic acid at 160 °C in the bulk resulted in the targeted polyester comb type polymers. The polymers were soluble in a range of organic solvents and compatible with commercial alkyd resins. Model paint formulations containing up to 40 wt% of the linoleyl-based comb polymers exhibited a dramatic reduction in viscosity (from 35 to 13 Poise at 25 °C) with increasing quantities of polymer added. Dynamic mechanical analysis (DMA) studies revealed that the drying rate of the model paint formulations containing the comb polymers was enhanced when compared with that of commercial alkyd resins.

Synthesis of novel hyperbranched polymers featuring oxazoline linear units and their application in fast-drying solvent-borne coating formulations

Novel acid-terminated hyperbranched polymers (HBPs) containing adipic acid and oxazoline monomers derived from oleic and linoleic acid have been synthesized via a bulk polymerization procedure. Branching was achieved as a consequence of an acid-catalyzed opening of the oxazoline ring to produce a trifunctional monomer in situ which delivered branching levels of >45% as determined by 1H and 13C NMR spectroscopy. The HBPs were soluble in common solvents, such as CHCl3, acetone, tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide and were further functionalized by addition of citronellol to afford white-spirit soluble materials that could be used in coating formulations. During end group modification, a reduction in branching levels of the HBPs (down to 12–24%) was observed, predominantly on account of oxazoline ring reformation and trans-esterification processes under the reaction conditions used. In comparison to commercial alkyd resin paint coatings, formulations of the citronellol-functionalized hyperbranched materials blended with a commercial alkyd resin exhibited dramatic decreases of the blend viscosity when the HBP content was increased. The curing characteristics of the HBP/alkyd blend formulations were studied by dynamic mechanical analysis which revealed that the new coatings cured more quickly and produced tougher materials than otherwise identical coatings prepared from only the commercial alkyd resins.

Estudo do impacto da variabilidade de resinas alquídicas nas propriedades de tintas

Este trabalho de conclusão tem como tema a relação entre as especificações de resinas alquídicas e de tintas preparadas com estas resinas, com foco nas características de teor de sólidos e viscosidade, fazendo uso das técnicas projeto de experimentos, superfície de resposta e análise de regressão. O objetivo principal é o estudo dos limites de especificação ideais para a resina alquídica, de forma que os lotes de tinta apresentem propriedades dentro da especificação já ao final do processamento, reduzindo a incidência de lotes fabris com necessidade de ajuste. Como conseqüência, temos redução de retrabalho e lead time fabril, adequação de custo de produtos, maior qualidade intrínseca e maior confiança na sistemática de desenvolvimento, produção e controle de qualidade. Inicialmente, foi realizada uma revisão bibliográfica sobre a tecnologia de tintas e resinas alquídicas, conceitos de controle de qualidade, planejamento de experimentos, análise por superfície de resposta e análise de regressão. Na seqüência, foi conduzido o estudo de caso, realizado na empresa Killing S.A. Tintas e Adesivos, planta localizada na cidade de Novo Hamburgo. Os resultados experimentais indicaram modelos de regressão polinomial válidos para as propriedades avaliadas. Foram tomadas as propriedades teor de sólidos e viscosidade Copo Ford #2 da mistura A+B como parâmetros para análise dos limites de especificação da resina alquídica, onde se comprovou que a variabilidade atualmente permitida é excessiva. A aplicação dos modelos de regressão indicou novos limites de especificação para a resina alquídica, mais estreitos, viabilizando a obtenção de tintas com propriedades especificadas.

Kinetic parameters obtained for thermal decomposition of acrylic resins present in commercial paint emulsions

Samples of water based commercial acrylic resin paints were spread in a film form on slides, dried at room temperature and exposed to solar radiation for up to eight months.The characterization and quantification of resins and charges in the white paint emulsion were carried out for the thermal decomposition. Besides this, X-ray diffractometry was used to identify CaCO3 as charge and TiO2 (rutile phase) as pigment.It was observed through thermal techniques similar behavior to the samples even though with varied exposure time.Kinetic studies of the samples allowed to obtain the activation energy (Ea) and Arrhenius parameters (A) to the thermal decomposition of acrylic resin to three different commercial emulsion (called P-1, P-2, P-3) through non-isothermal procedures. The values of E. varied regarding the exposition time (eight months) and solar radiation from 173 to 197 U mol(-1) (P-1 sample), from 175 to 226 W mol(-1) (P-2 sample) and 206 to 197 kJ mol(-1) (P-3 sample).Kinetic Compensation Effect (KCE) observed for samples P-2 and P-3 indicate acrylic resin s present in these may be similar in nature. This aspect could be observed by a small difference in the thermal behavior of the TG curves from P I to P-2 and P-3 sample.The simulated kinetic model to all the samples was the autocatalytic estdk Berggreen.

Delamination of oil paints from acrylic grounds

Many modern artists paint in oil or oil-modified alkyd paints over acrylic grounds. In some cases the oil based paints do not remain adhered to the ground. In a set of composite samples of oil or alkyd paints, over acrylic grounds, naturally aged for nine years, some of the samples delaminated. Samples were analyzed with X-ray fluorescence (XRF), inductively coupled plasma (ICP), Fourier transform infrared - attenuated total reflectance (FTIR-ATR), scanning electron microscopy (SEM), pyrolysis gas-chromatography mass-spectrometry (PY-GC/MS), laser desorption/ionization mass-spectrometry (LDI-MS), atomic force microscopy (AFM) and other methods, in order to find what the delaminating ones have in common. In addition, two examples of severely delaminating paintings were examined, to confirm the results from the laboratory-prepared samples. Results indicate the main cause of delamination is metal soaps in the oil paint and particularly zinc soaps. There is some evidence that metal soaps were more concentrated at the interface between the layers and this disrupted the adhesion. The ground is a minor consideration as well, rougher grounds providing better adhesion than smooth ones.

Weathering tests of photocatalytic facade paints containing ZnO and TiO2.

The photocatalytic properties of self-cleaning acrylic paint containing TiO2 and ZnO were studied using Acid Orange 7 as a model compound. Paints were exposed to simulated weathering tests in a QUV panel. The initial photoactivity of the unweathered paints with ZnO was significantly higher. In the case of paints containing P25 the photocatalytic activity increases with weathering time, due to increasing destruction of the polymer resin and consequent exposure of the photocatalyst pigment to the Acid Orange 7 test solution. In contrast, in the case of paints containing ZnO, a decrease in photocatalytic activity is observed after weathering, due to the loss and/or photocorrosion of ZnO particles during the weathering process.

Use of a cashew nut shell liquid resin as a potential replacement for phenolic resins in the preparation of panels - a review

The Cashew Nut Shell Liquid (CNSL) can be considered as a versatile raw material with wide applications in the form of surface coatings, paints and varnishes, as well as the production of polymers. Within this context, the chemical constituents of CNSL (anarcadic acid, cardanol, 2-cardol and methylcardol) become promising in the development of new materials components. Once separated, CNSL can be used in the research and development of additives, surfactants, pharmaceuticals, pesticides, polymers, resins and others. Being a byproduct, CNSL used in the preparation of new materials is characterized as a truly technological innovation.

Influence of artificial accelerated ageing on the colour stability of paints used for ocular prosthesis iris painting

Objectives: To evaluate the colour stability of paints used for ocular prosthesis iris painting submitted for accelerated artificial ageing (AAA). Materials and methods: Forty specimens of acrylic resin for sclera (16 x 2 mm) were made and separated into eight groups (n = 10) according to the type of paint (gouache, GP; oil, OP; acrylic AP; and composite resin for characterisation, CR) and the colours used (blue/brown). After drying (72 h), a new layer of colourless acrylic resin was applied and the initial colour readout was performed (Spectrophotometer PCB 6807). New colour readouts were performed after AAA, and Delta E was calculated. Results: Statistical analysis (two-way ANOVA-Bonferroni, p < 0.05) demonstrated that the brown colour showed lower Delta E means in comparison with the blue colour, with statistically significant difference for AP only. Blue colour showed no statistically significant difference with regard to the type of paint used. Brown AP showed lower Delta E than the other groups, with significant difference for OP and GP. GP showed greater alteration in Delta E for the brown colour, being statistically similar only to OP. Conclusions: Only the AP group for brown pigment shows clinically acceptable values for colour stability after AAA.

Study on microwave dielectric properties of epoxy resin mixtures used for rapid product development

This paper presents a preliminary study on the dielectric properties and curing of three different types of epoxy resins mixed at various stichiometric mixture of hardener, flydust and aluminium powder under microwave energy. In this work, the curing process of thin layers of epoxy resins using microwave radiation was investigated as an alternative technique that can be implemented to develop a new rapid product development technique. In this study it was observed that the curing time and temperature were a function of the percentage of hardener and fillers presence in the epoxy resins. Initially dielectric properties of epoxy resins with hardener were measured which was directly correlated to the curing process in order to understand the properties of cured specimen. Tensile tests were conducted on the three different types of epoxy resins with hardener and fillers. Modifying dielectric properties of the mixtures a significant decrease in curing time was observed. In order to study the microstructural changes of cured specimen the morphology of the fracture surface was carried out by using scanning electron microscopy.