A Comparison of Solvent and Water-Borne Alkyd Coatings Abstract Conventional solvent based alkyd coatings have gone out of favor due to concerns over volatile organic compound (VOC) content. However, due to recent focus on renewable raw materials, alkyds are making a comeback in waterborne form. Water based alkyd coatings are known to have poor shelf stability and corrosion resistance, as well as other problems during the formulation process. This project focused on comparing solvent borne to two types of water-borne alkyds, water reducible alkyds and alkyds emulsions. The purpose was to understand the differences between the three types of alkyds in terms of their production and final properties. It was ultimately hoped that the formulations used for this project would prove to solve the problems normally experienced by waterborne alkyds. After testing several chemical and physical properties, it was determined that the solvent borne alkyd coatings performed better than both water based systems in corrosion resistance, accelerated weathering, and shelf stability but the water reducible and emulsion alkyd coatings performed similarly to the solvent borne alkyd in gloss, contrast ratio, and durability. The VOC emissions for all three alkyd types were as expected; the solvent borne had the highest emission at 253 g/L, followed by water reducible with 166 g/L, and emulsion with 34 g/L. The History of VOC Regulations in the United States Abstract In another solvent based alkyd coating focused project within my research group, the question of the how volatile organic compound (VOC) regulation in the United States (U.S.) evolved came up. It quickly became apparent that no comprehensive answer to this question existed. Part two of this project is an attempt to answer this question in a comprehensive manner. VOC regulations started in California in the late 1970s, and paints and coatings became a nationally regulated emission source by the 1990s. The U.S. government limited harmful emissions, such as smog and compounds contributing to ozone depletion, through Clean Air Acts. The first Clean Air Act was enacted in 1965, but it wasn’t until the Clean Air Act of 1990 that VOC emissions became a focus. VOCs are not inherently hazardous but are a source of concern because they serve as a precursor to the formation of damaging ground level ozone. The Environmental Protection Agency (EPA) has established the minimum VOC emission limits in the Architectural and Industrial Maintenance (AIM) federal rule, but each state or state subdivision can enforce stricter limits within their borders. The strictest limits are set by the South Coast Air Quality Management District (SCAQMD) in Southern California, but other entities exist. This report thoroughly documents the history of VOC regulation in the United States by collecting, combining, organizing, and summarizing information gathered from various industries and government publications, agency members, and industrial and academic professionals.

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O crescimento da população mundial tem como consequência direta a busca cada vez maior de uma agricultura altamente produtiva e sustentável. Isto requer uso de nutrientes de modo que haja proporcionalidade entre a aplicação e a demanda de fertilizantes. Assim, surge uma crescente busca por materiais de revestimento, para que, ao serem aplicados sobre a superfície de sólidos, controlem a liberação de espécies fertilizantes ou mesmo, de um princípio ativo para o controle de pragas e doenças. Com isso, reduzem-se as quantidades aplicadas no solo e nas plantas, com grande impacto na redução de custos e de efeitos indesejáveis de deriva e excessos na aplicação, tornando a prática agrícola mais sustentável econômica e ambientalmente. Uma das mais importantes aplicações de materiais revestidos na agricultura consiste no revestimento ou encapsulamento da ureia. Este insumo mineral é útil devido ao seu elevado conteúdo de nitrogênio (entre 44 a 46% em massa). Porém, tem-se uma desvantagem devido às perdas por volatilização e por lixiviação, levando a um total que chega a 50%. Assim, este trabalho tem como finalidade desenvolver e avaliar novos sistemas de revestimentos poliméricos, a partir de poliuretanas (PU), para liberação controlada de ureia, além de propor uma nova abordagem de análise instrumental para ensaios acelerados de dissolução controlada de espécies revestidas. O trabalho foi dividido em três etapas: (i) preparação e caracterização dos materiais para revestimento, tendo por base polióis derivados do óleo de mamona e óleo de soja; (ii) desenvolvimento de uma célula de medida com controle de parâmetros físicos e geométricos, bem como um sistema de controle térmico e de agitação; (iii) execução dos ensaios de liberação em água para verificar a influencia da porcentagem de PU na taxa de liberação, assim como a cinética difusional e o tempo de retenção. A partir da caracterização dos revestimentos nota-se que os materiais à base de mamona apresentam melhor adesão à ureia, permitindo obter melhores resultados na retenção do macronutriente. Os ensaios de liberação mostraram que o aumento da porcentagem de polímero, retarda a taxa de liberação da ureia, visto que ensaios utilizando 5% estendem a liberação por até 40 dias. Também, observa-se que existe uma faixa ótima de recobrimento, sendo que valores superiores a 7% (PU mamona), não interferem significativamente na liberação, o que se confirma a partir da modulação de Peppas, mostrando valores baixos para a cinética de liberação desses materiais. Por fim, a célula de medida elaborada para adequar e padronizar procedimentos envolvendo liberação controlada permitiu o máximo de controle de parâmetros físicos e geométricos nos ensaios, mostrando-se uma excelente ferramenta para ensaios de liberação, além de evitar possíveis erros na determinação da espécie abordada. / The world population growth implies an increasingly search for a productive and sustainable agriculture. This requires the use of nutrient so that there is proportionality between the application and the demand for fertilizer demand. Thus, there is a growing search for coating materials, so that, when applied on the surface of solids, to control the release of fertilizers or even species of an active principle for the control of pests and diseases. So, it reduces the amounts used in soil and plants, with a major impact on reducing costs and undesirable drift effects and excesses in the applications, making it the most economical and environmentally sustainable practical agricultural. One of the most important applications of coating materials in agriculture consists on coating or encapsulation of urea. This mineral input is useful because of its high nitrogen content (between 43 to 46% by mass). However, it has a disadvantage due to losses by volatilization and lixiviation (about 17 to 50%), leading to a loss that reaches 50%. This study aims to develop and evaluate systems of polymeric coatings using polyurethane (PU) for controlled release urea. The experimental procedure was divided into three steps: (i) preparation and characterization of materials for coating based on derivatives of castor oil and soybean oil polyols; (ii) development of a measuring cell with control of physical and geometrical parameters as well as a system of thermal control and agitation; (iii) execution of release tests in water to check the influence of the percentage of PU in release rate as the diffusion kinetics and retention time. From the characterization of coatings is noted that the castor-based materials have better adherence to urea allowing better results in retention of macronutrient. Release tests showed that increasing the percentage of polymer retards the release rate of urea whereas tests using 5% extended release for up to 40 days. Also, it is observed that there is an optimum range of coating with values higher than 7% (PU castor oil) does not influence the release as confirmed from the Peppas modulation showing lower values for the kinetic of release these materials. Finally, the measuring cell designed to adapt and to standardize procedures involving controlled release allowed maximum control of physical and geometrical parameters in the tests being an excellent tool to release assays and avoid possible errors in determination of studied species.

O crescimento da população mundial tem como consequência direta a busca cada vez maior de uma agricultura altamente produtiva e sustentável. Isto requer uso de nutrientes de modo que haja proporcionalidade entre a aplicação e a demanda de fertilizantes. Assim, surge uma crescente busca por materiais de revestimento, para que, ao serem aplicados sobre a superfície de sólidos, controlem a liberação de espécies fertilizantes ou mesmo, de um princípio ativo para o controle de pragas e doenças. Com isso, reduzem-se as quantidades aplicadas no solo e nas plantas, com grande impacto na redução de custos e de efeitos indesejáveis de deriva e excessos na aplicação, tornando a prática agrícola mais sustentável econômica e ambientalmente. Uma das mais importantes aplicações de materiais revestidos na agricultura consiste no revestimento ou encapsulamento da ureia. Este insumo mineral é útil devido ao seu elevado conteúdo de nitrogênio (entre 44 a 46% em massa). Porém, tem-se uma desvantagem devido às perdas por volatilização e por lixiviação, levando a um total que chega a 50%. Assim, este trabalho tem como finalidade desenvolver e avaliar novos sistemas de revestimentos poliméricos, a partir de poliuretanas (PU), para liberação controlada de ureia, além de propor uma nova abordagem de análise instrumental para ensaios acelerados de dissolução controlada de espécies revestidas. O trabalho foi dividido em três etapas: (i) preparação e caracterização dos materiais para revestimento, tendo por base polióis derivados do óleo de mamona e óleo de soja; (ii) desenvolvimento de uma célula de medida com controle de parâmetros físicos e geométricos, bem como um sistema de controle térmico e de agitação; (iii) execução dos ensaios de liberação em água para verificar a influencia da porcentagem de PU na taxa de liberação, assim como a cinética difusional e o tempo de retenção. A partir da caracterização dos revestimentos nota-se que os materiais à base de mamona apresentam melhor adesão à ureia, permitindo obter melhores resultados na retenção do macronutriente. Os ensaios de liberação mostraram que o aumento da porcentagem de polímero, retarda a taxa de liberação da ureia, visto que ensaios utilizando 5% estendem a liberação por até 40 dias. Também, observa-se que existe uma faixa ótima de recobrimento, sendo que valores superiores a 7% (PU mamona), não interferem significativamente na liberação, o que se confirma a partir da modulação de Peppas, mostrando valores baixos para a cinética de liberação desses materiais. Por fim, a célula de medida elaborada para adequar e padronizar procedimentos envolvendo liberação controlada permitiu o máximo de controle de parâmetros físicos e geométricos nos ensaios, mostrando-se uma excelente ferramenta para ensaios de liberação, além de evitar possíveis erros na determinação da espécie abordada. / The world population growth implies an increasingly search for a productive and sustainable agriculture. This requires the use of nutrient so that there is proportionality between the application and the demand for fertilizer demand. Thus, there is a growing search for coating materials, so that, when applied on the surface of solids, to control the release of fertilizers or even species of an active principle for the control of pests and diseases. So, it reduces the amounts used in soil and plants, with a major impact on reducing costs and undesirable drift effects and excesses in the applications, making it the most economical and environmentally sustainable practical agricultural. One of the most important applications of coating materials in agriculture consists on coating or encapsulation of urea. This mineral input is useful because of its high nitrogen content (between 43 to 46% by mass). However, it has a disadvantage due to losses by volatilization and lixiviation (about 17 to 50%), leading to a loss that reaches 50%. This study aims to develop and evaluate systems of polymeric coatings using polyurethane (PU) for controlled release urea. The experimental procedure was divided into three steps: (i) preparation and characterization of materials for coating based on derivatives of castor oil and soybean oil polyols; (ii) development of a measuring cell with control of physical and geometrical parameters as well as a system of thermal control and agitation; (iii) execution of release tests in water to check the influence of the percentage of PU in release rate as the diffusion kinetics and retention time. From the characterization of coatings is noted that the castor-based materials have better adherence to urea allowing better results in retention of macronutrient. Release tests showed that increasing the percentage of polymer retards the release rate of urea whereas tests using 5% extended release for up to 40 days. Also, it is observed that there is an optimum range of coating with values higher than 7% (PU castor oil) does not influence the release as confirmed from the Peppas modulation showing lower values for the kinetic of release these materials. Finally, the measuring cell designed to adapt and to standardize procedures involving controlled release allowed maximum control of physical and geometrical parameters in the tests being an excellent tool to release assays and avoid possible errors in determination of studied species.

<p>Sintetisane su klasične alkidne smole polazeći od ricinolne kiseline, anhidrida ftalne<br />kiseline i tri poliola (glicerina, trimetilolpropana i etoksilovanog pentaeritritola), kao i<br />hiperrazgranati alkidi na osnovu ditrimetilolpropana, dimetilolpropionske kiseline i<br />ricinolne kiseline. Smole su karakterisane određivanjem hidroksilnog i kiselinskog broja,<br />viskoznosti, srednjih molskih masa i njihove raspodele. Struktura sintetisanih smola je<br />potvrđena infracrvenom spektroskopijom sa Furijeovom transformacijom (FTIR).<br />Sintetisani alkidi imaju veliki sadržaj hidroksilnih grupa, a mali kiselinski broj. Prisustvo<br />hidroksilnih grupa, kao krajnjih funkcionalnih grupa, omogućuje modifikaciju alkidnih<br />smola i dobijanje materijala različitih svojstava. Sintetisani alkidi su umrežavani sa<br />triizobutoksimetil i heksametoksimetil melaminskom smolom u cilju dobijanja umreženog materijala željene strukture i svojstava za primenu u premazima. Umrežavanje sme&scaron;a smola praćeno je FTIR spektroskopijom, dinamičko skanirajućom kalorimetrijom (DSC), reometrijom, kao i određivanjem sadržaja gela. Ispitivana su toplotna svojstva, dinamičkomehaničko pona&scaron;anje, fizičko-mehaničke karakteristike i hemijska otpornost filmova premaza. Umrežavanje sme&scaron;a smola teče uglavnom preko hidroksilnih i karboksilnih grupa alkida sa izobutoksimetil i metoksimetil grupama u melaminskim smolama. Sintetisane klasične alkidne smole u sme&scaron;i sa melaminskim smolama umrežavaju u temperaturnom opsegu od 90 do 170&nbsp;⁰C, a hiperrazgranati alkidi od 80 do 170&nbsp;⁰C, &scaron;to su uobičajene temperature u tehnologiji lakova koji umrežavaju &ldquo;pečenjem&ldquo;. Umreženi filmovi premaza su toplotno veoma stabilni, budući da početak razgradnje premaza započinje na temperaturama od 281 do 330 ⁰C. Potvrđeno je da postoji linearna zavisnost između modula izgubljene energije na 25 ⁰C, koji je mera viskoznog odgovora materijala, i tvrdoće premaza određene metodom klatna. Svi projektovani premazi, bez obzira na nesavr&scaron;enost nastale polimerne mreže, su pokazali zadovoljavajuća svojstva. Najbolja svojstva od klasičnih alkidnih premaza ima onaj na osnovu sme&scaron;e alkida sa etoksilovanim pentaeritritolom i heksametoksimetil melaminske smole. Kori&scaron;ćenje hiperrazgranatih alkidnih smola kao veziva u ekolo&scaron;ki prihvatljivim premazima ima prednost zbog manjeg sadržaja organskih rastvarača i manje viskoznosti u odnosu na klasične smole. Pretpostavljeno je da bi sme&scaron;e sintetisanih klasičnih i hiperrazgranatih alkida sa melaminskim smolama (maseni odnos 70:30) bile pogodne za primenu u industriji boja i lakova. Potvrđeno je da su sistemi alkid/melaminska smola veoma složeni. Dobijeni rezultati omogućuju da se objasni uticaj građe prekursora na strukturu nastale polimerne mreže, a time i na svojstva premaza.</p> / <p>Conventional alkyd resins based on ricinoleic acid, phthalic anhydride and three polyols (glycerin, trimethylolpropane or ethoxylated pentaerythritol), as well as hyperbranched alkyds based on ditrimethylolpropane, dimethylol propionic acid and ricinoleic acid were synthesized. Prepared alkyds were characterized by the determination of hydroxyl and acid numbers, viscosity, average molecular masses and molecular masses distribution. The structure of synthesized resins is confirmed by Fourier Transform Infrared Spectroscopy (FTIR). Obtained alkyd resins have high content of hydroxyl groups and low acid number. The presence of hydroxyl groups as functional end groups opens up a high potential for further chemical modifications and for obtaining materials with different properties. Synthesized alkyds were cured by triisobutoxymethyl- and hexamethoxymethyl melamine resins, in order to obtain crosslinked material with desired structure and properties for coating applications. Curing of the resin mixtures were examined by FTIR spectroscopy, dynamic scanning calorimety (DSC), rheometry and by the determination of gel content. Thermal properties, dynamic mechanical behavior, physico-mechanical characteristics and chemical resistance of coated films were determined. Curing of the resin mixtures proceeds via the reactions between hydroxyl and carboxyl groups of alkyds with isobutoxymethyl and metoxymethyl groups in melamine resins. Synthesized alkyd/melamine resin mixtures became cured in the temperature range from 80 to 170 0C, which is the usual temperature range employed in the baking enamel technology. Cured films are thermally very stable since the onset of films degradation starts at high temperatures (from 281 to 330 0C). It is confirmed that there is a linear dependence between the loss modulus at 25 0C, which is the measure of the material viscosity response, and the coating hardness determined by pendulum method. All projected coatings, despite of defects in the resulting polymer networks, show satisfying properties. Among the conventional systems coating based on mixture of alkyd with ethoxylated pentaerythritol and hexamethoxymethyl melamine resin show the best properties. Application of hyperbranched alkyd resins, as binders in environment friendly coatings has an advantage due to less content of organic solvent and lower viscosity, compared to conventional alkyd resins. It is supposed that the combination of synthesized conventional and hyperbranched alkyds with melamine resins (weight ratio of 70:30 based on dried mass) could be employed as new materials for the industrial preparation of baking enamels. It is confirmed that alkyd/melamine resin systems are very complex. Results obtained enable to explain the effect of precursor type on the structure of resulting polymer network, and thus, on the coating properties.</p>