Nos últimos anos, as indústrias têm mostrado muito interesse em procurar sistemas de pinturas que possam ser mais eficientes na proteção do substrato metálico. Os sistemas comuns de pinturas criam uma barreira passiva sobre substrato que evita o contato com a água e outras espécies agressivas. No entanto, a degradação do revestimento pode ocorrer como consequência de fatores externos como radiação UV, temperatura ou ação mecânica. Por este motivo, pesquisadores têm buscado sistemas de pintura com proteção ativa que sejam capazes de se autorreparar (self-healing), levando o substrato a um tempo de vida em serviço mais prolongado. Uma maneira para atingir este efeito ativo é a incorporação de sistemas de nanocontainers ou nanorreservatórios com material ativo encapsulado (inibidores de corrosão) na matriz do revestimento. O objetivo deste trabalho é avaliar o efeito na resistência à corrosão do aço carbono ABNT 1020 numa solução de NaCl 0,01 mol/L quando seja submetido a um prétratamento com camada de tinta alquídica aditivada com nanocontainers contendo o inibidor de corrosão dodecilamina. Três tipos de nanocontainers foram avaliados: 1) nanocontainers a base de nanopartículas de sílica revestida com diferentes camadas de polieletrólitos. 2) nanocontainers a base do mineral haloisita. 3) nanocontainers a base de uma sílica mesoporosa com arranjo ordenado hexagonal tipo SBA-15. Também foi estudada a cinética de liberação do inibidor dodecilamina dos diferentes tipos de nanocontainers usando a técnica de impedância eletroquímica. Os métodos eletroquímicos utilizados para avaliar a resistência a corrosão e o efeito de autorreparação ou self healing foram a técnica de varredura do eletrodo vibratório (SVET) e espectroscopia de impedância eletroquímica (EIS), obtidas em solução aerada de NaCl 0,01 mol/L para chapas de aço carbono revestidas. Testes acelerados de corrosão numa câmara de névoa salina (SSC) foram realizados seguindo a norma ASTM B 117-11. As imagens de microscopia ótica, microscopia eletrônica de varredura e microscopia eletrônica de transmissão foram obtidas para conhecer a estrutura e morfologia dos nanocontainers e o aspecto dos corpos de prova pintados. A caracterização da sílica mesoporosa foi realizada por termogravimetria (TGA), adsorção e dessorção de nitrogênio e difração de raios-X. Os estudos de cinética de liberação do inibidor foram realizados numa solução de NaCl 0,1 mol/L a diferentes valores de pH (2, 9 e 6.2) e contendo 1% m/m de nanocontainers carregados com inibidor dodecilamina, onde foi possível demonstrar que a pH 2 a velocidade de liberação do inibidor foi maior para os três tipos de nanocontainers estudados. Com relação aos resultados de espectroscopia de impedância eletroquímica (EIS) e técnica de varredura com eletrodo vibratório (SVET) para os corpos de prova revestidos com uma tinta alquídica contendo 10 % m/m de nanopartículas de sílica obtidas por Lb-L ou haloisita e 15 % m/m de sílica mesoporosa foi comprovado o efeito selfhealing da tinta pela liberação do inibidor dodecilamina encapsulado dentro da estrutura do nanocontainer. Este efeito também foi notado nos testes de névoa salina, onde o inibidor de corrosão é liberado pelo abaixamento do pH nas regiões anódicas ou de corrosão retardando o processo de corrosão na região do defeito. / In the last years, the industries have shown much interest in searching painting systems that may be more effective in protecting the metallic substrate. Common painting systems create a passive barrier over the substrate that avoids contact with the water and other aggressive species. However, degradation of the coating may occur as a result of external factors such as UV radiation, temperature or mechanical action. For this reason, researchers have sought paint active protection systems that are able to self-repair (self-healing) leading to a longer lifetime of the substrate. One way to achieve this active effect is the incorporation of nanocontainer systems with encapsulated active material (corrosion inhibitors) to the coating matrix. The objective of this study is to evaluate the effect on corrosion resistance of carbon steel ABNT 1020 in aerated 0.1 mol/L NaCl solution when it is subjected to a pretreatment with alkyd paint layer doped with nanocontainers containing dodecylamine as corrosion inhibitor. Three types of nanocontainers were evaluated: 1) SiO2 nanoparticles coated with polyelectrolytes multilayers. 2) halloysite nanoparticles. 3) type SBA-15 mesoporous silica particles of. The kinetics of release of the inhibitor dodecylamine from the different types of nanocontainers was also determined indirectly using electrochemical impedance spectroscopy technique. Electrochemical measurements were performed to evaluate the self-healing effect of coated carbon steel panels after a provoked defect with scanning vibrating electrode technique (SVET) and electrochemical impedance spectroscopy (EIS), all measurements were performed in an aerated NaCl 0.01 mol/L solution. Accelerated corrosion tests in salt spray chamber (SSC) were also carried out following the prescriptions of ASTM B 117-11 standard. The images from optical, scanning electron and transmission electron microscopy were obtained to show the morphology and structure of the nanocontainers and the aspect of coated samples. The characterization of mesoporous silica was made by transmission electron microscopy, thermogravimetry (TGA), adsorption/desorption of N2 and X-ray diffraction. Kinetic studies of the release of encapsulated corrosion inhibitor were performed in NaCl 0.1 mol/L solution at different pH values (2, 9 and 6.2) containing 1 wt. % of dispersed nanocontainers loaded with dodecylamine inhibitor, and it was possible to confirm that at pH 2 condition the release of inhibitor was more efficient in comparison to other pH conditions (9 and 6.2). On the other hand, the results obtained by electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET) of the coated carbon steel panels with alkyd paint loaded with 10 wt. % (SiO2 nanoparticles or halloysite) and 15 wt. % (mesoporous silica) has proven the self-healing effect by the release of corrosion inhibitor from nanocontainers on the defect area triggered by the pH decrease typical of anodic or corroding areas. This self-healing and protective effect was also noticed in salt spray tests, where the corrosion inhibitor was released slowing down the corrosion process on the defective region.

A corrosão nos materiais metálicos causa sérias perdas financeiras e impactos ambientais. Apesar de eficientes, os revestimentos orgânicos podem gerar fissuras com o tempo, propiciando locais favoráveis à corrosão. Diante disso, o conceito de autorreparação em revestimentos tem sido estudado, para que este tipo de dano seja minimizado, sem necessitar da intervenção humana. O método de encapsulamento de formadores de filme em microcápsulas poliméricas é bastante utilizado nos sistemas de autorregeneração. Neste trabalho, estudou-se o processo de emulsificação do óleo de linhaça, etapa determinante para a obtenção das microcápsulas, que serão posteriormente aditivadas em um primer de epóxi base água. Inicialmente, foi necessário aperfeiçoar o preparo da emulsão, analisando-se para isso três tipos diferentes de tensoativos em termos de propriedades e composições. Foi feito um planejamento estatístico no qual se adotou o modelo de projeto fatorial completo para cada um dos tensoativos, onde os fatores analisados foram a variação da fração mássica do tensoativo, a aplicabilidade do ultrassom ou dispersor Ultra-Turrax® e a adição ou não de cloreto de sódio. O pequeno número de ensaios envolvidos e a simplicidade para se analisar e interpretar os dados justificam a escolha deste modelo. As variáveis resposta foram a determinação do diâmetro médio volumétrico das gotículas e a medida do potencial zeta das emulsões para analisar a estabilidade das mesmas. Além disso, observou-se a forma, tamanho e característica das gotículas com o auxílio de um microscópio óptico. A estabilidade da emulsão também foi avaliada pela observação e registro fotográfico da separação de fases, depois de certo tempo em repouso, em um tubo de ensaio. Após a determinação do melhor tensoativo e condições de preparo da emulsão na obtenção das microcápsulas, estas foram obtidas e adicionadas no primer e o mesmo foi aplicado sobre corpos de prova de aço carbono. O efeito de autorreparação proporcionado pela ruptura das microcápsulas ao se provocar um defeito foi avaliado pelas técnicas de espectroscopia de impedância eletroquímica (EIS), técnica de varredura com eletrodo vibratório (SVET) e pelo ensaio acelerado de corrosão em câmara de névoa salina (SSC). As microcápsulas foram caracterizadas por microscopia óptica e microscopia eletrônica de varredura (SEM). / The corrosion of metallic materials causes serious financial losses and environmental impacts. Although efficient, organic coatings may generate cracks over time, generating potential sites for corrosion. Hence, the self-healing concept on coatings has been studied in order to minimize this type of damage, without requiring human intervention. The encapsulation method of film formers in polymeric microcapsules is widely used in self-healing systems. In this study, the emulsification process of linseed oil was investigated, since it is a determining step to obtain the microcapsules that will later be doped in a water based epoxy primer. Initially, it was necessary to improve the emulsion preparation, by analyzing three types of surfactants with different properties and compositions. A statistical planning adopting the full factorial design model was conducted for each of the surfactants, in which the factors considered were the variation of the weight fraction of surfactant, and the use or not of ultrasound, Ultra-Turrax® disperser and sodium chloride. The small number of trials involved and the simplicity to analyze and interpret the data justify the choice of this statistical model. The response variables were the determination of the droplet volumetric mean diameter and the measurement of the zeta potential of the emulsions to assess its stability. Moreover, the shape and characteristics of the droplets were observed with the aid of an optical microscope. The emulsion stability was also evaluated by observation and photographic register of phase separation after some rest time in a test tube. After determining the best surfactant and conditions for the emulsification to obtain the microcapsules, they were produced and added to the primer, which was applied on carbon steel specimens. The self-healing effect provided by the rupture of the microcapsules after an intentional defect was evaluated by electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET) and accelerated corrosion tests in a salt spray chamber (SSC). The microcapsules were characterized by optical and scanning electron microscopes (SEM).

Weathering steel has been a primary construction material for bridges in the United States. Notches caused by corrosion are observed on the flange of steel I-beams. These notches reduce the cross section area of the structure and are threats to bridge safety. A606-04 Type 4 cold rolled weathering steel samples were studied in this thesis to understand the effect of notches that caused by corrosion. Weathering steel samples were in the shape of plates, which simulated flange of I-beams. The plate samples were notched across their surfaces by applying electrical current through an electrochemical circuit composed of an anode, a cathode and electrolyte. Sixteen samples were notched and cut into appropriate shape for fatigue testing. S-N (Stress-Number of cycles to failure) diagram established from fatigue data indicated that the fatigue strength decreased below AASHTO category B. Weibull analysis was also performed to understand the reliability distribution. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2014. / FAU Electronic Theses and Dissertations Collection

Thesis submitted in fulfilment of the requirements for the degree Master of Technology: Chemistry in the Faculty of Applied Sciences at the Cape Peninsula University of Technology / Paperboard made from recycled fibres is being used more frequently in direct food packaging applications, in addition to its use as secondary and tertiary packaging. However, recent research has shown that there is a risk that harmful chemicals may migrate from the paperboard into the food. The simplest approach to reducing the migration of these contaminants is the use of barrier films. The barrier efficiencies of these various films can be examined by means of a migration test into a food simulant, followed by extraction in a suitable solvent. The extract can then be analysed by chromatographic techniques such as gas chromatography mass spectrometry (GC-MS) to determine the concentration of the specific contaminants. However on a production level, the availability of this type of highly specialised equipment is limited. A simple, cost effective method is needed to evaluate the barrier properties to specific chemical contaminants. The Heptane Vapour Transmission Rate (HVTR) test is a permeation test method for use at quality control level to determine barrier properties to the migration of organic vapours. The first part of the study focussed on establishing a universal correlation between HVTR and specific migration of diisobutyl phthalate (DiBP), dibutyl phthalate (DBP) and diethylhexyl phthalate (DEHP) that would be applicable to any type of functional barrier. However, experimental data demonstrated this was not possible as the correlation factor linking HVTR to specific migration was largely dependent on the type and morphology of the coating considered. The initial objective of the study was reconsidered in favour of building individual models specific to the nature of the coating and substrate considered. A correlation between HVTR and specific migration of DiBP, DBP and DEHP for a polyvinylidene chloride (PVDC) barrier polymer was constructed by varying the applied coating weight. The vapour transport mechanism for the HVTR test and the specific migration test were found to differ, showing that a direct correlation between HVTR and the specific migration was again not possible. However, an indirect correlation could be made. The HVTR method gives an indication of film integrity, whereas the coating weight could be used as an indicator of the specific migration. The correlation between the coating weight and the specific migration yielded an equation that can be used to calculate the specific migration through the PVDC barrier polymer, provided the quantity of the chemical contaminant originally present in the paperboard was known. This equation was specific to the type of barrier polymer, the specific chemical contaminant as well as the intended shelf-life of the food product to be packaged in the paperboard.

O titânio comercialmente puro (Ti-Cp) e suas ligas destacam-se como biomateriais metálicos devido a sua biocompatibilidade sendo amplamente utilizados. Buscando aprimorar o sucesso clínico dos implantes de Ti-Cp em longo prazo, é necessário revestir a sua superfície, proporcionando uma eficiente ancoragem mecânica do implante com o tecido ósseo. Dentre os diversos revestimentos superficiais destacam-se os revestimentos híbridos orgânicos-inorgânicos à base de precursores alcóxidos de silício, obtidos via processo sol-gel. Para que ocorra uma satisfatória adesão do revestimento no substrato, precisa-se levar em consideração a natureza e a preparação da superfície metálica antes da aplicação deste revestimento. Na etapa inicial do trabalho, pré-tratamentos superficiais foram propostos previamente à aplicação dos revestimentos buscando aumentar a aderência entre o titânio e este revestimento híbrido. Utilizou-se três diferentes pré-tratamentos na superfície do Ti-Cp: o "piranha" (ácido sulfúrico e peróxido de hidrogênio), o "kroll" (ácido fluorídrico, ácido nítrico e água) e o "hidróxido de sódio". Em sequência, aplicou-se por processo de dip-coating sobre as superfícies tratadas, um revestimento híbrido produzido a partir dos precursores alcóxidos de silício tetraetoxisilano (TEOS) e metiltrietoxisilano (MTES), obtido pelo processo de sol-gel. Em uma segunda etapa, sobre a superfície do Ti-Cp com o pré-tratamento superficial que proporcionou uma maior aderência do revestimento híbrido ao titânio, aplicou-se por dip-coating, um revestimento híbrido à base de precursores alcóxidos de silício TEOS e MTES com adição de partículas de hidroxiapatita buscando aprimorar a diferenciação celular sobre o revestimento híbrido. O pré-tratamento com o hidróxido de sódio promove o melhor resultado dentre os pré-tratamentos, pois o revestimento híbrido aplicado posteriormente apresenta recobrimento regular e adesão ao substrato de Ti-Cp. Os resultados morfológicos por MEV-FEG mostraram um revestimento híbrido com boa dispersão da hidroxiapatita e um recobrimento regular e adesão ao substrato de Ti-Cp. Nos resultados biológicos Ti-Cp revestido com TEOS/MTES com a presença de partículas de hidroxiapatita obteve uma adesão celular semelhante ao Ti-Cp sem tratamento. Porém este mesmo revestimento não propiciou a proliferação e diferenciação celular. Os resultados indicaram que a combinação de fatores como a sua superfície hidrofóbica (91°) e a presença da hidroxiapatita no revestimento tornou a superfície desorganizada, acarretando em uma superfície com comportamento desfavorável para o desenvolvimento das células-tronco mesenquimais. / Commercially pure titanium (cp-Ti) and its alloys stand out among the metallic materials due to their biocompatibility being widely used in biomaterials. In order to improve the clinical success of cp-Ti implants in the long term, it is necessary to coat the surface, providing an efficient mechanical anchoring of the implant with the bone tissue. Among the various surface coatings are the hybrid coatings based on silicon alkoxide precursors, obtained by the sol-gel process, however, considering the nature and the preparation of the metal surface prior to the application of this coating. In the initial stage of the work, surface pre-treatments were proposed prior to the application of the coatings seeking to increase the adhesion between the titanium and this hybrid coating. Three different pretreatments were used on the cp-Ti surface: "piranha" (sulfuric acid and hydrogen peroxide), "kroll "(hydrofluoric acid, nitric acid and water) and "sodium hydroxide". Subsequently, a hybrid coating produced by the tetraethoxysilane silicon (TEOS) and methyltriethoxysilane (MTES) precursors obtained by the sol-gel process was applied by the dip-coating process onto the treated surfaces. In a second step, on the surface of the cp-Ti with the surface pretreatment that gave a greater adhesion of the hybrid coating to the titanium, dip-coating, a hybrid coating based on precursors silicon alkoxides TEOS and MTES with the addition of hydroxyapatite particles to enhance cell differentiation on the hybrid coating. Pretreatment with sodium hydroxide promotes the best result among the pre-treatments, since the hybrid coating applied afterwards presents regular coating and adhesion to the cp-Ti substrate. The morphological results by SEM-FEG showed a hybrid coating with good dispersion of the hydroxyapatite and a regular coating and adhesion to the cp-Ti substrate. In the biological results Ti-Cp coated with TEOS / MTES with the presence of hydroxyapatite particles obtained a cell adhesion similar to Ti-Cp without treatment. However, this same coating did not promote cell proliferation and differentiation. The results indicated that the combination of factors such as its hydrophobic surface (91°) and the presence of the hydroxyapatite encapsulated in the coating rendering the surface disorganized led to a surface with unfavorable behavior for the development of mesenchymal stem cells.

Thermal barrier coatings (TBCs) of ZrO2-7wt% Y2O3 were deposited by electron beam physical vapor deposition (EB-PVD) onto stationary flat plates and cylindrical surfaces in a multiple ingot coater. Crystallographic texture, microstructure, and deposition rate were investigated in this thesis. The crystallographic texture of EB-PVD TBCs deposited on stationary flat surfaces has been experimentally determined by comparing pole figure analysis data with actual column growth angle data. It was found that the TBC coating deposited directly above an ingot exhibits <220> single crystal type crystallographic texture. Coatings deposited between and off the centerline of the ingots the exhibited a <311>-type single crystal texture. For coatings deposited in the far corners of the coating chamber either a <111> fiber texture or a <311> single crystal type texture existed. The crystallographic texture of EB-PVD TBCs deposited on cylindrical surfaces was characterized using x-ray diffraction (XRD) at different angular positions on the cylinder substrate. XRD results revealed that crystallographic texture changes with angular position. Changes in crystallographic texture are attributed to the growth direction of the columns and substrate temperature. Growth direction is controlled by the direction of the incoming vapor flux (i.e. vapor incidence angle), in which competition occurs between crystallites growing at different rates. The fastest growing orientation takes over and dominates the texture. Substrate temperature variations throughout the coating chamber resulted in different growth rates and morphology. Morphology differences existed between cylindrical and flat plate surfaces. Flat cross sectional surfaces of the coatings exhibited a dense columnar structure in which the columns grew towards the closest vapor source. Surface features were found to be larger for coatings deposited directly above an ingot than coatings deposited away from the ingots. Morphological differences result from substrate temperature changes within the coating chamber, which influences growth kinetics of the coating. Cylindrical surfaces revealed a columnar structure in which columns grew towards the closest vapor. Porosity of the coating was found to increase when the angular position changed from the bottom of the cylinder. Change in angular position also caused the column diameter to decreases. Morphology changes are attributed to self-shadow effects caused by the surface curvature of the cylinder and vapor incidence angle changes. Overall, the microstructure and crystallographic texture of EB-PVD coatings was found to depend on the position in the coating chamber which was found to influence substrate temperature, growth directions, and shadowing effects. The coating thickness profiles for EB-PVD TBCs deposited on stationary cylinders have been experimentally measured and theoretically modeled using Knudsen's cosine law of emissions. A comparison of the experimental results with the model reveals that the model must to be modified to account for the sticking coefficient as well as a ricochet factor. These results are also discussed in terms of the effects of substrate temperature on the sticking coefficient, the ricochet factor, and coating density.

To evaluate the effect of cool roof coatings containing Expancel® thermoplastic microspheres on industrial buildings, a warehouse was built-up in the computer simulation software IDA-ICE. The warehouse was modelled in line with ASHRAE 90.1. 2004 ”Energy Standard for Buildings Except Low-Rise Residential Buildings”. Four different cases were set up where the coating of the roof was the only variable. Two coatings containing Expancel® microspheres - one white and one red coating were compared to the same white coating without Expancel® microspheres and the ”base case” where there is no coating at all. The same circumstances were also implemented in a practical laboratory test using a model warehouse with a detachable roof. Four interchangeable roofs with different roof coatings constitute the various cases in the laboratory tests. A ”sun” consisting of statically mounted IR light bulbs were constructed, as well as a cooling system to measure the difference in cooling effect (maintaining a constant indoor temperature) between the different cases as a result of the change in insolation. The results of the computational simulations show that for a warehouse placed in Houston, Texas about 50 MWh in combined heating and cooling energy can be saved yearly between the best and the worst case, a reduction of 6.2%. Changing the geographic placement of the warehouse to Tepic, Mexico the corresponding savings were determined to 83 MWh or 13.5%. A way of determining the yearly savings in heating and cooling amount for the warehouse with a generic roof coating, only knowing the SRI value of the coating, was developed. It was determined that for every unit-increment of the SRI value the yearly savings for the warehouse placed in Houston, Texas were 718 kWh and 0.1%. The corresponding savings for the warehouse placed in Tepic, Mexico were determined to be 1252 kWh and 0.22%. The laboratory tests showed that the indoor temperature of the model warehouse decreased by close to 16°C between the best and the worst case.

A principal função das embalagens tradicionais utilizadas pela indústria de alimentos é a proteção dos alimentos de contaminações externas sem interagir com o mesmo. No entanto, a maioria dessas embalagens é produzida a partir de fontes não biodegradáveis e não renováveis. Para atender à crescente demanda em relação à sustentabilidade ambiental, os filmes e coberturas comestíveis têm despertado o interesse e atenção por parte de indústrias e pesquisadores. Além disso, tais filmes ou coberturas podem ser acrescidos de diferentes compostos, para conferir as mesmas um caráter ativo, com interação positiva com os alimentos, para auxiliar a conservação. Dessa forma, este trabalho teve por objetivo (1) desenvolver filmes ativos pela técnica de casting a partir de matrizes biodegradáveis, com atividade antimicrobiana devido a incorporação de nanopartículas de ouro (AuNPs) e óleos essenciais, além de filmes com atividade antioxidante pela adição de nanocápsulas de bixina, (2) avaliar as características mecânicas, físicas e de barreira dos filmes ativos, além da atividade antimicrobiana e antioxidante, e (3) verificar a eficiência na aplicação de coberturas comestíveis na conservação de alimentos. Os filmes com atividade antimicrobiana utilizaram como matérias primas o amido e a farinha integral de grãos quinoa (Chenopodium quinoa W.). Os filmes de amido de quinoa foram preparados com 4 % de matéria prima e 1 % de glicerol como plastificante e incorporados com solução de nanopartículas de ouro nas concentrações de 2,5 % e 5 % (v/v). A presença de AuNPs levou a uma melhoria nas propriedades mecânicas, ópticas e morfológicas dos filmes, sem alterar as propriedades térmicas e de barreira, além de exibirem forte atividade antibacteriana contra agentes patogênicos de origem alimentar, com porcentagens de inibição de 98 % contra E. coli e S. aureus. Nos filmes ativos elaborados com a farinha de quinoa (6 % de matéria prima e 1 % de glicerol como plastificante em 100 g de solução filmogênica), foram adicionados os óleos essenciais (OE) de orégano (Origanum vulgare L.) e tomilho (Thymus vulgaris L.) (0,5 %, 1 % e 2 % p/p). Observou-se que o tipo de OE não interferiu significativamente nos parâmetros físicos e de barreira dos filmes. Já o aumento na concentração dos OEs, produziu filmes mais elásticos e menos resistentes, bem como, menos solúveis em água e com menor permeabilidade aos vapores de água. Os filmes com 1 % e 2 % de OEs exibiram um efeito inibidor sobre o crescimento de S. aureus e E. coli. No entanto, o S. aureus mostrou-se mais sensível a ambos os OEs; e os filmes com orégano foram mais eficazes na inativação de ambos os microrganismos. As embalagens antioxidantes foram elaboradas a partir de amido de mandioca (4 % de matéria prima e 1 % de glicerol como plastificante em 100 g de solução filmogênica) incorporadas com solução de nanocápsulas de bixina (0 %, 2 %, 5%, 8 % e 10 %). Os filmes foram caracterizados em relação as suas propriedades de barreira, mecânicas e físicas e a atividade antioxidante foi avaliada pelo efeito protetor do óleo de girassol exposto a condições de oxidação aceleradas (13 dias a 65 % UR / 35 ºC). Embalagens com maiores concentrações de nanocápsulas demonstraram maior resistência e elasticidade, bem como, uma melhora significativa na proteção contra os raios UV e luz visível. O óleo de girassol embalado nos filmes contendo nanocápsulas de bixina apresentaram índices de peróxidos abaixo dos estipulados pelo Codex Alimentarius (<10 meq. O2 kg-1) para óleos frescos para o período de armazenamento testado. A cobertura comestível foi preparada à base de quitosana (1,5 %) e foi aplicada sobre tomates armazenados por 14 dias (20 ° C), com acompanhamento da perda de peso, sólidos solúveis totais (SST), firmeza e acidez titulável (AT), taxa de respiração, produção de etileno e quantificação de carotenoides e compostos fenólicos por CLAE. Os frutos revestidos demonstraram retardo no processo de amadurecimento com a diminuição da taxa respiratória e produção de etileno, bem como menores perdas de peso, firmeza -caroteno e menor degradação de compostos fenólicos durante o armazenamento, em comparação com frutos controle (não revestidos). Os resultados sugerem que o desenvolvimento de filmes ativos para conservação de alimentos é um campo promissor, pois além do forte apelo ambiental, filmes ativos podem auxiliar na conservação dos alimentos, para retardar a proliferação de microrganismos patogênicos e degradações oxidativas. Em relação a aplicações de coberturas comestíveis, os resultados indicaram ter potencial para uma utilização comercial no auxílio de prolongamento da vida útil de tomates. / The principal function of traditional packaging used by the food industry is the protection of food against external contamination without interacting with it. However, most of these packages are produced from non-biodegradable and non-renewable sources. Films and edible coatings have attracted the interest and attention from industries and researchers due increasing demand on environmental sustainability. In addition, this films and coatings can be added with different compounds to confer an active character, with positive food interaction and increased of preservation. This study aimed to (1) to develop active films by casting technique from biodegradable matrices with antimicrobial activity, incorporated of gold nanoparticles (AuNPs) and essential oils, as well as films with antioxidant activity by addition of nanocapsules of bixin, (2) evaluate the mechanical, physical and barrier characteristics of active films, and capacity antimicrobial and antioxidant, and (3) verify the efficiency in the application of edible coatings in food preservation. The active antimicrobial films it was used as raw material starch and flour quinoa (Chenopodium quinoa, W.). Starch quinoa films were prepared with 4 % raw material and 1% glycerol as plasticizer (100 g filmogenic solution), incorporating gold nanoparticles at concentrations of 2.5% and 5% (v / v). The presence of gold nanoparticles produces improvement in the mechanical, optical and morphological properties, maintaining the thermal and barrier properties unchanged when compared to the standard biofilm. The active biofilms exhibited strong antibacterial activity against food-borne pathogens with inhibition percentages of 99 % against E. coli and 98 % against S. aureus. The active films produced with flour quinoa (6% of raw material and 1% glycerol as a plasticizer in 100 g of filmogenic solution), incorporated with oregano (Origanum vulgare L.) and thyme (Thymus vulgaris L.) essential oils (EO) (0.5%, 1% and 2% p/p). It was observed that the kind of EO was not significant for the physical and barrier parameters of the films, however, the increase in the EOs concentration promote increase in the elongation but decrease in the tensile strength, solubility and water vapor permeability. Films containing 1% and 2 % EOs, inhibit the growth of S. aureus and E. coli. However, S. aureus was more sensitive to both EOs and the oregano oil was more efficient in the inactivation to both microorganisms. The antioxidant packages were prepared from cassava starch (4% raw material and 1% glycerol as plasticizer in 100 g of filmogenic solution), incorporated with solution of different concentrations of bixin nanocapsules (0 %, 2 %, 5%, 8 % e 10 %). Films with higher concentrations of bixin nanocapsules exhibited significant reduction tensile strength and increases in elongation at break, well as, improvement in protection against UV and visible light and decreased water solubility and increased water vapor permeability. The sunflower oil packed in films containing nanocapsules bixin exhibited lower oxidation rates, thus maintaining its freshness according to Codex Alimentarius guidelines (< 10 milliequivalent.kg-1), for the storage time tested (13 days / 65 % RH / 35 ºC). The edible coating was prepared based on chitosan (1.5 %), and it was applied on tomatoes stored for 14 days (20 °C). The analyses carried out on tomato fruit were: weight loss, total soluble solid (TSS), firmness, and titratable acidity (TA), respiration rate, ethylene production and quantification of carotenoids and phenolics by HPLC. Coated fruit delayed the ripening process by decrease of the rate of respiration and ethylene production, as well changes of weight, firmness and TSS concentration and delay peak of lycopene and b-carotene accumulation and degradation of phenolic compounds during storage, compared to uncoated control. The results suggest that the development of active films for food preservation is a promising field, because besides the strong environmental appeal, active films can increase the food preservation, to decrease the proliferation of pathogenic microorganisms and oxidative degradation. Regarding the edible coatings applications, the results indicated that coating is a promising tool for commercial use in helping to prolong the storage of tomatoes.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 1980. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Includes bibliographical references. / by Yolanda Leigh Hinton. / M.S.

O cobre e suas ligas constitui um dois metais mais amplamente utilizados para a produção de peças com interesse histórico. Isto se deve a sua grande capacidade de combinar com outros compostos, formando pátinas das mais diversas colorações. As peças metálicas do patrimônio histórico se encontram submetidas a condições de exposição atmosférica cada vez mais agressiva, porém frente à necessidade de preservação de nossas memórias históricas este patrimônio deve ser submetido a intervenções de natureza preventiva. O presente trabalho tem por objetivo investigar o comportamento de cobre em águas de chuva sintéticas de São Paulo e de Rio de Janeiro e em solução de NaCl 0,1 M. Investiga-se também o processo de consolidação destas patinas e a ação anticorrosiva das camadas de verniz geralmente utilizado para a proteção do patrimônio histórico (Paraloide B-72) nas soluções e águas de chuva sintéticas. As técnicas eletroquímicas empregadas foram o acompanhamento do potencial de circuito aberto, curvas de polarização anódica e catódica e a espectroscopia de impedância eletroquímica. Como técnicas de caracterização microestrutural e química foram empregadas a microscopia eletrônica de varredura, a difração de raios X e a espectroscopia de fotoelétrons de raios X. Os resultados mostraram que, entre os vernizes empregados para a proteção do patrimônio histórico, os do tipo paralóide são menos suscetíveis à umidade que a cera microcristalina. Para avaliar a resposta do sistema cobre + pátina é importante compreender como o substrato não-tratado responde eletroquimicamente quando é exposto às águas de chuva sintéticas. Os resultados mostraram que na água de chuva sintética do Rio de Janeiro, com baixa concentração de amônio, o ataque prosseguia nas regiões defeituosas da camada de cuprita. Na água de chuva de São Paulo, onde os íons de amônio são abundantes, a regeneração parcial da cuprita ocorre de maneira uniforme melhorando o comportamento eletroquímico. Por sua vez, as pátinas artificiais sobre o substrato de cobre apresentaram uma melhor consolidação quando expostas à atmosfera aberta (Laboratório de Eletroquímica e Corrosão) do que quando expostas a um ambiente com completa ausência de umidade (dessecador). Nos ensaios intermitentes, as pátinas desenvolveram respostas de impedância típica de eletrodo poroso com comprimento de poro semi-infinito seguindo um modelo clássico (DE LEVIE, 1964). Por outro lado, nas amostras de cobre revestidas com paralóide B-72, o grau de diminuição da capacidade protetora após períodos longos de exposição à luz foi atribuída a degradação foto-oxidativa do verniz. A associação do cobre com pátina, sobre a qual se aplicava o verniz Paralóide B-72, mostrou que o sistema de revestimento aumenta a proteção contra a corrosão em ensaios intermitentes. Nos ensaios de imersão contínua, nem as pátinas sozinhas nem quando protegidas com o verniz polaróide, suportaram esses ensaios sem apresentar destacamento. / Copper is one of the metals most widely used to produce metallic artifacts of the artistic and cultural heritage. This is partially due to its great ability to combine with other compounds, forming patinas of different colors. Many of such artifacts are permanently exposed to open air, being thus subjected to the action of atmospheric agents such as rain and pollutants. Thus, these cultural heritage monuments must be submitted to interventions of preventive nature. This work is devoted to investigate the electrochemical behavior of pure copper, with and without an artificial patina layer, in contact with São Paulo and Rio de Janeiro synthetic rainwater and in NaCl 0,1M solution. The consolidation process of these patinas and the anticorrosive action of varnishes generally used for the protection of the cultural heritage were also investigated. The electrochemical techniques used in this work were: cathodic and anodic potentiodynamic polarization curves and electrochemical impedance spectroscopy. Microstructural and chemical characterizations were performed by means of Scanning Electronic Microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results had shown that the varnishes of Paraloid type used for the protection of the historic monuments are less susceptible to the humidity than the microcrystalline wax. The experiments performed with copper in the synthetic rainwater evidenced an important role for the ammonium ions in the corrosion process. Although with a high complexation power towards copper, accelerating its dissolution rate, these ions participate in the partial regeneration of cuprite. Therefore, in the Rio de Janeiro synthetic rainwater, with low ammonium concentration, once the corrosive attack has started it proceeds in the defective regions of the cuprite layer. On the other hand, in the São Paulo synthetic rainwater, where ammonium ions are more abundant, partial regeneration of cuprite occurs and the electrochemical behavior of copper remains stable with time. The experiments performed with copper coated with an artificial patina layer showed better consolidation of these latter when exposed to the open atmosphere (Electrochemistry and Corrosion Laboratory) when compared to samples stored in a dissecator, where humidity is absent. In the intermittent tests patinated samples developed an impedance response which was typical from porous electrode with semi-infinite porous length, in accordance with the classical model proposed by de Levie (DE LEVIE, 1964). On the other hand, Paraloid B-72 coated samples presented a strong degradation when exposed to sunlight for long exposure periods, which was ascribed to the photooxidative degradation of the coating. The system copper plus patina with a Paraloid B-72 layer showed a good protection towards corrosion, as long as photooxidative degradation had not begun. On the other hand, in the continuous immersion tests, neither the patinas nor the Paraloid varnish exhibited a good performance and were detached after relatively short testing period.