Eletrosíntese de filmes de polímeros a partir de naftilaminas substituídas sobre metais oxidáveis e síntese química : aplicação na proteção contra a corrosão

Neste trabalho é apresentado um estudo da síntese e caracterização de polinaftilaminas substituídas com vistas à sua utilização na proteção contra a corrosão. É mostrada a possibilidade de eletrosíntese de filmes destes polímeros intrinsecamente condutores sobre metais oxidáveis passiváveis em meio aquoso ácido pelos métodos potenciostático e potenciodinâmico sem dissolução dos eletrodos. A caracterização química, morfológica e eletroquímica destes filmes poliméricos demonstrou que não há sensíveis diferenças em relação aos mesmos filmes obtidos sobre eletrodos inertes e que é preservada uma das funções na cadeia polimérica. Os filmes de naftilaminas substituídas oferecem uma barreira parcial contra a corrosão do aço carbono e quando polimerizado o 1,5-diaminonafttaleno juntamente com a anilina forma-se o compósito Poli 1,5-diaminonaftaleno/Polianilina que passiva anódicamente o Fe em meio sulfato pH 4. É apresentada também a síntese química do poli 5-amino 1-naftol, que se mostra passivante anódico do aço inox SS 430 em ácido sulfúrico aquoso 1M.

Avaliação de heterociclo do tipo mesoiônico solubilizado em sistema microemulsionado para aplicação em dutos

The efficiency of inhibition to corrosion of steel AISI 1018 of surfactant coconut oil saponified (SCO) and heterocyclic type mesoionics (1,3,4-triazólio-2-tiolato) in systems microemulsionados (SCO-ME and SCO-ME-MI) Of type O/A (rich in water emulsion) region with the work of Winsor IV. The systems microemulsionados (SCO-ME and SCO-ME-MI) were evaluated with a corrosion inhibitor for use in saline 10,000 ppm of chloride enriched with carbon dioxide (CO2). The assessment of corrosion inhibitors were evaluated by the techniques of linear polarization resistance (LPR) and loss of weight (MW) in a cell instrumented given the gravity and electrochemical devices. The systems were shooting speed of less than 60 minutes and efficiency of inhibition [SCO-ME (91.25%) and SCO-ME-MI (98.54%)]

Avaliação do potencial anticorrosivo de tiossemicarbazonas solubilizadas em sistemas microemulsionados

In this work thiosemicarbazones [4-N-cinnamoyl-thiosemicarbazone (CTSC), 4-N-(2'-methoxycinnamoyl)-thiosemicarbazone (MCTSC), and 4-N-(4'-hydroxy-3'-methoxybenzoyl)-thiosemicarbazone (HMBTSC)] were solubilized in an microemulsion system (ME_OCS) which is rich in aqueous phase (O/W system). The system ME_OCS was obtained with saponified coconut oil (OCS) as (surfactant), butanol (cosurfactant), and kerosene as oil phase (Fo), using 40% of C/T (cosurfactant/surfactant), 5% of Fo and 55% of aqueous phase. The microemulsions systems CTSC_ME_OCS, MCTSC_ME_OCS and HMBTSC_ME_OCS effectiveness on a AISI 1020 carbon steel corrosion inhibition process were evaluated in a saline solution (NaCl 0.5%), using a galavostatic method. The tested thiosemicarbazones (TSC) showed highest inhibitors effects (85.7% for CTSC_ME_OCS, 84.0% for MCTSC_ME_OCS, and 83.3% HMBTSC_ME_OCS) at lower concentrations [0.19% of CTSC, 0.07% (MCTSC), and 0.26% (HMBTSC)]. Comparatively, the surfactant OCS (solubilized in H2O) as well as the system ME_OCS showed lower efficacy [71% for OCS (at 0.20 - 0.25% of concentration) and 74% for ME_OCS (at 0.5% of concentration)]. Since the microemulsion systems ME_OCS showed satisfactory interfacial adsorption, the greatest inhibitory effect of those TSC_ME_OCS systems could be correlated to both chemical composition of each tested TSC (which is rich in heteroatoms and aromatic ring) and also the presence of the surfactant OCS

Avaliação de heterociclo do tipo mesoiônico solubilizado em sistema microemulsionado para aplicação em dutos

The efficiency of inhibition to corrosion of steel AISI 1018 of surfactant coconut oil saponified (SCO) and heterocyclic type mesoionics (1,3,4-triazólio-2-tiolato) in systems microemulsionados (SCO-ME and SCO-ME-MI) Of type O/A (rich in water emulsion) region with the work of Winsor IV. The systems microemulsionados (SCO-ME and SCO-ME-MI) were evaluated with a corrosion inhibitor for use in saline 10,000 ppm of chloride enriched with carbon dioxide (CO2). The assessment of corrosion inhibitors were evaluated by the techniques of linear polarization resistance (LPR) and loss of weight (MW) in a cell instrumented given the gravity and electrochemical devices. The systems were shooting speed of less than 60 minutes and efficiency of inhibition [SCO-ME (91.25%) and SCO-ME-MI (98.54%)]

Utilização de matérias primas vegetais para aplicabilidade como inibidores de corrosão

In the search for products that act as corrosion inhibitors and do not cause environmental, impact the use of plant extracts as corrosion inhibitors is becoming a promising alternative. In this work the efficiency of polar extracts (ethanol extracts) obtained from the plants Anacardium occidentale Linn (AO) and Phyllantus amarus Schum. & Thonn (PA) as corrosion inhibitors were evaluated in different concentrations. For that AO and PA extracts were solubilized in the microemulsion systems (SME) containing saponified coconut oil as surfactant (SME -OCS and SME-OCS-1) in saline (NaCl 3,5 %) solution, which was also used as electrolyte. Both SME-OCS and SME-OCS-1 were characterized by surface tension and viscosity methods showing a Newtonian fluid behavior. The SME-OCS and SME-OCS-1 systems satisfactorily solubilized the polar extracts AO and PA with measurements carried out by ultraviolet spectroscopy. The measurements of corrosion inhibition efficiencies were performed by the electrochemical linear polarization resistance (LPR) technique as well as weight loss, on the surface of AISI 1020 carbon steel. The maximum corrosion inhibition efficiencies were determined by extrapolation of Tafel plots, showing the following values: 95,6 % for the system SME-OCS-AO, 98,9 % for the system SME-OCS-AO-1 and 93,4 % for the system SME-OCS-PA

Avaliação do efeito de particulados sólidos na eficiência de um inibidor de corrosão recomendado para meios salinos com CO2

The main problem on the exploration activity on petroleum industry is the formation water resulted on the fields producing. The aggravating of this problem is correlated with the advancing technologies used on the petroleum extractions and on its secondary approach objecting the reobtainment of this oil. Among the main contaminants of the water formation are corrosives gases such as: O2, CO2 and H2S, some solids in suspension and dissolved salts. Concerning to those gases the CO2 is the one that produce significant damage for carbon steel on corrosion process of the petroleum and gas industries. Corrosion inhibitors for carbon steel in formation water is one of the most used agents in control of those damages. In this context, the poor investigations of carbon steel corrosion proceeding from solids in suspension is an opened field for studies. On this work the inhibitor effect of the commercial CORRTREAT 703 was evaluated on some specific solids in suspension at saline medium containing 10.000 ppm of de-aerated chloride using CO2 until non oxygen atmosphere been present. For that, quartz, calcium carbonate, magnetite and iron sulphide were subjected to this investigation as the selected solids. The effect of this inhibitor on corrosion process correlated with those specific solids, was measured using electrochemical (resistance of linear polarization and galvanic pair) and gravimetrical techniques. During all the experimental work important parameters were monitored such as: pH, dissolved oxygen, temperature, instantaneous corrosion rate and galvanic current. According to the obtained results it was proved that the suspension solids calcium carbonate and iron sulphide decrease the corrosion process in higher pH medium. Meanwhile the quartz and magnetite been hardness increase corrosion by broking of the passive layer for erosion. In the other hand, the tested inhibitor in concentration of 50 ppm, showed to be effective (91%) in this corrosion process

Avaliação da espécie vegetal Croton cajucara Benth como inibidor de biocorrosão em aço carbono Aisi 1020

Actually in the oil industry biotechnological approaches represent a challenge. In that, attention to metal structures affected by electrochemical corrosive processes, as well as by the interference of microorganisms (biocorrosion) which affect the kinetics of the environment / metal interface. Regarding to economical and environmental impacts reduction let to the use of natural products as an alternative to toxic synthetic inhibitors. This study aims the employment of green chemistry by evaluating the stem bark extracts (EHC, hydroalcoholic extract) and leaves (ECF, chloroform extract) of plant species Croton cajucara Benth as a corrosion inhibitor. In addition the effectiveness of corrosion inhibition of bioactive trans-clerodane dehydrocrotonin (DCTN) isolated from the stem bark of this Croton was also evaluated. For this purpose, carbon steel AISI 1020 was immersed in saline media (3,5 % NaCl) in the presence and absence of a microorganism recovered from a pipeline oil sample. Corrosion inhibition efficiency and its mechanisms were investigated by linear sweep voltammetry and electrochemical impedance. Culture-dependent and molecular biology techniques were used to characterize and identify bacterial species present in oil samples. The tested natural products EHC, ECF and DCTN (DMSO as solvent) in abiotic environment presented respectively, corrosion inhibition efficiencies of 57.6% (500 ppm), 86.1% (500 ppm) and 54.5% (62.5 ppm). Adsorption phenomena showed that EHC best fit Frumkin isotherm and ECF to Temkin isotherm. EHC extract (250 ppm) dissolved in a polar microemulsion system (MES-EHC) showed significant maximum inhibition efficiency (93.8%) fitting Langmuir isotherm. In the presence of the isolated Pseudomonas sp, EHC and ECF were able to form eco-compatible organic films with anti-corrosive properties

Filmes híbridos PMMA-siloxano modificados com nanotubos de carbono para proteção de materiais metálicos contra corrosão

Using the sol-gel process, organic-inorganic hybrid coatings were synthesized by incorporation of different concentrations of functionalized carbon nanotubes, to improve their mechanical strength and thermal resistance without changing its passivation character. The siloxane-PMMA hybrids were prepared by radical polymerization of methyl methacrylate (MMA) with 3-methacryloxipropiltrimethoxisilane (MPTS) using the thermal initiator benzoyl peroxide (BPO), followed by acid catalyzed hydrolysis and condensation of tetraethoxysilane (TEOS). The analysis of pristine and functionalized carbon nanotubes was carried out using Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy and Raman Spectroscopy. Structural analysis of hybrids was performed by Nuclear Magnetic Resonance, Atomic Force Microscopy and Raman Spectroscopy. For analysis of mechanical strength and thermal stability were performed mechanical compression tests and thermogravimetric analysis, respectively. Electrochemical Impedance Spectroscopy was used to evaluate the corrosion resistance in saline environment. The results showed an effective functionalization of carbon nanotubes with carboxyl groups and conservation of its structure. The hybrids showed high siloxane network connectivity and roughness of approximately 0.3 nm. The incorporation of carbon nanotubes in the hybrid matrix did not change significantly their thermal stability. Samples containing carbon nanotubes exhibit good corrosion resistance (on the order of MΩ in saline environment), but the lack of complete dispersion of carbon nanotubes in the hybrid, resulted in a loss of mechanical and corrosion resistance compared to hybrid matrix.

Utilização de matérias primas vegetais para aplicabilidade como inibidores de corrosão

In the search for products that act as corrosion inhibitors and do not cause environmental, impact the use of plant extracts as corrosion inhibitors is becoming a promising alternative. In this work the efficiency of polar extracts (ethanol extracts) obtained from the plants Anacardium occidentale Linn (AO) and Phyllantus amarus Schum. & Thonn (PA) as corrosion inhibitors were evaluated in different concentrations. For that AO and PA extracts were solubilized in the microemulsion systems (SME) containing saponified coconut oil as surfactant (SME -OCS and SME-OCS-1) in saline (NaCl 3,5 %) solution, which was also used as electrolyte. Both SME-OCS and SME-OCS-1 were characterized by surface tension and viscosity methods showing a Newtonian fluid behavior. The SME-OCS and SME-OCS-1 systems satisfactorily solubilized the polar extracts AO and PA with measurements carried out by ultraviolet spectroscopy. The measurements of corrosion inhibition efficiencies were performed by the electrochemical linear polarization resistance (LPR) technique as well as weight loss, on the surface of AISI 1020 carbon steel. The maximum corrosion inhibition efficiencies were determined by extrapolation of Tafel plots, showing the following values: 95,6 % for the system SME-OCS-AO, 98,9 % for the system SME-OCS-AO-1 and 93,4 % for the system SME-OCS-PA

Avaliação do efeito de particulados sólidos na eficiência de um inibidor de corrosão recomendado para meios salinos com CO2

The main problem on the exploration activity on petroleum industry is the formation water resulted on the fields producing. The aggravating of this problem is correlated with the advancing technologies used on the petroleum extractions and on its secondary approach objecting the reobtainment of this oil. Among the main contaminants of the water formation are corrosives gases such as: O2, CO2 and H2S, some solids in suspension and dissolved salts. Concerning to those gases the CO2 is the one that produce significant damage for carbon steel on corrosion process of the petroleum and gas industries. Corrosion inhibitors for carbon steel in formation water is one of the most used agents in control of those damages. In this context, the poor investigations of carbon steel corrosion proceeding from solids in suspension is an opened field for studies. On this work the inhibitor effect of the commercial CORRTREAT 703 was evaluated on some specific solids in suspension at saline medium containing 10.000 ppm of de-aerated chloride using CO2 until non oxygen atmosphere been present. For that, quartz, calcium carbonate, magnetite and iron sulphide were subjected to this investigation as the selected solids. The effect of this inhibitor on corrosion process correlated with those specific solids, was measured using electrochemical (resistance of linear polarization and galvanic pair) and gravimetrical techniques. During all the experimental work important parameters were monitored such as: pH, dissolved oxygen, temperature, instantaneous corrosion rate and galvanic current. According to the obtained results it was proved that the suspension solids calcium carbonate and iron sulphide decrease the corrosion process in higher pH medium. Meanwhile the quartz and magnetite been hardness increase corrosion by broking of the passive layer for erosion. In the other hand, the tested inhibitor in concentration of 50 ppm, showed to be effective (91%) in this corrosion process

Avaliação da espécie vegetal Croton cajucara Benth como inibidor de biocorrosão em aço carbono Aisi 1020

Actually in the oil industry biotechnological approaches represent a challenge. In that, attention to metal structures affected by electrochemical corrosive processes, as well as by the interference of microorganisms (biocorrosion) which affect the kinetics of the environment / metal interface. Regarding to economical and environmental impacts reduction let to the use of natural products as an alternative to toxic synthetic inhibitors. This study aims the employment of green chemistry by evaluating the stem bark extracts (EHC, hydroalcoholic extract) and leaves (ECF, chloroform extract) of plant species Croton cajucara Benth as a corrosion inhibitor. In addition the effectiveness of corrosion inhibition of bioactive trans-clerodane dehydrocrotonin (DCTN) isolated from the stem bark of this Croton was also evaluated. For this purpose, carbon steel AISI 1020 was immersed in saline media (3,5 % NaCl) in the presence and absence of a microorganism recovered from a pipeline oil sample. Corrosion inhibition efficiency and its mechanisms were investigated by linear sweep voltammetry and electrochemical impedance. Culture-dependent and molecular biology techniques were used to characterize and identify bacterial species present in oil samples. The tested natural products EHC, ECF and DCTN (DMSO as solvent) in abiotic environment presented respectively, corrosion inhibition efficiencies of 57.6% (500 ppm), 86.1% (500 ppm) and 54.5% (62.5 ppm). Adsorption phenomena showed that EHC best fit Frumkin isotherm and ECF to Temkin isotherm. EHC extract (250 ppm) dissolved in a polar microemulsion system (MES-EHC) showed significant maximum inhibition efficiency (93.8%) fitting Langmuir isotherm. In the presence of the isolated Pseudomonas sp, EHC and ECF were able to form eco-compatible organic films with anti-corrosive properties

Armazenamento de mirtilo 'Bluegem' em atmosfera controlada e refrigerada com absorção e inibição do etileno

O mirtilo é uma fruta rica em polifenóis e antocianinas que apresenta alta atividade antioxidante. No entanto, essa atividade pode ser alterada por condições de armazenamento e processamento dos frutos. O objetivo deste trabalho foi avaliar a manutenção das qualidades físicas e químicas de frutos de mirtilo (Vaccinium ashei Reade) do cultivar Bluegem em diferentes condições de armazenamento. O delineamento experimental utilizado foi o inteiramente casualizado com quatro repetições e unidade experimental composta por 400g de frutos. Os tratamentos utilizados foram: [1] armazenamento refrigerado (AR); [2] AR com absorção de etileno por sachês de permanganato de potássio; [3] atmosfera controlada (AC) com 2,0kPa O2 + 1 0,0kPa CO2; [4] AC com 2,0kPa O2 + 15,0kPa CO2; e [5] AC com 10,0kPa O2 + 15,0kPa CO2; [6] AC com 2,0kPa O2 + 10,0kPa CO2 e aplicação de 900ìg kg-1 de 1-metilciclopropeno. Os frutos submetidos a todos os tratamentos foram armazenados na temperatura de 0,5°C (± 0,1 °C). A avaliação da qualidade dos frutos foi realizada após sete semanas de armazenamento mais 84 horas (três dias e meio) de exposição a 20°C (± 0,2°C). A melhor conservação de mirtilo 'Bluegem' ocorreu em armazenamento refrigerado, em que se obteve maior acidez titulável, teor de sólidos solúveis totais e porcentagem de frutos firmes, conteúdo de antocianinas e polifenóis totais. Além de menor produção de etileno e CO2. A remoção do etileno da câmara de armazenamento favorece a conservação dos frutos.

Estudo da corrosão em diferentes tipos de aço

Mestrado em Engenharia Química - Ramo Optimização Energética na Indústria Química

Influência da fonte de carbono e da temperatura sobre a fermentação lática desenvolvida por cultura mista de bactérias láticas

Bactérias ácido láticas vêm sendo aplicadas em produtos cárneos como culturas iniciadoras. A finalidade das culturas iniciadoras em produtos cárneos é reduzir o pH no início da fermentação O que contribui na inibição de microrganismos indesejáveis, melhorar as propriedades sensoriais, reduzir o tempo de maturação e reduzir nitratos e nitritos. A composição do meio, assim como as condições de cultivo, são importantes para o bom desenvolvimento da cultura iniciadora, sendo necessário conhecer a influência da fonte de carbono e da temperatura no processo fermentativo. O objetivo deste trabalho foi estudar os efeitos da temperatura e de diferentes concentrações de glicose e lactose sobre a fermentação lática desenvolvida em caldo MRS (Man-Rogosa-Sharpe) pela cultura mista constituída de L. curvatus, L. plantarum, P. acidilactici e E. faecium. O caldo MRS foi suplementado com glicose e lactose, e as temperaturas de fermentação foram de 28ºC, 37ºC e 46ºC. Os ensaios foram delineados por desenho fatorial incompleto de 3³. Através da Superfície de Resposta, o modelo matemático mostrou que o caldo MRS suplementado de glicose 4,5% (m/v) e lactose 0,5% (m/v) e temperatura de incubação de 46ºC foram as condições mais adequadas para obtenção de ácido lático. A fermentação lática desenvolvida pela cultura mista, durante 48 horas nestas condições, forneceu em média 4,78% de ácido lático sendo a viabilidade celular de 1x10(15)UFC/mL.

Adição de plastificante à polianilina sintetizada quimicamente e avaliação dos filmes plastificados como proteção contra a corrosão do aço AISI 1010

Filmes de polianilina (PAni) puros não apresentam propriedades mecânicas satisfatórias quando depositados sobre metais e mergulhados em soluções aquosas. Propriedades mecânicas melhoradas podem ser obtidas adicionando um plastificante ao polímero. Neste caso foi utilizado o dodecilfenol (DDPh) e as condições mais adequadas de adição do DDPh a PAni previamente solubilizada em N-metilpirrolidinona (NMP) foram determinadas a partir da avaliação das propriedades dos filmes depositados sobre eletrodos metálicos de aço carbono. As melhores condições foram: adição de 5% de DDPh á PAni seguido de aquecimento sob vácuo a 200o C durante uma hora. A PAni sintetizada quimicamente foi utilizada nas condições dedopada e dopada com 5% de ácido para-toluenosulfônico (TSA). Também foi preparada uma mistura de PAni com poli(orto-metóxianilina) (POMA) em diversas proporções e igualmente dedopadas e dopadas com 5% de TSA. Os filmes obtidos nestas condições foram analisados por técnicas variadas (espectroscopia infravermelho, Raman e de massa), testados por técnicas eletroquímicas (voltametria cíclica e medida do potencial de corrosão ao longo do tempo) e ensaios acelerados de corrosão (névoa salina e câmara úmida) O melhor desempenho como filme protetor contra a corrosão foi apresentado pela PAni plastificada com 5% de DDPh e dopada com 5% de TSA. No ensaio de potencial de corrosão contra o tempo, este filme foi capaz de manter o potencial do sistema PAni-DDPh-TSA / aço carbono durante sete dias num valor positivo. Filmes da mistura PAni-POMA plastificados e dopados com TSA também atuaram conforme um mecanismo do mesmo tipo, porém por um período de tempo inferior, demonstrando a influência da POMA nas propriedades da PAni. Os ensaios acelerados de corrosão mostraram que os filmes de PAni plastificados com 5% de DDPh e dopados com 5% de TSA são muito superiores na proteção contra a corrosão do aço quando comparados ao filme de PAni pura. No ensaio de névoa salina o aço revestido pelo filme de PAni plastificado com 5% de DDPh e dopado com 5% de TSA, não apresentou corrosão por um período de sete dias.