Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-12-12T18:02:42Z No. of bitstreams: 1 DenisePorfirioEmerenciano_TESE.pdf: 5967121 bytes, checksum: 6c15d6a4ccd96bffd068397c96e41a2b (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-12-13T18:22:53Z (GMT) No. of bitstreams: 1 DenisePorfirioEmerenciano_TESE.pdf: 5967121 bytes, checksum: 6c15d6a4ccd96bffd068397c96e41a2b (MD5) / Made available in DSpace on 2017-12-13T18:22:54Z (GMT). No. of bitstreams: 1 DenisePorfirioEmerenciano_TESE.pdf: 5967121 bytes, checksum: 6c15d6a4ccd96bffd068397c96e41a2b (MD5) Previous issue date: 2017-04-19 / A efici?ncia de inibi??o ? corros?o de sistemas coloidais preparados a base de ?leos vegetais provenientes das esp?cies Azadirachta indica A. Juss (SMEOAI) e Copaifera L. (SMECO) foi avaliada via t?cnicas eletroqu?micas. Os formulados coloidais SMEOAI e SMECO foram analisados em diferentes concentra??es (5 ppm - 150 ppm) na corros?o do a?o AISI 1018, em meio salino (3,5% de solu??o NaCl). O extrato hidroalco?lico obtido das folhas de A. indica (EAI) veiculado no sistema SMEOAI, forneceu o formulado SMEOAI-EAI que foi avaliado como inibidor verde de corros?o. O sistema SMEOAI foi preparado com Tween? 80 (fase tensoativo), ?leo isolado de A. indica (OAI, fase ?leo) e de ?gua bidestilada (fase aquosa neutra). Este sistema veiculou, satisfatoriamente, o extrato EAI, resultando na microemuls?o SMEOAI-EAI. Similarmente, o sistema coloidal SMECO foi preparado com Tween? 80, ?leo de copaiba (CO) e ?gua bidestilada. Diagramas de fases tern?rios foram obtidos para SMEOAI e SMECO, tendo sido comprovada a forma??o de microemuls?o com regi?o caracter?stica de Winsor IV (WIV). As caracteriza??es destes sistemas foram realizadas pelas seguintes an?lises: determina??o do ?ndice de refra??o, comportamento reol?gico, tens?o superficial e di?metro de got?cula. O efeito de inibi??o dass microemuls?es obtidas a base de A. indica (SMEOAI e (SMEOAI-EAI) foram analisadas pelas t?cnicas de resist?ncia a polariza??o linear (LPR) e imped?ncia (EIS). A microemuls?o obtida a base de Copaifera (SMECO) foi avaliada via m?todo LPR. Comparativamente, SMECO (100 ppm) apresentou a menor efici?ncia de inibi??o ? corros?o (77,15%), seguido de SMEOAI (25 ppm) com inibi??o mediana (79,28%). A presen?a do extrato EAI no formulado SMEOAI, otimizou a efici?ncia de inibi??o, tendo sido comprovado que o sistema SMEOAI-EAI (50 ppm) apresentou a efici?ncia m?xima (91,79%) de inibi??o. Para estes inibidores, comprovou-se tamb?m, efeitos antioxidantes realizados em experimentos in vitro. De forma abrangente, o efeito antioxidante mais eficaz foi observado para a microemuls?o SMEOAI-EAI. Estes formulados coloidias foram avaliados pelas an?lises de capacidade antioxidante total: 18,74% (SMEOAI) e 36,14% (SMEOAI-EAI); poder redutor: 56,34% (SMEOAI) e 290,49% (SMEOAI-EAI); quela??o de ?ons ferro: 58,97% (SMEOAI) e 51,29% (SMEOAI-EAI); bem como sequestro dos radicais hidroxila: 60,16% (SMEOAI) e 87,33% (SMEOAI-EAI). As diverg?ncias percentuais observadas encontram-se relacionadas aos diferentes mecanismos antioxidativos de cada modelo, bem como pela presen?a do extrato EAI no formulado SMEOAI. O sistema a base de ?leo de copa?ba (SNECO), apresentou 47,89% de efeito antioxidante na an?lise do poder redutor e valor mais elevado (72,92%), para o sequestro de radicais hidroxila. Os inibidores verde de corros?o SMEOAI, SMEOAI-EAI e SMECO s?o biodegrad?veis e em fun??o do amplo uso destes vegetais, poder?o despertar o interesse do setor industrial com diferentes possibilidades de aplica??es, tais como: bioinseticida, purificador de ?guas residuais, agente efluente, agente de recupera??o de petr?leo, dentre outros. / The corrosion inhibition efficiency of colloidal systems based on vegetable oils such as Azadirachta indica A. Juss (SMEOAI) and Copaifera L. (SMECO) were evaluated by electrochemical techniques. The colloidal formulations SMEOAI and SMECO were analyzed in different concentrations (5 ppm - 150 ppm) in the corrosion of AISI 1018 steel in corrosive saline medium (3.5% NaCl solution). The hydroalcoholic extract obtained from the leaves of A. indica (EAI) was loaded in the colloidal system SMEOAI and then applied as a green corrosion inhibitor. The SMEOAI system was prepared by using Tween? 80 as surfactant, A. indica oil (OAI) as the oil phase and bidistilled water (as a neutral aqueous phase). The SMEOAI system satisfactorily loaded the EAI extract providing a derivative formulation so called SMEOAI-EAI. Similarly, the SMECO system was prepared by using Tween? 80, copaiba oil (CO), and bidistilled water. The formation of Winsor IV microemulsion region (WIV) on both systems (SMEOAI and SMECO) was evidenced through the construction of the ternary phase diagrams. The colloidal systems characterizations were performed by using the following analyzes: determination of the refractive index, rheological behavior, surface tension and droplet diameter. The coloidal formulations SMEOAI and SMEOAI-EAI were analyzed by using electrochemical techniques of linear polarization resistance (LPR) and impedance spectroscopy (EIS). Meanwhile, SMECO system was only analyzed by using the LPR method. Comparatively, the SMECO system (100 ppm) showed the lowest corrosion inhibition efficiency (77.15%), followed by SMEOAI (25 ppm) which showed median inhibition (79.28%) and the maximum inhibition efficiency (91.79%) was found to the SMEOAI-EAI (50 ppm) system, justified by the presence of the EAI extract in the loading system SMEOAI. For all of those green inhibitors systems the antioxidant effect was analyzed by using in vitro experiments and the best result was found to SMEOAI-EAI system. For that analysis it was applied: total antioxidant capacity, 18.74% (SMEOAI) and 36.14% (SMEOAI-EAI); reducing power, 56.34% (SMEOAI) and 290.49% (SMEOAI-EAI); iron ion chelation, 58.97% (SMEOAI) and 51.29% (SMEOAI-EAI); sequestration of hydroxyl radicals, 60.16% (SMEOAI) and 87.33% (SMEOAI-EAI). The observed percentage divergences were related to the different antioxidative mechanisms of each applied model, as well as the presence of the A. indica extract (EAI) in the SMEOAI-EAI system. The colloidal system prepared with copaiba oil (SNECO) showed the lower effect 47.89% in the analysis of reducing power. Meanwhile, for this system a higher result (72.92%) was evidenced in the sequestration of hydroxyl radicals analysis. The green corrosion inhibitors SMEOAI, SMEOAI-EAI and SMECO are biodegradable and due to the wide use of these plants, may arouse the interest of the industrial sector focusing some different possible applications such as: bio-insecticides, biological drug carriers, waste water purifiers, effluents, oil recovery agents, among other applications.

Made available in DSpace on 2014-12-17T14:06:56Z (GMT). No. of bitstreams: 1 AnaCeciliaVN.pdf: 4627476 bytes, checksum: 03aa7ea0e615f64c7e42bf3a39bdd226 (MD5) Previous issue date: 2008-04-25 / Portland-polymers composites are promising candidates to be used as cementing material in Northeastern oil wells of Brazil containing heavy oils submitted to steam injection. In this way, it is necessary to evaluate its degradation in the commonly acidizind agents. In addition, to identify how aggressive are the different hostile environments it is an important contribution on the decision of the acidic systems to be used in. It was investigated the performance of the Portland-polymer composites using powdered polyurethane, aqueous polyurethane, rubber tire residues and a biopolymer, those were reinforced with polished carbon steel SAE 1045 to make the electrochemical measurements. HCl 15,0 %, HCl 6,0 % + HF 1,5 % (soft mud acid), HCl 12,0 % + HF 3,0 % (regular mud acid) and HAc 10 % + HF 1,5 % were used as degrading environment and electrolytes. The more aggressive acid solution to the plain Portland hardened cement paste was the regular mud acid, that showed loss of weight around 23.0 %, followed by the soft mud acid, the showed 11.0 %, 15.0 % HCl with 7,0 % and, at last the 10.0 % HAc plus HF 1.5 % with just 1.0 %. The powdered polyurethane-composite and the aqueous polyurethane one showed larger durability, with reduction around 87.0 % on the loss of weight in regular mud acid. The acid attack is superficial and it occurs as an action layer, where the degraded layer is responsible for the decrease on the kinetic of the degrading process. This behavior can be seen mainly on the Portland- aqueous polyurethane composite, because the degraded layer is impregnated with chemically modified polymer. The fact of the acid attack does not have influence on the compressive strength or fratography of the samples, in a general way, confirms that theory. The mechanism of the efficiency of the Portland-polymers composites subjected to acid attack is due to decreased porosity and permeability related with the plain Portland paste, minor quantity of Ca+2, element preferentially leached to the acidic solution, wave effect and to substitute part of the degrading bulk for the polymeric one. The electrolyte HAc 10 % + HF 1,5 % was the least aggressive one to the external corrosion of the casing, showing open circuit potentials around +250 mV compared to -130 mV to the simulated pore solution to the first 24 hours immersion. This behavior has been performed for two months at least. Similar corrosion rates were showed between both of the electrolytes, around 0.01 μA.cm-2. Total impedance values, insipient arcs and big polarization resistance capacitive arcs on the Nyquist plots, indicating passivity process, confirm its efficiency. In this way, Portlandpolymers composites are possible solutions to be succeed applied to oilwell cementing concomitant submitted to steam injection and acidizing operation and the HAc 10,0 % + HF 1,5 % is the less aggressive solution to the external corrosion of the casing / Comp?sitos Portland-pol?meros s?o promissores candidatos ? cimenta??o de po?os de petr?leo contendo ?leos pesados submetidos ? inje??o de vapor nos campos do Nordeste do Brasil. Assim, faz-se necess?rio avaliar sua degrada??o frente aos ?cidos comumente utilizados em opera??es de acidifica??o. Al?m disso, identificar a agressividade dos diferentes meios hostis ? corros?o externa do revestimento constitui uma importante contribui??o na decis?o dos sistemas ?cidos a serem utilizados. Foram avaliados comp?sitos adicionados de poliuretana em p?, poliuretana em solu??o aquosa, borracha de pneu mo?da e um biopol?mero atrav?s das API Spec. 10, sendo refor?ados com a?o carbono polido SAE 1045 para os ensaios eletroqu?micos. HCl 15,0 %, HCl 6,0 % + HF 1,5 % (soft mud acid), HCl 12,0 % + HF 3,0 % (regular mud acid) e HAc 10,0 % + HF 1,5 % foram aplicadas como meios degradantes e eletr?litos. A solu??o ?cida mais agressiva ? pasta de cimento Portland convencional ? a regular mud acid, que apresenta perda de massa em torno de de 23,0 %, seguida da soft mud acid, com perda de massa de 11,0 % e da solu??o HCl 15,0 %, em torno de 7,0 %. As menores perdas de massa, no entanto, s?o relativas ao meio agressivo HAc 10,0 % + HF 1,5 %, com perdas no patamar de 1,0 %. Os comp?sitos com poliuretana em p? e poliuretana em solu??o aquosa apresentaram maior durabilidade, com redu??o em torno de 87,0 % na perda de massa frente ao regular mud acid. O ataque ?cido ? superficial e ocorre como uma frente de a??o, sendo a camada degradada respons?vel pela minimiza??o da cin?tica do processo de degrada??o, principalmente no comp?sito Portland-poliuretana em dispers?o aquosa, por ser impregnada por pol?mero quimicamente modificado. O fato de n?o haver, de uma forma geral, influ?ncia do ataque ?cido na resist?ncia ? compress?o e fratografia das amostras, ap?s ataque ?cido, ratifica essa teoria. O mecanismo da maior efici?ncia dos comp?sitos Portland-pol?meros frente ao ataque ?cido ? regido por menores porosidades e permeabilidades que a pasta de cimento convencional, menor quantidade de Ca+2, elemento prioritariamente lixiviado para a solu??o ?cida, efeito tortuosidade e substitui??o de massa degrad?vel por massa polim?rica. O eletr?lito HAc 10,0 % + HF 1,5 % foi o menos agressivo ? corros?o externa do revestimento, com potenciais de circuito aberto superiores ? solu??o simuladora dos poros como eletr?lito, +250 mV frente a -130 mV para as primeiras 24 horas de imers?o, mantendo esse comportamento ao longo de, pelo menos, 2 meses de imers?o. Correntes de corros?o semelhantes entre esses dois eletr?litos, em torno de 0,01 μA.cm-2, e valores de imped?ncia total, arcos incipientes e grandes arcos capacitivos de resist?ncia de polariza??o, indicadores de passiva??o nos diagramas de Nyquist, confirmam sua efici?ncia. Assim, comp?sitos Portland-pol?meros s?o solu??es poss?veis de serem empregadas em cimenta??o de po?os de petr?leo submetidos concomitantemente ? inje??o de vapor e opera??es de acidifica??o, sendo a solu??o HAc 10,0 % + HF 1,5 % menos agressiva ? corros?o externa do revestimento ap?s opera??es de acidifica??o

Made available in DSpace on 2014-12-17T14:07:20Z (GMT). No. of bitstreams: 1 MichelePT.pdf: 1085937 bytes, checksum: 9dafe388fed079c9a3f014f2d96a5186 (MD5) Previous issue date: 2007-04-27 / Petr?leo Brasileiro SA - PETROBRAS / 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 / O principal problema ligado ? atividade de explora??o de petr?leo ? a ?gua que se produz nos campos produtores. O agravamento deste problema se deve aos avan?os obtidos nos processos de extra??o de petr?leo, bem como ?s opera??es secund?rias que objetivam a recupera??o de petr?leo. Os principais contaminantes presentes nesta ?gua que contribuem para o desenvolvimento de processos corrosivos s?o: gases (que se encontram dissolvidos na ?gua, tais como O2, CO2 e H2S), s?lidos em suspens?o e sais dissolvidos. Dentre os gases destaca-se o CO2 que provoca desgaste significativo nas tubula??es (de a?o carbono) de ind?strias de petr?leo e g?s natural. O uso de inibidores de corros?o ? uma pr?tica comum no combate aos processos corrosivos. Neste contexto, os contaminantes do tipo particulados s?lidos s?o pouco avaliados. Desta forma, neste trabalho, o efeito do inibidor de uso comercial CORRTREAT 703 em particulados s?lidos comumente encontrados em oleodutos. Utilizou-se um meio salino contendo 10.000 ppm de cloreto desaerado com CO2 at? obten??o de um meio isento de oxig?nio. Para tanto, os s?lidos escolhidos foram: quartzo, magnetita, carbonato de c?lcio e sulfeto de ferro. A efici?ncia de inibi??o do CORRTREAT 703 na corros?o provocada por estes s?lidos, foi medida com o uso de t?cnicas eletroqu?micas (resist?ncia de polariza??o linear e par galv?nico) e gravim?tricas. Durante todo o trabalho experimental, foram monitorados os seguintes par?metros: pH, oxig?nio dissolvido, temperatura, taxa de corros?o instant?nea e corrente galv?nica. De acordo com os resultados obtidos comprovou-se que o carbonato de c?lcio e o sulfeto de ferro est?o envolvidos em um processo corrosivo mais lento em fun??o do aumento do pH do meio. No entanto, o quartzo e a magnetita em virtude da sua dureza aceleram a corros?o pela quebra da camada passiva por eros?o. Por outro lado, o inibidor avaliado foi eficaz (91 %) em uma concentra??o de 50 ppm no processo avaliado