The diploma thesis deals with the issue of surface treatment by pickling. In the research part the pickling technology is described in detail. The next chapters are focused on the TIG welding method and the weldability of austenitic stainless steels. In the experimental part an experiment is carried out focusing on the comparison of weight loss and surface quality depending on the pickling time. Part of the conclusion is the implementation of pWPS documentation for the specified component and a brief manual for customers of pickling plant.

The excellent corrosion resistance of stainless steels arises from the presence of a passive film on its surface. Above 10.5wt% Cr a chromium oxide of 1-3 nm is formed on the surface of the metal that in case of damage will reform and hinder further dissolution of the metal. However, the passivity of the stainless steel can be altered by material factors and external factors; such as the composition of the underlying phases, external loads or thermal treatments. In this work the local electrochemical techniques Scanning Vibrating Electrode Technique (SVET) and Scanning Kelvin Probe Force Microscopy (SKPFM) and the local characterization techniques X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES) have been used to investigate corrosion phenomena of stainless alloys based on measurements of corrosion current density, work function, thickness and composition of the oxide. The effect on work function of the thickness of the passive film and composition of the underlying phases was investigated for 301LN austenitic stainless steel (Paper I) and a heat treated superduplex 25Cr7Ni type stainless steel (Paper II). It was shown that the work function can be an indicator of corrosion resistance of the phases in the microstructure, and that the composition of the underlying phases had a greater effect on the work function than the thickness of the passive film. External factors such mechanical deformation (Paper I) and welding (Paper III) altered the passivity of the steel and work function. It was found that plastic deformation decreased irreversibly the work function, whereas elastic deformation did not have any permanent effect. Thermal oxides affected the passivity of stainless steels welded joints and were detrimental for its corrosion resistance. Anodic activity, observed with SVET, and pitting corrosion were detected at the heat tint and attributed to the interaction between the composition and the thickness of the oxide. Brushing combined with pickling was recommended for recovering the passivity of stainless steels. / <p>QC 20160516</p>

L'étude du comportement électrochimique des phases intermétalliques Al2Cu, Al2CuMg, Al7Cu2Fe, (Al,Cu)16Mn4Si3 et MgZn2, caractéristiques des alliages d'aluminium 2214-T6 et 7050-T74 et réalisée à partir d'échantillons massifs synthétisés, a montré que la formation de défauts majeurs dans la couche d'oxyde, obtenue par anodisation des alliages en milieu H2SO4 200 g/l, était directement due à la présence de ces particules au sein des alliages. L'important dégagement gazeux d'oxygène qui se produit à la surface de ces particules lors de l'étape d'anodisation explique la formation de trous et de fractures dans la couche d'oxyde. En milieu marin, ces défauts facilitent la migration des ions chlorures à la surface de l'alliage mise à nu localement et favorisent par conséquent le développement de la corrosion localisée. Les résultats obtenus en milieu NaCl 35g/l ont permis de mieux comprendre le mécanisme de corrosion des phases intermétalliques ainsi que leur rôle sur la propagation des piqûres. L'élimination des particules intermétalliques de la surface des alliages lors de l'étape de décapage (avant anodisation) permet de favoriser une croissance plus régulière de la couche d'oxyde lors de l'anodisation. Par conséquent, la résistance à la corrosion des alliages 2214 et 7050 augmente considérablement, permettant d'atteindre les objectifs fixés lors de ce projet / The electrochemical behaviour of the bulk intermetallic particles such as Al2Cu, Al2CuMg, Al7Cu2Fe, (Al,Cu)16(Mn,Fe)4Si3 and MgZn2 showed that the formation of wide defects in the oxide layer during the 2214-T6 and 7050-T74 alloys anodization was directly due to the presence of these kind of particles in the microstructure which are able to sustain both high dissolution rate and high water oxidation kinetics in acidic electrolyte. In marine environment, these defects facilitate the migration of aggressive ions like chloride on the locally bare alloys and are the onset of the pitting corrosion. The results obtained in 3.5 wt.% sodium chloride electrolyte permit to understand the corrosion mechanism of the intermetallic phases and their influence on the pits propagation. The optimization of the alloys pickling conditions in order to remove this kind of particles (prior to the anodization step) has been investigated in this work. Consequence of removing intermetallic particles, the aluminium enrichment of the surface facilitates the oxide growth and the formation of regular layer. The corrosion tests on treated aluminium alloys have clearly showed the influence of the pickling step on the resistance corrosion of 2214 and 7050 alloys, reaching the objectives fixed in this project

O comportamento eletroquímico do aço inoxidável 304 foi estudado em meios de ácido sulfúrico a várias temperaturas, utilizando reagentes de diferentes graus de pureza, na ausência e presença de benzotriazol (BTAH). Foram feitos ensaios gravimétricos, medidas de potencial de circuito aberto e curvas de polarização potenciostática anódicas e catódicas e análise dos produtos de corrosão por espectrometria de emissão atômica. O objetivo deste estudo foi avaliar a performance do BTAH como inibidor em banhos de decapagem industriais de H2SO4. O BTAH mostrou-se um inibidor efetivo para o aço 304 em toda a faixa de concentração de ácido e temperatura estudadas. A eficiência do inibidor- decresce com o aumento de temperatura e da concentração de H2SO4. O filme inibidor obedece à isoterma de Langmuir, tanto a 28,0 &#176;C quanto 70,0&#176;C, e os valores de energia livre de adsorção sugerem adsorção química. As impurezas presentes nos reagentes exercem pouco efeito na eficiência do inibidor. Estudos potenciostáticos mostraram que o BTAH é um inibidor anódico em toda a faixa de potencial e temperatura estudadas. Do ponto de vista tecnológico, os resultados mais importantes são: o BTAH inibe o processo de corrosão do aço, mas não impede a dissolução dos óxidos (carepa); o BTAH não promove dissolução seletiva dos elementos de liga. / The electrochemical behaviour of 304 stainless steel in sulfuric acid media containing benzotriazole (BTAH), was studied at different temperatures, using reagents of different purity grades. Weight loss experiments, open circuit potential measurements, anodic and cathodic potentiostatic polarisation curves and corrosion product analysis by atomic emission spectrometry were made. This study had as objective to evaluate the BTAH perfonnance as corrosion inhibitor in H2SO4 pick1ing baths. BTAH showed to be an effective inhibitor for 304 SS on the entire range of acid concentration and at alI studied temperatures . Inhibitor efficiency decreases as the temperature or acid concentration mcrease. The inhibitive film obeys to Langmuir isothenn, at 28,0 &#176;C as well at 70,0 &#176;C, and free energy adsorption values suggest chemical adsorption. The impurities present in the reagents have little effect on the inhibitor efficiency. Potentiostatic studies have shown that BTAH is an anodic inhibitor on the entire range of potential and at alI studied temperatures. The principal result for pickling baths aplication are that BTAR prevents the steel corrosion, but it does not avoid the scale dissolution and it does not promote selective steel dissolution.

Submitted by Luciana Sebin (lusebin@ufscar.br) on 2016-09-19T12:04:47Z No. of bitstreams: 1 DissEGAL.pdf: 1800823 bytes, checksum: 4f41eff6959b3c2f54964803282c02bb (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-20T18:12:10Z (GMT) No. of bitstreams: 1 DissEGAL.pdf: 1800823 bytes, checksum: 4f41eff6959b3c2f54964803282c02bb (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-20T18:12:17Z (GMT) No. of bitstreams: 1 DissEGAL.pdf: 1800823 bytes, checksum: 4f41eff6959b3c2f54964803282c02bb (MD5) / Made available in DSpace on 2016-09-20T18:12:27Z (GMT). No. of bitstreams: 1 DissEGAL.pdf: 1800823 bytes, checksum: 4f41eff6959b3c2f54964803282c02bb (MD5) Previous issue date: 2015-07-24 / Não recebi financiamento / This project aims the evaluation of some amines as corrosion inhibitors in carbon steel alloys amid hydrochloric acid (pickling bath). For that, analytical aspects of corrosion process has been considered and the results were interpreted considering the molecular interaction with the metal surface. / Este projeto visa avaliação de algumas aminas como inibidores de corrosão em ligas de aço carbono na presença de ácido clorídrico. Para tal, foram considerados os aspectos reacionais e comportamentais, e os resultados foram interpretados considerando a interação molecular com a superfície metálica.

O comportamento eletroquímico do aço inoxidável 304 foi estudado em meios de ácido sulfúrico a várias temperaturas, utilizando reagentes de diferentes graus de pureza, na ausência e presença de benzotriazol (BTAH). Foram feitos ensaios gravimétricos, medidas de potencial de circuito aberto e curvas de polarização potenciostática anódicas e catódicas e análise dos produtos de corrosão por espectrometria de emissão atômica. O objetivo deste estudo foi avaliar a performance do BTAH como inibidor em banhos de decapagem industriais de H2SO4. O BTAH mostrou-se um inibidor efetivo para o aço 304 em toda a faixa de concentração de ácido e temperatura estudadas. A eficiência do inibidor- decresce com o aumento de temperatura e da concentração de H2SO4. O filme inibidor obedece à isoterma de Langmuir, tanto a 28,0 &#176;C quanto 70,0&#176;C, e os valores de energia livre de adsorção sugerem adsorção química. As impurezas presentes nos reagentes exercem pouco efeito na eficiência do inibidor. Estudos potenciostáticos mostraram que o BTAH é um inibidor anódico em toda a faixa de potencial e temperatura estudadas. Do ponto de vista tecnológico, os resultados mais importantes são: o BTAH inibe o processo de corrosão do aço, mas não impede a dissolução dos óxidos (carepa); o BTAH não promove dissolução seletiva dos elementos de liga. / The electrochemical behaviour of 304 stainless steel in sulfuric acid media containing benzotriazole (BTAH), was studied at different temperatures, using reagents of different purity grades. Weight loss experiments, open circuit potential measurements, anodic and cathodic potentiostatic polarisation curves and corrosion product analysis by atomic emission spectrometry were made. This study had as objective to evaluate the BTAH perfonnance as corrosion inhibitor in H2SO4 pick1ing baths. BTAH showed to be an effective inhibitor for 304 SS on the entire range of acid concentration and at alI studied temperatures . Inhibitor efficiency decreases as the temperature or acid concentration mcrease. The inhibitive film obeys to Langmuir isothenn, at 28,0 &#176;C as well at 70,0 &#176;C, and free energy adsorption values suggest chemical adsorption. The impurities present in the reagents have little effect on the inhibitor efficiency. Potentiostatic studies have shown that BTAH is an anodic inhibitor on the entire range of potential and at alI studied temperatures. The principal result for pickling baths aplication are that BTAR prevents the steel corrosion, but it does not avoid the scale dissolution and it does not promote selective steel dissolution.

Denna studie har utförts på Calamo AB som arbetar med elektropolering och betning av rostfritt stål. Efter ytbehandlingssteget krävs sköljning av godset för att avlägsna kemikalierester vilket medför att stora mängder surt sköljvatten uppstår. Idag används våtkemisk fällningsanläggning för att rena sköljvattnet. Det befintliga reningsverket kräver flertalet tillsatser samtidigt som mängden slam som går till deponi är stor. Företaget vill utreda miljönyttan med att installera en vakuumindunstare för att ersätta det befintliga reningsverket som reningsmetod samt se över möjligheten att minska sin vattenförbrukning i samband med sköljning av gods för att bland annat kunna reducera storleken på indunstaren, minska belastningen på reningsstegen samt reducera mängden avfall. Studiens mål var att kartlägga uppkomsten av förorenat sköljvatten, identifiera potentiella vattenbesparande åtgärder och hur dessa åtgärder påverkar effektiviteten hos reningsanläggningarna. Samt visa hur installation av en vakuumindunstare förändrar företagets miljöpåverkan och utreda om det finns möjligheter att återanvända eller återvinna kemikalier och metaller från processen. Kartläggning och flödesmätningar av sköljvattenbehovet utfördes med hjälp av information av personal på Calamo samt en ultraljudsmätare. Vattenbesparande åtgärder, påverkan på reningsanläggning samt möjligheter till återvinning av kemikalier undersöktes genom litteraturstudie samt modellering i Excel. Utredningen av miljönyttan genom att ersätta befintligt reningsverk med vakuumindunstare utfördes med hjälp av LCA-värden hämtade från databasen SimaPro 8.0.4. Flera olika förslag på vattenbesparande åtgärder studerades och dessa gav en total vattenreduktion till reningsverket på mellan 5 - 81 % beroende på hur många samt vilka åtgärder som vidtogs. Enligt miljöberäkningarna genererar vakuumindunstaren 3 gånger högre utsläpp av koldioxidekvivalenter och 7 gånger större behov av icke förnyelsebar energi jämfört med det befintliga reningsverket. Genom att installera sprutskölj med motströmsteknik i stycke, sammankoppla befintliga sköljkar i avdelningarna betning, AVFKA samt automaten och installera sparsköljstank i alla avdelningar uppnås en reduktion av förorenat vatten till reningsstegen på 81%, vilket ytterligare kan optimeras genom installation av jonbytare, återanvändning av varmt vatten från renrum. Dessutom ökar föroreningshalten med 61% då dessa åtgärder vidtas vilket gynnar reningseffektiviteten i reningsanläggningarna och därav rekommenderas detta alternativ. Även kemikalieanvändningen och förluster av metalljoner reduceras avsevärt i processen genom användningen av sparskölj. Att installera vakuumindunstare rekommenderas inte på grund av dess stora energianvändning, dock kan andra resultat uppstå då andra LCA-värden används samt genom andra antaganden och hänsyn till kemikalie- och metallåtervinning istället för deponi. / This study has been carried out at Calamo AB, which works with electropolishing and pickling of stainless steel. After the surface treatment step, rinsing of the material is required to remove chemical residues, which results in large amounts of acid rinse water. Today, wet chemical precipitation plant is used to clean the rinse water. The existing treatment plant requires most additives, while the amount of sludge that goes to landfill is large. The company wants to investigate the environmental benefits of installing a vacuum evaporator to replace the existing sewage treatment plant as a purification method and to review the possibility of reducing its water consumption in connection with rinsing of goods in order to reduce the size of the evaporator, reduce the load on the purification steps and reduce the amount of waste. The aim of the study was to map the emergence of polluted rinse water, identify potential water-saving measures and how these measures affect the efficiency of the treatment plants. And show how the installation of a vacuum evaporator changes the company's environmental impact and investigate whether there are opportunities to reuse or recycle chemicals and metals from the process. Mapping and flow measurements of the rinse water requirement were performed using information from staff at Calamo and an ultrasonic meter. Water-saving measures, impact on treatment plant and opportunities for recycling of chemicals were investigated through literature study and modeling in Excel. The study of the environmental benefits by replacing existing treatment plants with vacuum evaporators was carried out using LCA values obtained from the database SimaPro 8.0.4. Several different proposals for water-saving measures were studied and these gave a total water reduction to the treatment plant of between 5 - 81% depending on how many and what measures were taken. According to the environmental calculations, the vacuum evaporator generates 3 times higher emissions of carbon dioxide equivalents and 7 times the need for non-renewable energy compared to the existing treatment plant. By installing spray rinse with countercurrent technology in one piece, interconnecting existing rinses in the cuttings departments, AVFKA as well as the dispenser and installing sparse rinse tank in all departments, a reduction of contaminated water to the purification steps of 81% is achieved, which can be further optimized by installation of ion exchangers, reuse of hot water from clean room. In addition, the pollutant content increases by 61% as these measures are taken, which favors the purification efficiency of the treatment plants and hence this option is recommended. The use of chemicals and losses of metal ions are also considerably reduced in the process through the use of savings rinses. Installing vacuum evaporators is not recommended due to its large energy use, however, other results may arise when other LCA values are used, as well as through other assumptions and considerations for chemical and metal recycling instead of landfill.

No description available.

No description available.

Este trabajo ha estado dirigido al estudio de un proceso eficaz de separación que posibilite la recuperación de zinc de efluentes de decapado ácido de elevada toxicidad, así como su posterior concentración en una fase de características físico-químicas adecuadas para posibilitar su reciclado en baños electrolíticos. Para ello se propone la extracción líquido-líquido no dispersiva como tecnología limpia de elevada eficacia y con bajo requerimiento energético.Tras una exhaustiva revisión bibliográfica, se seleccionan el fosfato de tributilo y el agua de red como agentes extractante y reextractante respectivamente. A lo largo del trabajo y tras una etapa previa dirigida a la evaluación de la viabilidad técnica del proceso, se caracterizaron experimentalmente las reacciones responsables de las etapas de extracción y reextracción, así como la cinética del proceso de separación, para a continuación plantear el modelo matemático y determinar los parámetros característicos del sistema necesarios para el diseño y optimización del proceso de separación-concentración de zinc de efluentes de decapado ácido metálico. / The work was focused on the study of the recovery of zinc from spent pickling effluents, under conditions that permitted the recovery of electrolytic grade metal, thus, reducing the effluent toxicity and with valorisation, at the same time, of the component of higher added value. After a deep literature review, non dispersive solvent extraction using tributyl phosphate (TBP) and service water as extraction and back extraction agents, respectively, was selected as the best separatión alternative. The work started with the analysis of the process viability and included an experimental design of the equilibrium, and kinetics of the phenomena involved in the metal valorisation. The kinetic analysis of the membrane assisted process of zinc recovery from spent pickling effluents was carried out, obtaining the mathematical model and parameters needed for design and optimisation of the metal separation step in a valorisation process.