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Alternative Protective Coatings for Hot Stamped Automotive Body Parts Damien Close

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Alternative Protective Coatings for Hot Stamped Automotive Body Parts Damien Close Alternative protective coatings for hot stamped automotive body parts Damien Close To cite this version: Damien Close. Alternative protective coatings for hot stamped automotive body parts. Material chemistry. Université de Lorraine, 2018. English. NNT : 2018LORR0083. tel-01920933 HAL Id: tel-01920933 https://hal.univ-lorraine.fr/tel-01920933 Submitted on 17 Jan 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. AVERTISSEMENT Ce document est le fruit d'un long travail approuvé par le jury de soutenance et mis à disposition de l'ensemble de la communauté universitaire élargie. Il est soumis à la propriété intellectuelle de l'auteur. Ceci implique une obligation de citation et de référencement lors de l’utilisation de ce document. D'autre part, toute contrefaçon, plagiat, reproduction illicite encourt une poursuite pénale. Contact : [email protected] LIENS Code de la Propriété Intellectuelle. articles L 122. 4 Code de la Propriété Intellectuelle. articles L 335.2- L 335.10 http://www.cfcopies.com/V2/leg/leg_droi.php http://www.culture.gouv.fr/culture/infos-pratiques/droits/protection.htm École doctorale SESAMES THÈSE Pour l’obtention du titre de : DOCTEUR DE L’UNIVERSITÉ DE LORRAINE CHIMIE Spécialité : Chimie, Electrochimie et Science des Matériaux Présentée par : DAMIEN CLOSE Alternative protective coatings for hot stamped automotive body parts Soutenance publique le 22 Mars 2018 à Metz devant le jury composé de : Juan CREUS Professeur Rapporteur LaSIE, Université de La Rochelle - La Rochelle, France Marjorie OLIVIER Professeur Rapporteur Faculté Polytechnique de Mons - Mons, Belgique Muriel VERON Professeur Examinatrice Grenoble INP, SIMAP - Grenoble, France Albert TIDU Professeur Examinateur LEM3, Université de Lorraine - Metz, France Nathalie ALLAIN Professeur Examinatrice LEM3, Université de Lorraine - Metz, France Nicolas STEIN Maître de Conférences HDR Directeur de thèse IJL, Université de Lorraine - Metz, France Clotilde BOULANGER Professeur Invitée IJL, Université de Lorraine - Metz, France Régis LALLEMENT Dr. -Ing Invité Daimler AG - Sindelfingen, Allemagne Institut Jean Lamour – Equipe 208 – 1 Boulevard Arago 57078 Metz CEDEX Université de Lorraine – Pôle M4 : matière, matériaux, métallurgie, mécanique 1 Conformément aux exigences de l’École Doctorale SESAMES, la thèse étant rédigée en anglais, l’introduction, les objectifs, les résumés des chapitres 4, 5 et 6 ainsi que la conclusion sont également rédigés en français. 2 3 This work has been carried out at the Institut Jean Lamour (IJL) and at the laboratory of study of microstructures, mechanics and material sciences (LEM3) of the Université de Lorraine (UL) in the framework of an industrial project in cooperation with the Daimler AG. First of all, I would like to express my sincere gratitude to Dr. Nicolas Stein, Prof. Nathalie Allain and Prof. Albert Tidu for their continuous support and input throughout the entire thesis. Their help in regard to the various scientific and technical challenges I encountered as well as the insightful comments on the manuscript helped me to improve my work. I enjoyed the endless brain storming sessions in which we were trying to understand the Zn-Mn alloys. My sincere thanks go to my advisor Nicolas for his outstanding supervision, his personal support in the rough phases as well as for sharing his immense knowledge with me. I am deeply grateful for everything I learned from you. All this would not have been possible without the support of Dr. Régis Lallement, who originally had the idea about this interesting topic and initiated the project. He has taught me a lot about academic and industrial environments, which was an important requirement to conduct this thesis. Beyond, I would like to express my gratitude to Dr. Peter Feuser for his great expertise in the domain of hot forming, his valuable supervision and his numerous comments which improved the quality of this thesis. I am also thankful to Mr. Raschke, Prof. Paul Dick and Mr. Bachmann for the opportunity of conducting this research and for initiating the financial support. I am also appreciative to Prof. Merklein who provided me the opportunity to carry out hot stamping experiments as well as to Dr. Sven Hildering for his support with the research facilities. I would like to thank Prof. Marjorie Olivier, Prof. Muriel Veron, Prof. Juan Creus, and Prof. Clotilde Boulanger for being part of my thesis committee and for their helpful comments on the manuscript and the presentation. I am also thankful to Prof. Albert Tidu who made me the honor of being the president of the committee. Furthermore, I would like to take the opportunity to thank Florian Claudel for his support in the last months of my PhD thesis. I am also thankful to my colleagues from the IJL and LEM3 laboratories for their contribution in conducting the experiments, in particular Dr. Julien Guyon for his FIB-SEM and EBSD analyses, Dr. Sebastien Diliberto and Laetitia Garoux for the XRD analyses, Dr. Marie Georgel for the Raman measurements as well as Dr. Abdel Danine and Prof. Jaafar Ghanbaja for the TEM analyses. Thanks to Estelle, Nicolas, Jamal, Thu Hang, Victor, Romain, Daniela, Alexander and Florian for their support in the experiments as well as to José Lopez for the construction of the electroplating cell. I also would like to thank the staff of the RD/KSO, TF/VFT and RD/KRU departments, in particular Dr. Michael Bayer and Carmen Schmidt for their help in the characterisation studies. I also have a thought for Bernard for his contribution in the start of the project. Lastly, I would like to express my gratitude to my family and friends for their support during the last years as well as to my partner, Anna, who has encouraged me during the entire process. I am thankful for your understanding, your patience, your love and your humour, which have brightened up the sometimes dark days of thesis writing. 4 5 SUMMARY Alternative protective coating systems for hot stamped automotive body parts Various coatings are currently available for press-hardened steels used for the automotive construction, mainly with the aim of providing good anticorrosive properties to the body components. In order to improve performance of the coated products in terms of hot formability, corrosion protection and suitability for subsequent manufacturing processes, steelmakers and car manufacturers investigated various alternative coating materials. Only a few solutions resulted in a serial production. The aim of this study is to proceed to a screening of the performance of current coating variants, to identify new concepts for alternative coating materials and assess their suitability for the hot stamping application. The present work is focused on the study of Zn-Mn alloy coatings. Various electroplating baths and electric parameters were studied in order to determine optimal deposition conditions for obtaining Zn-Mn alloys with high Mn contents. The deposits obtained on large-scale steel plates were characterized with regards to their crystallographic, microstructural and anticorrosive properties. The behavior of the coating materials during austenitizing treatment was studied after heat treatment to different temperatures and heating durations. A particular attention was given to the evolution of the composition, the interdiffusion phases formed as well as to the presence of oxidation and evaporation mechanisms at high temperature. At last, the forming properties of the alternative coating materials and their susceptibility for liquid metal embrittlement were assessed on the basis of direct hot stamping experiments. KEY WORDS Coatings Electrodeposition Microstructural Characterization Corrosion Protection Hot Stamping Surface Engineering 6 7 RÉSUMÉ Revêtements alternatifs pour pièces automobiles embouties à chaud De nombreux revêtements sont actuellement disponibles pour les aciers emboutis à chaud et trempés pour le domaine de la construction automobile. Afin d’augmenter les performances des produits actuels en termes d’aptitude à la mise en forme à chaud, de résistance contre la corrosion et de compatibilité avec les procédés de fabrication ultérieurs, les constructeurs automobiles et les sidérurgistes ont développé de nombreux types de matériaux alternatifs. Peu de produits ont trouvé une place importante dans l’utilisation industrielle. L’objectif de ce travail est de procéder à une vue d’ensemble des performances des produits actuels, d’identifier de nouveaux concepts de revêtements et d’étudier leur compatibilité pour l’application de la mise en forme à chaud. Cette étude porte sur les revêtements d’alliages de Zn-Mn. De nombreux bains électrolytiques et paramètres électriques ont été étudiés afin de déterminer des conditions de déposition optimales pour obtenir des alliages Zn-Mn avec une forte teneur en Mn. Les propriétés cristallographiques, microstructurales et anticorrosives de couches obtenues sur des plaques d’acier de grandes dimensions ont été caractérisées avec de nombreuses techniques. La compatibilité
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