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Surface Composition and Corrosion Behavior of an Al-Cu Alloy Jun Tao

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Surface Composition and Corrosion Behavior of an Al-Cu Alloy Jun Tao Surface composition and corrosion behavior of an Al-Cu alloy Jun Tao To cite this version: Jun Tao. Surface composition and corrosion behavior of an Al-Cu alloy. Chemical Physics [physics.chem-ph]. Université Pierre et Marie Curie - Paris VI, 2016. English. NNT : 2016PA066159. tel-01412882 HAL Id: tel-01412882 https://tel.archives-ouvertes.fr/tel-01412882 Submitted on 9 Dec 2016 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. THÈSE DE DOCTORAT DE L’UNIVERSITÉ PIERRE ET MARIE CURIE ÉCOLE DOCTORALE: ED388 - Chimie physique et chimie analytique de Paris Centre Présentée par M．Jun Tao Pour obtenir le grade de DOCTEUR de l’UNIVERSITÉ PIERRE ET MARIE CURIE Spécialité: Chimie physique des surface Sujet de la thèse : Surface composition and corrosion behavior of an Al-Cu alloy Soutenue le: 07 juin 2016 Devant le jury composé de : M. Roland Oltra Directeur de recherche au CNRS Rapporteur Université de Bourgogne Franche-Comté M. Dominique Thierry Président de l'Institut de la Corrosion Rapporteur Institut de la Corrosion Mme. Eliane Sutter Professeur Examinateur Université Pierre et Marie Curie M. Jean-Michel Lameille Ingénieur-chercheur Examinateur CEA M. Philippe Marcus Directeur de recherche au CNRS Directeur de thèse Chimie ParisTech Mme. Jolanta Światowska Chargée de recherche au CNRS Encadrante Chimie ParisTech Table of content Abstract ......................................................................................................................... 1 Chapter 1 State-of-the-art and objectives .................................................................. 3 1.1 Aluminium and aluminium alloys ............................................................... 4 1.2 Thermal treatments of Al-Cu series alloys .................................................. 5 1.3 Corrosion of Al-Cu alloys............................................................................ 9 1.3.1 Introduction to corrosion of aluminium alloys ....................................... 9 1.3.2 Corrosion behavior of aluminium alloys and influence of intermetallic particles .......................................................................................................... 12 1.4 Corrosion protection of aluminium alloys ...................................................... 18 1.4.1 Generalities about corrosion protection of aluminium alloys ............... 18 1.4.2 Conversion coatings .............................................................................. 18 1.4.3 Anodizing .............................................................................................. 20 1.4.4 Organic coatings ................................................................................... 22 1.4.5 Coatings prepared by Atomic Layer Deposition ................................... 22 1.5 Objectives of this thesis .................................................................................. 26 1.6 Contents of the thesis ...................................................................................... 27 Chapter 2 Techniques and sample preparations ..................................................... 37 2.1 X-ray Photoelectron Spectroscopy (XPS) ...................................................... 38 2.1.1 Principle ................................................................................................ 39 2.1.2 Instrument ............................................................................................. 41 2.1.3 Characterization .................................................................................... 42 2.2 Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) .................... 48 2.2.1 Principle ................................................................................................ 49 2.2.2 Instrument ............................................................................................. 51 2.2.3 Characterization .................................................................................... 52 2.3 Scanning Electron Microscopy (SEM) and Energy-dispersive X-Ray Spectroscopy (EDX) ............................................................................................. 55 2.4 Sample preparations ........................................................................................ 56 2.4.1 Mechanical polishing ............................................................................ 56 2.4.2 The annealing and aging thermal treatments ........................................ 57 Chapter 3 Influence of thermal aging treatments on surface chemical modifications of model Al-Cu alloy studied by in situ XPS and ToF-SIMS ......... 63 3.1 Introduction ..................................................................................................... 64 3.2 Experimental ................................................................................................... 67 3.3 XPS results ...................................................................................................... 69 3.4 ToF-SIMS results ............................................................................................ 80 3.5 Conclusions ..................................................................................................... 86 Chapter 4 Corrosion performances of model Al-Cu alloy after thermal treatments (annealing and aging) – surface studies by means of XPS and ToF- SIMS ............................................................................................................................ 91 4.1 Introduction ..................................................................................................... 92 4.2 Experimental ................................................................................................... 95 4.3 Results and discussions ................................................................................... 97 4.3.1 Surface characterization of the polished and aged Al-Cu alloy before corrosion ........................................................................................................ 97 4.3.2 Corrosion performance of the polished and thermally treated Al-Cu alloys – immersion tests ............................................................................... 103 4.3.3 Surface chemical modifications of the polished and thermally treated Al-Cu alloys after immersion tests .............................................................. 105 4.4 Conclusions ................................................................................................... 124 Chapter 5 Corrosion protection of the model Al-Cu alloy by ALD alumina thin film coatings .............................................................................................................. 133 5.1 Introduction ................................................................................................... 134 5.2 Experimental ................................................................................................. 135 5.3 Results and discussions ................................................................................. 138 5.3.1 Surface characterization of the pristine and alumina-coated Al-Cu alloy samples ......................................................................................................... 138 5.3.2 Corrosion resistance of the alumina ALD coated Al-Cu alloys – immersion tests ............................................................................................ 142 5.3.3 Surface characterization of non-coated and coated Al-Cu alloys after immersion tests ............................................................................................ 145 5.4 Conclusions ................................................................................................... 160 Chapter 6 Conclusions and perspectives ............................................................... 165 Abbreviations and acronyms .................................................................................. 173 Acknowledgements .................................................................................................. 175 Abstract Al-Cu series alloys are the most widely used heat treatable alloys for the aircraft materials, machine parts, and structural materials mainly due to their high strength to weight ratio and good mechanical properties. However, the Cu-rich precipitations (Al2Cu intermetallic particles present in these alloys as the most important strengthening phase), have negative effects on the corrosion performances of these alloys. In this thesis, Al-Cu model alloy was employed to investigate the influence of thermal aging treatments in ultra-high vacuum (UHV) on the chemical modifications of the alloy using surface analytical techniques (XPS, ToF-SIMS). The in situ XPS characterization showed that the Al-Cu alloy was oxidized as a function of exposure to the low pressure (LP) of O2 and temperatures from 300 to 400 °C via the mechanism - the preferential oxidation of Al in the alloy leading to a growth of aluminium oxide layer, and the enrichment/segregation
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