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Influence of Zinc on Surface Treatments of Aluminium-Zinc Alloys

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Influence of Zinc on Surface Treatments of Aluminium-Zinc Alloys Influence of Zinc on Surface Treatments of Aluminium-Zinc Alloys A thesis submitted to the University of Manchester for the degree of Doctor of Philosophy in the Faculty of Engineering and Physical Sciences 2010 Marialuisa Gentile Corrosion and Protection Centre School of Materials 1 aaa 2 List of Contents List of Contents List of Figures................................................................................................................7 List of Tables................................................................................................................16 Abstract........................................................................................................................17 Declaration...................................................................................................................18 Copyright Statement.....................................................................................................19 Acknowledgements......................................................................................................20 Chapter 1 Introduction…………………………………………………………………............21 Overview......................................................................................................................21 Objectives………………….........................................................................................23 Chapter 2 Properties, Corrosion and Surface Treatments of Aluminium and Aluminium Alloys...........................................................................................................................25 Introduction..................................................................................................................25 Properties of Aluminium..............................................................................................26 The Al-H2O Pourbaix Diagram....................................................................................27 Properties of Zinc.........................................................................................................29 The Zn-H2O Pourbaix Diagram...................................................................................31 Aluminium Alloys........................................................................................................32 Classification System of Aluminium Alloys................................................................32 Metallurgy of Aluminium Alloys.................................................................................34 Effect of Composition and Microstructure on Corrosion Resistance of Aluminium Alloys...………………………………………………………………………………35 Properties of Al-Zn Alloy…..………………………………………………………..36 The Aluminium-Zinc Equilibrium Diagram…………………………………………36 Corrosion of Aluminium..............................................................................................37 Pitting Corrosion..........................................................................................................37 Theories of the Mechanism of Pitting Corrosion.........................................................41 Pitting Corrosion of Aluminium and its Alloys……………………………………...43 Surface Treatments of Aluminium…………………………..….................................45 3 List of Contents Mechanical Polishing...................................................................................................45 Electropolishing............................................................................................................45 Relationship Between Current and Voltage.................................................................46 Alkaline Etching...........................................................................................................48 Chapter 3 Oxides of Aluminium and Aluminium Alloys..........................................................61 Introduction..................................................................................................................61 Properties of Aluminium Hydroxide/Oxyhydroxides and Oxides …..........................61 Aluminium Trihydroxides……………………………………………........................62 Aluminium Oxide Hydroxides.....................................................................................63 Aluminium Oxide.........................................................................................................64 Anodic Oxides Formed by Anodic Polarization of Aluminium........... .......................65 Barrier Anodic Films....................................................................................................66 Porous-type Anodic Films........................................................................................... 67 Mechanisms of Ionic Transport through Oxide Films……………………………….69 The High Field Conduction Theory………………………………………………….69 Oxidation of Aluminium Alloys……………………………………………………...74 Enrichment of Aluminium Alloys…………………………………………………....75 Chapter 4 Experimental Procedure............................................................................................90 Introduction..................................................................................................................90 Materials.......................................................................................................................90 Surface Treatments.......................................................................................................91 Mechanical Polishing...................................................................................................91 Electropolishing...........................................................................................................91 Etching and Desmuting................................................................................................91 Anodizing……………………………………………………………………...……..92 Open Circuit Potential Responses………………………………………...…………92 Weight Loss Measurements………………………………………………………….93 Analytical Techniques...................................................................................,..............94 Rutherford Backscattering Spectroscopy (RBS)..........................................................94 Medium Energy Ion Scattering (MEIS)……………………………………………...94 4 List of Contents Glow Discharge Optical Emission Spectroscopy (GDOES)………………………....95 Scanning Electron Microscopy (SEM)…………………………………………….....95 Atomic Force Microscopy (AFM) and Interferometry…...……………………….....95 Electron Backscattered Diffraction (EBSD)………………………………………....97 Transmission Electron Microscopy (TEM)..................................................................97 Chapter 5 Influence of Surface Treatments on Zinc Enrichment in Al-Zn Alloys………..104 Introduction................................................................................................................104 Results........................................................................................................................105 RBS and MEIS Spectra…...………………………………………...........................105 GDOES Spectra……….…………………………….................................................107 Transmission Electron Microscopy............................................................................107 Etching Rate…………………………............................................................................108 Discussion..................................................................................................................108 Conclusions................................................................................................................111 Chapter 6 Influence of Zinc on the Surface Morphologies of Al-Zn Alloy...........................128 Introduction................................................................................................................128 Results........................................................................................................................129 Scanning Electron Microscopy (SEM) of Al-Zn Alloys ………..…….......................129 Potential-time Behaviour during Anodic Alkaline Etching………………………...131 Potential-time Behaviour during Etching in Alkaline Solution………………….....131 Discussion..................................................................................................................132 Conclusions................................................................................................................137 Chapter 7 Influence of Surface Pretreatments on Anodizing of Al-Zn Alloys.....................149 Introduction................................................................................................................149 Results…………………………………………………………………………...….149 Voltage-time Response of the Al-Zn Alloy...............................................................149 Scanning Electron Microscopy (SEM) of the Anodized Al-Zn Alloys………….…151 5 List of Contents Transmission Electron Microscopy of Anodized Al-Zn Alloys................................153 Discussion…………………………………………………………..........................153 Conclusions……………………………………………………………………........156 Chapter 8 Influence of Grain Orientation on Zinc Enrichment and Surface Morphologies of Al-Zn Alloys……………………………………..…….......................................165 Introduction................................................................................................................165 Results……………………………………................................................................166 FEG-SEM-EBSD.......................................................................................................166
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