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The corrosion behaviour of aluminium alloy B206 in seawater Singh, Harshmeet 2016

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THE CORROSION BEHAVIOUR OF ALUMINIUM ALLOY B206 IN SEAWATER  by  Harshmeet Singh  B.Tech., PEC University of Technology, 2013  A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF  MASTER OF APPLIED SCIENCES in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Materials Engineering)  THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver)  January, 2016  © Harshmeet Singh, 2016 ii  Abstract  Aluminium alloy B206 is one of the strongest and toughest alloys in the cast aluminium family. Although it is light and has excellent low cycle fatigue strength, AA B206 has been known to perform adversely due to its poor corrosion resistance. Thus corrosion has been identified as one of the major issues that jeopardizes the long-term use and performance of B206.  The corrosion behaviour of B206 in seawater is studied through immersion testing and electrochemical techniques such as Potentiodynmaic Polarization, Potentiostatic Polarization, Cyclic Potentiodynmic Polarization and Linear Sweep Thermmametry in two different solutions, namely natural seawater and simulated seawater, at various temperatures. Techniques like Optical Microscopy, Energy Dispersive X-ray Spectroscopy and Scanning Electron Microscopy have been used to investigate the microstructure and surface morphology before and after the electrochemical tests. Heat treatment has been performed on the as-received samples using RRA and T7 heat treatment techniques to compare the corrosion behaviour of the former with the latter using electrochemical techniques and image analysis. Lastly, hardness tests have been performed on various heat treated and as-cast samples to establish a comparison in mechanical properties.  This study shows that the extent of B206 corrosion depends on the oxidizing nature of the seawater environment i.e. low or high redox potential rather than on the temperature of the seawater. Natural seawater is more aggressive than simulated seawater. Also, heat treatment improved the corrosion resistance as compared to as-cast B206 which was determined by the iii  values of corrosion current density and surface analysis. Furthermore, heat treatment has led to better mechanical properties as determined by hardness tests.                     iv  Preface  I was responsible for designing the experimental program presented in this thesis, conducting all immersion tests, electrochemical tests and surface characterization, and analyzing the results. Professor Edouard Asselin extensively helped with all the aspects of the research work.                 v  Table of Contents  Abstract .......................................................................................................................................... ii Preface ........................................................................................................................................... iv Table of Contents .......................................................................................................................... v List of Tables ................................................................................................................................. x List of Figures .............................................................................................................................. xii List of Symbols ............................................................................................................................ xv List of Abbreviations ................................................................................................................. xvi Acknowledgements ................................................................................................................... xvii 1. Introduction ............................................................................................................................... 1 1.1 Through-Process Modelling ................................................................................................................ 1 1.2 Issues surrounding Through-Process Modelling of aluminium alloy ................................................. 2 1.3 Development of AA B206 .................................................................................................................. 3 2. Literature review ...................................................................................................................... 4 2.1 Corrosion............................................................................................................................................. 4 2.2 Aluminium corrosion .......................................................................................................................... 5 2.2.1 Pitting corrosion of Al .................................................................................................................. 6 2.2.1.1 Metastable pitting ...................................................................................................................... 7 2.2.2 Intergranular corrosion of Al ....................................................................................................... 7 vi  2.2.3 Effect of alloying elements on Al corrosion ................................................................................ 8 2.2.4 Effect of heat treatment ................................................................................................................ 9 2.2.5 Effect of intermetallics ............................................................................................................... 10 2.3 Aluminium and Al alloy corrosion in seawater ................................................................................ 10 2.3.1 Eh-pH diagram of aluminium .................................................................................................... 11 2.3.2 Electrochemistry of aluminium corrosion .................................................................................. 13 2.3.3 Effect of chlorides in seawater ................................................................................................... 14 2.3.4 Galvanic corrosion in seawater .................................................................................................. 15 2.3.5 Effect of pitting in seawater ....................................................................................................... 16 2.3.6 Other forms of Al corrosion in seawater .................................................................................... 17 2.3.7 Effect of dissolved oxygen ......................................................................................................... 18 2.3.8 Effect of temperature and pH in seawater .................................................................................. 19 2.3.9 Effect of velocity of solution ..................................................................................................... 20 2.4 Aluminium alloy B206 ..................................................................................................................... 20 2.4.1 Properties of AA B206 ............................................................................................................... 21 2.4.2 Composition of AA B206 .......................................................................................................... 21 2.4.3 Corrosion of AA B206 ............................................................................................................... 22 2.4.4 Heat treatment of AA B206 ....................................................................................................... 23 2.4.4.1 Mechanism of B206 heat treatment ........................................................................................ 24 2.4.4.2 T7 heat treatment .................................................................................................................... 25 vii  2.4.4.3 Retrogression and Re-ageing heat treatment ........................................................................... 25 3. Objectives................................................................................................................................. 27 4. Approach and methodology ................................................................................................... 28 4.1 Materials selection ............................................................................................................................ 28 4.1.1 As-cast AA B206 ....................................................................................................................... 28 4.2 Heat treatment ................................................................................................................................... 29 4.2.1 Solution treatment ...................................................................................................................... 29 4.2.2 Artificial ageing ......................................................................................................................... 31 4.3 Solution preparation .......................................................................................................................... 33 4.3.1 Simulated seawater .................................................................................................................... 33 4.3.2 Natural seawater ......................................................................................................................... 34 4.4 Corrosion and electrochemical testing .............................................................................................. 34 4.4.1 Open Circuit Potential ................................................................................................................ 35 4.4.2 Potentiodynamic Polarization .................................................................................................... 35 4.4.3 Potentiostatic Polarization .......................................................................................................... 36 4.4.4 Cyclic Potentiodynamic Polarization ......................................................................................... 36 4.4.5 Linear Sweep Thermammetry .................................................................................................... 36 4.4.6 Immersion test ............................................................................................................................ 37 4.5 Equipment ......................................................................................................................................... 38 4.6 Surface characterization .................................................................................................................... 39 viii  4.6.1 Optical Microscopy .................................................................................................................... 39 4.6.2 Scanning Electron Microscopy .................................................................................................. 39 4.6.3 Energy Dispersive X-Ray Spectroscopy .................................................................................... 40 4.7 Micro-hardness testing ...................................................................................................................... 40 5. Results and discussion ............................................................................................................ 41 5.1 AA B206 microstructure ................................................................................................................... 41 5.2 Effect of chloride .............................................................................................................................. 43 5.3 Effect of solution environment ......................................................................................................... 44 5.3.1 Compressed air (aerated) sparged .............................................................................................. 47 5.3.2 Nitrogen (de-aerated) sparged .................................................................................................... 48 5.3.3 Oxygen sparged ......................................................................................................................... 50 5.4 Effect of temperature on pitting corrosion ........................................................................................ 52 5.5 Effect of heat treatment ..................................................................................................................... 55 5.5.1 Retrogression and Re-ageing heat treatment.............................................................................. 57 5.5.2 T7 heat treatment ....................................................................................................................... 67 5.5.3 Low temperature ageing treatment ............................................................................................ 72 5.6 Summary ........................................................................................................................................... 77 6. Conclusions .............................................................................................................................. 79 7. Future work ............................................................................................................................. 80 References .................................................................................................................................... 81 ix  Appendix ...................................................................................................................................... 92                  x  List of Tables  Table 2-1: Various heat treatment processes used for aluminium based alloys ........................... 24 Table 4-1: Different heat treated samples represented with their ageing temperature and time .. 32 Table 4-2: Stock 1 and stock 2 solutions for preparing the simulated seawater ........................... 33 Table 4-3: Composition of natural seawater as detected using ICP-AES .................................... 34 Table 5-1: Value of corrosion potential and breakdown potential obtained at different temperatures using CPP ................................................................................................................ 54 Table 5-2: Corrosion rate determination for RRA 220 samples using immersion testing in natural seawater......................................................................................................................................... 65 Table A-1: Hardness comparison of as-cast and RRA heat treated samples using Vickers micro-hardness tester ............................................................................................................................... 92 Table A-2: Hardness comparison of as-cast, T7 and low temperature aged heat treated samples using Vickers micro-hardness tester ............................................................................................. 93 Table A-3: Ecorr and icorr values for as-cast B206 in solution with different NaCl concentration . 93 Table A-4: Ecorr and icorr values for RRA 220 at different temperatures in aerated simulated seawater......................................................................................................................................... 94 Table A-5: Ecorr and icorr values for RRA 210 at different temperatures in aerated simulated seawater......................................................................................................................................... 94 Table A-6: Ecorr and icorr values for RRA 200 at different temperatures in aerated simulated seawater......................................................................................................................................... 94 Table A-7: Ecorr and icorr comparison between as-cast B206 and various RRA heat treated B206 samples at 15°C in aerated simulated seawater ............................................................................ 95 xi  Table A-8: Ecorr and icorr values for T7 sample at different temperatures in aerated simulated seawater......................................................................................................................................... 95 Table A-9: Ecorr and icorr comparison of as-cast, T7 and RRA heat treated samples at 15°C in aerated simulated seawater ........................................................................................................... 95 Table A-10:: Ecorr and icorr comparison of as-cast, T7 and RRA heat treated samples at 15°C in aerated natural seawater ................................................................................................................ 96 Table A-11: Ecorr and icorr values of low temperature ageing samples aged for 20 h at different temperatures in aerated natural seawater ...................................................................................... 96 Table A-12: Ecorr and icorr values of low temperature ageing samples aged for 40 h at different temperatures in aerated natural seawater ...................................................................................... 96 Table A-13: Ecorr and icorr comparison of as-cast, T7 and low temperature aged samples at 15°C in aerated natural seawater ............................................................................................................ 97          xii  List of Figures  Figure 2-1: Basic corrosion cell ...................................................................................................... 4 Figure 2-2: Eh-pH diagram for aluminium-water system at 25°C [76] ........................................ 12 Figure 2-3: The dissolution mechanism of aluminium precipitating Al(OH)3 [77] ..................... 13 Figure 2-4: Galvanic corrosion of aluminium in seawater [77] .................................................... 16 Figure 2-5: Mechanism of pitting corrosion in seawater environment in the presence of second phase intermetallic particles [77] .................................................................................................. 17 Figure 2-6: Concentration of dissolved oxygen, salinity, temperature and pH as a function of depth [94] ...................................................................................................................................... 19 Figure 4-1: Circular samples extracted from as-received AA B206 ingot ................................... 28 Figure 4-2: 2-step solution treatment schedule ............................................................................. 30 Figure 4-3: 3-step solution treatment schedule ............................................................................. 31 Figure 4-4: Immersion test setup containing natural seawater solution ....................................... 38 Figure 5-1: AA B206 microstructure at 100X as observed under OM ......................................... 42 Figure 5-2: AA B206 grain at 500X as observed under SEM ...................................................... 42 Figure 5-3: PDP curves for as-cast B206 in solution with different NaCl concentration............. 43 Figure 5-4: PDP curves for as-cast B206 in different gas purged seawater environment ............ 44 Figure 5-5: SEM images of as-cast B206 after PDP test in (a) aerated, (b) de-aerated and (c) oxygen purged environment, in seawater ..................................................................................... 46 Figure 5-6: PSP curves for B206 in aerated seawater for a duration of 6 hrs. .............................. 47 Figure 5-7: SEM image at 500x of as-cast B206 after 6 hours of PSP at -0.465 V in aerated seawater......................................................................................................................................... 48 xiii  Figure 5-8: PSP curves for B206 in de-aerated seawater for a duration of 6 hrs. ........................ 49 Figure 5-9: SEM image of as-cast B206 after 6 hours of PSP (a) -1.009 V in de-aerated seawater at 500x, (b) intergranular corrosion at 700x ................................................................................. 50 Figure 5-10: PSP curves for B206 in oxygen purged seawater for a duration of 6 hrs. ............... 51 Figure 5-11: SEM image at 500x of as-cast B206 after 6 hours of potentiostatic polarization at -0.495 V in oxygen purged seawater .............................................................................................. 52 Figure 5-12: CPP curves for as-cast B206 at different temperatures in aerated simulated seawater....................................................................................................................................................... 53 Figure 5-13: Thermammogram for B206 in aerated seawater at a potential of -0.450 V ............. 55 Figure 5-14: Equilibrium phase diagram of Al-Cu system [147] ................................................. 56 Figure 5-15: OM images of etched RRA heat treated B206 samples aged at (a) 220C at 200x, (b) 220C at 100x, (c) 200C at 200x, and (d) 210C at 100x ................................................................ 58 Figure 5-16: EDX of as-cast B206 precipitates at, (a) Al matrix, (b) grain boundary ................. 59 Figure 5-17: EDX of RRA 220 B206 precipitates, (a) at grain boundary, (b) spherical precipitate in matrix ........................................................................................................................................ 60 Figure 5-18: PDP curves of RRA 220 at different temperatures in aerated simulated seawater .. 62 Figure 5-19: PDP curves of (a) RRA 200, (b) RRA 210 at different temperatures in aerated seawater solution ........................................................................................................................... 63 Figure 5-20: PDP comparison between as-cast and various RRA heat treated samples at 15°C in aerated seawater ............................................................................................................................ 64 Figure 5-21: Front and side view of RRA 200 sample after 90 day immersion test .................... 66 Figure 5-22: Hardness comparison of as-cast and RRA heat treated samples with respect to position from one end of diameter to other ................................................................................... 67 xiv  Figure 5-23: OM images of etched T7 heat treated sample aged at 199°C at (a) 100x, (b) 200x 68 Figure 5-24: PDP curves of T7 samples at different temperatures in aerated simulated seawater69 Figure 5-25: PDP comparison of as-cast, T7 and RRA 220 heat treated samples at (a) 15°C in aerated simulated seawater, (b) 15°C in aerated natural seawater ................................................ 70 Figure 5-26: Surface morphology of samples (a) T7, (b) RRA 220 and (c) as-cast, after PDP tests at 15°C in natural seawater ........................................................................................................... 72 Figure 5-27: OM images of etched low temperature aged samples aged at 155C° for (a) 20 h, (b) 40 h, at 200x .................................................................................................................................. 73 Figure 5-28: PDP curves of low temperature aged samples (a) 20 h, (b) 40 h, at different temperatures in natural seawater ................................................................................................... 74 Figure 5-29: PDP comparison of as-cast, T7 and low temperature aged samples at 15°C in natural seawater ............................................................................................................................ 75 Figure 5-30: Graphical representation of hardness comparison of as-cast, T7 and low temperature aged heat treated samples with respect to position from one end of diameter to other ................ 76          xv  List of Symbols  A  Area (in cm2) βa    Anodic Tafel Slope (V/dec) βc  Cathodic Tafel Slope (V/dec) D  Density (in gm/cm3) E   Measured Potential (V) Ebd  Breakdown Potential Ecorr  Corrosion Potential Erp  Re-passivation Potential i  Current density (in µA/cm2) icorr  Corrosion Current Density (in A/cm2) M  Molar Concentration N  Normality T  Time W  Weight loss (in mg)         xvi  List of Abbreviations  AA  Artificial Ageing ASTM  American Society for Testing and Materials CPP  Cyclic Potentiodynamic Polarization DI  Deionized EDX  Energy Dispersive X-ray Spectroscopy HVN  Hardness Vickers Number IGC  Intergranular Corrosion OCP  Open Circuit Potential OM  Optical Microscopy PDP  Potentiodynamic Polarization PSP  Potentiostatic Polarization RRA  Retrogression and Re-ageing SCC  Stress Corrosion Cracking  SEM  Scanning Electron Microscopy SHE  Saturated Hydrogen Electrode TPM  Through Process Modelling       xvii  Acknowledgements  I would like to express my sincere gratitude to my supervisor, Professor Edouard Asselin, for giving me an opportunity to work in the field of my interest, i.e. Corrosion Engineering, and also for guiding and challenging me to improve my research, presentation and instructional skills. I will take this invaluable experience and learning with me.  Also, I would like to acknowledge the financial support provided by the University of British Columbia (UBC), CanmetMATERIALS (CMAT), Defence Research and Development Canada (DRDC), ENSMA, CAF and Marine Renewable-Energy Consortium (MREC). Special thanks to Prof. Maijer and Prof. Phillion for providing the questions and tools to apply my knowledge in corrosion research.   I owe thanks to my fellow students of Hydrometallurgy and Corrosion group for their continuous help and insight during my research. In particular, I offer my enduring gratitude to S. Pournazari, whose answers always helped me to improve my work.  I also want to thank the staff of the Materials Engineering Department for their support during my work: Fiona Webster, Michelle Tierney, Mary Jansepar, Norma Donald, Glenn Smith, Ross Mcleod, Wonsang Kim and Jacob Kabel.  Finally, I want to express my recognition to my parents who have supported me in countless ways throughout my life and always encouraged and supported me in my years of education. 1  1. Introduction  1.1 Through-Process Modelling  Through-Process Modelling (TPM) is a recently developed materials engineering design approach to enhance component performance by taking the complete manufacturing process into consideration [1-3]. One important area requiring the application of innovative research methodologies is Canada’s aluminium alloy foundry industry, which has been suffering since the economic downturn of 2008. The aluminium alloy foundry industry has excellent potential to exploit the TPM approach since the typical manufacturing process consists of a series of processing stages where the microstructure and defects resulting from one stage will greatly affect the next.   This thesis is part of a broader initiative aimed at developing TPM.  The target application identified through this initiative is a critical component in tidal-based, hydrokinetic energy generation systems – the hub that transfers the load from the turbine’s blades to the shaft of the generator. This application was selected in part because of the significant potential for tidal energy generation in Canada (~42 000 MW, 63% of current electricity demand [4]), and in part because a recent US National Academy of Sciences study recommended that the TPM approach be pursued as a means to facilitate cost-effective clean energy generation [1].    2  1.2 Issues surrounding Through-Process Modelling of aluminium alloy   Aluminium alloys have seen extensive use in shape casting applications because of their high strength to weight ratio, good durability and low production costs. Shape casting is most often used for making complex shapes that would be difficult or uneconomical to make by other methods.   Using the TPM approach, it would be possible to predict a component’s fatigue life since the microstructural state is completely described as a function of each manufacturing stage. The component, which is part of a tidal-based energy generating system, will be susceptible to corrosion due to the aggressive seawater environment once it will be placed in service. Cast aluminium alloys have seen extensive service in marine applications due to their good corrosion resistance, which is generally seen to be less than 0.5μm per year, and good resistance to stress corrosion cracking [5]. However, as the corrosion resistance is due to the stability of the aluminium oxide film, any process affecting the stability of the film, such as pitting, can result in high rates of corrosion [6]. Pitting behaviour is collectively due to environmental conditions, and the state of the microstructure (grain size, defect distribution, etc.) [7]. Reasonably high rates of pit penetration have been observed on some aluminium alloys immersed in seawater as well as with decreased seawater temperature [8]. Furthermore, corrosion may influence fatigue life through corrosion fatigue, as fatigue strengths as low as 20% of those observed in air have been found for some aluminium alloys in a 3% NaCl solution [5]. Thus, for aluminium alloy castings utilized in marine applications, good corrosion data is required to predict the corrosion response and its influence on fatigue behaviour, and therefore further research is needed.  3  1.2 Development of AA B206  New casting alloys, such as A206 (Al-4.6wt%Cu- 0.35wt%Mg-0.25wt%Mg-0.2wt%Ti) developed for specialty aerospace applications, offer enhanced strength but casting defects including the formation of hot tears and embrittling secondary phases currently limit this alloy’s application to components of simplified geometry [9]. Recently, Sigworth [10,11] has shown that a modified composition of A206, referred to as B206, can be successfully shape cast with careful control of the cooling conditions. Further research must be conducted in order to fully characterize this alloy’s susceptibility to defect formation under various casting conditions especially as it relates to fatigue performance and corrosion response. The application of TPM to B206 will provide the knowledge and experience necessary for the Canadian foundry industry to fabricate new components from this high-strength aluminium foundry alloy.  This research aims to determine the corrosion behaviour of as-cast B206 in seawater at different solution temperatures and further to heat treat the as-cast alloy with various heat treatment techniques while investigating and comparing the corrosion effect of latter with the as-cast B206 alloy. Seawater was chosen as the medium to study the corrosion behaviour of B206 because one potential use for this alloy is for cast components in hydrokinetic tidal energy generation.        4  2. Literature review  2.1 Corrosion  Corrosion is the degradation of a material due to its interaction with the environment. Corrosion can take place on any possible material, be it metals, ceramics, polymers or composites. For corrosion to take place, except in polymers, mainly four fundamental elements are required which complete the corrosion cell. These fundamental elements are (i) an anode, (ii) a cathode, (iii) an electronic path, and (iv) an ionic path as shown in Figure 2-1.   Figure 2-1: Basic corrosion cell  If any of the fundamental elements are removed from the picture, a corrosion cell will not form and thus no corrosion will take place. The fundamental elements may not need to be a separate entity. In some cases, an anode and a cathode can coexist on a single electrode, as is in the case of a grain and a grain boundary in a two-phase microstructure. The ionic path in a corrosion cell is provided by the medium in which the anode and cathode are placed while the electronic path is 5  generally provided by the electrodes. The anode is the area where the metal is dissolved and subsequent ions are produced while the cathode is the area where these ions or species in the solution are reduced and deposited on the surface. Thermodynamics and electrochemistry are the most important factors to understand corrosion and its related phenomena. Thermodynamics deal with the spontaneity or possibility of a corrosion reaction while electrochemistry provides the tools to study the kinetics of the reaction.   2.2 Aluminium corrosion   The study of aluminium and its alloys is a vast field of research because of their use in a wide range of applications including marine, aerospace, industrial and household environments. This is because they have excellent mechanical characteristics such as good machinability, weldability, high fatigue strength and good corrosion resistance in seawater [12,13]. The corrosion resistance of these alloys is attributed to the fact that they naturally develop an oxide film on their surface under normal atmospheric conditions [14-19]. The oxide film is generally non-uniform, thin and non-coherent in nature. The metal is prone to all kinds of corrosion phenomena once the layer breaks. Pitting corrosion is the main corrosion phenomenon that occurs due to breakage of the oxide layer. The corrosion process occurs under very specific conditions and is characterized by low temperature, high oxygen content in the solution, high halide ion concentration, presence of CO2 and H2S, microorganisms and the presence of dissolved salts [20-23]. Uniform corrosion is not usually a problem in marine environments but pitting can be. Therefore, corrosion protection studies of these alloys are important for marine applications.  6  2.2.1 Pitting corrosion of Al  It is widely accepted that the resistance of metals to pitting is determined by the physical, electrical and mechanical properties of the passive film. Due to their excellent passivity with a highly uniform corrosion resistance in seawater, pitting is the primary concern for Al alloys in seawater environment. Pitting can be divided into three phases, i.e. pit initiation, pit development and passivation. Several views have been advanced to explain the film breakdown and pitting initiation through: (a) attack at weak spots or impurity centres in the oxide film [24], (b) local dissolution of the film [25], (c) electric field-stimulated anion penetration or cation egress [26,27], (d) a field-independent anion exchange reaction permitting Cl- penetration of the surface oxide film [28] or through dissolution of the free aluminium surface exposed at the base of the film flaws [29,30]. The corrosion dissolution of aluminium preferentially takes place along [100] crystal plane [31] while it undergoes pitting corrosion in solutions containing Cl- or F- ions [32-34]. This is found to be particularly severe in the presence of oxidizing cations like Cu2+ [35,36]. Pitting corrosion is accelerated in view of the galvanic coupling between aluminium and copper where the cupric ion reduction to copper offers cathodic areas of lower overpotential. The standard electromotive force potentials [37] of Al+3/Al and Cu+2/Cu are −1.662 and +0.342V, respectively. The significant difference between the Cu-rich segregated phase and the aluminium matrix greatly facilitates galvanic coupling in a corrosive environment.   7  2.2.1.1 Metastable pitting  Aluminium alloys exposed to a chloride environment produce both stable and metastable pits and it is believed that they follow the same basic mechanism i.e. initiation, growth and repassivation [38,39].  The vast majority of pits only grow for a small duration of time and to a very small depth. These pits are known as metastable pits. These pits, unlike the stable pits, are not responsible for the corrosion damage but stable pits are known to result from metastable pits and thus they are important to study. Thus the study of metastable pits is a key factor in determining the susceptibility of aluminium alloys towards pitting. Frankel [40] concluded in his paper on the critical factors of pitting that the study of metastable pitting has provided unique opportunities for understanding pitting corrosion; it is easier to address the stochastics of pitting using large numbers of metastable pits than by generating fewer stable pits. He concluded that the repassivation of metastable pits provides information on the stability criteria for pit growth. The metastable pit size may determine if the transition from a metastable to stable pit occurs [41]. Metastable pits unlike stable pits only grow to a very small size (approximately 10 µm in diameter) at which stage their growth is arrested [42]. The only possible reason for these pits to cease growing in light of the reactivity of the metal is that the protective oxide coating is regenerated on the pit’s surface.  2.2.2 Intergranular corrosion of Al  Among different forms of corrosion phenomena observed, IGC is another phenomenon in aluminium and its alloys in various environments. Intergranular corrosion can lead to potential sites for cracks resulting in the failure of aluminium alloys due to stress corrosion cracking or 8  fatigue. Intergranular corrosion, like pitting, initiates with breakdown of the oxide layer on the aluminium surface but is restricted only to the grain boundaries. In aluminium alloys chloride ions have been reported to be necessary for IGC [43]. But the growth of IGC solely depends on the pitting potential [44]. During pitting, as the pits grow, they can develop into IGC that can penetrate deep into microstructure [45,46]. Adding elements like Cu, Si, Zn etc. to aluminium for strengthening purposes increases its mechanical properties but also reduces the corrosion resistance due to accumulation of these elements at the grain boundaries, causing intergranular corrosion after ageing. In Al-Cu series alloys, due to precipitation of copper in the form of CuAl2 at the grain boundaries, intergranular corrosion is often observed.   2.2.3 Effect of alloying elements on Al corrosion   In general, Al alloys are spontaneously passive and anodic polarization leads to pitting corrosion. Anodic polarization, that is when the initial anode potential becomes more positive due to current flow, causes disruption of polarization in Al alloys by forming anodic sites and results in accelerated local corrosion. Alloying elements have shown a major effect on the electrochemical behaviour of aluminium-based alloys. Alloying can prevent the development of the oxide layer by introducing localized galvanic cells. The addition of Mg, Cu, Fe, and Si increases in the galvanic potential of aluminium alloys as compared to pure Al. This results in the formation of galvanic couples between the alloying elements and the aluminium matrix. It is also observed that the addition of Mg, Cu, Fe, Si increases the density of particle distribution [47]. Thus, the addition of alloying components to aluminium produces in all cases, a considerable activation of the resulting alloy. The activation is manifested by a negative shift of the open circuit potential, the pitting potential and significant reduction of the passive region. Polarization measurements 9  showed that the activation of Al alloys could be interpreted on the basis of an autocatalytic attack model. [48] In the autocatalytic attack model, once pitting is initiated, the corrosion products promote further reactions.  2.2.4 Effect of heat treatment  Wider use of aluminium alloys has been restricted by problems on the design and maintenance side and the tendency of these alloys to pit under long-term use [49]. Nevertheless, heat treatable aluminium alloys are used in seawater applications and are susceptible to localized corrosion in chloride environments such as pitting, crevice corrosion, intergranular corrosion, corrosion fatigue and stress corrosion cracking. Variations in thermal treatments are known to affect the corrosion resistance of aluminium alloys because of the changes brought about in microstructure [50,51]. The composition, quantity, and distribution of phases and their corrosion potential relative to the solid solution matrix is reported to have an important bearing on the corrosion resistance of aluminium alloys [52]. The heat-treated specimens have a lower current density at cathodic polarization than the non-heat treated specimens. This is because the heat treatment cathodically polarizes the cathode and the corrosion current density is reduced to diminish corrosion. The polarization trends, in all specimens, reveal the effects of concentration polarization due to oxygen reduction or activation polarization due to hydrogen generation [53-58]. Therefore, heat treatment improves the corrosion properties because it lowers the corrosion current density. Heat treatment of aluminium alloys is necessary to obtain desired mechanical properties. It is seen that the non-heat-treated specimens have lower hardness values than all of the heat-treated specimens. In general, heat treatment results in precipitation strengthening of the 10  Al alloys [59] except when over-ageing of the specimen occurs. Over-ageing is exposure of the alloy to longer times at temperature, which may lead to loss of strength.  2.2.5 Effect of intermetallics   Intermetallic compounds in Al alloys, which are either intentionally developed to obtain the desired mechanical properties or are present as natural impurities, introduce second phases in the bulk material and therefore play an important role in corrosion behaviour of Al alloys. Since Al alloys of various series contain specific alloying elements, it is expected that different intermetallic second phase particles will be formed to influence the Al alloy corrosion through distinct mechanisms [49-52, 60–62]. The second phases enriching in Cu, Si and Fe have been studied due to their negative effects on the corrosion resistance of Al alloy substrate [63-67]. In the case of Al alloys in near-neutral bulk solutions, it is well established that pitting is influenced by intermetallic particles that exhibit different surface film characteristics from those of the matrix, and may be either anodic or cathodic relative to the matrix [63, 68-74].  2.3 Aluminium and Al alloy corrosion in seawater  Use of aluminium and its alloys in seawater has been an area of scientific study for several decades. These alloys are used in marine applications because they have low density, excellent mechanical properties and good uniform corrosion resistance. Corrosion resistance in Al alloys is due to the formation of the oxide film that naturally develops under atmospheric conditions. It is more advantageous to use than carbon steel, as it has far better corrosion resistance than the latter. The structural characteristics of the film formed on the aluminium surface, and the 11  intensity of corrosion attack are influenced by (a) the chemical composition of the exposed alloy, (b) the presence and distribution of micro-defects (vacancies, voids, etc.) as well as macro-defects (inclusion, second phase particles—their size and shape) and (c) by electrolyte composition (e.g. pH, halide concentration, temperature, fluid velocity) [75]. Although the corrosion rate of pure aluminium in chloride media is very low, aluminium alloys suffer from a susceptibility to pitting attack. The pitting corrosion of aluminium depends on its purity.   2.3.1 Eh-pH diagram of aluminium  The potential pH diagram for the aluminium-water system does not take into account the possibility of pitting corrosion which is the most common form of corrosion of aluminium and its alloys in chloride containing environments. The general corrosion resistance of aluminium can be determined using a potential-pH diagram in which thermodynamic metal-water reaction are represented as shown in Figure 2-2. The diagram essentially shows the thermodynamic regions where the metal is prone to corrosion attack, passivity areas where the formation of an oxide layer is possible, and immunity areas where the metal is thermodynamically stable. For aluminium-copper alloys, pitting corrosion is most common form of corrosion in chloride medium and occurs in the passive area, and thus can’t be predicted using potential-pH diagram. Some of the major reactions involved and relevant to aluminium corrosion in seawater are shown below in Eq. (1-4).                                           3e- + Al3+ = Al (1)  Pure aluminium in seawater lies in the region marked as “immune” on the Eh-pH diagram and  isn’t affected by the vigorous seawater environment below the potential of -1.8 V and pH of 4. 12                                           6e- + Al2O3.H2O +6H+ = 2Al + 4H2O (2)                                          Al2O3.H2O + 6H+ = 2Al3+ + 4H2O (3)  Oxidation of aluminium forms species like AlO2- and Al3+ which lie in the region marked as “corrosion” of the diagram. This shows that these species are result of various corrosion phenomena occurring on aluminium surface in seawater. The formation of AlO2- occurs at a pH above 9 while the formation of Al3+ occurs below a pH of 4.                                           Al2O3.H2O = 2AlO2-+ 2H+ (4)  Unfortunately, Eh-pH diagrams do not have much use in predicting the corrosion of Al and its alloys, which is often due to localized corrosion phenomena.  Figure 2-2: Eh-pH diagram for aluminium-water system at 25°C [76] Corrosion Immune Corrosion Passive 13  2.3.2 Electrochemistry of aluminium corrosion  Aluminium corrosion is an electrochemical process that involves the transfer of electrons. The electrons are transferred from the anode, where aluminium dissolution takes place, to the cathode as shown in Figure 2-3 [77].  Figure 2-3: The dissolution mechanism of aluminium precipitating Al(OH)3 [77]  The reaction for anodic dissolution is shown in Eq. (5) below.  Al = Al3+ + 3e-                                                         (5)  The other half is the cathodic reaction, which consumes the electrons generated due to anodic dissolution. If the oxygen is present in the solution, the cathodic reaction is represented as in Eq. (6). O2 + 2H2O + 4e- = 4OH-                                          (6) 14  This reaction causes an increase in pH due to production of hydroxyl ions. It is known that the reduction of oxygen is rapid when it occurs on copper or iron precipitates and that is why single phase aluminium has better corrosion resistance than aluminium alloys containing second phase particles. In de-aerated solutions, where oxygen is absent, the dominant cathodic reaction is the reduction of hydrogen as shown in Eq. (7).  2H+ + 2e- = H2                                                           (7)  The hydrogen evolution reaction also increases the pH. Once the dissolution takes place, the ionic products react to form gelatinous aluminium hydroxide as shown in Eq. (8) and (9).  Al3+ + 3OH- = Al(OH)3                                                                     (8) Al3+ + 3H2O = Al(OH)3 + 3H+                                                     (9)  This is found on the surface of aluminium as a powder once dried. Thus the precipitation of aluminium hydroxide leads to acidification of the solution.  2.3.3 Effect of chlorides in seawater  Chlorides dissolved in water can lead to severe corrosion of aluminium. The chlorides increase the conductivity of the solution and thus help in dissolution of aluminium and its alloys. The chlorides, being smaller than hydroxyl ions migrate faster and combine with aluminium ions in the solution making the solution chemistry acidic. The positively charged pits attract the negative chloride ions, which increase the local acidity of the electrolyte. The formation of hydrochloric acid due to chloride migration leads to instability of the oxide film that causes the underlying 15  aluminium to be exposed to the harsh acidic environment. The formation of hydrochloric acid is shown in Eq. (10).                                    H+ + Cl- = HCl (10)  Thus the pitting corrosion initiates due to exposure of aluminium surface to the acidic environment. The aluminium combines with the chlorides in the pits to form aluminium chloride as shown in Eq. (11).  Al3+ + 3Cl- = AlCl3                                                                         (11)  The chloride clusters form about the aluminium cations and these can diffuse a short distance and then react with hydroxyl ions or water and precipitate out as aluminium hydroxide as shown in Eq. (12) [78].  AlCl3 + 3OH- = Al(OH)3 + 3Cl-                                                    (12)  Therefore, these chloride ions are released and they return to the pits to continue the dissolution of the aluminium.   2.3.4 Galvanic corrosion in seawater  Galvanic corrosion is another corrosion phenomenon to which aluminium and its alloys are subjected in seawater environments. In aluminium alloys, due to dissimilar corrosion potentials of the alloying elements within the aluminium matrix, galvanic couples are formed leading to severe anodic dissolution. In the 2000 series of aluminium alloys, which contain more than 1 16  wt% copper, the copper precipitates (CuAl2) can act as cathodic sites and thus can reduce the corrosion resistance of the alloys. Even impurities in the form of Fe, Si and Mg can combine forming intermetallic precipitates and can act as a cathode to the aluminium matrix and, therefore, cause matrix dissolution in seawater as shown in Figure 2-3 [77].  Figure 2-4: Galvanic corrosion of aluminium in seawater [77]   2.3.5 Effect of pitting in seawater  It is well established that pit growth occurs in seawater only when acidic conditions are established within pits. Pitting is initiated at the sensitive points of the film where the Cl- diffusion is easier as at the lattice defects or at regions of lower thickness. Chloride accumulation within pits accelerates anodic dissolution of aluminium. The increase in the pitting susceptibility in seawater at pH = 8.2 resulted from the stimulation of anodic aluminium dissolution and was correlated with the adsorption of depolarizing ions (C1- and SO42-) [79]. The strong anion adsorption occurring at the sensitive sites of the protective film together with the specific adsorption of the hydrogen ions from the acid medium, which enhance the movement of electrons through the defects in oxide lattice [80], would cause the initiated pitting corrosion. 2H+ 17  This would propagate rapidly so as to develop partial or total undermining of the film and the spreading of attack over the entire aluminium surface. The surface of aluminium, together with solution acidity, sustains the propagation of dissolution and thus enables severe pitting corrosion as shown in Figure 2-5. Formation of metastable complexes like AlCl4- takes place within the pits next to the metal surface.   Figure 2-5: Mechanism of pitting corrosion in seawater environment in the presence of second phase intermetallic particles [77]  2.3.6 Other forms of Al corrosion in seawater  Aluminium alloys are often exposed to seawater and thus other corrosion phenomena like corrosion fatigue and erosion corrosion may occur. The corrosive ions, like halides in seawater, penetrate into the defect in oxide film as the passive state is destroyed in the corrosion process [81, 82]. Corrosion fatigue may be defined as the combined action of an aggressive seawater environment and a cyclic stress leading to premature failure of metals by cracking [83, 84]. There are many factors influencing the corrosion fatigue behaviours of metallic materials such as seawater composition, pH, and temperature and load frequency [85]. In general, the resistance of aluminium and its alloys to corrosion fatigue is associated more with its inherent corrosion Oxide  18  resistance than with high mechanical strength. Numerous investigations have shown that corrosion fatigue cracks start from corrosion pits [86-88]. The corrosion pits that appear to be associated with precipitates in the aluminium matrix act as preferential fatigue crack initiation sites. This reduces the time required for fatigue crack initiation and decreases the total fatigue life. Examination of the fracture surface suggests that the fatigue life reduction can be attributed to rapid fatigue crack initiation from corrosion pits. These pits act as stress raisers and seem to be associated with precipitates within the aluminium matrix. [89] It is indicated that the reduction in fatigue resistance in corrosive environments results from pit formation and growth, and this is attributed to the high Cl- concentration and low pH value within the pits in seawater.  2.3.7 Effect of dissolved oxygen  Dissolved oxygen has been seen to increase the corrosion rate of aluminium and its alloys in seawater. The corrosion rate of aluminium alloy 6061 in seawater was three to four times greater in the presence of oxygen than in its absence [90]. Oxygen promotes cathodic reaction and causes a positive shift of the free-corrosion potential up to a pitting potential [91,92]. Furthermore, an excess of oxygen, when promoting passivation, shifts the potential in the same direction of the pitting initiation potential by acting as an oxidizer and thus counteracts it in adjacent areas. Dissolved oxygen promotes dissolution in working pits. Dissolved oxygen has a violent effect on Al-Cu alloys and is one of the main reasons for their pitting nature. Laboratory studies concerned with the behaviour of aluminium in seawater strongly indicate that elimination of dissolved oxygen from the electrolyte suppresses the corrosion of aluminium alloys 5052, 5454, 6061, and 6063 [93]. 19  2.3.8 Effect of temperature and pH in seawater  Generally, it is expected that a rise in temperature increases the corrosion of metals. However, rise in temperature of seawater decreases oxygen solubility due to decomposition of organic matter and increases biological activity, which may also increase corrosion rates. Despite these changes in conditions, it is observed that aluminium alloys behave similarly in warm and cold ocean waters. This is likely due to the fact that the pH of seawater is very stable and close to 8.2, which is within the domain of stability of the natural oxide film for aluminium and its alloys. Figure 2-6 shows the effect of temperature, pH and salinity in seawater as a function of depth.   Figure 2-6: Concentration of dissolved oxygen, salinity, temperature and pH as a function of depth [94]  20  2.3.9 Effect of velocity of solution  In seawater, the high velocity of flow is also a factor responsible for corrosion damage to aluminium alloys. Most investigators agree that the corrosion resistance of aluminium alloys derives from the formation of a protective duplex oxide film [95-103]. The duplex film is made up of a thin amorphous barrier layer, Al(OH)3, and a thicker hydrated outer layer. In seawater, the outer layer is probably composed of monohydrate orthorhombic crystalline boehmite, γ-Al2O3.H2O or tri-hydrate monoclinic bayerite, β-Al203.3H20. In a chloride environment such as seawater, the film may be locally disrupted by the formation of metastable complexes and pitting subsequently occurs. The high velocity of seawater erodes the oxide layer and exposes the surface for corrosion to take place.   2.4 Aluminium alloy B206  The 206 family of aluminium casting alloys includes some of the strongest, toughest aluminium foundry alloys in current use. Since the alloys also have excellent low cycle fatigue strength, they could potentially be used in a number of automotive applications. Aluminium alloy B206 is a binary Al-Cu cast alloy with copper content ranging from 4.5-5.1%. Mn, Mg, Si, Ti and Fe are also present in the alloy while the balance is aluminium. The Al-Cu casting alloys have excellent mechanical properties, high temperature strength and low cycle fatigue properties; but they are difficult to cast, primarily because of hot cracking [104]. Al-Cu B206 alloy offers high strength and excellent ductility which is significantly higher than for Al 356 and has values that approach some grades of ductile iron. Although high strength is achieved by the presence of Cu, this 21  element is particularly deleterious to the corrosion behaviour of Al alloys due to the galvanic couple formation [105].  2.4.1 Properties of AA B206  B206 exhibits mechanical properties superior to conventional Al-Si-Mg and Al-Si-Cu alloys [106]. The B206 alloy (up to 5wt% Cu) is one of the strongest foundry alloys in current use with elongations up to 25%, and having one-third of the density to iron. B206 can be used in a number of automotive applications, e.g. suspension arms or knuckles to reduce vehicle weight. The intermetallic phase Al2Cu is responsible for the precipitation hardening and precipitates either in a block-like form (coarse Al2Cu precipitates) directly from the liquid or in a eutectic-like form (Al+Al2Cu) as fine Al2Cu particles interspersed with Al [107]. Due to problems related to hot tearing, B206 exhibits relatively poor castability which increases the casting cost due to the requirement for casting process modifications.   2.4.2 Composition of AA B206  In the B206 microstructure, the net-shaped continuous Cu rich segregated phase appears at the inter-dendritic and grain boundaries of the α-phase matrix. The main eutectic reaction that takes place is the formation of the CuAl2 strengthening phase at 548°C. The composition of the precipitation phases other than CuAl2 (θˊ and Ω) is close to that of the eutectic phase but different in crystal structure. The tetragonal structure of the θˊ-phase with a = b = 0.404 nm and c = 0.580 nm, is the main strength-providing phase of binary Al–Cu alloys [108]. The thermally 22  stable Ω-phase, with a chemical composition similar to that of CuAl2, is present as a hexagonal plate-like precipitate on the matrix {1 1 1}α planes. It has a face-centered orthorhombic structure, with a = 0.496 nm, b = 0.859 nm and c = 0.848 nm [109–114]. Apart from CuAl2, a spherical shaped phase, also known as S-phase, is also present within the grains and contributes to the strengthening mechanism of B206.  2.4.3 Corrosion of AA B206  The intermetallic particles that exist in the microstructure significantly reduce the resistance to localized corrosion [115]. The corrosion behaviour of these intermetallic particles depends mainly upon their potential difference with respect to the matrix in the solution. Particles that are electrochemically nobler than the matrix, act as cathodes whereby the surrounding matrix undergoes anodic dissolution. This process could lead to localized corrosion [115]. Among the different forms of localized corrosion, pitting and intergranular corrosion are encountered most often in technologically important metallic materials like B206 that suffer severe degrees of various corrosion types in different environments [116, 117]. Pits and intergranular corrosion can be potential sites for initiation of cracks, which can result in catastrophic failure by stress corrosion cracking or corrosion fatigue. SEM analysis of intergranular corrosion of cast B206 revealed that even a small amount of un-dissolved Al2Cu particles contribute greatly to the attack on the grain boundaries. Larger intermetallic precipitates within the grains appear to lead to deeper pitting.   The resistance of as cast B206 to Stress Corrosion Cracking is very high. This is because of the fact that Al2Cu precipitates at the grain boundaries are cathodic to the matrix and thus are not 23  attacked. This is totally different from the Al2CuMg precipitates that are anodic to the Al matrix and are attacked preferentially. Heat treated B206 test samples exhibited a low level of micro chemical Cu homogeneity and irregular distribution of precipitates. Aging treatments that lead to grain boundary denuded zones and larger intermetallic precipitates along grain boundaries, suffered from intergranular attack. Larger intermetallic precipitates within the grain lead to deeper pitting [118]. Future aging treatments need to be designed which do not produce denuded zones but produce a homogeneous distribution of intermetallic precipitates that do not adversely affect either the ductility or the general corrosion resistance.   2.4.4 Heat treatment of AA B206  As with the 3xxx, 5xxx and 7xxx series of wrought aluminium alloys, 2xxx series alloys can also be heat treated to modify the microstructure for corrosion resistance and increase the mechanical properties. The same is true for the aluminium cast alloys. But heat treatments that produce the desired mechanical properties can cause the alloy to become susceptible to SCC or IGC. In the case of binary alloys containing low-melting point alloying elements of low solid solubility, like AA B206, heat treatment causes segregation of the alloying element to the surface. The transport of the alloying element is presumably firstly by segregation along grain boundaries and secondly by diffusion along the grain boundaries to the surface [119-121]. The purpose of heat treating the B206 is to segregate the copper from the grain boundaries to the grains so as to prevent the galvanic coupling which can lead to dissolution of aluminium and to prevent the chances of IGC at the grain boundaries. Heat treatment of B206 leads to uniform distribution of the second phase throughout the grains and thus prevents the corrosion of grain boundaries by IGC. There are a number of heat treatment operations which have been performed on B206 alloys to modify its 24  microstructural and mechanical properties, namely T4, T6, T7 and Retrogression and Re-ageing. These heat treatment processes are explained in Table 2-1. It has been observed that not all heat treatments have positive impact on the mechanical properties of the alloy.  Table 2-1: Various heat treatment processes used for aluminium based alloys Heat Treatment Description T4 Solution heat treated and quenched.  T6 Solution heat treated, quenched and artificially aged T7 Solution heat treated, quenched and artificially overaged T8 Solution heat treated, quenched and cold-rolled before ageing. RRA Solution heat treated, quenched, artificially aged, retrogressed and then aged again.  2.4.4.1 Mechanism of B206 heat treatment  The brittle copper-aluminide present at the grain boundaries of the B206 deteriorates the mechanical properties and increases the corrosion susceptibility of the alloy. Therefore, the first step is intended to homogenize the structure. To achieve this solution treatment homogenization is performed near the eutectic temperature. The temperature can go up as high as 540°C as the melting temperature of the eutectic is 548°C. At this temperature, the total amount of copper present in B206 goes into solution. After the solution treatment is performed, the alloy is quenched into hot water to trap the copper dissolved in aluminium. With time the copper present in the structure combines with the vacancies to form very fine precipitates known as the GP 25  zones. These precipitates are the main reason of strengthening in heat-treated B206 structure. During artificial aging, the copper accumulates at the grain boundaries and becomes anodic to copper precipitates present within the grain causing corrosion of grain boundaries. Thus over-aging is preferred as it ensures accumulation of copper within the precipitates at the grains and thus preventing a galvanic cell formation leading to grain boundary dissolution.  2.4.4.2 T7 heat treatment  The T7 temper involves temperatures which are generally higher than those used to produce T6 tempers in Al alloys but for a shorter period of time. The T7 temper is a heat treatment technique that involves solution treatment and long over-ageing steps to control the intergranular corrosion of the alloy. However, the over-ageing condition leads to decrease in mechanical properties. T7 heat treatment causes the aluminium alloy to lose 10-17% of its strength. The temper, as a result of over-ageing, increases fracture toughness and in some cases even reduces fatigue fracture propagation [123]. The T7 is applied to Al-Cu alloys to carry them past the point of maximum strength to prevent residual stresses.   2.4.4.3 Retrogression and Re-ageing heat treatment  Retrogression and Re-ageing (RRA) is a heat treatment process that was developed to allow aluminium alloys to display T7 corrosion resistance with T6 strength. The heat treatment process of RRA involves a material being heated to a high temperature below the solvus line for a short period of time. This step of the process is called retrogression. The material is then re-aged back 26  to its peak strength by performing artificial ageing to provide a better corrosion resistance. The artificial ageing causes segregation of precipitates from the grain boundaries and uniform distribution of precipitates within the grains which improves the corrosion resistance of the material.  It was reported that retrogression is essentially a grain boundary precipitate coarsening treatment [124]. In general, RRA is applied as a method to extend the service life of aging aircrafts. RRA is recommended for use in components that are life limited by corrosion due to decreasing fatigue strength and tensile properties [125-131]. RRA heat treatment is the usual method for reducing the susceptibility of Al–Mg wrought alloys to SCC. Such a method of heat treatment coarsens the grain boundary precipitates, resulting in a discontinuous structure, thereby decreasing the susceptibility of Al–Zn–Mg (7xxx series) alloys to SCC [132–134]. Several studies have indicated that RRA treatment changes the morphology of the Mg-rich or Cu-rich segregated phase at the grain boundaries of 7XXX wrought alloys and reduced the dislocation density, and therefore, reduced the susceptibility to SCC [135–137]. It was found that the only differences were the size and size distribution of matrix precipitate and coarsening of grain boundary precipitates in the RRA condition. The beneficial effects of RRA are due to the disappearance of these dislocations that are said to cause SCC rather than the precipitates.      27  3. Objectives  In view of the preceding literature and discussion, a number of objectives were set out:  1. To determine the corrosion behaviour of B206 in seawater, both natural and simulated environments. 2. To evaluate the corrosion rates of B206 under various immersion conditions by both mass loss and electrochemical measurements. 3. To study the effect of both temperature (5°C, 10°C, 15°C & 20°C) and different gas purging conditions (aerated, de-aerated and oxygen purged) on the pitting corrosion of B206. 4. To improve and apply previously tested heat treatment methods in order to increase the corrosion resistance of B206, mainly RRA and T7 techniques. 5. To analyse the precipitate distribution of different heat-treated structures and compare them with the as-cast B206 using various image analysis techniques. 6. To find the hardness of the as-cast, RRA and T7 heat-treated samples while making a comparison among them to determine the effect on mechanical behaviour of the alloy after heat treatment.                      28  4. Approach and methodology  The purpose of conducting these experiments was to quantify the corrosion behavior of B206 in seawater environments. In this chapter, the selection of materials, heat treatment, solution preparation, the electrochemical and surface characterization methods and hardness procedures are discussed.  4.1 Materials selection  4.1.1 As-cast AA B206  The electrochemical tests were performed using aluminium alloy B206 samples with an exposed area of 2 𝑐𝑚2. The samples were cut from two different as-received ingots as shown in Figure 4-1, with a chemical composition of 5.1% Cu, 0.249% Mg, 0.477% Mn, 0.039% Fe, 0.079% Si, 0.016% Zn, 0.023% Ti and the balance of Al.   Figure 4-1: Circular samples extracted from as-received AA B206 ingot 29  The cut samples were ground with no. 800 silicon carbide paper, washed and cleaned with ethyl alcohol, and dried before immersion in the test solution for electrochemical analysis. For microstructure analysis, the cut samples were ground with no. 1200 silicon carbide paper, polished by alumina to a 1 µm finish, etched, washed and cleaned with ethyl alcohol, and then dried for observation under metallurgical microscopes. Meanwhile, before the cut samples were prepared for experimental analysis, they were mounted in epoxy resin and wired to establish an electric connection between the specimen and the current source.  4.2 Heat treatment  4.2.1 Solution treatment  The cut as-cast B206 samples were heat-treated using 2-step solution treatment and 3-step solution treatment methods that were performed separately. It was observed during SEM analysis that even small amounts of CuAl2 precipitates contribute to the corrosion attack at the grain boundaries. Therefore, an optimized solution treatment and ageing step was needed to homogenize the distribution of CuAl2 precipitates within the matrix while preventing any incipient melting due the to aggressive solution treatment technique. Thus, the aim of the solution treatment was the complete dissolution of the CuAl2 phase rather than melting, which leads to lower mechanical properties as the melted phase remains as a defect after quenching.  The 2-step solid solution treatment of B206 as represented in Figure 4-2 was as follows:  Heat the furnace to 515°C 30   Hold at 515°C for 2 hour  Ramp from 515°C to 525°C rapidly  Hold at 525°C for 8 hour  Quench the sample in water at 65°C  Figure 4-2: 2-step solution treatment schedule  The 3-step solid solution treatment of B206, which is schematically represented in Figure 4-3, was as follows:  Heat furnace to 515°C  Hold at 515°C for 2 hours  Ramp from 515°C to 530°C rapidly  Hold at 530°C for 6 hours 31   Ramp from 530°C to 538°C rapidly  Hold at 538°C for 4 hours  Quench the sample in water at 65°C  Figure 4-3: 3-step solution treatment schedule  4.2.2 Artificial ageing  Multistep ageing treatments are often used to improve the properties of aluminium alloys. These ageing steps can be either a combination of natural and artificial ageing, or can simply be a combination of two or more steps of the latter. Here the effect of both single step and multistep ageing of the AA B206 has been studied. For the single step ageing, T7 heat treatment and low 32  temperature ageing heat treatments were done while for multistep ageing, RRA was performed on the samples. This ageing treatment involved an intermediate quenching at 65°C which was done between the two artificial ageing steps. The different ageing procedures are depicted in Table 4-1 shown below:  Table 4-1: Different heat treated samples represented with their ageing temperature and time Specimen ID (solid solution steps) Artificial Ageing    Temperature (°C)  Holding Time (hrs.)  Total Time (hrs.)  RRA 200 (3-step) 155°C 20  40.25 200°C 0.25 155°C 20  RRA 210 (3-step) 155°C 20  40.16 210°C 0.16 155°C 20  RRA 220 (2-step) 155°C 20  40.08 220°C 0.08 155°C 20  Specimen ID (solid solution steps) Artificial Aging    Temperature (°C)  Holding Time (hrs.)  Total Time (hrs.) T7 (2-step) 199°C 4 4 LTA 20 (3-step) 155°C 20 20 LTA 40 (3-step) 155°C 40 40 33  4.3 Solution preparation  There were two types of solutions used, i.e. the simulated seawater and the natural seawater.  4.3.1 Simulated seawater   The solution for carrying the electrochemical and immersion test was prepared in the laboratory under the ASTM standard D1141-98. For a 1 litre of solution, 24.53 gm of sodium chloride and 4.094 gm of anhydrous sodium sulphate was mixed along with 20 ml of stock 1 solution and 10 ml of stock 2 solution as mentioned in Table 4-2. After the solution was prepared, the pH was adjusted to 8.2 for final use by adding 0.1 M sodium hydroxide solution. During various tests, the simulated seawater was purged with compressed air for aeration, nitrogen for de-aeration and oxygen for oxygen purged test environment.  Table 4-2: Stock 1 and stock 2 solutions for preparing the simulated seawater                           Stock solution 1                  Chemical                 Concentration (g/L)  Stock solution 2        Chemical                    Concentration (g/L) 1. MgCl2.6H2O 555.6 1. KCl 69.5 2. CaCl2 57.9 2. NaHCO3 20.1 3. SrCl2.6H2O 2.1 3. KBr 10.0   4. H3BO3 2.7   5. NaF 0.3   34  4.3.2 Natural seawater  The second set of solutions was collected at Canadian Force Base Esquimalt, near Victoria, British Columbia, where the water was collected from the Pacific Ocean. The composition of natural seawater as detected using Inductive Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) is shown in Table 4-3.  Table 4-3: Composition of natural seawater as detected using ICP-AES Serial No. Element Concentration (mg/L) 1. Na 9821.0 2. Mg 1190.0 3. S 896.0 4. K 373.0 5. Ca 371.4 6. Sr 6.22 7. B 3.6 8. V 2.5  4.4 Corrosion and electrochemical testing  To study the corrosion behaviour of B206 in seawater environment, a number of accelerated corrosion tests were done, namely Potentiodynamic Polarization (PDP), Potentiostatic Polarization (PSP) and Cyclic Potentiodynamic Polarization (CPP). To ensure that the samples have reached potential stability, Open Circuit Potential measurement (OCP) was performed 35  before every test. Furthermore, an immersion test was done to measure the weight loss and determine the corrosion rate. For every test, a fresh solution was prepared to ensure reliability of results.  4.4.1 Open Circuit Potential  Before every electrochemical test, the OCP was observed and monitored until potential stability was reached. This was determined by observing the potential vs time plot. If in a range where potential did not vary more than 10 mV in a time span of 600, the OCP was judged to be stabilized. For most situations, a stable value was obtained within 1 hour of immersion but for some situations the time period had to be extended to observe a stable behaviour.  4.4.2 Potentiodynamic Polarization  PDP tests were performed in seawater solution from -0.250V with respect to the OCP to -0.250V with respect to the Ag/AgCl reference with a scan rate of 0.166 mV/s. All of the tests were repeated at least twice to ensure the reliability of test results. A test is said to be repeatable if the shape of the curve and the Ecorr values almost similar in the different runs. With this test it was possible to determine the corrosion potential (Ecorr) and the corrosion current density (icorr), as well as the active, passive and transpassive behaviour of the material. The icorr was given by the intersection of the cathodic Tafel slope (βb) with the Ecorr and the point of intersection was used to determine the value. In all the cases, the cathodic Tafel slope was defined in a linear region at least 50 mV below the Ecorr value. 36  4.4.3 Potentiostatic Polarization  The PSP test was performed on the samples at different constant potentials with respect to the Ag/AgCl reference electrode for a duration of 6 hours in different test environments and at different temperatures. After obtaining the value of Ecorr from the PDP test, the potentiostatic potentials were set to the value of 25 mV, 50 mV, 100 mV and -25 mV above the corrosion potential before the tests were conducted.     4.4.4 Cyclic Potentiodynamic Polarization  These kinds of tests were conducted in seawater solution at different temperatures from an initial potential of -0.2V with respect to OCP to a final potential of -0.2V with respect to the Ag/AgCl reference electrode, keeping the vertex potential as 9V. The vertex potential is the maximum potential at which the scan reverses in CPP experiments. The threshold current was kept as 100 mA while the start level potential or the potential of reversion was chosen to be 0V. The aim was to observe the repassivation potential (Erp) and the breakdown potential (Ebd) to determine the pitting susceptibility which is the difference between Erp and Ebd, and furthermore to choose an appropriate potential to conduct the linear sweep thermammetry.  4.4.5 Linear Sweep Thermammetry   Linear Sweep Thermammetry was performed to determine the initiation of metastable pitting. The technique was based on recording of the current in the investigated system at a constant potential. The potential was chosen through performing cyclic PDP tests, as a function of the 37  operating temperature. The value of potential determined by CPP was -0.450V vs Ag/AgCl. Potentiostatic polarization test was conducted at -0.450V vs Ag/AgCl at an initial temperature of 5°C and the solution temperature was increased with time from 5°C to 25°C at an approximate rate of 1°C/min.   4.4.6 Immersion test  Immersion tests were conducted on the RRA 220 heat-treated samples for a duration of 90 days in natural seawater. For the immersion test, the test solution was 500 ml. For reliability of results, four samples were used for immersion test. The test specimens were ground with no. 120 silicon carbide paper to remove any oxide layer on the surface and weighed thereafter before immersion. The test was performed at room temperature while the solution was kept naturally aerated and the solution flask was equipped with an air inlet, thermometer and sample supporting device to complete the setup as shown in Fig. 4-4. After the test was completed, the samples were washed, dried, and the adhering corrosion product was removed using concentrated Nitric acid. The specimen was placed on a petri dish and the concentrated Nitric acid (15.8 N) was poured over it till the sample surface was fully covered [138]. The samples were removed after 20 minutes of exposure, washed, dried and weighed to determine the corrosion rates.  38   Figure 4-4: Immersion test setup containing natural seawater solution  4.5 Equipment  The electrochemical tests were carried out in a conventional three-electrode corrosion cell. The mounted samples, also called working electrodes, were held in a glass sample holder. The counter electrode was a graphite rod while the reference electrode was Ag/AgCl ([Cl-] = 4M). Sparging was introduced in the corrosion cell to maintain different solution chemistry. The temperature of the solution was varied from 0°C to 25°C for different test conditions using a 39  VWR water bath and was measured using a laboratory thermometer. The measurements for the accelerated tests were taken using a Princeton Applied Research Versastat 4 potentiostat.   4.6 Surface characterization  The surfaces of the samples were characterized to determine the microstructure and the morphology after corrosion. Basically there were three techniques, which are as follows:  4.6.1 Optical Microscopy  Before and after the various heat treatment processes, the polished samples were observed under metallurgical microscope for microstructural changes and precipitate distribution. The sample surface was etched using 92 ml distilled water + 6 ml nitric acid + 2 ml hydroflouric acid (commonly known as Krolls Reagent) for 15 seconds before observation.   4.6.2 Scanning Electron Microscopy   After the electrochemical tests the samples were extracted, rinsed with DI water and dried. Thereafter, the samples were observed under the SEM to determine the corrosion products and the surface morphology.   40  4.6.3 Energy Dispersive X-Ray Spectroscopy  The Energy Dispersive X-Ray Spectroscopy (EDX) was used to determine the elemental composition of different areas of the surface, mainly the precipitate composition within the grains and at the grain boundaries.   4.7 Micro-hardness testing  The hardness measurements were performed using Vickers micro-hardness tester at a load of 0.1 kgf. The test specimens were ground and polished resulting in a mirror finish so as to observe the grain boundaries and grain orientation under the microscope attached to the hardness tester. The polished samples were mounted on the tester and readings were recorded along the diameter of the specimen at a distance of 1 mm, 3 mm, 5 mm, 7 mm, 9 mm, 11 mm and 13 mm from the edge. The indenter had a diamond shaped indentation and the load was applied for 10 secs. The two diagonals of the indentation left in the surface of the material after removal of the load were measured using a microscope and their average was calculated. The Vickers hardness was the quotient obtained by dividing the kgf load by the area (mm2) of indentation and can be represented by the following formula in Eq. (13).   HVN = 1.854 F/d2 (13)  where HVN = hardness Vickers number, F = force in kgf and d = arithmetic mean of two diagonals in mm.  41  5. Results and discussion  Mass loss and electrochemical tests are the two most common methods to determine corrosion rates of a metal. With proper experimental design and the right procedures, the corrosion rates of metals obtained should be comparable to each other. This chapter represents the effect of various parameters on the corrosion behaviour of the B206 in different solution environments. The kinetic parameters were obtained by potentiodynamic, cyclic potentiodynamic and potentiostatic polarization techniques while the surface characterization was observed with the help of OM and SEM.  The hardness of B206 samples was observed using vickers hardness tester.  5.1 AA B206 microstructure  The alloy B206, as discussed in the literature review section, is an Al-Cu alloy with a matrix of aluminium (α-phase) and copper mainly concentrated at the grain boundaries in form of Al2Cu. Figure 5-1 and 5-2 show the distribution of θˊ-phase along the grain boundaries and the spheroidal Al2CuMg (S-phase) within the grains as observed under OM and SEM. It is well known that the addition of traces of Mg to binary Al-Cu alloys stimulates the precipitation of S-phase that enhances age hardening [139-144].  The B206 microstructure shows the presence of Al2Cu in the form of dendrites. The SEM image shows the inter-metallic phase present in the grain boundaries as well as spheroidal particles within the grains. 42   Figure 5-1: AA B206 microstructure at 100X as observed under OM  Figure 5-2: AA B206 grain at 500X as observed under SEM Al2CuMg Al2Cu 43  5.2 Effect of chloride   Prior to the use of simulated seawater, the samples were tested for different chloride concentration to see the effect of chloride on the corrosion of as-cast B206. The samples were tested electrochemically in different weight percent NaCl solutions, namely 3.2%, 3.5% and 3.8%. The potentiodynamic results as shown in Figure 5-3 were observed.  Figure 5-3: PDP curves for as-cast B206 in solution with different NaCl concentration  The PDP curves in all three cases look almost identical showing a minimal effect due to change in NaCl concentration on the corrosion and surface morphology of AA B206. The corrosion phenomenon was seen to be transpassive. The quantitative analysis of the corrosion potential and corrosion current density for the samples is shown in the Table A-3 in the Appendix. The corrosion current densities didn’t vary on changing the NaCl concentration from 3.2% to 3.8% and the values were seen to be close to 4 mA/cm2.  44  5.3 Effect of solution environment  To observe the behaviour of B206 in simulated seawater, a number of changes were made as to see the effect of different solution environments. In one case, the seawater was purged with constant flow of nitrogen to reduce the mole fraction of oxygen and other gases, therefore making it de-aerated. In the second case, oxygen was purged into the solution to increase its mole fraction and thus making it saturated with oxygen content. Thirdly, compressed air was purged and dissolved in the seawater at constant rate to see the behaviour of aeration on the corrosion of B206. All three purging processes were performed separately and effect of each was recorded using PDP as shown in Figure 5-4.  Figure 5-4: PDP curves for as-cast B206 in different gas purged seawater environment 45  The figure above showed the behaviour of different gas purging on the corrosion behaviour of the as-cast B206 samples. For the de-aerated seawater, the Evans curve was similar to that often seen for alloys like stainless steel 316 etc. that form passive films in solution after exposure [145]. In the anodic region, the active, passive and transpassive regions are present. This is in contrast to the aerated and oxygen purged seawater conditions where no active and passive regions were observed and the corrosion phenomena was judged to be transpassive immediately after immersion. After the PDP test the samples were observed under SEM, as shown in Figure 5-5, to obtain a detailed surface morphology and for any hint of intergranular corrosion. The PSP test were performed at room temperature after determining the values of Ecorr from the curves above, and thereafter the static potential tests were carried out in different solution environment and at different potentials. The PSP tests were performed to see the change in the current density at potentials closer to Ecorr to see the effect of transpassive behaviour occurring in the as-cast B206 due to various gas purged conditions.        46         (a) (b)  (c)  Figure 5-5: SEM images of as-cast B206 after PDP test in (a) aerated, (b) de-aerated and (c) oxygen purged environment, in seawater 47  5.3.1 Compressed air (aerated) sparged   The PSP curves for the aerated seawater were studied and plotted for the change in current density with time. The tests were carried out for 6 hours while the potentials were maintained at +25 mV, +50 mV and +100 mV above and -25 mV below the Ecorr (V vs Ag/AgCl) as shown in Figure 5-6. The value of Ecorr for aerated environment was determined to be -0.565 V.   Figure 5-6: PSP curves for B206 in aerated seawater for a duration of 6 hrs.  It was seen that the corrosion current density barely changed with time for potentials below Ecorr while for potentials above Ecorr, an abrupt increase in current density was seen initially. This tended to decrease as the time progressed except when potential was +25 mV above the 48  corrosion potential, where the current density increased continuously. The decrease in corrosion current density might have occurred due to passivation of pits with time for higher potentials. Figure 5-7 shows the surface of the alloy after 6 hours of potentiostatic polarization at -0.465 V and the extent of macro pitting affecting the alloy’s surface.   Figure 5-7: SEM image at 500x of as-cast B206 after 6 hours of PSP at -0.465 V in aerated seawater  5.3.2 Nitrogen (de-aerated) sparged  The 6 hour PSP tests for the de-aerated seawater environment were carried out separately and the static potentials were set to +25 mV, +50 mV and +100 mV above the Ecorr (V vs Ag/AgCl) as shown in Fig. 5-8. The value of Ecorr for de-aerated environment was determined to be -1.109 V. 49   Figure 5-8: PSP curves for B206 in de-aerated seawater for a duration of 6 hrs.  The curves showed negligible change in corrosion current density with time for all the three cases. This was also observed by looking at the surface morphology, as the surface barely had pits, which can be seen in Figure 5-9 (a). Hints of IGC were also observed after 6 hours of exposure as seen in Figure 5-9 (b). 50      Figure 5-9: SEM image of as-cast B206 after 6 hours of PSP (a) -1.009 V in de-aerated seawater at 500x, (b) intergranular corrosion at 700x  5.3.3 Oxygen sparged  The PSP tests for oxygen purged seawater environment were carried out with a static potential of +25 mV, +50 mV and +100 mV above and -25 mV below the Ecorr  (V vs Ag/AgCl) for 6 hours as seen in Figure 5-10. The value of Ecorr for oxygen purged environment was determined to be -0.595 V after observing the Fig. 5-4. 51   Figure 5-10: PSP curves for B206 in oxygen purged seawater for a duration of 6 hrs.  Here the trend of change in corrosion current density with time was as expected due to oxygen being present as an oxidizer and the corrosion current densities observed were very high. For the higher value of potential i.e. +100 mV above Ecorr, the curve showed the same behaviour as in aerated seawater with the current density increasing and then decreasing with time. This might have occurred because of formation of passive layer. Fig. 5-11 shows the SEM image after 6 hours of exposure. Macro pits were observed on the sample surface as seen in Figure 5-11. The -25 mV below Ecorr curve showed showed negligible change in current density with time as was observed in aerated and de-aerated seawater environments too. 52   Figure 5-11: SEM image at 500x of as-cast B206 after 6 hours of potentiostatic polarization at -0.495 V in oxygen purged seawater  5.4 Effect of temperature on pitting corrosion  After the PSP tests were performed in various gas purged environments, the surface morphology was observed and pitting corrosion was found to be one of the major reasons for degradation of the alloy in seawater. Thus to observe the initiation of metastable pitting and then the stable pitting, CPP was performed. This was done to investigate the temperature dependence of the breakdown potential (Ebd) and the re-passivation potential (Erp) at different seawater temperatures. This experiment was performed to define the Metastable Pitting Temperature Threshold (MPTT) using Linear Sweep Thermammetry measurements.  53  The experiments were performed in the simulated seawater environment. The solution was sparged with compressed air throughout the experiment. Before performing the CPP experiments, the working electrode was stabilized at open circuit for 1 hour. The solution temperatures were chosen to be 5°C, 10°C, 15°C, 20°C and 25°C, which is the seawater temperature range, and the results are as seen in Figure 5-12 and Table 5-1. This figure shows the cyclic curves at different temperatures and the hysteresis loops formed during this cyclic process are indicative of pitting. The bigger the difference between Ebd and Erp, the more susceptible is the alloy to pitting corrosion [146]. The size of the loop is an indication of the amount of pitting that took place on the samples.  Figure 5-12: CPP curves for as-cast B206 at different temperatures in aerated simulated seawater 54  The CPP curves were used to determine the values of Ebd and Erp. Generally, Ebd is defined as the potential where the current density continuously exceeds 1 mA cm-2. Erp is the potential below which the pits no longer propagate. Pitting was seen to be uniform and continuous over the specimen and it can be observed by the transpassive behaviour of the curves.  Table 5-1: Value of corrosion potential and breakdown potential obtained at different temperatures using CPP  No.  Temperature (°C)  Pitting/ No pitting  Ecorr (V)  Ebd (V) 1 5 Pitting -0.491 -0.695 2 10 Pitting -0.511 -0.720 3 15 Pitting -0.625 -0.702 4 20 Pitting -0.561 -0.738 5 25 Pitting -0.568 -0.819  As the curves showed no passivation phenomena and the Erp was below the corrosion potential, the value of the static potential for Linear Sweep Thermammetry as shown in Figure 5-13 was taken to be -0.450 V, i.e. just above the value of corrosion potential. 55   Figure 5-13: Thermammogram for B206 in aerated seawater at a potential of -0.450 V  The thermammogram above showed no sign of initiation of metastable pitting because the metastable spikes in the potentiostatic curve weren’t observed. Also, no stable pitting was observed in the thermammogram. It was determined that the pitting initiated well before the curve reached the active region i.e. Epit < Ecorr. Therefore, it was concluded that the pitting started at the OCP.    5.5 Effect of heat treatment  The as-cast B206 was thermally treated using various heat treatment techniques to analyse the improvement in corrosion resistance of the alloy. The phase diagram of Al-Cu shows the 56  temperature limit of the eutectic reaction to which the alloy can be solution heat treated before any incipient melting of the secondary phases can take place, which can lead to degradation of mechanical properties of the alloy.   For the B206 which is Al-5.1%Cu alloy, the solid solution treatment temperature was fixed to be near and below the eutectic point so that the most of the intermetallics gets dissolved. The eutectic point, i.e. 548°C, of the alloy was determined by studying the phase diagram as shown in Figure 5-14, and the different solid solution temperatures were determined as discussed in section 4.2.1.  Figure 5-14: Equilibrium phase diagram of Al-Cu system [147]  57  5.5.1 Retrogression and Re-ageing heat treatment  The as-cast B206 samples were heat treated using an RRA technique which is commonly used in  7xxx series aluminium alloys for improving their corrosion resistance and mechanical properties. The microstructure of the RRA heat treated sample as observed under OM is shown in Figure 5-15. It had been observed that the copper which was formerly deposited at the grain boundaries in the as-cast B206 as Al2Cu was distributed throughout the grains after the RRA heat treatment process. This result was even observed when the as-cast and RRA heat treated B206 samples were compared while looking at the EDX graphs.             58     (a) (b)      (c) (d) Figure 5-15: OM images of etched RRA heat treated B206 samples aged at (a) 220C at 200x, (b) 220C at 100x, (c) 200C at 200x, and (d) 210C at 100x  It can be clearly observed that the first two microstructures were from a different casting than the latter two. The latter microstructures show more dendritic growth while the former are more uniformly cooled which, in Fig. 5-22, would show the change in mechanical properties too.  The compositional analysis of strengthening second phase particles in B206 after RRA treatment was studied using Energy Dispersive X-ray Spectroscopy (EDX) as seen in Figure 5-17, and was compared to the as-cast B206 sample as shown in Figure 5-16. 59   (a)  (b) Figure 5-16: EDX of as-cast B206 precipitates at, (a) Al matrix, (b) grain boundary  60   (a)  (b) Figure 5-17: EDX of RRA 220 B206 precipitates, (a) at grain boundary, (b) spherical precipitate in matrix  61  The EDX results for the as-cast B206 showed that the precipitate concentration and composition at the grain boundaries and within the grains is mostly aluminium and copper. This might suggest the presence of CuAl2 as the major strengthening phase in the alloy.   The PDP tests were carried out for various RRA heat treated samples at different seawater temperatures while the solution was sparged with compressed air to keep the conditions aerated. The temperature for accelerated tests were chosen to be 5°C, 10°C, 15°C and 20°C and all the tests were carried out separately to understand the behaviour of seawater temperature on the alloy’s performance. Figure 5-18 shows the effect of seawater temperature on RRA 220 sample which was 2-step solution treated and retrogressed at 220°C. The quantitative analysis showing the corrosion potential and corrosion current density for the RRA 220 samples is presented in Table A-4 in the Appendix section.    62   Figure 5-18: PDP curves of RRA 220 at different temperatures in aerated simulated seawater  As seen in the above curves, seawater temperature hardly affected the corrosion current density of the alloy. Both the anodic and the cathodic part of the Evan’s curve showed similar behaviour for all different temperatures. The anodic behaviour was seen to be transpassive with no active or passive regions to be observed. The same behaviour was observed for the RRA 200 and RRA 210 samples. The behaviour of the latter two heat treated alloys is shown in Figure 5-19 below.    63    Figure 5-19: PDP curves of (a) RRA 200, (b) RRA 210 at different temperatures in aerated seawater solution 64  It was clearly observed that the RRA 220 heat treated sample at a potential of -0.25 V vs Ag/AgCl showed a tenfold current density difference when compared to as-cast sample at similar conditions as seen in Figure 5-20. The quantitative analysis showing the corrosion potential and corrosion current density for the RRA 200 and RRA 210 samples is shown in Table A-5 and Table A-6. For the comparison of RRA and as-cast samples please refer to the data given in Table A-7 in the Appendix section.  Figure 5-20: PDP comparison between as-cast and various RRA heat treated samples at 15°C in aerated seawater  Apart from accelerated tests, a 90-day immersion test was carried out on the RRA 220 samples to determine the corrosion rate by another method and to study the surface morphology after 65  exposure. The exposed samples after 90 days were taken out, cleaned and weighed, and were then compared to the initial mass as seen in Table 5-2. The surface morphology after the test is shown in Figure 5-21. The corrosion rate was calculated using the following formula as shown in Eq. (14).   Millimeter per year (mm/y) = 87.6W (14)                                               DAT  where W = weight loss in mg, D = density of specimen in g/cm3, A = area of specimen in sq. cm. and T = exposure time in hr.  Table 5-2: Corrosion rate determination for RRA 220 samples using immersion testing in natural seawater  Specimen No.  Initial mass (mg.)  Final mass (mg.)  Weight loss (mg.)  Corrosion rate (mm/y) 1 3302.5 3293.1 9.4 0.07 2 3268.1 3257.3 10.8 0.08 3 2854.5 2841.3 13.2 0.10 4 3334.2 3325.7 8.5 0.06  Here, the exposure time is 2160 hours; the density of the AA B206 is 2.7 g/cm3 and area of the sample being 2 cm2. The corrosion rates in all the four samples were seen to be almost similar and no macro pits were observed on the sample surface.  66           Figure 5-21: Front and side view of RRA 200 sample after 90 day immersion test  The hardness test for RRA heat treated samples was performed to compare the mechanical effect of heat treatment. Hardness tests were performed on a Vickers micro-hardness tester with an impact force of 0.1 kgf for duration of duration of 10 sec. The test readings were taken through a straight line across the diameter of the specimen. Figure 5-22 shows the graphical comparison of the hardness of the as-cast and RRA heat treated samples. The hardness table (Table A-1) in the Appendix section shows the hardness values of the different RRA heat treated and as-cast B206 samples.  It is seen that the RRA 220 samples showed the highest hardness values ranging from 150-170 HVN while the as-cast B206 had the lowest hardness values ranging from 80 to 90 HVN. The RRA 200 and the RRA 210 samples had similar hardness values ranging from 125 to 140 HVN. Overall it was observed that the RRA heat treatment method increased the hardness properties of the AA B206.  67   Figure 5-22: Hardness comparison of as-cast and RRA heat treated samples with respect to position from one end of diameter to other  5.5.2 T7 heat treatment  The as-cast B206 samples were heat treated using T7 which is generally used for Al-Cu alloys to improve the mechanical properties while increasing the corrosion resistance of the alloy. The T7 heat treated microstructure as shown in Figure 5-23 looks similar to the RRA heat treated microstructure except the grain growth is less and the θˊ-phase distribution is non-uniform in the former.   68     (a) (b) Figure 5-23: OM images of etched T7 heat treated sample aged at 199°C at (a) 100x, (b) 200x  It can be clearly seen that the θˊ-phase which was solely concentrated at the grain boundaries in as-cast B206 has now been distributed within the grains and therefore it can improve the resistance of the alloy to IGC.   The PDP tests for the T7 heat treated specimen were performed at different temperatures as seen in Figure 5-24. The data for the corrosion potential and corrosion current density at different temperatures is shown in Table A-8 in the Appendix. T7 was performed to compare with the RRA heat treated samples and to study the corrosion resistance of the B206 after heat treatment. Figure 5-25 is an example of comparison of PDP curves of the as-cast, RRA and T7 heat treated samples in natural and simulated seawater. 69   Figure 5-24: PDP curves of T7 samples at different temperatures in aerated simulated seawater       70   (a)  (b) Figure 5-25: PDP comparison of as-cast, T7 and RRA 220 heat treated samples at (a) 15°C in aerated simulated seawater, (b) 15°C in aerated natural seawater  71  It can be seen that the effect of temperature on T7 heat treated samples is negligible as the Tafel curves look similar to each other. On the other hand, the comparison of as-cast curves with the heat treated curves in simulated seawater shows an improvement of almost tenfold in corrosion current density at a potential of -0.250 V vs Ag/AgCl, while for natural seawater the case is different. In natural seawater environment, RRA heat treated sample results in better anodic current density than its other two counterparts and therefore shows a better tendency to corrosion resistance, which was observed by looking at the surface morphology too. In natural seawater, uniform macro pits were observed on the as-cast B206 while for the RRA 220 and T7 heat treated samples only micro pits were seen. A hint of IGC was also observed on the T7 heat treated sample. The surface morphology is shown in Figure 5-26. The quantitative analysis showing the corrosion potential and corrosion current density for the as-cast and various heat treated samples in simulated seawater is shown in Table A-9, and in natural seawater in Table A-10 of the Appendix. It was seen that the RRA heat treated sample had better corrosion current density than T7 and as-cast B206. In both the cases, i.e. natural and simulated seawater, the RRA heat treated sample had a corrosion current density value of 4 µA/cm2 while the as-cast B206 had a value of 10 µA/cm2. The T7 heat treated sample also showed better corrosion resistance than as-cast B206 for both the immersion conditions         72                                (a) (b)    (c) Figure 5-26: Surface morphology of samples (a) T7, (b) RRA 220 and (c) as-cast, after PDP tests at 15°C in natural seawater  5.5.3 Low temperature ageing treatment  To study the effect of ageing with time, certain samples were artificially aged for longer times at  73  relatively lower temperatures than T7. The temperature of ageing was chosen to be 155°C. Ageing for longer duration was performed for the rapid precipitation growth to result in precipitation hardening. According to the microstructure of the samples, aged for 20 h and 40 h, it was observed that the line and spherical precipitates were larger in size when aged for 40 h than for 20 h. Figure 5-27 shows the effect of low temperature ageing on B206 samples which were 3-step solution treated before being aged.     (a) (b) Figure 5-27: OM images of etched low temperature aged samples aged at 155C° for (a) 20 h, (b) 40 h, at 200x  As shown earlier, PDP tests were performed on the heat treated samples as shown in Figure 5-28. The low temperature ageing treated curves were observed for 5°C, 10°C and 15°C in natural seawater solution. It was observed while looking at the curves that there was not much effect on increasing the ageing time on the corrosion current density of the alloy and the change in solution temperature didn’t affect the performance of the samples. The quantitative analysis of the corrosion potential and corrosion current density for the low temperature aged samples is shown in Table A-11 in Appendix. 74   (a)  (b) Figure 5-28: PDP curves of low temperature aged samples (a) 20 h, (b) 40 h, at different temperatures in natural seawater 75  The average values of the corrosion current density were seen to be 5 µA/cm2 for both 20h and 40 h ageing treatment showing that the increase in ageing time didn’t have any significant effect on the corrosion resistance of the alloy. Subsequently, the low temperature aged sample curves were compared with the as-cast and T7 sample curves using PDP to understand the effect of no ageing, low temperature ageing and high temperature ageing on the corrosion behaviour of B206. The result is seen in Figure 5-29 depicting the comparison between the three different ageing specimens with the as-cast sample. The quantitative analysis showing the comparison in the corrosion potential and corrosion current density of as-cast B206 with T7 and low temperature aged samples is mentioned in Table A-12 in Appendix.  Figure 5-29: PDP comparison of as-cast, T7 and low temperature aged samples at 15°C in natural seawater  The low temperature aged samples had less corrosion current density than as-cast samples showing that the prolonged ageing leads to better corrosion resistance of the alloy. But as the 76  corrosion current values didn’t vary much between the T7 and the low temperature aged samples, the longer ageing time with lower temperature is not likely to be adopted as a replacement of T7 as the latter technique is equally effective and less time consuming as the ageing time for T7 is 4 h while for low temperature aged samples is 20 and 40 h. After PDP tests, the heat-treated samples were polished again and were used for hardness testing using Vickers micro-hardness tester to compare the mechanical properties. Figure 5-30 depicts the graphical comparison of the as-cast, T7 and low temperature aged samples. Table A-2 in Appendix section shows the hardness values of the different low temperature aged and T7 heat treated and as-cast B206 samples.  Figure 5-30: Graphical representation of hardness comparison of as-cast, T7 and low temperature aged heat treated samples with respect to position from one end of diameter to other 77  Hardness testing was beneficial to determine whether the samples after exposure to high solid solution temperature had incipient melting of secondary phases which would have resulted in deterioration of the mechanical properties. It was observed that the T7 samples which were aged for 4 hours at 199°C had maximum hardness range of 130 to 140 HVN while the low temperature aged samples ranged from 115 to 130 HVN. In the as-cast sample, a few anomalies were noticed where hardness was about 120 HVN. This might have been the hardness of the secondary phase particles which were present at the grain boundaries in the as-cast B206. Overall, the hardness properties of heat treated samples were observed to be higher than the as-cast B206.  5.6 Summary  In summary, PSP for potentials above Ecorr result in pitting with intensity varying with the type of seawater solution environment. For potentials below Ecorr no pitting was detected. Pitting is uniform and covers the alloy’s surface with hints of IGC in seawater as observed under SEM and OM. In aerated and oxygen purged environments, no passive layer formation takes place and pitting corrosion starts at the OCP. Heat treatment causes the grain boundary precipitates to dissolve in the solid solution and further aging creates uniform Al-Cu intermetallic precipitates in the grains and at the grain boundaries. Immersion test data shows positive results for RRA heat treated samples as the corrosion resistance of the alloy is seen to be improved. For all the heat treatment techniques used, i.e. RRA, T7 and low temperature ageing, there is an average improvement of three fold in the corrosion resistance of the alloy as compared to as-cast B206. 78  Also, due to different precipitation distribution within the grain after heat treatment techniques, the hardness of the alloy is observed to be increased as compared to as-cast B206.                 79  6. Conclusions  The results of electrochemical tests, surface analyses and hardness tests presented in the thesis lead to following conclusions:  1. Corrosion of B206 in chloride media is not affected by varying the chloride concentration from 3.2 wt. % to 3.8 wt. %. 2. The corrosion resistance of B206 is maximum in de-aerated seawater solution while aerated and oxygen-purged seawater environments show higher corrosion rates. 3. Changes in seawater temperature from 5°C to 25°C have minimal effect on the corrosion of B206. 4. The corrosion behaviour of B206 in aerated seawater is trans-passive i.e no passive region of stability is observed during corrosion.  5. No metastable pitting is observed in aerated seawater environments confirming the trans-passive behaviour of B206. 6. The current density observed for RRA heat-treated samples is lower by tenfold than the as-cast B206 showing improved corrosion resistance in both natural and simulated seawater. 7. From PDP results, T7 and other low temperature ageing techniques resulted in better corrosion current density when compared to as-cast B206 while low temperature aged samples showed better corrosion current density when compared to T7. 8. The hardness test results indicate the following trend in hardness for heat treated and non-heat treated B206 alloys: RRA > T7 > LTA > as-cast.  80  7. Future work  1. Perform different heat treatment techniques to further improve the corrosion resistance of AA B206, like T8 heat treatment which involves cold working along with the artificial ageing of the alloy. 2. Develop new coatings and claddings for protection of B206 in seawater environments to provide better corrosion resistance. 3. 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J I M, Vol.12, 1971. 92  Appendix  Table A-1: Hardness comparison of as-cast and RRA heat treated samples using Vickers micro-hardness tester Position from edge  As- cast (HVN) RRA 220.1 (HVN) RRA 220.2 (HVN) RRA 210 (HVN) RRA 200 (HVN) Force (kgf) 1 122 165 151 137 125 0.1 3 79 165 154 119 129 0.1 5 76 158 158 126 135 0.1 7 112 165 155 124 131 0.1 9 79 151 154 141 12 0.1 11 84 168 151 130 134 0.1 13 85 161 164 135 135 0.1             93  Table A-2: Hardness comparison of as-cast, T7 and low temperature aged heat treated samples using Vickers micro-hardness tester Position from edge  As-cast (HVN) T7  (HVN) LTA 20 (HVN) LTA 40 (HVN) Force  (kgf) 1 122 145 119 133 0.1 3 79 133 126 138 0.1 5 76 130 120 129 0.1 7 112 138 116 126 0.1 9 79 129 118 137 0.1 11 84 125 115 100 0.1 13 85 137 113 127 0.1   Table A-3: Ecorr and icorr values for as-cast B206 in solution with different NaCl concentration NaCl concentration (%wt.) Ecorr (mV) icorr (mA) 3.2 -593 5 3.5 -597 3 3.8 -622 3      94  Table A-4: Ecorr and icorr values for RRA 220 at different temperatures in aerated simulated seawater Temperature (°C) Ecorr (mV) icorr (µA) 5 -529 5 10 -589 3 15 -574 4 20 -548 3  Table A-5: Ecorr and icorr values for RRA 210 at different temperatures in aerated simulated seawater Temperature (°C) Ecorr (mV) icorr (µA) 5 -506 3 10 -509 4 15 -517 3   Table A-6: Ecorr and icorr values for RRA 200 at different temperatures in aerated simulated seawater Temperature (°C) Ecorr (mV) icorr (µA) 5 -598 1 10 -516 4 15 -514 5   95  Table A-7: Ecorr and icorr comparison between as-cast B206 and various RRA heat treated B206 samples at 15°C in aerated simulated seawater Sample Ecorr (mV) icorr (µA) As-cast -599 10 RRA 200 -514 5 RRA 210 -517 3 RRA 220 -574 4   Table A-8: Ecorr and icorr values for T7 sample at different temperatures in aerated simulated seawater Temperature (°C) Ecorr (mV) icorr (µA) 5 -602 1 10 -606 16 15 -590 7 20 -600 9   Table A-9: Ecorr and icorr comparison of as-cast, T7 and RRA heat treated samples at 15°C in aerated simulated seawater Sample Ecorr (mV) icorr (µA) As-cast -599 10 RRA 220 -574 4 T7 -590 7  96   Table A-10:: Ecorr and icorr comparison of as-cast, T7 and RRA heat treated samples at 15°C in aerated natural seawater Sample Ecorr (mV) icorr (µA) As-cast -549 10 RRA 220 -592 4 T7 -587 5   Table A-11: Ecorr and icorr values of low temperature ageing samples aged for 20 h at different temperatures in aerated natural seawater Temperature (°C) Ecorr (mV) icorr (µA) 5 -528 6 10 -575 5 15 -530 4   Table A-12: Ecorr and icorr values of low temperature ageing samples aged for 40 h at different temperatures in aerated natural seawater Temperature (°C) Ecorr (mV) icorr (µA) 5 -492 4 10 -517 5 15 -555 4   97  Table A-13: Ecorr and icorr comparison of as-cast, T7 and low temperature aged samples at 15°C in aerated natural seawater Sample Ecorr (mV) icorr (µA) As-cast -599 10 T7 -587 5 LTA 20 -530 4 LTA 40 -555 4   

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