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Excimer Laser Surface Melting Treatment on 7075-T6

Aluminium Alloy for Improved Corrosion Resistance

A thesis submitted to The University of Manchester for the degree of

Doctor of Philosophy

in the Faculty of Engineering and Physical Sciences

2012

Bader M H M Elkandari

School of Materials

1
Table of Contents
Table of Contents ................................................................................................. 2
List of Tables ....................................................................................................... 6
List of Figures ...................................................................................................... 7
List of Abbreviations ......................................................................................... 16
Abstract .............................................................................................................. 19
Declaration ......................................................................................................... 21
Copyright Statement .......................................................................................... 22
Acknowledgments ............................................................................................. 23
Chapter 1 Introduction ................................................................................... 24
1.1 Rational of the Research Project ........................................................ 24
1.2 Research Objectives ........................................................................... 25
1.3 Thesis Layout ..................................................................................... 26
Chapter 2 Literature Review .......................................................................... 28
2 Introduction to Aluminium Alloys .................................................... 28
2.1 7xxx Aluminium Alloys .................................................................... 30
2.2 Elements and Impurities in 7xxx Aluminium Alloys ........................ 34
2.3 Stages of Heat Treatment of 7xxx Aluminium Alloys ...................... 38
2.3.1 Age Hardening .................................................................................. 39
2.3.2 Precipitate Free Zones (PFZ) ............................................................ 40
2.3.3 Hydrogen Effects............................................................................... 41
2.3.4 Temper Effects .................................................................................. 43
2.4 List of Figures .................................................................................... 48
Chapter 3 Corrosion ........................................................................................ 52
3 Introduction to Corrosion .................................................................. 52
3.1 Surface Oxide Film ............................................................................ 53
3.2 Electrochemical Polarization ............................................................. 53
3.2.1 Thermodynamics ............................................................................... 55
3.2.2 Kinetics.............................................................................................. 57
3.2.3 Passivity and Breakdown of Passivity .............................................. 58

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Table of Contents

3.3 Types of Corrosion ............................................................................ 59


3.3.1 Uniform Corrosion ............................................................................ 60
3.3.2 Localized Corrosion .......................................................................... 60
3.3.3 Pitting Corrosion ............................................................................... 60
3.3.4 Crevice Corrosion ............................................................................. 63
3.3.5 Filiform Corrosion............................................................................. 63
3.3.6 Galvanic Corrosion ........................................................................... 64
3.3.7 Cavitation Corrosion ......................................................................... 64
3.3.8 Waterline Corrosion .......................................................................... 65
3.3.9 Intergranular Corrosion (IGC) .......................................................... 65
3.3.10 Stress Corrosion Cracking (SCC) ..................................................... 66
3.4 Corrosion at High Strength Aluminium Alloys ................................. 69
3.5 Corrosion Behaviour of Intermetallic Particles ................................. 70
3.6 Aluminium Alloy Surface Protection Methods ................................. 73
3.6.1 Non-galvanic Methods ...................................................................... 74
3.6.2 Chemical Methods............................................................................. 74
3.6.3 Electrolytic Methods ......................................................................... 74
3.7 List of Figures .................................................................................... 76
Chapter 4 Laser ............................................................................................... 82
4 Introduction........................................................................................ 82
4.1 Basic Principle of Laser Works ......................................................... 82
4.2 Laser Light Characteristics ................................................................ 84
4.3 Laser Surface Melting (LSM) ............................................................ 86
4.3.1 Heating Principle ............................................................................... 86
4.3.2 Formation of the Melt Pool ............................................................... 87
4.3.3 Cooling and Solidification ................................................................ 88
4.3.4 Nucleation ......................................................................................... 89
4.3.5 Growth ............................................................................................... 90
4.4 Effect of LSM Interaction .................................................................. 92
4.5 Effect of LSM Processing Parameters ............................................... 93
4.5.1 Energy ............................................................................................... 94
4.5.2 Wavelength........................................................................................ 95
4.5.3 Pulse Duration and Interaction Time ................................................ 96
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4.5.4 Number of Pulses per Unit Area ....................................................... 97


4.5.5 Process Environment ......................................................................... 98
4.6 Microstructure of LSM Alloys .......................................................... 98
4.7 Corrosion Behaviour of LSM Alloys............................................... 102
4.8 Excimer Laser for LSM ................................................................... 105
4.9 Safety of Using Laser ...................................................................... 107
4.9.1 Laser Classification ......................................................................... 107
4.9.2 Risk Assessment.............................................................................. 109
4.9.3 Protection from Laser ...................................................................... 109
4.10 List of Figures .................................................................................. 111
Chapter 5 Experimental Procedures ........................................................... 119
5 Introduction...................................................................................... 119
5.1 Substrate Materials .......................................................................... 120
5.2 Surface Preparation for LSM Treatment ......................................... 120
5.3 Anodising ......................................................................................... 121
5.4 Corrosion Investigation.................................................................... 122
5.4.1 Potentiodynamic Polarization Test.................................................. 122
5.4.2 Immersion Test ................................................................................ 123
5.4.3 Exfoliation (EXCO) Test ................................................................ 123
5.5 Specimen Preparation for Metallographic Examination .................. 123
5.6 Field Energy Gun Scanning Electron Microscopy (FEG-SEM) ..... 124
5.7 Transmission Electron Microscopy (TEM) ..................................... 125
5.8 X-ray Diffraction (XRD) ................................................................. 125
Chapter 6 Results ........................................................................................... 127
6 Microstructure and Corrosion of the As-Received AA 7075-T6 Alloy .. 127
6.1 Microstructural Examination ........................................................... 127
6.2 X-Ray Diffraction ............................................................................ 128
6.3 Corrosion Test Results ..................................................................... 128
6.3.1 Potentiodynamic Polarization Test.................................................. 128
6.3.2 Immersion Test ................................................................................ 129
6.3.3 Exfoliation Test ............................................................................... 130
6.4 Conclusions...................................................................................... 131
6.5 List of Figures .................................................................................. 132

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Table of Contents

Chapter 7 ........................................................................................................ 144


7 Laser Surface Melting (LSM) Operation Conditions.............................. 144
7.1 List of Figures .................................................................................. 149
Chapter 8 Microstructure and Corrosion of the LSM AA 7075-T Alloy 159
8 Microstructural Examination ........................................................... 159
8.1 X-ray Diffraction ............................................................................. 162
8.2 Corrosion Test Results after LSM ................................................... 162
8.2.1 Potentiodynamic Polarization Test.................................................. 162
8.2.2 Immersion Test ................................................................................ 163
8.2.3 Exfoliation Test ............................................................................... 163
8.3 Conclusions...................................................................................... 165
8.4 List of Figures .................................................................................. 166
Chapter 9 Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
after Anodising ............................................................................................... 188
9 Introduction...................................................................................... 188
9.1 LSM and Anodising ......................................................................... 188
9.2 Surface and Cross Section Results .................................................. 189
9.3 Corrosion Test Results ..................................................................... 190
9.3.1 Potentiodynamic Polarization Test.................................................. 190
9.3.2 Exfoliation Test ............................................................................... 191
9.4 Conclusions...................................................................................... 192
9.5 List of Figures .................................................................................. 193
Chapter 10 Discussion ................................................................................... 207
10 AA 7075-T6 Alloy ........................................................................... 207
10.1 AA 7075-T6 Alloy after LSM ......................................................... 211
10.1.1 Corrosion of LSM Alloy ................................................................. 215
10.2 LSM of AA 7075-T6 Alloy after Anodising ................................... 219
Chapter 11 Conclusions and Suggestions for Future Work ...................... 223
11.1 Conclusions...................................................................................... 223
11.2 Suggestions for Future Work ........................................................... 227
Chapter 12 Appendix 1 ................................................................................. 228
References ....................................................................................................... 230
Word count 45,930

5
List of Tables
Table 2-1: Four-digit designation system for Aluminium Alloys [29]. .............. 48
Table 2-2: Mechanical properties of AA7xxx alloys with different temper
processes [28]. ...................................................................................... 49
Table 2-3: Solid solubility and influence of elements in Al properties [28]. ...... 50
Table 4-1: Examples of LSM types and their wavelengths [164] ..................... 113
Table 5-1: The chemical composition of the as-received AA 7075-T6 alloy ... 120
Table 6-1: The corrosion potential (Ecorr), pitting potential (Epit), passive
current density (Ipass) and passive range potential (Epass) from Fig
6-8. Potentials are given with respect to SCE. ................................... 140
Table 7-1: Conditions of laser operation (high pulse energy density) .............. 149
Table 7-2: Conditions of laser operation (low pulse energy density) ............... 149
Table 7-3: Corrosion potential (Ecorr), pitting potential (Epit), passive
current density (Ipass) and passive range potential (Epass) for both
as-received and laser treated alloys in Fig. 7-8. Potentials are
given with respect to SCE. ................................................................ 158
Table 8-1: Corrosion potential (Ecorr), pitting potential (Epit), passive
current density (Ipass) and passive range potential (Epass) for both
as-received and laser treated AA 7075-T6 alloy determined from
the potentiodynamic polarisation curves of Fig. 8-17. Potentials
are given with respect to SCE............................................................ 181
Table 9-1: Corrosion potential (Ecorr), pitting potential (Epit), passive
current density (Ipass) and passive range potential (Epass) for the
as-received (AR), laser-treated (LT), AR and anodised, and LSM
and anodised alloys determined from the potentiodynamic
polarisation curves of Fig. 9-4. Potentials are given with respect
to SCE. ............................................................................................... 202

6
List of Figures
Figure 2-1: Three main stages of heat treatment (SHT refers to solution
heat treatment, Q is quenching, and A* is aging) with
precipitation scheme for the 7xxx aluminium alloys ........................... 51
Figure 3-1: Schematic diagram showing the thin oxide layer (Al2O3) that
protects the metal surface (aluminium) from environmental
attack. ................................................................................................... 76
Figure 4-1: Energy level diagram for a three electron energy level of a
laser and a pulse system [126] ........................................................... 111
Figure 4-2: Energy level diagram for a four electron energy level of a
continuous (CW) laser system [126] .................................................. 111
Figure 4-3: Variation in total free energy of solid-liquid system as the size
of the solid changes. The solid is stable nuclei with radius above
the critical value r* [132] .................................................................... 112
Figure 4-4: Various growth structures that show planar (a), cellular (b),
columnar dendrites (c), and equiaxed dendrites (d) [130] ................. 112
Figure 4-5: Schematic representing the solidification transformation from
cell (a), cellular dendrites (b), columnar (c), and to columnar
dendrite branches (d) [125] ................................................................ 113
Figure 4-6: Schematic illustration of the laser beam interaction with the
surface of a material [138] ................................................................. 114
Figure 4-7: Influence of the pulse duration in LSM of pure metals on the
maximum depth of the melting layer [159] ....................................... 114
Figure 4-8: Cross-section of CW-Nd:YAG LSM on AA 2014-T6 alloy,
following etching, that shows different regions of the
solidification structure [161] .............................................................. 115
Figure 4-9: Modelling results of excimer LSM of AA 2024 alloy for a
single pulse that show the solidification growth velocity as a
function of position within the modified layer, including different
layer thicknesses [166] ....................................................................... 115

7
List of Figures

Figure 4-10: Scanning electron micrographs of 3 kW CW-Nd:YAG LSM


AA 2014-T6 alloy showing the variation in growth rate and
dendrite spacing with position in modified layer [161] ..................... 116
Figure 4-11: Electron probe micro-analysis X-ray mapping of 3 kW CW-
Nd:YAG LSM AA 2014-T451 alloy, show element segregation
throughout the modified layer [161] .................................................. 116
Figure 4-12: Variation in cell spacing with melt depth for AA 2024-T3
alloy using a variety of pulsed treatment methods with scanning
electron micrographs of the microstructure at different depths
[166] ................................................................................................... 117
Figure 4-13: High resolution EBSD map showing LSM layer morphology
obtained with excimer laser treatment in Zr-free alloy (AA 2024)
and Zr-containing alloys (AA 7150) [166] ........................................ 117
Figure 4-14: Cross-section micrographs through excimer LSM treated
layers formed over (a) AA 2096 alloy containing Zr and (b) AA
7075 Zr-free alloys, showing the layer grain structure with
behaviour opposite to that found in Fig 4-13 [166] ........................... 118
Figure 6-1: Scanning electron micrographs showing the surface of the AA
7075-T6 alloy at different magnification after grinding and
polishing up to 1 µm diamond paste. (a) Secondary electrons. (b-
d) Backscattered electrons. ................................................................ 132
Figure 6-2: Scanning electron micrographs for the AA 7075-T6 alloy. The
cross-section is normal to the rolling direction (a,c). Particles are
shown in two different regions, while (b,d) are given the
dimensions of the particles and cavities. (a,b) Secondary
electrons. (b,d) Backscattered electrons. ............................................ 133
Figure 6-3: SEM-EDX line scan measurements that show the elements
present in the constituent particles and precipitates in AA 7075-
T6 alloy of the cross-section that is shown also in Fig.(8-2). The
scans show Cu and Fe in the large particles, while Mg and Si are
present at the cavities where residual particles are present. Zn
appears to be distributed in both the alloy matrix and the
particles. ............................................................................................. 134

8
List of Figures

Figure 6-4 : SEM-EDX line scan measurement on intermetallic particles


on the AA 7075-T6 alloy surface. (a,b) Scanning electron
micrographs (backscattered electrons). (c) EDX line-scan
analysis. .............................................................................................. 135
Figure 6-5: SEM-EDX mapping analysis of AA 7075-T6 alloy. (a)
Micrograph of the surface revealing the presence of intermetallic
particles. (b) Aluminium. (c) Zinc. (d) Silicon. (e) Magnesium.
(f) Manganese. (g) Iron. (h) Copper. .................................................. 136
Figure 6-6: SEM-EDX mapping analysis of AA 7075-T6 alloy at the
region shown previously in Fig 6-3. (a) Micrograph of the
surface (b) Aluminium. (c) Zinc. (d) Manganese. (e) Copper. (f)
Iron. (g) Magnesium. (h) Silicon. ...................................................... 137
Figure 6-7: Results of SEM-EDX spot analysis of different area of the
matrix of AA 7075-T6 alloy. (a) and (c) Scanning electron
micrographs showing the location of the analysis region. (b) and
(d) EDX spectrum. ............................................................................. 138
Figure 6-8: Results of low angle X-ray diffraction measurments for the as-
received AA 7075-T6 alloy................................................................ 139
Figure 6-9: Anodic potentiodynamic polarization scan of the as-received
and polished AA 7075-T6 alloys, in deaerated 0.1 M NaCl. The
scan starts at point 1 and terminates at point 2. Point A shows the
corrosion potential (Ecorr), while point B shows pitting potential
(Epit). Point C shows second breakdown potential on AR-
polished alloy. .................................................................................... 140
Figure 6-10: Scanning electron micrographs (BSE) of cross-sections of
AA 7075-T6 alloy after immersion in 0.1 M NaCl, open to the
air, for 24 h. (a, c) Low magnification images. (b, d) Increased
magnification images of (a, c). Images (a, b) reveal pitting
corrosion adjacent to intermetallic particles on the alloy surface.
Images (c, d) show pits free of second phases. .................................. 141
Figure 6-11: Scanning electron micrographs of the top surface of the AA
7075-T6 alloy before and after immersion in EXCO solution for
180 minutes. (a, b) AR alloy before immersion. (c, d) AR alloy
after immersion. ................................................................................. 142
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List of Figures

Figure 6-12: Scanning electron micrographs (BSE) of cross-sections of the


AA 7075-T6 alloy after immersion in EXCO solution for (a) 30,
(b) 60, (c) 90 and (d) 120 minutes. .................................................... 143
Figure 7-1: Schematic illustration of the excimer laser that shows the
focusing of the laser beam onto the surface of the alloy sample
that is placed on a motorised holder allowing movements in the
X and Y directions. ............................................................................ 150
Figure 7-2: Schematic diagram representing the laser scanning pattern and
the incidence of the laser pulse on specimen surface......................... 151
Figure 7-3: Scanning electron micrographs (backscattered electron) of
cross-sections of the LSM AA 7075-T6 alloy after treatment with
high pulse energy density (10 J/cm2), using 10 (a), 25 (b), and 50
(c) pulses. ........................................................................................... 152
Figure 7-4: Scanning electron micrographs (secondary electron) of the top
surface of LSM AA 7075-T6 alloy, after treatment with low
pulse energy density. (a) 10 pulses, (b) 25 pulses, (c) 40 pulses
and (d) 50 pulses ................................................................................ 153
Figure 7-5: Scanning electron micrographs (BSE) of cross-sections of the
LSM AA 7075-T6 alloys treated with low pulse energy density
(3.3 J/cm2), using 70 (a), 80 (b) and 90 (c) pulses. ............................ 154
Figure 7-6: Average thickness of the laser melted layer and the largest
pore size in LSM AA 7075-T6 alloy vs. the number of pulses
(NOP), as determined from scanning electron micrographs of
cross-sections for laser-treatments, using high and low energy
densities. ............................................................................................. 155
Figure 7-7: Potentiodynamic polarisation scans in deaerated 0.1 M NaCl
solution of the as-received (AR) AA 7075-T6 alloy and after
LSM using a high energy density (10 J/cm2), with 10, 25 and 50
pulses. ................................................................................................. 156
Figure 7-8: Potentiodynamic polarisation scans in deaerated 0.1 M NaCl
condition of the as-received (AR) AA 7075-T6 alloy and after
LSM with high energy density (10 J/cm2), using 10, 25 and 50
pulses, and with low energy density (3.3 J/cm2), using 70, 80 and
90 pulses. ............................................................................................ 157
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List of Figures

Figure 8-1: Scanning electron micrographs (SE) of the top surface of the
AA 7075-T6 alloy after LSM using 80 pulses. (a), (b), (c) and (d)
show images at increasing magnification. The laser track
direction and the overlap region (10 %) are indicated. ...................... 166
Figure 8-2: Scanning electron micrographs (BSE) of the AA 7075-T5
alloy after LSM. (a) Alloy with and without treatment by LSM.
(b) Untreated alloy, revealing the presence of intermetallic
particles. (c) Alloy after LSM treatment. ........................................... 167
Figure 8-3: Scanning electron micrographs (SE) of the top surface of the
AA 7075-T6 alloy after LSM using 80 pulses. (a) and (b) show
laser tracks, re-heating and overlap regions. (c) Higher
magnification in overlap region. (d) and (e) Higher magnification
in re-heating area. ............................................................................... 168
Figure 8-4: Results of SEM-EDX spot analysis of the AA 7075-T6 alloy
after LSM. (a) EDX spectrum. (b) Scanning electron micrograph
showing the location of the analysis region. (c) Elements in
weight and atomic percentages. ......................................................... 169
Figure 8-5: Results of SEM-EDX spot analysis of a different area of the
LSM AA 7075-T6 alloy from that shown in Fig 8-4. (a) EDX
spectrum. (b) Scanning electron micrograph showing the location
of the analysis region. (c) Elements in weight and atomic
percentages. ........................................................................................ 170
Figure 8-6: Scanning electron micrographs of cross-sections of the AA
7075-T6 alloy after LSM using 80 pulses. (a) and (c) Secondary
electrons. (b) and (d) Backscattered electrons. .................................. 171
Figure 8-7: High magnification scanning electron micrographs showing a
cross-section of AA 7075-T6 alloy after LSM using 80 pulses. ........ 172
Figure 8-8: Scanning electron micrographs (BSE) of a cross-section of the
AA7075-T6 alloy after LSM, with the presence of a thin melted
layer on the alloy surface indicated in (a) and (b). Higher
magnification images in (c) and (d) show the thinner melted layer
produced above a large second phase particle that was partially
dissolved after LSM treatment. .......................................................... 173

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List of Figures

Figure 8-9: SEM-EDX mapping analysis of Fig 8-8 (d) showing the LSM
layer and the alloy matrix in (a), and the imaging of Al (b), Zn
(c), Cu (d), Fe (e), and Mg (f). ........................................................... 174
Figure 8-10: Scanning electron micrographs (BSE) of cross-sections of the
AA 7075-T6 alloy after LSM using 80 pulses, showing the laser
melted layer in more detail, disclosing porosity in the layer with
pores of dimension about 1 µm. ......................................................... 174
Figure 8-11: Transmission electron micrographs of ultramicrotomed cross-
sections of the AA 7075-T6 alloy after LSM using 80 pulses.
Micrographs (a) and (b) reveal the LSM layer and alloy matrix
with pores indicated by arrows in laser-treated layer. Micrograph
(c) shows bands in LSM layer, which are due to the presence of
precipitates. The bands are separated by distances of 0.3 to 0.4
μm. ..................................................................................................... 175
Figure 8-12: Transmission electron micrographs of an ultramicrotomed
cross-section of the AA 7075-T6 alloy after LSM using 80
pulses. (b) Higher magnification of (a). The Fig. shows the
interface region, as indicated by arrows in red, between the LSM
layer and the alloy matrix. The arrows in white and black show
pores and scratches in the LSM layer. ............................................... 176
Figure 8-13: TEM-EDX spot analysis of the micrograph cross-section of
Fig. 8-12 (b); the 5 locations of EDX analysis are indicated in
(a). ...................................................................................................... 177
Figure 8-14: High angle annular dark field (HAADF) images of an
ultramicrotomed cross-section of the AA 7075-T6 alloy after
LSM using 80 pulses. (b) Higher magnification of (a). (c) Results
of of EDX analysis of (b). .................................................................. 178
Figure 8-15: Low angle XRD analysis of the AA 7075-T6 alloy after LSM
using 80 pulses. .................................................................................. 179
Figure 8-16: Low angle XRD analysis for both as-received and LSM AA
7075-T6 alloy treated with 70, 80, and 90 pulses. ............................. 180
Figure 8-17: Potentiodynamic polarization scans in deaerated 0.1 M NaCl
for AA 7075-T6 alloy and after LSM using 80 pulses. ..................... 181

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List of Figures

Figure 8-18: Scanning electron micrographs of the AA 7075-T6 alloy after


LSM using 80 pulses and immersion in 0.1 M NaCl, open to air,
for 24 h. The Fig. reveals that no evidence of corrosion product
in low magnification (a, b) and high magnification (c, d) images. .... 182
Figure 8-19: Scanning electron micrographs (BSE) of the AA 7075-T6
alloy after LSM using 80 pulses and immersion in naturally-
aerated EXCO solution for (a) 30, (b) 60, (c) 120, (d) 150 and (e)
180 min. The cross-sections of the laser surface treatment alloys
(a-d) reveal no corrosion products after immersion for 150 min.
With increasing time of immersion, corrosion causes
delamination of the LSM layer, as evident in (e). .............................. 183
Figure 8-20: Scanning electron micrographs of cross-sections of the AA
7075-T6 alloy in the as-received condition and after laser-surface
treatment (LT) using 80 pulses, following immersion in (EXCO)
solution for 30 min (a, b) and 60 min (c, d). ...................................... 184
Figure 8-21: Scanning electron micrographs of cross-sections of the AA
7075-T6 alloy in the as-received condition and after laser surface
treatment alloys using 80 pulses and immersion in EXCO
solution for 120 min (a, b) and 150 min (c, d). .................................. 185
Figure 8-22: Scanning electron micrographs of cross-sections of the AA
7075-T6 alloy in the as-received condition (a, c) and after laser
surface treatment (b, d) using 80 pulses immersion in EXCO
solution for 180 min. .......................................................................... 186
Figure 8-23: Scanning electron micrographs of LSM AA 7075-T6
revealing micro-cracks in the re-heating area of the 1st laser track
as in (a) and (b), while (c) and (d) show micrographs of cross-
sections after exfoliation testing for 180 min..................................... 187
Figure 9-1: Current density (I) vs time (s) behaviour of the as-received
(AR) and LSM AA 7075-T6 alloy during anodising at 12 V
(SCE) in 0.46 M H2SO4 at 295 K for (a) 240 s, (b) 720 s, and (c)
1200 s. ................................................................................................ 193
Figure 9-2: Scanning electron micrographs of the top surface of the LSM
AA 7075-T6 alloy after anodising at 12 V in 0.46 M H2SO4 at
295 K for 1200 s; (a) the overlap area in the second-laser track
13
List of Figures

and the reheating area in the first-laser track; (b) high


magnification of the reheating area; (c) high magnification of the
overlap area. The arrows in (c) show the micro-cracks in the re-
heating region. .................................................................................... 194
Figure 9-3: Results of SEM-EDX spot analysis of the LSM AA 7075-T6
alloy following anodising. (a) Scanning electron micrograph
showing the location of the analysis region. (b) EDX spectrum.
(c) Elements in weight and atomic percentages. ................................ 195
Figure 9-4: Results of SEM-EDX spot analysis of the LSM AA 7075-T6
alloy following anodising. (a) Scanning electron micrograph
showing the location of the analysis region. (b) EDX spectrum.
(c) Elements in weight and atomic percentages. ................................ 196
Figure 9-5: Results of SEM-EDX spot analysis of the LSM AA 7075-T6
alloy following anodising. (a) Scanning electron micrograph
showing the location of the analysis region. (b) EDX spectrum.
(c) Elements in weight and atomic percentages. ................................ 197
Figure 9-6: Scanning electron micrographs of cross-sections of the LSM
AA 7075-T6 alloy following anodising in sulphuric acid for 1200
s. (b) High magnification of (a). ........................................................ 198
Figure 9-7: Transmission electron micrograph of an ultramicrotomed
cross-section of LSM AA 7075-T6 alloy anodised at 12 V in 0.46
M H2SO4 at 295 K for 1200 s. (b) High magnification of (a). ........... 199
Figure 9-8: Scanning electron micrographs of cross-sections of the as-
received AA 7075-T6 alloy following anodising in sulphuric acid
for 1200 s. (a) to (d) show images at different locations of the
alloy surface. ...................................................................................... 200
Figure 9-9: Potentiodynamic polarization tests in deaerated 0.1 M NaCl
solution of the as-received (AR) AA 7075-T6 alloy, laser surface
treated (LSM) alloy, and following anodising in 0.46 M H2SO4
for 1200 s. (LSM+Anod., AR+Anod.). .............................................. 201
Figure 9-10: Scanning electron micrographs of top surface of the anodised
AA7075-T6 alloy after EXCO corrosion test for an exposure
time of 180 min. (b) shows high magnification image of (a). (c)

14
List of Figures

shows high magnification image of the location marked with


yellow arrow. ..................................................................................... 203
Figure 9-11: Scanning electron micrographs of cross-sections of the
anodised AA7075-T6 alloy after EXCO corrosion test for an
exposure time of 180 min. (a), (b) and (c) are images at
increasing magnification. ................................................................... 204
Figure 9-12: Scanning electron micrographs of the top surface of the
anodised LSM AA 7075-T6 alloy after EXCO testing for a time
of 180 min. (a) overlap and reheating areas. (b, c) middle of
laser-treated layer. .............................................................................. 205
Figure 9-13: Scanning electron micrographs of cross-sections of the
anodised LSM AA7075-T6 alloy after EXCO corrosion test for
an exposure time of 180 min. (a) to (d) are images at increasing
magnification. .................................................................................... 206

15
List of Abbreviations
A* Ageing
A Area
AA Aluminium alloy
AR As received
AEL Accessible emission limit
ASM American society of materials
ASTM American standard for testing materials
B Brightness
BCC Body centred cubic
BSD Berkeley software distribution
BSE Back-scattered electron
c Velocity of light
CR Corrosion rate
CO2 Carbon dioxide
CW Continuous wave
D Density
DC Direct current
Ecorr Corrosion potential
E° Standard potential
Ee Electrode potential
Epit Pitting potential
Epass Passive potential ranges
EDX Energy dispersive X-ray
EXCO Exfoliation corrosion
f Focal length
F Farady’s constant
FCC Face centred cubic
FEG-SEM Field energy gun scanning electron
microscopy
G Thermal gradients
GL Thermal gradient of liquid
GS Thermal gradient of solid
∆G Total Gibbs free energy
GP Guinier preston zone
HAADF High angle annular dark field

16
List of Abbreviations

HAZ Heat affected zone


HRTEM High resolution transmission electron
microscopy
I Current density
Icorr Corrosion current density
Ipass Passive current density
IGC Intergranular corrosion
K Equilibrium constant
KrF Krypton fluoride
lcoh Coherence length
LSM Laser surface melting
M Mole
MEP Maximum permissible exposure
n Index of refraction
Nd-YAG Neodymium-doped yttrium aluminium
garnet
NOP Number of pulses
OCP Open circuit potential
P Power
Pp Peak power
PFZ Precipitate free zone
pH Hydrogen ion activity
r* Critical growth radius
R Gas constant
R* Growth rate
PRF Pulse repetition frequency (Hz)
q Emitted power
Q Quenching
RRA Retrogression and re-ageing
SCC Stress corrosion cracking
SCE Saturated calomel electrode
SDZ Solute-depleted zone
SE Secondary electron
SHT Solution heat treatment
SKPFM Scanning Kelvin probe force microscopy
SSSS Supersaturated solid solution

17
List of Abbreviations

t Pulse duration
tcoh Coherence time
T Temperature
Tb Boiling temperature
Tf Freezing temperature
Tm Melting temperature
∆T Thermal undercooling
Tin Interaction time
TEM Transmission electron microscopy
UV Ultraviolet
V Vapour
XeCl Xenon monochloride
-
xe Number of electrons
XRD X-ray diffraction
θ Scattering angle
2θ Diffracted angle
θB Brewster angle
ω Beam waist radius
σ Stefan-Boltzmann constant
λ Wavelength
βa Tafal anodic slop
βc Tafal cathodic slop
η Over-voltage polarization
Ω Solid angle
at.% Atomic percent
wt.% Weight percent

18
Abstract

High strength 7xxx aluminium alloys are used extensively in the aerospace

industry because the alloys offer excellent mechanical properties. Unfortunately,

the alloys can suffer localised corrosion due to the presence of large intermetallic

particles at the alloy surface that are aligned in the rolling direction. Laser

surface melting (LSM) techniques offer the potential to reduce and/or to

eliminate the intermetallic phases from the surface of the alloy without affecting

the alloy matrix.

The present study concerns the application of LSM using an excimer laser to

enhance the corrosion resistance of AA 7075-T6 aluminium alloy. The initial

stage of the project was aimed at optimising the laser conditions for production

of a uniform microstructure, with the increase in the corrosion resistance of the

alloy being determined by potentiodynamic polarization measurements in sodium

chloride solution. Low and high laser energy densities were used with a different

number of pulses per unit area to treat the alloy surface, which were achieved by

changing both the laser fluence and the pulse repetition frequency. A laser

fluence of 3.3 J/cm2 with 80 pulses was subsequently selected as the optimum

condition to treat the surface of the alloy. The composition and microstructure of

the alloy before and after LSM treatment, and following corrosion tests, were

characterized by scanning electron microscopy (SEM), transmission electron

microscopy (TEM) and X-ray diffraction (XRD).

After the laser treatment, the surface and the cross-sections of the alloy showed a

significant reduction in the number of large intermetallic particles and a

19
List of Abbreviations

relatively homogenous melted layer was generated that provided significant

improvement in the resistance of the alloy against corrosion, as assessed by

several corrosion test methods, including exfoliation corrosion (EXCO) tests.

However, delamination of the melted layer was observed after extended testing

in the EXCO solution which is possibly related to the formation of bands of fine

magnesium and zinc-rich precipitates within the melted layer. Therefore,

anodising in sulphuric acid was applied to the LSM alloy, in order to further

increase the corrosion resistance and to protect the laser treated layer from

delamination by generating a thin oxide film over the LSM layer. The results

revealed that the anodic treatment increased the resistance of the alloy to

exfoliation attack.

20
Declaration

No portion of the work referred to in this thesis has been submitted in support of
an application for another degree or qualification of this or any other university
or any other institution of learning.

Bader M H M Elkandari
(2012)

21
Copyright Statement

i. The author of this thesis (including any appendices or schedules to this


thesis) owns any copyright in it (the Copyright) and he has given The
University of Manchester the right to use such Copyright for any
administrative, promotional, educational and/or teaching purposes.

ii. Copies of this thesis, either in full or in extracts, may be made only in
accordance with the regulation of the John Rylands University Library of
Manchester. Details of these regulations may be obtained from the
Librarian. This page must form part of any such copies made.

iii. The ownership of any patents, designs, trade marks and any and all others
intellectual property right except for the Copyright (the “Intellectual
Property Rights”) and any reproductions of copyright works, for example
graphs and tables (“Reproduction”), which may be described in this
thesis, may not be owned by the author and may be owned by third
parties. Such intellectual Property Right and Reproduction cannot and
must not be made available for use without the prior written permission of
the owner(s) of the relevant Intellectual Property Right and/or
Reproductions.

iv. Further information on the conditions under which disclosure, publication


and commercialisation of this thesis, the Copyright and any Intellectual
Property and/or Reproductions described in it may take place is available
in the University IP Policy in any relevant Thesis restriction declarations
deposited in the University Library, The University Library‘s regulations
(see http://www.manchester.ac.uk/library/aboutus/regulations) and in The
University‘s policy on presentation of Theses.

22
Acknowledgments

First, I would like to gratefully acknowledge my supervisor, Professor Peter

Skeldon, for his guidance and patience throughout my graduate study at the

University of Manchester. I appreciate his time available and the time he gave

me to learn from him. I would be impossible to finish this thesis without his

inspiration, encouragement and advice. I would like to thank my second advisor,

Dr. Zhu Liu, for her valuable comments and suggestions, precisely on the laser

field. I would like also to thank the staff and technicians of the school of

materials, particularly, the technicians of the Corrosion and Protection Centre for

their help, guidance and cooperation during the experimental work (namely Chris

Wilkins for SEM, Teruo Hashimoto for TEM, Judith for XRD, Shirley for SEM,

and Gary for XRD). I would like to thank my friends who always encouraged me

during my study until I finished my thesis (namely Zakria Aburas, Ramadan

Abuaisha, Mohsen Rakhes, Abdeslam Mhich, Ahmed Limnifi, Ahmed Shieki,

and Wei Go). I would like to thank my father, mother and wife for their

supportive and patience with all my problems. I appreciated their understanding

and hospitality. Finally, I would like to take this opportunity to thank the Public

Authority for Applied Education and Training (PAAET) back in Kuwait for their

financial support of my PhD study at the University of Manchester in the United

Kingdom.

23
Chapter 1 Introduction

1.1 Rational of the Research Project

7xxx series aluminium alloys have many applications, notably in aerospace

construction, due to the excellent properties of the alloys, including high strength

and low density. Unfortunately, these alloys may be highly susceptible to

localised corrosion in the presence of aggressive environments containing

chlorides. It has been reported that different alloying elements such as

magnesium, zinc, copper and iron can have great influences on the corrosion

properties of the alloy [1-5].

Aluminium alloy 7075-T6 contains a large number of intermetallic particles,

which are either developed purposely to improve the mechanical properties or

are present as impurities that can lead to localised corrosion, i.e. pitting and

intergranular attack [6-12]. In order to reduce the localised corrosion of the alloy,

a number of surface protection methods have been applied [13, 14]. However,

none of these protecting methods have significantly reduced the corrosion

problems without affecting the other properties of the alloy. For example,

methods of surface protection using thermal and heat treatments can affect the

composition of the alloy (bulk properties) and reduce its strength due to

difficulties in controlling the temperature [15-17]; cladding increases the

resistance to stress corrosion cracking, but causes a reduction in fatigue life and

microhardness [18, 19]. Further chemical protecting techniques, such as chromic

24
Introduction

acid anodising (CAA), can be highly toxic and potentially damaging to the

environment.

Therefore, it is important to improve the corrosion resistance of the AA 7075-T6

alloy by eliminating or reducing the sizes of the large second phases on the

surface of the alloy, without affecting its bulk properties. At the same time, a

process is required that has no damaging effect on the environment.

1.2 Research Objectives

In this study laser surface melting (LSM) is employed, using an excimer laser,

which allows modification of the alloy surface structure without reducing the

bulk properties of the alloy [20-26]. The use of the excimer laser associated with

a high cooling rate, hence leading to rapid solidification, can significantly reduce

the number of intermetallic particles on the surface of the alloy. Such particles

have a high cathodic activity compared with the alloy matrix. For example, the

presence of large intermetallic particles rich in copper and iron can promote the

formation of micro-galvanic couples with the adjacent matrix, leading to

preferential dissolution of the alloy matrix [27]. On the other hand, the

microstructure of the alloy surface is homogenised under the short pulse duration

(~ 13 ns) of UV radiation of the excimer laser that can dissolve the large second

phase particles and redistribute the elements within the solidification layer in

very short times (less than 1 μs). Further improvement in the corrosion resistance

may be expected if LSM is combined with other protection methods, such as

anodising. Thus the objectives of the present project are to optimise the laser

processing conditions to generate uniform melted layers, free of large second

25
Introduction

phases; to assess the corrosion resistance of the laser treated surface in

comparison with the untreated alloy using several corrosion test methods; and to

explore the possibility of further improving the corrosion resistance by anodising

of the laser treated surface.

1.3 Thesis Layout

The first part of this thesis, after the introduction (Chapter 2), is a literature

review of aluminium and aluminium alloy properties, with a focus on 7xxx

aluminium alloys including heat treatments, age hardening, tempering and

hydrogen effects. The fundamental understanding of localised corrosion of 7xxx

alloys, including the effect of microstructure, potential, temper and environment

will be discussed in Chapter 3. This part will further explain the general forms of

corrosion attack and corrosion problems of 7xxx alloys, and the methods of

corrosion prevention. Chapter 4 will consider LSM techniques and their use with

aluminium alloys. Methods of heating, cooling and rapid solidification by LSM

will be described and reviewed. Safety aspects of using a laser are briefly

explained also. Chapter 5 is devoted to the experimental study, including the

characterization of the alloy that is used in this project (AA 7075-T6). The

surface preparation of the alloy for the laser treatment, as well as anodising

details of the procedure, will be explained. Furthermore, the methods of

corrosion evaluation, including potentiodynamic polarization, immersion and

exfoliation (EXCO) tests will be described. The methods used in material

characterisation before and after LSM, as well as before and after corrosion tests,

including field energy gun scanning electron microscopy (FEG-SEM),

transmission electron microscopy (TEM) and X-ray diffraction (XRD) will be

26
Introduction

explained. Chapter 6 presents the results of the surface and microstructure

examinations of the as-received (AR) AA 7075-T6 alloy before and after

corrosion testing. Chapter 7 shows the results of optimisation of the laser

operation conditions of the AA 7075-T6 alloy. Chapter 8 presents the results of

the LSM AA 7075-T6 alloy in terms of surface and cross-section analyses before

and after corrosion evaluation tests. The results are compared with those of the

as-received alloy results to show the differences in corrosion behaviour of the

laser-treated and untreated alloys. Chapter 9 provides the results for the

anodising of the LSM alloy in 0.4 M sulphuric acid (H2SO4) and the evaluation

of the corrosion behaviour of the LSM alloy with and without anodising. Chapter

10 will discuss the overall findings for the AR, LSM and the LSM anodised

alloys. Finally, the conclusions and suggestions for future work are given in

Chapter 11.

27
Introduction to Aluminium Alloys

Chapter 2 Literature Review

2. Introduction to Aluminium Alloys

Aluminium is the second most used metal after steel. It is bright, shiny, and light.

It is in group 3 on the periodic table. Pure aluminium has a face centred cubic

(FCC) crystal structure. Aluminium has an excellent electric conductivity, high

strength to weight ratio, with a specific weight of 2.7 g/cm³, which is about one-

third that of steel and has high corrosion resistance [4]. It has many applications,

especially in combination with other elements to form high strength alloys.

Aluminium alloys such as 7xxx alloys and 2xxx alloys have the ability to

withstand high temperature and pressure, which has advanced the use of such

materials in aerospace applications, where aluminium alloys play an important

part in aeroplane structures. For example, AA 7075-T6 is used in aeroplane wing

structures and AA 2024-T3 is used in the fuselage [4, 28].

Aluminium alloys are divided into wrought and cast products. Cast alloys are

directly cast into their final form by one of various methods, such as sand-

casting, die or pressure die casting. Wrought alloys are initially cast as ingots or

billets and subsequently hot and/or cold worked mechanically into the final

desired form. There are 9 series of wrought alloys. These are designated by a 4

digit number that may be preceded or followed by letters. The first digit indicates

the alloy group number. The second digit indicates alloy modifications. The third

and fourth digits indicate the aluminium purity. For example, 7xxx alloys are in

group number 7 as zinc is the main alloying element with additions of minor

28
Introduction to Aluminium Alloys

percentages of other elements, such as silicon, magnesium, copper...etc. Table 2-

1 provides details of the aluminium alloy classification system [29].

In order to specify the thermal processing in the alloys, a system of thermal

temper nomenclature has been designed to distinguish between one alloy temper

and another. The letter T and accompanying digits are added as suffixes to the

alloy number to distinguish the temper. For example, T6 in aluminium alloy

7075-T6 is used to distinguish solution heat treatment and then artificially

ageing, whereas T7 in aluminium alloy 7150-T7 is related to solution heat-

treatment and artificially over-ageing. The mechanical properties of 7xxx alloys

at different tempers are given in Table 2-2. Further discussion will be given of

the stages of heat treatment of AA 7xxx alloys and temper effects later in this

Chapter.

Adding elements such as copper, zinc and magnesium to the aluminium to form a

super-saturated solid solution (SSSS), by different heat treatment cycles, can

improve the strength properties, but at the same time this will alter other

properties, such as corrosion resistance. For example, alloys of the AA 7xxx

series are very strongly heat treatable, due to precipitation hardening based on

combination of zinc and magnesium, but the corrosion resistance is decreased.

Adding other elements, such as copper with a small amount of chromium, into

aluminium-zinc-magnesium alloys can result in the highest strength aluminium

alloys available [28]. However, copper decreases the general corrosion

resistance. In contrast, the stress corrosion cracking (SCC) resistance increases

29
Introduction to Aluminium Alloys

with a small addition of chromium. Table 2-3 presents more details on the solid

solubility of the major elements and their effects on the alloy properties.

Different types of localised corrosion, such as pitting, intergranular (IGC) and

exfoliation corrosion, and stress corrosion cracking (SCC), have been found in

different areas of wing structures made of 7xxx aluminium alloys [28]. These

forms of localised corrosion initiate at local sites and accelerate to cause a failure

of the structure. For that reason, the microstructures of 7xxx aluminium alloys

have been investigated by many researchers and much information has been

reported that will be reviewed in detail in the next section.

2.1 7xxx Aluminium Alloys

7xxx series aluminium alloys, or more precisely Al-Zn-Mg-Cu alloys, have been

investigated extensively over several decades. Rosenhain and his colleagues at

the National Physical Laboratory in Britain in 1917 obtained a high tensile

strength of around 580 MPa for an alloy composition of Al-20%Zn-2.5%Cu-

0.5%Mg-0.5%Mn. In comparison, the tensile strength of Duralumin (Germany)

was around 420 MPa. For the next two decades, the alloy seemed to be

unsuitable for structural use due to a high susceptibility to intergranular corrosion

(IGC) and stress-corrosion cracking (SCC). However, because of the major

importance of Al-Zn-Mg-Cu alloys for aerospace construction, these corrosion

problems have attracted continuing research [28].

AA 7075 in the T6 temper condition has an heterogeneous microstructure,

consisting of an Al matrix, second phase particles and grain boundary regions.

30
Introduction to Aluminium Alloys

Mg(ZnCuAl)2 particles, with size about 50-100 nm, have been observed at the

grain boundaries using transmission electron microscopy (TEM) [5, 30]. On

either side of the grain boundary is a precipitate-free zone (PFZ) or solute-

depleted zone (SDZ), about 30-70 nm wide and zinc and copper were usually

found to be depleted in this region [10, 31].

Second phase particles in the alloy matrix usually fall into three categories,

hardening precipitates, dispersoids, and constituent particles. Hardening

precipitates are formed by nucleation and growth from supersaturated solid

solution (SSSS); their sizes range from several to tens of nanometres [4]. For

example, η and other precipitates forms, such as Mg2Al3, Al2Cu, and Al32Zn49,

have been observed in the grain boundary regions [32]. Dispersoids are used to

retard recrystallization and control the grain size; they contain aluminium and

other elements such as chromium, titanium, manganese, and zirconium. Their

sizes are bigger than precipitates, with sizes up to several hundred nanometres.

Typical dispersoids are Al3Ti, Al6Mn, Al20Cu2Mn3 and Al3Zr [4, 32]. Constituent

particles are relatively large and can be seen easily by optical microscopy or

scanning electron microscopy (SEM). These particles form during solidification

and survive subsequent heat treatment. Their sizes range from a few tenths of a

micron up to tens of microns, and these particles often break into smaller

particles during hot or cold working and align along the working direction. Such

particles in AA 7075 alloys consist of Al3Fe, Al2Cu, Al7Cu2Fe, and Mg2Si [4, 32,

33].

31
Introduction to Aluminium Alloys

The alloys have been studied over a wide range of heat treatment processes. AA

7075 with T73 temper shows a fine dispersion of η precipitates through

nucleation from pre-existing GP zones, with improvement in SCC; however, the

tensile properties are about 15% below those AA 7075 with the T6 temper [34].

Another duplex ageing treatment, T76, has been applied successfully to 7xxx

alloys to increase the resistance to exfoliation corrosion, but again the alloy

strength is decreased [28]. Other researchers have successfully achieved a

combination of high resistance to SCC with maximum levels of tensile properties

by adding 0.25-0.4% silver to Al-Zn-Mg-Cu alloys, enabling a high response to

age-hardening to be achieved in single ageing treatment at 160-170˚C [28, 50].

More recently, AA 7050 (Al-6.2%Zn-2.25%Mg-2.3%Cu-0.12%Zr) was

developed in the United States in which the level of copper present in the alloy

was raised in order to increase the strength with a second stage of T73 treatment.

The presence of large intermetallic compounds can be minimised by increasing

the limit of copper content, but with adverse effect on toughness and tensile

properties. Modelling indicates that the sum of Cu + Mg wt% should be < 3.6%

for an alloy containing around 6% Zn. Another heat treatment, known as

retrogression and re-ageing (RRA), has been developed that enables alloys such

as AA 7075 to exhibit a high level of tensile properties expected of the T6

condition combined with a resistance to SCC equal to that of the T73 condition

[35, 51]. The process has been given a temper designation T77 and can be

applied to highly alloyed compositions such as AA 7055 (Al-8%Zn-2.05%Mg-

2.3%Cu-0.16%Zr) that has been used for structural members of the Boeing 777

wings [35].

32
Introduction to Aluminium Alloys

As mentioned above, heat treatment processing of 7xxx aluminium alloys can

result in improved resistance to SCC but with adverse influence on toughness

and strength. At the same time, difficulties in controlling the temperatures and

the level of deformation can cause a problem in the material decomposition

during age-hardening processes [36].

Compositional changes such as a reduction in the levels of iron and silicon

impurities in alloy AA 7075 (0.9%), with a maximum combined amount of

0.22% in the higher purity alloy AA 7475, can improve the alloy toughness. [37]

Furthermore, in AA 7475 the manganese content is reduced, from 0.3% to 0.06%

(maximum), whereas the content of other alloying elements is essentially the

same as in AA 7075. The size and number of intermetallic particles, that assist

crack propagation, is reduced and similar tensile properties are obtained as with

the T735 heat treatment [35, 36]

Another modification has utilized 0.08-0.25% zirconium as a recrystallization

inhibitor, either in place of chromium or manganese or in combination with a

smaller amount of these elements, in order to reduce quench sensitivity so that

slower quench rates can be used without loss of strength on subsequent ageing.

Examples are the alloys 7050, 7150, 7055, and the British alloy 7010 [37, 38, 39]

Modifications to alloying additions, purity, and heat treatment have allowed high

values of fracture toughness to be sustained in AA 7150-T651 and AA 7055-

T7751. However, the corrosion behaviour has not shown a significant

33
Introduction to Aluminium Alloys

improvement. One compositional trend has been to raise the Zn:Mg ratio from

2.25 for the early AA 7075 to 5.0 for the latest AA 7085. Another trend has been

to reduce the allowable limits on Mn and Cr, as well as the Fe and Si impurities,

each to below 0.1%. For example, AA 7085 alloy, with Fe < 0.08% and Si <

0.06%, has a low quench sensitivity, which enables very thick sections (150 mm)

to be heat treated, with tensile properties higher than early alloys such as AA

7050. This has been a major factor for selection of AA 7085 for large extruded

wing spars and die-forged wing rib components for the European A380 Airbus

[37, 38, 39].

Reference has already been made to the fact that 7xxx alloys tend to show a high

strength and that depends on the elements and impurities in alloy composition

and the method of heat treatment [38, 39]. However, none of these approaches to

alloy development has achieved a significant improvement of the corrosion

resistance without affecting the other alloy properties.

2.2 Elements and Impurities in 7xxx Aluminium Alloys

Alloying elements are added to 7xxx alloys mainly for precipitation hardening

[4]. Zinc and magnesium offer the highest potential for strengthening through

age-hardening, but also lead to a high susceptibility to stress corrosion cracking

(SCC) [4, 40]. Copper is added to these alloys to improve the age-hardening, as

well as to increase the resistance to SCC [2]. The process of heat treatment and

age-hardening will be described in detail in the next section of this Chapter.

34
Introduction to Aluminium Alloys

Zinc, magnesium, and copper are important alloying elements in AA 7xxx alloys.

Each of these elements results in different corrosion properties of Al when

present in solid solution. Muller and Galvele studied binary Al-Zn alloys, with

Zn content ranging from 1.07 to 4.85% [7]. They measured the breakdown

potential of these alloys with polarization in chloride solution and they found that

the shapes of the polarization curves were similar to those found with pure Al.

However, the breakdown potential decreased when Zn was present [7]. Other

studies observed similar results [8, 9, 41]. Muller and Galvele also measured the

breakdown potential of Al-Mg alloys in chloride solution [7]. Their results

showed that the breakdown potential is independent of Mg content and is close to

that pure Al. They found only aluminium inside the pit. Therefore, they

suggested that Mg would be dissolved preferentially from Al-Mg alloys. The

corrosion potential of Al-Cu alloys in chloride environment was found to

increase with increase of the Cu content [6] It is reported that addition of Cu to

Al has the opposite effect on the corrosion behaviour of adding Zn to Al [6,7].

Ramgopal and Frankel measured the repassivation potential of binary solid

solution Al-Cu alloys and observed that even with an amount as small as 0.022

wt% Cu can raise the repassivation potential by 30 mV relative to that of pure Al

[9]. Adding Cu was found to increase the dissolution kinetics because the

potential required to achieve a given current density increased with Cu content.

In addition to change in the electrochemical property, Cu also plays an important

role in the microstructure as it can alter the kinetics of precipitation reactions

[11]. Moreover, Muller and Galvele observed Cu enrichment inside the pit in a

Al-Cu binary alloy [6]. This led to the suggestion that Al is preferentially

35
Introduction to Aluminium Alloys

dissolved and Cu stays in the alloy which increases the Cu concentration locally

and affects the corrosion mechanism.

From the above studies in chloride environment, Zn lowers the breakdown

potential of Al, and Cu increases the breakdown potential of Al; however, Mg

has little effect on the breakdown potential of Al. It is reported that Mg is

dissolved preferentially from Al-Mg alloys and Al is dissolved preferentially

from Al-Zn and Al-Cu alloys [6, 7, 42]. Since Zn and Cu have opposite effects

on Al dissolution, it is possible that these two alloying elements have different

corrosion products at AA 7xxx alloys. However, the relationship is still not clear.

Second phase particles usually have different electrochemical characteristics and

different effects on the corrosion behaviour of the surrounding matrix [12]. They

can be cathodic or anodic to the alloy matrix. The presence of these phases can

lead to non-uniform attack at specific areas of the alloy surface and are often

associated with corrosion problems [4, 45]. The corrosion potential of MgZn2 (η)

phase in 1 M NaCl was measured between -1035 and -1100 mV (SCE), which

was more negative than the corrosion potential of Al (-700 mV) [43, 44].

Therefore, MgZn2 phase is active with respect to the alloy matrix. Ramgopal and

his colleagues studied the η phase as a function of Cu, Zn and Al concentration

by using a flash evaporation technique to generate thin film compositional

analogs of the intermetallics [9]. For MgZn2 with no Cu content, they observed a

sharp current increase at a potential which was close to the reversible potential of

Zn/Zn2+. They suggested that the breakdown potential of the η phase is

associated with the dissolution of Zn. By adding Cu to more than 17 at %, the

36
Introduction to Aluminium Alloys

corrosion potential increases as well as the breakdown potential. They did not

observe any change in the breakdown potential with adding to 10 at % of Cu [9].

Iron and silicon are reported to be the main impurities in commercial grade

aluminium alloys [45, 46]. The solubilities of iron and silicon are high in molten

aluminium, but are low in solid aluminium [46]. Therefore, most of iron and

silicon will precipitate out during solidification and form large second phase

particles. The iron rich particles, such as Al3Fe and Al7Cu2Fe, usually act as

cathodes on the surface of the alloy, promoting electrochemical attack. Murray et

al. reported that the presence of Cu ions in the solution would cause metallic

copper to plate onto the iron-rich particles [47]. If the matrix adjacent to the iron-

rich particles contains copper, aluminium will be dissolved and the copper will

remain inside pits and plate onto iron-rich particles, which makes the particles

more cathodic with respect to aluminium [47].

From the above investigations, second phase particles can be noble and /or active

to the adjacent matrix. Cu and Fe-rich particles can be more noble than the

matrix and act as cathodes. Mg and Zn- rich particles are more active than the

matrix and are usually dissolved preferentially. Adding aluminium to the MgZn2

phase has little effect on corrosion and breakdown potentials, while adding

copper to the MgZn2 phase will increase its corrosion and breakdown potential.

Some elements will leave the pit after being dissolved, such as magnesium, but

some will stay, such as zinc and silicon. The change in concentration inside the

pit will affect the subsequent corrosion. Overall, the presence of different second

phase particles in AA 7xxx alloys affects their corrosion behaviour strongly.

37
Introduction to Aluminium Alloys

2.3 Stages of Heat Treatment of 7xxx Aluminium Alloys

A key purpose of heat treatment is to increase the strength and hardness

(mechanical properties) of the aluminium alloys in order to achieve a final

product that can be employed in different environmental applications. For 7xxx

series aluminium alloys, the heat treatment process usually comprises three main

stages, as follows:

1- Solution heat treatment (SHT) at high temperature within a single

phase region to dissolve the alloying elements in the α-Al matrix.

2- Quenching (Q) in order to form a supersaturated solid solution (SSSS)

of the dissolved elements in the α-Al matrix.

3- Ageing (A*) at temperature below the solvus in order to control the

decomposition of the supersaturated solid solution to form a fine

dispersion of precipitates (GP zones) → (η) → (η’)

The temperature-time diagram of Figure 2-1 shows the three main stages of the

heat treatment process, with the precipitation scheme, for the AA 7xxx alloys.

Solution heat treatment involves heating the aluminium alloy above the solvus

temperature so that all the constituents are taken into the solid-solution (α-Al).

During quenching, if the alloy were slowly cooled, β-phase would nucleate and

grow at heterogeneous sites to form an equilibrium α + β structure. A faster

quenching rate reduces the time for diffusion and freezes the alloying elements in

the non-equilibrium α-phase structure, forming a supersaturated solid solution

(SSSS). Upon ageing, the SSSS will tend to transform toward an equilibrium

38
Introduction to Aluminium Alloys

structure and form a fine dispersion of Guinier Preston zones (GP zones). In AA

7xxx alloys, the GP zones are reported usually, to have spherical shapes, while η

(MgZn2) is hexagonal [48]. Commonly used heat treatments in AA 7xxx series

alloys are T6 and T7 tempers. The T6 temper provides a peak aged condition,

which has the maximum strength [4]. It is achieved by SHT with about 465 °C

and Q, followed by a single stage heat treatment at temperatures in the range

120-135 °C for 24 h [49]. The tensile strength can reach around 550-610 MPa,

depending on the alloy composition [4].

Unfortunately, AA 7xxx alloys in the T6 temper have a relatively low resistance

to SCC. To improve the SCC resistance, a duplex heat treatment or over-aging

T7 temper was developed. It involves two steps of artificial aging treatment. The

first step is at 107-120 ˚C for a few hours to nucleate GP zones [49]. The second

step is at 160-170 ˚C and produces a refined dispersion of particles (η’) from the

pre-existing GP zones [49]. The refined dispersion of particles reduces the

strength by about 15% from that in T6 temper, but was reported to increase the

resistance to SCC [4, 52].

2.3.1 Age Hardening

In age hardening, the complete decomposition of the SSSS usually occurs by a

complex process, which may involve several stages, initially involving formation

of Guinier-Preston (GP) zones, a solute rich groups of atoms. They retain the

structure of the alloy and are coherent with the matrix. Diffusion associated with

their formation involves the movement of atoms over short distances, assisted by

vacant lattice sites that are present due to quenching [28]. Depending on the alloy

39
Introduction to Aluminium Alloys

composition, the rate of nucleation of the GP zones may be influenced by the

presence of the excess vacant lattice sites. On the other hand, the intermediate

precipitates are much larger in size than the GP zones and are only partly

coherent with the lattice planes of the matrix. When a critical dispersion of the

GP zones or intermediate precipitates, or a combination of both, occurs,

maximum hardening in commercial alloys can be achieved. For increased

stability of the alloys, the GP zones solvus lies between the quench-bath

temperature and the ageing temperature. This gives an advantage of nucleation of

intermediate precipitates from pre-existing GP zones (duplex ageing treatment)

that can improve the SCC resistance in high strength aluminium alloys [28].

2.3.2 Precipitate Free Zones (PFZ)

Precipitate free zones (PFZ) can be formed in alloys during ageing. A narrow

region (~50 nm) on either side of the grain boundary is depleted of solute due to

diffusion of solute atoms to the boundary where relatively large precipitates are

formed [10, 50]. The PFZ arises because of a depletion of vacancies to levels

below that needed to assist with nucleation of precipitates at the particular ageing

temperature. Higher solution heat treatment temperature and faster quenching

rate to a lower aging temperature, usually below the solvus, increase the excess

vacancy content and narrow the PFZs. At the same time, the concentration of the

solute becomes higher, that means that smaller nuclei are stable. This will reduce

the critical vacancy concentration required for nucleation to occur. Therefore, the

vacancy depleted part of PFZ cannot be formed in alloys aged at temperatures

below the GP zones solvus, as the GP zones can form homogeneously with no

need of vacancies. Viana et al. observed the microstructure of AA 7075-T6 by

40
Introduction to Aluminium Alloys

TEM and found very fine precipitates distributed homogeneously inside the

grains and coarser continuous precipitates distributed at the grain boundaries

[51]. Puiggali [52] and Ramgopal [10] found precipitates in AA 7010-T6 and

AA7150-T6 to be of size up to 50 nm in the matrix and from 50 to 120 nm at the

grain boundaries. The width of the PFZ is about 30 nm [10, 52]. The precipitates

at the grain boundaries for the T7 temper are coarser and more spaced than with

the T6 temper, while inside the grains, the precipitates are rather coarse and

uniformly distributed [51]. It is suggested that the precipitates in the T7 temper

are essentially η. The elongated η precipitates in AA 7150-T7 were reported to

be of sizes up to 70 nm and 250 nm in the matrix and the grain boundaries

respectively [52]. The width of PFZ at the grain boundaries was measured to be

between 40 and 50 nm [52]. Overall, the PFZ may be influenced by temper

reactions; as has been discussed, the T6 temper maximises the tensile strength of

AA 7xxx alloys, while the T7 temper improves the SCC resistance. Fine

precipitates inside the grains of alloys in the T6 temper are responsible for a high

mechanical property, while coarser and more spaced grain boundary precipitates

in the T7 temper alloys seem to enhance the SCC resistance.

2.3.3 Hydrogen Effects

Hydrogen embrittlement is one of the main factors that can cause SCC.

Generally, hydrogen acts to weaken interatomic bounds in the plane strain region

at the crack tip [53]. In aluminium alloys, localised corrosion is generally

accompanied by hydrogen evolution. The pH is reduced inside pits, owing to

cation hydrolysis as well as drops in the ohmic potential. Therefore, the potential

inside pits or with other forms of localised corrosion is below the reversible

41
Introduction to Aluminium Alloys

potential for hydrogen evolution. Furthermore, the hydrogen evolution reaction is

a cathodic reaction ( 2 H 2e H2 ) that consumes a portion of the

electrons generated by the localised corrosion. This portion of electrons was

reported to be about 20% and even higher in some cases [54, 55]. As a result,

hydrogen evolution inside pits occurs at a high rate during localised dissolution

of the alloy. Moreover, the presence of hydrogen atoms either at the crack tip or

after transport into the alloy ahead of the crack tip can result in loss of ductility

of the alloy and brittle cracking [44, 53]. Several authors have demonstrated

hydrogen embrittlement in aluminium alloys [44, 45, 56]. The occurrence of

intergranular fracture and a small reduction area in a tensile test usually indicates

the loss of ductility [45]. Albrecht et al. performed a series of tensile tests on

equiaxed AA 7075 alloy and found a significant embrittling effect, as manifested

by a decreased reduction area, when precharging with hydrogen [56]. They

interpreted the embrittlement as a result of the presence of cathodic-charged

internal hydrogen and further straining enhanced the transportation of additional

hydrogen by the movement of dislocations. Therefore, a large amount of

hydrogen can be transported by dislocations deeply into the interior of alloys.

This provides a more rapid transport mode than the lattice transport mode of

hydrogen in aluminium alloys, which can explain the existence of hydrogen

embrittlement.

In aluminium alloys, the grain boundaries are the preferred locations of hydrogen

accumulation [56, 57]. It was reported that Mg segregation promotes hydrogen

entry into the grain boundaries in aluminium [58]. Pickens and Langan studied

Al-Zn-Mg alloys and observed the presence of segregated Mg at the grain

42
Introduction to Aluminium Alloys

boundaries [59]. Pickens et al. proposed that the segregated Mg can promote

hydrogen to concentrate at the grain boundaries in sufficient quantities to cause

embrittlement [60].

From the above discussion, hydrogen can be transported by dislocations and

accumulate at the grain boundaries, causing embrittlement in aluminium alloys

that enhances localised corrosion attack. However, mechanisms of hydrogen

effects in SCC and IGC in AA 7xxx alloys are still being investigated.

2.3.4 Temper Effects

As mentioned earlier the decomposition of the SSSS of the alloy can be achieved

with different tempers during hard ageing. The most common tempers of the AA

7xxx alloys are T6 and T7. T6 provides the highest strength for AA 7xxx alloys,

but results in susceptibility to localised corrosion [4]. T7 is an overaging temper

that provides improved SCC resistance, but reduced strength [52, 59, 61-66].

Najjar used slow strain rate experiments in 3% NaCl solution with AA 7075

alloys in T6 and T7 tempers [67]. The results showed that AA 7075-T6 was

highly sensitive to SCC, while overaged AA 7075-T7 had a lower IGC and

improved SCC resistance. He observed the possibility that overaging induces a

reduction of the following factors.

A- Localised anodic dissolution at the grain boundary regions

B- Hydrogen diffusion into the grain boundaries.

C- Local stress concentrations through the homogeneity of deformation at

the grain boundaries.

43
Introduction to Aluminium Alloys

Therefore, overaged grain boundary regions are less sensitive to SCC and the

fracture has to propagate by discontinuous, cleavage-like cracks [67].

Coarsening of the grain boundary precipitates is another factor that has been

reported to be responsible for the improvement in the resistance to SCC [52, 66,

68]. Rajan and his colleagues studied the grain boundary precipitates of AA 7075

in T6, T73, and RRA (retrogression re-aging) tempers and performed SCC

testing [66]. The results showed that the heat treatments that produced more SCC

resistance have larger grain boundary precipitate sizes than the T6 condition.

Tsai reported similar observations in AA 7475 alloys between T6 and RRA

tempers [63, 69]. It seemed that the RRA temper can produce larger and more

spaced grain boundary precipitates than the T6 temper [63, 66, 69]. The wide

spaced grain boundary precipitates can delay the localised anodic dissolution and

can act as trap sites for hydrogen, where hydrogen bubbles can form. Therefore,

the hydrogen concentration at grain boundaries can be reduced to below the

critical value for inhibiting of hydrogen embrittlement and improved SCC

resistance. As mentioned earlier, dislocations can increase hydrogen

transportation to grain boundary precipitates during quenching following solution

treatment and that reduces the SCC resistance of the alloys. Talianker and Cina

observed a high density of dislocations adjacent to grain boundaries and in the

bulk of the grains of several 7xxx alloys in the T6 temper [70]. However, those

dislocations disappeared after an RRA temper [70]. They suggested that the short

time and high temperature of retrogression could annihilate dislocations without

causing overaging. The disappearance of dislocations results in retarded transport

of hydrogen into the alloy and improved SCC resistance. They believed that a

44
Introduction to Aluminium Alloys

major change in dislocation density, rather than a minor change in the precipitate

structure, could increase the SCC resistance of 7075 aluminium alloys with an

RRA temper.

Potential measurements are a useful tool to evaluate the effects of solution heat

treatment and the subsequent aging process. Anodic polarization curves for AA

7xxx-T6 in chloride solution typically exhibit two breakdown potentials, whereas

the T7 exhibits only one [10, 42, 71, 72]. Maitra observed only IGC between the

two breakdown potentials and both pitting and IGC above the second breakdown

potential in AA 7075-T6 [71]. This finding is the same as that of Galvele and

Micheli in Al-Cu alloys. The alloy in the T7 temper was immune to IGC and

pitting only occurred above the breakdown potential [73]. Therefore, Maitra

suggested that the disappearance of the second breakdown potential in T7 alloy

resulted in an improvement of the IGC resistance. However, Ramgopal and his

colleagues observed different results from Maitra. They found only pitting

occurred in AA 7075-T6 between the two breakdown potentials [42]. They

further investigated AA 7150 in T6 and T7 tempers. Similar to AA 7075 alloy,

two breakdown potentials were shown in the T6 temper and only one breakdown

potential in the T7 temper [10]. This time they performed a short time (1 h) and a

long time (24 h) potentiostatic tests separately on their samples. In short time

tests, the results were the same as those in the AA 7075: only pitting in T6

samples between the two breakdown potentials and both pitting and IGC

appeared above the more noble breakdown potential while T7 samples were

immune. However, in long time tests (24 h), both pitting and IGC were shown on

all their specimens. As a result, they assumed that IGC of AA 7150 is a time-

45
Introduction to Aluminium Alloys

dependent phenomenon [10]. Meng and his colleagues made other observations

of the corrosion process in relation to the breakdown potentials in AA 7xxx-T6

[72]. Between the two breakdown potentials, dark uniform corroded regions were

observed on the sample surface. These regions were examined by SEM and no

large or deep pits were seen on the surface. Above the second breakdown

potential, selective grain attack and IGC were evident. They concluded that the

first breakdown potential corresponds to transient dissolution, while stable

dissolution occurs above the second breakdown potential. Issacs ground

AA7075-T6 to 600 grit and exposed the sample at the OCP (open circuit

potential) for 1 h before polarization. He used image subtraction and found

streaking attack along the scratched lines on the surface. The streaking attack

was not observed in the T7 temper. He suggested that streaking attack was

caused by mechanical grinding and resulted in two breakdown potentials [74].

However, he did not explain why AA 7xxx alloys in the T7 temper are immune

to streaking attack, since the sample preparation by grinding was the same as for

the AA 7xxx-T6 temper. Ramgopal examined the grain boundary precipitates of

AA 7150 alloy in T6 and T7 tempers. He found that the copper concentration in

the grain boundary precipitates was higher in the T7 temper than that in the T6

temper [10, 42]. He presumed that the presence of a high concentration of copper

ions in solution due to dissolution of T7 grain boundary precipitates may be

responsible for preventing dissolution of the PFZs near the grain boundary region

and making the T7 temper less susceptible to IGC. As a result, he suggested that

the breakdown potential in the T7 temper is due to pitting in the matrix.

However, a high copper environment in the PFZs is needed to dissolve the grain

boundary precipitates first. If no dissolution of grain boundary precipitates

46
Introduction to Aluminium Alloys

occurs, the PFZs are still more susceptible than the matrix. Since the T7 temper

has a higher IGC resistance, it could be suggested that the breakdown potential is

due to dissolution of precipitates in this type of temper.

From the above discussions, the corrosion resistance for an over-aging (T7)

temper is higher than with a peak-aging (T6) temper for AA 7xxx alloys. It is an

evident that the AA 7xxx-T6 alloy exhibits two breakdown potentials after

examined in 0.1 M NaCl deaerated solution using potentiodynamic polarization

test as well discuss later in details in corrosion test results of the as-received alloy

section on chapter eight of this report. The first breakdown potential is associated

with pitting in the matrix, pitting in the solute enriched region of the grain

boundary, or streaking attack created by mechanical grinding. Some authors

proposed that coarsening of precipitates and more space between precipitates at

the grain boundary in AA 7xxx alloy with T7 temper can improve the corrosion

resistance, although others proposed that this may occur because of annihilation

of dislocations and retarding of hydrogen transportation into the alloys. It seems

that heat treatment cycles can decrease the corrosion susceptibility to SCC in

7xxx aluminium alloys.

47
Introduction to Aluminium Alloys

2.4 List of Figures

Table 2-1: Four-digit designation system for Aluminium Alloys [29].

Alloy Type Four digit designation


Wrought alloys Casting alloys
99% Aluminum 1XXX 1XX.X
Copper 2XXX 2XX.X
Manganese 3XXX 3XX.X
Silicon 4XXX 4XX.X
Magnesium 5XXX 5XX.X
Magnesium and silicon 6XXX
Zinc 7XXX 7XX.X
Lithium 8XXX
Others 9XXX
Note: Designations are based on aluminium content or main alloying
elements [29].

48
Introduction to Aluminium Alloys

Table 2-2: Mechanical properties of AA7xxx alloys with different temper


processes [28].

Thickness Tensile St. Yield St. Elongation Condition


Temper
(mm) (MPa) (MPa) (%) Definition

O 0.38-50.8 276 145 9-10 Fully Annealed


SHT at 465˚C,
T6 0.20-6.32 510-538 434-476 5-8 quenched then
artificially aged
SHT, quenched,
stress relieved
by stretching at
T651 6.35-101.6 462-538 372-462 3-9
0.5–3%,
permanent then
naturally aged
SHT, quenched,
T76 3.18-6.32 503 427 8 two steps of
artificially aged
SHT, quenched,
stabilised, 3%
T73 1.02-6.32 462 386 8 cold worked,
two steps of
artificially aged
SHT, quenched,
cold worked,
stabilised, stress
relieved by
T7351 6.35-101.6 421-476 331-393 6-7 stretching 0.5-
3% permanent
set and two
steps artificially
aged

49
Introduction to Aluminium Alloys

Table 2-3: Solid solubility and influence of elements in Al properties [28].

Solid
Element Symbol Solubility Effect on Aluminium properties
in Al
Increases strengthening, permits
precipitation hardening, reduces
Copper Cu Low
corrosion resistance, ductility and
weldability
Increases strength through solid solution
Magnesium Mg High strengthening, improves work hardening
ability. Cause intergranular corrosion
Increases strength, improves work
Manganese Mn Low
hardening ability
Increases strength and ductility, in
combination with Mg produce
Silicon Si Low
precipitates hardening, cast-ability and
ductility.
Increases strength, permits precipitation
Zinc Zn High
hardening, cause stress corrosion
Chromium Cr Low Increases stress corrosion resistance
Improves the strength at elevated
Nickel Ni Low
temperature
Added as a grain-refining element
Titanium Ti Low
particularly in filler metals
Zirconium Zr High Inhibiting re-crystallization

50
Introduction to Aluminium Alloys

SSSS (GP zones) → (η) → (η’)

Figure 2-1: Three main stages of heat treatment (SHT refers to solution heat
treatment, Q is quenching, and A* is aging) with precipitation scheme for
the 7xxx aluminium alloys

51
Chapter 3 Corrosion

3. Introduction to Corrosion

All common metals used in engineering are polycrystalline, being composed of

many crystallites of varying size and orientation. These crystallites meet together

to form grains and grain boundaries in the solid material. Corrosion attack

according to the ASM-Materials Engineering Dictionary [78] is a chemical or

electrochemical reaction between a material, usually a metal and its environment,

that produces dissolution on the metal grains and their boundaries which leads to

a deterioration of the material properties. Aluminium and its alloys are usually

protected by a thin film of oxide, aluminium oxide (Al2O3) that acts as a barrier

to protect the surface in various environments. In acidic and/or alkaline

environments, this thin film may undergo dissolution, with consequent corrosion

of the substrate. In general corrosion, oxidation and reduction reactions take

place on the metal surface. The oxidation reaction results in the generation of the

electrons at the anodic areas of the corroding metal, while the reduction reaction

consumes these electrons at the cathodic areas of the same metal. The section on

electrochemical polarization in this chapter is concerned with the reactions in

detail. Different corrosion forms can be initiated on aluminium alloys of the 7xxx

series. The type of corrosion depends to a large extent on the alloy composition

and the chemical nature of the environment, as will be reviewed in this Chapter.

52
Corrosion

3.1 Surface Oxide Film

Aluminium and its alloys are relatively stable in most natural environments due

to the rapid formation of the natural oxide film of alumina on their surfaces that

acts as barrier to environmental attack. Figure 3-1 depicts the thin oxide film on

the aluminium surface [75]. The oxide film is stable in aqueous solutions of pH

in the range 4.5-8.5, while it is soluble in strong acid or alkaline environments

[77, 78]. The film thickness is typically several nanometres (5-15 nm). The rate

of film growth increases at higher temperatures and higher relative humidities.

Much thicker surface oxide films can be produced by various chemical and

electrochemical treatments. For example, the natural film can be thickened 500

times by immersion of the aluminium in certain hot acid or alkaline solutions. In

highly aggressive environments containing chloride ions, the oxide layer may be

dissolved, once the chloride ions have replaced oxygen anions, and the film loses

its protective ability [79, 80]. In order to understand the chemical reactions

between the environment and the surface of the alloy, electrochemical

polarization is reviewed in the next section.

3.2 Electrochemical Polarization

Electrochemical polarization measurements employ an anode, cathode, and an

electrical conductive solution between them. A DC current is applied in the

electrolyte solution making electrons transfer from the anode site to the cathode

site. The hydrated ions flow in the opposite direction in the electrolyte, from the

anode through the electrolyte to the cathode. In this case, the anode will become

53
Corrosion

positive due to loss of electrons and the cathode will become negative due to gain

of electrons. The oxidation reaction on the anode area can be represented by the

following reaction;

M Mx xe (1)

where M represents the metal or alloy, M x is the metal ion, and xe is the

number of electrons involved in the oxidation process. On the cathodic area, a

reduction reaction takes place, and which may be represented by the following

reaction;

Mx xe M (2)

The anodic and cathodic reactions must maintain charge neutrality [81].

M Mx xe (3)

The potential difference between the anodic and cathodic reactions on the metal

surface is the driving force for the corrosion reaction and therefore; current flows

through the corrosion cell. For example, corrosion of aluminium in acid solution

involves the transfer of electrons from the anodic site into the cathodic site. The

oxidation reaction is Al Al 3 3e and the reduction reaction in acid solution

is the reduction of hydrogen ions. This reaction can be written as follows,

2H 2e H2 . The current on the other hand is a measure of the number

of electrons flowing per second, and the greater the current the more electrons

transfer between the anode and the cathode. Similarly, more hydrogen ions react

to form uncharged hydrogen atoms. Therefore, the potential and current are of

the primary interest in the study of corrosion. Potential provides a value of the

thermodynamic driving force of the corrosion, and the current provides a

measure of the electrochemical reaction rates that take place during the

corrosion.

54
Corrosion

3.2.1 Thermodynamics

For corrosion to be spontaneous, the change in the Gibbs free energy ∆G must be

negative. The free energy for the individual oxidation and reduction reactions is

related to a reversible electromotive force or cell potential (Ec) through the

equation

G xe FE c

where xe is the number of electrons, and F is faraday’s constant. Therefore, E is

directly related to the driving force (change in the Gibbs free energy) for the

reaction. For example, for a chemical reaction

aA+bB = cC+dD

where A and B are reactants and C and D are products, the equilibrium constant

for the reaction is given by;

and;

G G RT ln K

Then;

xeFEc xeFE RT ln K

By rewriting this equation;

55
Corrosion

This equation is called the Nernst equation, that relates the cell potential Ec to the

standard potential E˚ and activity/concentration of the electro-active ions [82].

Furthermore, the Nernst equation is a powerful tool in constructing Pourbaix

Diagrams (Potential-pH) that predict the regions of thermodynamic stabilities of

metal species at different combinations based on measurement of the potential

and pH values, such that the corrosion behaviour of a metal in an aqueous

solution can be predicted. However, Pourbaix Diagrams provide no guidance on

the rate of the reactions within a region where corrosion is possible [81]. In

general, the metal can exist in one of the three states in an aqueous solution.

These correspond to regions of corrosivity, immunity, and passivity in the

relevant Pourbaix Diagrams as shown in Figure 3-2. In corrosive regions,

corrosion occurs by general dissolution of the metal, while in the immune region,

the potential of the metal is so far depressed that the oxidation reaction is not

thermodynamically possible. In the passive region, the potential of the metal is

elevated and the metal becomes covered with a protective film, isolating the

metal from its environment. The metal is possibly resistant to corrosion in areas

where the film is stable, because this thin layer, usually based on oxide, leads to a

reduction in the rate of anodic dissolution on the metal surface.

56
Corrosion

3.2.2 Kinetics

Kinetics is the study of the rate at which reactions will occur. The potentials of

the oxidation and reduction reactions on a metal surface are polarized from their

equilibrium values. For example, when corrosion occurs and current flows

between anodic and cathodic areas, the potential of the anode increases to more

positive values (noble), and the potential of the cathode decreases to more

negative values (active). Therefore, both anodic and cathodic potentials will

approach a common value called the corrosion potential (Ecorr). A better way of

visualising the relationship between potential and current is by means of an

Evans Diagram, where potential is plotted on the vertical Y axis and log current

density is plotted on the horizontal X axis (Fig.3-4) [83].

In equilibrium, the corrosion current density (icorr) at the corrosion potential

(Ecorr) is directly proportional to the corrosion rate (CR). This current can be

converted to an actual corrosion rate (CR) using Faraday’s law [84].

iM
CR
ZFD

where i is the current density, M is the atomic weight of the metal, F is Faraday’s

constant (96,500 C/g equivalent), and D is the density of the metal. By returning

to the Evans Diagram, the slopes of the anodic and cathodic lines are referred to

as Tafel slopes and have units of mV or V per decade of current. In general, the

corrosion rate (CR) is determined by extrapolating the anodic and cathodic Tafel

regions to the corrosion potential (Ecorr). At the corrosion potential, the

extrapolated anodic and cathodic Tafel regions of the respective curves intersect.

57
Corrosion

At this intersection, the rate of the cathodic reaction equals the rate of the anodic

reaction and the value of the current is the corrosion current density (icorr).

This is the Butler-Volmer equation, where I is the applied current density, icorr is

the corrosion current density, is the over-voltage polarization (E – Ecorr),

and a and c are the anodic and cathodic Tafel slopes that are represented in

Figure 3-3 [85].

3.2.3 Passivity and Breakdown of Passivity

Since both driving force and kinetic considerations are crucial in determining the

extent of corrosion on a metal surface, the phenomena of passivity and its

breakdown are crucial factors in corrosion initiation, such as by pitting for

certain metals and alloys [86]. Because of the presence of the protective film that

naturally forms on aluminium and aluminium alloys in the passive region during

an electrochemical procedure, the breakdown of passive region can vary during a

polarization scan. The most common way to observe the breakdown potential

(Ep) in a wide range of metals and alloys is by potentiodynamic polarization. In

this process, Ep is the potential at which the current dramatically increases after a

period of passivity, marking the point above which pits initiate and grow [53].

An effective film is one that resists the breaching (breakdown) of the passivity.

58
Corrosion

Breakdown of the passivity leads to a localized corrosion that can lead to

corrosion failures by pitting, crevice, and intergranular corrosion, and stress

corrosion cracking. Figure 3-4 shows Ep, Ecorr, and the passive region in a

potentiodynamic polarization curve. All the breakdown mechanisms involve a

damaging species. For example, one of the major species causing breakdown of

passivity and lowering of Ep is the concentration of chloride ions. Competing

with passive film breakdown is the passive film repassivation. Thus, an effective

alloy for resisting localized corrosion would be one that its surface not only

forms a passive film but also is capable of repassivating at a rate sufficiently

high. Once breakdown has occurred, the alloy surface is exposed to the corrosive

environment [83]. However, Ep is often a function of experimental parameters,

such as potential scan rate, and may consequently not be a real measurement for

assessing the exact pitting potential [87, 88]. Therefore, it is important to

undertake further corrosion tests to clarify the result of the investigations.

3.3 Types of Corrosion

Corrosion can take different forms depending on the alloy composition and its

environments. In this part of the report, different types of corrosion will be

reviewed and the circumstances in which these areas are indicated. In general for

7xxx alloys, localized forms of corrosion, such as pitting, intergranular (IGC),

and stress corrosion cracking (SCC), are the most types of corrosion of the alloy

surfaces.

59
Corrosion

3.3.1 Uniform Corrosion

This type of attack means that the metal lost to form corrosion products is about

the same over the entire surface of the metal. It is the simplest form of corrosion,

occurring in the atmosphere, in solution, and in soil under normal service

conditions. Passive materials such as aluminium alloys are generally subjected to

localized corrosion. Uniform corrosion commonly occurs on the metal surface

and starts in the oxide layer before continuing to attack the underlying material.

Only in very acidic solution or very alkaline solution (4 > pH > 8), is aluminium

homogenously corroded [89].

3.3.2 Localized Corrosion

Localized corrosion can be defined as the selective removal of metal by

corrosion at small areas on the metal surface in contact with a corrosive

environment, usually liquid [90]. It takes place when small local sites are

attacked at a much higher rate than the rest of the original surface. There are

many different types of localized corrosion, including pitting, crevice, filiform,

galvanic, cavitation, waterline, intergranular, and stress corrosion cracking,

which will be described next.

3.3.3 Pitting Corrosion

This type of attack is a very severe form of localized corrosion that leads to very

small holes in the metal surface. The lack of oxygen around these holes is the

driving power for pitting corrosion. This area becomes anodic while the area

with excess of oxygen becomes cathodic, leading to very localized galvanic

60
Corrosion

corrosion. The attack penetrates the mass of the metal, with limited diffusion of

ions further promoting the localized lack of oxygen [91]. The initiation of pitting

often starts with the presence of local defects at the metal surface, such as flaws

in the oxide or segregates of alloy elements. In the presence of an aggressive

environment containing chlorides, Cl‾ anions are believed to disrupt the oxide

layer at pre-existing defects resulting in micro-cracks [92]. Recent studies show

that the pits initiate and propagate in aluminium when the following chemical

reaction takes place;

1- In pit initiation, aluminium is dissolved, according to the following

reaction;

Al 3 cations react with Cl‾ anions to form AlCl4-. Hydrolysis of this species

results in acidification of the bottom of the pit to pH < 3 (due to formation of H+

ions). The highly aggressive environment results in auto-propagation of the pit.

2- Al 3 cations concentrated at the bottom of the pit, diffuse out the pit

where an alkaline environment is generated by the cathode process of the

hydrogen gas evolution, or oxygen reduction reaction;

As a result, aluminium hydroxide (Al(OH)3) is formed and precipitates at the pit

borders blocking the pit hole for further ionic exchange processes [92]. In

polarization, pitting develops at potentials more positive than the pitting or

breakdown potential (Ep). The potential to which the aluminium is polarized by

specific cathode reaction determines the corrosion current density and corrosion

61
Corrosion

rate [89]. Aluminium alloys of the 7xxx series are normally clad to protect

against pitting [89, 93, 94]. However, it has been noted that the strength of the

alloys will be reduce by about 15% compared with un-clad alloys [4, 95]. It is

clear that pitting initiation reduces the passivity of the alloys, which lowers the

corrosion resistance and enables other corrosion types such as intergranular

corrosion (IGC), exfoliation corrosion (EXCO), and stress corrosion cracking

(SCC) to propagate along the grains and their boundaries resulting in

catastrophic failure. Several authors have classified the stages of pitting as

breakdown of the passive film (breakdown potential), metastable pit formation,

and pit growth [87, 96]. As mentioned above, breakdown of the passive film in

pure aluminium generally occurs with weak points in the material surface that

often occur at flaws in the oxide layer, such as locations of scratches and

impurities, in association with the presence of an aggressive environment. On the

other hand, aluminium alloys usually contain second phase particles and solute-

rich regions that may disrupt the protective oxide layer and increase local

corrosion attack on the surface, especially in the presence of a chloride-

containing environment [4, 97-99]. However, some initiated pits do not

propagate; they can be repassivated, hence causing metastable pitting. Once a pit

is stable, propagation is autocatalytic as the process forms metal cations that

attract the solution anions (Cl-) into the pit, the cations undergo hydrolysis which

lowers the pH value that adds further aggressiveness to the pit solution [100,

101]. The highly aggressive solution and the low pH values favour more

dissolution of the metal that causes pit growth and pit propagation [86].

62
Corrosion

3.3.4 Crevice Corrosion

Another localized type of corrosion attack develops between metal-to-metal or

non metal-to-metal components contacting areas due to the formation of a

crevice with an oxygen differential cell in a corrosive environment [28, 89].

Recent researches indicate that both the potential drop and the change in

composition of the crevice electrolyte are caused by de-oxygenation of the

crevice and a separation of electro-active areas, with a net anodic reaction

occurring within the crevice and a net cathodic reaction occurring on the metal

surface. Examples of crevices are gaps and contact areas between parts, under

gaskets or seals, and inside cracks and seams [101].

3.3.5 Filiform Corrosion

Filiform corrosion is another case of localized corrosion that may occur on an

aluminium surface under an organic coating [89]. The source of initiation is

usually a defect or scratch in the coating. Filiform corrosion is associated with an

oxygen concentration cell in which the anodic active area is the head of the

filament and the cathode is the area surrounding it, including the tail. When

aluminium ions hydrolyse, hydrogen ions are formed and reduced at the tip

forming hydrogen gas. The pH value of the tip becomes more acidic. The

cathodic reaction (oxygen reduction on the intermetallics that are present at the

surface) takes place behind the anode. Aluminium ions and hydroxide ions form

insoluble aluminium hydroxide in the tail. The active anodic reaction at the tip

results in propagation of the filament and causes detachment of the coating from

the substrate [102].

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Corrosion

3.3.6 Galvanic Corrosion

Another type of localized corrosion attack may be initiated when electrical

contact occurs between two different metals that are immersed in an electrolyte.

Such galvanic corrosion is an electrochemical process that forms between metals

with electrode potentials that differ by at least 50 mV and are indirect contact

with each other [89]. The electrolyte (environment) provides a means for ion

migration, with metallic ions moving from the anode to the cathode. This leads to

the anodic metal corroding more quickly than it otherwise would be. For

example, aluminium and its alloys under most environment conditions are the

anodes in galvanic cells with most other metals, protecting them by corroding

sacrificially. Contact of aluminium with more cathodic metals results in an

increase of the breakdown potential of the aluminium and this must be avoided in

any environment in which aluminium itself is subjected to pitting corrosion [89].

3.3.7 Cavitation Corrosion

This type of corrosion usually combines electrochemical action with mechanical

damage. For example, a turbulent flow of liquid below the vapour pressure can

initiate voids (gas bubbles) that interact with component surfaces to dislodge the

protective film during service and even alter the state of work hardening of the

metal at the surface. The severity of this type of corrosion depends on the

aggressiveness of the environment. Weight loss is the standard result of such

attack [28].

64
Corrosion

3.3.8 Waterline Corrosion

Waterline corrosion can affect semi-submerged structures such as those in sea

water. With aluminium alloys, waterline corrosion may arise due to a difference

in the chloride level between the sea water at the air/water parting line. This

effect is weak in water that is in motion because the meniscus is constantly being

renewed and not as concentrated with chloride [28].

3.3.9 Intergranular Corrosion (IGC)

Intergranular corrosion (IGC) is recorded as localized attack along the grain

boundaries, or immediately adjacent to the grain boundaries, while the bulk of

the grains remain largely unaffected. This type of corrosion is usually associated

with segregation effects (impurities enriched at the grain boundaries) or specific

phases precipitated on the grain boundaries [89]. Such precipitation can produce

zones with anodic behaviour that reduce the corrosion resistance in their

immediate vicinity [103, 104]. The attack usually progresses a narrow path along

the grain boundaries. Aluminium alloys are susceptible to intergranular attack on

account of either phases anodic to aluminium being presented along the grain

boundaries or due to depleted zones of copper adjacent to the boundaries in

copper-containing alloys. Dix et al. studied the corrosion behaviour of Al-4%Cu

in NaCl-H2O2 environment [105, 106]. They observed Al2Cu precipitates along

grain boundaries and Cu-depleted zones were observed adjacent to the grain

boundaries. They found that the Cu-depleted zone has a higher corrosion

potential, by about 44 mV, than that of the grain matrix. They concluded that

65
Corrosion

IGC in Al-Cu alloys is caused by the difference in the corrosion potential

between these regions. In AA 7xxx alloys, such as AA 7075 and AA 7150, both

zinc and copper were found to be depleted in the PFZ [10, 68]. As was discussed

in the previous chapter, zinc and copper have opposite effects on the dissolution

of aluminium. Depletion of Cu makes the PFZ more susceptible than the matrix,

while depletion of Zn can be beneficial to the PFZ. Therefore, it is not easy to

determine the role of the PFZ in the process of IGC in AA 7xxx alloys compared

with binary alloys. In AA 7xxx alloys, the grain boundary precipitates of η are

reported to be more active than the surrounding matrix [42-44]. Therefore, η

would be preferentially dissolved, leaving the alloy matrix with more corrosion

products. It has been observed that the IGC morphology in AA 7xxx alloys in

NaCl solution is irregular and complicated and that the matrix near the grain

boundary is also dissolved. This is probably due to the acidic and crevice

environment that Buchheit et al. described in the IGC mechanism in Al-Cu-Li

alloys [107]. Overall, the composition change at the grain boundary due to

formation of either precipitates or a PFZ changes the electrochemical properties.

The difference in potential between grain boundary precipitates, the PFZ and the

grain matrix makes aluminium alloys such as 7xxx susceptible to IGC attack.

3.3.10 Stress Corrosion Cracking (SCC)

SSC is a phenomenon which results in brittle failure in alloys normally

considered ductile, when the alloys are subject to a tensile stress in a particular

corrosive environment. It involves time-dependent interaction between the alloy

microstructure, mechanical deformation, and environmental conditions. Only

aluminium alloys with a high level of Cu, Mg, Si, Zn, or Li in solution may be

66
Corrosion

susceptible to SCC. In practice, Al-Cu-Mg (2xxx series) and Al-Zn-Mg-Cu

(7xxx series) may suffer SCC [108]. When a crack occurs, it is characteristically

intergranular and involves the presence of an active anodic constituent in the

region of the grain boundaries [89]. The recrystallization area in the alloys is the

most susceptible to SCC, and it is for this reason that composition, work

hardening, and elevation in heat treatment temperatures are normally adjusted for

wrought alloys to prevent recrystallization. However, the resistance of Al-alloys

to SCC depends upon the direction of stressing with respect to the elongated

grain structure. Maximum attack occurs if stressing is normal to the grain

direction, i.e. in the short transverse direction of the components, because the

crack path along grain boundaries is clearly defined [28].

Solution heat treatment and quenching introduces residual stresses into the alloy

component. Quenching places surface regions of a component into compression,

with the centre in tension. If the central regions are exposed for example by

machining away sections in a component that has not been stress relieved, then

the internal residual tensile stresses will be added to any tensile stress imposed in

service, increasing the probability of SCC. Therefore, alloy products are usually

given a mechanical stretch of 1 to 3% after quenching in order to reduce the level

of residual stresses and increase the level of resistance onto the SCC.

In precipitation-hardening aluminium alloys aged at elevated temperatures, the

resistance to SCC varies with the ageing condition. Understanding the

mechanisms of SCC in aluminium alloys has involved consideration of the

following microstructural features.

67
Corrosion

Precipitate-free zones (PFZ) at the grain boundaries. In a corrosive

environment, PFZs are considered to show as anodic behaviour with respect

to the grain centres. Moreover, strain is concentrated in these zones because

they are relatively soft.

Nature of the matrix precipitate, since cracks occur in an alloy when GP

zones (initial formation zones of precipitates as they form from the solid

solution) are present. In this situation, deformation tends to be concentrated

in discrete slip bands. Stress generated where these bands impinge upon grain

boundaries can contribute to intercrystalline cracking under SCC conditions.

Dispersion of precipitate particles in grain boundaries. In some aged

aluminium alloys, SCC occurs more rapidly when particles in grain

boundaries are closely spaced.

Solute concentrations in the region of the grain boundaries. During ageing of

aluminium alloys, local electrochemical potentials due to the solute elements

are varied due to differences in solute levels. For example, it has been

observed that a higher magnesium content in grain boundary regions results

in the adjacent oxide layer having an increased MgO content, which is a less

effective barrier against environmental influences [28].

Hydrogen embrittlement may occur due to rapid diffusion of hydrogen atoms

along the grain boundaries, as has been explained in Chapter 2 [109].

The chemical nature of atom species at the crack surface may result in

lowering of the cohesive strength of the interatomic bonds in the crack-tip

region resulting in an advancing crack.

68
Corrosion

Recent studies have shown that stress corrosion cracking (SCC) at grain

boundaries initiates in brittle regions [35, 92, 108, 109]. Furthermore, the

presence of hydrogen diffusion along the grain boundaries plays a vital part in

SCC. However, the overall process is complex and it seems probable that one or

more of the above microstructural factors are involved. The relative importance

of each of these factors may depend upon the particular combination of alloy and

environment.

3.4 Corrosion at High Strength Aluminium Alloys

The presence of a highly stable oxide film on pure aluminium (reaction 1)

increases the corrosion resistance in neutral conditions (4.5< pH < 8.5).

2Al + 3H2O → Al2O3 + 6H+ + 6e- (1)

The oxide film is an insulator and therefore, decreases the cathodic reactivity by

blocking electron conduction [97]. However, the oxide can be decreased in

thickness and lost due to the presence of aggressive species, such as chloride

ions, or by changes in the pH. For example, in acidic and/or alkaline atmosphere,

the oxide is removed by reactions 2 and 3.

Al2O3 + 6H+ → 2Al3+ + 3H2O (2)

Al2O3 +3H2O + 2OH-→ 2 Al(OH)4- (3)

Once the passive oxide breaks down, aluminium dissolution occurs anodically at

all pH values as can be seen in reactions 4 and 5.

Al → Al3+ + 3e- (4)

Al + 4OH-→ Al (OH)-4 + 3e- (5)

69
Corrosion

The metal ions can be released into the solution and undergo hydrolysis as shown

in reaction 6. This increases the acidity and further aluminium dissolution due to

reaction 4.

Al3+ + H2O → AlOH2+ + H+ (6)

The pH of the environment plays a significant role in determining both the

anodic and cathodic reactions. In neutral and alkaline conditions, the cathodic

reaction is oxygen reduction as given by reaction 7. In acidic environment, the

cathodic reaction is hydrogen evolution, as shown by reaction 8.

O2 + 2H2O + 4e- → 4OH- (7)

2H+ + 2e- → H2 (8)

In general, corrosion reactions depend on the environment in which the alloy is

employed, which in turn affects the stability of the surface oxide. Also, alloying

of aluminium affects the surface oxide, as the presence of the intermetallic

particles can decrease the protectiveness of the surface oxide film and increase

the electron conductivity between the anodic and cathodic sites [110]. All of the

electrons produced by the anodic reaction are consumed in the cathodic reaction

which means that the anodic and cathodic rates must be the same.

3.5 Corrosion Behaviour of Intermetallic Particles

As mentioned earlier, pure aluminium has a high corrosion resistance due to

having a highly stable oxide film. However, the corrosion resistance is decreased

for aluminium alloys due to the presence of constituent particles. Generally,

intermetallic particles are classified as anodic or cathodic relative to the alloy

matrix. Particles that have corrosion potentials (Ecorr) more negative than that of

alloy matrix are considered anodic (active), while those which are less negative

70
Corrosion

than that alloy matrix are considered cathodic (noble). More details are giving on

the physical properties of the intermetallic particles at 7xxx alloys in Appendix 1.

As mentioned in the electrochemical polarization section, the OCP (Ecorr) is

functioning of the anodic and cathodic reaction kinetics on each of the individual

components of the alloy and their respective proportions in the bulk of the alloy.

In polarization, these particles are polarized towards the bulk alloy OCP and that

leads to formation of micro-galvanic cells, which normally results in the

protection of the more noble component at the expense of corroding the other [1,

96]. Consequently, active (anodic to the matrix) particles undergo anodic self-

dissolution, while noble (cathodic to the matrix) particles corrode the

surrounding matrix. Figure 3-6 demonstrates the concepts of this mechanism

[111].

The preferentially dissolved particles which are deemed anodic to the matrix do

not reveal a breakdown potential [1]. That indicates that they are unable to

maintain a passive film, either because the films are soluble in the aggressive

solution or the particles are polarized to values at which they are rapidly

dissolved. These particles are always at risk of attack. The more noble particles

exhibit different forms of corrosion mechanisms to the alloy matrix. Due to

galvanic coupling [112, 113] or elevation of the pH [110, 114], these particles

lower the breakdown potential of the surrounding matrix and lead to localised

attack. These particles always increase the attack of the surrounding matrix. High

strength aluminium aerospace alloys, such as 7xxx series are susceptible to

corrosion attack. The major alloying additions, zinc, magnesium, and copper,

form a number of precipitates of varying composition. The precipitates of interest

71
Corrosion

to the corrosion behaviour contain copper as these are preferential sites for the

cathodic reaction and cause pit initiation. Another precipitate of interest is the

MgZn2 phase, which can continuously precipitate along the grain boundaries;

this phase is highly reactive and can dissolve rapidly resulting in IGC attack [10].

Much attention has been focused on potential differences between the matrix and

intermetallics [1, 72, 87, 88, 96, 115-117]. Recently, Andreatta et al. used a

micro-capillary cell and scanning Kelvin probe force microscopy (SKPFM)

measurements at random positions on AA 7075-T6 and solution heat-treated AA

7075. They found Al7Cu2Fe, (Al,Cu)6(Fe,Cu), and Mg2Si intermetallic particles

distributed on both alloy surfaces. They measured the potentials for each phase

and found that Al7Cu2Fe intermetallics induce a higher cathodic breakdown

potential than the (Al,Cu)6(Fe,Cu) intermetallics that corresponded to the higher

Volta potential differences for the former particles (-475 mV) compared with the

later particles (-282 mV versus SCE) [118]. They concluded that the breakdown

potential of areas containing intermetallics is related to the Volta potential

difference between the intermetallics and the surrounding matrix [118]. On the

other hand, Birbilis investigated the electrochemical properties on a phase-by-

phase basis by fabricating test alloys that could provide a population of the

intermetallics of interest large enough to be studied independently by the

potentiodynamic polarization microcell. He studied the intermetallic particles in

AA 7075 in 0.1 M NaCl and found differences in potential between them and

that the corrosion rates for each phase can be extracted from polarization curves

by inspection of the current at the OCP of the specific alloy in the same solution

[1].

72
Corrosion

It is clear from the above discussion that the presence of various second phase

particles in 7xxx alloys affects their corrosion behaviour strongly and leads to

localised (micro-galvanic coupling with the matrix) corrosion attack which at the

end reduce the alloy resistance to corrosion and causes more dissolution of the

surrounding matrix.

The reduction or elimination of all of these particles from the alloy surface

without affecting other alloy properties would significantly increase the

corrosion resistance of the aluminium alloys. That improvement may be expected

to result from the use of laser surface melting (LSM) techniques and that will

discuss later in the next Chapter.

3.6 Aluminium Alloy Surface Protection Methods

There are several surface protection methods that can be applied to aluminium

alloy surfaces in order to increase their corrosion resistance for a given

application. The basic idea for surface treatment is to provide the aluminium

alloy surface with a stable layer or coating that protects the alloy from

environmental attack. The processes for surface protection of aluminium alloys,

including non-galvanic, chemical, and electrolytic methods, will be reviewed in

this section [13, 14].

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Corrosion

3.6.1 Non-galvanic Methods

Surface enhancement of aluminium that does not include chemical or electrolytic

action is considered to be a non-galvanic method. It includes mechanical

finishes, such as grinding, polishing, buffing, rolling or blasting to remove any

scratches or dirt from the surface, and the application of organic finishes, such as

primer/top-coats, plastic coatings, protective coatings or powder coatings. These

processes are mostly used in architecture and light components to increase the

corrosion resistance of the alloy and give it a suitable selected colour [13, 14].

3.6.2 Chemical Methods

Surface treatment of aluminium by a chemical reaction, with no external source

of electric power used, is considered to be a chemical method. Etching, chemical

polishing, chemical conversion coating and electroless processes are all examples

of chemical methods. For applications such as aerospace, chemical conversion

coating is extensively used to protect alloys against corrosion [13, 14].

3.6.3 Electrolytic Methods

Surface treatment of aluminium including electrochemical action and external

power supply is considered to be an electrolytic method; examples include

elctropolishing, electroplating and anodising. Anodising is the more commonly

used electrolytic method for surface treatment of aluminium and aluminium

alloys. This is due to a number of properties offered by this technique, such as

increase corrosion resistance, provision of hard and wear resistant surfaces, and

electrical and thermal insulation, and the surface can be used as a base for

74
Corrosion

organic finishing and plating. This technique has an advantage that, with contain

anodising processes, it does not require use of toxic chemical or heavy metals

[14, 119].

In most protection methods, the presence of different constituent particles and

precipitates, which are the source of most corrosion problems, cannot be

removed and/or decreased at the surface of the alloys. In the presence of an

aggressive environment containing chloride ions, these particles may be harmful,

for example leading to IGC and SCC. It is often difficult to detect the corrosive

attack and repair it before it causes massive failures. Therefore, it is important to

eliminate or reduce the number of intermetallic particles from the alloy surface

without affecting the alloy bulk properties in order to increase the corrosion

resistance which can be done using LSM as can be shown later in this work. The

principles of the lasers technique and the theory of rapid solidification of the

alloy surface will be discussed and reviewed in the next chapter.

75
Corrosion

3.7 List of Figures

Figure 3-1: Schematic diagram showing the thin oxide layer (Al2O3) that
protects the metal surface (aluminium) from environmental attack.

76
Corrosion

acid
corrosion
alkaline
corrosion

passivity

immunity

Figure 3-2: Pourbaix diagram for the Al-H2O system at 25 oC that shows
regions of immunity, passivity, and corrosion [120].

77
Corrosion

Figure 3-3: Corrosion polarisation diagram showing Tafel extrapolated


slopes for the both anodic and cathodic current density. The intersecting
point indicates the both corrosion potential (Ecorr) and the corrosion current
density (Icorr) [85].

78
Corrosion

Figure 3-4: Schematic diagram of the polarization behaviour of a metal


showing the transformation from active to passive states and the breakdown
of passivity at point F [121, 122].

79
Corrosion

Figure 3-5: Intergranular corrosion (IGC) of a failed aircraft component


made of 7075-T6 aluminium alloy (width of image = 500 µm) [104].

80
Corrosion

Figure 3-6: Schematic diagram showing the corrosion behaviour due to


intermetallic particles that are anodic and cathodic with respect to the alloy
matrix [111].

81
Chapter 4 Laser

4. Introduction

The surface treatment of metals and alloys using a laser is a subject of

considerable interest in present because it offers the chance to save strategic

materials or to improve components by optimizing surface and bulk properties

[123, 124]. This Chapter will present the basic principle of the laser, laser beam

characteristics, LSM including heating principles, the formation of a melt pool,

cooling and solidification of the melted surface layer, nucleation and growth. The

microstructure as well as the corrosion behaviour of LSM alloys will be

discussed and reviewed. Finally, the safety aspects of the use of lasers, including

laser classifications and laser protection forms, will be explained.

4.1 Basic Principle of Laser Works

The name Laser is an acronym for Light Amplification by Stimulated Emission

of Radiation [123, 124]. Light of the laser is generally accepted to be

electromagnetic radiation ranging from 1 nm to 1000 µm in wavelength. It is

reported that the wavelength of the visible laser light ranges from approximately

400 to 700 nm. From 700 nm to 10 µm is considered the near-infrared (NIR), and

beyond this limit is the far-infrared (FIR). In contrast, 200 to 400 nm is

considered ultraviolet (UV); while below 200 nm is deep ultraviolet (DUV) [124,

123].

82
Laser

General lasers employ a resonator that typically consist of two mirrors are placed

parallel to each other in order to form an optical oscillator in which a light can

move back and forth between the mirrors in an active medium that consists of

high purity material state(gas, liquid or solid) which is capable of amplifying the

laser light. An external source of energy (electric current) pumps in the gain

medium, laser radiation is generated then in the medium which consists of atoms

or molecules that have specific electron energy levels. The movement of

electrons between the energy levels causes a spontaneous emission of radiation.

A minimum of three electron energy levels are required for a laser to generate

[123, 126]. These energy levels are ground level, a metastable level and a high

level, as indicated in the Figure 4-1. When an electron is excited from the ground

state to the high level with energy input, laser then can produce. The number of

electrons in the high energy level must be increased to more than the number of

electrons in the ground level, and this is referred to as population inversion. To

invert the electron population requires that more than half of the electrons to be

raised to the high energy level. Following the population inversion, electrons

then lose energy and consequently reduce the energy levels (electron decay), and

therefore, the photons are emitted by the movement of the electron from the

metastable level down to the ground level. To amplify the amount of photons

produced, the reduction of electrons is stimulated by the interaction of additional

photons excited atoms in the gain medium. The radiation emission of laser light

can be generated then in the form of a continuous wave (CW) or pulses. For a

continuous laser, the energy required to invert the electron population must be

83
Laser

reduced so that the inversion can be easily maintained, and that can be achieved

by increasing the number of electron energy levels to a minimum of four with

two metastable levels, as illustrated in Figure 4-2, while in a pulsed laser, the

energy input must be high enough to maintain the population inversion and that

can be achieved in three electron energy levels, as this can provide the same peak

energy to invert the electron population, but the overall average input energy is

lower than that in four electron energy levels [123, 126]. It is mentioned that

once continuous radiation has been produced, it can be changed to provide

radiation of pulses by using Q-switching that enables storage of enough radiation

and controls the release of this radiation in a form of pulses [123]. The length of

the laser pulse can vary from tenths of seconds to a few femtoseconds (10-15 s).

The average power may vary between milliwatt and kilowatt levels, with peak

power attaining the order of gigawatts [127].

4.2 Laser Light Characteristics

Laser light has four main characteristics that differentiate it from the other form

of lights. It is monochromatic, has low divergence, coherent, and high brightness

[123, 124, 126]. Monochromatic laser light is employed in applications such as

measurement, alignment, and holography. Low divergence is the property that

enables a laser beam to retain high brightness over a long distance, and is the

basis of alignment systems. Coherent radiation comprises waves travelling with

the same wavelength, amplitude and wave-front. It is a measure of the degree to

which light waves are in phase in both time and space. The light of the laser

radiation has a high coherence. Coherent laser light is up to 100000 times higher

in intensity than incoherent light of the same equivalent power, since the

84
Laser

divergence or dispersion of energy is very low as the beam propagates from the

laser. The coherence length ( l coh ) depends on the wavelength (λ), and the

bandwidth (∆λ),

l coh

The coherence time ( t coh ) depends on the ( l coh ), and the velocity of light (c),

l coh
t coh
c

Brightness (B) is a measure of intensity of light at a particular location. It is the

emitted power (q) per unit area (A) to the solid angle (Ω),

q
.
A

The Intensity (I) obtained by focussing a beam of light, and is directly

proportional to the brightness (B).

I = π w2 / f2

Where f is the optical focal length, and w is the beam waist radius. The beam

intensity can be related to the temperature through the Stefan-Boltzmann law,

4
.

Where σ is Stefan-Boltzmann constant (5.67 x 10-8 J/m2s K-4) and T is the

absolute temperature of the emitting surface. By focusing, the intensity of a beam

can be increased as well as the temperature of the emitting structure that causes

more phonon-electron energy exchanges. These are more likely to interact with

structure rather than oscillate and reradiate. Therefore, the absorptivity on the

structure surface will increase and reflectivity will decrease.

85
Laser

Thermal mechanisms of material processing take advantage of the high

brightness (high power density) of a laser beam. Athermal (photonic)

mechanisms are based on the short wavelength (high energy) of the beam, and

the short duration of the pulses that can be produced. The beam characteristics

influence the beam propagation and focusability, and therefore have an important

effect on the suitability of the beam for material processing. The polarization of a

laser beam also affects the amount of light observed in many material processing

applications. Light sources interact differently with a material surface as the

angle of incidence, θB, increases (The angle at which complete absorption occurs

and is called the Brewster angle). It is related to the index of refraction, n, by

θB = tan-1 (n). Beam polarization affects the amount of energy observed by the

material, and therefore enhances the efficiency and quality of laser processing

[126,127].

4.3 Laser Surface Melting (LSM)

LSM improves the corrosion resistance of the alloy surface microstructure

through localised melting and rapid solidification. To understand the change

from an heterogeneous microstructure into an homogeneous by LSM, requires

understanding the laser heating source, formation of melt pool, cooling and

solidification, as well as nucleation and growth.

4.3.1 Heating Principle

The energy input to the substrate is low in comparison with a conventional

means of surface melting. Heating rates associated with laser surface melting are

86
Laser

therefore orders of magnitude higher than conventional methods. It is reported

that the heating rates for typical continuous laser surface melting are on the order

of 105 K s-1 for an energy input of 0.1 J m-1 associated with large-scale

processing, while for a nanosecond duration excimer laser can reach 109 K s-1

with energy of 10 J. [124] Therefore, melting occurs rapidly with an increase in

the absorptivity of the material to the focusing laser beam.

4.3.2 Formation of the Melt Pool

The melting of the surface results in formation of a melt pool. It is reported that

temperature gradients of an order of 104-106 K m-1 develop between the centre

and the cooler solid/melt interface at the bottom of the pool [124]. In most

materials, the coefficient of surface tension increases with a decrease in

temperature. Therefore, surface tension gradients induce fluid flow from the

centre of the melt towards the edges (called Marangoni flow) [124]. Marangoni

flow is the dominant convection mechanism in the melt pool since there are no

other forces induced on moving charged particles in the presence of magnetic

and electric field. The Marangoni number (Ma) is the mass transfer along an

interface between two fluids due to surface tension gradients. Therefore, it is the

ratio of the convection rate and the conduction rate of molten material. Typical

Marangoni numbers for metals during melting lie in the range 103-106 [124]. For

metal solutes in molten metals, it is reported that the diffusion coefficients of the

liquid state lie in the range of 10-6-10-7 m2 s-1. [124] Therefore, the diffusion

length for a very short melt times is considerably smaller than the melt depth,

such that homogenisation occurs mainly by convection. Material flow by

87
Laser

convection due to surface tension gradients is preferential in LSM as the

dispersion rate of the solute is faster.

4.3.3 Cooling and Solidification

Cooling rates during LSM are significantly high. It is reported that cooling rates

~ 103 K s-1 for a mutikilowatt surface melting, rising to 1011 K s-1 for very low

energy input surface skin processing [128]. In rapid solidification of metals and

alloys, thermal and constitutional undercooling temperatures are important

parameters to be considered (Temperature gradients). Thermal undercooling

(∆T) is the degree of liquid cooling below the equilibrium freezing temperature

(Tf) before solidification takes place (∆T = Tf – T), and occurs during rapid

solidification in pure metals due to high cooling rates. The composition of the

alloy changes over the liquidus range in the solidification process. As the

composition changes ahead of the solidification interface, the actual temperature

(T) may not match the temperature required by the alloy liquidus, and this leads

to constitutional undercooling. Therefore, the constitutional undercooling

temperature has an influence on solidification structure of alloys, which may

cause by thermal gradients being less steep than melting point gradients [129,

130]. On the other hand, the driving force for solidification is the thermal

gradients (G) within both solid (GS) and liquid (GL) at the interface that also

influence the solidification structure. GL is more critical than GS since it controls

stability and the morphology at the interface. Therefore, any movement of the

material within melt pool formation will affect GL and solidification

microstructure. The rate of solid/liquid interface with respect to the liquidus is

the interface growth rate (R*). It is reported that G influences the solidification

88
Laser

morphology microstructure, and R* influences the scale of solidification and

solute distribution. Therefore, G and R* are important, as they influence the

solidification morphology, and the scale of solidification substructure

respectively [130, 131]. Nucleation and growth scenarios will take place during

solidification and that explain in the next sections.

4.3.4 Nucleation

In LSM application, once the melt in pool area of laser treated surface is mixed

in the liquid state, the nucleation of solid is required (amorphous or crystalline).

The formation of a solid particle from a liquid can be controlled by the change in

total free energy of the applied system (∆G). It is reported that the difference in

the volume free energy of the particle and surface free energy of the solid/liquid

created interface. Figure 4-3 shows the relationship between surface, volume,

and total free energy [132]. The Fig. shows that the volume free energy is

negative and supporting the nucleation process (growth of cluster), whereas the

surface free energy is positive and is therefore an activation barrier for the

formation of a stable nucleus. An increase in thermal undercooling (∆T) may

then increase the energy barrier for nucleation and reduces the critical size for

stable nuclei (r*) (dissolving of cluster) [132]. Two types of nucleation can form,

namely homogeneous and heterogeneous. Homogeneous nucleation occurs when

atoms cluster together to form a stable nucleus, without the aid of foreign bodies

such as impurities, inclusions, or interaction with the substrates. A large amount

of undercooling is required in homogeneous nucleation to supply the energy

needed for the formation of the new surfaces, which described above. In

heterogeneous nucleation, less undercooling is required as this type of nucleation

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uses the surfaces of foreign bodies (e.g. particles suspended within the melt) to

significantly reduce the surface energy requirement [130, 131]. Heterogeneous

nucleation is the standard situation for most cases of solidification [131].

Heterogeneous nucleation occurs as the liquid fully wets the solid substrate it is

in contact with, so there is no nucleation energy barrier and nucleation occurs

spontaneously. The full wetting of the surface by the liquid also means that the

solid that grows is influenced by the substrate [133].

4.3.5 Growth

Once nucleus formation has been stabilised, growth of solid starts at the interface

with addition of atoms from the liquid. The growth structure morphology that

occurs with more adding of atoms is controlled by the shape and stability of the

liquid/solid interface. The stable interface shape for growth depends on a number

of conditions, including heat flow rate, thermal gradients, mass flow rate,

composition gradients and growth rate [125, 130, 131]. Typical growth

morphologies are planar, cellular, and dendritic; Figure 4-4 shows different

growth morphologies that can be formed during solidification [125]. The

direction of growth in the planar mode is perpendicular to the flat solidification

front and parallel to the thermal gradient (G). In planar growth, the role of

crystallography is limited but can affect the growth rate (R*), as some

crystallographic directions can grow faster than others. The aligned grains in the

faster growth direction will develop at a faster rate and can dominate the

microstructure [125, 130]. Cellular growth occurs where the direction of grain

growth is controlled by heat flow conditions with very small influence from

crystallography. Cellular growth is not the same as planar growth since it occurs

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at faster cooling rates. Therefore, the solute in the alloy cannot redistribute fast

enough, leading to rejection of solute ahead of the interface. This rejection in

solute results in a change in composition ahead of the interface and constitutional

undercooling occurs. Constitutional undercooling means that the liquid ahead of

solidification exists below its freezing temperature and solid protrusion start to

develop on the planar interface. The protrusion can then grow into the liquid with

more stability, following the maximum thermal gradient. The growth of a single

protrusion rejects solute laterally, that lowers the solidification temperature and

produces cavities that help the formation of more protuberances. These

protuberances break down the planar interface and form a cellular structure with

more uniformly spaced cells that grow parallel to the maximum thermal gradient.

An increase in the cooling rate decreases the cell size dimension. Therefore,

growth like cellular can be formed to each other [125, 130, 131]. The transition

from cellular to dendritic solidification is not completely recognised, but it is

thought to be due to constitutional undercooling between the cells that causes

instability perpendicular to the growth direction. This unstable growth of the cell

sides causes to ramify the cells into dendrites, as shown in Figure 4-5 [130]. The

increase in the interface instability forming dendrites from cells is related to an

increase in the cooling rate. Fast cooling rates can influence the crystal structure

and growth direction. Therefore, a dendritic growth morphology occurs in

specific crystallographic directions and has been identified in two forms,

columnar and equiaxed. Columnar dendrites are not affected by heat flow rate

and can grow along the same crystallographic direction parallel to each other

(Figs. 4-4 (c) and 4-5 (d)), while equiaxed dendrites grow in different orientation

depending on crystallography and neighbouring dendrites are not necessarily

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parallel to each other. Therefore, each separate grain can form equiaxed dendrites

(Fig. 4-4 (d)) [125, 130, 134]. As the dendritic structure is influenced by

crystallography, the increase of the cooling rate can influence the dendrite

spacing, resulting in a fine structure. In the other way, there is a limit to the

refinement of the dendritic structure with the increasing cooling rate. This is due

to the decrease in atom diffusion time with very high cooling rates [129, 135].

For stable growth dendrite structure, the liquid/solid interface must be able to

form stable protuberances along the interface. For stable and growing

protuberances, it must be able to accumulate atoms by diffusion that means that

the distance between interface protuberances must be less than the atomic

diffusion distance during solidification. Increasing the solidification cooling rates

reduces the diffusion distance and interface protuberances distance and this

requires very high surface energy. Once the high surface energy for stable

protuberances can no longer be reached, planar growth again becomes stable and

that means there is a limit of stability for such planar growth [130, 131].It is

reported that above this limit, planar growth produces a segregation free

microstructure by trapping the solute in solid solution. Therefore, a uniform

composition across the melted layer can be produced with no signal of second

phases and extended element solubility limits.

4.4 Effect of LSM Interaction

Some lasers operate continuously, and are termed continuous wave (CW) lasers,

while other lasers operate discontinuously and are known as pulse lasers. For

CW lasers, their interaction time is controlled by the translation speed of either

the laser or the sample. For pulse lasers, the pulse duration is the interaction time.

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Different lasers produce different wavelengths. Table 4-1 shows examples of

LSM types and their wavelengths [164]. The laser gain medium is responsible

for producing these wavelengths which then can be used as a selection criterion

for particular applications of LSM [136, 137,164].

In LSM, radiation is absorbed into a thin surface region of metal or alloy and

thermal energy is then conducted away from the surface to the material bulk

[138]. Figure 4-6 shows a schematic illustration of the laser beam interaction

with the surface of the material [138]. The red arrows in the Fig. represented the

thermal diffusion on the surface. The high temperatures that are produced by the

laser are enough to melt the surface and a fusion interface can develop that

propagates from the substrate. Further increasing in the heating rates can result in

vaporisation of the material that causes problems in the LSM as it creates an

intense plasma which can deflect the laser beam and lower the energy density at

the surface. As vaporised material escapes from the molten material, it can cause

poorer and un homogeneous surface with an increase in the surface tension

sideways movement in the melted area [139-141]. Therefore, rapid cooling

occurs once the radiation is removed from the surface that freezes the material to

form non-equilibrium structure as there is not sufficient time for diffusion or

precipitation [142-144]. The high cooling rates occur as the substrate material

acts as a heat sink and it is reported that the cooling rates in excimer LSM can

reach 109-1011 K/s in comparison with CW-CO2 laser that reach 103-105 K/s

[145, 146].

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4.5 Effect of LSM Processing Parameters

As have been mentioned in the previous section, different lasers produce

different wavelengths that depend on the laser gain medium, which are then used

as laser selection criteria for an application such as LSM. The selection process

of LSM is usually based on its inherent characteristics, including pulse duration

and wavelength. In some lasers, the pulse duration and the wavelength can vary

due to change in the gain medium excitation that alters the resultant pulse

duration [147]. The changes in these characteristics, as well as other processing

variables such as energy, a number of pulses per unit area, scan rate, atmosphere,

spot size, and the beam overlap area, can affect the surface of the laser treated

layer [148]. In excimer LSM, the laser energy density and the number of pulses

per unit area have great influences on the laser melted layer than that of the other

laser processing variables.

4.5.1 Energy

The objective of LSM processing on metals and alloys is to modify their surface

structures and that depends strongly on the laser energy density or laser fluence

(J/cm2) as well as the number of pulses of the laser used. Laser processing with a

very low fluence may not induce material modification as there is not enough

energy to cause melting. However, there might be sufficient energy available for

removing any contamination from the surface, such as strongly bound dirt or

paint [141, 149]. In laser processing with a high fluence (high energy density),

the degree of surface heating causes more material melting that results in an

increase in the thickness of the melting layer [150-153]. An increase in the

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fluence means an increase in the energy input to the substrate to a level higher

than required for melting alone. At this higher level, evaporation occurs for the

melted regions that affect the thickness of the modified layer and produces poor

melting. Therefore, there will be a maximum layer thickness that can be reached

by increasing the laser fluence [148]. To induce material modification through

surface melting requires an increase in the laser fluence up to the melting

threshold value [147, 148, 150]. Under this value, there is a step change in the

material state as well as enhancement of radiation absorptivity [147]. The change

in the radiation absorptivity of the melted regions means that in the LSM process,

the energy absorbed is not constant over the pulse duration. If the changes in

absorption during LSM could be controlled by varying the fluence over the pulse

duration, there would be an increase in process efficiency and decrease in

material vaporisation [147].

4.5.2 Wavelength

For CW-LSM, the absorption of the laser radiation into a surface is related to the

radiation wavelength, while in pulsed-LSM there is no clear relationship between

wavelength and absorption due to the influence of the pulse duration, but

generally an increase in pulse duration will increase absorptivity [135, 152]. The

surface to be treated can also affect the radiation absorptivity in different ways

including roughness, oxidation, temperature and state [150, 152, 154]. For

example, there is higher radiation absorptivity when the substrate surface is

rough or in the presence of surface oxide [155]. In term of highly reactive

materials, such as aluminium, the application of an absorbent coating such as

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graphite may be used to enhance the radiation absorptivity on their surfaces

[135].

4.5.3 Pulse Duration and Interaction Time

It is mentioned in the section 4-5 that the interaction time for continuous wave

(CW) lasers is controlled by the translation speed of either the laser or the sample

whereas in pulse lasers the interaction time is determined by the pulse duration.

Generally, the interaction time of CW-lasers is longer than that of most pulsed

lasers due to limitations in the scanning speed systems that have to be employed.

It is reported that longer interaction times for CW-lasers tend to form thicker

modified layers with slower solidification rates and more segregation than with

layers produced by pulsed lasers [142-157]. Increased segregation in a thicker

solidification structure will cause a decrease in corrosion resistance, so thinner

layers produced by pulsed lasers with more rapid cooling rates would be

beneficial in terms of corrosion resistance [158-163]. The layer thickness

produced in LSM processes is influenced by both the interaction time and the

fluence [145-150]. This influence can be explained using the surface temperature

gradients and vaporisation threshold [150-152]. Initially, the laser surface

melting temperature is higher than the melting temperature but less than

vaporisation threshold and therefore, the melt depth can be increased by an

increase in energy density and melting until the temperature at the surface

exceeds the vaporisation temperature (boiling temperature) and the maximum

possible melt depth is reached. Since any further increases in energy density will

cause vaporisation and loss of material, the pulse duration becomes important as

an increase in pulse duration will further increase the melt depth at constant

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power [159]. Figure 4-7 shows the influence of pulse duration in the LSM of

pure metals with respect to the maximum depth of the melting layer [159]. On

the other hand the interaction time of the laser beam is influenced by the pulse

repetition frequency (PRF), and if the PRF is decreased, the interaction time will

be increased at constant power. Therefore, an optimum processing interaction

time can be controlled under PRF. Note that the fluence value required for the

surface temperature to reach the vaporisation temperature may be dependent on

the pulse duration too [158].

4.5.4 Number of Pulses per Unit Area

The number of pulses per unit area used in LSM processes has been observed to

affect the melting structure in a number of ways. It is reported that an increase in

the number of pulses per unit area causes an increase in melt depth [180, 201-

204]. If each pulse interacts with the surface material to create an increase in

melt depth, several pulses can increase the region of melted depth and

subsequently the thickness of the melted layer. However, as an increase in the

number of pulses causes movement to be induced in the liquid material

(explained in section 4.4.2). This movement in the liquid state pushes the

material away from the centre of the laser pulse to the edges and with increasing

the repeated number of pulses per unit area results in an increase in the peak

layer thickness and the surface roughness [159, 160, 180]. Also, to apply a large

number of pulses to a single location would lead to an extremely slow process

time when treating large areas of material. This will then impose a limit on the

number of pulses and hence a level of homogenisation that can be achieved

[161]. Further studies of samples treated with a large number of pulses per unit

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area showed that they can suffer from severe porosity [162, 180]. Generally,

metals need to be treated with a large number of pulses per unit area practically

influenced by laser energy density, pulse duration, interaction time, and scan

rate. If these parameters are set correctly with respect to material composition,

then the quality of the modified-melted layer can be improved.

4.5.5 Process Environment

LSM processes can be applied in different environments; each has its own

advantages [123, 139, 142, 177-179]. For example, excimer LSM can be used in

air and/or gas atmospheres. In both environments, the structure of the substrate

surfaces can be modified. In order to compare between these modifications, it is

important to know the nature of the reactions at their surfaces. In a nitrogen

environment, the nature of the chemical reaction is to increase the amount of

nitride precipitates within the modified layer, which is beneficial in increasing

wear resistance and hardening, while in an open environment, the modified layer

is beneficial in terms of corrosion resistance as the main principle in using

excimer laser in this project is to eliminate the large number of intermetallic

particles and precipitates from the alloy surface and produce a uniform melted

layer that assist in improving the corrosion resistance without affecting the alloy

bulk properties.

4.6 Microstructure of LSM Alloys

At very high solidification rates (higher than the local diffusion rate), equilibrium

at the liquid/solid interface cannot be established and the solute atoms are frozen

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into the solid at the same composition as they arrive at the interface (solute

trapping). However, at low solidification rates (less than the diffusion rate), local

equilibrium can be established and interface crystals can achieve the same

composition as the melt [124, 163]. Therefore, a high cooling rate, as in LSM

results in a fine solidified microstructure, which may contain non-equilibrium

phases, new precipitates and extended solid solubility. Rapid solidification

microstructures have been investigated after using different LSM techniques

[129, 135, 153, 164, 165]. Studies, by TEM, of microstructures produced by

CW-CO2 LSM of Al-Cu alloy confirmed that the microstructure morphology was

a function of the dendrites growth rate in rapid solidification [153]. Furthermore,

for LSM of Al-Cu alloy, a map has been created that correlates the

microstructure to both the growth rate and the material composition [165]. A

variation in solidification structure due to composition and growth rate changes

has been shown to occur through the thickness of modified layers. For example,

a planar growth region was observed at the base of modified layers in CW-

Nd:YAG LSM of AA 2014-T6, whereas the rest of the layer had a segregated

cellular structure, as can be shown in Figure 4-8 [161]. The base of the modified

layer is often referred to as the fusion boundary. Solidification always starts and

accelerates from the fusion boundary, that means that the depth of the modified

layer has an effect on the growth rate and the fastest solidification front velocity

that can be achieved within it. Ryan et al. have modelled the variation of

solidification in excimer LSM of AA 2024 for a single radiation pulse [166].

They observed that there is an initial transient region on re-solidification

following each pulse, and the growth front is rapidly accelerating. They found

that the growth front travels at speed of 5 m s-1 after a distance of ~500 nm,

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whereupon it appears to obtain stability. They concluded there will be a narrow

initial region of growth at start of re-solidification of each pulse where the front

can become morphological unstable, resulting in the formation of solute

segregation or banded structures. Figure 4-9 shows the results from this

modelling [166]. CW-Nd:YAG LSM of AA 2014-T6 alloy showed that the

variation in the growth rate changed the dendrite arm spacing from 5 µm at

fusion boundary into 2 µm near the top surface as illustrated in Figure 4-10

[161]. However, more segregation of elements was observed at the dendrite

boundaries, as can be clearly seen in the BSD image in Figure 4-11 [161]. It is

clear that the growth rate has been varied throughout the modified layer depth

and this would indicate that changing the modified layer thickness would also

change the growth rate along the solidification structure. Variations in modified

layer thickness have been attributed to the solidification structure scale [161]. An

increase in LSM layer thickness causes a decrease in the growth rate which in

turn increases the cell spacing and therefore, dendrites can be growth, and that

can be seen clearly in Figure 4-12, where different LSM processes have been

used to treat AA 2024-T3 [161]. A strong influence of the substrate material on

solidification was shown in studies of excimer LSM on AA 2024 and AA 7150

[166, 167]. LSM of these two alloys under identical processing conditions

produced different solidification structures. Planar growth was observed in AA

2024, and cellular growth observed in AA 7150 as shown in Figure 4-13. The

authors explained the differences in the solidification structures as being due to

differences in the alloying compositions. In AA 7150, cellular growth grew from

an equiaxed grain region that nucleated from either seed grains that were

coherent with the base layer or Al3Zr particles that solidified ahead of the

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solidification front. Therefore, the presence of zirconium in AA 7150 was

considered to be the main cause for cellular growth initiation and the

dramatically changed solidification structure compared with AA 2024 [166]. In

contrast, the authors investigated excimer LSM on both Zr-free AA 7075 and AA

2096 containing Zr/Li. The solidification layers on both alloys showed opposite

behaviour relative to AA 7150 containing Zr and AA 2024. A fine columnar

grain structure formed over AA 2096, which contains Zr, and a thin planar on Zr-

free AA 7075. Figure 4-16 shows the cross-sections of both alloys after LSM

treatments [166].

Several workers have carried out investigations on Al-Cu binary alloys after

LSM [168-170]. The solidification of the melted layer has shown to be epitaxial,

starting with a very thin layer of planar front growth [168, 169, 170]. For alloys

containing less than 5 wt% of Cu, the growth after the planar front region has

been reported to consist of dendrites of α-Al with either CuAl2 precipitates [168,

169] or CuAl2-Al eutectic as interdendritic phase. Muntiz showed the existence

of solute banding within the resolidified layer, which results from the differences

in the microstructure of the precipitated interdendritic phase due to local

changing in the solidification rate [173]. Milewski et al. used Nd:YAG LSM on

AA 2024 and observed similar solidification microstructure results to those

reported by Muntiz [176]. Noordhuis an De Hosson studied the nucleation of

precipitates in this alloy following 1.3 kW CO2 LSM and noted that the

nucleation could be induced after surface melting by shot peening for as little as

10 s [177]. In terms of Al-Zn alloys, Lasek et al. treated Al-Zn alloys with a CO2

laser operating at 200-1400 W. In Al 30 wt.% Zn, small spherical GP zones were

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seen to form in the partially melted grains at the heat affected zone (HAZ) region

[178]. Epitaxial planar front solidification was seen to occur at the maximum

melt depth, and transformation from planar front solidification to dendritic

growth was preceded at the region of planar front growth also contained solute

enriched droplets that solidified and precipitated β-Zn spheroids on the final

cooling [178]. For Al with 1 wt.% Zn, Lasek et al. found that there was no

cellular structure within the resolidified structure. In alloys containing 1, 6 and

10 wt.% Zn, a banded structure was observed [179]. Lasek mentioned that

cracking occured along the grain boundaries into the melted region and the

presence of high residual stresses concentrated in the HAZ and at grain

boundaries enabled the heterogeneous nucleation of equilibrium β-Zn particles

during room temperature ageing. Roosz et al. [181] investigated the surface

melting of Al 6 wt.% Zn and 2 wt.% Mg alloy. The microstructure of the

modified layer, in this case, consisted of planar front region at the maximum melt

depth that extended to the melt by as much as one quarter of the total melt depth

(~40/150 µm). The rest of the melt zone then solidified with a coarse cellular

dendritic structure [181].

Overall, the solidification microstructure of LSM on aluminium alloys can be

varied with different forms and shapes depending on the material composition

and the laser surface melting used. Planar, cellular and dendritic are the most

common solidification structure types that are formed in alloy surfaces. Planar is

the most appropriate structure for more corrosion resistance due to production of

uniform and homogenous melting layer above the bulk alloy. The variation of the

growth rate with rapid solidification can affect the melted layer thickness as well

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as the structure morphology. As mentioned above, decreasing growth rate will

increase the layer thickness and cell spacing that favours the formation of more

dendrites.

4.7 Corrosion Behaviour of LSM Alloys

In this part, corrosion investigations will be reviewed for different LSM of

aluminium alloys. Some workers noted an improvement of alloy surface

properties regarding corrosion attack. Bonora et al. were the first to study the

effect of LSM on the corrosion behaviour of pure Al using a Q-switched ruby

laser [154].Comparison between laser treated Al and untreated Al, showed that

the passive current density was lower in LSM Al than untreated Al under both

potentiostatic and potentiodynamic control, while the breakdown potential was

unchanged after LSM. They concluded that the lower corrosion rates were due to

a chemically inert, amorphous aluminium surface layer produced by LSM. This

effect was also produced for pure Al after LSM using a Q-switched Nd:YAG

laser, with corrosion tests carried out in boric-borate solution containing 1 g/l

NaCl [171]. Moore et al. studied the effect of LSM on the electrochemical

behaviour of AA 3003. They melted the alloy surface with a single pulse CO2

laser in vacuum. In anodic polarization tests, they observed that the rate of

anodic dissolution was less for the melted samples. However, the pitting

potential in deaerated 0.1 M NaCl was not improved and the free corrosion

potential was increased by 300 mV, having the unexpected effect of decreasing

the difference between the free corrosion potential and the pitting potential [182].

Moore et al. also used CO2 LSM to study the effect of laser surface modification

on the pitting behaviour of AA 2024. No improvement in the pitting resistance

after LSM was found due to many cracks and pores that were present in the

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melted layer that increased localised corrosion [182]. Another problem with

cracks and localised corrosion is that once the base of the melted layer is

breached, i.e. the transient region zone, there is an accelerated corrosion

perpendicular to the surface along this region causing layer delamination [162,

165]. It is reported that even with no cracks, layer delamination has been

observed once uniform corrosion has occurred over the surface and exposed the

transient region (interface) that contains different forms of solidification

microstructure [165]. McMahon [184] and Watkins et al. [185] reported that the

corrosion resistance was increased in LSM AA 2014, as the potential required to

cause appreciable pitting (Ep) was up to 100 mV higher after LSM. Ferreira et

al.[186] showed that for LSM of AA 2024-T351, the form of corrosion in 3 wt.%

NaCl solution was changed compared with the untreated alloy. For the as

received alloy, both pitting and intergranular corrosion were observed, while for

the LSM alloy only pitting corrosion was present. In AA 7075, there was a

decrease in the corrosion potential and an increase in the passive range during

polarization in deaerated 0.1 M NaCl solution. The increase of the passive range

may be that the LSM has low cathodic reactivity. Also, galvanic corrosion is less

of a risk if the LSM layer acts as a sacrificial layer for zinc-containing aluminium

alloys, where zinc can go into the solid solution providing more anodic

dissolution which led to the LSM layer being dissolved and the exposed substrate

being cathodically protected [157]. Further to these investigations, LSM can

remove surface precipitates by dissolving them into the melted solid solution,

which can reduce corrosion behaviour by protecting the alloy matrix. For

example, increase of Cu in the matrix will decrease the anodic activity [24].

However, in wide range of LSM studies, complete removal of precipitates and

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generation of a homogenous surface layer on base alloy has not been achieved

[145, 162, 178, 179]. Therefore, LSM reduces or eliminates the number of

precipitates in the surface region and modifies the structure [161, 162, 179].

Also, it has been mentioned that the corrosion in LSM layer is associated with

segregated regions within the melted layer [24, 166, 178]. Certain solidification

structures, such as cellular and dendritic, are more likely to produce segregation

that arises from low cooling rates. Therefore, reducing dendrite or cell spacing by

high cooling rates can lead to improvement in the corrosion resistance [20-24,

180-188].

In general, corrosion behaviour may vary with the material composition used and

the laser type, as well as laser processing parameters, particularly the cooling rate

induced by LSM that affects the solidification microstructure and any element

segregation within the modified layer [130]. Ideally, to improve the resistance of

LSM to corrosion, the melting layer has to be smooth, crack-and pore-free, and

uniform, with complete precipitate removal and containing no sensitive regions

from processing. The sensitive regions are always found in the overlap area

between the two tracks of pulse movements. This is due to the re-heating of the

laser area inducing further microstructure changes and causing micro-segregation

within very small regions [190].

4.8 Excimer Laser for LSM

The name Excimer laser derives from the excited dimer molecules which are the

lasing species. This laser is slightly different in that the gain is so strong that it

does not need an oscillator. In KrF excimer laser, an electric discharge is

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generated in a gas mixture of krypton (Kr) and fluorine (F). An excited dimer

KrF is formed which undergoes the stimulated emission process. It generates

ultraviolet photons in brief pulse for each discharge of the condenser bank into

the gas mixture. The generated pulses are usually very short, around 10 to 30 ns,

but are very powerful. The energy range of the light pulses vary between

milliJoules to Joules, average power up to several hundred watts, pulse repetition

frequency rate between 1 to 100 Hz. Operational limits are determined by the

rate of the high speed switching and the resonator length. The maximum gas flow

velocity determines the maximum pulse frequency obtainable. The short

wavelength ultraviolet (UV) light has high absorption, high spatial resolution,

and high photon energy. Therefore, it can be focused to a small spot size and

positioned with accuracy to process a wide range of materials including metals

and alloys. The short pulse width and high peak power of an excimer laser can

reduce the heat affected zone (HAZ) in most materials to a minimum. A further

advantage of the excimer laser is the generation of a very high cooling rate,

around 109-1011 K/s that can produce rapid solidification structure in the melted

area without affecting the bulk properties of the material being used. Studies of

the interaction of the KrF excimer laser with aluminium alloy surfaces, such as

Al-Cu-Mg alloys [24, 26, 201] indicated a melted layer with a uniform depth of

about 20 µm. The Laser beam was homogenized producing a square spot area.

The laser-treated surfaces exhibited a higher corrosion resistance than as received

material. Yue et al. [20, 21, 192] used an excimer laser to treat AA 7075 alloy.

The melted layer was about 8 µm thick. They also used the excimer laser with

another alloy, AA 6013. A laser melted layer of about 5 µm thickness was

formed at the surface [23]. The excimer laser was found to be effective in

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improving the pitting corrosion resistance and reducing intergranular corrosion

cracking onto the aluminium alloy surfaces. Ryan and Prangnell [166] indicated

that the pulse laser surface melting treatment by an excimer laser produces a

chemically more uniform layer on the top of AA 2024 friction stir weld material

and thus can give more protection of the alloy surface from environmental

corrosion attack. Overall, optimization of the operating parameters of the

excimer laser, such as energy density, number of pulses per unit area, pulse

repetition frequency and speed rate, will result in a highly refined surface layer of

the alloy without affecting the bulk properties. This is the aim of using KrF

excimer laser in the present work for treatment of the AA 7075-T6 alloy, which

is explained in detail in subsequent sections of the thesis.

4.9 Safety of Using Laser

4.9.1 Laser Classification

Lasers are categorized into four classes from low to high risk. The higher the

category, the more powerful and dangerous the laser is. Basically, all lasers used

for material processing fall into highest categories. The Accessible Emission

Limit (AEL) is the maximum emission level permitted within a particular class,

and is used to define the laser class. The Maximum Permissible Exposure (MPE)

is the maximum level of the laser radiation to which a human can be exposed

without adverse biological effects to the eye or skin. A pulsed laser is defined as

one of that delivers energy in single or multiple pulses which are less than or

equal to 0.25 s in duration.

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4.9.1.1 Class 1 Laser

Class 1 laser systems are considered incapable of producing damaging levels of

radiation during operation since the output of the laser is very low or because of

installed safeguards. The emitted radiation is enclosed and is not accessible. The

lasers can be installed anywhere and no eye protection is required for workers.

Class 1M lasers present no risk for skin damage, but could result in damage to

the eye if viewed with optical instruments such as binoculars.

4.9.1.2 Class 2 Laser

Class 2 laser systems emit visible radiation (370-750 nm) of low power (below 1

mW). They cannot damage a person accidently, but could damage the retina if

viewed directly for more than 0.25 s. For continuous wave (CW) lasers, the

power must not exceed 1 mW. It is the only class that applies exclusively to

visible lasers operating in CW and pulsed modes.

4.9.1.3 Class 3 Laser

Class 3 lasers are subdivided into class 3R and class 3B. Class 3R lasers may

emit visible or invisible radiation or both. If the beam is focused it presents a

hazard. Outside the visible range, these lasers cannot exceed five times the class

1 AEL. In the visible range, they may not exceed five times class 2 AEL (5 mW).

Class 3B lasers mark the border between medium and high power devices. The

beam of the visible class 3B laser may be safe to view on diffuse surface for less

than 10 seconds at a distance greater than 130 mm. However, eye protection

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should be worn. The power of visible class 3B laser must not exceed 0.5 W.

Exposure to 0.5 W for periods longer than 0.25 s is considered dangerous.

4.9.1.4 Class 4 Laser

Class 4 lasers operate above 0.5 W and produce radiant energy greater than 0.125

J within an exposure time of less than 0.25 s. Therefore, eye protection must be

worn. Fire and skin hazards are also associated with this class type of laser.

4.9.2 Risk Assessment

Risk assessment is a management tool that allows the user to be familiar with the

basis of both the specification of safety equipment and the content of safety

procedures. After checking with the safety manager, the user can ensure that

most important problems are recognized. The precautions taken to minimize risk

from these potential problems are noted. Once the necessary precautions have

been taken and noted, the risk assessment is kept for future reference.

4.9.3 Protection from Laser

4.9.3.1 Screening

All laser products require a protective housing that prevents access to radiation in

excess of the limits of class 1. When class 3B or class 4 lasers are in use, screens,

curtains, roller blinds, and window blocks are designed as passive guards to

enclose these areas. Window blocks are acrylic filters that enable the processing

zone to be viewed while stopping laser radiation from coming out. Shutters and

109
Laser

emission indicators (visible or audible) are required in all lasers above class 1

level. Operating controls must be located such that the user is not exposed to

radiation. Safety and remote interlocks must be installed to prevent access to

radiation above class 1 level. Also, systems such as 3B and 4 classes must have a

key control that cannot be removed during operation.

4.9.3.2 Protective Eyewear

The eye can detect and focus light in the range of wavelength 350-750 nm that

corresponding to the spectrum of colours in the rainbow. The eye also has an

ocular focus region that includes wavelengths from the end of the red to 1400

nm. CW lasers can cause damage by thermal processes that overheat the tissue.

Pulsed lasers can cause damage from acoustic and vibrational shocks that rupture

blood vessels in the retina. Absorption eyewear is the most commonly used type

of eye protection. The laser beam is blocked by absorption of the relevant

frequency. Glass or plastic absorption filters, with incorporated organic dye for

the plastic filters, can easily be made specific to a particular wavelength or

power, which reduces colour distortion and protects the eye from any damage.

110
Laser

4.10 List of Figures

Figure 4-1: Energy level diagram for a three electron energy level of a laser
and a pulse system [126]

Figure 4-2: Energy level diagram for a four electron energy level of a
continuous (CW) laser system [126]

111
Laser

Figure 4-3: Variation in total free energy of solid-liquid system as the size of
the solid changes. The solid is stable nuclei with radius above the critical
value r* [132]

Figure 4-4: Various growth structures that show planar (a), cellular (b),
columnar dendrites (c), and equiaxed dendrites (d) [125]

112
Laser

Figure 4-5: Schematic representing the solidification transformation from


cell (a), cellular dendrites (b), columnar (c), and to columnar dendrite
branches (d) [130]

Table 4-1: Examples of LSM types and their wavelengths [164]

Laser Wavelength Pulse length Operation

Excimer (KrF) 248 nm 13-25 ns Pulsed


Excimer (XeCl) 308 nm 25 ns Pulsed
Ruby 0.694 μm 0.2-5 ms Pulsed
Nd:YAG 1.06 μm 200 ns Repetitively
(Q-switched)
CW-Nd:YAG 1.06 μm - Continuous
CO2 10.6 μm 50-200 ns Repetitively
(Q-switched)
CW-CO2 10.6 μm - Continuous

113
Laser

Figure 4-6: Schematic illustration of the laser beam interaction with the
surface of a material [138]

Figure 4-7: Influence of the pulse duration in LSM of pure metals on the
maximum depth of the melting layer [159]

114
Laser

Figure 4-8: Cross-section of CW-Nd:YAG LSM on AA 2014-T6 alloy,


following etching, that shows different regions of the solidification structure
[161]

Figure 4-9: Modelling results of excimer LSM of AA 2024 alloy for a single
pulse that show the solidification growth velocity as a function of position
within the modified layer, including different layer thicknesses [166]

115
Laser

Figure 4-10: Scanning electron micrographs of 3 kW CW-Nd:YAG LSM


AA 2014-T6 alloy showing the variation in growth rate and dendrite spacing
with position in modified layer [161]

Figure 4-11: Electron probe micro-analysis X-ray mapping of 3 kW CW-


Nd:YAG LSM AA 2014-T451 alloy, show element segregation throughout
the modified layer [161]

116
Laser

Figure 4-12: Variation in cell spacing with melt depth for AA 2024-T3 alloy
using a variety of pulsed treatment methods with scanning electron
micrographs of the microstructure at different depths [166]

117
Laser

Figure 4-13: High resolution EBSD map showing LSM layer morphology
obtained with excimer laser treatment in Zr-free alloy (AA 2024) and Zr-
containing alloys (AA 7150) [166]

Figure 4-14: Cross-section micrographs through excimer LSM treated


layers formed over (a) AA 2096 alloy containing Zr and (b) AA 7075 Zr-free
alloys, showing the layer grain structure with behaviour opposite to that
found in Fig 4-13 [166].

118
Chapter 5

Experimental Procedures

5. Introduction

This project aims to increase the resistance of AA 7075-T6 aluminium alloy to

corrosion, without affecting its bulk properties, by laser surface melting (LSM),

using an excimer laser. In order to optimise the corrosion improvement, the

excimer laser was used with different numbers of pulses per unit area and

varying energy density of the laser pulses.

After LSM, anodising was used with the aim of adding more protection to the

laser-treated area. The corrosion susceptibility of the alloy in the as-received,

laser-surface melted, and laser surface melting followed by anodising conditions

was assessed by electrochemical measurements (potentiodynamic polarization),

immersion testing in sodium chloride solution and exfoliation testing in EXCO

solution in order to evaluate the pitting and intergranular corrosion resistances of

the as-received alloy in comparison with the alloy treated by LSM with and

without anodising. This Chapter describes the procedures of surface preparation,

corrosion test evaluations and the characterisation techniques.

119
Experimental Procedures

5.1 Substrate Materials

The material used in the experiments was aluminium alloy AA 7075-T6 sheet of

4 mm thickness supplied by Dolgarrog Aluminium Limited, North Wales, UK.

Table 5-1 shows the chemical composition in wt% of the alloy that was provided

by the supplier.

Table 5-1: The chemical composition of the as-received AA 7075-T6 alloy

Element Zn Mg Cu Cr Fe Mn Si Ti

Wt% 5.83 2.45 1.67 0.21 0.24 0.08 0.12 0.03

5.2 Surface Preparation for LSM Treatment

The following preparation of the specimens was carried out before applying

LSM.

Specimens of dimension 20x20 mm, were cut from the as-received AA 7075-

T6 alloy sheet to provide L-ST faces for testing.

Specimens were then wet ground on the top surface using emery papers in

the sequence 400, 600, 800 and 1200 grit. A new paper was used for grinding

each specimen surface.

Specimens were then cleaned in an ultrasonic bath, using deionised water

followed by ethanol for about 20 minutes in each case.

Specimens were then dried in air for about 24 h before applying the LSM

treatment.

120
Experimental Procedures

Laser surface melting (LSM) was carried out in air using a Lumonics IPEX-848

excimer laser, operated at 80 W with a wavelength of 248 nm. The conditions of

LSM are given in Chapter 7, which shows the results of studies carried out to

optimize the laser parameters. After LSM, the specimens were cleaned with

deionised water and dried in air for 24 h. An aluminium rod of 1 mm in diameter

was attached for electrical connection for electrochemical tests. Lacquer (45-

stopping-off) was used to mask regions not treated by LSM.

5.3 Anodising

The alloy after LSM, with an area of about 80 mm2, was anodised in order to

further protect the laser surface melting layer from corrosion. In the anodising

procedure, stirred 0.46 M sulphuric acid (H2SO4) solution at a temperature of 297

K was used, with anodising carried out potentiostatically at 12 V (SCE) for a

total time of 240, 720 and 1200 s. A two-electrode cell was employed with the

specimen as the anode and an aluminium sheet as the cathode. All the electrodes

were electrically connected to a potentiostat (Solartron SI 1287 Electrochemical

Interface). During anodising, the current-density (I) vs. time (t) was monitored.

The selected anodising condition ensures the generation of a well-developed

porous anodic oxide [198]. After anodising, sealing the anodic films was

accomplished by immersion of the alloy specimens in boiling deionised water for

30 min. In addition, the as-received alloy was ground to 1200 SiC, then anodised

and sealed under similar conditions to those used for the LSM specimens, to

provide a reference condition for comparison purposes.

121
Experimental Procedures

5.4 Corrosion Investigation

Three different types of corrosion tests have been employed. Each was repeated

for a minimum of three times. Potentiodynamic polarization and immersion

testing in sodium chloride solutions, and exfoliation testing in EXCO solution,

were used, with comparison made between as-received and LSM alloy

specimens.

5.4.1 Potentiodynamic Polarization Test

In potentiodynamic polarization measurements, each specimen of AA 7075-T6

alloy, in the as-received, laser-treated and laser-treated followed by anodising

conditions, was masked with (45-stopping-off) lacquer, leaving about 20 mm2

unmasked. A second layer of masking was applied after 2 h. The two mask layers

were left to dry in air for (24 h) at room temperature before commencement of

the electrochemical measurements. Deaerated 0.1 M NaCl was used as the test

solution. Deaeration was achieved by passing nitrogen in a closed cell containing

the electrolyte for 2400 s before immersion of the specimens. Each specimen was

then immersed in the solution for 40 minutes to stabilize the open circuit

potential (OCP), with continued purging of the cell with nitrogen carried out

throughout the test. The working electrode (specimen), counter electrode

(platinum), and reference electrode (saturated calomel electrode (SCE)) were

connected to a potentiostat (1280 Solatron), which allowed the change of the

potential of the specimen in a controlled manner and measurement of the current

flow, with a current resolution of 0.1 μA, as a function of potential. Anodic

polarization was applied from about 100 mV below the open circuit potential,

122
Experimental Procedures

with a potential scan rate of 0.1667 mV/s, according to the ASTM standard [78,

195].

5.4.2 Immersion Test

In immersion tests, each of the laser-treated and untreated substrates was

immersed for 24 h in 0.1 M NaCl solution, open to air, at room temperature. This

type of corrosion test is used to evaluate the susceptibility of the alloy to pitting

and intergranular corrosion.

5.4.3 Exfoliation (EXCO) Test

The as-received and laser-treated AA 7075-T6 alloy was immersed in the EXCO

test solution for various times, up to several hours. The test solution was

prepared according to the ASTM G-34-01 standard test method for exfoliation

corrosion susceptibility in 2XXX and 7XXX series aluminium alloys [196]. The

test was carried out at room temperature and the solution contains 4.0 M NaCl,

0.5 M KNO3 and 0.1 M HNO3 [196].

5.5 Specimen Preparation for Metallographic Examination

In order to prepare the specimen after LSM for surface and microstructure

examinations, the following steps were undertaken.

Specimens were cut in cross-section, using a Struers Accutom-5 disc cutting

machine, with a high speed coolant fluid to prevent temperature rises,

generated due to friction that could affect the LSM layer.

123
Experimental Procedures

Cut specimens were mounted in conducting resin, containing graphite.

Mounted specimen surfaces were ground with SiC paper in the sequence 400,

600, 800, 1200, 2500 and 4000 grit.

Ground specimens were polished with 6, 3, and 1 µm diamond paste.

Specimens were washed with deionised water after each step of polishing,

with changing of the clothes for each paste.

After polishing, specimens were cleaned in an ultra-sonic bath containing

ethanol for 15 minutes.

Finally, specimens were cleaned with deionised water and dried in a stream of

air for several hours prior to investigation.

5.6 Field Energy Gun Scanning Electron Microscopy (FEG-

SEM)

Scanning electron microscopy (SEM) is capable of producing high-resolution

images of the specimen surface. Secondary electron (SE) images were taken, in

which most of the electrons collected by the detector originate from the near-

surface region of the sample. Backscattered electron (BSE) images convey

information on the atomic number from a greater depth in the sample. An EDX

spectrometer was used to analyse elemental compositions and the distribution of

the elements, the latter using the mapping analysis option. In this project, a

Philips XL30 FEG-SEM microscope, operated at 20 kV, was employed for

examining the surface and cross-sections of specimens.

124
Experimental Procedures

5.7 Transmission Electron Microscopy (TEM)

In transmission electron microscopy, a beam of electrons is transmitted through a

specimen, then an image is formed, either on a florescent screen or layer of

photographic film, or using a sensor such as a CCD camera [193]. The main use

of the transmission electron microscope is to examine in sub-microscopic detail

the structure and composition of specimen. The specimen for TEM investigation

was prepared using a Leica Ultracut ultramicrotome. Sections of the specimen

(approx. 20 nm thick) were cut using a diamond knife and collected on nickel

grids for examination. In the present work, JEOL 2000 FX II and FEI F30 Tecnai

microscopes were employed. The microscopes were operated at 120 and 300 kV

respectively. The Tecnai microscope was equipped with high angle annular dark

field (HAADF) imaging and EDX analysis systems.

5.8 X-ray Diffraction (XRD)

X-ray diffraction is an analytical technique used to obtain information about

crystallographic structure, chemical composition, and physical properties of

materials. XRD is based on observing the scattered intensity of the X-ray beam

of a selected wavelength (λ) hitting a sample as a function of the incident and

scattered angles (θ) [194]. The intensity of the diffracted beam as a function of

2θ, the angle between the incident ray and the scattering planes, is recorded and

peaks are observed at the Bragg’s law condition (λ = 2dsinθ). The results are

compared with the powder diffraction index that contains the d-spacing between

planes in the atomic lattice and the relative intensity values for a large number of

elements and compounds in order to determine the phase structure. An X' Pert

125
Experimental Procedures

MPD Diffractometer was used in the present work, with low angle X-ray

scattering (~2º), which allows to identify compounds in thin layer on the surface

of the alloy.

126
Chapter 6 Results
6. Microstructure and Corrosion of the As-
Received AA 7075-T6 Alloy

6.1 Microstructural Examination

The FEG-SEM images of Fig. 6-1 show that relatively large constituent particles

(examples are circled in yellow) are present at the surface of the as-received AA

7075-T6 alloy specimens after mechanical grinding and polishing of the sheet

surface up to 1 µm diamond paste. The particles are aligned in the rolling

direction. Fig. 6-2 shows constituent particles on a polished alloy cross-section of

the sheet normal to the direction of rolling. The particles range in size from about

1.5-12 µm. Examination at high magnification shows also the presence of

cavities on the alloy surface (see arrow in Fig. 6-2 (a)), where particles have been

either removed or dissolved during polishing of the specimens. Some cavities

appear to contain remnants of second phase particles, as indicated by the arrow in

Fig 6-2 (c). The EDX line scans of Fig. 6-3 and 6-4, indicate the presence of

aluminium, copper and iron in the large particles, while the cavities reveal the

presence of magnesium and silicon. The arrows in Fig. 6-3 (c) show a region of

relatively high copper, and the presence of iron, suggesting the presence of

copper-iron-rich precipitates at these area locations, while the green arrows in the

Fig. 6-4 (c) show a region rich in iron and relatively low in copper. The EDX

mapping analysis, shown in Figs. 6-5 and 6-6, confirms the presence of copper

and iron in the large constituent particles, while magnesium and silicon are

present at the locations of cavities. An iron-rich particle of low copper content is

also evident. The EDX spectrum analysis, as shown in Fig. 6-7, indicates that

127
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

zinc and magnesium are distributed relatively uniformly in the alloy matrix. It is

reported in the literature that the large constituent particles consist of Al7Cu2Fe,

Al2Cu (θ-phase) and Al3Fe (β-phase), while smaller particles containing

magnesium and silicon consist of Mg2Si (β-phase) [4, 12, 32, 33,]. Magnesium

and zinc precipitates along the grain boundaries as MgZn2 (η-phase) [3, 5, 7, 32,

33].

6.2 X-Ray Diffraction

Fig. 6-8 shows the results of the XRD measurements on the as-received AA

7075-T6 alloy. The low angle X-ray diffractometer analysis on the alloy surface

indicates the presence of two types of second phases (Al7Cu2Fe and Mg2Si),

evident from low intensity peaks. No peaks are detected from Al2Cu and Al3Fe,

suggesting that such phases are minor constituents of the alloy. Al(Cu,Fe) second

phase was also observed in the EDX line scan analysis of the large second phase

particles, using FEG-SEM, confirming that most of the large intermetallic

particles of the AA 7075-T6 alloy contain copper and iron. The presence of

magnesium and silicon was also evident by EDX analysis in cavities on the alloy

surface, where remnants of Mg2Si particles inside.

6.3 Corrosion Test Results

6.3.1 Potentiodynamic Polarization Test

Fig. 6-9 shows the anodic potentiodynamic polarization scans of the AA 7075-T6

alloy, in the as-received condition and in the polished condition, in 0.1 M NaCl

128
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

deaerated solution. The potential scan starts from point 1 and progresses in the

positive direction until termination at point 2. At point A, the open circuit

potential (OCP), the sum of the anodic and cathodic currents on the specimen

surface of the working electrode is equal to zero. The corrosion potentials (Ecorr)

of the as-received and as-polished alloy were recorded as -0.920 and -0.930 V vs

SCE, respectively. As the potential increases, the current increases and a low

current density of about 1.0x10-7 A/cm2 for the as-received alloy and 3.3x10-7

A/cm2 for the polished alloy is recorded in the passive region that terminates at

point B. The passive film then breaks down and the current density rapidly

increases. This increase in the current density is due to pitting corrosion. The

pitting potential (Epit) was recorded as about -0.710 V (SCE) for the as-received

alloy and -0.695 V (SCE) for the as-polished alloy. Point C shows a second

breakdown potential of the polished alloy. With further increase in potential, pits

propagate on the alloy surface [27, 197].

6.3.2 Immersion Test

Fig. 6-10 shows scanning electron micrographs of the as-received AA 7075-T6

alloy surface after immersion in 0.1 M NaCl solution, open to the air, for an

exposure time of 24 h. Figs. 6-10 (a) and (b) show pits adjacent to intermetallic

particles on the alloy surface, while Figs. 6-10 (c) and (d) show pits free of

second phase, possibly due to particles being removed by corrosion during

immersion in the NaCl solution. Corrosion around particles may also lead to their

undermining, with the particles then falling from the alloy surface. In the

examples shown in Fig. 6-10, the size and depth of the pitting adjacent to

intermetallic particles were slightly greater than those at sites where intermetallic

129
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

particles were absent (10 and 5 μm in Fig. 6-10 (b) and 5 and 4 μm in Fig. 6-10

(d)). Cavities may also result from dissolution of Mg2Si phase and possibly also

from loss of particles during preparation of the cross-section.

6.3.3 Exfoliation Test

Fig. 6-11 shows the top surface of the as-received AA 7075-T6 alloy after

exfoliation corrosion testing for 180 min. Fig. 6-11 (a) and (b) show the surface

of the alloy before testing, while Fig. 6-11 (c) and (d) show the surface of the

alloy after testing. The arrows in the Fig. 6-11 (c, d) show that the corrosion

occurred due to the presence of second phase particles. Fig. 6-12 shows a cross-

section of the as-received AA 7075-T6 alloy after exfoliation corrosion testing

for different times (30, 60, 90 and 120 minutes). Fig. 6-12 (a) shows the presence

of corrosion products after the shortest time of immersion (30 min). The

corrosion extends laterally under the alloy surface. The depth of the attack

increases with increasing the time of immersion, and results in relatively thick,

cracked layers of corrosion product, with the presence of directional attack along

the rolling direction as in Fig. 6-12 (c) and (d). The depth of the attack was

measured to be 15 μm after 30 min, 75 μm after 60 min, 100 µm after 90 min and

140 μm after 120 min of immersion The occurrence of intergranular corrosion

(IGC) on the AA 7075-T6 alloy is generally accepted to be due to precipitates of

MgZn2-η phases on the grain boundaries [3, 5, 7, 10]. The anodic behaviour of

these precipitates allows preferential dissolution along the grain boundary

regions.

130
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

6.4 Conclusions

The AA 7075-T6 alloy after surface and cross-section examinations revealed

different sizes of intermetallic particles that are aligned in the rolling direction.

Large particles were copper-and iron-rich, and small particles were magnesium-

and silicon-rich. XRD disclosed the presence of Mg2Si and Al7Cu2Fe phases. In

potentiodynamic polarization tests in 0.1 M NaCl (deaerated condition), the

corrosion potential (Ecorr) and the pitting potential (Epit) of the alloy were

measured to be -0.930 V and -0.695 V (vs SCE) respectively, and the average

passive range of potential was 0.235 V. After immersion testing in 0.1 M NaCl,

the alloy exhibited pitting adjacent to second phase particles, associated with

dissolution of the surrounding matrix. Exfoliation (EXCO) tests show that

corrosion occurred within 30 min of immersion, and extended into the matrix

with increasing time of immersion. The aggressiveness of the test solution with

presence of second phase particles on the alloy surface allows intergranular

corrosion (IGC) to propagate along selected grain boundaries.

131
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

6.5 List of Figures

Figure 6-1: Scanning electron micrographs showing the surface of the AA


7075-T6 alloy at different magnification after grinding and polishing up to 1
µm diamond paste. (a) Secondary electrons. (b-d) Backscattered electrons.

132
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-2: Scanning electron micrographs for the AA 7075-T6 alloy. The
cross-section is normal to the rolling direction (a,c). Particles are shown in
two different regions, while (b,d) are given the dimensions of the particles
and cavities. (a,b) Secondary electrons. (b,d) Backscattered electrons.

133
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-3: SEM-EDX line scan measurements that show the elements
present in the constituent particles and precipitates in AA 7075-T6 alloy of
the cross-section that is shown also in Fig.(8-2). The scans show Cu and Fe in
the large particles, while Mg and Si are present at the cavities where
residual particles are present. Zn appears to be distributed in both the alloy
matrix and the particles.

134
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-4 : SEM-EDX line scan measurement on intermetallic particles on


the AA 7075-T6 alloy surface. (a,b) Scanning electron micrographs
(backscattered electrons). (c) EDX line-scan analysis.

135
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-5: SEM-EDX mapping analysis of AA 7075-T6 alloy. (a)


Micrograph of the surface revealing the presence of intermetallic particles.
(b) Aluminium. (c) Zinc. (d) Silicon. (e) Magnesium. (f) Manganese. (g) Iron.
(h) Copper.

136
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-6: SEM-EDX mapping analysis of AA 7075-T6 alloy at the region


shown previously in Fig 6-3. (a) Micrograph of the surface (b) Aluminium.
(c) Zinc. (d) Manganese. (e) Copper. (f) Iron. (g) Magnesium. (h) Silicon.

137
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-7: Results of SEM-EDX spot analysis of different area of the


matrix of AA 7075-T6 alloy. (a) and (c) Scanning electron micrographs
showing the location of the analysis region. (b) and (d) EDX spectrum.

138
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-8: Results of low angle X-ray diffraction measurments for the as-
received AA 7075-T6 alloy.

139
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-9: Anodic potentiodynamic polarization scan of the as-received and


polished AA 7075-T6 alloys, in deaerated 0.1 M NaCl. The scan starts at
point 1 and terminates at point 2. Point A shows the corrosion potential
(Ecorr), while point B shows the pitting potential (Epit). Point C shows a
second breakdown potential on AR-polished alloy.

Table 6-1: The corrosion potential (Ecorr), pitting potential (Epit), passive
current density (Ipass) and passive range potential (Epass) from Fig 6-8.
Potentials are given with respect to SCE.
Sample Ecorr (V) Epit (V) Ipass (A/cm2) Epass (V)

AR -0.920 -0.710 1.0x10-7 0.210

AR-polished -0.930 -0.695 3.3x10-7 0.235

140
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-10: Scanning electron micrographs (BSE) of cross-sections of AA


7075-T6 alloy after immersion in 0.1 M NaCl, open to the air, for 24 h. (a, c)
Low magnification images. (b, d) Increased magnification images of (a, c).
Images (a, b) reveal pitting corrosion adjacent to intermetallic particles on
the alloy surface. Images (c, d) show pits free of second phases.

141
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-11: Scanning electron micrographs of the top surface of the AA


7075-T6 alloy before and after immersion in EXCO solution for 180
minutes. (a, b) AR alloy before immersion. (c, d) AR alloy after immersion.

142
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy

Figure 6-12: Scanning electron micrographs (BSE) of cross-sections of the


AA 7075-T6 alloy after immersion in EXCO solution for (a) 30, (b) 60, (c) 90
and (d) 120 minutes.

143
Chapter 7

7. Laser Surface Melting (LSM) Operation


Conditions

Laser surface melting was carried out in air using a Lumonics IPEX-848 excimer

laser, operated at 80 W with a wavelength of 248 nm. Krypton fluoride (KrF)

was the laser active medium. The pulse duration was fixed at 13 ns. Different

numbers of laser pulses were used on the alloy surface, with an incident focused

laser beam of either high or low energy density. The laser spot size was

measured to be approximately 1.0 × 3.0 mm. Figures 7-1 and 7-2 show schematic

illustrations of excimer LSM and the incident of laser pulses at the surface of the

alloy specimen.

In the high pulse energy density condition, the fluence was 10 J/cm2. 10, 25 or 50

pulses were applied with pulse repetition frequencies (PRF) of 4, 10 and 20 Hz

respectively. In order to treat a relatively large area of the alloy surface sufficient

for corrosion evaluation, two laser tracks were used with an overlap ratio of 10%

between them to generate a total treated area of 100 mm2. Table 7-1 summarises

the laser operation conditions using the high pulse energy density.

In the low pulse energy density condition, the fluence was equal to 3.3 J/cm2. 70,

80 or 90 pulses per unit area were employed with pulse repetition frequencies of

25, 28 and 31 Hz respectively. Two tracks, with an overlap ratio of 10%, were

144
LSM Operation Conditions

used to generate a treated area of 100 mm2. Table 7-2 summarises the laser

operation condition using the low pulse energy density.

The peak power of the laser pulse (Pp), is giving by;

E
Pp [W] (1)
t

where E is the pulse energy in Joules and t is the pulse duration in seconds.

The power density or irradiance which refers to the power of the pulse applied

per unit area is given by;

P
Irradiance [W / cm2] (2)
A

The fluence refers to the total amount of pulse energy applied over the area of the

laser spot beam.

E
fluence [J / cm2] (3)
A

During LSM, the interaction time of the laser pulse, Tin, can be calculated by the

following equation;

Tin = length of laser pulse / scan rate velocity (4)

where the length of laser pulse in mm and the scan rate velocity in mm / s. The

number of pulses (NOP) produced is determined by the product of the laser pulse

repetition frequency (PRF) and interaction time;

NOP = PRF x Tin (5)

From the above equations, there is a direct relationship between the number of

pulses and the interaction time. For example, an increase in the number of pulses

increases the interaction time, and oppositely, a decrease in the number of pulses

145
LSM Operation Conditions

decreases the interaction time. Scanning electron micrographs of cross-sections

of the LSM AA 7075-T6 alloy treated with a high pulse energy density (10

J/cm2) shown in Fig. 7-3, disclosed a large number of pores and cracks in the

melted layers, which were more numerous with increase in the number of pulses.

The thickness of the melted layer increased with increasing of the number of

pulses from about 5 µm to about 15 µm between 10 and 50 pulses. The high

fluence of the laser pulses appeared to cause vaporisation of the alloy, and

therefore, porosity in the melted layer. Treating the alloy surface with excimer

LSM using a low pulse energy density needed a relatively high number of pulses

(i.e 70, 80 or 90) to achieve diffusion and mixing in the melt pool area of the

alloy surface. In contrast, treatments using a low fluence and a low number of

pulses (≤ 50 pulses) were insufficient to melt the large intermetallic particles at

the surface of the alloy; some of these particles (highlighted by yellow circles)

still remained in the melted layer, as evident in Fig. 7-4. Scanning electron

micrographs of cross-sections of the alloy treated with a low pulse fluence (3.3

J/cm2), using 70, 80 and 90 pulses, showed a relatively low number of pores and

a relatively uniform melted layer was produced at the surface of the alloy,

especially when using 80 pulses, as illustrated in Fig. 7-5, although some

porosity still remained. Fig. 7-6 demonstrated the influence of the number of

pulses of the excimer laser using both high and low energy densities on the

average thickness of the laser-melted layer and the size of the largest pores in the

melted layers, as measured from the scanning electron micrographs of the cross-

sections. It is shown from the graph that the alloy treated with 80 pulses at low

energy density has the lowest ratio of the pore size to the average thickness.

After LSM, each of the laser-treated areas of the alloy produced using high and

146
LSM Operation Conditions

low laser pulse energy densities was examined using potentiodynamic

polarisation tests in deaerated 0.1 M NaCl solution. The tests reveal the corrosion

potential, the pitting potential, the passive potential range and the passive current

density, and therefore, are a useful tool for corrosion evaluation. The AA 7075-

T6 alloy treated with a high pulse fluence, using 10, 25 and 50 pulses, showed a

reduction in the corrosion potential by about -181, -230 and -220 mV in

comparison with the corrosion potential of the as-received alloy, as shown in Fig.

7-7. This reduction in the corrosion potential could be attributed to a decrease in

the cathodic reactivity of the alloy surface after LSM by dissolution of the large

cathodic particles. Further, there was a reduction by one order of magnitude in

the passive current density for 10 and 25 pulses in comparison with the as-

received alloy, from 1.0x10-7 to 4.6x10-8and 7.3x10-8 A/cm2 respectively, and

less than one order of magnitude for 50 pulses from 1.0x10-7 to 1.6x10-7 A/cm2.

However, the pitting potential is not affected greatly, being about -670, -680 and

-695 mV (SCE) for 10, 25 and 50 pulses and -710 mV (SCE) for the as-received

alloy. Potentiodynamic polarisation tests, as presented in Fig 7-8, revealed a

further reduction in the passive current density of the LSM alloy treated with low

fluence, using 70, 80 and 90 pulses (3.4x10-9, 5.7x10-9 and 5.1x10-9 A/cm2)

respectively in comparison with the as-received alloy as well as the LSM alloy

treated with high fluence. Table 7-4 presents the measured values of the

corrosion potentials (Ecorr), pitting potentials (Epit), passive current densities (Ipass)

and passive potential ranges (Epass) from polarisation tests for specimens treated

with both high and low fluence; the potentials are expressed with respect to

(SCE). The alloy treated using 80 pulses and low fluence (3.3 J/cm2) shows the

147
LSM Operation Conditions

greatest reduction in the passive current density in comparison with the as-

received alloy and the alloy treated with high fluence.

From the previous conditions, it is important to select the appropriate parameter

values for LSM treatment in order to produce enough melting to dissolve

constituent particles at the substrate surface, since the aim of this project is to use

LSM to eliminate those large particles, which have been reported to increase the

corrosion in environments containing chloride ions [4, 12, 32, 33, 45-47].

From the above observations of the cross-sections and the results of

potentiodynamic polarisation tests of the excimer laser-treated on AA 7075-T6

alloys, it is more appropriate to use the low pulse energy density, rather than the

high pulse energy density, to treat the surface of the AA 7075-T6 alloy for

further improvement in corrosion resistance. The condition of low fluence with

80 pulses was selected for further evaluation of the corrosion properties of the

laser-treated alloy. The results are presented in Chapter 8.

148
LSM Operation Conditions

7.1 List of Figures

Table 7-1: Conditions of laser operation (high pulse energy density)

NOP Fluence
J/cm²
10 10
25 10
50 10

NOP: Number of pulses per unit area

Table 7-2: Conditions of laser operation (low pulse energy density)

NOP Fluence
J/cm²
70 3.3
80 3.3
90 3.3

149
LSM Operation Conditions

Figure 7-1: Schematic illustration of the excimer laser that shows the
focusing of the laser beam onto the surface of the alloy sample that is placed
on a motorised holder allowing movements in the X and Y directions.

150
LSM Operation Conditions

Figure 7-2: Schematic diagram representing the laser scanning pattern and
the incidence of the laser pulse on specimen surface.

151
LSM Operation Conditions

Figure 7-3: Scanning electron micrographs (backscattered electron) of


cross-sections of the LSM AA 7075-T6 alloy after treatment with high pulse
energy density (10 J/cm2), using 10 (a), 25 (b), and 50 (c) pulses.

152
LSM Operation Conditions

Figure 7-4: Scanning electron micrographs (secondary electron) of the top


surface of LSM AA 7075-T6 alloy, after treatment with low pulse energy
density. (a) 10 pulses, (b) 25 pulses, (c) 40 pulses and (d) 50 pulses

153
LSM Operation Conditions

Figure 7-5: Scanning electron micrographs (BSE) of cross-sections of the


LSM AA 7075-T6 alloys treated with low pulse energy density (3.3 J/cm2),
using 70 (a), 80 (b) and 90 (c) pulses.

154
LSM Operation Conditions

Figure 7-6: Average thickness of the laser melted layer and the largest pore
size in LSM AA 7075-T6 alloy vs. the number of pulses (NOP), as
determined from scanning electron micrographs of cross-sections for laser-
treatments, using high and low energy densities.

155
LSM Operation Conditions

Figure 7-7: Potentiodynamic polarisation scans in deaerated 0.1 M NaCl


solution of the as-received (AR) AA 7075-T6 alloy and after LSM using a
high energy density (10 J/cm2), with 10, 25 and 50 pulses.

156
LSM Operation Conditions

Figure 7-8: Potentiodynamic polarisation scans in deaerated 0.1 M NaCl


condition of the as-received (AR) AA 7075-T6 alloy and after LSM with high
energy density (10 J/cm2), using 10, 25 and 50 pulses, and with low energy
density (3.3 J/cm2), using 70, 80 and 90 pulses.

157
LSM Operation Conditions

Table 7-3: Corrosion potential (Ecorr), pitting potential (Epit), passive current
density (Ipass) and passive range potential (Epass) for both as-received and
laser treated alloys in Fig. 7-8. Potentials are given with respect to SCE.

Sample Ecorr (V) Epit (V) Ipass (A/cm2) Epass (V)

AR -0.920 -0.710 1.0x10-7 0.210

10 P -1.111 -0.670 4.6x10-8 0.441

25 P -1.160 -0.680 7.3x10-8 0.480

50 P -1.150 -0.695 1.6x10-7 0.454

70 P -0.920 -0.700 3.4x10-9 0.216

80 P -1.030 -0.680 5.7x10-9 0.329

90 P -0.940 -0.660 5.1x10-9 0.280

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Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Chapter 8 Microstructure and Corrosion of


the LSM AA 7075-T6 Alloy

8. Microstructural Examination

It is evident from scanning electron micrographs, shown in Fig. 8-1, that the top

surface of the AA 7075-T6 alloy after excimer LSM treatment, using 80 pulses

with an energy density of 3.3 J/cm2, has a wavy morphology. The micrographs

display the two tracks of the laser and the region of overlap, which is 300 µm

wide. No large second phase particles are evident on the melted area, as can be

seen by comparison with an untreated area of the alloy shown in Fig. 8-2, (b) and

(c). Fig. 8-3 shows another area of the alloy after LSM treatment. The Fig.

discloses the overlap and the re-heating regions. The overlap region forms part of

second laser track, while the re-heating region lies within the first laser track, as

indicated in (a) and (b). The width of the re-heating region is determined by the

heat-transfer properties of the alloy; modelling studies are required to evaluate

the temperature profile in the reheated zone. Fig. 8-3 (c) shows a higher

magnification image in the overlap region. No cracking is evident in the overlap

region. Fig. 8-3 (d) and (e) show higher magnification images of the re-heating

area. Micro-cracks are evident in this area, which are marked with red arrows in

Fig. 8-3 (e). EDX spectra of Figs. 8-4 and 8-5 reveal that aluminium, zinc,

copper, and oxygen are present in the LSM layer. The EDX spot focused on very

small area of LSM alloy and because of low content of magnesium, this element

may not show in the spectrum analysis of the selected regions. The EDX analysis

shows a high of oxygen (12.4 and 10.8 wt.%), with copper and zinc contents

appearing to be similar to those in the bulk alloy (1.6 and 1.7 wt.% for Cu and

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Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

5.6 and 5.8 wt.% for Zn respectively). The high oxygen content suggests the

presence of an oxide film on the laser-melted surface. The percentages of the

elements that resulted from the EDX analysis are recorded in the Tables that

accompany both Figs. Micrographs at relatively high magnification of cross-

sections of the LSM area, shown in Fig. 8-6, disclose a relatively rough surface

with a melted layer of about 3 μm thickness. The rapid solidification of the

molten materials produced by excimer laser pulses causes the melted layer to be

frozen with a wavy surface. As shown in Chapter 7, an increase of the number of

laser pulses per unit area, resulted in a rougher melted layer, which is attributed

to the turbulent flow of molten fluid from the centre of the melt pool to the

adjacent areas [180]. Fig. 8-7 shows details of the roughness; the peak-to-trough

distance is approximately 1.6 µm.

Scanning electron micrographs of cross-sections of the melted layer and the alloy

matrix are shown in Fig. 8-8. They reveal a thin melted layer on top of the alloy,

and a partially-melted second phase particle. The thickness of the melted layer is

about 2.5 μm in the particular region of the specimen, compared with about 3.0

µm in Fig. 8-6. The arrows in the scanning electron micrograph of Fig. 8-8 (d),

show thin solute-rich bands in the melted layer, particularly above the partially-

melted particle. Fig. 8-9 shows a cross-section and EDX mapping analysis of a

region of the melted layer at a location of a partially-dissolved second phase

particle. The EDX maps indicate that the particle consists of Al-Cu-Fe phase.

The backscattered scanning electron micrograph of Fig. 8-10 (a) shows local

enrichment of copper in the melted layer, above the partially-melted particle.

Cross-sections of another region of the melted layer are shown in Fig. 8-10. The

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Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

melted layer above both the matrix and partially-melted second phase particle is

revealed in the backscattered electron images with a thickness between 2 to 3

µm. It appears that the pulses of the excimer LSM melt the intermetallic particles

and redistribute the alloying elements within the solid solution formed on cooling

of the melted layer. Porosity on the other hand is also evident in the melting

layer, with pores of diameter up to ~ 1 µm. Porosity may arise due to release of

hydrogen and evaporation of magnesium from the bulk alloy, or from absorption

of gas in the atmosphere during LSM treatment [180,166-167].

Fig. 8-11 shows transmission electron micrographs of an ultramicrotomed cross-

section of the LSM layer and the alloy matrix. It appears that the melted layer in

the sectioned regions contains a number of pores, indicated by white arrows. The

thickness of the melted layer is between 2.8 to 3.0 μm, in agreement with

findings from SEM. Fig. 8-11 (c) shows thin bands within melted layer, which

are considered later; these bands contain fine precipitates. The bands are

separated by distances of about 0.3 to 0.4 μm. Fig. 8-12 shows another area of

the ultramicrotomed cross-section of the LSM layer and alloy matrix. Fig. 8-12

(a) reveals pores, indicated by white arrows, in the LSM layer. The average

thickness of the LSM layer is about 3.0 μm. Cavities and scratches are shown in

the laser treated layer, which are due to damage produced by sectioning, as

indicated with black arrows. Fig. 8-12 (b) shows a higher magnification image of

the cross-section micrograph of Fig. 8-12 (a). It reveals the region between the

LSM layer and alloy matrix (interface), as indicated with red arrows. The vertical

striations in images are chatter lines which are formed during ultramicrotomy

due to the hardness of the melted layer. For more detailed examination, EDX

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Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

spot analyses were taken at five locations in the cross-section, as indicated in Fig.

8-13 (a). EDX analysis at the locations of Figs. 8-13 (b) and (c) shows

enrichment of zinc and magnesium at the interface region in comparison with the

matrix (Fig. 8.13 (f)). Fig. 8-13 (d) shows enrichment of zinc and magnesium

also in the precipitates within the LSM region The EDX analysis of Fig. 8-13 (e)

shows zinc-magnesium-rich and chromium-rich precipitates in the matrix. Fig. 8-

14 (a) shows a high magnification image of an ultramicrotomed cross-section of

the laser-melted layer in the high angle annular dark field mode. It is evident that

distances of approximately 0.3 to 0.4 µm separated the precipitate bands, as also

evident in Fig. 8-11 (c). Fig. 8-14 (c) shows the results of EDX analysis of a

band of Fig. 8-14 (b). The band reveals enrichment of zinc and magnesium.

8.1 X-ray Diffraction

Fig. 8-15 shows the results of low angle X-ray diffraction of the AA 7075-T6

alloy after LSM. It reveals peaks due to the Al of the matrix and the laser-melted

layer. No significantly high peaks from large second phases were observed. In

comparison with the XRD of the LSM alloy, the as-received alloy (Fig. 8-16)

shows relatively large peaks due to second phase particles.

8.2 Corrosion Test Results after LSM

8.2.1 Potentiodynamic Polarization Test

Fig. 8-17 shows potentiodynamic polarization curves for the laser-treated and the

as-received AA 7075-T6 alloy in deaerated 0.1 M NaCl solution. The curves

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Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

reveal that there is a reduction by two orders in magnitude in the passive current

density for the LSM specimen in comparison with the as-received alloy, from

1.0x10-7 to 5.7x10-9 A/cm2. At the same time, there is a significant increase in the

passive range of the LSM alloy. Table 8-1 shows the measured values of the

corrosion potential (Ecorr), pitting potential (Epit), passive current density (Ipass)

and passive potential range (Epass) for the both laser-treated and the as-received

alloy. Laser melting of the alloy surface results in a reduction of the corrosion

potential by about -100 mV. However, the pitting potential is not significantly

affected, being about -685 mV (SCE) for the laser-treated alloy and -710 mV

(SCE) for the as-received alloy.

8.2.2 Immersion Test

Fig. 8-18 shows scanning electron micrographs of the LSM AA 7075-T6 alloy

after immersion in 0.1 M NaCl, open to the air, for 24 h. The cross-sections,

examined at a range of magnifications, reveal no evidence of corrosion products

after LSM. The thickness of the laser-melted layer was similar to that before the

immersion test. The findings indicate an improvement in corrosion resistance of

the alloy after laser surface melting treatment in comparison with as-received

alloy. The latter showed pitting corrosion, (see Fig. 6-10), due to the presence of

second phase particles on the alloy surface.

8.2.3 Exfoliation Test

Fig. 8-19 shows scanning electron micrographs of cross-sections of the LSM AA

7075-T6 alloy tested in naturally-aerated EXCO solution for times of 30, 60,

163
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

120, 150 and 180 min. The cross-sections of the laser treated (LT) alloys, as

shown in Fig. 8-19 (a-d), reveal no corrosion product after immersion for up to

150 min. However, with increasing time of immersion, up to 180 min, the alloy

shows corrosion underneath the laser-treated layer (Fig. 8-19 (e)).

Figs. 8-20 and 8-21 show higher magnification scanning electron micrographs of

cross-sections of the as-received and laser-treated alloy after immersion testing.

It is evident that no significant corrosion attack of the laser-treated alloy occurs

within exposure times of 30, 60, 120 and 150 min, in comparison with the alloy

without laser surface treatment. On the other hand, Fig. 8-22 shows scanning

electron micrographs of cross-sections of the laser-treated and untreated alloys

after immersion for 180 min. The high magnification micrograph of Fig. 8-22 (c)

reveals severe IGC of the as-received alloy. However, corrosion was limited in

the laser-treated alloy and located within the melted layer, which caused the layer

to delaminate from the alloy matrix, as shown in Fig. 8-22 (d). The corroding

solution may find a way to attack the base of the melted layer due to the presence

of defects and/or microcracks that allow access of the solution to the substrate

region. Cracks were observed in the re-heated region of the LSM layer, as shown

in the scanning electron micrograph of Fig. 8-23. However, LSM reduces the

severe exfoliation corrosion attack that occurs with the as-received alloy in a

similar test condition.

164
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

8.3 Conclusions

AA 7075-T6 alloy after excimer LSM shows a relatively thin melted layer with a

wave-like surface. The thickness of the LSM layer produced under the selected

LSM conditions was 2.5 to 3.5 μm. Rapid solidification of the melted metal

caused dissolution of constituent particles and generated a relatively uniform

melted layer that was free from large second phases. After LSM, the alloy

exhibits a reduction in the passive current density by two orders in magnitude in

comparison with the untreated alloy when examined under similar conditions of

electrochemical polarization in sodium chloride solution. The LSM alloy shows

no significant attack after immersion in 0.1 M sodium chloride solution, open to

air, for 24 h. In comparison, the as-received alloy shows pitting corrosion in the

same environment. The results from exfoliation corrosion tests show a large

reduction in the corrosion damage of alloy following LSM. However, the

presence of cracks in the re-heated region caused by the influence of the second

laser track on the first laser track enables electrolyte to penetrate to the matrix.

The presence of a zinc and magnesium rich bands in the melted layer, and

between the LSM layer and the bulk alloy, facilitates corrosion along these bands

which causes delamination of the LSM layer from the alloy.

165
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

8.4 List of Figures

Figure 8-1: Scanning electron micrographs (SE) of the top surface of the AA
7075-T6 alloy after LSM using 80 pulses. (a), (b), (c) and (d) show images at
increasing magnification. The laser track direction and the overlap region
(10 %) are indicated.

166
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-2: Scanning electron micrographs (BSE) of the AA 7075-T5 alloy


after LSM. (a) Alloy with and without treatment by LSM. (b) Untreated
alloy, revealing the presence of intermetallic particles. (c) Alloy after LSM
treatment.

167
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-3: Scanning electron micrographs (SE) of the top surface of the AA
7075-T6 alloy after LSM using 80 pulses. (a) and (b) show laser tracks, re-
heating and overlap regions. (c) Higher magnification in overlap region. (d)
and (e) Higher magnification in re-heating area.

168
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-4: Results of SEM-EDX spot analysis of the AA 7075-T6 alloy after
LSM. (a) EDX spectrum. (b) Scanning electron micrograph showing the
location of the analysis region. (c) Elements in weight and atomic
percentages.

169
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-5: Results of SEM-EDX spot analysis of a different area of the


LSM AA 7075-T6 alloy from that shown in Fig 8-4. (a) EDX spectrum. (b)
Scanning electron micrograph showing the location of the analysis region.
(c) Elements in weight and atomic percentages.

170
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-6: Scanning electron micrographs of cross-sections of the AA 7075-


T6 alloy after LSM using 80 pulses. (a) and (c) Secondary electrons. (b) and
(d) Backscattered electrons.

171
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-7: High magnification scanning electron micrographs showing a


cross-section of AA 7075-T6 alloy after LSM using 80 pulses.

172
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-8: Scanning electron micrographs (BSE) of a cross-section of the


AA7075-T6 alloy after LSM, with the presence of a thin melted layer on the
alloy surface indicated in (a) and (b). Higher magnification images in (c) and
(d) show the thinner melted layer produced above a large second phase
particle that was partially dissolved after LSM treatment.

173
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-9: SEM-EDX mapping analysis of Fig 8-8 (d) showing the LSM
layer and the alloy matrix in (a), and the imaging of Al (b), Zn (c), Cu (d), Fe
(e), and Mg (f).

Figure 8-10: Scanning electron micrographs (BSE) of cross-sections of the


AA 7075-T6 alloy after LSM using 80 pulses, showing the laser melted layer
in more detail, disclosing porosity in the layer with pores of dimension about
1 µm.

174
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-11: Transmission electron micrographs of ultramicrotomed cross-


sections of the AA 7075-T6 alloy after LSM using 80 pulses. Micrographs (a)
and (b) reveal the LSM layer and alloy matrix with pores indicated by
arrows in laser-treated layer. Micrograph (c) shows bands in LSM layer,
which are due to the presence of precipitates. The bands are separated by
distances of 0.3 to 0.4 μm.

175
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-12: Transmission electron micrographs of an ultramicrotomed


cross-section of the AA 7075-T6 alloy after LSM using 80 pulses. (b) Higher
magnification of (a). The Fig. shows the interface region, as indicated by
arrows in red, between the LSM layer and the alloy matrix. The arrows in
white and black show pores and scratches in the LSM layer.

176
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-13: TEM-EDX spot analysis of the micrograph cross-section of Fig.


8-12 (b); the 5 locations of EDX analysis are indicated in (a).

177
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-14: High angle annular dark field (HAADF) images of an


ultramicrotomed cross-section of the AA 7075-T6 alloy after LSM using 80
pulses. (b) Higher magnification of (a). (c) Results of of EDX analysis of (b).

178
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-15: Low angle XRD analysis of the AA 7075-T6 alloy after LSM
using 80 pulses.

179
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-16: Low angle XRD analysis for both as-received and LSM AA
7075-T6 alloy treated with 70, 80, and 90 pulses.

180
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-17: Potentiodynamic polarization scans in deaerated 0.1 M NaCl


for AA 7075-T6 alloy and after LSM using 80 pulses.

Table 8-1: Corrosion potential (Ecorr), pitting potential (Epit), passive current
density (Ipass) and passive range potential (Epass) for both as-received and
laser treated AA 7075-T6 alloy determined from the potentiodynamic
polarisation curves of Fig. 8-17. Potentials are given with respect to SCE.
Sample Ecorr (V) Epit (V) Ipass (A/cm2) Epass (V)

AR -0.920 -0.710 1.0x10-7 0.210

LT -1.030 -0.685 5.7x10-9 0.349

181
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-18: Scanning electron micrographs of the AA 7075-T6 alloy after


LSM using 80 pulses and immersion in 0.1 M NaCl, open to air, for 24 h.
The Fig. reveals that no evidence of corrosion product in low magnification
(a, b) and high magnification (c, d) images.

182
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-19: Scanning electron micrographs (BSE) of the AA 7075-T6 alloy


after LSM using 80 pulses and immersion in naturally-aerated EXCO
solution for (a) 30, (b) 60, (c) 120, (d) 150 and (e) 180 min. The cross-sections
of the laser surface treatment alloys (a-d) reveal no corrosion products after
immersion for 150 min. With increasing time of immersion, corrosion causes
delamination of the LSM layer, as evident in (e).

183
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-20: Scanning electron micrographs of cross-sections of the AA


7075-T6 alloy in the as-received condition and after laser-surface treatment
(LT) using 80 pulses, following immersion in (EXCO) solution for 30 min (a,
b) and 60 min (c, d).

184
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-21: Scanning electron micrographs of cross-sections of the AA


7075-T6 alloy in the as-received condition and after laser surface treatment
alloys using 80 pulses and immersion in EXCO solution for 120 min (a, b)
and 150 min (c, d).

185
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-22: Scanning electron micrographs of cross-sections of the AA


7075-T6 alloy in the as-received condition (a, c) and after laser surface
treatment (b, d) using 80 pulses immersion in EXCO solution for 180 min.

186
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy

Figure 8-23: Scanning electron micrographs of LSM AA 7075-T6 revealing


micro-cracks in the re-heating area of the 1st laser track as in (a) and (b),
while (c) and (d) show micrographs of cross-sections after exfoliation testing
for 180 min.

187
Chapter 9 Microstructure and Corrosion of
the LSM AA 7075-T6 Alloy after Anodising

9. Introduction

Anodising, as mentioned in Chapter 3, is an electrochemical procedure that is

used to increase the thickness of the protective oxide layer on the surface of

aluminium and aluminium alloys in order to improve their corrosion resistances.

In this section of the thesis, results are presented for anodising of laser surface

melted AA 7075-T6 alloy. The anodising was carried out at 12 V in stirred 0.46

M sulphuric acid (H2SO4) electrolyte at a temperature of 295 K for times of 240,

720, and 1200 s. The aim was to protect the laser surface melted layer from

delamination during exfoliation testing. Specimens are examined by SEM and

TEM, with the corrosion resistance of the laser-treated and anodised alloy

evaluated in sodium chloride solution using potentiodynamic polarization and

exfoliation immersion tests.

9.1 LSM and Anodising

The current density / time behaviour of the LSM specimen, as well as the as-

received alloy, was recorded during anodising at 12 V (SCE) in 0.46 M H2SO4,

as shown in Fig. 9-1. The specimens, with an area of approximately 80 mm2,

show an initial surge in the current density followed by a decrease to a minimum

value and an increase to a steady current density. The initial surge of the current

density is related to the growth of a barrier film. The steady current density

corresponds to the growth of a porous film [26]. A significant reduction of the

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Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

steady current density, by about 50 %, was evident after LSM in comparison

with the as-received AA 7075-T6 alloy following anodising for times of 240, 720

and 1200 s. The values of the current density for the as-received and laser-treated

alloys are approximately 1.7x10-3 and 7.7x10-4 A/cm2 respectively. Following

anodising the film was sealed by immersion in deionised boiling water for 30

min.

9.2 Surface and Cross Section Results

Figure 9-2 shows scanning electron micrographs of the top surface of LSM AA

7075-T6 alloy after anodising in 0.46 M H2SO4 for 1200 s. Fig. 9-2 (a) shows the

overlap area in the second laser-track and the re-heating area in the first laser-

track. Figs. 9-2 (b) and (c) show higher magnification images of the re-heating

area and the overlap area, with the presence of micro-cracks evident in the re-

heated region of the LSM layer, as indicated by arrows in Fig. 9-2 (b). Fig. 9-3

(a) shows a scanning electron micrograph and the results of EDX analysis of the

re-heating area after anodising. Oxygen, aluminium, magnesium and zinc are

indicated by EDX analysis, as shown in Fig. 9-3 (b), with oxygen at about 27

wt% , magnesium at about 1.6 wt% and zinc at about 4.5 wt% (Fig. 9-3 (c)). Fig.

9-4 (a) shows a scanning electron micrograph with an EDX spectrum taken on

the overlap region. Fig. 9-4 (b) shows the EDX analysis, with oxygen at about

26.1 wt%, magnesium at about 1.4 wt% and zinc at about 4.5 wt% (Fig. 9-4 (c)) .

Fig. 9-5 (a) shows a scanning electron micrograph with an EDX spectrum taken

on the middle of the laser-track. Fig. 9-5 (b) shows the EDX analysis, with

oxygen at about 39.8 wt%, magnesium at about 1.6 wt% and zinc at about 3.9

wt% (Fig. 9-5 (c)). From the EDX measurements, the anodising of the LSM AA

189
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

7075-T6 alloy in 0.46 M H2SO4 for 1200 s has increased the level of oxygen, and

slightly reduced the content of magnesium and zinc in the LSM layer in

comparison with LSM alloy without anodising (see Figs. 8-4 and 8-5). Fig. 9-6

(a) shows a scanning electron micrograph of a cross-section of the LSM AA

7075-T6 alloy after anodising in sulphuric acid for 1200 s. Fig 9-6 (b) shows a

high magnification image of Fig. 9-6 (a). The cross-sections reveal a thin anodic

film of about 313 to 332 nm thickness above the laser-melted layer. Fig. 9-7

shows a transmission electron micrograph of an ultramicrotomed cross-section of

the anodised LSM AA 7075-T6 alloy. The micrographs in Fig. 9-7 (a) and (b)

disclose a bubble-like texture of the anodic film, which has a relatively uniform

thickness of about 380 nm over the laser-treated layer. For the purpose of

comparison, Fig. 9-8 shows high resolution scanning electron micrographs of the

as-received alloy cross-sections after anodising in H2SO4 for 1200 s. The

micrographs in Figs. 9-8 (a), (b) and (c) reveal a thin anodic film over the as-

received alloy with a thickness of about 200 nm. Fig 9-8 (d) shows anodic film

over a large intermetallic particle with a thickness of about 2 µm. The yellow

arrows in the Figure disclosed cracks in the anodic film formation.

9.3 Corrosion Test Results

9.3.1 Potentiodynamic Polarization Test

A potentiodynamic polarization scan of the LSM alloy after anodising is shown

in Fig. 9-9, revealing a reduction in the passive current density (7.4x10-10 A/cm2)

and increase in the corrosion potential (-0.780 V) (SCE) in comparison with the

as-received alloy (1.0x10-7A/cm2, and -0.930 V) (SCE), AR and anodised alloy

190
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

(1.2x10-7 A/cm2, and -0.790 V) (SCE) and LSM alloy (5.7x10-9 A/cm2, and -

0.103 V) (SCE).The pitting potential was not significantly affected, being around

-0.670 to -0.700 V (SCE) The reduced passive current density could be attributed

to the anodic film formation which increases the thickness of the oxide layer in

comparison with those on the as-received alloy before and following anodising

and after LSM. Table 9-1 shows the measurement values of the Ecorr, Epit, and

Ipass determined from Fig. 9-9.

9.3.2 Exfoliation Test

Figures 9-10 (a) and (b) showed scanning electron micrograph of the top-surface

of the anodised as-received alloy after immersion in naturally aerated EXCO

solution for 180 min, with the presence of area of corrosion and cracks evident.

The high magnification scanning electron micrograph, of Fig. 9-10 (c) reveals

cracks of width about 1 to 1.65 µm. Fig. 9-11 presents scanning electron

micrographs of cross-sections of the anodised alloy, disclosing the presence of

exfoliation corrosion in the as-received alloy matrix. The depth of the exfoliation

attack is about 65 µm. Fig. 9-12 shows scanning electron micrographs of the top-

surface of the anodised LSM alloy after immersion in naturally aerated EXCO

solution for 180 min. Fig. 9-12 (a) discloses the re-heating area and the overlap

area. The red arrows in the first-track of the laser-treated layer show corrosion

products. Figs. 9-12 (b) and (c) show scanning electron micrographs in the

middle of the anodised and laser treated layer after immersion testing, where

corrosion products are marked with red rings. Fig. 9-13 shows scanning electron

micrographs of cross-sections of the LSM AA 7075-T6 alloy following

anodising, after exfoliation testing for 180 min. Fig. 9-13 (b) is higher

191
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

magnification of Fig. 9-13 (a) and Fig. 9-13 (d) is a higher magnification of Fig.

9-13 (c). The thickness of the laser-melted layer is about 2.8 to 3.1 µm. Pores

with less than 0.4 µm diameter are shown with arrows in Fig. 9-13 (c) and (d).

No evidence of delamination of the laser-melted layer from the alloy surface

occurred after corrosion testing for 180 min.

9.4 Conclusions

Anodising of LSM AA 7075-T6 alloy in sulphuric acid results in improvement in

the corrosion performance of the alloy. Potentiodynamic polarization testing

revealed a decrease by one order of magnitude of the passive current density and

increase in the corrosion potential in comparison with the LSM alloy without

anodising. LSM resulted in an increase the thickness of the anodic film from

about 200 nm to 320-380 nm. The anodic film formed on the LSM alloy acted as

an effective barrier, and significantly limited the exfoliation attack. Therefore,

there was no evidence of exfoliation or the occurrence of delamination of the

anodised-LSM alloy after immersion testing for 180 min, in contrast to the

behaviour of the LSM alloy without anodising which has been described in

Chapter 8.

192
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

9.5 List of Figures

Figure 9-1: Current density (I) vs time (s) behaviour of the as-received (AR)
and LSM AA 7075-T6 alloy during anodising at 12 V (SCE) in 0.46 M
H2SO4 at 295 K for (a) 240 s, (b) 720 s, and (c) 1200 s.

193
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-2: Scanning electron micrographs of the top surface of the LSM
AA 7075-T6 alloy after anodising at 12 V in 0.46 M H2SO4 at 295 K for 1200
s; (a) the overlap area in the second-laser track and the reheating area in the
first-laser track; (b) high magnification of the reheating area; (c) high
magnification of the overlap area. The arrows in (c) show the micro-cracks
in the re-heating region.

194
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-3: Results of SEM-EDX spot analysis of the LSM AA 7075-T6 alloy
following anodising. (a) Scanning electron micrograph showing the location
of the analysis region. (b) EDX spectrum. (c) Elements in weight and atomic
percentages.

195
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-4: Results of SEM-EDX spot analysis of the LSM AA 7075-T6 alloy
following anodising. (a) Scanning electron micrograph showing the location
of the analysis region. (b) EDX spectrum. (c) Elements in weight and atomic
percentages.

196
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-5: Results of SEM-EDX spot analysis of the LSM AA 7075-T6 alloy
following anodising. (a) Scanning electron micrograph showing the location
of the analysis region. (b) EDX spectrum. (c) Elements in weight and atomic
percentages.

197
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-6: Scanning electron micrographs of cross-sections of the LSM AA


7075-T6 alloy following anodising in sulphuric acid for 1200 s. (b) High
magnification of (a).

198
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-7: Transmission electron micrograph of an ultramicrotomed cross-


section of LSM AA 7075-T6 alloy anodised at 12 V in 0.46 M H2SO4 at 295
K for 1200 s. (b) High magnification of (a).

199
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-8: Scanning electron micrographs of cross-sections of the as-


received AA 7075-T6 alloy following anodising in sulphuric acid for 1200 s.
(a) to (d) show images at different locations of the alloy surface.

200
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-9: Potentiodynamic polarization tests in deaerated 0.1 M NaCl


solution of the as-received (AR) AA 7075-T6 alloy, laser surface treated
(LSM) alloy, and following anodising in 0.46 M H2SO4 for 1200 s.
(LSM+Anod., AR+Anod.).

201
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Table 9-1: Corrosion potential (Ecorr), pitting potential (Epit), passive current
density (Ipass) and passive range potential (Epass) for the as-received (AR),
laser-treated (LT), AR and anodised, and LSM and anodised alloys
determined from the potentiodynamic polarisation curves of Fig. 9-4.
Potentials are given with respect to SCE.

202
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-10: Scanning electron micrographs of top surface of the anodised


AA7075-T6 alloy after EXCO corrosion test for an exposure time of 180
min. (b) shows high magnification image of (a). (c) shows high magnification
image of the location marked with yellow arrow.

203
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-11: Scanning electron micrographs of cross-sections of the


anodised AA7075-T6 alloy after EXCO corrosion test for an exposure time
of 180 min. (a), (b) and (c) are images at increasing magnification.

204
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-12: Scanning electron micrographs of the top surface of the


anodised LSM AA 7075-T6 alloy after EXCO testing for a time of 180 min.
(a) overlap and reheating areas. (b, c) middle of laser-treated layer.

205
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising

Figure 9-13: Scanning electron micrographs of cross-sections of the


anodised LSM AA7075-T6 alloy after EXCO corrosion test for an exposure
time of 180 min. (a) to (d) are images at increasing magnification.

206
Chapter 10 Discussion

10. AA 7075-T6 Alloy

The microstructure of the as-received AA 7075-T6 alloy surface, after being

polished up to 1 μm diamond paste, revealed intermetallic particles of different

size and composition that are often aligned along the rolling direction of the alloy

sheet (Fig. 6-1). The dimensions of the large intermetallic particles typically

varied between 3 to 11 µm. Some of these intermetallic particles appeared to be

broken into small particles during rolling. The other particles were clustered with

measured dimensions of the groups of closely-spaced particles being between 20

and 25 µm (Fig. 6-2). The presence of the particles increases the susceptibility of

the alloy surface to corrosion, as such particles are reported to be the main cause

of corrosion due to their different electrochemical properties with respect to the

alloy matrix [32-33, 44-47]. SEM and EDX line scans and mapping revealed

copper and iron in the particles. Other particles of size between 1.5 to 5 µm

revealed magnesium and silicon (Figs. 6-3, 6-4, 6-5 and 6-6). SEM-EDX

analysis detected zinc and magnesium that are distributed uniformly in the matrix

(Fig. 6-7). It is reported that the alloy contains MgZn2 particles and their sizes are

very small in comparison with other second phases (hundreds of nanometres) [4,

32]. In addition to the alloy matrix, low angle XRD on the as-received alloy (Fig.

6-8) indicated the presence of two second phases (Al7Cu2Fe and Mg2Si). The

overall findings are consistent with previous reports that the second phases of

AA 7075 alloy consist of Al3Fe, Al7Cu2Fe, and Mg2Si with the presence of

MgZn2 [4, 32, 33, 44-47].

207
Discussion

Intermetallic particles on the surface of the alloy usually have different

electrochemical characteristics and different effects on the corrosion behaviour

of the surrounding matrix [12]. They can exhibit either cathodic or anodic

behaviour with respect to the alloy matrix. The presence of these phases can lead

to non-uniform attack at specific areas of the alloy surface and are a key reason

for the initiation of pitting corrosion (Fig. 6-10) [4].

The potentiodynamic polarisation scan of the polished AA 7075-T6 alloy in

deaerated 0.1 M NaCl solution (Fig. 6-9) revealed two breakdown potentials. The

first break-down potential may be attributed to pitting. The second break-down

potential may be related to pitting propagation and dissolution of a reactive

surface layer [27, 197]. The process of mechanical polishing of an alloy surface

can be responsible for production of a thin surface layer with an increased

electrochemical activity. Other investigators have made similar observations of

the potentiodynamic polarisation in deaerated sodium chloride solution of AA

7075 alloy after polishing to those of the present work [27, 197]. They concluded

that the formation of a thin zinc-rich layer due to the polishing operation results

in a higher anodic electrochemical reactivity than that of the underlying alloy.

According to the observations of the potentiodynamic polarisation found in the

present study and of other authors, it seems that the first breakdown potential is

responsible for the pitting in the matrix, while the second may be associated with

the dissolution of the electrochemical active layer. In the present work, the

pitting potential was not changed significantly after LSM, which eliminates the

active surface layer, and a second breakdown potential was not observed.

208
Discussion

Scanning electron micrographs shown in Fig. (6-11) disclosed the as-received

alloy surface after an exfoliation corrosion test. Corrosion initiates near sites of

second phase particles. These intermetallic particles act as cathodes, with the pH

rise due to the cathodic reaction resulting in corrosion of the adjacent matrix

(Fig. 6-12). However, other particles are preferentially dissolved after corrosion

testing, leaving cavities in the alloy surface. The former phases mainly contain

copper and/or iron, while the latter phases mainly contain magnesium, zinc

and/or silicon.

Table B of Appendix 1 provides details of the intermetallic particles that are

formed in AA 7075-T6 alloy and their corrosion behaviour. The corrosion

potential (Ecorr) vs (SCE) and the average current density at Ecorr of the

intermetallic particles with respect to the matrix of the alloy are recorded in the

Table. The data in the Table were determined elsewhere using a microcapillary

electrochemical cell that facilitated investigation of intermetallic particles in the

micrometer size range in 0.1 M NaCl solution [1]. The anodic phases, such as

MgZn2 (η-phase) and Mg2Si (β-phase), have a low Ecorr (-1029 and -1538 mV

(SCE)) in comparison with the cathodic phases, Al3Fe (β-phase) and Al2Cu (θ-

phase) (-539 and -665 mV (SCE)) as well as the alloy matrix (-799 mV (SCE)).

Iron and silicon are reported to be basic impurities in commercial grade

aluminium alloys [45]. The solubilities of iron and silicon are high in molten

aluminium, but are low in solid aluminium [46]. Therefore, most of the iron and

silicon will precipitate out during solidification and form large second phase

209
Discussion

particles. The iron-rich particles, such as Al3Fe and Al7Cu2Fe, usually act as

cathodes on the surface of the alloy, promoting electrochemical attack. Murray et

al. reported that the presence of copper ions in the solution would cause metallic

copper to plate onto the iron-rich particles [47]. If the matrix adjacent to the iron-

rich particles contains copper, aluminium can be dissolved and the copper will

remain inside pits, which makes the particles more cathodic with respect to the

aluminium matrix [47]. On the other hand, constituent particles containing

magnesium, such as Mg2Si and MgZn2 phases, are more active than the matrix of

the alloy and are usually dissolved preferentially. Some elements of an active

particle will leave the pit after being dissolved, such as magnesium, but some

will stay, such as silicon. The change in concentration of the elements inside the

pit will affect the further corrosion mechanism.

Overall, the presence of different second phase particles in AA 7xxx alloys

affects their corrosion behaviour strongly. Therefore, reduction or elimination of

such intermetallic particles from the surface of the alloy, without affecting the

properties of the alloy matrix, by using LSM can lead to an improved corrosion

resistance of the alloy by reducing the micro-galvanic coupling between the

aluminium matrix and the second phase particles. The next section will discuss

the AA 7075-T6 alloy surface after laser treatment using an excimer laser.

210
Discussion

10.1 AA 7075-T6 Alloy after LSM

In the present excimer LSM, adequate solute dispersion, with an increase in

corrosion resistance, was achieved by using a laser pulse fluence of 3.3 J/cm2, as

was assessed from the results of SEM examination of LSM cross-sections and of

the potentiodynamic polarisation tests (Figs. 7-5, 8). An increase in the thickness

of the melted-layer by increasing the fluence of the excimer laser led to an

increased number of defects, such as a pores and cracks (Fig. 7-3), which can

reduce the corrosion resistance. Ryan et al. showed that a large degree of solute

dispersion occurs by diffusion and mixing in excimer LSM of AA 7075 and AA

2024 alloys, which provided an improvement of the corrosion resistance [166]. It

is evident that the excimer laser pulse heats and melts the surface of the alloy and

due to rapid solidification associated with a high cooling rate, a wave-like melted

layer can be generated (Figs. 8-1, 2). However, the production of such a melted

layer can be affected by a number of different processes, particularly

vaporisation and surface tension gradients. A high fluence received from the

laser pulse can produce a high temperature on the surface of the alloy. It is

reported that vaporisation requires high temperatures and surface tension

gradients depend on the temperature differences in the melt pool [143, 144, 167].

Once the temperature of the alloy surface is at the vaporisation temperature, large

thermal stresses can be induced, which may be sufficient to produce defects such

as pores caused by evaporation of elements, i.e. zinc and magnesium, that have a

boiling temperature lower than the temperatures that result from the laser pulse,

and subsequent cracking can reduce the improvement of the corrosion resistance.

Details of the physical properties of the elements in the AA 7075-T6 alloy,

211
Discussion

including their melting and boiling temperatures, are provided in Table A of

Appendix 1. Ideally, the laser fluence is required to be controlled to produce a

melted layer with few defects. This was achieved in the present work by using a

low pulse energy density instead of a high pulse energy density. Therefore, an

excimer laser fluence of 3.3 J/cm2 and 80 pulses per unit area was selected as the

preferred condition for further improvement to corrosion resistance after

evaluation of several different laser treatment conditions, as explained in Chapter

7.

Following LSM treatment of the AA 7075-T6 alloy, the melted layer exhibited

bands of precipitates in the solidified structure (Figs. 8-11, 12, 13, 14). Other

investigators have made similar observations after treating AA 7075, AA 2024

and AA 2025 alloys using an excimer LSM [166, 167, 180]. The maximum

number of bands that can be present within a modified melted layer and still

provide corrosion resistance improvement is unknown, but the corrosion

resistance is more likely to be improved if the bands can be minimised. EDX

analysis (Figs. 8-13, 14) disclosed zinc and magnesium enrichment in these

bands which may be expected to dissolve if the corrosive electrolyte reaches

these regions within the melted layer. Dissolution along the bands may then

cause delamination of the laser treated layer. Other investigators found bands

with enrichment of copper and magnesium after treating AA 2024 alloy using

excimer LSM [166, 167]. They suggested that these bands within the melted

layer could be generated as the result of an initial transient caused by the

acceleration of the advancing growth front, combined with the solute enriched

trails, that extends the interface stability criteria to greater growth velocity [166,

212
Discussion

167]. Other works found fine discontinuous bands, containing the main elements

of precipitates of the alloy after excimer LSM of AA 2024 and AA 2050 alloys

[26, 180]. They concluded that the short duration of each laser pulse prevented

complete diffusion of the alloying elements of the intermetallic precipitates

within a melted layer. It might be possible that these bands result from the short

time spent in the liquid state after each laser pulse, which does not give sufficient

time for the main alloying elements to be mixed. Therefore, precipitates as they

arrived in the melt pool area leave behind band of discontinuous precipitates of

bands within laser melted layer.

The high resolution TEM micrographs of Figs. 8-11 and 8-14 revealed a distance

of around 0.3 to 0.4 µm separating two bands. It might be suggested that

increasing the thickness of the melted layer by increasing the laser fluence may

increase the number of bands [166, 180]. However, the presence of defects, such

as large pores, may increase the localised attack and reduce the corrosion

resistance in environments that contain chloride ions. In contrast, generating a

thin melted layer by reducing the laser fluence and increasing the number of

pulses could minimise the number of bands in the melted layer and that may

enhance the improvement of the corrosion resistance. Therefore, the laser fluence

was reduced to 3.3 J/cm2 and the laser pulses were increased to 80 pulses to treat

the surface of the alloy in this study. Other investigators found that increasing the

number of laser pulses from 10 to 50 can reduce the precipitation bands in LSM

AA 2024 and AA 2050 alloys and subsequently improve the corrosion resistance

and reduce the localised attack in the melted layer [202]. It has also been

reported that in LSM the solidification front moves from the base of the melted

213
Discussion

layer to the surface of the melt pool, following the thermal gradient. There is a

region of slow growth of the solidification front at the base of the melted layer,

which has been reported as an interface [166]. The authors suggested that

excimer LSM treatment provides a mixing of the aluminium matrix and the

second phase particles in solid solution of the melted layer. The solid solution

should then solidify quickly to prevent interface instability, trapping the solute in

solid-solution. However, due to the short melt time (nano-seconds) after each

repeated number of pulses, it might be possible that precipitation can occur

[166]. Other investigators showed that due to the short duration of each laser

pulse (~13 ns), it is difficult to achieve complete dissolution of the intermetallic

precipitates in the melted layer and, therefore, precipitation and segregation may

develop in the melt pool area [180, 201]. From the above discussion, it is

possible that the high cooling rate of the excimer laser, with the presence of

different alloying elements that have different physical properties in the solid

solution of the melted layer, influences the solidification microstructure by

generating thin bands of precipitates, which are enriched with the alloying

elements.

The XRD for both the as-received and the LSM alloy are compared in Fig. 8-16.

It revealed that Al7Cu2Fe and Mg2Si were present in the as-received alloy, and

that these phases are reduced after LSM treatment, with increasing reduction

being achieved by increasing the number of pulses. Other investigators made the

same observation of a reduction in the signal intensities of the large second

phases after treating AA 2050-T8 alloy using excimer LSM [180]. It is reported

214
Discussion

also that increasing the number of the laser pulses enhanced the dissolution of the

intermetallic phases, as revealed by XRD [201, 202].

10.1.1 Corrosion of LSM Alloy

The results of potentiodynamic polarisation tests in deaerated 0.1 M NaCl

solution (Fig. 8-17), as summarised in Table (8-1), showed a reduction in the

passive current density by two orders of magnitude for the LSM alloy in

comparison with the as-received alloy. There was also a significant increase in

the passive range of the LSM alloy due to the formation of the 3-4 µm thick

melted layer. The increased range can be attributed to a reduction in the cathodic

reactivity of the alloy surface after laser surface treatment due to reduction in the

presence of copper-and iron-rich intermetallic phases. Other work reported

similar observations after treating AA 2024-T531 friction stir welds by excimer

LSM [203]. The findings of an extended passive range and the reduction in the

passive current density are also consistent with the results found by Viejo et al.

on AA 2025-T8 alloy and Liu et al. on AA 2024-T351 alloy after excimer LSM

[201, 202] In contrast, the breakdown potential (pitting potential) was not

significantly affected by the LSM process. Other authors made similar

observations after excimer of LSM AA 7449-T7951 alloy [204]. They suggested

that the incorporation of zinc in solid solution in the LSM layer creates a

relatively active layer, which is anodic with respect to the base alloy and

detremines the electrochemical behaviour [204]. The reduction in the cathodic

reactivity and the increase in the anodic activity of the alloy surface may be

responsible for the change in the electrochemical behaviour of the present LSM

alloy, which revealed only one breakdown potential. Yue et al. studied the effect

215
Discussion

of excimer LSM on the corrosion resistance of AA 7075-T651 alloy using

potentiodynamic polarisation in 3.5% NaCl solution open to air. They found a

reduction by six-times in the passive current density following LSM, and a

passive region was obtained, in contrast to the behaviour of the untreated alloy.

The untreated alloy suffered from widespread pitting corrosion [192]. They

investigated the surface of laser-treated and untreated alloys and concluded that

the improvement in the corrosion resistance was due to presence of an oxide

layer on top of the laser-melted zone, which is a chemically stable phase (α-

Al2O3) that serves as an effective barrier to protect the matrix against corrosion

[192]. The present work also showed (Figs. 8-4, 5, 13, 14) an increased oxygen

content after treating the alloy with the excimer laser, as evident by EDX

analysis of the alloy surface.

The results of immersion tests of the LSM AA 7075-T6 alloy in 0.1 M NaCl

solution, open to the air, for 24 and 48 h, revealed no evidence of pitting

corrosion, with the laser melted layer being similar to that before the immersion

test (Fig. 8-18). The findings are consistent with an improvement in the corrosion

resistance of the LSM alloy. The improvement can be related to

dissolution/removal of the large (noble) second phase particles that are copper-

rich and/or iron-rich elements from the surface of the alloy, which may act as

preferential sites for oxygen reduction or hydrogen evolution in chloride

environments, and the absence of the other active constituent particles that are

rich with magnesium element which can be dissolved uniformly. In comparison,

the untreated alloy disclosed pitting corrosion due to the presence of these second

phase particles on the alloy surface (see Fig. 6-10). Other investigators found an

216
Discussion

improvement in the pitting corrosion resistance of LSM AA 2024-T351 friction

stir welds after immersion in the same solution [203]. They concluded that LSM

using an excimer laser decreases and homogenises the anodic and the cathodic

reactivity in both the weld region and the parent material by dissolution of the

intermetallic particles and redistribution of the alloying elements in the laser

melted layer [203].

Treating a sufficiently large area of the alloy surface, using an excimer laser,

required the use of two adjacent laser tracks. High magnification scanning

electron micrographs of the top surface of the melted area (Fig. 8-3 (e)) disclosed

defects, such as micro-cracks on the first-laser-track direction that occurred due

to tempering or re-heating from the second-laser-track movement. The SEM

micrographs of cross-sections of the laser melted layer (Figs. 8-6, 7-10) show

that the cracks do not penetrate deeply, suggesting that these cracks may only

occur in a thin surface layer of melted alloy or may only penetrate the surface of

an oxide layer. It appears that during exfoliation testing of the LSM AA 7075-T6

alloy, partial delamination of the melted layer occurred after 180 min (Figs. 8-22

and 8-23). The test solution is able to propagate along the melted layer interfaces

without attacking the alloy matrix significantly. In contrast, observations of the

as-received alloy revealed deeply penetrating intergranular corrosion (Figs. 8-21,

22, 23). The zinc and magnesium precipitates in the melted layer and at the

interface may dissolve preferentially and subsequently reduce the corrosion

resistance, causing localised attack in the presence of an aggressive environment.

It is reported that the different microstructure in the interface region, together

with presence of bands of precipitates in the melted layer, makes LSM alloys

217
Discussion

more susceptible to corrosion and can lead to delamination of the melted layer

[162, 165, 180, 201, 202, 203, 204]. The delamination of the melted layer can not

be avoided once the top layer is breached by the corrosion solution, and the

solution has access to the reactive precipitation bands.

Optimising the energy density and selecting a suitable number of pulses of the

excimer LSM is a one of the key factors in increasing the corrosion resistance of

the AA 7075-T6 alloy, and that starts with careful control of the laser pulse

energy density to cause only melting of the alloy and mixing of the alloying

elements in solid solution and hence to produce a uniform melted layer.

From the above discussion of LSM, the improvement in corrosion resistance was

due to formation of a thin homogenous melted layer by dissolution of the

intermetallic particles into the α-Al solution. The solute is then maintained in the

surface layer through planar solidification due to the high cooling rate that is a

characteristic of the excimer laser. However, due to very short melt times, the

melted layer exhibited bands of precipitates that contain zinc and magnesium.

Generating more than one laser-track can influence the treated area due to over-

heating that may cause micro-cracks at the previous laser-track that may reduce

the resistance of the laser treated alloy to corrosion. Therefore, protecting of the

LSM alloy is required to improve the resistance of the laser melted layer to

delamination after exfoliation testing, Anodising of the LSM alloy in 0.46 M

sulphuric acid to further protect the alloy will be discussed in the next section.

218
Discussion

10.2 LSM of AA 7075-T6 Alloy after Anodising

Anodising of aluminium and aluminium alloys followed by the application of an

organic coating, such as paint, is commonly used in the aerospace industry to

protect the substrates from corrosion. The oxidation behaviour depends on the

composition of the substrate and the nature of the electrolyte. The as-received

AA 7075-T6 alloy showed large second phases rich with copper and/or iron

elements, aligned on the rolling direction, of the alloy surface. In comparison, the

LSM AA 7075-T6 alloy showed zinc, magnesium and copper in solid solution or

as fine precipitates in the melted layer, with the presence of oxygen that is

attributed to alumina formation on the alloy surface (Figs. 8-4, 5, 13, 14). During

anodising of LSM alloys at 12 V (SCE) in 0.46 M H2SO4 for 240, 720 and 1200

sec, the steady current density was reduced by about 50 % in comparison with

the as-received alloy, respectively (Fig. 9-1), suggesting that the LSM alloy can

grow a porous film more efficiently than the as-received alloy. The presence of

copper-rich and iron-rich intermetallic particles on the as-received alloy

decreases the efficiency of the anodising due to favouring secondary

electrochemical reactions during the anodising process, in particular oxygen

generation. As a result, the current density is increased. It is reported that during

anodising of Al-Cu and Al-Cu-Fe second phases in acidic solution, the presence

of copper leads to extension oxygen evolution [199, 200]. In contrast, as the large

intermetallic particles are dissolved by laser surface melting, the process of

electron discharge is less favoured and, therefore, less oxygen evolution takes

place. This results in a reduction of anodic current density. Sealing the alloys

after anodising with deionised boiling water is important. It is reported that the

219
Discussion

hydration of alumina in boiling water produces aluminium hydroxide (Al(OH)3)

that blocks the pores of the anodic film, hence preventing aggressive ions from

the corrosive solution accessing the underlying alloy [200, 205].

The EDX analysis of the LSM AA 7075-T6 alloy after anodising for 1200 s,

(Figs. 9-3, 4 and 5) revealed that the level of oxygen is increased on the anodised

alloy, in comparison with the level of oxygen in the LSM alloy without anodising

(Figs. 8-4 and 5).The high magnification of SEM cross-sections revealed a thin

film generated over the LSM alloy (Fig. 9-6). TEM of ultramicrotomed cross-

sections (Fig. 9-7) disclosed a bubble-like texture of the anodic film. The film

was about 330 to 380 nm thick, according to the results of SEM and TEM, and

had developed uniformly above the laser treated layer. Elements of the melted-

layer and the electrolyte are incorporated into the anodic film, which is

composed mainly of amorphous alumina. The oxygen is generated by oxidation

of O2- ions of the alumina and is present in bubbles in the anodic film [200], as

well as being released to the electrolyte. The as-received alloy after anodising

showed an anodic film about 200 nm thick developed over the alloy matrix and a

2 µm thick layer developed over the large second phase particles, with the

presence of defects, such as micro-cracks, at both locations (Fig. 9-8). It is

expected that the presence of intermetallic particles enriched with copper and/or

iron increases the level of oxygen evolution and, therefore, results in less

efficient formation of the anodic film compared with the anodic film generated

after LSM.

220
Discussion

The potentiodynamic polarisation measurements in sodium chloride, (presented

in Fig. 9-9 and in Table 9-1), revealed that the LSM AA 7075-T6 alloy after

anodising showed a reduction in the passive current density by more than two

orders of magnitude in comparison with the as-received alloy before and after

anodising, and by one order of magnitude in comparison with the LSM alloy.

Thus, the anodising provided an improvement in the resistance of the laser-

treated alloy to corrosion initiation. Further corrosion investigation, using EXCO

test, showed that the anodised as-received alloy after exfoliation testing for 180

min (Figs. 9-10 and 9-11) suffered from exfoliation corrosion. The depth of the

exfoliation attack was about 65 µm. In contrast, scanning electron micrographs

of both top surface and cross-section of the anodised LSM alloy after exfoliation

testing (Figs. 9-12 and 9-13) revealed that the alloy was not attacked

significantly. Corrosion products were found only locally in a few locations and

no evidence of delamination was found, unlike the behaviour of the LSM alloy

without anodising following a similar EXCO corrosion test (Fig. 8-23). It is

evident that anodising can reduce further the corrosion susceptibility of the laser-

treated alloy due to the generation of a uniform oxide film above the alloy, which

acts as a protective layer that prevents the corrosive solution from attacking the

melted layer. Other investigators made the same observations of the corrosion

resistance of the LSM AA 2050 and LSM AA 2024 after anodising in sulphuric

acid [201, 202]. They concluded that the improvement was attributed to the

formation of thick oxide layer that protected the alloys from corrosion attack in

environments containing chloride ions.

221
Discussion

From the above discussion, LSM of the AA 7075-T6 alloy followed by anodising

in H2SO4 produced a stable film above the melted layer, which acted as an

effective barrier that protects the substrate surface from further exfoliation

corrosion. The dissolution of the large intermetallic particles combined with

refinement of the alloy surface after LSM is responsible for the improvement of

the anodising performance in comparison with as-received alloy.

222
Conclusions and Suggestions for Future Work

Chapter 11 Conclusions and Suggestions for


Future Work

11.1 Conclusions

The AA 7075-T6 alloy after surface and cross-section examinations revealed

different sizes of intermetallic particles that are aligned in the rolling direction.

Large particles were copper-and iron-rich, and small particles were magnesium-

and silicon-rich. XRD disclosed the presence of Mg2Si and Al7Cu2Fe phases.

After immersion testing in 0.1 M NaCl, the alloy exhibited pitting adjacent to

second phase particles, associated with dissolution of the surrounding matrix.

Exfoliation (EXCO) tests show that corrosion occurred within 30 min of

immersion, and extended into the matrix with increasing time of immersion. The

aggressiveness of the test solution with the presence of second phase particles on

the alloy surface allows intergranular corrosion (IGC) to propagate along

selected grain boundaries.

In terms of optimization of the LSM, the results from SEM examinations of

cross-sections and potentiodynamic polarisation tests of the excimer laser-treated

AA 7075-T6 alloy, showed that a low pulse fluence (3.3 J/cm2) reduced the

porosity and generated a more homogenous melted layer. A reduction was

observed in the passive current density in comparison with the alloy treated using

a high pulse fluence (10 J/cm2). Therefore, the condition of low fluence (3.3

J/cm2) with 80 pulses was selected for further evaluation of the corrosion

properties of the laser-treated alloy.

223
Conclusions and Suggestions for Future Work

In LSM, using an excimer laser, of the AA 7075-T6 alloy, a thin homogenous

melted layer, between 3 to 4 µm thick, was produced on the alloy surface.

Increase of the number of laser pulses per unit area and a reduction of the laser

fluence level (from 10 to 3.3 J/cm2) caused dissolution of the large intermetallic

particles and precipitates on the alloy surface. The high cooling rate (nano-

second) associated with the rapid solidification of the excimer laser caused a

wave-like top surface of the melted alloy. Generating more than one laser-track

can influence the treated area, with re-heating causing defects, such as micro-

cracks, in the previous laser-track. The cracks were restricted to a thin surface

layer of the laser-treated material, possibly being limited to the oxide film on the

alloy surface. Additionally, cross-sections of the melted layer showed bands of

discontinuous solutes that were rich in magnesium and zinc. The width of the

individual bands was about 10 to 15 nm.

In general, LSM AA 7075-T6 alloy displayed improved passivity in comparison

with the as-received alloy, with a significant reduction, by two orders of

magnitude, in the passive current density as assessed by potentiodynamic

polarization testing. SEM and TEM micrographs of the surface and cross-

sections showed a large reduction in the number of large intermetallic particles

for the alloy surface treated by LSM in comparison with the as-received alloy.

XRD measurements on the LSM alloy supported the observed reduction of the

presence of large intermetallic phases on the laser-treated alloy surface.

Corrosion evaluation after immersion testing in sodium chloride open to air

showed an improvement in the resistance to pitting initiation on the LSM alloy

224
Conclusions and Suggestions for Future Work

compared with the as-received alloy at the same time of exposure to the solution.

Further, evaluation of the exfoliation corrosion resistance by immersion of both

the LSM and as-received alloy in EXCO solution (4.0 M NaCl, 0.5 M KNO3 and

0.1 M HNO3) for 3 h showed a much greater resistance of the LSM alloy to

intergranular corrosion (IGC) than the as-received alloy, which revealed severe

IGC. The LSM layer revealed delamination of the melted layer after EXCO test,

which is possibly related to the generation of magnesium- and zinc-rich bands

within melted layer that are readily attacked by the solution.

Combining the LSM of the alloy with anodising in sulphuric acid electrolyte

gave a further improvement in the exfoliation corrosion resistance, due to

formation of a protective oxide film, about 380 nm thick, which can heal defects

present after the LSM treatment. Consequently, delamination of the melted layer

in the EXCO test was prevented. In comparison, the thickness of the anodic film

on the as-received alloy was about 200 nm. The presence of intermetallic

precipitates enriched with copper and/or iron resulted in a less protective film.

Therefore, the anodised as-received alloy after the EXCO test showed exfoliation

corrosion in the alloy matrix. However, the depth of attacked on the as-received

alloy matrix after anodising was generally reduced (65 µm) in comparison with

the depth of attacked in as-received alloy without anodising (140 µm).

Previous work on 7xxx series using excimer LSM including investigations of the

microstructures of welds by Ryan and Prangnell. The work focused 2000 series

aluminium alloy, with more limited study of alloys of the 7000 series. Unlike the

present work, the corrosion resistance of the alloys was not given attention.

225
Conclusions and Suggestions for Future Work

Notably, the study revealed the formation of copper-rich precipitate bands in AA

2024 aluminium alloy. Only two works have examined the corrosion resistance

of 7000 series alloys treated by an excimer laser. Davenport carried out both

short- and long-term corrosion tests on friction stir welds (FSW), which

disclosed delamination of the melted layer due to corrosion. This was suggested

to due to the presence of precipitate banding, similar to that reported by Ryan

and Prangnell, although no microstructural evidence for the banding was

presented. The corrosion resistance of LSM AA 7075 aluminium alloy was

investigated by Yue et al, but the work was limited to electrochemical impedance

spectroscopy and potentiodynamic polarisation tests in sodium chloride solution.

The corrosion previous studies have generally indicated an improvement in the

corrosion resistance following LSM treatments.

The present study has added to the knowledge on LSM of 7000 series aluminium

alloys, presenting evidence of the influence of different laser processing

conditions on the morphology of the melted layer and showing a benefit of using

a lower fluence than used in earlier studies. Furthermore, microstructural

examination has shown that MgZn2-rich bands are formed in the LSM layer,

which have not been reported before. The corrosion testing regime has also been

extended to relatively long-term exfoliation corrosion tests, revealing the benefits

from LSM of the alloy. Finally, it has been demonstrated that a further

improvement in the resistance of the alloy to delamination can be achieved post-

treatment of the laser-treated surface using anodizing to generate a protective

oxide film.

226
Conclusions and Suggestions for Future Work

11.2 Suggestions for Future Work

The investigations of LSM of the AA 7075-T6 alloy showed an improvement in

the corrosion resistance of the alloy due to the generation of a thin homogenous

melted layer that was free from large intermetallic particles. However, the

presence of defects in the melted layer, particularly in the re-heating region of the

first laser-track, suggests scope for further improvement the corrosion resistance.

i- Investigate the relationship between the multiple laser track movements,

number of pulses per unit area and crack initiation due to over-heating.

ii- Modelling the rate of heat diffusion with respect to the number of laser

pulses to identify the location of heat affected zones of the laser treated

area.

iii- Investigate the effect of different anodising conditions on the LSM layer

with respect to the alloy matrix to identify the best solution for anodising

and the optimum thicknesses of the resulting oxide.

iv- Investigate the relationship between the number of the lateral bands in the

melting layer and their corrosion behaviour with respect to the alloy

matrix before and after anodising.

v- In the present wok, precipitation bands have been identified by TEM in

the melted layers above the matrix and solute trails have been identified

by SEM above the copper-rich second phase particles. Further studies can

investigate by TEM the distribution of precipitates above the latter

particles in order to determine the distribution of fine precipitates

throughout the melted layer.

227
Chapter 12 Appendix 1

A- Physical properties of the elements in 7xxx alloys.

Element Wt. Melting Boiling Vapour Heat.of Crystal


% Point Point Pressure. Vap. Structure.
(K) (K) (Pa/K) (kJ/mol)
Zn 5.83 693 1180 610 123.6 Hexagonal

Mg 2.45 923 1363 701 128 Hexagonal

Cu 1.56 1358 2835 1509 300 FCC

Fe 0.24 1811 3134 1728 340 BCC

Cr 0.21 2180 2944 1656 339.5 BCC

Si 0.12 1687 3538 1908 359 DC

Mn 0.08 1519 2334 1228 221 BCC

Ti 0.03 1914 3560 1982 425 Hexagonal

Al Bal. 933.5 2792 1482 294 FCC

228
Appendix 1

B- Corrosion behaviour of the intermetallic particles on


AA 7075-T6 alloy after immersion test in 0.1 M NaCl

Intermetallic Phase Ecorr Icorr Behaviour Comments


Particles (mV) (A/cm2) with respect
(SCE) to matrix

Al7Cu2Fe S-phase -551 -3.1 x 10-4 Cathodic Constituent


Particles

Al2Cu θ -665 -4.7 x 10-4 Cathodic Constituent

Al3Fe β -539 -9.9 x 10-5 Cathodic Constituent

Mg2Si β -1538 1.9 x 10-4 Anodic Precipitates


and
Constituent

MgZn2 η -1029 1.0 x 10-3 Anodic Precipitates


along grain
boundaries

Matrix α -799 -8.1 x 10-5 Anodic ------

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