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Doctor of Philosophy
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
2
Table of Contents
4
Table of Contents
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
8
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
11
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
12
List of Figures
14
List of Figures
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
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
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
eliminate the intermetallic phases from the surface of the alloy without affecting
The present study concerns the application of LSM using an excimer laser to
stage of the project was aimed at optimising the laser conditions for production
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
After the laser treatment, the surface and the cross-sections of the alloy showed a
19
List of Abbreviations
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
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
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.
22
Acknowledgments
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
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
and Wei Go). I would like to thank my father, mother and wife for their
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
Kingdom.
23
Chapter 1 Introduction
construction, due to the excellent properties of the alloys, including high strength
magnesium, zinc, copper and iron can have great influences on the corrosion
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,
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
resistance to stress corrosion cracking, but causes a reduction in fatigue life and
24
Introduction
acid anodising (CAA), can be highly toxic and potentially damaging to the
environment.
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
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
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
anodising. Thus the objectives of the present project are to optimise the laser
25
Introduction
comparison with the untreated alloy using several corrosion test methods; and to
The first part of this thesis, after the introduction (Chapter 2), is a literature
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
will be described and reviewed. Safety aspects of using a laser are briefly
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
characterisation before and after LSM, as well as before and after corrosion tests,
26
Introduction
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
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
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
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,
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
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
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
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
improve the strength properties, but at the same time this will alter other
series are very strongly heat treatable, due to precipitation hardening based on
Adding other elements, such as copper with a small amount of chromium, into
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.
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
7xxx series aluminium alloys, or more precisely Al-Zn-Mg-Cu alloys, have been
was around 420 MPa. For the next two decades, the alloy seemed to be
30
Introduction to Aluminium Alloys
Mg(ZnCuAl)2 particles, with size about 50-100 nm, have been observed at the
depleted zone (SDZ), about 30-70 nm wide and zinc and copper were usually
Second phase particles in the alloy matrix usually fall into three categories,
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
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
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
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
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 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%
retrogression and re-ageing (RRA), has been developed that enables alloys such
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
2.3%Cu-0.16%Zr) that has been used for structural members of the Boeing 777
wings [35].
32
Introduction to Aluminium Alloys
and strength. At the same time, difficulties in controlling the temperatures and
0.22% in the higher purity alloy AA 7475, can improve the alloy toughness. [37]
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
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
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
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
Alloying elements are added to 7xxx alloys mainly for precipitation hardening
[4]. Zinc and magnesium offer the highest potential for strengthening through
(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
34
Introduction to Aluminium Alloys
Zinc, magnesium, and copper are important alloying elements in AA 7xxx alloys.
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
that pure Al. They found only aluminium inside the pit. Therefore, they
solution Al-Cu alloys and observed that even with an amount as small as 0.022
[9]. Adding Cu was found to increase the dissolution kinetics because the
[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
from Al-Zn and Al-Cu alloys [6, 7, 42]. Since Zn and Cu have opposite effects
corrosion products at AA 7xxx alloys. However, the relationship is still not clear.
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
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
36
Introduction to Aluminium Alloys
corrosion potential increases as well as the breakdown potential. They did not
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
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
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
37
Introduction to Aluminium Alloys
series aluminium alloys, the heat treatment process usually comprises three main
stages, as follows:
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
quenching rate reduces the time for diffusion and freezes the alloying elements in
(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
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
120-135 °C for 24 h [49]. The tensile strength can reach around 550-610 MPa,
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
strength by about 15% from that in T6 temper, but was reported to increase the
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
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
stability of the alloys, the GP zones solvus lies between the quench-bath
that can improve the SCC resistance in high strength aluminium alloys [28].
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
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
below the GP zones solvus, as the GP zones can form homogeneously with no
40
Introduction to Aluminium Alloys
TEM and found very fine precipitates distributed homogeneously inside the
[51]. Puiggali [52] and Ramgopal [10] found precipitates in AA 7010-T6 and
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
respectively [52]. The width of PFZ at the grain boundaries was measured to be
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
Hydrogen embrittlement is one of the main factors that can cause SCC.
Generally, hydrogen acts to weaken interatomic bounds in the plane strain region
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
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
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
This provides a more rapid transport mode than the lattice transport mode of
embrittlement.
In aluminium alloys, the grain boundaries are the preferred locations of hydrogen
entry into the grain boundaries in aluminium [58]. Pickens and Langan studied
42
Introduction to Aluminium Alloys
boundaries [59]. Pickens et al. proposed that the segregated Mg can promote
embrittlement [60].
effects in SCC and IGC in AA 7xxx alloys are still being investigated.
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,
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
43
Introduction to Aluminium Alloys
Therefore, overaged grain boundary regions are less sensitive to SCC and the
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.
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,
treatment and that reduces the SCC resistance of the alloys. Talianker and Cina
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
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
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
colleagues observed different results from Maitra. They found only pitting
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
[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
AA7075-T6 to 600 grit and exposed the sample at the OCP (open circuit
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
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 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
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
However, a high copper environment in the PFZs is needed to dissolve the grain
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
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
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
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
that heat treatment cycles can decrease the corrosion susceptibility to SCC in
47
Introduction to Aluminium Alloys
48
Introduction to Aluminium Alloys
49
Introduction to Aluminium Alloys
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
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
many crystallites of varying size and orientation. These crystallites meet together
to form grains and grain boundaries in the solid material. Corrosion attack
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
environments, this thin film may undergo dissolution, with consequent corrosion
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
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
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
[77, 78]. The film thickness is typically several nanometres (5-15 nm). The rate
Much thicker surface oxide films can be produced by various chemical and
electrochemical treatments. For example, the natural film can be thickened 500
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
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
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
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
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
equation
G xe FE c
directly related to the driving force (change in the Gibbs free energy) for the
aA+bB = cC+dD
where A and B are reactants and C and D are products, the equilibrium constant
and;
G G RT ln K
Then;
xeFEc xeFE RT ln K
55
Corrosion
This equation is called the Nernst equation, that relates the cell potential Ec to the
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.
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
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
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
Evans Diagram, where potential is plotted on the vertical Y axis and log current
(Ecorr) is directly proportional to the corrosion rate (CR). This current can be
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
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
and a and c are the anodic and cathodic Tafel slopes that are represented in
Since both driving force and kinetic considerations are crucial in determining the
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
polarization scan. The most common way to observe the breakdown potential
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
corrosion cracking. Figure 3-4 shows Ep, Ecorr, and the passive region in a
damaging species. For example, one of the major species causing breakdown of
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
high. Once breakdown has occurred, the alloy surface is exposed to the corrosive
such as potential scan rate, and may consequently not be a real measurement for
Corrosion can take different forms depending on the alloy composition and its
reviewed and the circumstances in which these areas are indicated. In general for
and stress corrosion cracking (SCC), are the most types of corrosion of the alloy
surfaces.
59
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,
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
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
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
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
environment containing chlorides, Cl‾ anions are believed to disrupt the oxide
that the pits initiate and propagate in aluminium when the following chemical
reaction;
Al 3 cations react with Cl‾ anions to form AlCl4-. Hydrolysis of this species
2- Al 3 cations concentrated at the bottom of the pit, diffuse out the pit
borders blocking the pit hole for further ionic exchange processes [92]. In
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
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
other hand, aluminium alloys usually contain second phase particles and solute-
rich regions that may disrupt the protective oxide layer and increase local
propagate; they can be repassivated, hence causing metastable pitting. Once a pit
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
Recent researches indicate that both the potential drop and the change in
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
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
63
Corrosion
contact occurs between two different metals that are immersed in an electrolyte.
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
increase of the breakdown potential of the aluminium and this must be avoided in
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
attack [28].
64
Corrosion
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
the grains remain largely unaffected. This type of corrosion is usually associated
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
account of either phases anodic to aluminium being presented along the grain
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
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,
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
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
alloys [107]. Overall, the composition change at the grain boundary due to
The difference in potential between grain boundary precipitates, the PFZ and the
grain matrix makes aluminium alloys such as 7xxx susceptible to IGC attack.
considered ductile, when the alloys are subject to a tensile stress in a particular
aluminium alloys with a high level of Cu, Mg, Si, Zn, or Li in solution may be
66
Corrosion
(7xxx series) may suffer SCC [108]. When a crack occurs, it is characteristically
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
to SCC depends upon the direction of stressing with respect to the elongated
direction, i.e. in the short transverse direction of the components, because the
Solution heat treatment and quenching introduces residual stresses into the alloy
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
of residual stresses and increase the level of resistance onto the SCC.
67
Corrosion
zones (initial formation zones of precipitates as they form from the solid
in discrete slip bands. Stress generated where these bands impinge upon grain
are varied due to differences in solute levels. For example, it has been
in the adjacent oxide layer having an increased MgO content, which is a less
The chemical nature of atom species at the crack surface may result in
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.
The oxide film is an insulator and therefore, decreases the cathodic reactivity by
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,
Once the passive oxide breaks down, aluminium dissolution occurs anodically at
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.
anodic and cathodic reactions. In neutral and alkaline conditions, the cathodic
employed, which in turn affects the stability of the surface oxide. Also, alloying
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.
having a highly stable oxide film. However, the corrosion resistance is decreased
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
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
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-
[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
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
corrosion attack. The major alloying additions, zinc, magnesium, and copper,
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
distributed on both alloy surfaces. They measured the potentials for each phase
Volta potential differences for the former particles (-475 mV) compared with the
later particles (-282 mV versus SCE) [118]. They concluded that the breakdown
difference between the intermetallics and the surrounding matrix [118]. On the
phase basis by fabricating test alloys that could provide a population of the
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
to result from the use of laser surface melting (LSM) techniques and that will
There are several surface protection methods that can be applied to aluminium
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
73
Corrosion
scratches or dirt from the surface, and the application of organic finishes, such as
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].
polishing, chemical conversion coating and electroless processes are all examples
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].
for example leading to IGC and SCC. It is often difficult to detect the corrosive
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
75
Corrosion
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
78
Corrosion
79
Corrosion
80
Corrosion
81
Chapter 4 Laser
4. Introduction
[123, 124]. This Chapter will present the basic principle of the laser, laser beam
cooling and solidification of the melted surface layer, nucleation and growth. The
discussed and reviewed. Finally, the safety aspects of the use of lasers, including
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
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
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
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
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
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
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
Laser light has four main characteristics that differentiate it from the other form
enables a laser beam to retain high brightness over a long distance, and is the
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
emitted power (q) per unit area (A) to the solid angle (Ω),
q
.
A
I = π w2 / f2
Where f is the optical focal length, and w is the beam waist radius. The beam
4
.
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
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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
angle of incidence, θB, increases (The angle at which complete absorption occurs
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].
understanding the laser heating source, formation of melt pool, cooling and
means of surface melting. Heating rates associated with laser surface melting are
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Laser
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
The melting of the surface results in formation of a melt pool. It is reported that
and the cooler solid/melt interface at the bottom of the pool [124]. In most
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
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,
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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
(∆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
(T) may not match the temperature required by the alloy liquidus, and this leads
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
stability and the morphology at the interface. Therefore, any movement of the
the interface growth rate (R*). It is reported that G influences the solidification
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respectively [130, 131]. Nucleation and growth scenarios will take place during
4.3.4 Nucleation
In LSM application, once the melt in pool area of laser treated surface is mixed
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
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,
atoms cluster together to form a stable nucleus, without the aid of foreign bodies
needed for the formation of the new surfaces, which described above. In
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uses the surfaces of foreign bodies (e.g. particles suspended within the melt) to
Heterogeneous nucleation occurs as the liquid fully wets the solid substrate it is
spontaneously. The full wetting of the surface by the liquid also means that the
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
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
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
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
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 cooling rate. Fast cooling rates can influence the crystal structure
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
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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
the distance between interface protuberances must be less than the atomic
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
composition across the melted layer can be produced with no signal of second
Some lasers operate continuously, and are termed continuous wave (CW) lasers,
while other lasers operate discontinuously and are known as pulse lasers. For
the laser or the sample. For pulse lasers, the pulse duration is the interaction time.
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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
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
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
occurs once the radiation is removed from the surface that freezes the material to
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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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
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
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
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
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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
threshold value [147, 148, 150]. Under this value, there is a step change in the
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
4.5.2 Wavelength
For CW-LSM, the absorption of the laser radiation into a surface is related to the
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
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[135].
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 with more rapid cooling rates would be
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
melting temperature is higher than the melting temperature but less than
increase in energy density and melting until the temperature at the surface
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
time can be controlled under PRF. Note that the fluence value required for the
The number of pulses per unit area used in LSM processes has been observed to
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
(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
time when treating large areas of material. This will then impose a limit on the
[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,
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
wear resistance and hardening, while in an open environment, the modified layer
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.
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
CW-CO2 LSM of Al-Cu alloy confirmed that the microstructure morphology was
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
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
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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initial region of growth at start of re-solidification of each pulse where the front
segregation or banded structures. Figure 4-9 shows the results from this
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
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
[166, 167]. LSM of these two alloys under identical processing conditions
2024, and cellular growth observed in AA 7150 as shown in Figure 4-13. The
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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considered to be the main cause for cellular growth initiation and the
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
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,
of solute banding within the resolidified layer, which results from the differences
changing in the solidification rate [173]. Milewski et al. used Nd:YAG LSM on
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
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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
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
10 wt.% Zn, a banded structure was observed [179]. Lasek mentioned that
cracking occured along the grain boundaries into the melted region and the
during room temperature ageing. Roosz et al. [181] investigated the surface
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
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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increase the layer thickness and cell spacing that favours the formation of more
dendrites.
properties regarding corrosion attack. Bonora et al. were the first to study the
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
unchanged after LSM. They concluded that the lower corrosion rates were due to
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
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
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
microstructure [165]. McMahon [184] and Watkins et al. [185] reported that the
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
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].
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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
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
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
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generated in a gas mixture of krypton (Kr) and fluorine (F). An excited dimer
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
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
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
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.
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
formed at the surface [23]. The excimer laser was found to be effective in
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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
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
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
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Laser
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
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
Class 3 lasers are subdivided into class 3R and class 3B. Class 3R lasers may
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.
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.
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.
4.9.3.1 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
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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 above class 1 level. Also, systems such as 3B and 4 classes must have a
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
frequency. Glass or plastic absorption filters, with incorporated organic dye for
power, which reduces colour distortion and protects the eye from any damage.
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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]
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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]
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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]
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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]
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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]
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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]
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Chapter 5
Experimental Procedures
5. Introduction
corrosion, without affecting its bulk properties, by laser surface melting (LSM),
excimer laser was used with different numbers of pulses per unit area and
After LSM, anodising was used with the aim of adding more protection to the
the as-received alloy in comparison with the alloy treated by LSM with and
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Experimental Procedures
The material used in the experiments was aluminium alloy AA 7075-T6 sheet of
Table 5-1 shows the chemical composition in wt% of the alloy that was provided
by the supplier.
Element Zn Mg Cu Cr Fe Mn Si Ti
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-
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
Specimens were then dried in air for about 24 h before applying the LSM
treatment.
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Experimental Procedures
Laser surface melting (LSM) was carried out in air using a Lumonics IPEX-848
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
was attached for electrical connection for electrochemical tests. Lacquer (45-
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
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
Interface). During anodising, the current-density (I) vs. time (t) was monitored.
porous anodic oxide [198]. After anodising, sealing the anodic films was
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
121
Experimental Procedures
Three different types of corrosion tests have been employed. Each was repeated
were used, with comparison made between as-received and LSM alloy
specimens.
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
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
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].
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
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,
In order to prepare the specimen after LSM for surface and microstructure
123
Experimental Procedures
Mounted specimen surfaces were ground with SiC paper in the sequence 400,
Specimens were washed with deionised water after each step of polishing,
Finally, specimens were cleaned with deionised water and dried in a stream of
SEM)
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-
information on the atomic number from a greater depth in the sample. An EDX
the elements, the latter using the mapping analysis option. In this project, a
124
Experimental Procedures
photographic film, or using a sensor such as a CCD camera [193]. The main use
the structure and composition of specimen. The specimen for TEM investigation
(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
materials. XRD is based on observing the scattered intensity of the X-ray beam
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
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
the sheet normal to the direction of rolling. The particles range in size from about
cavities on the alloy surface (see arrow in Fig. 6-2 (a)), where particles have been
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
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,
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].
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 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
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
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
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
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
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-
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
MgZn2-η phases on the grain boundaries [3, 5, 7, 10]. The anodic behaviour of
regions.
130
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy
6.4 Conclusions
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
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
corrosion occurred within 30 min of immersion, and extended into the matrix
with increasing time of immersion. The aggressiveness of the test solution with
131
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy
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
135
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy
136
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy
137
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy
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
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)
140
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy
141
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy
142
Microstructure and Corrosion of the As-received AA 7075-T6 Alloy
143
Chapter 7
Laser surface melting was carried out in air using a Lumonics IPEX-848 excimer
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
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
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
P
Irradiance [W / cm2] (2)
A
The fluence refers to the total amount of pulse energy applied over the area of the
E
fluence [J / cm2] (3)
A
During LSM, the interaction time of the laser pulse, Tin, can be calculated by the
following equation;
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
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
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
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
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,
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
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
comparison with the corrosion potential of the as-received alloy, as shown in Fig.
the cathodic reactivity of the alloy surface after LSM by dissolution of the large
the passive current density for 10 and 25 pulses in comparison with the as-
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
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-
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].
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
80 pulses was selected for further evaluation of the corrosion properties of the
148
LSM Operation Conditions
NOP Fluence
J/cm²
10 10
25 10
50 10
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
152
LSM Operation Conditions
153
LSM Operation Conditions
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
156
LSM Operation Conditions
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.
158
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
the temperature profile in the reheated zone. Fig. 8-3 (c) shows a higher
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
159
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
elements that resulted from the EDX analysis are recorded in the Tables that
sections of the LSM area, shown in Fig. 8-6, disclose a relatively rough surface
molten materials produced by excimer laser pulses causes the melted layer to be
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
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
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
Cross-sections of another region of the melted layer are shown in Fig. 8-10. The
160
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
melted layer above both the matrix and partially-melted second phase particle is
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
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
161
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)
the laser-melted layer in the high angle annular dark field mode. It is evident that
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.
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)
Fig. 8-17 shows potentiodynamic polarization curves for the laser-treated and the
162
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
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,
after LSM. The thickness of the laser-melted layer was similar to that before the
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
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
Figs. 8-20 and 8-21 show higher magnification scanning electron micrographs of
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
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
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
melted layer that was free from large second phases. After LSM, the alloy
comparison with the untreated alloy when examined under similar conditions of
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
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
165
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
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
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
170
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
171
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
172
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
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).
174
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
175
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
176
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
177
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
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
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)
181
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
182
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
183
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
184
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
185
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
186
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy
187
Chapter 9 Microstructure and Corrosion of
the LSM AA 7075-T6 Alloy after Anodising
9. Introduction
used to increase the thickness of the protective oxide layer on the surface of
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
720, and 1200 s. The aim was to protect the laser surface melted layer from
TEM, with the corrosion resistance of the laser-treated and anodised alloy
The current density / time behaviour of the LSM specimen, as well as the as-
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
188
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising
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
anodising the film was sealed by immersion in deionised boiling water for 30
min.
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
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
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
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
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
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
Figures 9-10 (a) and (b) showed scanning electron micrograph of the top-surface
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
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
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).
9.4 Conclusions
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
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
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
198
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising
199
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising
200
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising
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
203
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising
204
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising
205
Microstructure and Corrosion of the LSM AA 7075-T6 Alloy after Anodising
206
Chapter 10 Discussion
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
broken into small particles during rolling. The other particles were clustered with
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
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
207
Discussion
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
deaerated 0.1 M NaCl solution (Fig. 6-9) revealed two breakdown potentials. The
surface layer [27, 197]. The process of mechanical polishing of an alloy surface
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
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
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.
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
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)).
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
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
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
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
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
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
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
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
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
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.
211
Discussion
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
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
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
analysis (Figs. 8-13, 14) disclosed zinc and magnesium enrichment in these
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
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
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
The high resolution TEM micrographs of Figs. 8-11 and 8-14 revealed a distance
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
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
[166]. Other investigators showed that due to the short duration of each laser
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
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
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
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
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
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
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
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
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
The results of immersion tests of the LSM AA 7075-T6 alloy in 0.1 M NaCl
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
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
environments, and the absence of the other active constituent particles that are
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
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
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
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
22, 23). The zinc and magnesium precipitates in the melted layer and at the
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
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
From the above discussion of LSM, the improvement in corrosion resistance was
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
sulphuric acid to further protect the alloy will be discussed in the next section.
218
Discussion
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
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
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
that blocks the pores of the anodic film, hence preventing aggressive ions from
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
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
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
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.
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
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
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
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
refinement of the alloy surface after LSM is responsible for the improvement of
222
Conclusions and Suggestions for Future Work
11.1 Conclusions
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
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
AA 7075-T6 alloy, showed that a low pulse fluence (3.3 J/cm2) reduced the
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
223
Conclusions and Suggestions for Future Work
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
discontinuous solutes that were rich in magnesium and zinc. The width of the
polarization testing. SEM and TEM micrographs of the surface and cross-
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
224
Conclusions and Suggestions for Future Work
compared with the as-received alloy at the same time of exposure to the solution.
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,
Combining the LSM of the alloy with anodising in sulphuric acid electrolyte
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
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
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
investigated by Yue et al, but the work was limited to electrochemical impedance
The present study has added to the knowledge on LSM of 7000 series aluminium
conditions on the morphology of the melted layer and showing a benefit of using
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
from LSM of the alloy. Finally, it has been demonstrated that a further
oxide film.
226
Conclusions and Suggestions for Future Work
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.
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
iv- Investigate the relationship between the number of the lateral bands in the
melting layer and their corrosion behaviour with respect to the alloy
the melted layers above the matrix and solute trails have been identified
by SEM above the copper-rich second phase particles. Further studies can
227
Chapter 12 Appendix 1
228
Appendix 1
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