The effects of friction stir welding on the mechanical

properties and microstructure of a third generation Al-Cu-Li

alloy.

Rosen Ivanov

Mining and Materials Engineering

McGill University, Montreal

July, 2012

A thesis submitted to McGill University in partial fulfillment of the

requirements of the degree of Masters in Materials Engineering

© Rosen Ivanov March, 2012

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2
Table of Contents

Table of Contents _____________________________________ 3

Abstract _____________________________________________ 4
Acknowledgements ____________________________________ 5
1.0 Introduction _______________________________________ 7
2.0 Literature Review __________________________________ 9
2.1 Historical overview ________________________________________________________________________________ 9
2.2 Physical metallurgy of Al-Cu-Li alloys ___________________________________________________________ 11
2.3 Friction stir welding ______________________________________________________________________________ 19
3.0 Objectives _______________________________________ 27
4.0 Instrumentation and experimental procedures ___________ 28
4.1 The welding of the material AA2199 ____________________________________________________________ 28
4.2 Mechanical testing ________________________________________________________________________________ 32
4.3 Differential scanning calorimetry ________________________________________________________________ 35
4.4 Microscopy ________________________________________________________________________________________ 36
5.0 Results and Discussion _____________________________ 41
5.1 Sample description ________________________________________________________________________________ 41
5.1.1 FSW Parameters studied _______________________________________________________________________ 42
5.2 Optical characterization __________________________________________________________________________ 45
5.3 Differential scanning calorimetry ________________________________________________________________ 46
5.4 Hardness ___________________________________________________________________________________________ 54
5.5 Hardness map of select welds (B1 and G1) _____________________________________________________ 58
5.6 Scanning and transmission electron microscopy characterization____________________________ 61
5.6.2 Grain size measurement ________________________________________________________________________ 64
5.6.3 Precipitates in back scattered electron mode _________________________________________________ 67
5.6.4 Transmission electron microscopy ____________________________________________________________ 96
5.7 Mechanical properties of welds ________________________________________________________________ 113
5.8 Fracture surfaces ________________________________________________________________________________ 117
6.0 Summary _______________________________________ 127
7.0 References _____________________________________ 131

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Abstract

The effect of friction stir welding on the microstructure, precipitation, mechanical

properties, and tensile fracture has been studied. Friction stir welding has been
applied to a third generation Al-Cu-Li alloy, the AA2199, in the T3 condition. Post
weld heat treatment (PWHT) to the T8 condition, was carried out to artificially age
the welds and improve mechanical properties. Welds were characterised using
field emission scanning electron microscopy (FE-SEM) with electron channeling
contrast imaging (ECCI), differential scanning calorimetry (DSC), micro-
hardness, and tensile testing. Welds created with tool rotation speed of 877RPM
showed ultimate tensile strength level of 93% of base metal in the T8, an
elongation of 6% at fracture, and microhardness values ranging between 120-
140 HV across the welds. The ability of welds to gain in hardness and strength
during PWHT has been linked to the limited formation of large scale precipitates
which act as sinks for alloying elements.

L'effet du soudage par friction-malaxage sur la microstructure, la precipitation, les

propriétés mécaniques et la rupture par traction ont été étudiés. Le soudage par
friction-malaxage a été appliqué à une troisième génération d’alliage d’Al-Cu-
Li, le AA2199-T3. Un traitement thermique après soudage (PWHT) sur l’alliage
AA2199-T8 a été réalisé pour vieillir les soudures artificiellement et en améliorer
les propriétés mécaniques. Les soudures ont été caractérisées par microscopie
électronique à balayage (FE-SEM), par imagerie en contraste
cristallographique (ECCI), par calorimétrie différentielle à balayage (DSC) et par
des essais de micro-dureté et de traction. Les soudures créées avec une vitesse
de rotation d’outil de 877RPM ont montré une limite à la rupture de 93% par
rapport la plaque de depart, un allongement à la rupture de 6% , et des
valeurs de microdureté variant entre 120 à 140 HV dans les soudures. Le gain
en dureté et en résistance du matériau dans les zones soudées au cours du
traitement thermique PWHT est lié à la formation à grande échelle de
précipités absorbant les éléments d'alliage.

4
Acknowledgements

To my family.

The work presented in this master thesis has been kindly funded by ALCOA Inc. I
would like to also 2thank McGill University and the Montreal environment for
being a great habitat for the duration of my studies there. Special mention is paid
to everyone working with REGAL for providing a forum for young engineers in
Quebec, Canada.

The final product is a result of great collaborations between staff at ALCOA

Technical Centre and reseachers McGill University. This project would not have
been as smooth without the significant contributions by Diana Denzer, Daniel M.
Myers and Kyle L. Williams for all the friction stir welding at the ALCOA Technical
Centre, and R. Roija and C. Giummarra for being a constant source of
information on Al-Li alloys. A very special thank you is well deserved by Dr.
Julien Boselli for all his time and efforts in the coordination of this project. His
particularly friendly and extremely helpful advises and comments towards my
professional development are greatly appreciated.

My master’s thesis is the culmination result of the remarkable supervision and

many intriguing and inspiring discussions spearheaded by Prof. M Brochu and
Prof. R. Gauvin. The pair have allowed me to develop and express my ideas and
supported me in doing whatever it takes to get the job done. They guided through
the development of my scientific, managerial and interpersonal skills. Their lust
for science and proof of concepts has been the greatest inspiration! You guys are
and hopefully will remain outstanding supervisors!

Furthermore, the work presented in this thesis would not have been possible
without the help of Prof. D. Larouch, D. Marcotte, D. Liu, Dr. F. Paray, H.
Cambell, M. Riendeau, R. Langlois, R. Paquette, Dr. P. Wanjara and X. Pelletier.
An absolutely special thank you is well deserved by Barbara – you are the
reason why graduate studies in the Materials Engineering program flow so easily!

5
Nicolas Brodusch deserves his own paragraph! Working with him on the SU-
8000 has been an absolute pleasure. His desire of achieving what has not been
done and ameliorating it has yielded the majority of the outstanding micrographs
presented. His sharp focus on microscopy and his down to Earth attitude make
spending hours in the basement of the Wong actually enjoyable! Thank you
Nicolas!

My colleagues and scholar friends are certainly a very important part of my life as
a graduate student at McGill University. I thank you: David Levasseur, Bamidele,
Nesli, Rabab, Michael Shockley, Pantcho, Holger, Jessica, Renaud, Andrew
O’Reilly, Florencia, Derek, Cecile, Christoph, Bikram, Dom, Dmitri, Manas,
Maziar, Deniz, Ramona, Lidia, Vicky, Frank, and those who I’ve missed! Thank
you Marie-Pier Cote, you’re your outstanding help with writing abstracts in
French and everything else! Absolutely special thank you is well deserved by:
David Heard, Mert Celikin, Phillipe Pinard, Prof. Nate Quitoriano, Jason Milligan,
David Walker, and Jesús Pérez for their constant and very helpful discussion on
life, board games, drinking and some material science!

I leave them for last but my friends are certainly the a very important part of my
life as a graduate student in Montreal. Thank you all for being awesome: Shiela,
Raph, Tony, Lucie, Oli, Seb, Theo, Seb, Paul, Mass, Niko, Nil, Mel, Vanessa,
Alexandra, Aurore and all the other girls in my life. 

Thank you father and mother for supporting me through this endeavour. And
finally to my loving, caring and extremely good hearted grandmother who is 90
and sick but to this day holds her humour up high. You are an inspiration.

6
1.0 Introduction

Materials with high mechanical properties and low density have been of interest
for applications in the aerospace and naval industries. The potential lighter
vessels, allowing for fuel savings and reduced operating costs, has sparked
interest in such materials since the first fuel crisis in the 1970s. Many aluminium
alloys from the 2xxx and 7xxx series have been developed to cater for such
applications and are commonly used for wing and fuselage materials [1]. A
further potential improvement of aluminium alloys can be achieved via alloying
with lithium, as its addition results in an increased Young’s modulus and reduced
density.

One of the first applications of Al-Li alloys was in the construction of the wings of
the US-Navy Vigilante supersonic bomber [2]. The US space shuttle external
tank was designed and built from an Al-Li alloy, which allowed for ~1000kg in
weight savings compared to previous alloy used and reduced flight cost by 11
million US$ [3]. More recently, Al-Li alloys have been employed in the
construction of commercial airplanes such as the A380 by Airbus [4]. Competition
for light weight structural applications arises from polymer based carbon fiber
composites; however components made from Al-Li alloys can be manufactured
via conventional aluminium processing routes; unlike polymer based composites
which require expensive re-design of fabrication facilities. Furthermore, Al-Li
alloys are more easily repaired and exhibit inherent lighting protection.

The joining of aluminium alloys through conventional welding methods has been
characterized by poor solidification microstructure, high volume fraction of
porosity in the fusion zone and the potential for segregation of alloying elements.
These microstructural changes would lead to significant loss in mechanical
properties. Techniques such as spot resistance welds have been suggested [5,
6], however, the high cost of surface preparation has not made this method a
replacement for mechanical joining. As mechanical joints add weight to
assemblies, research into alternative joining methods is of interest.

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Friction stir welding (FSW) is a solid state joining process that was developed by
The Welding Institute (TWI) of the UK in 1991 [7]. A permanent rotating tool is
inserted between two abutting plates, and pushed along a weld line forcing
mixing of softened plasticised material. The resulting joints have low porosity,
ultrafine microstructure and minimal distortions. Furthermore, weight savings can
be achieved with FSW as it requires no external material feed and is suitable for
many weld geometries which would normally require material overlap when
mechanically fastened by rivets. [8]

The FSW process exposes the weld zones to elevated temperature and
mechanical mixing, which inevitably lead to changes in microstructure and hence
mechanical properties. Post weld heat treatment (PWHT) is a common technique
used to recover such changes during welding; however, PWHT may be a
manufacturing challenge on large structures such as an airplane fuselage or wing
components.

The focus of this thesis is to characterise the observed microstructural changes

due to FSW of an Al-Cu-Li alloy in the as-welded condition and the PWHT
condition. Analyses presented consist of macroscopic weld observations,
differential scanning calorimetry (DSC), hardness line and map tests of weld
zones, electron microscopy, and tensile mechanical properties. The
microstructural changes are related to the observed changes in mechanical
properties upon PWHT and linked to the FSW parameters used.

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2.0 Literature Review

2.1 Historical overview

Precipitation hardened aluminium alloys were first reported by Alfred Wilm in

1906 for the Al-4Cu-0.6Mg wt% alloy [9]. Understanding of the evolution of such
alloys has been central to the development of many aluminium alloys, such as
the 2xxx, 6xxx, 7xxx, and 8xxx series. Metallurgists and material scientists have
explored the periodic table to implement alloying elements for specific results.
Figure 1 highlights the effect of such alloying elements on the density and
Young’s modulus of aluminium binary alloys. The bulk of the research has been
focussed on alloying elements such as Cu, Si, Mg, Zn, Mn, Ni and Zr. The only
alloying elements which decrease density and increase Young’s modulus of the
aluminium alloy are Be and Li (see Figure 1). The toxicity of Al-Be alloys and the
price of beryllium have limited their development. Consequently optimized
solutions arise from Al-Li alloys.

Lithium has the lowest density and is the lightest metal with a density of 0.534
g/cm3. Alloying Al with Li can provide up to 3% density reduction and 6% Young’s
modulus increase for every 1 wt% Li addition [10]. The large increase of Young’s
modulus for Al-Li solid solutions has been attributed to a change of electronic
environment for the alloy. Charge density is increased and results in increased
atomic bonding strength. Atomic size difference and hence lattice strain have
been reported to have a much smaller effect on the elastic modulus of Al-Li
alloys [11, 12].

Early attempts at maximizing the content of Li in Al produced alloys such as

AA2020, along with Russian alloys 01420 and 01421, which were the first
generation Al-Li alloys. These alloys only saw limited application due to their low
ductility, poor fracture toughness, unpredictable crack morphologies in wrought
products, and high cost.

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 a) b)

Figure 1 Effect of alloying elements on a) density and b) Young's modulus [10]

The second generation Al-Li alloys included AA2090, AA2091, AA8090, and the
USSR versions 01430, 01440, 01450, and 01460. These alloys had Li content
above 2.0 wt.% with the aim of mitigating the problems that plagued the first
generation. Alloys were designed to be used as gauge-to-gauge replacements of
the commonly used AA2024 and AA7075 [13]. Some of these alloys contained
other elements, such as Cu and Mg in the 01430 and 01440, which were added
to further increase mechanical properties [6]. These alloys still suffered from low
fracture toughness, accelerated fatigue crack growth in corrosive conditions, and
highly anisotropic mechanical properties [4, 6, 13].

The third generation Al-Li alloys have below 2.0 wt. % Li. The Weldalite ® series
with alloys such as 2094-2099 for extrusions and 2195, 2099-2199, 2050 and
2198 for plates and sheet products make up the majority of this generation [14].
The Li content was reduced in this generation as developers realised that weight
savings via Li addition could be matched by increasing the mechanical properties
and utilizing thinner gauges. The third generation Al-Cu-Li alloys also include Mg,
Mn, Zr, Zn, and in some cases Ag as alloying elements. These alloys provide
increased mechanical properties, good fracture toughness, good corrosion
resistance and damage tolerance compared to earlier generation Al-Li alloys. [4,
15]

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2.2 Physical metallurgy of Al-Cu-Li alloys

2.2.1 Al-Li

The binary phase diagram of the Al-Li system shown in Figure 2a , shows up to
4.0 wt.% Li solubility in α-Al at 600°C [6]. At lower temperatures, the solubility
decreases to 0.06 wt.% at 50°C and Li is forced out of the solid solution as the
material enters the two phase equilibrium region. Heat treatment processes have
been designed that make use of this solid state phase transformation and hence
Al-Li alloys have been named “heat treatable” and “age hardenable”. The
common first step heat treatment involves solution treatment at high temperature
to achieve a solid solution, i.e. in the single phase region of the phase diagram.
The material is quenched to “freeze” this solid solution and create a super-
saturated solid solution (SSSS) which can subsequently break down via
precipitation of both metastable (δ’ – Al3Li) and stable (δ – AlLi) secondary
phases. The generally accepted precipitation sequence for binary Al-Li alloys is
as follows [10, 16-18]:

SSSS  δ’ (Al3Li)  δ (AlLi)

The formation of the δ’ phase results in little strengthening of Al-Li alloys as it is a

small scale, coherent and shearable precipitate with minimal lattice miss-match
with the α-Al matrix. The δ’ phase has a L12 structure with the Li atoms
occupying the corners of the FCC structure. The phase has been reported to
preferentially nucleate on dislocations. Large volume fractions of the δ’ phase
result in an increased hardness however; strain localization has also been
associated with these precipitates. [19-25]

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 b)
a)

Figure 2 a) Al-Li binary phase diagram [6] b) The metastable two-phase region for binary Al-Li with
regions A and D being metastable and regions B and C being prone to undergo spinodal
decomposition [26]

The decomposition of SSSS to the metastable δ’ phase has been discussed in

the literature and several authors have reported possible precursors of the δ’
phase [27]. Ordered solute-rich zones known as GP zones, common to
aluminium alloys, have been suggested by Papazian et al [28]. More complex
spinodal decomposition and ordering process has been described and related to
the alloy composition as shown in Figure 2b [26, 27, 29, 30]. The position of the
phase fields may differ from that on the equilibrium Al-Li phase diagram due to
the presence of other alloying elements as discussed in the following sub
sections.

Formation of the δ (AlLi) phase has been linked to exposure to elevated

temperatures. This precipitate is an equilibrium phase that commonly grows on
grain boundaries during short high temperature exposure which facilitates Li
diffusion. The δ phase has been observed in grains for prolonged exposure to
temperatures above 200°C. As Li is pulled from the matrix to form the δ phase,
reports have shown the formation of precipitate free zones (PFZ) which result in
local material softening. The presence of the δ phase has also been associated
with slip homogenization therefore affecting fracture mechanics. Stress corrosion
cracking has also been linked to the δ phase. [10, 24, 31-34]

Binary Al-Li alloys have limited application due to the above described problems
associated with the precipitates present. The addition of other alloying elements
promotes changes in the precipitation sequences observed and created

12
possibility for further improvement in mechanical properties via newly formed
phases. The primary elements added to Al-Li alloys are Cu, Mg, Zn, Mn, Zr, and
in some cases even Ag. Due to the large number of elements present in these
chemistries, the precipitation sequences become significantly more complex as
shown by Starke et al, in Figure 3 [35]. It should be noted that the majority of the
precipitates described in Figure 3 can co-precipitate and therefore further
complicate observable microstructures in Al-Li-X alloys. The interactions between
alloying elements should also be kept in mind as they may lead to changes of the
solubility of Li in Al and hence influence the formation of Li bearing phases. The
formation of dispersoid secondary phases such as the β’ (Al3Zr) has also been
reported.

Figure 3 A series of possible precipitation sequences for combined elemental addition to the Al-Li
system [35]

2.2.2 Al-Li-Cu

One of the most common alloying elements for age hardenable aluminium alloys
is Cu. Its addition results in the precipitation of a series of phases that range from
fully coherent to incoherent as shown by the following sequence:

SSSS  coherent GP zones  semi-coherent θ’’/θ’(Al2Cu)  incoherent θ(Al-Cu)

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As a SSSS is left to stand the solute atoms of Cu form very small clusters which
have been termed GP zones. Upon further aging or at a slightly elevated
temperature the GP zones transform to a more organised and semi-coherent
form - the θ’’/θ’ phases. It is this phase that is responsible for the maximum
hardness observed in binary Al-Cu alloys as it forms on the (100) family of planes
and resists slip. Prolonged exposure to elevated temperature brings about the
formation of the θ phase which is an incoherent Al-Cu phase. Its formation soaks
Cu atoms from previously present smaller precipitates, the GP zones and θ’’/θ’,
thereby leaving precipitate free zones and reducing the hardness of the alloys.

Addition of Cu to the Al-Li system result in a reduced solubility of Li in the α-Al.

The formation of the δ’ phase is promoted and is reported to co-exist with phases
common to the Al-Cu system. During short, low temperature aging the δ’ phase is
known to co-precipitate surrounding GP zones and θ’ phases. This reaction is
energetically favourable as the mismatch between the α-Al and the Al-Cu
cluster/phase results in a strain field that can be reduced by the existence of an
Al-Li low mismatch boundary zone. [21, 36-38]

Prolonged exposure at elevated temperatures during artificial aging results in

higher density of the θ’ and new Al-Cu-Li phases. The ratio between these
phases is dependent on the Cu/Li ratio in the system. High Cu/Li results in more
θ’ phase and less of the Al-Cu-Li phases. Precipitation of these new phases
decreases the volume fraction of the δ’ phase as Li migrates to surround or be
part of the new phases. [39, 40]

The T1 (Al2CuLi) phase, first identified by Hardy and Silcock, forms as hexagonal
plate shaped precipitates occupying the (111) family of planes [19, 41]. These
high aspect ratio platelets are a major obstacle to dislocation motion in aged Al-
Cu-Li alloys and are hence responsible for a significant portion of the mechanical
properties. The precipitation of the T1 phase is promoted with the introduction of
dislocation prior to aging. Variants of the T1, e.g. T2 and Tb phases have also
been observed in Al-Cu-Li alloys as shown in Figure 4a. The formation of these

14
phases is linked to the Cu/Li ratio and the degree of aging (e.g. overaging) and
aging at higher temperatures. These phases have been observed to
preferentially occupy high angle grain boundaries. The Tb phase has been
related to poor corrosion in some Al-Cu-Li alloys[42]. [43-49]

2.2.3 Al-Li-Cu-Mg

Mg can be alloyed to further provide beneficial precipitates without compromising

the density of Al-Cu-Li alloys. Mg additions create a more complicated
precipitation sequence as has been described for alloys such as AA8090,
AA8091, AA2090 and AA2091. Simultaneous precipitation of the δ’ with the T1
and S (Al2CuMg) is expected for alloys with composition similar to AA2090 as
shown in Figure 4b. Mg has also been reported to substitute with Li in the T1
phase. These phases are of prime interest as they both contribute to
strengthening and their formation can be promoted via introduction of dislocation
prior to artificial aging. Overall, the addition of Mg further reduces the solubility of
Li and promotes the uniform distribution of the T1 phase in the matrix. [50-52]

Exposure to elevated temperature for prolonged periods of time may result in the
solid state formation of other intermetallics containing Al, Cu, Li and Mg. The
formation of a T2 - Al6Cu(Li/Mg)3 phase on high angle grain boundaries has been
observed in Mg containing alloys [53]. Once again the ratios between the alloying
elements can be used to estimate the likely phases to be observed in an alloy.
Accurate reports for the compositions of these phases are very limited and
contain wide variance as their presence is influenced by other possible elements.

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Figure 4 Isothermal sections through the Al-Cu-X phase diagrams a) X=Li at 327°C and b) X=Mg with
the 2-3wt.% Li at 190°C [50]

2.2.4 Effect of Zn to Al-Li-Cu-Mg alloys

Zinc additions are common to the 7xxx series along with additions of Mg. The
combination of these elements results in very strong heat treatment responses
through a series of phases that are absent from the alloy under investigation in
this thesis due to the low wt.% Zn added. The presence of Li is purported to
reduce the mobility of Zn due to Li’s greater affinity for vacancies, which typically
aid Zn diffusion. In the 2xxx series, small additions of Zn have been reported to
remain in solid solution with the α-Al and provide an improvement to the
corrosion behaviour and mechanical properties through solute hardening. [54,
55]

2.2.5 Effect of Mn on Al-Li-Cu-Mg alloys

Manganese has been added to form an Al20Cu2Mn3 incoherent dispersoid phase

to aid homogenization of slip and hence improve fatigue and fracture toughness.
The δ phase has been observed to heterogeneously precipitate around Mn
containing dispersoids. Small Mn additions have been shown to have a beneficial
effect on grain refinement and texture characteristics of the alloy. [15, 31, 39, 56,
57]

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2.2.5 Effect of Zr on to Al-Li-Cu-Mg alloys

Zirconium is added to form the coherent β’ (Al3Zr) L12 structured perfectly

spherical precipitates during processing at temperature above 400°C. The
primary use of this dispersoid is to control recrystallization and its presence
results in finer microstructures and improved fatigue properties. Epitaxial
precipitation of the δ’ phase on the surface of the β’ phase has been observed.
[15, 58, 59]

2.2.6 Precipitation hardening though artificial aging of complex Al-Cu-Li alloys

In 1911 A. Willm first reported that a quenched Al-Cu-Mg alloy increased its
hardness with aging at room temperature – i.e. natural aging [9]. The
microstructural changes explaining this phenomenon were reported by Guinier
[60] and Preston [61] in 1938 when they identified the formation of clusters of
solute atoms in Al-Cu system later termed GP zones. Since then, the
development of age hardenable aluminium alloys has progressed and resulted in
some of the highest strength 2xxx, 6xxx and 7xxx series of aluminium.

Age hardenable aluminium alloys show high solubility of alloying elements at

high temperatures, which drops close to zero at lower temperatures. Systems
like Al-Cu at temperature above 500°C (i.e. during solutionizing) can have a lot of
Cu atoms in solution. If cooled extremely slowly, these atoms form the
thermodynamically stable Al2Cu phase with the help of vacancy diffusion. If the
alloy is rapidly cooled – quenched – then the Cu atoms will remain in the solid
solution and form a metastable super SSSS with high density of quenched in
vacancies. The minimization of the Gibbs’ free energy for such frozen SSSS into
a more stable state – for example clusters of Al-Cu atoms (GP zones) finely
dispersed around the aluminium matrix – is called precipitation. Similar ordering
effects have been reported for Al-Cu-Mg [62, 63] and Al-Li-Cu [21, 64] systems.
Precipitation can be encouraged through elevated temperature exposure which
facilitates Cu atom (or other solute) and vacancy diffusion. This is known as
artificial aging. During prolonged elevated temperature exposure atoms are able

17
to order into the lowest Gibbs’ free energy configurations and form equilibrium
phases such as the θ (Al2Cu) in the Al-Cu system.

The nucleation of precipitates as described above can occur spontaneously and

randomly in the matrix of aluminium, corresponding to homogenous nucleation.
This effect is related to the aim of any system to minimize its internal energy. The
formation of GP zones, δ’ and θ’ phases in Al-Cu-Li system [21, 65] occurs
homogenously during natural aging and is labelled the T3 condition. If such
systems are artificially aged at elevated temperatures above 150°C the formation
of metastable phases, such as the T1 and S’ phases, can occur simultaneously
with the previous phases if the alloy composition favours that type of precipitation
[66, 67]. Optimization of the temperature and duration of artificial aging resulting
in the best mechanical properties for a given system can be performed. This
condition is known as the T6 peak hardness artificially aged condition.

The precipitation of plate shaped phases of the Al-Cu-(Li/Mg) type is considered

thermodynamically hard as they are semi-coherent. The event can be
accelerated and achieved at lower temperature if the material received was
stretched before aging – termed the T8 condition. Stretch results in more
dislocations which act as nucleation sites for such phases. Higher density of the
T1 phase precipitating in Al-Cu-Li alloys results in an increase in mechanical
properties and is hence of great interest [48, 68-70]. The introduction of
nucleation sites through stretch has also been shown to be beneficial for the
formation of the δ’ phase in Al-Li alloys [24]. In some cases age hardenable
alloys may be soultionized and stabilized to the T7 condition, also known as
over-aged condition. For wrought alloys the T7 condition is often employed to
improve corrosion resistance [71].

Variations to the aging sequence have been introduced to control the

precipitation temperature, density and special distribution of precipitates [72, 73].
The methodology used for obtaining the T8 Prime condition in 2199 sheet,
corresponding to an underaged condition, is best described by C. Giummarra et
al. [15, 74] and is proprietary to Alcoa. In Figure 5a summarised processing route
18
is suggested for obtaining more isotropic Al-Cu-Li alloys as the AA2199 in plate
form. Details on the amount of deformation introduced to the material in the final
stretch and the temperature and duration of the final artificial aging procedure are
kept proprietary by Alcoa. The suggested base metal microstructure achieved
though the above mentioned processing route is described in Figure 6. The high
density of fine scale strengthening precipitates and dispersoids helps achieve the
outstanding mechanical properties of the base metal. For the use of this thesis
the T8Prime condition is referred to as the T8 condition.

Figure 6 Schematic of precipitates and

Figure 5 Schematic of AA2199 fabrication process
dispersoids that contribute to strength and
map [74]
toughness in Al-2199 [15]

2.3 Friction stir welding

Friction stir welding was invented by The Welding Institute (TWI) of UK in 1991
with the goal of providing a cheap and efficient solid state joining process for Al
alloys [7]. During the past 20 years the development of FSW has remained
mainly in-house with only 38 US licensed companies as GE, United Defence LP,
NASA, Lockheed Martin Corporation, The Boeing Company and Alcoa in the US.
In Canada the NRC and Bombardier utilize FSW. Worldwide knowledge of the
process has remained highly proprietary as it has great potential economic
returns in the aerospace, construction, marine, rail, military, power, and oil and
gas industries as it is effective in joining highly alloyed materials which are

19
difficult to join by conventional methods. The major benefits of FSW are
summarized in Table 1 [8].

Table 1 Key benefits of friction stir welding [8]

Metallurgical Benefits Environmental Benefits Energy benefits

• Solid phase process
• No loss of alloying
elements
•Excellent metallurgical
properties in the joint
area
• Fine microstructure
• Absence of cracking
• Low distortion of work
piece
• Replace overlap of
parts joined by fasteners
• No shielding gas • Improved materials use
required (e.g. joining different
• No surface cleaning thickness) allows
required reduction in weight
• Eliminate grinding
wastes
• Eliminate solvents • Only 2.5% of the
required for degreasing energy needed for a
laser weld
• Consumable materials • Decreased fuel
saving, such as rugs, consumptions in light
wire, or any other weight aircraft,
gases automotive and ship
applications

2.3.1 The friction stir welding process

Generating a FSW consists of two surfaces brought and fastened together to be

joined by the propagation of a non consumable rotating tool (Figure 7). The
rotating tool is inserted between the surfaces and the rotation speed is increased.
Many tools have a threaded design in order to promote stirring of the material.
Material brought out by the tool pin is pushed back into the weld region by a
shoulder and the downward force. Contact between the shoulder and the weld
results in considerable frictional heat necessary to plasticise the material. Hence
pin and shoulder designs are crucial factors in the temperature evolution. While
the tool pin rotates material is moved from the advancing side to the retreating

20
side along the tool rotation direction. When the material is sufficiently plasticised
and mixing of the two weld pieces is possible, the tool is moved along the weld
direction. The large degree of plastic deformation and mixing at elevated
temperature results in a weld with fine and recrystalised grains. [8, 75-78]

Figure 7 Schematic drawing of friction stir welding [8]

The quality of the welds is highly dependent on the tool used and process
parameters. The tool geometry has a crucial part as it is responsible for the
majority of the material flow in the weld region. The friction between the pin and
the material provides some localised heating however it is mainly responsible for
the material flow [79, 80]. The friction between the shoulder and the surface of
the weld, once the pin has been fully plunged, provides the primary component of
heating. The shoulder also confines the volume of heated material to be within
the weld zone. Common tools consist of a threaded cylindrical pin and concave
shoulders, however, variations exist. Tool design also allows for a wider range of
welding configurations and can allow for higher penetration welds. [8]
2.3.2 Macroscopic overview of a typical weld zone

The welds formed by friction stir welding can be divided in sections

corresponding to microstructural changes observed. As the tool rotates and is
pushed along the weld line, two sides exist. The advancing side lies where the
tool rotation direction is parallel to the welding direction and the retreating side is
where the tool rotation is in the opposite direction to the welding direction, Figure
7. On the advancing side material carried by the tool is extruded against the base

21
metal as welding progresses. This results in a thin zone where the microstructure
is highly deformed. On the retreating side material is pulled from the base metal
and brought into the weld region resulting in a broader and more diffused highly
deformed zone.[81]

The stir zone (SZ), also referred to as weld zone (WZ) or nugget zone,
corresponds to the central part of the weld where material has experienced
significant plastic deformation by the tool pin (Figure 8). In this region, the
microstructure is very fine due to dynamic recrystallization. The dislocation
density in this zone has been reported to vary depending on the degree of
recrystallization and high density of subgrains and sub-grain boundaries is
reported. The shape of the stir zone depends on the process parameters, tool
geometry, and the material being welded. The high temperature exposure of this
zone can cause dissolution, growth, and re-precipitation of secondary phases.
Microstructural changes relate to the lower mechanical properties observed when
compared to the base metal. [82-84]

The temperature reached in the SZ is highly dependent on the process employed

however it often lies above 400°C but below the melting point of the alloys being
joined [85-87]. Depending on the time of exposure at this temperature the
majority of precipitates in Al-Cu-Li alloys will be affected by dissolution,
coarsening and/or possibly re-precipitation [88]. Studies for FSW AA2195-T81
have shown some presence of T1, θ’, and TB (Al7Cu4Li) phases in this zone [89].
Full precipitate dissolution has been reported for the as welded AA2199-T8 [84];
however some degree of re-precipitation should naturally occur as a super-
saturated solid solution is thermodynamically unstable.

22
 Advancing

Retreating

Figure 8 Common cross-section overview of friction stir welded thin aluminium sheet [90]

The thermo-mechanically affected zone (TMAZ) lies between the base material
and the stir zone as shown in Figure 8. As the name suggests, this zone is
subjected to elevated temperature and plastic deformation. The microstructure
resembles that of extrusions with high degree of deformation, as plasticised
material is forged against the parent material. Grains in this zone are larger than
in the SZ, with high density of sub-grain boundaries; only a limited degree of
recrystallization occurs. The temperature exposure can bring about dissolution of
precipitates with low temperature stability and promote the coarsening of other
phase such as the θ’ and T-type phases in Al-Cu-Li alloys. [83, 84, 88, 89]

Further away from the weld centre is the heat affected zone (HAZ) where
material has experienced elevated temperature exposure but no plastic
deformation (Figure 8). The grain structure in this zone remains similar to that of
the base metal but the temperature exposure can change the precipitates
present in age hardenable alloys. Precipitates with low solvus temperature,
below 250°C, as for δ’ and GP zones may dissolve. If grain boundary precipitates
are present they may coarsen and create/widen PFZs. [85, 88, 91]

23
2.3.3 Parameters for friction stir welding

The most important parameter of FSW is the tool rotation speed in revolutions
per minute (rpm). A high rotation speed will always result in more frictional heat
generated and hence lead to a hotter weld. This relationship is not linear as the
coefficient of friction is bound to change as the temperature of the material
changes and the interaction between the shoulder and the material is altered.
The travel speed (mm/min) will determine the dwell time of the tool and therefore
the amount of material available to dissipate heat. The travel speed is also
important as it determines the productivity of a given FSW set up and hence its
cost effectiveness. The downward table force provided on the tool will also play
an important part as it affects the frictional heat generated between the shoulder
and the material. The higher the downward table force the higher the heat
generated; however a limit exists where the tool will effectively thin the weld
region as material is forced out of it and hence result in a warped weld. The tilt
angle of the tool is also important as it helps stirred material be guided effectively
around the tool by the shoulder. The interactions between these parameters are
complex and span beyond the scope of this project. The primary effect of welding
parameters is on the temperature of the weld, as summarised below:

 Higher tool rotation speed results in hotter weld – provided all other
welding parameters are constant
 Lower travel speed results in hotter weld – provided all other welding
parameters are constant
 Higher table force results in hotter weld – provided all other welding
parameters are constant
 Higher revolutions per mm results in a hotter weld

The parameters further influence the size of the zones of a created joint, the
residual stresses and the overall quality of the weld created. The focus of this
project is on the microstructure and age hardening potential of welds considered
to have good quality and therefore the tool rotation speed, travel speed and table
force are considered.
24
The final goal of optimizing the FSW tool design and parameters is to achieve a
suitable temperature, such that the material softens sufficiently to be plastically
deformed. Limitations arise when there is possibility of precipitation of detrimental
phases or the dissolution of strengthening phases. This has promoted some
researchers to study and model the heat evolution during friction stir welding and
to conclude that the temperature varies between 0.6Tm and 0.9Tm. These
temperatures are often in the range for solution heat treatment for precipitation
strengthened aluminium alloys. [8, 85, 87, 88, 92]

2.3.4 Properties of friction stir welded aluminium

The temperature exposure and plastic deformation of the weld zones during
friction stir welding brings about changes to the microstructure of the material
and hence affects its mechanical properties. It is common to observe a hardness
drop of ~60-80 HV in the TMAZ and SZ of welds [82, 89, 93-96]. In 2xxx and
7xxx series the grain size reduction due to FSW results in minimal hardness
increase as these series are predominantly precipitation hardened. The change
in precipitate density and morphology observed in the TMAZ and SZ causes a
drastic drop in hardness. Growth of PFZ has also been reported [97]. The overall
changes in hardness have been associated with the dissolution of precipitates
present in the base metal before welding [84, 98] and the coarsening of other
phases. The TB phase in AA2195 has been observed in the SZ and has been
linked to lower hardness values [89].

Limited studies on the application of post weld heat treatment (PWHT) to recover
hardness have been performed. Some recovery of the hardness of a FSW
AA2050-T81 alloy was reported as shown in Figure 9 [96]. The hardness minima
correspond to the HAZ where coarsening has occurred. The minima are in the
TMAZ regions surrounding the SZ where the grains have been plastically
deformed and remain with high dislocation density, yielding good precipitation
during PWHT.

25
Figure 9 The effect of PWHT on a FSW AA2050-T81 [96]

26
3.0 Objectives
A large section of the literature, focused on FSW of Al-Cu-Li alloys as AA2199,
describes welds performed in the T8 condition. Changes to the microstructure,
precipitates, residual stress and mechanical properties are reported. Limited
literature is available on the application of PWHT to welds performed in the T3
condition. The limited literature available motivates this thesis to focus on the
effect of FSW on AA2199-T3 and the potential for hardening of welds through the
application of PWHT to the T8 condition. It should be noted that the T8 temper
designation is utilized despite the lack of specific stretch being applied to the
welded assemblies prior to heat treatment.

The objectives of this study are as follows:

 Record the microstructural change arising from FSW of AA2199 in the T3

condition
 Record the mechanical properties of welds in the T3 condition
 Analyse the precipitates and precipitation sequence observed in welds are
the base metal
 Apply a heat treatment, as would be common for the base metal, to
increase mechanical properties
 Record changes in mechanical properties up PWHT
 Record the microstructural changes arising from PWHT
 Relate the ability of welds to react positively and negatively to PWHT with
the respective microstructure, precipitation and FSW process parameters

These objectives are met via optical microscopy (OM), field emission scanning
electron microscopy (FE-SEM) with electron channelling contrast imaging
(ECCI), tensile measurements, micro-hardness, differential scanning calorimetry
(DSC), and transmission electron microscopy (TEM).

27
4.0 Instrumentation and experimental procedures

Within this chapter the methodology, experimental procedures and

instrumentation used to obtain the results presented in chapter 5.0 are described.
The sub-sections appear in an order which is consistent with the Results and
Discussions chapter.

4.1 The welding of the material AA2199

4.1.1 Composition, aging condition and mechanical properties

The Aluminium Association registered composition of the aluminium alloy

AA2199 is presented in Table 2 as reported by Alcoa [15]. The material was
received in thin gauge, 1.6mm (0.065”), sheet samples that were joined via
friction stir welding. All joining was performed in the T3 naturally aged conditions.
A subsequent post weld heat treatment to the T8Prime, an artificially aged
condition, was performed to the entire assemblies in an attempt to achieve the
mechanical properties known for the base metal.

Table 2 AA2199-T3 elemental composition [15]

Alloying
Cu Li Zn Mg Mn Zr Fe Si Al
Element
Min wt% 2.30 1.40 0.20 0.050 0.10 0.05
- - Rem.
(at%) (0.95 (5.30) (0.08) (0.05) (0.05) (0.01)
Max wt% 2.90 1.80 0.90 0.40 0.50 0.12 0.07 0.05
Rem.
(at%) (1.20) (6.81) (0.36) (0.43) (0.24) (0.03) (0.03) (0.04)

The samples tested in this study followed a proprietary aging sequence to a

T8Prime condition which is sub-peak hardening. The artificial aging performed on
the welded samples did not involve post welding solution heat treatment or any
stretch but only artificial aging. For the remainder of this document the T8
condition will be used to designate the artificially aged samples.

The reported mechanical properties for AA2199 in the T8Prime condition are
compared to common aerospace aluminium alloys in Table 3.

28
Table 3 Typical mechanical properties of AA2199, 2024 and 7075 [15]

Ultimate Tensile
Young's
tensile yield Elongation Density
Properties modulus
strength strength (%) (g/cm3)
(GPa)
(MPa) (MPa)
AA2199
420 343 9 78 2.64
T8Prime
2024-T81
427-448 372-386 5 72 2.78
Sheet
7075-T651 434-455 352-372 8 72 2.80

4.1.2 Welding of the plates

All samples were joined at Alcoa Technical Centre in Pittsburgh, PA. All welding
was performed along the rolling direction of the starting material in the T3
condition as shown in Figure 11. The initial and final 2” of the welds were not
used for analysis to remove any artefact from the initiation and ending of the
weld. The welds were examined for large scale imperfections and sections were
tested via face and root bending tests as shown in Figure 10.

Figure 10 Face and root bending tests for good friction stir weld samples [99]

29
Figure 11 AA2199 plates welded along rolling direction [99]

The FSW parameters used and recorded during welding are presented in Table
4. The readings were taken in imperial units but are converted to metric for the
purpose of this thesis. The clamping and backing plate used for welding are

30
shown in Figure 12. Note that the sample presented is of the smallest plates
joined for this study.

Table 4 Welding parameters used to join AA2199 plates

Figure 12 Clamping and backing plate set up details[99]

31
A truncated cone pin with a convex shoulder tool made of high strength steel was

used to make these welds and is schematically shown in Figure 13. Details

regarding the threading of the tool pin and shoulder were not provided.

Figure 13 Welding tool used

4.2 Mechanical testing

4.2.1 Tensile tests

Tensile samples were prepared using conventional machining in accordance with

ASTM E04-08 standard for flat samples. The origin of samples was
perpendicular to the welding direction/rolling direction such as to ensure that the
weld zones remained in the centre of the tensile dog-bone sample (Figure 14).

The tensile testing presented in the following sections was performed on an

APEX T20000 machine at Laval University. The elongation was recorded using a
2” gauge digital extensometer fixed around the centre of the weld sample being
tested. All tests were performed under the ASTM E08-08 standard for flat
samples in tension. The measurements for yield strength were taken at 0. 2 %
offset yield and tensile ultimate strength were taken as the maximum value.

32
 Rolling Direction

Figure 14 Origin of tensile samples

4.2.2 Hardness tests

A centre line hardness profiles were taken for each sample using a Clark CM-
100AT manual micro-hardness tester equipped with a Vicker’s indenter (Figure
15). Clemex digital camera and software were used to take the hardness
readings at x500 magnification. The readings were taken from a clear focused
optical image. All indents were performed at 300gf loading and at least 250μm
apart as to ensure x3 diagonal spacing between indents as per ASTM E384
standard.

33
Figure 15 Clark CM-100AT micro-hardness tester equipped with Clemex digital image acquisition
system

Hardness maps were generated for full cross-sections of welds using a Struers
DuraScan fully automated micro-hardness tester located at AMTC Montreal.
Readings were collected using the available ecos Workflow software from clear
focused optical images. All images were double checked manually for edge miss-
identification by the software. The maps were set up using a grid of 200μm
horizontal spacing and 250μm vertical spacing between indents allowing the
coverage of as much of the cross-sectional area. Maps were plotted in excel
using contour step range of 5HV.

34
4.3 Differential scanning calorimetry

Differential scanning calorimetry experiments were carried out at CANMET

Ottawa using a heat flow calorimeter Netzsch 449C tool. The experiments were
conducted at least 12 months post welding by which time all natural aging effects
would be stabilized. Standard closed alumina crucibles were used to prevent
possible reaction of the samples with the crucible. All tests were run from room
temperature to 600°C at a heating rate of 10°K/min, followed by a hold at 600°C
and an air quench (Figure 16). Argon was used as a protective and a purge
(50ml/min) gas for all stages of the experiment. All data collected to generate
specific heat vs. temperature curves were taken from the continuous heating
ramp in the range of 75°C to 550°C which corresponds to a range where all solid
state precipitation and dissolution reactions occur[25].

Figure 16 Differential Scanning Calorimetry temperature program

The DSC samples were obtained from the welds using a slow speed diamond
saw from roughly the centre of the stir zone as highlighted in Figure 17. The
mass of the samples was recorded and used to normalize the heat signals during
the analysis. The obtained data was baseline corrected to remove any effect of
the experimental set up and variation between sample/reference holders on the
heats measured. A linear baseline was further subtracted from the data to correct
for displacement of samples from the Tzero thermocouple as described elsewhere
[100].

Figure 17 Differential Scanning Calorimetry sample source (highlight grey)

35
4.4 Microscopy

The images presented in this report were obtained using optical, scanning
electron microscopy (SEM) and transmission electron microscopy (TEM). Optical
microscopy was used to provide low magnification images capturing the entire
weld, SEM helped obtain grain size analysis in the weld regions together with
imaging of the majority of precipitates in the welded and heat treated samples,
while TEM was used to confirm the very fine, nanometre scale precipitates
present in the samples.

4.4.1 Optical microscopy

Bulk sample for optical microscopy were hand ground using increasing grit silicon
carbide paper to a maximum of 1200 followed by a final polish of 9, 3, and 1μm
diamond suspension. The samples were then etched using Keller’s etchant for 3-
5s until the grain structure was revealed. Samples observed all contained the
entire weld zone in the T3 condition and two base metal samples for the T3 and
T8 condition respectively.

Optical microscopy was carried out using an inverted automatic stage Nikon
Epiphot 200 equipped with a Clemex Image acquisition and analysis system.
Image series were obtained at low magnification, x50 or x100, in order to capture
the entire weld cross section. The series were then stitched together using
Microsoft Image Composite Editor to obtain entire weld cross-sections [101].

4.4.2 Scanning Electron Microscopy

Bulk samples for SEM observation were prepared using the same grinding and
polishing steps as described above; however an extra final polishing step was
employed using a Buehler VibroMet 2 vibratory polisher and colloidal silica to
achieve a mirror finish surface. Bulk samples were farther argon ion beam
polished using a Hitachi IM-3200 Flat Ion Milling system with an ion incidence at
85°, accelerating voltage of 3kV, beam current at 100μA and milling time ranging
between 10 and 45 minutes. The bulk samples used to generate images
contained the entire weld zone and the spot focus during ion beam milling was
36
such as to allow polishing of the base metal, the heat affected zone, the thermo-
mechanically affected zone and stir zone. Ion beam polishing was used to help
minimize surface topography and remove contamination and oxidation layers. No
etching procedure was employed for bulk samples.

Thin foils analysed using the scanning transmission electron microscopy (STEM)
mode were prepared by mechanical thinning to a sub 100μm range via grinding
and polishing of bulk specimens on 320, 600, and 1200 grit silicon carbide paper.
Sample discs of 3mm diameter were punched using a manual horizontal tool for
ductile materials. The discs were then twin-jet electro-polished using Struers
TenuPol 2 twin jet polisher. Electro-polishing was performed using a 20 vol.%
nital solution -20°C with a current of 0.15A and a voltage of 15V. The samples
were cleaned using DI-water and place in acetone until observations which was
performed no later than 48 hour post final electro-polishing step.

A Hitachi Cold Field Emission Scanning Electron Microscope SU-8000 (Figure

18) was employed for the SEM images and micro-analysis presented. The FE-
SEM possesses the ability of providing accelerating voltages from 0.1 to 30.0kV
with a maximum current in the range of 20nA. The snorkel lens allows for the
efficient electron collection by the top and upper detectors within the column. The
four quadrant photo-diode backscattered electron detector (PD-BSE) was used
to generate compositional and crystallographic contrast images. Transmitted
electrons were detected using a YAG type (TE) detector placed below the
sample. Bulk imaging was performed at accelerating voltage between 3kV and
5kV and STEM mode imaging was achieved at 30kV. Energy dispersive
spectroscopy with a silicon drift detector by Oxford, was performed at
accelerating voltage of 10kV to allow for qualitative chemical composition
analysis of the precipitates observed. A homemade graphite STEM sample
holder was used to minimize chemical spectrum overlap which would be
expected when using a conventional Al-Cu-Si-Sn STEM holders.

Grain size observations were performed using the PD-BSE detector via electron
channelling contrast imaging. The images were obtained using BSE detectors at

37
low accelerating voltage of 5kV to allow for Bloch wave interactions with the
sample and yield a larger difference in BSE; thereby better contrast. The signal
to noise ratio was kept high by analysing very clean and flat surfaces and using a
high probe current and long scanning times. This experimental set up comes at a
cost of loss of resolution and hence very fine scale, sub 100nm, precipitates are
not easily imaged. Furthermore, the contrast arising from such fine scale
precipitates can be lost in the contrast of the surrounding Al matrix. To achieve
high resolution imaging of fine scale precipitates in AA2199 the STEM mode was
employed at 30kV as this minimizes the interaction volume for thin samples and
yields better resolution.

Image analysis was carried out to characterise the observed precipitate surface
area fraction, size and shape and the grain size of select zones of the welds.
RML-Image software was used to processes and analyse images [102]. The
image background was extracted by a threshold resulting in holes for
precipitates. These were filled and the overall image followed a smoothing before
being subtracted from the original image. Precipitates were then selected by a
series of thresholds and cleaning steps. The final precipitate map was overlaid
on the original image for quality check purposes. The surface area fraction of
precipitates calculated by this procedure is representative of the volume fraction
of precipitates observed; however it is limited to large scale precipitate close to
the sample surface.

38
Figure 18 Hitachi Cold Field Emission Scanning Electron Microscope SU-8000 (FE-SEM)

4.4.3 Transmission electron microscopy

Thin foils for TEM observations were prepared in parallel with the procedure for
STEM samples. The same samples were used in both microscopes to provide
higher certainty. It should be noted that due to the higher accelerating voltage
used in TEM compared to STEM the sections in the samples which are electron
transparent are different.

TEM analyses were carried out using a Philips CM200 at an accelerating voltage
of 200kV. Both bright field (BF) and dark field (DF) imaging were used. Phase
selection and imaging in DF mode was carried out by selecting the specific spots

39
in diffraction patterns. The selected area electron diffraction (SAED) patterns
were obtained using an aperture of 100nm diameter and therefore patterns may
contain base metal and precipitate diffraction spots. SAED phase identification
was carried out following the Weiss zone law as described elsewhere [103].

40
5.0 Results and Discussion

5.1 Sample description

Seven 1.6mm thick sheets of AA2199 alloy were friction stir welded at the Alcoa
Technical Centre (ATC), Pittsburgh, and provided for the purpose of this study as
shown in Table 5. The designated sample names e.g. B1 or G1 have been given
to facilitate the representation of welds that react in a negative (B#) or positive
(G#) manner to post weld heat treatment respectively. All of the welds were
performed in the T3 temper; however sample B5 was artificially age hardened to
T8 post welding. Figure 19 demonstrates the as welded sheet product and
highlights the areas analysed.

The results further described in the following sections were obtained between
September 2010 and December 2011; hence allowing at least 24 months for the
samples to stabilize any degree of naturally aging. The samples were all
prepared on the same welding machine using the same welding tool and the
staring materials were of the same batch therefore any variation between
samples should be attributed to welding parameters. The starting plates were of
comparable dimensions and same gauge, to eliminate variation in cooling rates
which could arise due to sample size [104].

Table 5 - Sample name designation

Sample
Alcoa Name Temper welded Temper received
Name
2008-06-02-FSW3B T3 T3 B2
2008-06-03-FSW1 T3 T3 B3
2008-06-05-FSW1 T3 T3 B1
2008-06-18-FSW2 T3 T3 B4
2008-06-19-FSW2 T3 T8 B5
2008-06-23-FSW1 T3 T3 G1
2008-06-23-FSW2 T3 T3 G2

41
 a) b)

40cm

Figure 19 - As welded AA2199 sheet product. a) Full length weld, b) weld width and c) plate
thickness.

5.1.1 FSW Parameters studied

The weld parameters used for the fabrication of each weld were provided and are
shown in Table 6. The tool used to perform each of the welds was made of high
strength steel. The tool geometry has been described as a threaded tapered-
cone with a convex shoulder similar to reported by [105]. The same tool was
used for all welds described in this thesis.

42
Table 6 - Friction stir welding parameters

All welding parameters described above play a role during the processing and
towards the quality of the final joints. The temperature during welding, the
cooling, the amount of deformation, the residual stress, and the behaviour during
post weld heat treatment (PWHT) are influenced by these parameters.
Furthermore the interactions between these parameters are of importance for
understanding the final weld results. In this thesis, the behaviour during PWHT is
of primary focus.

The tool rotation speed (RPM) shows high variation between samples. The
higher tool rotation speed used for samples G1 and G2 promotes a hotter weld
with more deformation of the welded zone. This higher tool rotation speed allows
for a shorter ramp to temperatures suitable for plastic flow of the material being
welded and in turn allows for faster travel speeds with comparable measured
travel force in the x-axis. This interaction can be demonstrated by sample B1
having a travel speed of 235.97 mm/min at a force of 732N and sample G2 with a
travel speed of 1015.85 mm/min with a force of 731 N.

The tool travel speed (mm/min) is representative of the time spent at elevated
temperature and the rate at which material is joined. Faster tool travel speeds
allow for shorter durations at an elevated temperature. The tool travel speed
prevents the tool from remaining in place for too long and hence helps avoid
temperatures that could lead to partial melting in the weld zone [106, 107].

The table force is the necessary vertical force applied to the tool such that the pin
can penetrate the material and the shoulder can come into contact. Once contact
43
has been established a threshold is reached. This force is involved through the
coefficient of friction, to the amount of energy released at the interface between
the tool shoulder and the material below it. The importance of this parameter
decreases at values above this threshold as at very high values, the friction force
will increase and hence more heat will be generated. Such effect is likely to
cause thinning of the welded region as plasticised material can be pushed out of
the weld region and resulting welds will have material ejected around the
shoulder as a flash [105].

It has been shown [108] that the ratio of (Tool rotation speed * table
force)/(Travel speed) is indicative of the energy input to the material during
welding. As described above the table force is maintained between-10343 and -
16539N throughout the seven welds studied here and hence the ratio of (tool
rotation speed / travel speed) is used as a variable proportional to the energy
input during welding and is shown in Table 6. The ratios vary widely for all
samples. The value for sample G1 defines a lower limit and the value for G2
defines a higher limit. All other welds, with the exception of sample B2, are within
this range. This ratio is hence inconclusive and does not allow one to differentiate
between samples.

The welding parameters are of great importance to industrial application of

friction stir welding as they dictate the production of good quality welds and
furthermore the speed and competitiveness of the welding process used. The
above-described welding parameters should only be used as a guide and not as
absolute values as their influence on weld quality was not the central focus of this
study. Furthermore, the effect of welding parameters varies greatly between
welds performed using different welding machines, different welding tools and
joint geometries as described in Friction stir welding: from basics to applications
[104].

44
5.2 Optical characterization

The cross-sections of all welds analysed are presented in the as received state in
Figure 20. The advancing side of the weld lies on the left hand side for all images
with the exception of Figure 20b where it is inverted. The zones of the welds
correspond directly to Figure 7. The thick TMAZ is consistently on the advancing
side of all the welds observed whereas wider TMAZ corresponds to the retreating
side. Bulk sample handling and preparation have resulted in surface scratches
which are seen in Figure 20a and f.

a)

b)

c)

d)

e)

f)

g)
Figure 20 Optical mosaic overview of welds a) B1; b) B2; c) B3; d) B4; e) B5; f) G1; g) G2; dashed line
indicates the TMAZ, micron bar indicates 2mm

The stir zone of welds B1, B3, B4 and B5 appear larger than those of welds B2,
G1 and G2. This effect can be related to the combination higher tool rotation
speed and travel speed of the latter welds which results in a smaller overall weld
zone. The HAZ of all welds corresponds to the regions spanning away from the
centre and within the 2mm adjacent to the TMAZ. The grains in the heat affected
zone show little size variation compared to the base metal. The grains of the
TMAZ have clearly experienced plastic deformation and elongated between the
HAZ and SZ. Finally the grains within the SZ have experienced sever plastic
deformation. These grains are very fine and cannot be resolved at this
magnification.

45
5.3 Differential scanning calorimetry

Differential scanning calorimetry (DSC) was employed to reveal the precipitation

and dissolution of secondary phases in the base metal and welded samples.
DSC results are coupled with extensive literature data, involving reactions and
microstructural observation, in order to identify the reactions occurring in the
tests performed. Similar techniques have previously been used to study such
microstructural features and their evolution during aging and heat treatment of Al
friction stir welds [25, 27, 51, 62, 100, 109-111]. In particular, A. Steuwer et al.
have shown the thermal traces for AA2199 FSW in the T8 condition and variation
due to welding [84]. In situ TEM and SAXS have also been used to help identify
the reaction observed in DSC [49, 112]. In this section, all the DSC samples are
from near the centre of the stir zone.

The results presented in this section are organized such that endothermic
reaction show positive peaks and are representative of dissolution and other heat
consuming reactions. The exothermic reactions are shown as negative peaks
indicating solid-state precipitation reactions and the formation of ordered
structures that result in the release heat. The reader is guided through the trace
changes observed between the T3 and T8 condition for the base metal followed
by the observations made for welded samples.

Figure 21 shows the characteristic trace of the AA2199 base metal in the T3 and
T8 condition. All the peaks have been numbered and their corresponding location
and a description have been shown in Table 7. Peak 1 is the dissolution of fine
scale, naturally aged G.P. zones that have formed during cooling form elevated
temperature processing of the alloy and during the course of natural aging [25].
Peak 2 is characteristic of the dissolution of ’ precipitates that have formed via a
natural aging process. Variation of the size and the location of the naturally
formed δ’ phase may lead to the observed overlap between peak 1 and peak 2 in
Figure 21 as reported by Cassada et al. and Yoshimura et al. [21, 24].
Heterogeneous Al-Li precipitates form by a minimization of strain energy
between already present Al-Cu/other precipitates or dislocations and the α-Al

46
solid solution [21, 24, 64, 69]. These coupled precipitates are more stable and
hence require a higher temperature to dissolve. Peak 3 is in agreement with
artificially aged δ’ dissolution peaks reported by Nozato et al. and Steuwer et al.
in their studies of Al-Li alloys and AA2199 friction stir welds, respectively [25, 84].
Peak 4 is the large exothermic peak representing the precipitation of the Al-Cu-Li
phases T type phases as the metastable T1 (Al2CuLi). Formation of these
phases is limited by diffusion of Cu and Li within the matrix. The metastable T1
phase is therefore often seen to heterogeneously precipitate on dislocation within
the grains – only 1 Cu and 1 Li atom required [43, 45, 49]. The T2 stable phase is
observed to form on grain boundaries where the supply of atoms is facilitated
and forms in the 250-305°C range [113]. The endothermic peak 5 demonstrates
the dissolution of already present precipitate phases to provide alloying elements
for an Al-Cu-Mn/Mg phase observed. Precipitation of high temperature ’ (Al3Zr)
dispersoid phase occurs in the 350-375°C range [36]. At temperature above
375°C the dissolution of all precipitate phases is recorded in peak 5. In particular
the large and non-coherent phase with high fractions of Cu and Mn dissolves
above the 425°C range [114].

47
Table 7 Differential scanning calorimetry peak numbering sequence

Peak Temperature Found in

Description
ID # Range (C) samples:
Dissolution of Al-Cu G.P. zones formed
T3 BM, T8
due to natural aging. This peak over laps
BM, B1-
1 80-120 with dissolution of Li compositional
B5, G1
variance formed during cooling via spinodal
and G2
decomposition. [25-27, 29, 30, 62, 115]
Dissolution of δ’(Al3Li) phase formed due to
T3 BM,
natural aging. Broadness of this peak is
2 140-165 B1, B2, G1
dependent on the size and location of the
and G2
precipitate. [24, 51, 62, 109, 115]
T8 BM and Dissolution of artificially aged δ’ (Al3Li) and
3 185-210
B5 θ’ (Al2Cu) phases. [19, 25, 115]
Overlapping precipitation and growth of the
T1 (Al2CuLi) and other AlxCu(Li,Mg)
4 250-305 All
phases. Variation indicates a kinetics
driven process. [25, 43, 51]
5 325-500 All A large cumulatively endothermic peak
showing the overlapping dissolution of T1,
dissolution of stable grain boundary
phases, and the precipitation of Al20Cu2Mn3
and Al3Zr phases.[36, 114, 116]

Figure 21 Differential scanning calorimetry traces for base metal T3 (red) and base metal T8 (blue)

48
In the T8, artificially aged condition, for the base metal, there are four distinct
peaks. Peak 1 closely corresponds to the shoulder observed in the T3 condition
of the alloy. It should be noted that this dissolution reaction appears at a
temperature below the aging temperature employed for the T8 condition and is
therefore indicative of a structure formed during natural aging which dissolves or
re-enters solid solution upon the DSC run. It is suspected that during aging for
the T8 condition, the solubility of Li and Cu in Al is larger than that at room
temperature and therefore a fraction of the Li and Cu remain in solid solution.
Furthermore, this solid solution is encouraged in areas of the material where
grain size is large and there are no large scale precipitates to act as sinks.
During the course of natural aging, this solid solution may re-precipitate into the
’ (Al3Li) phase or form wavelike compositional variation via a spinodal
decomposition mechanism, depending on the local concentration of Li in solution
[26, 30]. The Cu is likely to form GP zones within the matrix. Peak 3, at 200C,
demonstrates the strong endothermic dissolution of ’ (Al3Li) precipitates that
have been aged, where some may be found flanking the T1 (Al2CuLi) [64] and
the θ’ (Al2Cu) [21] precipitates. The presence of Al-Cu dissolving precipitates
surrounded by an Al-Li solid solution allows for further precipitation of the T1
(Al2CuLi) and hence generates the strong exothermic peak 4. This peak is
followed by the previously described endothermic peak 5 which consists of
several overlapping reactions involving the T1, T2, Al-Cu-Mn and Al3Zr phases.

In Figure 22 the DSC curves for samples B1-B4 are shown. All samples are
tested in the T3 condition. Samples B1 and B2 show very close results and will
be described together. Peak 1 is consistent with that previously observed in the
T3 base metal, where fine scale naturally aged precipitates are dissolving. Peak
2 is indicative of the dissolution of ’ precipitates around dislocations and Al-Cu
complexes. The magnitude of this peak is smaller than the one observed in the
base plate material hence indicating fewer of these small scale heterogeneities.
The close link and overlap between peak 1 and peak 2 is indicative of a variation
of the ’ and θ’ precipitate type and size. Peak 4, at 275°C, corresponds to the

49
precipitation of T1 (Al2CuLi) phase with possible Mg substitution. The peak
appears at a higher temperature and smaller depth when compared to the T3
base metal sample. The higher peak temperature of this peak can be related to
the formation of variations of Al-Cu-Li phase, the T2 (Al6CuLi3) phase [113, 117]
or due to the composition of the alloy [112]. The precipitation reactions of Al-Cu-
Li phase are influenced by the supply of Cu and Li and therefore diffusion. The
final peak 5 confirms the overlapping dissolution and precipitation of high
temperature, above 325°C, phases.

Figure 22 Differential scanning calorimetry traces for samples B1-B4 in the T3 as welded condition

Samples B3 and B4 also demonstrate DSC curves that are very similar. Peak 1
for these samples is very broad further indicating variation of size and location of
the ’ phase and Al-Cu complexes. The shouldering of this peak on the left hand
side could be related to small, local variation of Li concentration. The absence of
a clear peak at 150C demonstrates the lack of ’ precipitates flanking
dislocations and Al-Cu complexes; however a small-scale shoulder to peak 1 is
observed in the 150C range indicating a noticeably smaller volume fraction of
these phases. This variation between samples B1-B2 and B3-B4 may have been
caused due to variation of the location the samples were taken from with respect

50
to the weld zones. Closer to the centre of the weld, the high degree of
deformation and exposure to high temperature may promote recrystalization
which would result in new grains with fewer dislocations hence giving rise to a
smaller peak 2. Exothermic peak 4 and endothermic peak 5 are consistent with
those described for samples B1 and B2. There exists a precipitation reaction in
these samples at 420-430C range for these samples that is in close agreement
with the formation temperature for the Al3Zr phase.

In Figure 23 the DSC traces for two welds performed with comparable welding
parameters, weld B4 and B5, in the two heat treatment conditions are shown.
The greater size and broadness of peak 1 in the T3 sample suggests a larger
volume fraction of naturally aged ’ precipitates when compared to the T8
condition. This observation is supported by the lower Li concentration in the -
aluminium matrix due to Li being locked up in precipitates in the T8 condition.
The small size of peak 2 in the T8 condition and the right hand side shouldering
of peak 1 in the T3 condition are indicative of a much smaller fraction of ’ found
surrounding dislocations and Al-Cu complexes. The latter case can be expected
as such Al-Cu complexes are expected to be less frequent due to Cu being
soaked up by precipitates observed in these samples. The appearance of peak 3
in the T8 condition demonstrates the dissolution of aged ’ precipitates and some
which are found flanking the T1 phase. This peak is consistent with the one
observed in the T8 condition for the base metal. The exothermic peak 4 appears
earlier in the T8 condition then in the T3 condition and this can be related to the
easier growth of already present T1 precipitates due to the localised presence of
Li in their surroundings. Variability in peak 5 is predominantly due to the overlap
between dissolution of T1 (Al2CuLi) phase, growth of Al20Cu2Mn3 phase and
precipitation of the Al3Zr phase.

51
Figure 23 Differential scanning calorimetry traces for comparable parameter welds in two heat
treatment conditions (B4-T3 and B5-T8)

In Figure 24, the traces for sample welds G1 and G2 are compared with that for
the base metal in the T3 condition. Peak 1 which is observed in the base metal is
not as pronounced in the welds and hence indicating a lower fraction of naturally
aged δ’ precipitates and possibly less lithium concentration variation. Peak 2 on
the other hand has very close temperature agreement between the 3 samples
and shows that δ’ precipitates formed on dislocations and Al-Cu complex are
present in these samples. Peak 4 shows a significant temperature difference
between the T3 condition for the base metal and the two welded samples. As
previously explained this is the precipitation and growth of the T1 phase which is
dominated by the diffusion of Cu [118]. In the case of the base metal there is an
absence of T1 precipitates prior to the DSC run and hence a large number
precipitate during the scan. In the welded samples the zones studied have been
previously exposed to elevated temperature where T1 could nucleate and hence
the growth of these precipitates is dominant giving a peak at a higher
temperature. Peak 5 appears to also hold some temperature delay however this
is expected due to the complex nature of the overlapping precipitation and
dissolution reactions.

52
Figure 24 Differential scanning calorimetry traces for base metal in T3 and welds G1 and G2

53
5.4 Hardness

The effect of welding and post weld heat treatment was studied via mid-cross
section hardness profiles for all samples in the T3 and T8 condition. The profile
for sample B1 is shown with a corresponding optical mosaic of the weld
examined shown in Figure 25a. The profile for the T3 condition shows some
scattering however the hardness across the weld remains between 80 and 105
HV. In the T8 condition the hardness profile shows significant variation. Values in
the centre of the weld remain close those observed in the T3 condition, hence
indicating a minimal age hardening response. Values beyond ±5.0 mm from the
weld centre show significant hardening to a range of 125-145 HV as observed in
the T8 condition of the base material.

The hardness profiles for samples B2, B3, B4 and B5 are shown in Figure 25b, c,
d, and e respectively. The hardness values in the T3 condition remain
consistently between 75-100HV for the entire welds. The higher end values often
occur in the thermo-mechanically affected zone. In the T8 condition all these
samples have a central zone showing limited hardening upon PWHT. This region
is bounded by material which hardens substantially to values above 130HV with
the exception of sample B5.

The observed changes between harder and softer zones in T8 appear to be

either steady or abrupt. The steady transition corresponds to the retreating side
of the weld where material has been pulled from to create a wider thermo-
mechanically affected zone. The abrupt transition corresponds to the advancing
side of the weld where a thin line of extruded material defines the thermo-
mechanically affected zone. The regions with limited hardening upon PWHT
correspond well with areas of reduced grain size as shown in the supporting
optical micrographs (Figure 25).

Figure 26a demonstrates the positive response to post weld heat treatment
shown by sample G1. The hardness in the T3 condition shows variation with
values peaking in the thermo-mechanically affected zone. The microstructure in

54
these regions has experienced sufficient temperature and exposure to partially
harden. This hardening is farther completed upon post weld heat treatment as is
outlined by the results in Figure 26a.

Figure 26b show the hardness response observed in sample G2. The hardness
profile in the T3 condition shows little variation throughout the weld. The high
hardness point observed at 3.8 is believed to be an error. Significant hardening is
observed throughout the weld upon post weld heat treatment. A plateau region
between -8 and 7 with a hardness range of 115-130 HV indicates that the weld
zone has gained hardness during post weld heat treatment. The higher observed
hardness beyond this region corresponds to the hardness gained in the base
metal.

Overall the poor hardness upon PWHT observed in sample B1- B5 indicates the
loss of hardening potential for these samples. Samples G1 and G2 on the other
hand have demonstrated hardness values within range of those obtained for the
base metal in the T8 condition; hence having good hardening potential. By
comparing the hardening potential of the welds and the DSC traces shown in
Section 5.3, it can be observed that samples with poor PHWT hardness have a
strong exothermic peak in at 105°C, shouldered by a small peak at 150°C.
Samples that exhibit high PWHT hardness have a much smaller exothermic peak
at 105°C and a strong and well defined peak in the 150°C region, making the
overall trace a close replica of the base metal trace. It can therefore be
suggested that the precipitation of secondary phases is responsible for the
observed hardening potential in sample G1 and G2. To further validate this
conclusion, microscopy will be necessary and the results are shown in Section
5.6.

55
a)

b)

c)

d)

56
 e)

Figure 25 Micro-hardness line profiles and macroscopic optical overview for a) sample B1, b) sample
B2, c) sample B3, d) sample B4, and sample B5 in the T3 (cross) and T8 (box) conditions (2mm)

a)

b)

Figure 26 Micro-hardness line profiles and macroscopic optical overview for a) sample G1 and b)
sample G2 in the T3 (cross) and T8 (box) conditions (2mm)

57
5.5 Hardness map of select welds (B1 and G1)

In Figure 27a, a cross-sectional micro-hardness map for sample B1 in the T3

condition is shown. The hardness for the entire sample is consistent in a range of
85-105 HV. There exists a region on the advancing side where the hardness is in
the higher part of this range. This region corresponds to the transition between
thermo-mechanically affected zone and heat affected zone. In this region, it is
suspected that some small volume fraction of hardening phases may have
precipitated during welding.

Figure 27b demonstrates the hardness map observed upon post weld heat
treatment of sample B1. The centre of the weld zone of this sample does not gain
significant hardness and remains in a 90-110HV range, thus limited PWHT
response. Moving away from the centre of the weld zone, the hardness increases
in the thermo-mechanically affected zone, with a larger transition zone on the
retreating side and slightly thinner on the advancing side. The hardness range in
these zones is between 110-125HV. Beyond these zones the material gains
significantly hardness of 130HV and above. There exists a degree of through
thickness hardness variation in this sample that can be related to the nature of
deformation during rolling. The central zone of thin plates receives less
deformation and thereby it forms a smaller fraction of strengthening precipitates.

Figure 27c is the micro-hardness map for sample G1 in the T3 condition. The
hardness of this sample shows very little variation. The region at 18.48mm X-rel
that shows slightly higher hardness value is suspected to be due to proximity to
the sample holder during testing.

In Figure 27d the micro-hardness map of a weld, G1 T8, which shows

outstanding post weld heat treatment hardening, is shown. The weld zone of this
sample gains significant hardness in the T8 condition and is in a range of 125-
135HV. Moving out of the centre of the weld zone the hardness increases slightly
to a range of 125-145HV. Finally in the edges of the sample the hardness is
representative comparative to that of the base metal, 145-155HV. Once again

58
small through-thickness variation in hardness is observed, which is believed to
be due to the rolling of the materially to its thin gauge.

The micro-hardness maps have confirmed the negative and positive age
hardening behaviour of the weld zones. The small scale, 200μm x 250μm, grid
used to create these maps allows for the allocation of hardness to specific
regions in the weld which were later studied by SEM and TEM to report on the
microstructural components present and causing the observed hardness values.
The samples selected for mapping were only B1 and G1 due to the time
consuming nature of the tests performed. These samples are representative of
the samples observed as shown by the hardness line results. In conclusion it is
important to note that sample G1 demonstrates hardness values upon post weld
heat treatment in the range of the base metal and is therefore is indicative of
good and successful welding.

59
 a)

b)

c)

d)

Figure 27 Cross-sectional micro-hardness map for a) B1-T3; b) B1-T8; c) G1-T3; d) G2-T8; Contour plot in 5HV steps

60
5.6 Scanning and transmission electron microscopy characterization

5.6.1 Microstructure via SEM

Using the Hitachi SU-8000 FE-SEM at McGill University has enabled

observations of the macro and microstructure of welded samples with
great ease and in a significantly faster manner compared to other
techniques. The ability to observe the entire weld at a macroscopic level
and focus to the nm range in a desired zone allows for greater precision
and knowledge of the weld zone being studied. The images presented in
this section are obtained with the SU-8000 from bulk samples and from
thin foils that have been prepared as described in section 2. The ability to
achieve grain contrast with the help of electron channelling contrast
imaging (ECCI) has allowed sample surfaces to be analysed without
etching, which could lead to changes of the chemistry of surface
precipitates [119]. Finally the in-house designed graphite STEM sample
holder has enabled chemical analysis via energy dispersive spectroscopy
(EDS) at high magnification with minimal signal contamination from
sample holders, which are usually made from Al-Cu alloys. Figure 28
highlights the possible imaging modes and magnifications achieved with
the SU-8000 on welded samples.

a) HAZ b)

TMAZ

SZ

61
 c) d)

e) f)

Figure 28 Images taken from welded samples and base metal. Boxing indicate scale
propagation. a) Macroscopic overview of HAZ, TMAZ and part of SZ; b) Low magnification of
large grains and precipitates; c) Intermediate magnification for base metal with fine
precipitates; d) High resolution bulk imaging of grain boundary precipitates, and
intergranular spherical and ultrafine plate precipitates; e) STEM mode back-scattered image
on thin film with fine scale spherical precipitates; f) STEM mode transmitted electron image
of same zone as in e) but revealing ultrafine scale plate precipitates.

A typical cross-section of a frictions stir weld, as observed in the SU-8000,

is shown in Figure 29. The heat affected zone (HAZ) covers the left hand
side. The boundary dividing the large grains on the left and fine grains on
the right is the thermo-mechanically affected zone (TMAZ). This boundary
is thin and well defined as it is on the advancing side. Material here has
undergone a process resembling extrusion of the stirred and plasticized
metal between the hard parent metal and the driving tool. A part of the stir
zone can be seen in the bottom left hand side of the image. The dark
spots observed in this image are due to contamination of the surface that
is charging.

62
 HAZ

TMAZ

SZ

Figure 29 Typical FSW cross-section showing the HAZ, TMAZ on the advancing side and
part of the SZ

63
5.6.2 Grain size measurement

Analysis of the grain size observed in the stir zone of welds were
performed using EBSD and compared to values obtained via image
analysis of micrographs taking using electron channelling contrast. The
analysis performed using EBSD are time consuming and scanning took in
excess of 1h per sample hence obtaining many images to provide
statistical relevance is very time consuming. On the other hand ECCI
performed with the aid of the SU-8000 were easy to obtain and in a
significantly shorter time. The EBSD maps presented in Figure 30 and
Figure 31 are not obtained over the same regions imaged by ECCI in part
b of these figures but in similar location with respect to the whole weld.

The grain size distribution of the stir zone for sample G1 in the as welded
condition is presented in Figure 30. The EBSD image with the
corresponding distribution graph revealed maxima of grains in with
diameters in the range of 2.0-3.0μm. Grain sizes below this range may
correspond to sub-grains resulting in variable Kikuchi patterns and hence
the confidence limits used for the analysis between grains marks them as
new grains. Several grains appear to have aspect ratios deviating from
unity hence indicating that despite the region being affected by dynamic
recrystallization, directionality may be present. Such effects can arise from
un-even distribution of secondary phase particles and formation of
stringers along the deformation direction which in turn affect grain
boundary pinning. The colours of the map represent the deviation from the
(001), (101), and (111) poles of aluminium and hence show the existence
of randomly oriented grains.

In Figure 30b the ECCI reveals sufficient information to analyse the grain
size via image analysis. The average grain size calculated from several
micrographs resulted in a value of 2.85 ±1σ 0.97μm which is in agreement
with the data obtained via EBSD. ECCI is advantageous as it also
incorporates type 1 BSE information dependant on the average z number

64
and hence large scale precipitates which are heavier can also be imaged
and easily differentiated – where as they might be considered as small
grains in EBSD or interpreted as error through the software analysis of the
Kikuchi data.

a) b)

Figure 30 Grain size distribution via a) EBSD and b) ECCI for sample G1-T3 in the SZ

The grain size for the stir zone of sample B1 in the as welded condition
was significantly smaller as shown in Figure 31. The grains observed in
the EBSD analysis revealed maxima in the rage of 550nm. These grains in
this sample have aspect ratios close to unity and there for yield a
smoother distribution curve. The same color index was used to generate
the map shown in Figure 31 a. The indexed orientation of grains is random
and hence it is evident that dynamic recrystallization took place in this
region.

65
 a) b)

Figure 31 Grain size distribution via a) EBSD and b) ECCI for sample B1-T3 in the SZ

In Figure 31b the ECCI reveals that grain structure of the material and the
presence of many secondary phases which are described below. The
average observed grain size from several images in this region is 0.58 ±1σ
0.15μm which is in close agreement with the EBSD data. It should be
noted that due to the z number information present in the BSE image
precipitates of sizes comparable to the grain size in the region are
observed and excluded from the calculation of the grain size via the image
analysis technique.

66
5.6.3 Precipitates in back scattered electron mode

In the following sub-sections the precipitates observable on micrographs

obtained with the Hitachi SU8000 are described. The photo-diode
backscattered electron detector (PDBSE) was used in obtaining the
images. It is important to note that in backscattered imaging the contrast
depends highly on the chemical composition with heavy atoms, e.g. Zr and
Cu, resulting in a high backscattered coefficient and hence appearing
brighter. In Table 8 the precipitates observed in AA2199 are described
with respect to their stoichiometry and their average Z number. The Z
number and its % value with respect to Al is indicative of the contrast
variation caused by such precipitates. Unfortunately these values do not
take into account any dimensional factors, and the depth and location of
the precipitate within the volume of material which generates BSEs.

Table 8 Al-Cu-Li-X alloy precipitates Z number comparison with respect to the Al matrix [10, 15,
31, 114]

Precipitate Average Z Fraction w.r.t Z

Comment
Stoichiometry number Al = 13
δ - AlLi 8 0.62 Large
δ’ - Al3Li 10.5 0.81 Small
θ’/θ - Al2Cu 18.3 1.41
High aspect ratio
T1 - Al2CuLi 14.5 1.12
thin plate
T2 - Al6CuLi3 11.6 0.89 Thick plate
TB - Al7Cu4Li 17.5 1.35 Large
Al6CuMn 15.7 1.21 Orthorhombic
Rectangular
Al20Cu2Mn3 16.5 1.27
dispersoid
S/S’ - Al2CuMg 17 1.31 Thin plate
Spherical
Al3Zr 19.8 1.52
dispersoid

67
5.6.3.1 Base metal in T3

Grain sizes vary depending on the position with respect to through

thickness of the thin rolled base metal. Figure 32a highlights the observed
microstructure for the base metal in the T3 condition towards the centre of
the plate. The grains in this region are large and commonly >75μm;
however they are more equiaxed than the higher aspect ratio grains closer
to the samples surface. The bright spots in the image indicate secondary
phase particles which are of Al-Cu-Mn, Al-Cu-Mg or Al-Zr chemical
makeup, with possible Li presence, which cannot be detected by EDS.
The larger precipitates frequently contain Mn and have previously been
reported to be the Al20Cu2Mn3 phase and will be identified as such here on
[120]. The much smaller, spherical precipitates contain Zr and are
identified as the Al3Zr phase here on. Craters, as observed in Figure 32b,
are artefacts from sample preparation. At this higher magnification, the
fine scale precipitates that populate the grains are also observed more
clearly. It should be noted here that grain contrast is only achieved via
electron channelling and the contrast of precipitates is due to their high
average atomic mass when compared to the aluminium matrix and hence
higher back-scattered electron coefficient. Finally, in Figure 32b the grain
boundary pinning effect of small spherical precipitates, commonly Al3Zr,
on grain boundaries is exemplified and related to their recrystalization
controlling phase in aluminium alloys as reported elsewhere [121-123].
These precipitates are also often observed within the grains. In Figure 32c
a lath-like precipitate on the grain boundary in the top-right hand side
corner can be observed. These precipitates have an Al-Cu make up via
EDS; however they are suspected of being the T 1 type (Al2CuLi) grain
boundary precipitate phase reported for this alloy [15]. Contrast variation
in the grains is common and is due to the presence of sub-surface
precipitates which give rise to a diffuse contrast due to electron interaction
volume effects and hence limit the resolution and imaging of very fine sub

68
100nm thin precipitates in bulk specimens. More powerful techniques as
STEM and TEM will be used to characterise this types of precipitates.

a)

Al20Cu2Mn3

Al3Zr/Al2Cu

b)
Craters

Al3Zr

69
 c)
Grain

boundary T type
Al2Cu(Li/Mg

Al3Zr

Figure 32 Base metal grains structure and precipitate observations in BSE mode; a) low
magnification revealing large grains with large Mn bearing precipitate; b) Zr bearing
precipitates on curved grain boundaries; c) Very small scale spherical (Al3Zr) and grain
boundary plate (Al2CuLi) precipitates observed.

5.6.3.2 Base metal in the T8 condition

The microstructure of the base metal in the T8 condition is comparable to

that in the T3 condition when observed at low magnification as shown in
Figure 33a. Large grains are common and they are frequently populated
by many fine scale secondary phase particles. The low grain contrast in
Figure 33a is due to poor channelling for the grains surrounding the dark
grain in the centre; further loss of contrast is observed in areas where
material with different orientation is overlapped – lower central part of the
image. In Figure 33b, improved grain contrast is achieved and the fine
scale precipitates within grains and at grain boundaries can be seen. The
number of secondary phase particles has increased from 143 in Figure
32b in the T3 condition to 421 in Figure 33b in the T8 condition.

70
 a)

Al20Cu2Mn3

b)
Al3Zr/Al-Cu

Figure 33 a) Base metal in the T8 condition with secondary phases; b) Higher magnification
showing uniform distribution, within grains and on grain boundaries, of the secondary
phase.

71
In Figure 34, a triple point between grains is focused and a wide variety of
precipitates can be observed. The two large rod like precipitates are of the
Al-Cu-Mn type, which are normally observed within these large grains.
These precipitates appear to have a dark halo around them which could
be due to an effect of differential polishing and hence topographic
contrast. Another possibility is the presence of lithium surrounding these
precipitates and hence a lower backscattered coefficient. The wave-like
contrast variation throughout the image is known to be a topographic
effect which originates from the ion beam polishing performed just prior to
observation. One of these waves traverses the rod like precipitate (line
between the arrows in Figure 34a) demonstrating different thickness layer
of matrix above and below the line. As the dark halo observed exists in
both cases, below and above, then the possibility of it being due to
differential polishing in minimized.

A degree of interaction between the grain boundary Al-Cu-Li-Mg phase

and the spherical Al3Zr dispersoid is shown close to the triple point in
Figure 34b. A similar rod shaped phase is observed at the triple point. In
this image the matrix has a large degree of contrast variation that is
suspected of being very fine scale precipitates. This was confirmed as
shown in Figure 34c where a very small scale round precipitate is seen
and many line precipitates are also observed. The small scale <50nm
round precipitates have not been unambiguously identified; however many
of them contain Cu and trace Zn via EDS. The 50nm line precipitates are
suspected to be Al2CuLi, the T1 major strengthening phase in their close
to edge-on position with respect to the incident beam. This phase has not
been previously observed via SEM in bulk samples and was hence
confirmed via TEM and is described in the following section.

72
a)

b)

Al3Zr

AlxCu (Li/Mg)

73
 c)
T1 (Al2CuLi)

Figure 34 Base metal microstructure in the T8 condition at high magnification. a) Large

scale secondary phase particles with dark halo; b) Precipitation of AlxCu(Li/Mg) phase and
Al3Zr at grain boundary, with some interaction; c) Very fine, sub 50nm, line T1 type (Al2CuLi)
precipitates within grains.

In summary, a shift in microstructure is observed between the T3, naturally

aged, and the T8, artificially aged conditions. In both conditions the
presence of round Zr bearing precipitates, usually above 50nm diameter,
are observed. Fewer large (>300nm) irregular shaped precipitates of Al-
Cu-Mn composition were observed in the T3 base metal. The presence of
small precipitates on grain boundaries is only observed in the T8
condition. The grain interior of the T3 sample remains free of very fine,
<50nm, precipitates whereas this scale precipitates are abundant in the T8
condition. These are suspected of being the T1 (Al2CuLi) major
strengthening phase of the AA2199 alloy and can be related to the
increase of mechanical properties observed between the T3 and T8
condition.

74
5.6.3.3 Sample B1 stir zone in T3

The sub micron grain size that was common for the central stir zone of
welded samples, which would not gain hardness during post weld heat
treatment, is shown in Figure 35. Secondary phase particles are very
frequent in this type of welds as shown in Figure 35a and some of the
particles have grown very large and are comparable in size to the actual
aluminium grains. In the centre of the micrographs there are a few dark
spots which resemble debris; however they are not appear charging and
lack topographic emphasis. These are voids within the matrix that
originated from secondary phase particles being pulled out during
polishing and are less likely to have been created during the welding
process.

In Figure 35b, the fine grain size and presence of 10.5% of the surface
area as secondary phase is shown. The secondary phases appear to
consist of several large (>250x200 nm2) particles, often located at grain
boundaries, with many smaller scale particles (<200x200 nm2) that
populate the grains and grain boundaries. At an even higher magnification,
as shown in Figure 35c, a variation in shape and size of precipitates is
observed. Chemical analysis of these precipitates was very difficult due to
their high density in the matrix grains; however EDS analysis of
precipitates on the surface of the samples, as the ones in the top left
corner of Figure 35c, reveal the presence of Cu and Mn. Traces of Mg and
Zn ware also observed in finer particles as indicated. The perfectly circular
and bright precipitates always contained Zr and are of the Al3Zr phase.
The very small and less bright precipitates also registered Zn traces.

75
a)

Void

Large scale
secondary phase

b)

Al-Cu Al20Cu2Mn3

76
 c) Irregular shaped
Al20Cu2Mn3

Zn trace
precipitates

Spherical
Al3Zr
Mg trace
precipitates

Figure 35 The microstructure of the central stir zone for sample B1 in the T3 condition a)
The common very fine grain size; large portion of secondary phase observed along with
some voids; b) Variation of secondary phase sizes and location; c) Secondary phase shape
and size variability

5.6.3.4 Sample B1 stir zone in T8

Post weld heat treatment had little effect on the microstructure of sample
B1 through comparison of Figure 36 and Figure 35. Secondary phase
particles continue to populate the microstructure and are on occasion as
large as the aluminium grains. The sub micron grains observed in the stir
zone for sample B1 allow for large grain boundary area which facilitates
the migration of Cu, Mn, Mg and Zr species. During welding, the exposure
to high temperature has further promoted diffusion of such species and
allowed for the precipitation and growth of the secondary phase particles.
During post weld heat treatment the Li remaining in solid solution has
heterogeneously precipitated in the form of the δ’ (Al3Li) phase around
already present Al-Cu and Al-Cu-Mn phases giving rise to dark halo’s as
shown in Figure 36.

77
At higher magnification, as shown in Figure 36b, the location of these
secondary phase particles is better revealed. The precipitates tend to
preferably be located on grain boundaries where nucleation and growth of
such particles would be more favourable. The particles, which are located
on grains boundaries, have more irregular shapes that are oriented such
that they mimic the grain boundaries. Particles within the grains, shown in
Figure 36c, are less frequent and smaller than in the T3 condition (Figure
35c). Dissolution of such particles can be related to the sub 150°C
dissolution peak from the DSC analysis in Section 3.3 - Figure 23. This
suggests that dissolution of fine precipitates occurs during artificial aging
and alters the local chemistry of the weld zone. These alloying elements
are available for the growth of grain boundary precipitates. This effect is
present only for samples where the grain size in the stir zone is small and
hence migration alloying elements to grain boundaries is facilitated. This
results in no hardness gain in the weld zone during post weld heat
treatment as shown Figure 25, Figure 26a and b.

a)

Large scale Mn
bearing phase

78
 b)
Irregular shaped
Al20Cu2Mn3

Al-Cu-Mg grain
boundary phase

c)

Al-Cu-Mn with
dark halo

Spherical
Al3Zr

Figure 36 Microstructural observation of central stir zone for sample B1 in the T8 condition.
a) Sub micron grain size with a large portion of secondary phase; b) Secondary phase
particles of varying shape and size; c) Secondary phase particles preferentially located on
or close to grain boundaries

79
5.6.3.5 Sample B1 heat affected zone in T3

The heat affected zone has been exposed to elevated temperature during
welding; however it has not experienced any direct mechanical
deformation. The result of the high temperature exposure on the
microstructure is demonstrated in Figure 37a. The large scale particles in
Figure 37b are with comparable chemical composition to those observed
in the base metal (Figure 32b); however their average area has increased
from 0.054μm2 to 0.070μm2. Nucleation of new secondary phase particles
has also occurred in these regions as is evident in the Figure 37b.

In Figure 37c the presence of grain boundary precipitates is confirmed.

The large precipitate visible in the top right corner is of the Al-Cu-(Li)
composition with a trace of Mg and is surrounded by a dark halo indicating
the presence of lithium in its vicinity as explained previously. This phase
resembles the previously reported Tb (Al7.5CuLi) equilibrium grain
boundary phase with possible Mg substitution [113, 124]. The very small
scale (<1μm) precipitates on grain boundaries were commonly observed
as shown in Figure 37c. These precipitates were of Al-Cu-(Li) nature;
however Li presence is suspected and they resemble the T1 (Al2CuLi)
phase on grain boundaries in such alloys [42, 67, 124]. Their orientation
was often seen to mimic the direction of the grain boundary and their
location was at points where the grain boundary exhibits a curvature;
however some were located on flat grain boundaries too. The circular
precipitates in the grains were identified as the Al3Zr phase via EDS.

80
a)

Al20Cu2Mn3

b)

Al3Zr/Al-Cu

Al20Cu2Mn3

81
 c)
T-type
AlxCu(Li/Mg)

T1 (Al2CuLi)

Al3Zr

Figure 37 Heat affected zone microstructure for sample B1 in the T3 condition; a) Presence
of large scale precipitates; b) Growth of Al-Cu-Mn/Mg precipitates; c) Precipitation of the T
type phases with different morphologies at the grain boundary

5.6.3.6 Sample B1 heat affected zone in T8

The microstructural changes to the heat affected zone during post weld
heat treatment for sample B1 is exemplified in Figure 38. The area fraction
of secondary phases has increased from 1.3% in Figure 37b to 1.5% in
Figure 38a. The average number of precipitates with a cross-section
greater than 20000nm2 has also increased from 56 to 79 respectively.
These results suggest a small change to precipitate size in the heat
affected zone during heat treatment for the two images observed. It is
suggested that the presence of such precipitates locks up alloying
elements and offset local stoichiometry hence affecting the formation of
the fine scale T1 strengthening precipitates during aging. Further support
of limited T1 precipitation arises from the previously lower than base metal
T8 microhardness of this zone.

82
The location of secondary phases is farther shown in Figure 38b, where
grain boundary precipitates are shown to co-exist with the fine scale
intergranular precipitates. The grain boundary phases observed in this
sample resemble those in Figure 37c. The large precipitates on the grain
boundary have fine extensions in the direction of the grain boundary and
this is suspected to be an interaction between the growing grain boundary
T type phase and the Al3Zr phases. In some zones, individual very fine T
type plate precipitates on grain boundaries were observed independently
as shown in Figure 38c. In this image some contrast can be observed in
the darker grain which may be due to a small volume fraction of fine T1
(Al2CuLi) strengthening phase.

During welding, the heat affected zone has developed a wide variety of
precipitates within the grains and on grain boundaries due to the high
temperature exposure. The formation of large scale precipitates shown in
Figure 37a and b utilizes a portion of the alloying elements available for
precipitation hardening in AA2199. This has resulted in the partial increase
in hardness of the HAZ. Upon PWHT these precipitates grow as they act
as sinks for alloying elements. Only a limited number of the T1 phase
precipitates and hence lower HAZ hardness upon PWHT.

83
a)

b) Grain boundary
precipitate
interaction

84
 c)

T type grain boundary

AlxCu(Li/Mg)

Suspected T1
(Al2CuLi)

Figure 38 Heat affected zone in the T8 condition for sample B1; a) Limited growth of larger
scale intergranular secondary phases; b) Location of finer precipitates and interactions
between grain boundary phases; c) Individual grain boundary T type phase and matrix
contrast variation indicative of the T1 phase

5.6.3.7 Sample G1 stir zone in T3

The microstructure observed in a sample that reacts positively to post

weld heat treatment, G1, is shown in Figure 39. The observed grain size is
larger than that shown for bad welds in Figure 35b. Grain size of the stir
zone of samples G1 is on the order of 2.85 ±1σ 0.97μm grains as opposed
to 0.58 ±1σ 0.15μm for the same zone in sample B1. The grain contrast
observed in Figure 39a is only due to electron channelling as has
previously been described. There exist circular contrasts variations which
are due to topographic effects caused by the ion beam milling.

The secondary phases observed in Figure 39a tend to be randomly

distributed across the image. The majority of the phases are spherical if
found within the grains and irregular if found on grain boundaries and vary
in size. A line shaped secondary phase on grain boundaries is also

85
observed and has been highlighted in Figure 39b. Farther, in Figure 39b
the presence of irregularly shaped secondary phase at triple points is
highlighted. The large grain boundary precipitate phase is of an Al-Cu-Mn
composition by EDS hence labeled as the Al20Cu2Mn3 . The irregular
shaped precipitates within the grains contain Cu and Mg. The fine
spherical precipitates are predominantly of Al-Zr make up but occasionaly
show traces of Zn instead. The line precipitate observed in Figure 39b was
confirmed to be an Al-Cu precipitate with traces of Mg via EDS and is
hence suspected to be of the AlxCu(Li/Mg) grain boundary phase.

In Figure 39c the fine scale spherical precipitates within grains and on
grain boundaries are clearly shown. Some diffuse bright contrast is seen
on precipitates in the centre of the micrograph and is artefact of polishing.
The absence of thin line precipitates paired with the low hardness value
observed in this region of the weld confirm the lack of the T1 Al2CuLi
phase, however dissolution of all precipitate phases has clearly not been
achieved as opposed to suggestions by A. Steuwer et al [84].

a)

86
 b)

Grain boundary
precipitates Line precipitate
(Al20Cu2Mn3) AlxCu (Li/Mg)

Al3Zr and
Al-Zn

c)

Figure 39 Overview of microstructure in the stir zone for sample G1 in the T3. a) Grain size
distribution and large secondary phases; b) Variability of secondary phases observed, G.B.
Al20Cu2Mn3, thin line AlxCu(Li/Mg), and Al3Zr; c) absence of very fine scale thin plate
precipitates

87
5.6.3.8 Sample G1 stir zone in T8

The effect of artificial aging to T8 condition for sample G1 is shown in

Figure 40. Craters are once again present on the surface of the sample
and give rise to a contrast effect. A large rectangular secondary phase
particle is observed in the centre of the image. The chemical analysis via
EDS revealed the presence of Al-Cu-Mn. This particle is also located close
to a triple point between grains where supply of these alloying elements
would be facilitated [125]. Other smaller phases are also observed with
similar location with respect to the surrounding grains. Spherical
secondary phase particles are also present within the grains and close to
the grain boundaries.

In Figure 40b the presence and location of precipitate phases is shown

more clearly. The large observed particle is again the Al20Cu2Mn3 phase
and is similarly located on the triple point between grain boundaries. The
clear line precipitate close to the centre of the image had an AlxCu(Li)
make up with trace Mg. Similar line precipitates are also visible on the
right of the image; however these appear to be extension from spherical
origins indicating co-precipitation.

Secondary phase particles of both large and small sizes exist in the stir
zone of this sample; however the observed surface fraction is only 2.9%
for Figure 40b including the unusually large precipitate whereas it was
8.4% in Figure 36b for sample B1 in the same temper. The larger grain
size of this sample and hence lower amount of grain boundary area have
reduced the diffusion of alloying elements and restricted the growth of
large precipitates at grain boundaries as shown in Figure 40c. A limited
amount of irregular precipitates is formed during welding (Figure 39)
hence they soak up less alloying elements during post weld heat
treatment. The remaining elements can form the major strengthening
phase T1 (Al2CuLi) during post weld heat treatment. The result is the

88
higher hardness of the stir region when compared to that of sample B1
(Figure 27).

a)

Grain boundary
precipitates
(Al20Cu2Mn3)

b)

Grain boundary
precipitate
(Al20Cu2Mn3)
Line precipitate
AlxCu (Li/Mg)

Al3Zr

Al-Zn

89
 c)
Al3Zr

Al-Zn

Line precipitate
AlxCu(Li/Mg)

Figure 40 Stir zone microstructure for sample G1 in T8. a) Large grain and precipitates; b)
Al20Cu2Mn3 large precipitates with line precipitates at grain boundaries; c) Grain boundary
fine scale precipitates;

5.6.3.9 Sample G1 heat affected zone in T3

In the heat affected zone for sample G1, the grains are only exposed to
elevated temperatures during welding with very limited mechanical
deformation; therefore they remain large (>50x20μm) as shown in Figure
41a. The secondary phase particles have formed in this region and are
seen to occur mainly within the grains. The shape of these particles varies
with the large ones (Al-Cu-Mn), some rectangular (Al-Cu-Mn) and finer
spherical particles (Al-Cu and Al-Zr). Contrast variations, as dark contrast
in bright grains and vice versa, is observed and is due to ion beam milling
or a material smearing effect.

The phases present on grain boundaries are highlighted in Figure 41b.

There appears to be no precipitate free zone despite of these grain
boundary precipitate. The variation in size of secondary phase particles
within the grains is also shown. The fine spherical precipitates yield an

90
EDS signal indicating the presence of Zr and are hence suspected to be
the Al3Zr phase; whereas the slightly larger particles have presence of Al-
Cu-Mn and on occasion Al-Cu-Mg. Some of the very fine scale
precipitates revealed traces of Zn via EDS; however presence of Zn in a
precipitate phase has not been confirmed for this alloy. At a higher
magnification as shown in Figure 41c, the co-existence of line precipitates
with AlxCu(Li/Mg) make up and fine spherical precipitates Al3Zr is
observed. Some degree of grain curvature is also observed indicating that
grain boundaries may have shifted during the high temperature exposure
while the material was being welded.

a)

91
 b)

Presence of
Al20Cu2Mn3
Al3Zr

c)

Al3Zr

AlxCu(Li/Mg)

Figure 41 Microstructure of the heat affected zone of sample G1 in the T3. a) Large grain size
with a variety of secondary phases; b) Submicron precipitates of Al 20Cu2Mn3 composition
and very small scale Al3Zr; c) Grain boundary precipitates of AlxCu(Li/Mg) and Al3Zr.

92
5.6.3.10 Sample G1 heat affected zone in T8

Upon PWHT to the T8 condition, the large secondary phase is observed to

grow, as shown in Figure 42a. These particles were randomly distributed
through the sample with the majority occurring within the grains rather
than on grain boundaries. A dark halo effect has been observed on
particles within the grains, which is suspected to be due to lithium
migrating in those regions, as shown in Figure 42b. The absence of such
observable dark halo around similar precipitates in the darker contrast
grains can be explained as the majority of contrast arises from crystal
orientation rather than the small Z number difference between the Al
matrix and the Al-Li phase surrounding such precipitates. The presence of
fine scale line precipitates is also observed. At an even higher
magnification, as shown in Figure 42c, the line precipitates appear to be
defining the grain boundary in a zigzagged manner. Linking these
observations to the examined grain boundary curvature in Figure 42a, it is
possible to conclude that grain boundaries have moved slightly around the
line precipitates that were encountered during processing.

93
a)
Al20Cu2Mn3

b) Al20Cu2Mn3 with
dark halo

Grain boundary
AlxCu(Li/Mg)

94
 c)
Grain boundary T
type AlxCu(Li/Mg)

Figure 42 Heat affected zone of sample G1 in the T8 condition. a) Large grain size with
presence of grown secondary phases; b) Very small scale precipitates distributed uniformly
throughout grains and grain boundaries; c) Zigzag plate precipitate orientation on grain
boundaries.

95
5.6.4 Transmission electron microscopy

TEM was carried out to compare the observed microstructure within the
base material and the welds and further to compliment the high resolution
SEM observation performed. The natural and artificially aged base metal
microstructures were studied with focus on the precipitates observed in
them to act as controlled boundary conditions. The as welded condition of
the stir zone of welded samples was also analysed with respect to the
precipitates present and is compared to the base metal in the T3
condition. The welded and heat treated weld samples were compared to
the base metal in the T8 condition. It should be noted that samples were
observed more than 12 month after welding hence any effect of natural
aging should be stabilized. High resolution TEM (HRTEM) was employed
to reveal the ~1nm thick T1 (Al2CuLi) plates present in the T8 condition for
AA2199.

5.6.4.1 Base metal in the T3 condition

In Figure 43 bright field (BF), the presence of large scale Al20Cu2Mn3

precipitates is highlighted. These precipitates were selected for
observation as the microstructure of this sample generally free of other
precipitates. The existence of dislocation surrounding these phases is
clearly shown, suggesting these precipitates were present during
processing of the starting material. The difference in contrast between the
3 observable particles may be related to the relative thickness of the
particles with increased thickness causing increased diffraction and darker
contrast. The matrix of this sample reveals some degree of contrast
variation that is believed to be due to the chemical method used to
prepare the thin foils. Small precipitates visible in the matrix are common
and have Al-Cu and in some cases Zr chemistries.

96
Figure 43 AA2199 base metal in the T3 condition BF revealing strain surrounding large
Al20Cu2Mn3 precipitates

Observing the matrix of this sample in dark field (DF Figure 44) revealed
strong contrast due to the presence of small scale precipitates such as
naturally aged θ’ (Al2Cu) and δ’ (Al3Li) as confirmed by SAED shown in
the extract in Figure 44. A large dispersoid, thought to be of the Al3Zr
phase, can be observed in the bottom left of the micrograph. The high
density of the δ’ and the θ’ phases results in the mechanical properties of
the base metal. As observed in the DSC traces for the base metal, in
Figure 21, the dissolution of these phases occurs below 160°C and can

97
hence provide alloying elements for strong precipitation of the T1 phase
during artificial aging – a characteristic of the base metal [21, 57].

Al3Zr

Figure 44 AA2199 base metal in the T3 condition DF mode revealing the presence of delta and
theta in the matrix; large spherical precipitate is Al3Zr dispersoid

5.6.4.2 Base metal in the T8 condition

The presence of a large precipitate of Al20Cu2Mn3 nature is shown in

Figure 45 for the base metal in the T8 condition. Dislocations surrounding
this precipitate are common as described for the T3 condition. The
presence of fine scale thin plates is observed in the matrix of the material.

98
Further contrast variation arises in the matrix due to fine scale, sub 10nm,
spherical precipitates present. The plate shaped phase was identified as
the T1. Chemical spot analysis were conducted via EDS in locations a, b,
and c.

b
a

Figure 45 AA2199 base metal in the T8 condition BF revealing strain surrounding large
Al20Cu2Mn3 precipitate; presence of plate shaped T1 precipitates in the matrix and spherical
Al3Zr, a, b, c indicate location of EDS

Observation of the same zone in DF (Figure 46) with focus around a new
spot appearing on the SAED patterns highlights the presence of the T1
phase. This phase consistently appears in the same direction, on one of

99
the variants of the (111) planes with respect to the Al matrix. From the
SAED (extract in Figure 46) extra spots appear around the matrix points
and these are used to identify the T1 phase. The presence of the very
small, <10nm, spherical phase in the matrix was not unambiguously
identified. Chemically analysis in areas where these particles are present
revealed an Al-Cu composition. The large phases were also chemically
identified via EDS as shown in Figure 47.

b
a

Figure 46 AA2199 base metal in the T8 condition DF of large Al20Cu2Mn3 precipitate with high
density of plate shaped T1 precipitates in the matrix, 1, 2, 3 indicate location of EDS

100
The large rectangular phase showed clear presence of Mn and Cu via
EDS as shown in Figure 47 a. This phase is identified as Al20Cu2Mn3 due
to the relative intensity of the Cu Kα and the Mn Kα peaks. The spherical
phase observed revealed Cu and Zr peaks and is hence believed to be the
Al3Zr phase. The high Cu presence may be due to counts from other
phases in the vicinity of the Al3Zr phase or contamination signal from the
sample holder. The matrix EDS analysis was focused on the plate
precipitate in close proximity to fine spherical phase. The peaks revealed
show Cu, Mn and Zn with the unidentified peak corresponding to the
location of the Ar Kα peak.

101
 c

Ar Kα

Figure 47 EDS spectra for precipitates observed in Figure 45 and Figure 46. a) Large rectangular
phase b) small spherical phase c) matrix with presence of fine precipitates (from location a, b, c)

5.6.4.3 Weld B1 in the T3 condition

The BF image obtained for the stir zone of sample B1 in the T3 condition
is shown in Figure 48. A sub-grain boundary is observed to divide the
image through the middle with a small density of largely spaced thick plate
shaped precipitates, a T-type phase. Low density of fine scale precipitates
within the matrix is believed to give rise to the diffuse contrast observed
there. In the DF image presented in Figure 49 the T-type phase is
highlighted. The fine scale precipitates within the matrix are also
highlighted in this micrograph. These phases were not successfully
identified due to the complex SAED resulting from miss aligned incident
beam; however they give rise to faint rings around the direct beam due to
their very fine nature.

The lack of thin plates of the T1 type and the lower density of fine scale
phases, the δ’ and θ’, results in the low mechanical properties observed in
this zone of the welds. The presence of large T-type phase and high
density of sub-grain boundaries coupled with the large surface area
occupied by big precipitates as seen in the SEM section results in easy
transport routes and high density of sinks for alloying elements which
would otherwise precipitate as the T1 Al2CuLi phase during PWHT. During
PWHT this sample showed little hardening in this zone as shown by
Section 5.5.

102
Figure 48 AA2199 BF of weld B1 in the T3 condition. Presence of low density thick plate
precipitates - the T2 phase on a sub grain boundary; some defuse contrast is observed through
the grains.

103
Figure 49 DF of weld B1 in the T3 condition. T type thick plate precipitates highlight ed. Low
density of fine precipitates in the matrix is observed.

5.6.4.4 Weld B1 in the T8 condition

Upon PWHT the weld zone of sample B1 does not gain hardness and this
effect is attributed to the lack of the strengthening T1 precipitate phase. In
Figure 50 a BF image demonstrate the high density of large scale grain
boundary phases that dominate the microstructure of this sample.
Contrast variations arise from dislocations which are often pinned by
particles as the Al3Zr phase. It is clear that the large grain boundary area
and high density of secondary phase particles on it have left a matrix
largely depleted from alloying element; hence no fine scale T1 (Al 2CuLi)
phase has precipitated during PWHT.

104
Figure 50 Low magnification overview for sample B1 in the T8 condition. High density of grain
boundary phases present

At higher magnification, as shown in Figure 51, the interaction between

large dislocations and precipitates is highlighted. Furthermore, the large
precipitates are shown to have contrast variations throughout them which
is suspected to be due to overlap between individual phases. Such
observations further support the occurrence of co-precipitation in this
sample as was shown in section 5.6.3.6. Finally the lack of contrast
variation within the matrix, observed at a wide range of inclination angles,
goes to confirm that no fine scale, in particular the T1 (Al2CuLi), phases
have precipitated during the PWHT of this sample.

105
Figure 51 High magnification for sample B1 in the T8 condition revealing interaction between
large scale precipitates and dislocations

5.6.4.5 Weld G1 in the T3 condition

The BF image for the weld zone of sample G1 in the T3 condition is

presented in Figure 52. The sample revealed many small scale precipitate
in the 20nm range. These precipitates are believed to be naturally aged θ’
phase with presence of δ’ phase in close proximity. There were no thick
plate precipitates as the ones observed for sample B1-T3 and the density
of large scale precipitates was shown to be low in the SEM section. The
Al3Zr phase was occasionally observed in the stir zone of this sample as
highlighted.

106
 Al3Zr

Figure 52 BF of weld G1 in the T3 condition. Lack of plate shaped precipitates. High density of
fine scale precipitates in the matrix.

In the DF mode this zone revealed the matrix precipitates - Figure 53.
These are frequently of irregular shape and appear to have dark contrast
incorporated with their structures suggesting the presence of Li – yielding
lower diffraction. Density of such observed precipitates was higher than
that of the sample B1-T3 and no PFZ zones were observed in the areas
analysed. The SAED of this sample revealed only very little diffuse
contrast around the matrix spots.

107
Figure 53 DF of weld G1 in the T3 condition highlighting the high density of fine scale
precipitates in the matrix

5.6.4.6 Weld G1 in the T8 condition

Upon PWHT the stir zone of sample G1 gains significant hardness which
has been associated with the high special density of T1 (Al2CuLi) phase
precipitation in the matrix. Figure 54 demonstrates the microstructure of
sample G1-T8 as is focused on one of the sub grain boundary large scale
precipitates which were not very common. In the vicinity of this phase co-
precipitation has taken place and 2 other phases are present which are
suspected of containing Cu, Mg and Li. A well defined precipitate free
zone exists around this particle and further highlights the ability of such
grain boundary phases to soak up alloying elements from the surrounding

108
matrix and hence reduce the density of other fine scale precipitates.
Furthermore, the sub grain boundaries have a high density of fine scale
precipitates, namely the T1 (Al2CuLi) phase, which preferentially forms
there. Finally matrix contrast variation arises from the presence of the T1
phase in the matrix as was observed in the case of the base metal in the
T8 condition.

SGB precipitate Matrix T1

SGB T1
PFZ

Co-precipitation

Figure 54 BF TEM image showing co-precipitation on sub grain boundary (SGB) and fine scale
T1 (Al2CuLi) phase giving rise to matrix contrast variation. A clear precipitate free zone (PFZ) is
observed around the grain boundary phase.

At high resolution the precipitate phases observed in the matrix of sample

G1-T8 are shown in Figure 54. The existence of an Al-Cu phase is clearly
shown as the dark rectangular precipitates. An edge-on variant of the T1

109
(Al2CuLi) phase is also observed with a high density. The phase is
consistently sub 30nm long and ~1nm tick which are dimensions that have
been reported as optimal for strengthening of Al-Cu-Li alloys [112]. The
SAED image, extract in Figure 54, shows the extra spots arising from the
Al-Cu phase present and very fine Kikuchi line through the image that are
a common effect of the strong directionality of the T1 phase. It should be
noted here that this sample gained significant hardness during post weld
heat treatment.

Figure 55 HRTEM revealing the presence of fine scale Al-Cu phase particles the very thin (~1nm)
T1 (Al2CuLi) phase. SAED image demonstrating extra spots due to the Al-Cu phase and Kikuchi
lines due to the directionality of the T1 phase.

110
The presence of high density of Al-Cu and Al-Li phases in close proximity
allows for the formation of the Al2CuLi T1 phase during PWHT of sample
G1. The low grain boundary area reduces the number of easy pathways
for diffusion of alloying elements during elevated temperature aging and
hence promotes precipitation within the grains. Such precipitation is further
promoted by the low density of large grain boundary phases present post
welding that act as sinks for alloying elements. Finally the dislocation
density for samples with large dynamically recrystalized grains in the stir
zone of a weld is believed to be higher when compared to finer grains. The
high density of θ’ and δ’ phases in the naturally aged condition for sample
G1 supports this suggestion. Further support arises from the high density
of matrix T1 (Al2CuLi) phase in the T8 condition as this phase is known to
require the dissociation of dislocations as to nucleate its basal planes
parallel to the (111) planes of the Al matrix [126].

5.6.4.7 High resolution TEM of base metal in the T8 condition

High resolution TEM was carried out on the base metal material to reveal
the presence and morphology of the T1 phase. The thin plate shaped
phase was observed to exist with high aspect ratios. The plates were not
thicker than 3nm and their length ranged between 25-80nm as shown in
Figure 56. Strain fields surrounding this phase give rise to dark contrast in
the image; however this dark contrast appears to be reduced with the
presence of a well organised surrounding layer. These layers are the δ’
phase which has heterogeneously formed surrounding the T1 phase
during artificial aging. Their formation is based on an attempt to minimize
the misfit between the α-Al and the T1 phase.

Observation of these phases in the SEM studies presented is limited due

to the small BSE z number contrast they yield. Further limitations arise
from the small scale of these phases. As shown in Table 8 the δ’ phase
would yield a contrast of 0.81 with respect to the Al matrix and the T1
phase only 1.12 if these were bulk precipitates on the scale of the

111
interaction volume generating BSE electrons. The contrast of the T1
phase is further limited due to its very thin dimension being ineffective in
generation of BSE electrons unless it lies in the edge-on close to Bragg
position to the incident beam. It can be suggested that only grains who’s
orientation is such as to place the (111) planes parallel to the incident
beam and hence generate sufficient scattering to give rise to contrast
variation and observed the T1. Further work needs to be conducted in to
understand and explain this possible phenomenon and help observe fine
scale phases within bulk samples in an SEM using the electron
channelling contrast imaging technique.

Figure 56 BF of base metal in the T8 condition revealing the presence of the T1 phase. Diffused
contrast surrounding the plates is due to the presence of δ’ phase heterogeneously precipitates
on the T1 phase [21, 64].

112
5.7 Mechanical properties of welds

The tensile test results are shown in Figure 57 and Figure 58 for both T3
and T8 conditions. The yield strength (YS) and the ultimate tensile
strength (UTS) both increase for all samples from the T3 to the T8
condition. The YS in the T3 condition varies little in the range of 200-
230MPa for all samples. The small variation between weld samples
remains consistent for the UTS with values ranging between 270-325MPa
in the T3 condition. When post weld heat treated the YS for samples B1 –
B4 shows an average increase of 24, 35, 21 and 5MPa respectively. The
same heat treatment results in a YS increase of 64 and 61MPa for
samples G1 and G2 respectively. The UTS shows a similar trend for the
tested samples. The UTS for sample G1 and G2 has a 390MPa average
which represents 93% of the base metal value of 420±10MPa, in the T8
condition [15]. This is indicative of high quality welds that react well to post
weld heat treatment. These welds, in the T8 condition, posses properties
approaching those for base metal and are of prime interest for industrial
future applications.

Figure 59 demonstrates the effect of post weld heat treatment on the %

elongation at fracture during tensile testing. A general drop in %
elongation is shown for all samples when heat-treated from T3 to T8
condition. The drop for samples B1-B4 is 2.09, 2.79, 2.41 and 1.44%
respectively compared to 0.25 and 1.30% for samples G1 and G2. The
large decrease in grain size of the material in the weld zone and increase
grain boundary area attribute lower possible plastic deformation and
therefore the overall % elongation for all welded samples is below that of
the base metal in the T8 condition. This effect is further emphasised upon
post weld heat treatment when the material strength increases.

113
Figure 57 - Tensile yield strength for all FSW in T3 (Blue) and T8 (Red). AA2199 corresponds
to the base metal in T8

Figure 58 - Ultimate tensile strength for all FSW in T3 (Blue) and T8 (Red). AA2199
corresponds to base metal in T8

114
Figure 59 The % elongation at fracture during tensile tests for all FSW samples in T3 (Blue)
and T8 (Red). The AA2199 corresponds to base metal in T8

Figure 60 demonstrates the macroscopic location of failure for select

samples during tensile testing. All samples in the T3 condition failed within
the weld zone with the exception of sample G1 and G2. The location of the
failures in samples G1 and G2 suggest that the lowest mechanical
properties occur approximately 12mm and 10mm away from the centre
respectively, within the heat affected zone. The failure for all samples in
the T8 condition occurred in the weld zone. The transition observed for
samples G1 and G2 is related to the exposure to heat during welding and
the modified precipitates. Finite element modelling of FSW on aluminium
alloys has shown that the necessary temperature for the material to
plasticise is likely to exceed 300°C, which is well above that required to
alter precipitation in AA2199 [127]. The presence of small amounts of
precipitates lowers the ductility and hence strain is concentrated within
these regions and failure occurs there. Upon post weld heat treatment the
presence of strengthening precipitates is dramatically increased and their

115
distribution is homogeneous therefore avoiding the localization of strain in
one particular zone.

a) b)

c) d)

e) f)

Figure 60 Failure location during tensile testing. a) Sample B1 in T3; b) Sample B1 in T8; c)
Sample G1 in T3; d) Sample G1 in T8; e) Sample G2 in T3; f) Sample G2 in T8

116
5.8 Fracture surfaces

The fracture surfaces for samples tested under uniaxial tension for select
samples in the T3 and T8 condition are presented and discussed in this
section. The fracture surface of all welded samples we analyze and the
brought up examples and discussion summarize the findings. All samples
fractured within the stir zone of the weld, with the exception of samples G1
and G2 in the T3 condition, as shown in Figure 60. As the latter two
samples fractured in the heat affected zone, a variation of grain size may
induce effects on the overall fracture morphology.

Figure 61a and b show macroscopic variations on the surface of samples

with poor response to post weld heat treatment. For sample B1 (Figure
61a) there exists a region at 45° to the vertical axis of the image, defining
a height differential between two regions. This type of fracture surface
variation was observed and can be related to the fracture occurring in a
non-perpendicular direction to the applied tension during testing, as shown
in Figure 60. An observed crack in sample B4 (Figure 61b) is suspected to
have formed during tensile testing. This fracture occurs in the stir zone
where material has experienced plastic deformation during welding and
well aligned pancake grains should be limited. It has been reported
however that during friction stir welding with a threaded tool some of the
material flow may be uniform [128-130]. Such material flow can cause
alignment of the welded material in a similar manner to an extrusion
process [114]. If this was the case, directional inconsistencies in material
properties would cause cracks as shown in Figure 61b.

117
 a)

b) Crack

Surface
Contaminatio

Figure 61 Low magnification fracture surface for samples with poor post weld heat
treatment response. a) Sample B1 in the T3 – surface roughness; b) Sample B4 in the T3 –
crack

118
A relatively flat zone was selected for higher magnification observations
and is presented in Figure 62. The fracture surface appears to very rough
and abundant with dimples. Dimple size is sub 2μm and can be linked to
the small scale grains reported for the stir zone of samples with minimal
response to post weld heat treatment. The predominant cup and cone
morphology demonstrates that the sample has undergone some degree of
plastic deformation prior to fracture. The presence of larger scale dimples
was also noted.
The fracture surface for samples with limited response to post weld heat
treatment is presented in Figure 63. At low magnification, in Figure 63a,
the surface of sample B1 in the T8 condition appears rough. Many vertical
wavy striations are observed and represent edges where fracture direction
has changed during failure. A crack, similar to the one observed in Figure
62b, is also seen in this sample. Finally some degree of contamination can
also be observed.

Figure 62 Sample B1 in the T3 condition at high magnification

119
At higher magnification, Figure 63b, the finer surface roughness is
revealed. The cup and cone morphology is still present; however to a
smaller degree when compared to the T3 condition. Some very fine dark
features have been observed. These are suspected of corresponding to
locations where secondary phases may have been present and removed
during failure. Furthermore, some small bright features are also observed
and appear to be secondary phase particles. Overall these observations
are in agreement with the observations made in the SEM section.

a)
Crack

120
 b)
Secondary
phase

Removed
particles

Figure 63 Sample B1 in the T8 condition a) low magnification; b) high magnification

The fracture surface for sample G1 in the T3 condition is shown in Figure

64. The surface appears to be rougher when compared to previously
observed surfaces. There exists some degree of contamination and hence
charging can be observed in the image. From the low magnification image
it is possible to observe that a high degree of deformation has preceded
the fracture. There exist many small-scale tears in the material similar to
the larger ones observed in samples B1. These were observed in more
detail in Figure 65. Regions of high surface roughness are observed
where fracture has occurred via a ductile mechanism. Some zones appear
to have a less rough surface; indicative of lower degree of plastic
deformation prior to fracture, and it is in these zones that secondary
phases are seen. The tears appear to be regions that join such zones and
cross-linking chain-like structures have been observed in these zones.
These structures are suspected of being grain boundary precipitates as
have been shown by microscopy. In Figure 66, a zone containing a

121
boundary between a ductile and a less ductile type fracture zones is
presented. A cup and cone surface morphology is observed in zones
where a higher level of plastic deformation has occurred. In zones where a
more cleave-like surface is left, as on the top of the image, a significantly
lower degree of plastic deformation has preceded the fracture; however
voids are still observed. It is important to note that these observations
were on a fracture surface with in the heat affected zone of the base metal
and hence grain size was significantly larger than in the stir zone.

Contamination
Charging

Figure 64 Sample G1 in the T3 condition at low magnification exemplifying rough surface

The cross-linked tare zones observed in Figure 65 tend to separate

regions of smooth surface and the rougher and more ductile regions. This
phenomenon can be linked to the processing of the material in this zone of
the weld. The starting material has been rolled and grains are elongated
hence permitting for large portion of grain boundary in plane with the
thickness of the plate. During welding these regions have been exposed to

122
elevated temperatures, as they are in the heat affected zone, and
promoted the development some precipitates. During tensile testing,
imperfection of the alignment of the grains boundaries to the strain
direction creates moments around long grain boundaries hence causing
their separation and exposure of grain boundary phases. The remainder of
the material continues to carry the load until ductile fracture of grains is
achieved (Figure 66).

Tare like
structure

Secondary
phases

Figure 65 Sample G1 in the T3 condition at intermediate magnification highlighting

intergranular tare zones

In Figure 67a the fracture surface of the same sample G1 but in the T8
hardened condition is shown. This fracture occurred within the stir zone of
the weld. From a low magnification prospective, the surface appears flat.
There are a series of fault lines (brighter edges we can see) that have
previously been observed. Contamination is present and has a charging
effect; however not all the dark spots on the surface are due to
contamination charging – some arise from voids.

123
Figure 66 Sample G1 in the T3 condition at high magnification

At a higher magnification, as shown in Figure 67b, the degree of surface

roughness is clearly visible. The observed zones show some degree of
large scale dimples corresponding to the relevant zone grain size and
whose surface is covered by significantly smaller dimples. There are
secondary phases present throughout the sample. In Figure 67c the
source of the large scale dimples is shown to originate from rectangular
shaped secondary phases. The smaller scale roughness does not have
any observable origins; however it is believe these originate from a finer
scale precipitate which cannot be resolved at this magnification.

124
a)
Voids

Contamination
charging

b)

Secondary
phases

125
 c)

Secondary
phases

Figure 67 Sample G1 in the T8 condition a) Low magnification surface; b) High magnification

showing dimple size variation; c) high magnification revealing large scale rectangular
secondary phase particles

126
6.0 Summary

AA 2199 was friction stir welded in the naturally aged T3 condition.

Macroscopic inspection of the welds revealed sound welding quality with
lack of defects. All of the welds presented survived the root and face
bending test showing their outstanding properties. Samples from these
welds were artificially age hardened to the T8 condition and provided for
testing.

The parameters used to create the welds were recorded and used a
starting point to distinguish between the welds. Samples B1-B5 were
welded with significantly lower tool rotation speed compared to sample G1
and G2. As a result of the higher tool rotation speed higher travel speed
was possible for samples G1 and G2. The table force used was within
range for all welds with the exception of weld B2 where it was lower. The
interaction between tool rotation speed and travel speed was such as to
allow sufficient temperature generation and dwell time to soften the
material and allow for plastic mixing.

Optical observation of the welds revealed the distinct welding zone of

friction stir welds. The stir zone corresponded to the centre of the welds
where severe plastic deformation has resulted in dynamically
recrystallized grain with very small sizes. The thermo-mechanically
affected zone was found to be the boundary between the stir zone and
adjacent material. Grains in this zone were plastically deformed at
elevated temperature and resembled forged microstructures. The heat
affected zones were also observed between the parent material and the
TMAZ.

Differential scanning calorimetry was carried out on all the welds in the T3
condition and revealed differences in precipitation behaviour. Welds B1
and B2 have a double dissolution peaks with maxima at 100°C and 150°C
where as welds B3 and B4 have a broad peak in the 100°C. Peaks in this

127
ranged were related to the dissolution of the GP zones, Al2Cu, Al3Li of
natural aging. Welds G1 and G2 had only the peak at 150°C and were in
close agreement with the DSC results for the base metal in the T3
condition.

Hardness line profiles demonstrated limited hardness variation for all the
welds in the T3 condition. Application of post weld heat treatment resulted
in hardness gain in the base metal and part of the HAZ of all welds. The
hardness of welds B1-B4 did not change upon PWHT. The hardness of
welds G1 and G2 increase upon PWHT. Hardness maps confirmed that
hardness gain during PWHT was limited in the stir zone and TMAZ of
sample B1 where as it was significant in the same zones for sample G1.

SEM was carried out using electron channelling contrast imaging which
helped reveal the microstructure of bulk samples without etching – hence
limited chemical deterioration of the surface. Large scale phase observed
in the bulk samples were identified in both the base metal and welds in the
T3 and T8 conditions. Fine scale plate precipitates, believed to be the T1
phase were observed in some grains of the base metal in the T8 condition.

The small grain size within the stir zone of the welds was analysed via
EBSD and image analysis of ECCI corresponds well. The grain size of
sample B1 in the T3 is 0.58 ±1σ 0.15μm where as it was 2.85 ±1σ 0.97μm
for sample G1 in the T3. Due to the significantly larger grains of sample
G1 less grain boundary area is available for the precipitation of secondary
phase which soak up alloying elements from within the grains. This was
confirmed by the high density of secondary phases in sample B1
compared to that of sample G1. The density of secondary phases was
higher within the weld zone of welds when compared to the base metal.

TEM studies revealed the presence of very fine scale precipitates within
the stir zone of AA2199-T3 FSW. The presence of dislocation surrounding
large Al20Cu2Mn3 phase was observed in the base metal as well as in the

128
welds. Sample B1 had low precipitate density and the presence of thick
plates within the grains and at sub-grain boundaries was observed. These
plates are suspected of being the T2 stable Al-Cu-Li phase. The
precipitate density of sample G1 was higher than that of sample B1 and no
plate precipitates were observed in the T3 condition.

Sample B1 contained the T2 plates, low density of fine scale precipitates

observed in the TEM, small grain size, large grain boundary area and high
surface fraction of large precipitates observed in SEM. The combination of
these factors allows for limited precipitation hardening via the formation of
T1, θ’ and δ’ phase during artificial PWHT. Alloying elements are believed
to diffuse readily to large precipitates present through the grain boundaries
and leave the grain interior free of precipitates.

Sample G1 contained no T2 plates, high density of fine scale precipitate

observed in TEM, larger grain size hence lower grain boundary area, and
a lower surface fraction of large precipitates observed in SEM. These
factors promote higher potential for precipitation hardening via formation of
the T1, θ’ and δ’ phase during artificial PWHT.

The PWHT applied to all welds resulted in an increase in mechanical

properties. The yield and ultimate tensile strength increase was limited for
sample B1-B4. The increase of these properties for sample G1 and G2
was significant. The PWHT resulted in a drop in % elongation for all
samples from the T3 to T8 condition. Samples G1 and G2 have a lower
drop in % elongation when compared to sample B1-B4.

During tensile testing fracture occurred in the weld zone for all samples in
the T3 condition with the exception of sample G1 and G2. In these
samples fracture was in the HAZ. The nature of the fracture surface
revealed plastic deformation for all samples; however dimples originated
from rectangular precipitates. Dimple size was larger for sample G1 and

129
G2 in the T3 condition due to the larger grain size in the HAZ. In the T8
condition all samples failed within the weld region.

Overall the microstructure of FSW AA2199 thin sheet was analysed in

both the T3, as welded condition, and the T8 PWHT condition. The
precipitation of secondary phases of both beneficial and detrimental type
was observed. The presence of these precipitates was related to the
mechanical properties observed in the as welded condition and further
linked to the ability of welds to artificially age. Welds with high tool rotation
speed yielded the best results upon PWHT with UTS levels of about 93%
of the base metal, elongation of 6% at fracture and uniform hardness in
the 120-140HV range throughout the weld.

130
7.0 References

[1] The Aluminum Association. 1525 Wilson Blvd, Arlington, VA 22209,

2009.
[2] Aeroflight.co.uk. North-American A-5 Vigilante. vol. 2012: Aeroflight,
2009-2011.
[3] NASA. Super Lightweight External Tank. vol. 8. Huntsville: NASA. p.2.
[4] Rendis K-H. Airbus and current aircraft metal technologies. Airbus
Germany, Bremen, 2008. p.55.
[5] Gittos MF. The application of resistance and laser welding to the Al-Li
alloy 8090. TWI research report, 1990.
[6] Kostrivas A, Lippold JC. Weldability of Li-bearing aluminium alloys.
International Materials Reviews 1999;44:217.
[7] C. Dawes WT. Friction stir welding/processing. TWI Bulletin
1995;Nov/Dec:124.
[8] Mishra RS, Ma ZY. Friction stir welding and processing. Materials
Science and Engineering: R: Reports 2005;50:1.
[9] Wilm A. Physical-metallurgical Investigation of Aluminium-
Magnesium Alloys. Metallurgie 1911;8:225.
[10] Lavernia EJ, Grant NJ. Aluminium-lithium alloys. Journal of Materials
Science 1987;22:1521.
[11] Noble B, Harris SJ, Dinsdale K. The elastic modulus of aluminium-
lithium alloys. Journal of Materials Science 1982;17:461.
[12] Fox AG, Fisher RM. The origin of the high elastic modulus in Al-Li
alloys. Journal of Materials Science Letters 1988;7:301.
[13] Roberto J R. Fabrication methods to manufacture isotropic Al-Li alloys
and products for space and aerospace applications. Materials Science and
Engineering: A 1998;257:100.
[14] AA. International Alloy Designations and Chemical Composition Limits
for Wrought Aluminum and Wrought Aluminum Alloys. The Aluminum
Association, 2009.
[15] Giummarra C, Thomas B, Rioja RJ. New Aluminum Lithium Alloys for
Aerospace Applications. Light Metals Technology, 2007.
[16] Williams DB, Edington JW. The Precipitation of Al3Li in Dilute
Aluminium;Lithium Alloys. Metal Science 1975;9:529.
[17] Silcock JM. The structural ageing characteristics of aluminum-copper-
lithium alloys. Journal of Instititue of Metals;88:357.
[18] Chanani G, Narayan GH, Telesman J. High Strength PM Aluminum
Alloys
In: Koczak MJ, Hildeman GH, editors. The Metals Society of AIME, 1982.
p.341.
[19] Noble B, Thompson GE. Precipitation Characteristics of Aluminium-
Lithium Alloys. Metal Science;5:114.
[20] Noble B, Bray SE. On the [alpha](Al)/[delta]'(Al3Li) metastable solvus
in aluminium-lithium alloys. Acta Materialia 1998;46:6163.

131
[21] Yoshimura R, Konno TJ, Abe E, Hiraga K. Transmission electron
microscopy study of the early stage of precipitates in aged Al-Li-Cu alloys.
Acta Materialia 2003;51:2891.
[22] Noble B, Bray SE. Use of the Gibbs–Thompson relation to obtain the
interfacial energy of δ′ precipitates in Al–Li alloys. Materials Science and
Engineering: A 1999;266:80.
[23] Schlesier C, Nembach E. Strengthening of aluminium-lithium alloys by
long-range ordered δ'-precipitates. Acta Metallurgica et Materialia
1995;43:3983.
[24] Cassada WA, Shiflet GJ, Jesser WA. Heterogeneous nucleation and
growth of δ′ in Al at.% Li. Acta Metallurgica et Materialia 1992;40:2101.
[25] Nozato R, Nakai G. Thermal Analysis of Precipitation in Al-Li Alloys.
Transactions of the Japan Institute of Metals 1977;18:679.
[26] Khachaturyan A, Lindsey T, Morris J. Theoretical investigation of the
precipitation of δ' in Al-Li. Metallurgical and Materials Transactions A
1988;19:249.
[27] Noble B, Trowsdale AJ. Evidence for pre {delta}{prime} precipitation
events in an Al-Li alloy. Journal Name: Scripta Metallurgica et Materialia;
Journal Volume: 33; Journal Issue: 1; Other Information: PBD: 1 Jul 1995
1995:Medium: X; Size: pp. 33.
[28] Papazian JM, Sigli C, Sanchez JM. New evidence for GP zones in binary
Al Li alloys. Scripta Metallurgica 1986;20:201.
[29] Radmilovic V, Fox AG, Thomas G. Spinodal decomposition of Al-rich
Al-Li alloys. Acta Metallurgica 1989;37:2385.
[30] Shaiu B, Li H, Lee H, Chen H. Decomposition and dissolution kinetics of
δ′ precipitation in Al-Li binary alloys. Metallurgical and Materials
Transactions A 1990;21:1133.
[31] Kulkarni G, Banerjee D, Ramachandran T. Physical metallurgy of
aluminum-lithium alloys. Bulletin of Materials Science 1989;12:325.
[32] Jha SC, Sanders Jr TH, Dayananda MA. Grain boundary precipitate free
zones in Al-Li alloys. Acta Metallurgica 1987;35:473.
[33] Vasudévan AK, Ludwiczak EA, Baumann SF, Doherty RD, Kersker MM.
Fracture behavior in Al Li alloys: role of grain boundary δ. Materials
Science and Engineering 1985;72:25.
[34] Sruble L, Pickens JR, Christodoulou L. Stress-corrosion cracking in Al-
Li binary alloys. In: Starke EA, Sanders Jr TH, editors. Aluminium-Lithium
Alloys II, 1983. p.561.
[35] Starke Jr EA, E. QW. The microstructure and Propreties of Aluminum-
Lithium alloys. New Light Allloys 1990;174:1.
[36] Kumar KS, Brown SA, Pickens JR. Microstructural evolution during
aging of an AlCuLiAgMgZr alloy. Acta Materialia 1996;44:1899.
[37] Park TW, Song YB. A Study on the Aging Behavior of Al-Li-Cu-Zr Alloy.
Key Engineering Materials August, 2007;345 - 346:1525.
[38] Gault B, de Geuser F, Bourgeois L, Gabble BM, Ringer SP, Muddle BC.
Atom probe tomography and transmission electron microscopy

132
characterisation of precipitation in an Al-Cu-Li-Mg-Ag alloy.
Ultramicroscopy;In Press, Corrected Proof.
[39] Pao PS, Sankaran KK, O'Neal JE. MICROSTRUCTURE, DEFORMATION,
AND CORROSION-FATIGUE BEHAVIOR OF A RAPIDLY SOLIDIFIED Al-Li-Cu-
Mn ALLOY. Bulletin de l'Association Technique Maritime et Aeronautique
1981:307.
[40] Kang S, Grant NJ. The Microstructure of Mechanically Alloyed
Aluminum Alloys. In: Starke EA, Sanders Jr TH, editors. Aluminium-Lithium
Alloys II, 1983. p.469.
[41] Hardy HK, Silcock JM. The Phase Sections at 500 and 350°C of Al Rich
Al-Cu-Li Alloys. J. Inst. Metals 1956;84:423.
[42] Li JF, Li CX, Peng ZW, Chen WJ, Zheng ZQ. Corrosion mechanism
associated with T1 and T2 precipitates of Al-Cu-Li alloys in NaCl solution.
Journal of Alloys and Compounds 2008;460:688.
[43] Cassada WA, Shiflet GJ, Starke Jr EA. Electron diffraction studies of
Al2CuLi [T1] plates in an Al-2.4Li-2.4Cu O.18Zr alloy. Scripta Metallurgica
1987;21:387.
[44] Huang JC, Ardell AJ. Crystal structure and stability of T1, precipitates
in aged Al&#8211;Li&#8211;Cu alloys. Materials Science and Technology
1987;3:176.
[45] Dwyer C, Weyland M, Chang LY, Muddle BC. Combined electron beam
imaging and ab initio modeling of T[sub 1] precipitates in Al--Li--Cu alloys.
Applied Physics Letters 2011;98:201909.
[46] Herring RA, Gayle FW, Pickens JR. High-resolution electron
microscopy study of a high-copper variant of weldalite 049 and a high-
strength AI-Cu-Ag-Mg-Zr alloy. Journal of Materials Science 1993;28:69.
[47] Howe J, Lee J, Vasudévan A. Structure and deformation behavior
of&lt;i&gt;T&lt;/i&gt;&lt;sub&gt;1&lt;/sub&gt; precipitate plates in an Al-
2Li- 1 Cu alloy. Metallurgical and Materials Transactions A 1988;19:2911.
[48] Gable BM, Zhu AW, Csontos AA, Starke Jr EA. The role of plastic
deformation on the competitive microstructural evolution and mechanical
properties of a novel Al–Li–Cu–X alloy. Journal of Light Metals 2001;1:1.
[49] Donnadieu P, Shao Y, De Geuser F, Botton GA, Lazar S, Cheynet M, de
Boissieu M, Deschamps A. Atomic structure of T1 precipitates in Al-Li-Cu
alloys revisited with HAADF-STEM imaging and small-angle X-ray scattering.
Acta Materialia 2011;59:462.
[50] Flower HM, Gregson PJ. SOLID STATE PHASE TRANSFORMATIONS IN
ALUMINIUM ALLOYS CONTAINING LITHIUM. Materials Science and
Technology 1987;3:81.
[51] Wang SC, Starink MJ. Precipitates and intermetallic phases in
precipitation hardening Al-Cu-Mg-(Li) based alloys. International Materials
Reviews 2005;50:193.
[52] Huang BP, Zheng ZQ. Independent and combined roles of trace Mg and
Ag additions in properties precipitation process and precipitation kinetics of
Al–Cu–Li–(Mg)–(Ag)–Zr–Ti alloys. Acta Materialia 1998;46:4381.

133
[53] Meyer P, Dubost B. Production of aluminium-lithium alloy with high
specific properties. In: Baker C, Gregson PJ, Harris SK, Peel CJ, editors.
Aluminium-lithium alloys III. University of Oxford, 1986. p.37.
[54] Fang W, Jinshan L, Rui H, Hongchao K. Influence of 1.0 wt% Li on
Precipitates in Al-Zn-Mg-Cu Alloy. Chinese Journal of Aeronautics
2008;21:565.
[55] Rioja RJ, Cho A, Bretz PE. Al-Li Alloys Having Improved Corrosion
Resistance Containing Mg and Zn. vol. 4,961,792: U.S. Patent, 1990.
[56] Suresh S, Vasudevan AK, Tosten M, Howell PR. Microscopic and
macroscopic aspects of fracture in lithium-containing aluminum alloys. Acta
Metallurgica 1987;35:25.
[57] Coyne EJ, Sanders Jr TH, Starke Jr EA. Aluminum-Lithium Alloys. In:
Sanders Jr TH, Starke Jr EA, editors, 1981.
[58] Sanders Jr RE, Starke Jr EA. The effect of grain refinement on the low
cycle fatigue behavior of an Aluminum Zinc Magnesium (Zirconium)
alloy. Materials Science and Engineering 1977;28:53.
[59] Wu L-M, Wang W-H, Hsu Y-F, Trong S. Effects of homogenization
treatment on recrystallization behavior and dispersoid distribution in an Al–
Zn–Mg–Sc–Zr alloy. Journal of Alloys and Compounds 2008;456:163.
[60] GUINIER A. Structure of Age-Hardened Aluminium-Copper Alloys.
Nature 1938;142:569.
[61] PRESTON GD. Structure of Age-Hardened Aluminium-Copper Alloys.
Nature 1938;142:570.
[62] Starink MJ, Wang SC. The thermodynamics of and strengthening due
to co-clusters: General theory and application to the case of Al–Cu–Mg alloys.
Acta Materialia 2009;57:2376.
[63] Fonda RW, Cassada WA, Shiflet GJ. Accomodation of the misfit strain
surrounding {III} precipitates (Ω) in Al Cu Mg (Ag). Acta Metallurgica et
Materialia 1992;40:2539.
[64] Yoshimura R, Konno TJ, Abe E, Hiraga K. Transmission electron
microscopy study of the evolution of precipitates in aged Al-Li-Cu alloys: the
[theta]' and T1 phases. Acta Materialia 2003;51:4251.
[65] Berezina AL, Kolobnev NI, Chuistov KV, Kotko AV, Molebny OA.
Coherent Composite Phases Formation in Aged Al-Li Base Alloys. Materials
Science Forum 2002;396-402:977.
[66] Gayle FW, Heubaum FH, Pickens JR. Structure and properties during
aging of an ultra-high strength Al-Cu-Li-Ag-Mg alloy. Scripta Metallurgica et
Materialia 1990;24:79.
[67] Chen PS, Bhat BN. Time-Temperature-Precipitation Behavior in Al-Li
alloy 2195. NASA technical report: NASA, February 2002.
[68] Cassada W, Shiflet G, Starke E. The effect of plastic deformation on
Al2CuLi (T1) precipitation. Metallurgical and Materials Transactions A
1991;22:299.
[69] Kumar KS, Brown SA, Pickens JR. Effect of a prior stretch on the aging
response of an Al-Cu-Li-Ag-Mg-Zr alloy. Scripta Metallurgica et Materialia
1990;24:1245.
134
[70] Gabble BM, Csontos AA, Starke Jr EA. The Role of Mechanical Stretch
on Processing-Microstructure-Property Relationships of AF/C 458. Materials
Science Forum 2000;331-337:1341.
[71] Liverpool TUo. aluSelect: Tempers. vol. 2011: alumatter, 2011.
[72] Chen PS, Stanton WP. Artificial Aging Effects on Cryogenic Fracture
Toughness of the Main Structural Alloy for the Super Lightweight Tank. NASA
METALS AND METALLIC MATERIALS 2002:1.
[73] Chen PS, Stanton WP. A New Aging Treatment for Improving
Cryogenic Toughness of the Main Structural Alloy of the Super Lightweight
Tank. NASA METALLIC MATERIALS 1996:1.
[74] Giummarra C, Rioja RJ, Bray GH, Magnusen PE, Morgan JP. Al-Li Alloys:
Development of Corrosion Resistant, High Toughness Aluminum-Lithium
Aerospace Alloys. ICAA11, vol. Volume 1, 2008. p.176.
[75] Elangovan K, Balasubramanian V. Influences of tool pin profile and
tool shoulder diameter on the formation of friction stir processing zone in
AA6061 aluminium alloy. Materials &amp; Design 2008;29:362.
[76] Jata KV, Semiatin SL. Continuous dynamic recrystallization during
friction stir welding of high strength aluminum alloys. Scripta Materialia
2000;43:743.
[77] Kazi SH, Murr LE. Complex flow phenomena associated with friction-
stir welding of aluminum alloys. 2001. p.139.
[78] Salem HG, Reynolds AP, Lyons JS. Microstructure and retention of
superplasticity of friction stir welded superplastic 2095 sheet. Scripta
Materialia 2002;46:337.
[79] Seidel TU, Reynolds AP. Visualization of the material flow in AA2195
friction-stir welds using a marker insert technique. Metallurgical and
Materials Transactions A: Physical Metallurgy and Materials Science
2001;32:2879.
[80] Reynolds AP. Visualisation of material flow in autogenous friction stir
welds. Science and Technology of Welding and Joining 2000;5:120.
[81] James M, Mahoney M. Proceedings of the First International
Symposium on Friction Stir Welding. Thousand Oaks, CA, USA, 1999.
[82] Jata K, Sankaran K, Ruschau J. Friction-stir welding effects on
microstructure and fatigue of aluminum alloy 7050-T7451. Metallurgical and
Materials Transactions A 2000;31:2181.
[83] Sato YS, Kokawa H, Enomoto M, Jogan S. Microstructural evolution of
6063 aluminum during friction-stir welding. Metallurgical and Materials
Transactions A: Physical Metallurgy and Materials Science 1999;30:2429.
[84] Steuwer A, Dumont M, Altenkirch J, Birosca S, Deschamps A, Prangnell
PB, Withers PJ. A combined approach to microstructure mapping of an Al-Li
AA2199 friction stir weld. Acta Materialia;In Press, Corrected Proof.
[85] Mahoney MW, Rhodes CG, Flintoff JG, Spurling RA, Bingel WH.
Properties of friction-stir-welded 7075 T651 aluminum. Metallurgical and
Materials Transactions A: Physical Metallurgy and Materials Science
1998;29:1955.

135
[86] Kwon YJ, Saito N, Shigematsu I. Friction stir process as a new
manufacturing technique of ultrafine grained aluminum alloy. Journal of
Materials Science Letters 2002;21:1473.
[87] Tang W, Guo X, McClure JC, Murr LE, Nunes A. Heat input and
temperature distribution in friction stir welding. Journal of Materials
Processing and Manufacturing Science 1998;7:163.
[88] Su JQ, Nelson TW, Mishra R, Mahoney M. Microstructural investigation
of friction stir welded 7050-T651 aluminium. Acta Materialia 2003;51:713.
[89] Schneider JA, Nunes AC, Chen PS, Steele G. TEM study of the FSW
nugget in AA2195-T81. Journal of Materials Science 2005;40:4341.
[90] Ivanov R, Boselli J, Denzer D, D.Larouche, Gauvin R, Brochu M. Friction
Stir Welding of Al-Li AA2199: Parameters, Precipitates and Post Weld Heat
Treatment. Thermec 2011. Quebec Canada, 2011.
[91] Kwon YJ, Shigematsu I, Saito N. Mechanical properties of fine-grained
aluminum alloy produced by friction stir process. Scripta Materialia
2003;49:785.
[92] Liu G, Murr LE, Niou CS, McClure JC, Vega FR. Microstructural aspects
of the friction-stir welding of 6061-T6 aluminum. Scripta Materialia
1997;37:355.
[93] Li Y, Murr LE, McClure JC. Flow visualization and residual
microstructures associated with the friction-stir welding of 2024 aluminum
to 6061 aluminum. Materials Science and Engineering: A 1999;271:213.
[94] Sato Y, Urata M, Kokawa H. Parameters controlling microstructure and
hardness during friction-stir welding of precipitation-hardenable aluminum
alloy 6063. Metallurgical and Materials Transactions A 2002;33:625.
[95] Oertelt G, Babu SS, David SA, Kenik EA. Effect of Thermal Cycling on
Friction Stir Welds of 2195 Aluminum Alloy. WELDING RESEARCH
SUPPLEMENT 2001:71.
[96] Pouget G, Reynolds AP. Residual stress and microstructure effects on
fatigue crack growth in AA2050 friction stir welds. International Journal of
Fatigue 2008;30:463.
[97] Shukla AK, Baeslack Iii WA. Study of microstructural evolution in
friction-stir welded thin-sheet Al-Cu-Li alloy using transmission-electron
microscopy. Scripta Materialia 2007;56:513.
[98] Altenkirch J, Steuwer A, Peel MJ, Withers PJ, Williams SW, Poad M.
Mechanical Tensioning of High-Strength Aluminum Alloy Friction Stir Welds.
Metallurgical and Materials Transactions A 2008;39:3246.
[99] Boselli J. Private communications. In: Ivanov R, editor, 2010-2011.
[100] Enrique L, Consuelo G-C. Thermal Analysis of Aluminum Alloys.
Analytical Characterization of Aluminum, Steel, and Superalloys. CRC Press,
2005. p.293.
[101] Microsoft. Microsoft Image Composite Editor. vol. 2010: Microsoft,
2010.
[102] marin@rml-image.com. RML-Image. vol. 2011, 2011.
[103] Williams DB, Carter CB. Transmission electron microscopy : a
textbook for materials science. New York: Plenum Press, 1996.

136
[104] Lohwasser D, Chen Z. Friction stir welding : from basics to
applications. Cambridge: Woodhead Pub., 2010.
[105] Mishra RS, Mahoney MW. Friction stir welding and processing.
Materials Park, Ohio: ASM International, 2007.
[106] Chen CM, Kovacevic R. Joining of Al 6061 alloy to AISI 1018 steel by
combined effects of fusion and solid state welding. International Journal of
Machine Tools and Manufacture 2004;44:1205.
[107] John A W. Microstructures of friction stir weld joints between an
aluminium-base metal matrix composite and a monolithic aluminium alloy.
Scripta Materialia 2003;49:607.
[108] Buffa G, Fratini L. Proceedings of 8th NUMIFORM Conference.
Columbus, Ohio, 2004. p.1224.
[109] Starink MJ, Hobson AJ, Sinclair I, Gregson PJ. Embrittlement of Al-Li-
Cu-Mg alloys at slightly elevated temperatures: microstructural mechanisms
of hardening. Materials Science and Engineering A 2000;289:130.
[110] Gallais C, Denquin A, Bréchet Y, Lapasset G. Precipitation
microstructures in an AA6056 aluminium alloy after friction stir welding:
Characterisation and modelling. Materials Science and Engineering: A
2008;496:77.
[111] Genevois C, Fabrègue D, Deschamps A, Poole WJ. On the coupling
between precipitation and plastic deformation in relation with friction stir
welding of AA2024 T3 aluminium alloy. Materials Science and Engineering: A
2006;441:39.
[112] Deschamps A, Geuser Fd, Decreus B, Malard B. Precipitation in Al-Cu-
Li alloys: from the kinetics of T1 phase precipitation to microstructure
development in friction stir welds. 13th Internation Conference on
Aluminium Alloys. Pittsburgh PA: TMS, 2012.
[113] Bartges C, Tosten MH, Howell PR, Ryba ER. A combined single crystal
X-ray diffraction and electron diffraction study of the T2 phase in Al-Li-Cu
alloys. Journal of Materials Science 1987;22:1663.
[114] Ma Y, Zhou X, Thompson GE, Hashimoto T, Thomson P, Fowles M.
Distribution of intermetallics in an AA 2099-T8 aluminium alloy extrusion.
Materials Chemistry and Physics 2011;126:46.
[115] Starink MJ, Hobson AJ, Gregson PJ. DSC sample preparation for Al-
based alloys. Scripta Materialia 1996;34:1711.
[116] Knipling KE, Dunand DC, Seidman DN. Precipitation evolution in Al–Zr
and Al–Zr–Ti alloys during isothermal aging at 375–425&#xa0;°C. Acta
Materialia 2008;56:114.
[117] Michel DJ, Reed JR, Singh AK, Smith HH. Recrystalline of the T2 phase
in Al---Li---Cu alloys. Scripta Metallurgica 1988;22:525.
[118] Ahmadi S, Arabi H, Shokuhfar A. Formation mechanisms of
precipitates in an Al-Cu-Li-Zr alloy and their effects on strength and electrical
resistance of the alloy. Journal of Alloys and Compounds 2009;484:90.
[119] Brodusch N, Trudeau M, Michaud P, Rodrigue L, Boselli J, Gauvin R.
Contribution of new generation FE-SEM in the undersanding of a 2099 Al-Li
alloy. Montreal: McGill, 2011.

137
[120] Belov NA, Eskin DG, Aksenov AA. Chapter 8 - Alloys with Lithium.
Multicomponent Phase Diagrams. Oxford: Elsevier, 2005. p.257.
[121] Humphreys FJ. Recrystallization and related annealing phenomena /
F.J. Humphreys and M. Hatherly. Oxford, U.K. :: Pergamon, 1995.
[122] Robson JD, Prangnell PB. Modelling Al3Zr dispersoid precipitation in
multicomponent aluminium alloys. Materials Science and Engineering: A
2003;352:240.
[123] Kashyap K. Effect of zirconium addition on the recrystallization
behaviour of a commercial Al-Cu-Mg alloy. Bulletin of Materials Science
2001;24:643.
[124] Lee YS. Microstructures in Over-aged Al–Cu–Li–Mg–Ag Alloys. Journal
of Materials Science Letters 1998;17:1161.
[125] Johnson J, German R. Theoretical modeling of densification during
activated solid-state sintering. Metallurgical and Materials Transactions A
1996;27:441.
[126] Gault B, de Geuser F, Bourgeois L, Gabble BM, Ringer SP, Muddle BC.
Atom probe tomography and transmission electron microscopy
characterisation of precipitation in an Al–Cu–Li–Mg–Ag alloy.
Ultramicroscopy 2011;111:683.
[127] Buffa G, Hua J, Shivpuri R, Fratini L. Design of the friction stir welding
tool using the continuum based FEM model. Materials Science and
Engineering: A 2006;419:381.
[128] Colegrove PA, Shercliff HR. Development of Trivex friction stir
welding tool Part 1; two-dimensional flow modelling and experimental
validation. Science and Technology of Welding & Joining 2004;9:345.
[129] Colegrove PA, Shercliff HR. Development of Trivex friction stir
welding tool Part 2; three-dimensional flow modelling. Science and
Technology of Welding & Joining 2004;9:352.
[130] Colegrove PA, Shercliff HR. 3-Dimensional CFD modelling of flow
round a threaded friction stir welding tool profile. Journal of Materials
Processing Technology 2005;169:320.

138