materials

Article
Effects of the Mg/Si Ratio on Microstructure,
Mechanical Properties, and Precipitation Behavior of
Al–Mg–Si–1.0 wt %-Zn Alloys
Yong Li, Guanjun Gao *, Zhaodong Wang, Hongshuang Di, Jiadong Li and Guangming Xu
State Key Laboratory of Rolling and Automation, Northeastern University, Shenyang 110819, China;
liyong.neu@163.com (Y.L.); zhaodongwang@263.net (Z.W.); dhshuang@mail.neu.edu.cn (H.D.);
lijd@ral.nue.edu.cn (J.L.); xu_gm@epm.neu.edu.cn (G.X.)
* Correspondence: wwwgaoguanjun@126.com; Tel.: +86-159-4012-5505




Received: 10 November 2018; Accepted: 14 December 2018; Published: 19 December 2018


Abstract: Aluminum alloys are widely used as first-choice materials for lightweight automotive
applications. It is important that an alloy have a balance between strength and formability.
In this study, the alloys were melted, cast, hot rolled, and cold rolled into 1 mm-thick sheets.
The microstructure, mechanical properties, and precipitation behavior of Al–Mg–Si–1.0 wt %-Zn
alloys with Mg/Si ratios of 0.5, 1, and 2 after solution treatment were studied using optical and
electron microscopy, a tensile test, the Vickers hardness test, and differential scanning calorimetry.
The results showed that a high density and number of Al–Fe–Si particles were observed in the matrix,
thus causing the formation of more homogeneous and smaller recrystallized grains after treatment
with the solution. In addition, a higher volume fraction of cubeND and P-types texture components
formed during solution treatment. Also, a high r value and excellent deep drawability were achieved
in the medium-Mg/Si-ratio alloy. The formation of denser strengthening precipitates led to a better
paint-bake hardening effect in comparison with the other two alloys. Furthermore, the precipitation
kinetics were enhanced by the addition of Si, and the addition of Zn did not alter the precipitation
sequence of the Al–Mg–Si alloy. The dual-phase strengthening effect was not achieved in the studied
alloys during paint-bake treatment at 175 ◦ C.

Keywords: Al–Mg–Si–1.0 wt %-Zn alloy; Mg/Si ratio; recrystallization; texture; deep drawability;
paint-bake response

1. Introduction
Precipitation hardening of an Al–Mg–Si alloy is an ideal choice for the automobile industry
because of its high strength-to-weight ratio, good formability, excellent corrosion resistance, and low
cost [1–3]. Increased strength in alloys is acquired by paint-bake hardening after the solution is
heat-treated at 560 ◦ C and rapidly quenched to room temperature (RT) [4–6]. During paint-bake
hardening, a large number of transition phases are formed in the matrix, resulting in a strengthening
effect. It is reported that the generally accepted precipitation sequence of Al–Mg–Si alloys during
artificial aging is as follows [7–11]: SSSS → solute clusters → GP (Guinier Preston) zones/pre-β00 →
β00 → β0 , B0 , U1, U2 → β phase → Si particles, where SSSS denotes the supersaturated solid solution.
The GP zones are completely coherent with the matrix and are initially formed by the aggregation
of Mg and Si atoms. The precipitate is semi-coherent with the Al matrix and contains less Si atoms
than the GP zone [8]. Most of the rod-shaped U1, U2, and B0 phases form together with the rod-like
β0 during over-ageing, which results in less strength increments [9]. The equilibrium phase β is FCC
(Face center cubic) in structure. It forms in plates with the composition Mg2 Si. Previous studies have

Materials 2018, 11, 2591; doi:10.3390/ma11122591 www.mdpi.com/journal/materials

Materials 2018, 11, 2591 2 of 14

shown that the semi-coherent, needle-like β00 phase is the main hardening precipitates in Al–Mg–Si
alloys during paint-bake hardening [12].
Mg and Si are the main alloying elements in Al–Mg–Si alloys. The β00 phase forms with
enhanced yield strength during the paint-bake hardening process. Most of the Mg-rich clusters
are formed as a result of the segregation of high-Mg atoms, while high-Si atoms result in the
formation of dispersed Si-rich clusters. Spherical Si particles have a minimal effect on the conductive
behavior of the alloys [13,14]. An important research area is the study of the effects of additional
alloying elements on Al–Mg–Si alloys, because they directly affect the microstructures, as well as the
precipitate structures, during heat treatment [15]. Generally, Zn and Mg atoms form the η0 -MgZn2
hardening phase in Al–Zn–Mg alloys, leading to a strong precipitation-strengthening effect. In addition,
Zn is a trace element in aluminum scrap metal from the recycling process [11,16,17]. Therefore,
Zn-containing Al–Mg–Si alloys are thought to possess a potential bake-hardening response with
an acceptable formability.
In current applications of Al–Mg–Si alloys, different Mg/Si ratios have been extensively studied.
However, several views still remain controversial. For example, the effects of alloy composition on the
microstructure and formability of Zn-containing Al–Mg–Si alloys have yet to be fully explored. It is
not known whether the addition of Zn affects the precipitation behavior of Al–Mg–Si alloys during
an artificial aging treatment. In this study, the effects of adding 1.0 wt % Zn into an Al–Mg–Si alloy
and changing the ratio of Mg/Si during the age-hardening strengthening phases during paint-bake
treatment were studied. The influences of the Mg/Si ratio on the recrystallization behavior during
solid solution treatment and the mechanical properties after pre-aging treatment were also investigated.
The aim of the present work was to find the optimum composition of an Al–Mg–Si alloy with uniform
microstructure, good formability, and rapid aging response and to provide technical support and data
references for the composition design of new alloys and the selection of related heat treatments for in
situ production.

2. Materials and Methods

The compositions of the three tested groups of alloys are presented in Table 1. The total weight
percentages of Mg and Si (Mg + Si) were kept nearly identical for alloys A, B, and C. Three alloys with
Zn content of 1.0 wt % were prepared with 99.7 wt % industrial pure Al and master alloys (Al–20 wt %
Si, Al–20 wt %, Mg and Al–25 wt % Zn). The master alloys were first melted in a graphite crucible and
then poured into copper molds and water cooled at 720 ◦ C. The composition of the studied alloys was
independently determined using inductively coupled plasma atomic emissive spectrometry (ICP-AES,
SPECTRO Analytical Instruments GmbH, Boschstr, Kleve, Germany). After face milling, all ingots
with nominal dimensions of 210 mm × 110 mm × 25 mm were homogenized in an air circulation
furnace at 470 ◦ C for 5 h and then at 540 ◦ C for 16 h. The hot rolling schedule was 25.0 → 21.0 →
16.0 → 11.0 → 7.5 → 6.0 (mm), with the beginning and finishing temperatures of 500 ◦ C and 350 ◦ C,
respectively. In the cold rolling process, the reduction schedule was 6.0 → 3.9 → 2.6 → 1.8 → 1.3 →
1.0 (mm).

Table 1. Chemical composition (in wt %) of the tested alloys.

Alloy Zn wt % Mg wt % Si wt % Fe wt % Mg + Si Mg/Si Comment

A 1.04 0.75 0.76 0.129 1.51 0.99 Medium Mg/Si
B 1.06 1.04 0.52 0.126 1.56 2.00 Excess Mg
C 1.03 0.51 1.03 0.128 1.54 0.50 Excess Si

All sheets were completely recrystallized and solution-treated in an air circulation furnace at
560 ◦Cfor 30 min followed by quenching to RT. Then, the sheets were immediately pre-aged at 140 ◦ C
for 5 min after solution treatment. Finally, these sheets were kept at RT for two weeks (T4P state).
The stamping process was simulated with 2% deformation on a tensile tester. Furthermore, the alloys
Materials 2018, 11, 2591 3 of 14

were artificially aged at 175 ◦ C up to 16 h in an air circulation furnace for the paint-bake treatment.
A schematic representation of the heat treatment procedure is illustrated in Figure 1.
Materials 2018, 11, x FOR PEER REVIEW 3 of 14

Schematicrepresentation
Figure1.1.Schematic
Figure representationof
ofthe
theheat
heattreatment
treatmentprocess
process of
of aluminum
aluminum alloy
alloy sheets.
sheets.

A number
A number of of traditional
traditional testing
testing methods
methods werewere chosen
chosen for for this
this study.
study. According
According to to the
the results
results
obtained with these methods, reference data are provided for practical
obtained with these methods, reference data are provided for practical industrial production. The industrial production.
The artificial
artificial agingaging behavior
behavior of the
of the alloysalloys
waswas studied
studied using
using a Vickers
a Vickers hardnesstester
hardness tester(KB3000BVRZ-SA,
(KB3000BVRZ-SA,
KB Prüftechnik
KB Prüftechnik GmbH,
GmbH, Im Im Weichlingsgarten,
Weichlingsgarten, Hochdorf-Assenheim,
Hochdorf-Assenheim,Germany) Germany)with withaaload
loadof of 49
49 NN
and a dwell time of 10 s to study the artificial aging behavior of the alloys.
and a dwell time of 10 s to study the artificial aging behavior of the alloys. To reduce the error, five To reduce the error,
five indentations
indentations were to
were made made
obtain to the
obtain the hardness
average average hardness
value of each value of The
alloy. eachhardness
alloy. The hardness
values were
values
then were thenAmeasured.
measured. tensile testAwastensile test was at
performed performed
RT usingatan RTINSTRON-4206
using an INSTRON-4206 electronic
electronic universal
universal
testing testing
machine machine
(Instron (Instron Corporation,
Corporation, Norwood, MA, Norwood,
USA) with MA, USA)
a load withofa3 load
speed mm/min. speedThe of
3 mm/min. Theofmicrostructure
microstructure the alloys was ofobserved
the alloysusing
was observed
the Imager usingM2mthe ZEISS
Imagermetallurgical
M2m ZEISS metallurgical
microscope
microscope (ZEISS, Carl-Zeiss-Straße, Oberkochen,
(ZEISS, Carl-Zeiss-Straße, Oberkochen, Germany). The specimens usedGermany). The specimens used forforrecrystallization
recrystallization
microstructure observation
microstructure observation werewere mechanically
mechanically grounded
grounded and and electropolished
electropolished in in aa 10
10 vol
vol% %perchloric
perchloric
acid alcohol
acid alcohol solution
solutionatat25 25VVforfor30 30s.s.Then,
Then,thetheelectropolished
electropolished specimens
specimens werewere anodized
anodized using
using a
a solution consisting of 43 vol % phosphoric acid + 38 vol % sulfuric acid +
solution consisting of 43 vol % phosphoric acid + 38 vol % sulfuric acid + 19 vol % distilled water at 19 vol % distilled water
at V
20 20for
V 2for
min.2 min. The surface
The surface morphologies
morphologies were characterized
were characterized using ULTRA
using a ZEISS a ZEISS55 ULTRA 55 field
field emission
emission scanning electron microscope (SEM) (ZEISS, Carl-Zeiss-Straße,
scanning electron microscope (SEM) (ZEISS, Carl-Zeiss-Straße, Oberkochen, Germany) that was Oberkochen, Germany)
that was equipped
equipped with electron withbackscatter
electron backscatter
diffraction.diffraction. The precipitates
The precipitates formed during formed during
artificial agingartificial
were
aging were observed using a Tecnai G2 F20 transmission electron microscope
observed using a Tecnai G2 F20 transmission electron microscope (TEM) (FEI Company, Hillsboro, (TEM) (FEI Company,
Hillsboro,
OR, USA) OR, USA)
at 200 kV at 200 kV operating
operating voltage. voltage.
The TEM The TEM specimens
specimens were prepared
were prepared usingusing a TenuPol-5
a TenuPol-5 jet-
jet-polisher at an operating voltage of 15 V, and a 30 vol % nitric
polisher at an operating voltage of 15 V, and a 30 vol % nitric acid in methanol solution (stored acid in methanol solution
(stored between −25−30 ◦ C and −30 ◦ C) was used as the electrolyte. The TEM bright-field images
between −25 °C and °C) was used as the electrolyte. The TEM bright-field images revealed that
revealed
the that the
Al matrix wasAlaligned
matrix was
in thealigned
<001>indirection
the <001> in direction in all the
all the tested tested
alloys. alloys. Differential
Differential scanning
scanning calorimetry (DSC) was conducted using a Q100 system (with a heating rate of 10 ◦ C/min)
calorimetry (DSC) was conducted using a Q100 system (with a heating rate of 10 °C/min) under an
underatmosphere
an argon atmosphere in the temperature range of400 ◦
30 °C.C toThe ◦
400specimens
C. The specimens for DSC were
argon in the temperature range of 30 °C to for DSC were cleaned
cleaned
using anusing an ultrasonic
ultrasonic cleaning cleaning
machine, machine,
and an andempty
an emptypurepure aluminum
aluminum crucible
crucible waswasused
usedasasthe the
reference material.
reference material.

3. Results and Discussion

3. Results and Discussion
3.1. Microstructures
3.1. Microstructures
Figure 2 displays the recrystallized grains of the three groups of alloys after the solution treatment.
The medium2 Mg/Si
Figure displays the(alloy
alloy recrystallized grains
A) exhibited of the
smaller andthree groups
narrowly of alloysrecrystallized
distributed after the solution
grain
treatment.
sizes of 185The medium
µm. In contrast,Mg/Si alloyMg
the excess (alloy
alloy A) exhibited
(alloy smaller
B) and the excess and narrowly
Si alloy (alloy C)distributed
developed
recrystallized grain sizes of 185
coarse and inhomogeneous μm. In contrast,
recrystallized grainsthe excess
after Mg alloy
solution (alloy The
treatment. B) and the excess
average grain Si alloy
sizes of
(alloy C) developed coarse and inhomogeneous recrystallized
alloys B and C were found to be 203 and 259 µm, respectively. grains after solution treatment. The
average grain sizes of alloys B and C were found to be 203 and 259 μm, respectively.
Materials 2018, 11, 2591 4 of 14
Materials 2018, 11, x FOR PEER REVIEW 4 of 14

Figure 2.
Figure 2. Recrystallized
Recrystallizedgrain
grainstructures
structuresafter
aftersolution
solutiontreatment:
treatment:
(a)(a) alloy
alloy A;A;
(b)(b) alloy
alloy B; and
B; and (c) (c) alloy
alloy C.
C.
The SEM images showed the distribution of the particles (red arrow) in the alloys, as shown in
Figure
The3. It
SEMwasimages
observed that alloy
showed A caused a homogeneous
the distribution of the particlesparticle distribution;
(red arrow) the density
in the alloys, as shownof the
in
particles
Figure 3. decreased in alloys
It was observed thatBalloy
and C. It was also
A caused discernible that
a homogeneous somedistribution;
particle particles existed at the of
the density grain
the
boundary (GB), andin
particles decreased most particles
alloys B and were distributed
C. It was in the matrix.
also discernible Energy
that some dispersive
particles X-ray
existed analysis
at the grain
(EDS) revealed
boundary (GB),that
andthe particles
most contained
particles Al, Si, andinFe.
were distributed It matrix.
the is proposed thatdispersive
Energy the particles most
X-ray likely
analysis
consisted of stable
(EDS) revealed thatα-Al–Fe–Si phases,
the particles whichAl,
contained were often
Si, and Fe.observed in the that
It is proposed Al–Mg–Si alloy [18–20].
the particles most likely
consisted of stable α-Al–Fe–Si phases, which were often observed in the Al–Mg–Si alloy [18–20].
Materials 2018, 11, 2591 5 of 14
Materials 2018, 11, x FOR PEER REVIEW 5 of 14

Figure
Figure 3.3. SEM
SEMimages
imagesofofparticle
particledistribution
distributioninin
the solution-treated
the alloys:
solution-treated (a) (a)
alloys: alloy A; (b)
alloy alloy
A; (b) B; (c)
alloy B;
alloy C, and (d) EDS spectra of the particles.
(c) alloy C, and (d) EDS spectra of the particles.

The
The recrystallized
recrystallized grains
grains first
first nucleated
nucleated andand grew
grew at a position of high-energy fluctuation
(dislocation, large
large particles,
particles,andandsosoon)on)during
duringsolution
solution treatment.
treatment. TheThe number
number andand distribution
distribution of
of the
the
largelarge particles
particles had a had
greatainfluence
great influence on the recrystallization
on the recrystallization grains [21].grains
In this [21].
study,Inthethis study, the
homogeneous
homogeneous
and high-density andlarge
high-density
Al–Fe–Silarge Al–Fe–Si
particles particles
in alloy A acted in as
alloy A acted sites
nucleation as nucleation sites for the
for the recrystallized
recrystallized grains,the
grains, thus causing thus causingofthe
formation formation
smaller grains of smaller
during grainstreatment.
solution during solution
However, treatment.
in alloys
However,
B and C, the in alloys
number B of
and C, the
large number
Al–Fe–Si of largewas
particles Al–Fe–Si particles
relatively wasthe
low, and relatively low, was
distribution and thenot
distribution was not uniform, which led to the uneven nucleation of recrystallized
uniform, which led to the uneven nucleation of recrystallized grains (Figure 3). In addition, because grains (Figure 3).
In
theaddition, becauseofthe
recrystallization therecrystallization
alloy was completed of thebefore
alloy the
wassoluble
completed before
particles the soluble
re-dissolved intoparticles
the matrix,re-
dissolved into that
it was inferred the compared
matrix, it to was inferred
alloys B andthat compared
C, more solubletosmall
alloys B and existed
particles C, more soluble
in alloy small
A before
particles existed in alloy
solution treatment. TheseAsmall
before solutionexerted
particles treatment. These
a Zener small
drag andparticles exerted
effectively a Zener
retarded drag and
the migration
effectively retarded the
of grain boundaries, whichmigration of formation
led to the grain boundaries,
of uniformwhich
and led to recrystallized
small the formationgrains of uniform
[21]. and
small recrystallized grains [21].
3.2. Deep Drawability Analysis
3.2. Deep Drawability Analysis
Figure 4 shows the recrystallization textures in the three groups of alloys after solution treatment.
AlloyFigure
A displayed Cubethe
4 shows ND and P orientationstextures
recrystallization with intensities
in the ofthree
5.61 and 2.09, of
groups respectively.
alloys after Thesolution
volume
fraction of Alloy
treatment. the P A
component
displayedwas Cube 9.71%.
ND andIn P contrast,
orientationsthe with
B and C alloys consisted
intensities of 5.61 andof2.09,
lower intensities
respectively.
and volume
The smaller volume
fractionfractions of the P component
of the P component was 9.71%. (Table 2). Accordingly,
In contrast, the B andtheCdensity and distribution
alloys consisted of lower of
the large Al–Fe–Si particles affected not only the recrystallized grains but also the
intensities and smaller volume fractions of the P component (Table 2). Accordingly, the density and texture components
and intensities.
distribution of the large Al–Fe–Si particles affected not only the recrystallized grains but also the
texture components and intensities.
Materials 2018, 11, 2591 6 of 14
Materials 2018, 11, x FOR PEER REVIEW 6 of 14

Figure Recrystallization
4. 4.
Figure textures
Recrystallization texturesininthe
thesolution-treated
solution-treatedalloys:
alloys:(a)
(a)alloy
alloyA;
A;(b)
(b)alloy
alloyB;B;and
and(c)
(c)alloy
alloyC.
C. Table 2. Volume fractions of recrystallization textures in the solution-treated alloys.

Table 2. Volume
Alloy fractions of recrystallization
Component Intensitytextures in theFraction
Volume solution-treated
(%) alloys.

Alloy CubeND
Component 5.61
Intensity 5.72
Volume Fraction (%)
A
Cube
P ND 5.61
2.09 5.72
9.71
A
P
CubeND 2.09
13.12 9.71
9.82
B CubeND 13.12 9.82
B P 1.34 4.58
P 1.34 4.58
Cube 6.72 8.28
C CubeND
ND 6.72 8.28
C P 1.16 3.11
P 1.16 3.11

TheTher values
r valuesofofthe
thethree
threegroups
groupsof ofalloys
alloys were
were calculated using aa 15%
calculated using 15%deformation
deformationininthree
three
different
different directions,asasshown
directions, shownininFigure
Figure5.5.ItIt was
was obvious
obvious that
that the
the rr value
valueofofalloy
alloyAAwas
washigher
higherthan
than
those
those ofof
thethe othertwo
other twoalloys ◦
alloysatata a4545°direction.
direction. At
At a 90 ◦
90° direction,
direction,alloy
alloyCCmanifested
manifestedthe
thelowest
lowestr r
value.
value. TheThe averager value
average r value(Figure
(Figure5b) 5b)was
wascalculated
calculated using
using

r=◦ + 2r45◦ + r90, ◦ (1)

r= 0 , (1)
where , 45o , and 90o are the r values in three 4different directions. The result revealed that the
average
r0◦ , rrvalue decreased from alloy A to alloy C. Therefore, the alloy A possessed relatively better
where 45 , and r90 are the r values in three different directions. The result revealed that the
◦ ◦

deep drawability.
average r value decreased from alloy A to alloy C. Therefore, the alloy A possessed relatively better
deep drawability.
Materials 2018, 11, x FOR PEER REVIEW 7 of 14
Materials 2018, 11, 2591 7 of 14
Materials 2018, 11, x FOR PEER REVIEW 7 of 14

Figure 5. (a) Values of r in three different directions; (b) the calculated average r values of alloys A, B,
Figure
Figure 5. (a)
5. (a) Values
Values ofof r inthree
r in threedifferent
differentdirections;
directions; (b)
(b) the
the calculated
calculatedaverage
averager rvalues
valuesofof
alloys A,A,
alloys B, B,
and C.
and
and C. C.

The
The texture
texture components
components significantly
significantly affected
affected thethe rr values
r values and
andand the
thethe
cube cubeND ND and P components,
The texture components significantly affected the values ND and
cube andP components,
P components, and
and
these these
andwere
thesewere favorable
were favorable
favorable for
for deepfor deep drawability
deep drawability
drawability of the Al–Mg–Si
of the Al–Mg–Si
of the Al–Mg–Si alloys.
alloys.
alloys. It was It was
It wasthat
reported reported
reported thatthether
that
the stimulated
stimulated
stimulated
values r values
for the rcube
values forfor
and the
thecube
the Pcube and
andthe
component thePPwere
component
0.5 andwere
component were 0.5 and
0.5 and2.8,
2.8, respectively 2.8,respectively
respectively
[22–24]. Liu[22–24].[22–24].
et Liu
Liu
al. [25] et et
al.al.
posited
[25] posited
that[25]
theposited that
cubeND thatthe cube component
the cubeNDresulted
component ND component resulted
in aresulted in a
higher rinvalue higher
a higher r value
r value
(>0.5) (>0.5)
than(>0.5)
the cube than the
thancomponent. cube component.
the cube component. Moreover,
Moreover,
Moreover, when
when a certain
a certain number
number of
of coarse
coarse particles
particles (>1 μm)
μm) existed
existed
when a certain number of coarse particles (>1 µm) existed in the matrix, a particle stimulated nucleation in
in the
the matrix,
matrix, a aparticle
particle
stimulated nucleation (PSN) response occurred in the alloys during
(PSN) response occurred in the alloys during solution treatment. In alloy A, homogeneous A,
stimulated nucleation (PSN) response occurred in the during solution
solution treatment.
treatment. In In alloy
alloy A,
and
homogeneous
homogeneous and and high-density
high-density large
large Al–Fe–Si
Al–Fe–Si particles
particles were
were observed
observed
high-density large Al–Fe–Si particles were observed in the matrix, and recrystallization nuclei formed inin thethe matrix,
matrix, andand
recrystallization nuclei formedaround
recrystallization
around these large nuclei formed
particles. Thisaround
process theselarge
these large particles.
resulted particles. This
in This process
the increment of theresulted
process cubeNDinin
resulted the
and the
Pincrement
increment
components. of of
the the
cubecube and
and
ND ND P P components.InIncontrast,
components. contrast,aanonuniform
nonuniform distribution
distribution of
oflow-density
low-density large
large Al–Fe–Si
Al–Fe–Si
In contrast, a nonuniform distribution of low-density large Al–Fe–Si particles formed in both the B and
particles
particles formed
formed in boththetheBBand andCCalloys,
alloys,causing
causing aa decrease
decrease in the
thePvolume fraction ofofthe cube
aindecrease
both cubeND in volume fraction the cubeNDND
C alloys, causing in the volume fraction of the and components. Although a large
and P components.
and P components. Although a large number of clusters formed in the matrix of the three alloys after
number of clusters Although
formed inathe large number
matrix of clusters
of the three alloys formed afterin pre-aging,
the matrix this of the had three alloys
little effectafter
on
pre-aging,
pre-aging, this
this had hadlittle
littleeffect
effecton onthe
thedeep
deep drawability.
drawability. The The grain
grain morphology
morphology also
also profoundly
profoundly
the deep drawability. The grain morphology also profoundly influenced the r values. The small
influenced
influenced thethe r values.The
r values. Thesmall
smalland anduniform
uniform recrystallized
recrystallized grainsgrains contributed
contributed to a ahigher r value
and uniform
[24]. Hence,recrystallized
the alloy A achievedgrains contributed
improved deep higher r value
to adrawability. [24]. Hence, thetoalloy higher r value
A achieved
[24]. Hence, the alloy
improved deep drawability. A achieved improved deep drawability.
3.3. Simulated Paint-Bake Cycle and Precipitation-Hardening Behavior
3.3. Simulated
3.3. Simulated Paint-Bake
Paint-Bake Cycle and Precipitation-Hardening
Cycle and Precipitation-Hardening Behavior
Behavior
Figure 6 shows the engineering stress strain curves of the three groups of the alloys before 2%
Figure 6
Figure 6 shows
shows the the engineering stress strain
strain curves of the three groups of the
the alloys
alloys before 2%
deformation and afterengineering
the paint-bakestress
treatment curves
at 185of°Cthe forthree groups
30 min. Theofincrements before
of yield2%
deformation
deformation and0.2after thethe paint-bake treatment at ◦ 185
C for°C for
min.30 min. The increments of yield
strengths, andΔRpafter , before paint-bake
and after treatment at 185
the paint-bake treatment 30were The increments
measured (Figureof 7).
yield strengths,
Before 2%
∆Rp
strengths,
, ΔRp
before
deformation
0.2
0.2, before
(T4P state), the yield strengths of alloys A and B were similar, whereas alloy C2%
and after and
the after the
paint-bake paint-bake
treatment treatment
were measured were measured
(Figure 7). (Figure
Before 2% 7). Before
deformation
deformation
(T4P state), the
manifested (T4P
yield
a lower state),
value.the
strengths yield
ofthe
After strengths
alloys of alloyssimilar,
A and paint-bake
simulated B were A andwhereas
treatment,B were
the △Rpsimilar,
alloy0.2 C
whereas
manifested
value of alloy Aalloy
a was C
lower
manifested
value.
higherAfter athe
thanlower value.
simulated
those Aftertwo
the alloys,
paint-bake
of the other simulated
treatment, paint-bake
the 4
as shown in Rp treatment,
0.2 value
Figure 7. of alloythe △Rp
A was 0.2 value
higherofthan
alloythose
A was
of
higher than those of the other two
the other two alloys, as shown in Figure 7. alloys, as shown in Figure 7.

Figure 6. Cont.
Materials 2018, 11, 2591 8 of 14
Materials 2018, 11, x FOR PEER REVIEW 8 of 14
Materials 2018, 11, x FOR PEER REVIEW 8 of 14

Figure 6. Engineering stress–strain curves of the alloys before and after the paint-bake treatment at
Figure 6. Engineering stress–strain
stress–strain curves
curves of the alloys before and after the paint-bake treatment at
185 °C for 30 min: (a) alloy A; (b) alloy B; and (c) alloy C.
185 ◦°C
C for 30 min: (a) alloy A; (b) alloy B; and (c) alloy C.

Figure 7. Increment of yield strength before and after the simulated paint-bake treatment.
treatment.
Figure 7. Increment of yield strength before and after the simulated paint-bake treatment.
A
A clustering
clusteringofofsupersaturated
supersaturated solute atoms
solute occurred
atoms in the in
occurred matrix
the during
matrix the pre-aging
during treatment
the pre-aging
A ◦clustering of supersaturated solute atoms occurred in the matrix during the pre-aging
at 140 C for 5 min. Before the paint-bake treatment, the strength of the alloys
treatment at 140 °C for 5 min. Before the paint-bake treatment, the strength of the alloys dependeddepended on the
treatment at 140 °C for 5 min. Before the paint-bake treatment, the strength of the alloys depended
number of clusters
on the number and the and
of clusters recrystallized grain morphology.
the recrystallized Pre-agingPre-aging
grain morphology. was a short-term heat-treatment
was a short-term heat-
on the number of clusters and the recrystallized grain morphology. Pre-aging was a short-term heat-
process that occurred at a low temperature, resulting in a small number of clusters
treatment process that occurred at a low temperature, resulting in a small number of clusters thatthat formed in the
treatment process that occurred at a low temperature, resulting in a small number of clusters that
matrix
formed[26]. The
in the recrystallization
matrix microstructuremicrostructure
[26]. The recrystallization revealed an increase in an
revealed theincrease
size of the recrystallized
in the size of the
formed in the matrix [26]. The recrystallization microstructure revealed an increase in the size of the
grain in alloysgrain
recrystallized A and inC. AlloyACand
alloys exhibited
C. Alloyrelatively largerrelatively
C exhibited grains. Under
larger agrains.
similarUnder
applied stress,
a similar
recrystallized grain in alloys A and C. Alloy C exhibited relatively larger grains. Under a similar
the stress concentration on the smaller grains was weak. Plastic deformation of the
applied stress, the stress concentration on the smaller grains was weak. Plastic deformation of the adjacent grains
applied stress, the stress concentration on the smaller grains was weak. Plastic deformation of the
required a largerrequired
adjacent grains appliedastress.
largerThe conventional
applied stress. TheHall–Petch
conventional relationship
Hall–Petchis given by
relationship is given by
adjacent grains required a larger applied stress. The conventional Hall–Petch relationship is given by
/
= +k y d−1/2 / ,, (2)
σy == σo ++ , (2)(2)
where is the yield stress, is the lattice friction stress, and is a constant of yielding. The
where σy isisthe
where theyield
yield stress,
stress, is lattice
σo is the the lattice friction
friction stress, stress,
and kand is a constant
y is a constant of yielding.
of yielding. The
The smaller
smaller the grain size was, the higher the yield strength was [27]. However, the average grain size of
smaller
the grain the grain
size was,size was,
the the higher
higher the yieldthestrength
yield strength
was [27].was However,
[27]. However, the average
the average graingrain
size size of
of the
the three groups of alloys was large (≥180 μm), and was very small for Al in this study. Therefore,
the three
three groups
groups of alloys
of alloys was was large
large (≥(≥180 μm),and
180 µm), andk y was wasvery
verysmall
smallfor
forAlAlinin this
this study.
study. Therefore,
Therefore,
the contribution
the contribution of of grain
ofgrain size
grainsize totothe
sizeto theincrement
increment of thethe alloy’s strength was not significant [28]. The
contribution the increment of of alloy’s
the alloy’s strength
strength waswas not significant
not significant [28]. [28].
The
clusters
The rapidly
clusters grew
rapidly along
grew alongone direction during the paint-bake treatment, and lattice distortion in
clusters rapidly grew along oneone direction
direction during
during thethe paint-baketreatment,
paint-bake treatment,and andlattice
lattice distortion
distortion in
the matrix
the matrix was was introduced
introduced by by the
the grown
grown precipitates.
precipitates. Consequently, the precipitate pinning forces
precipitates. Consequently, the precipitate pinning forces
on moving dislocations were strong
on moving dislocations were strong and acted as and acted as effective
effective obstacles
obstacles for the dislocation
for the dislocation movement.
movement.
dislocation movement.
These factors
These factors eventually increased the strength of the alloys [12]. A high strength was achieved by
factors eventually
eventuallyincreased
increasedthe thestrength
strengthofofthethealloys [12].
alloys A high
[12]. A high strength
strengthwaswasachieved by the
achieved by
the formation
formation of strengthening
of strengthening precipitates
precipitates and
andand a sufficient
a sufficient supply
supply of supersaturated
of supersaturated solute
solute Mg
MgMg andand
Si
the formation of strengthening precipitates a sufficient supply of supersaturated solute and
Si atoms
atoms in in alloy
alloy A. A. Coarse
Coarse Al–Fe–Si
Al–Fe–Si particlesparticles
existed existed
in the in thebefore
matrix matrix and before
after and after paint-bake
paint-bake hardening.
Si atoms in alloy A. Coarse Al–Fe–Si particles existed in the matrix before and after paint-bake
hardening.
These coarse These coarse
particles particles possessed
possessed poor deformation-coordination ability and became the
hardening. These coarse particles poor deformation-coordination
possessed poor deformation-coordination ability andability
became the
and sourcethe
became of
source of cracks in the tensile deformation process of the alloy, which reduced the elongation of the
source of cracks in the tensile deformation process of the alloy, which reduced the elongation of the
Materials 2018, 11, 2591 9 of 14

Materials 2018, 11, x FOR PEER REVIEW 9 of 14

cracks in the tensile deformation process of the alloy, which reduced the elongation of the alloy [29].
Hence, theHence,
alloy [29]. elongation increased with
the elongation a decrease
increased with aindecrease
the number in theofnumber
Al–Fe–Siofparticles
Al–Fe–Sifrom alloyfrom
particles A to
alloy C
A (Figure
to alloy 6).C (Figure 6).
The Vickers hardness curves of the three groups of alloys with paint-bake treatment for 16 h are
Materials 2018, 11, x FOR PEER REVIEW 9 of 14
presented in Figure 8. The The figure shows that the hardness of the alloys increased with prolonged
aging alloy
time,[29]. ◦ C after 10
a nearly
andHence, the constant
elongationvalue
increased attained
waswith
attained at 175
a decrease in °C
the after
number10 of paint-baking
h Al–Fe–Si
of paint-baking treatment.
particles treatment.
from
The hardness of alloy A was
alloy A to alloy C (Figure 6). higher than that of alloys B and C and increased rapidly within the first
30 min. This Vickersagrees
Thefinding hardnesswith theof
curves result shown
the three in
in Figure
groups of alloys
Figure 7.
7.with paint-bake treatment for 16 h are
presented in Figure 8. The figure shows that the hardness of the alloys increased with prolonged
aging time, and a nearly constant value was attained at 175 °C after 10 h of paint-baking treatment.
The hardness of alloy A was higher than that of alloys B and C and increased rapidly within the first
30 min. This finding agrees with the result shown in Figure 7.

Figure
Figure 8.
8. Vickers
Vickers hardness curves of
hardness curves of the
the alloys
alloys with
with paint-bake
paint-bake treatment
treatment at 175 ◦°C
at 175 for 16
C for 16 h.
h.

Figure 99 displays the ◦ C for

displays thebright-field
Figure 8. Vickers
bright-field TEM
hardness curvesTEM ofimages
the
images ofof
alloys the
with
thealloys after
paint-bake
alloys paint-bake
treatment
after hardening
at 175 °C
paint-bake for 16 h. at 175
hardening at 175 °C
10 h. All images were acquired along
for 10 h. All images were acquired along the Al the <100> zone axis. In the three groups of alloys,
<100>Al zone axis. In the three groups of alloys, high high amounts
Figure 9 displays the bright-field TEM images of the alloys after paint-bake hardening at 175 °C
of fine dot-like
amounts of fine and needle-like
dot-like and precipitates
needle-like were uniformly
precipitates distributed
were uniformly in the Al in
distributed matrix.
the AlThe dot-like
matrix. The
for 10 h. All images were acquired along the <100>Al zone axis. In the three groups of alloys, high
precipitates
dot-like appeared
precipitates needle-like
appeared when viewed
needle-like when end-on
viewedin another
end-on direction.
in another In
amounts of fine dot-like and needle-like precipitates were uniformly distributed in the Al matrix. The
alloy A,
direction. a dense
In amount
alloy A, a
of strengthening
dense dot-like precipitates
amountprecipitates
of strengthening were
appeared observed
precipitates in
needle-like were the matrix,
when observed and
viewed end-on most of the
in theinmatrix, precipitates
anotherand most of
direction. were
Inthe larger than
precipitates
alloy A, a
those in
were largeralloys
dense than B and
amount of C.
those inThis wasB why
alloys
strengthening and alloy
C. This
precipitates Awere
possessed
was why theinhighest
alloy
observed A hardness
possessed
the matrix, and the among
highest
most the three among
of the hardness
precipitates groups
of
thealloys.
were
three The
groups HRTEM
larger than andinThe
those
of alloys. the corresponding
alloys B and C.
HRTEM fast
Thisthe
and was Fourier
why alloytransform
corresponding A possessed (FFT) patterns
the highest
fast Fourier of the
hardness
transform precipitates
among
(FFT) patterns
are
of the the threein
exhibited groups
precipitates areofexhibited
Figure alloys.
10. The The inHRTEM
Figureand
orientation the
Thecorresponding
relationships
10. between
orientation fast Fourier transform
the precipitates
relationships between (FFT)
and patterns
thethe Al matrix
precipitates
were of the
(010)Al precipitates are exhibited in Figure 10. The orientation relationships between the precipitates
and the β00 //(001)
matrix Al , [100]
were β00 //[320]
(010) β″//(001) Al,, and
Al [100][001] β00 //[130]
β″//[320] Al, and Al .[001]
Thisβ″observation
//[13̅0]Al. This is consistent
observation withis
and the Al matrix were (010)β″//(001)Al, [100]β″//[320]Al, and [001]β″//[13̅0]Al. This observation is
previous studies by Yang et al. [30]. On the basis of the HRTEM and
consistent with previous studies by Yang et al. [30]. On the basis of the HRTEM and FFT patterns, the FFT patterns, the precipitates
consistent with previous studies by Yang et al. [30]. On the basis of the HRTEM and FFT patterns, the
observed
precipitateswere identified
observed were the β00 phase,
as identified which
asasthe was the mainwas hardening precipitate in the Al–Mg–Si
precipitates observed were identified theβ″
β″ phase, which
phase, which was thethe main
main hardening
hardening precipitate
precipitate in in
alloy system.
the Al–Mg–Si alloy system.
the Al–Mg–Si alloy system.

Figure 9. Cont.
Materials 2018, 11, x FOR PEER REVIEW 10 of 14
Materials 2018, 11, 2591 10 of 14
Materials 2018, 11, x FOR PEER REVIEW 10 of 14

FigureFigure
9. TEM9. TEM
TEM images
images
images ofthe
ofofthe the alloysafter
alloys
alloys after the
afterthe paint-bake
thepaint-bake hardening
paint-bake treatment
hardening
hardening at 175
treatment
treatment at °C
at for
175 °C10◦for
175 h: for
C (a) 10(a)
10 h: h:
alloy A; (b) alloy B; and (c) alloy C.
(a) alloy
alloy A; (b)
A; (b) alloy
alloy B; and
B; and (c) (c)
alloyalloy
C. C.

Figure 10. (a) HRTEM and (b) FFT patterns of the precipitates in the alloys after the paint-bake
hardening treatment at 175 °C for 10 h.

FigureHigh
Figure 10. (a)
10. Zn HRTEM
(a) (1.0
HRTEM wt %)and was (b)
and added
(b) FFT
FFTtopatterns
the threeof
patterns of the precipitates
groups
the precipitates in the
the alloys
of alloys. However,
in alloys
only β”after the paint-bake
paint-bake
precipitates
after the were
observed along
hardening treatment
hardening the
treatment at <001>
at 175
175 °C
Al ◦direction,
for 10
C for while
10 h.
h. no plate-like precipitates were found on the {111} Al plane,
which was an effective strengthening phase for Al–Zn–Mg alloy system. This demonstrated that the
η′ phase
High Zn did
(1.0not
Zn (1.0 wtwtform
%)
%)was in the
was added studied
added totoalloys.
the three
the It isgroups
three worth noting that However,
of alloys.
groups of alloys.the normal agingonly
only
However, β” β00 precipitates
temperature
precipitatesof were
the
observed Al–Zn–Mg
alongalong alloys
the <001> was lower
Al direction,
than 120
while no°C. Therefore,
plate-like it was impossible
precipitates that
were foundthe η′ strengthening
on theon {111} plane,
were observed the <001> Al direction, while no plate-like precipitates were found theAl{111} Al
phase formed in the Al–Mg–Si alloy during paint-bake treatment at 175 °C [16]. The EDS analysis
which which
plane, was anwas effective strengthening
an effective phase for
strengthening phaseAl–Zn–Mg alloy system.
for Al–Zn–Mg This demonstrated
alloy system. that the
This demonstrated
(Figure 11) revealed that most of the Zn atoms existed in the Al matrix, and the alloys were
0 phase
η′ phase
that the did not form did in theformstudied alloys. It is worth noting that the normal agingthetemperature of
η
strengthened by thenot in the
solution strengthening studied
response.alloys. It is worth
Therefore, no othernoting that
precipitates formed normal
during aging
the Al–Zn–Mg
temperature alloys
of the hardeningwas
Al–Zn–Mg lower than
alloys 120 °C. Therefore, ◦
it was impossible that the η′ strengthening 0
the paint-bake at 175 °C, was lower
and the thanof120
addition Zn didC. not
Therefore,
alter the it was impossible
precipitation sequencethat
of the η
phase the
formed
strengthening in the
phase Al–Mg–Si
formed in the alloy duringalloy
Al–Mg–Si paint-bake treatment at
during paint-bake 175 °C [16].
treatment ◦
at 175The EDS The
C [16]. analysis
EDS
Al–Mg–Si alloy.
(Figure 11)
analysis revealed
(Figure that most
11) revealed thatof theofZn
most theatoms existed
Zn atoms in the
existed AlAl
in the matrix,
matrix,and
andthe
the alloys
alloys were
strengthened by the solution strengthening response. Therefore, no other precipitates formed during
the paint-bake hardening at 175 ◦°C,
C, and the addition of Zn did not alter the precipitation sequence of
the Al–Mg–Si alloy.
alloy.
Materials 2018, 11, 2591 11 of 14
Materials 2018, 11, x FOR PEER REVIEW 11 of 14
Materials 2018, 11, x FOR PEER REVIEW 11 of 14

Figure 11.
Figure 11. (a)(a)
11.(a) TheThe
The EDSEDS
EDS measurement
measurement point in
measurement
point in the matrix
point
the matrix and
in theand (b) the
matrix
(b) the EDS
and spectra
(b)spectra
EDS of the
the EDS
of the measurement
spectra of the
measurement
point.
measurement
point. point.

DSC analysis
DSC
DSC analysis was
analysis was conducted
was conductedto
conducted toinvestigate
to investigatethe
investigate theeffects
the effectsof
effects ofvarious
of variousMg/Si
various Mg/Si ratios
Mg/Si ratios and
ratios and Zn
and Zn content
Zn content on
content on
on
the
the precipitation
the precipitation sequence
precipitation sequence
sequence of of the
of the Al–Mg–Si
the Al–Mg–Si
Al–Mg–Si alloy. alloy. Figure
alloy. Figure
Figure 12 12 shows
12 shows
shows the the DSC
the DSC curves
DSC curves
curves of of the three
the three
of the groups
three groups
groups
of
of alloys
alloys after
after PA
PA (Pre-aging)
(Pre-aging) treatment
treatment at
at 140
140 ◦°C
C for
for 55 min.
min. Three
Three exothermic
exothermic peaks
peaks that
that coincided
coincided
of alloys after PA (Pre-aging) treatment at 140 °C for 5 min. Three exothermic peaks that coincided
with the
with the precipitations
precipitations of of the
the GP GP zone,
zone, ββ″ β″00 phase,
phase, and and β β′0 phase
phase were were observed
observed in in each
each alloy
each alloy in in the
the
with the precipitations of the GP zone, phase, and β′ alloy in the
temperature range
temperature range from
range from 30
from 30 °C◦
°C to 400
C to 400 °C◦°C [31–34]. In
C [31–34]. In alloys
alloys A A andand B,B, the
the exothermic
exothermic peakspeaks of ofthetheββ″ 00
β″
temperature 30 to 400 [31–34]. In alloys A and B, the exothermic peaks of the
phase appeared
phase appeared at at ~275
~275 °C.◦
°C.
C. However,
However, in in alloy
alloy C, C, the
the peak
peak of of thethe β 00
β″ phase
phase was was observed
observed at at ~255
~255 °C.◦°C.
C.
phase appeared at ~275 in alloy C, the peak of the β″ phase was observed at ~255
Excess
Excess
Excess Si Si effectively
Si effectively increased
effectively increased
increased the the precipitation
the precipitation
precipitation kinetics kinetics
kinetics by by changing
by changing
changing the the Mg/Si
the Mg/Si ratio
Mg/Si ratio in thein the initial
the initial
initial
clusters
clusters that
that formed
formed during
during PA
PA treatment.
treatment. Additionally,
Additionally, excess
excess
clusters that formed during PA treatment. Additionally, excess Mg decreased the solubility of Mg Mg
Mg decreased
decreased the
the solubility
solubility of
of MgMg222Si
Si
Si
in
in the
the matrix,
matrix, and
and the
the growth
growth of
of MgMg Si
2Si phase
phase consumed
consumed the
the
in the matrix, and the growth of Mg22Si phase consumed the supersaturated solute atoms, which ledsupersaturated
supersaturated solute
solute atoms,
atoms, which
which led
led
to aaa suppression
to suppression of of the
the precipitation
precipitationkinetics kineticsof ofthe
theββ″ 00 phase
β″ phase [35].
[35]. Hence,
Hence, this this indicated
indicated that that SiSi could
could
to suppression of the precipitation kinetics of the phase [35]. indicated that Si could
decrease the
decrease the peak
peak temperature
temperatureof ofthe
theβ 00
β″ precipitate
precipitate in in the
the DSC
DSC curves. Generally,
curves. Generally,
Generally, Zn Zn and
and Mg Mg formed
formed
formed
decrease the peak temperature of the β″ Zn and Mg
the
the strengthening phases, 0
η′ and η, in the Al–Zn–Mg alloy. The peaks at the temperatures of ~185 ◦°C
the strengthening
strengthening phases,
phases, ηη′ and and η, η, in
in the
the Al–Zn–Mg
Al–Zn–Mg alloy. alloy. The
The peaks
peaks at at the
the temperatures
temperatures of of ~185
~185 °C C
and
and ~230
~230 ◦
°CC were related to the η′
η 0 and
and η
η phases,
phases, respectively
respectively [11,16]. However,
However, no obvious exothermic
exothermic
and ~230 °C were related to the η′ and η phases, respectively [11,16]. However, no obvious exothermic
peaks existed
peaks
peaks existed at
existed at these
at these temperatures
these temperatures in
temperatures in the
in the DSC
the DSC curves.
DSC curves. The
curves. The η′ ηη′0 or ηη phase
or η phase did
phase did not
did not form
not form in
form in the
in the matrix
the matrix
matrix
during
during
during the the artificial
the artificial aging
artificial aging treatment.
aging treatment.
treatment. Hence, Hence,
Hence, the the peaks
the peaks related
peaks related
related to to the
to the precipitation
precipitation or
the precipitation or phase
or phase
phase in in the
in the DSC
DSC
the DSC
curves also
curves
curves also indicated
also indicated that
indicated that the
that the addition
the addition of
addition of elemental
of elemental Zn
elemental Zn did
Zn did not
did not alter
not alter the
alter the precipitation
the precipitation sequence
precipitation sequence of
sequence of the
of the
the
Al–Mg–Si
Al–Mg–Si
Al–Mg–Si alloy. alloy.
alloy.

Figure 12. DSC flow curves of the (a) alloy A; (b) alloy
alloy B; and
and (c) alloy
alloy C after
after PA (Pre-aged)
(Pre-aged) treatment
Figure 12. DSC flow curves of the (a) alloy A; (b)
(b) alloy B;
B; and (c)
(c) alloy C
C after PA
PA (Pre-aged) treatment
at 140 °C
at 140 ◦°C for 5 min.
C for 5 min.
Materials 2018, 11, 2591 12 of 14

4. Conclusions
The influence of Zn content and different Mg/Si ratios on the microstructure, mechanical
properties, and the precipitation behavior of Al–Mg–Si alloys was investigated in this study.
The following inferences can be drawn from the results of this research.

1. The composition-optimized alloy was a medium-Mg/Si-ratio alloy. In this alloy, more homogeneous
and smaller recrystallized microstructures combined with high r value and excellent deep
drawability were developed in comparison with the other two alloys.
2. In the medium-Mg/Si-ratio alloy, the denser and larger strengthening precipitates contributed to
a better paint-bake hardening response. Zn atoms existed in the matrix as supersaturated solute
atoms and strengthened the alloys to a certain extent.
3. The addition of Zn did not affect the precipitation sequence of the Al–Mg–Si alloy. No other
precipitates formed, and the dual-phase strengthening effect was not achieved in the three groups
of alloys during paint-bake treatment at 175 ◦ C.

Author Contributions: Conceptualization, Y.L. and G.G.; software, J.L.; validation, Y.L. and G.G.; investigation,
all authors; data curation, Y.L., G.G., H.D. and G.X.; writing—original draft preparation, Y.L. and G.G.;
writing—review and editing, Y.L. and G.G.; project administration, Y.L. and Z.W.; funding acquisition, Y.L.
and Z.W.
Funding: This project was supported by the National Natural Science Foundation of China, grant number 51790485.
Acknowledgments: The authors acknowledge financial support from the Project 51790485 supported by the
National Natural Science Foundation of China. We would like to thank LetPub (www.letpub.com) for providing
linguistic assistance during the preparation of this manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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