Materials Science & Engineering A 728 (2018) 88–94

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Bake hardening behavior and precipitation kinetic of a novel Al-Mg-Si-Cu T

aluminum alloy for lightweight automotive body
⁎
Hui Lia,b, , Zhaohui Yanb, Lingyong Caob
a
College of engineering, Yantai Nanshan University, Yantai 265700, Shandong, China
b
National engineering research center for plastic working of aluminum alloys, Shandong Nanshan aluminum Co Ltd, Yantai 265713, Shandong, China

A R T I C LE I N FO A B S T R A C T

Keywords: The natural aging (NA) phenomena and its negative effect on bake hardening (BH) response, and a wide tem-
Al-Mg-Si-Cu aluminum alloy perature/time range of pre-aging (PA) treatment on a novel Al-Mg-Si-Cu automotive aluminum alloy were in-
Natural aging vestigated systematically by micro-hardness measurement, tensile test, transmission electron microscopy (TEM)
Pre-aging treatment and differential scanning calorimetry (DSC) analysis. The precipitation kinetic of main strengthening β″ phase
Bake hardening response
was calculated according DSC curves based on JMA (Johnson-Mehl-Avrami) equation. The results indicate that
Precipitation kinetic
artificial aging (AA) immediately after solution treatment is helpful to achieve good BH response, while aging
temperature and time determine the value and arrival time of peak hardness. BH value is decreased with increase
of NA time. BH value is ranging from 40 MPa to 110 MPa after different PA treatment, and the optimal one is
obtained while PA at 160 °C for 10 min. The precipitation activation energy of β″ phase of T4P state (160 °C/
10 min) is reduced about 42 kJ/mol compared to T4 state, which is attributed to the increase of GP region size
during PA treatment.

1. Introduction
With the convenience brought by rapid development of science and
technology, the impact of global warming and energy crisis is becoming
obvious. The reduction of oil consumption and exhaust emission, im-
provement of safety performance are significant directions of the de-
velopment of automobile industry [1,2]. Lightweight is one of the ef-
fective measures to realize automobile energy saving and emission
reduction [3]. Aluminum alloy has the characteristics of low density,
high strength and good corrosion resistance, and achieves equivalent
mechanical properties with weight reduction [4,5].
6000 series (Al-Mg-Si) aluminum alloy, which has excellent com-
prehensive mechanical properties, has great potential for application on
automobile panels [2,4]. The problems existed during the fabrication
and service process restrict their application [6,7]. Macro performance
is an external phenomenon, while microstructure is the intrinsic es-
sence. Most of the harsh requirements could be achieved by strict
control of fine microstructures during the fabrication process.
The aluminum sheet after solution treatment, which is under ther-
modynamic instability state, has natural aging (NA) effect including
increase of strength and suppress of bake hardening (BH) response. The
negative effects of NA, which are attributed to the formation of Mg and
Si clusters, have been extensively studied [8–13]. The reduction of
vacancy density and solid solubility is occurred during NA process, and
increases the critical nucleation size of main strengthening β″ phase
which contribute to the decrease of BH response during artificial aging
(AA) process. The kinetic of clusters formation is based on the dis-
solvable amount of trace elements and their effect on diffusion re-
tardation, and solute clustering mechanisms in Al–Mg–Si alloys [14].
Pre-aging (PA) treatment is proposed to solve the adverse NA effects.
Ying [15] revealed that immediate PA after solution treatment im-
proved formability and BH response. Feng [16] reported that the quick
BH response in 6016 alloy was associated with the marked growth of
fine precipitates formed in the PA samples. Takaki [17] found the dif-
ferent effect of NA and AA on paint bake process and pointed out the
relationship between BH response and fraction of β″.
The NA hardening effect, low strength required for stamping, and
high BH response are pluralistic collection of contradiction. Their mu-
tual influencing relations and corresponding mechanisms are rarely
reported. The present work was undertaken to investigate the influence
of different NA time and PA treatment on BH response systematically,
to provide basis for the targeted design of heat treatment and promote
the development of light weight career.

⁎
Corresponding author at: College of engineering, Yantai Nanshan University, Yantai 265700, Shandong, China.
E-mail address: lhlwj8888@163.com (H. Li).

https://doi.org/10.1016/j.msea.2018.05.014
Received 8 December 2017; Received in revised form 15 March 2018; Accepted 5 May 2018
Available online 07 May 2018
0921-5093/ © 2018 Elsevier B.V. All rights reserved.
H. Li et al.
Fig. 1. Schematic diagram of heat treatment of experimental aluminum (a) AA after solution; (b) effect of NA time on AA; (c) PA and BH.
2. Materials and experimental procedure
The aluminum alloy sheet used in the present investigation was a
novel Al-Mg-Si-Cu alloy with a composition of Al-0.65Mg-1.05Si-
0.35Cu-0.15Fe-0.10Mn (wt%). The ingot was hot rolled to 12 mm thick
sheet after homogenization at 550 °C for 24 h, and then cold rolled to
1.1 mm thick. Specimens were cut from the cold rolled sheet. The
specimens were solution treated at 550 °C for 5 min with a SX2-4-10
chamber electric furnace and water quenched to room temperature, and
then immediately carried out heat treatment in a 101A-00 electro
thermal constant-temperature dry box as follows: 1) AA at 160 °C,
180 °C and 200 °C for 0–72 h (shown as Fig. 1a); 2) storage at room
temperature, and then baked the specimens at 200 °C for 120 min after
different NA times, shown as Fig. 1b; 3) PA at 140 °C, 160 °C, 180 °C and
200 °C for different holding times, then storage at room temperature for
14 days, and finally baked at 175 °C for 30 min.
Based on the sensitivity of mechanical properties of 6000 series
aluminum alloy to storage process, real time hardness test after dif-
ferent heat treatments were carried on a HV-1000 tester with 500 g
force and 10 s loading time. Nine indentations were measured and the
average value was obtained after removal of the maximum and
minimum ones. Precipitation phenomena was analyzed by differential
scanning calorimetry (DSC) using an argon atmosphere NETZSCH-F3
calorimeter, the test temperature was ranging from 30° to 500 °C with a
heating rate of 5 °C/min. The mechanical properties were tested on a
CMT5105 tester according to the international standard ISO 6892-1.
The displacement rate of 0.25 mm/min was used and a minimum of
Fig. 2. BH response after different heat treatment. (a) Baking after solution treatment immediately; (b) NA effect and influence on BH.
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Materials Science & Engineering A 728 (2018) 88–94
three tests were performed for each condition. Transmission electron
microscopy (TEM) measurements were carried out on a JEM-2010F
electron transmission microscope at an acceleration voltage of 200 V.
The specimens were mechanically grounded to 40 µm thickness and
punched out into a diameter of 3 mm, and then etched by double-jet
polishing using a solution of 1000 ml methanol and 500 ml HNO3 at
12 V voltage and − 20 °C temperature.
3. Results and discussion
3.1. BH response and influence of NA time
Fig. 2a presents the micro-hardness evolution of samples after
baking at different temperatures for different times. The samples show
good BH response at every baking temperature. The hardness increases
to a peak value and then decreases with the increasing of bake time.
The higher the baking temperature is, the faster the hardening rate to
reach the peak value. The hardness increases from 71 HV to 129 HV
after baking at 200 °C for 2 h, while to 123 HV at 160 °C/60 h and 124
HV at 180 °C/10 h respectively. The effect of NA time on hardness and
BH response is shown in Fig. 2b. The hardness of sample without baking
increases sharply with increasing NA time in the early stage and then
becomes slowly, while has decreasing trend after baking treatment
(200 °C/120 min). The BH value decreases from 58 HV to 46 HV after
1 day storage, while decreases to 32 HV after 14 days storage. The
decrease of BH value is based on two aspects: hardness increase of NA
state and decrease of AA state.
H. Li et al.
Fig. 3. TEM graphs after different heat treatment. (a)solution treated, (b)under aged (180 °C/1 h), (c) peak aging (180 °C/10 h), (e)over aging (180 °C/48 h).
Fig. 4. DSC curves of samples after aging at 180 °C for different times.
Fig. 3 shows the TEM graphs after solution treatment and different
baking times at 180 °C, and their DSC curves are given in Fig. 4. By
combining the TEM graphs and DSC curves, the precipitation structure
and evolution behavior are qualitatively analyzed. All precipitations
within grains are dissolved into matrix after solution treatment
(Fig. 3a). The specimen is under aged after baking for 1 h and a large
number of needle-shaped β" phase precipitates in matrix with an
average size of 10 nm (Fig. 3b). The needle-shaped precipitates are
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Materials Science & Engineering A 728 (2018) 88–94
identified by their circular end-on views and the strain contrast around
them when viewed face-on [18–20]. GP zones could not be found using
conventional TEM, but the DSC curves represent their existence. The
endothermic and exothermic phenomenon represents microstructure
evolution during the heat treatment. GP zone peak (125–150 °C) is still
existed of the under aged specimen (1 h), and dissolves into matrix until
the precipitation of β" at temperature range of 220–225 °C. The hard-
ness peak value is achieved after 10 h baking and the average length of
β" arrives about 14 nm. GP zone peak is disappeared of the peak aging
specimen, and the precipitation peak of β" is decreased and delayed
which illustrated that the solid solution elements in matrix was almost
consumed. A precipitation free zone (PFZ) with 50–70 nm width is
found near the grain boundary. Meanwhile, the grain boundary is de-
corated with incoherent precipitation with a length of 20–40 nm. Cur-
rently, there are two mechanisms of PFZ formation, one is the con-
sumption of solid solution atoms near the grain boundary caused by
nucleation and growth of grain boundary precipitates, and the other is
the existence of low vacancy concentration region. These two factors
affect the width of PFZ. The sample is over aging after 48 h holding, the
hardness decreases obviously. Amount of lath-shaped Q′ phase is pre-
cipitated which consumed a lot of β" phase and caused the decrease in
hardness. The lath-shaped precipitates are recognized by their rectan-
gular end-on and long face-on views [18,21]. For the over aging spe-
cimen (48 h), there only exists redissolution and endothermic reaction
of precipitates.
H. Li et al. Materials Science & Engineering A 728 (2018) 88–94

Fig. 5. Effect of PA time and temperature on mechanical properties. (a)2 min；(b) 5 min；(c)10 min；(d) BH value.

3.2. PA effect on mechanical properties

Fig. 5 gives the mechanical properties after PA treatment and 14

days room temperature storage. PA temperature and time has great
influence on yield strength, tensile strength, elongation and BH value.
For specimens without PA treatment, hardness increases from 88
HV to 102 HV, and the yield strength increases from 140 MPa to
175 MPa after baking at 175 °C for 30 min. BH value is increased after
different PA treatment, and has an elevation range from 40 MPa to
110 MPa after baking treatment. With the increase of PA temperature at
given time of 10 min, BH value increases first and then decreases, and
has a peak value of 110 MPa at 160 °C.
Fig. 6 presents the change of micro-hardness with increasing of NA
time after PA at 160 °C for different times. After 2 min PA treatment, the
hardness elevation range is from 71 HV to 88 HV during 14 days NA
process, while 72–85 HV after 5 min and 77–82 HV after 10 min. The
negative NA effect is reduced in different degrees compared to spe- Fig. 6. Micro-hardness curve of PA samples during NA process.
cimen without PA treatment (70–90 HV). The longer the PA time is, the
slower the hardness increasing rate during the storage process.
according to solution treatment. This high energy state is unstable, and
transits to low energy state at room temperature spontaneously during
3.3. Precipitation kinetic and microstructure evolution storage. PA treatment breaks this high energy state artificially and
achieves a transition state between solution and room temperature by
3.3.1. Stress-strain curves annihilation of part of the vacancy. The transition state makes against
The engineering stress-strain curves of T4 and T4P (PA at 160 °C/ the spontaneous NA process and is propitious to the precipitation of
10 min) state after storage at room temperature for 14 days are given in meta-stable β". PA temperature and time determine the transition state.
Fig. 7. The yield strength and tensile strength of T4P are lower than T4 Accordingly, it is essential to investigate the precipitation kinetic and
state, while uniform and total elongations are larger which is beneficial microstructure evolution of specimens of T4 (without PA) and T4P
to improvement of formability. (with PA) state.
The high temperature state is preserved to room temperature

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H. Li et al. Materials Science & Engineering A 728 (2018) 88–94

Y (T ) = A (T )/Af (3)

where A(T) is the integral area of DSC curve at T, Af is the integral area
of the whole precipitation peak.
The value of k depends on the nucleation rate and diffusion coef-
ficient of solute atoms; n is decided by precipitation type, diffusion
mechanism and growth mode, and a value of 3/2 is used for aluminum
[24].
By derivation of Eq. (1) to t, the transformation rate of volume
fraction during precipitation process can be written as follows.
dY 1
= k n f (Y )
dt (4)

where f(Y) is a function of Y.

n −1
f (Y ) = n (1−Y )[−ln (1−Y )] n (5)
Fig. 7. Stress-strain curves after 14 days storage time. According Eqs. (2) and (4)

dY 1 Q ⎞ 1 Q
ln ⎡ ( )/f (Y ) ⎤ = ⎛lnk 0 − = lnk 0 −
⎣ dt ⎦ n⎝ RT ⎠ n nRT (6)

Transformation rate dY/dt can be represented as

dY dY dT dY
= ⎛ ⎞⎛ ⎞ = λ ( )
dt dT dt
⎝ ⎠⎝ ⎠ dT (7)

where λ is heating rate (5 °C/min).

Fig. 8. DSC results of T4 and T4P state.
3.3.2. Precipitation kinetic
The JMA [22] equation is used to represent the precipitation kinetic
as follows.
Y = 1 − exp (−kt n )
k = k 0exp (− Q/ RT )
where k and n are temperature correlation coefficient and nucleation
growth coefficient respectively; k0 is a constant; Q is the precipitation
activation energy; R is the gas constant; Y is the volume fraction of
precipitation phase at T, which could be calculated by DSC curve [23].
It can be seen from the above deduction process that Y value could
be calculated according DSC curve, n value is ensured by nucleation
and growth mechanism, and then f(Y) and (dY/dt) are obtained. The
slope of ln[(dY/dt)/f(Y)] and 1/T could be fitting out according Eq. (6),
and then the activation energy Q.
The DSC curves of T4 and T4P state are shown in Fig. 8. There exists
an exothermic peak of GP zone in both of the curves. An endothermic
peak is found at temperature range of 200–225 °C of T4 state which
shows the redissolution of GP zone and causes the decrease of BH value
during baking process. An exothermic peak of β" precipitation is found
at temperature range of 225–275 °C, and Q′ exothermic peak at range of
275–325 °C.
The precipitation sequence of Al-Mg-Si-Cu alloys can be presented
as [18]
Supersaturated solid solution α→Clusters/GP zone→β" phase +Q′
(1) phase→Q+ β (Mg2Si).
The metastable β" phase is identified as the main strengthening
(2) phase.
The precipitation exothermic peak of β" phase could be acquired
from DSC curve. However, the peak of β" and Q′ is overlapped.
Therefore, a Gaussian decomposition method [25] is used to isolate the
β" phase peak, shown in Fig. 9.
Based on the DSC curve of β" precipitation phase, according to Eqs.

Fig. 9. Separation of the overlap precipitation peaks of β" phase and Q′ phase (a)T4; (b) T4P.

92
H. Li et al.
Fig. 10. Solution of precipitation activation energy. (a)precipitation peak of β" phase;(b)curve of Y-T; (c)curve of dY/dt-T;(d)curve of ln[(dY/dt)/f(Y)]-1/T.
(3), (6) and (7), Fig. 10a-d are obtained (T4 state). By applying linear
fitting of curve in Fig. 10d, the slope of line (-Q/nR) is calculated, and
then the precipitation activation energy of β′′ phase.
The precipitation activation energy of β" phase is 243.68 kJ/mol of
T4 state, while only 201.37 kJ/mol of T4P state. Murayama [25] con-
sidered that the size of GP zone formed during NA of T4 state was
smaller than the critical value above which they were stable due to the
capillary effects, thus dissolved into matrix during baking process. The
size of GP zone of T4P state is greater than the critical value and will be
the nucleus of β″ phase during AA treatment. Accordingly, a larger
activation energy and higher precipitation temperature is needed for
the precipitation of β″ phase after the redissolution of GP zones of T4
state. While GP zones are not redissolved and are beneficial for the
growth of β″ of T4P state.
A bigger precursor phase for β″ is obtained during PA treatment due
to the high concentration of vacancy after solution treatment, and
grows up to β″ phase according dislocation and other defects during AA
treatment which needs smaller activation energy. However, the NA
process after solution treatment consumes a large number of vacancy
and forms GP zones with small size, and redissolves into matrix first and
then precipitates and grows up to β″ phase which needs larger activa-
tion energy.
Fig. 11 gives the TEM bright field and HRTEM of GP zone and β″
phase. GP zone has a significant spherical feature with a diameter of
2 nm (as shown in Fig. 11c), and is alignment with the matrix lattice
after bake treatment of T4 state (Fig. 11d). Fig. 11e-f show the HRTEM
and correspond FFT pattern of precipitation phase of T4P state with a
size of 3–4 nm after baking treatment, which is distinctly different from
the morphology of GP zone. The FFT pattern illustrates the β″ structure
has orientation relation of (010)//(001), (4 4̄03)//（020）and (601)//
(200) with aluminum matrix [13].
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Materials Science & Engineering A 728 (2018) 88–94
4. Conclusions
The NA phenomena and its negative effect on BH response, AA
immediately after solution, and PA treatment on a novel Al-Mg-Si-Cu
automotive aluminum alloy were investigated systematically.
Compared to conventional 6000 series aluminum alloys, the novel alloy
has low NA effect and high BH value under same heat treatment. The
adjustment of alloy content has no effect on precipitation sequence, and
only has slight influence on precipitation temperature range. Some
important conclusions can be drawn from this study as follows:
1) AA immediately after solution treatment is helpful to achieve great
hardening ability. Aging temperature and time determine the value
and arrival time of peak hardness. The micro-hardness is increased
with increase of NA time, while decreased after AA. These two
factors synthetically determined the decrease of BH response.
2) PA treatment in a wide temperature/time range is effective for
suppress of NA and improvement of BH response. BH value is ran-
ging from 40 MPa to 110 MPa after different PA treatment, and the
optimal one is obtained while PA at 160 °C for 10 min
3) For T4P state (160 °C/10 min), the precipitation activation energy of
β″ phase is reduced about 42 kJ/mol compared to the T4 state. PA
treatment increases the size of GP regions which grow up and act as
nucleation sites of β″ phases. Redissolution of GP regions is occurred
during baking treatment of T4 state and causes the decreasing of BH
response.
Acknowledgements
The work was financially supported by National Key Research and
Development Program of China (Grant No. 2017YFB0306404), Key
Research and Development Plan of Shandong Province (Grant No.
2017GGX20119)
H. Li et al.
Fig. 11. TEM bright field and HRTEM graphs of different heat treatment process (14 days storage+BH). (a, b)TEM bright field of T4 and T4P; (c, d) HRTEM and FFT
pattern of GP zone; (e, f) HRTEM and FFT pattern of β″.
References
[1] W.S. Miller, L. Zhuang, J. Bottema, A.J. Wittebrood, P. De Smet, A. Haszler,
A. Vieregge, Mater. Sci. Eng. A 280 (2000) 37–49.
[2] J. Hirsch, T. Nonferr, Metal. Soc. 24 (2014) 1995–2002.
[3] J. Zhou, X.M. Wan, Y. Li, Mater. Today.: Proc. 2 (2015) 5015–5022.
[4] F. Henriksson, K. Johansen, Procedia CIRP 50 (2016) 683–688.
[5] I.N. Fridlyander, V.G. Sister, O.E. Grushko, V.V. Berstenev, L.M. Sheveleva,
L.A. Ivanova, Met. Sci. Heat. Treat. 44 (9–10) (2002) 365–370.
[6] S. Kleiner, P.J. Uggowitzer, C. Henkel, P. Schulz, Aluminium 77 (3) (2001)
185–189.
[7] S. Pogatscher, H. Antrekowitsch, H. Leitner, T. Ebner, P.J. Uggowitzer, Acta Mater.
59 (9) (2011) 3352–3363.
[8] D.Y. Yin, Q. Xiao, Y.Q. Chen, H.Q. Liu, D.Q. Yi, B. Wang, S.P. Pan, Mater. Des. 95
(2016) 329–339.
[9] M. Werinos, H. Antrekowitsch, T. Ebner, R. Prillhofer, P.J. Uggowitzer,
S.P. ogatscher, Mater. Des. 107 (2016) 257–268.
[10] L.F. Cao, Paul A. Rometsch, Malcolm J. Couper, Mater. Sci. Eng. A 559 (2013)
257–261.
[11] F. Vahid, L. Brian, O.O. Nana, R. Babak, P. Nikolas, E. Shahrzad, Acta Mater. 103
(2016) 290–300.
[12] M. Murayama, K. Hono, M. Sage, M. Kikuchib, Mater. Sci. Eng. A 250 (1998)
94
Materials Science & Engineering A 728 (2018) 88–94
127–130.
[13] C.D. Marioara, S.J. Andersen, J. Jansen, H.W. Zandbergen, Acta Mater. 51 (3)
(2003) 789–796.
[14] M. Werinos, H. Antrekowitsch, T. Ebner, R. Prillhofer, W.A. Curtin, P.J. Uggowitzer,
S. Pogatscher, Acta Mater. 118 (2016) 296–305.
[15] L. Ying, G.Z. Shen, P. Hu, A.D. Wang, N. Ma, Y. Chang, Chin. J. Mech. Eng. 47 (10)
(2011) 19–24.
[16] J.N. Feng, J.H. Chen, C.H. Liu, Y.F. Liu, L.X. Liang, J. Chin. Elec. Micro 31 (6)
(2012) 461–468.
[17] Y. Takaki, Y. Aruga, M. Kozuka, T. Sato, Mater. Sci. Forum 794 (2014) 1026–1031.
[18] S. Esmaeili, X. Wang, D.J. Lloyd, W.J. Poole, Metall. Mater. Trans. A 34 (2003)
751–763.
[19] J.H. Kim, E. Kobayashi, T. Sato, Mater. Trans. 56 (2015) 1771–1780.
[20] S. Wenner, C.D. Marioara, S.J. Andersen, R. Holmestad, Int. J. Mat. Res. 103 (2012)
948–954.
[21] L.P. Deng, Y. He, Z. Wen, P.Z. Zhao, Z.H. Jia, Q. Liu, J. Alloy. Compd. 647 (2015)
238–244.
[22] A. Luo, D.J. Lloyd, A. Gupta, W.V. Youdelis, Acta Metall. Mater. 41 (3) (1993)
769–773.
[23] B. Scharifker, G. Hills, Electrochim. Acta 18 (7) (1983) 879–894.
[24] G.J. Gao, Y. Li, J.D. Li, Z.D. Wang, H.S. Di, T. Mater, Heat. Treat. 37 (6) (2016)
76–81.
[25] S. Esmaeili, D.J. Lloyd, Mater. Charact. 55 (2005) 307–319.