Materials Science & Engineering A xxx (xxxx) xxx

Contents lists available at ScienceDirect

Materials Science & Engineering A

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

Effect of various aging treatment on thermal stability of a novel

Al-Zn-Mg-Cu alloy for oil drilling
Juangang Zhao a, b, Zhiyi liu a, b, c, *, Song Bai a, b, **, Tiantian Huang e, f, Jian Wang a, b,
Haoyu Xie a, b, Diping Zeng a, b, Lei Luo a, b
a
Key Laboratory of Nonferrous Metal Materials Science and Engineering, Ministry of Education, Central South University, Changsha, 410083, Hunan Province, PR China
b
School of Material Science and Engineering, Central South University, Changsha, 410083, Hunan Province, PR China
c
The National Key Laboratory of Science and Technology for National Defense on High-strength Structural Materials, Central South University, Changsha, 410083, PR
China
e
School of Mechanical and Electrical Engineering, Central South University, Changsha, 410083, Hunan Province, PR China
f
State Key Laboratory of High Performance Complex Manufacturing, Central South University, Changsha, 410083, Hunan Province, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Thermal stability plays an important role in practical application of Al-Zn-Mg-Cu alloy for oil drilling. In this
Al-Zn-Mg-Cu alloy work, a new four-stage aging treatment by employing a natural aging prior to re-aging is designed to improve
Thermal exposure thermal stability of Al-Zn-Mg-Cu alloy. The effect of T6, four-stage aging, three-stage aging and T74 on thermal
Atom probe tomography
stability was investigated by tensile testing, transmission electron microscopy (TEM) and atom probe tomog­
Natural aging
Precipitation
raphy (APT). The results showed that after thermal exposure at 120 ◦ C for 500 h, the tensile strength of the four-
stage aged sample decreased only by 5.05%. APT analysis indicated that natural aging accelerates the diffusion of
Mg atoms, and promotes the precipitation of GP zones during re-aging stage, and TEM observations also supports
this result. Natural aging for 24 h prior to re-aging enhance the formation of GP zones, leading to an effective
improvement of the strength properties and thermal stability of the studied alloy. In addition, precipitates in all
aging samples gradually coarsen with the thermal exposure time increase. The influence of precipitates on
mechanical properties of the investigative alloy after thermal exposure is also discussed.

1. Introduction
Al-Zn-Mg-Cu series alloys are widely used in aerospace industry,
advanced weapon systems and transportation industries, have drawn
intensive attention due to their high strength, high fracture toughness
and excellent formability [1–5]. At present, Aluminum alloys are also
used for oil drill pipes. In the field of oil drilling, a drill pipe is a rod that
connects a drill bit in a drilling tool to transmit power and transport
mud. The oil drill pipes are usually exposure high temperature (less than
200 ◦ C), high pressure (the formation pressure of an oil well with a depth
of 4000 m is about 50–60 MPa), corrosive environments (H2S, CO2 and
Cl-), wear, fatigue, wash out and other conditions. With the depletion of
shallow well oil resources and the discovery of more ultra-deep oil and
gas reservoirs, the future trend of oil exploration will gradually develop
towards deep well drilling and offshore drilling, which puts forward
higher requirements for drilling and production tools [6–8].
Compare with the traditional steel oil drill pipes, aluminum drill
pipes own low density, remarkable strength to weight ratio and good
corrosion resistance [9–11]. Therefore, aluminum drill pipe is promising
material to solve the drilling problems arising from complex working
conditions of the deep and super-deep well, horizontal well, extended
reach well, sour well and offshore well etc. Research on aluminum alloy
drill pipe technology to improve drilling efficiency, reduce energy
consumption and ensure drilling safety has extremely high scientific
research value.
During applications as oil drill pipes, the aluminum alloys is inevi­
tably exposed to high temperature for a long time [12,13]. The micro­
structure and mechanical properties of Al-Zn-Mg-Cu alloy under high
temperature environment significantly affect the quality and reliability
of the drill pipes. Therefore, it is necessary to investigate the effect of
thermal exposure on microstructure and mechanical properties evolu­
tion of Al-Zn-Mg-Cu alloy.

* Corresponding author. School of Materials Science and Engineering, Central South University, Changsha, 410083, PR China.
** Corresponding author. School of Material Science and Engineering, Central South University, Changsha, 410083, PR China.
E-mail addresses: liuzhiyi@csu.edu.cn (Zhiyi liu), baisongmse@163.com (S. Bai).

https://doi.org/10.1016/j.msea.2020.140490
Received 20 September 2020; Received in revised form 30 October 2020; Accepted 31 October 2020
Available online 4 November 2020
0921-5093/© 2020 Elsevier B.V. All rights reserved.

Please cite this article as: Juangang Zhao, Materials Science & Engineering A, https://doi.org/10.1016/j.msea.2020.140490
J. Zhao et al.
Table 1
The chemical composition of studied Al-Zn-Mg-Cu alloy (in wt. %).
Zn Mg Cu Zr Mn Ti Cr Ag
6.87 2.39 1.67 0.09 0.41 0.11 0.19 0.20
In recent years, some research has been conducted on the effect of
thermal exposure on microstructure and mechanical properties of Al-Zn-
Mg-Cu alloy [14–17]. For instance, Dai et al. [18] investigated different
thermal temperatures on tensile strength of the T7452-treated 7085
aluminum alloy. They found that the mechanical property of the alloy
decrease as thermal exposure temperature rises. Wang et al. [19]
investigated the effects of trace Er on the microstructural evolution and
mechanical properties of Al-Zn-Mg-Cu-Zr alloys for drilling pipes. The
results showed yield strength of the RRA-treated alloys increased with
increasing Er content. However, most of previous literatures, traditional
heat treatment processes or micro-alloying were used to improve the
thermal stability of Al-Zn-Mg-Cu-Zr alloys for drilling pipes. The stan­
dard RRA treatment is difficult to be applied for oil drill pipes in in­
dustrial manufacturing process. This is arising from the fact that the
retrogression time is very short [20]. Micro-alloying will increase the
manufacturing cost of the alloy [21–23]. Thus, it is necessary to develop
new heat treatment for actual industrial production by adjusting aging
parameters and process.
In the present work, a new four-stage aging is designed by applying
natural aging for 24 h before re-aging stage to increase the thermal
Fig. 1. Schematic diagram of different aging process (a) T6; (b) Four-stage aging; (c) Three-stage aging; (d) T74.
Fig. 2. (a) Schematic of the samples for room temperature tensile tests (unit: mm), (b) schematic of the samples for high temperature tensile tests (unit: mm), (c) the
location of the hardness, TEM and electrical conductivity specimens.
Materials Science & Engineering A xxx (xxxx) xxx
stability of the studied alloy. A low retrogression temperature (168 ◦ C)
and a long retrogression period (4 h) are intentionally selected to
Al simulate real industrial manufacturing process. The effects of various
aging treatment on the thermal stability of the Al-Zn-Mg-Cu alloy have
Bal.
been studied under the thermal exposure at 120 ◦ C for 100–500 h.
Meanwhile, the changes of electrical conductivity and hardness of
different aged samples have been investigated during thermal exposure.
Moreover, the strengthening mechanism and relationship between the
microstructure and mechanical properties after the thermal exposure
were also discussed.
2. Materials and methods
2.1. Sample preparation
The chemical composition of studied Al-Zn-Mg-Cu alloy was listed in
Table 1 (detected by ICP-OES). The alloy was prepared by melting and
casting under ambient condition in electrical resistance muffle furnace.
Appropriate amounts of Al-45% Cu, Al-4% Zr, Al-4% Ti, Al-4% Cr, Al-
10% Mn (in wt.%), pure Zn, Mg and Ag were added. The cast ingot was
carried out a two-double homogenization with 425 ◦ C for 24 h and
465 ◦ C for 72 h, and then hot extruded into Φ12.5 mm rods with an
extrusion ratio of 12.9:1.
Fig. 1 presents the schematic diagram of different aging treatment
processes. All specimens were solution treated at 470 ◦ C for 1 h, then
water quenched, and followed by different aging treatments.
2
J. Zhao et al.
2.2. Tensile testing, hardness testing and conductivity testing
In order to reveal the effect of different ageing on the tensile prop­
erties of the studied alloy after thermal exposure, all the specimens were
tested at room temperature on a MTS-810 electronic universal testing
machine with a tensile strain rate of 1.1 × 10-3 s-1. The high temperature
tensile tests were carried out on a material testing machine (SANS-
CMJ5105) at 120 ◦ C with the accuracy of ±5 ◦ C. The tensile samples
were prepared ASTM: E8M − 08 with a diameter of 5 mm and a gauge
length of 30 mm. For each ageing treatment condition, three specimens
were intentionally prepared and tested to obtain a reliable result.
Vickers hardness (HV) of specimens were measured by 8 Kg load for 15 s
using an HMV-2 sclerometer. Each hardness value was determined by
three specimens, and five measurements are performed on each sample.
Before hardness measurement, these samples were prepared by grinding
with 1000 grit SiC sandpaper. The electrical conductivity measurements
were performed on a D60K digital test instrument, and the size of
specimens for electrical conductivity measurement is 20 × 10 × 2 mm3.
These specimens for electrical conductivity measurement were also
prepared by grinding with 1000 grit SiC sandpaper. The geometry of
room temperature and high temperature tensile samples are shown in
Fig. 2 (a) and (b). The location of the hardness, TEM and electrical
conductivity specimens are shown in Fig. 2 (c).
2.3. Microstructures analysis
The microstructures of the investigative alloy after T6, four-stage
aging, three-stage aging and T74 treatments were performed by a Tec­
nai G2 20 transmission electron microscope (TEM) machine operating at
200 kV. The high resolution transmission electron microscope (HRTEM)
of different precipitates was recorded by a Tecnai F20 microscope
operating at 200 kV. The average diameter and number density of the
matrix precipitates in different aging samples are estimated according to
the TEM and HRTEM images (to verify the significance and consistency
of the results, the results are obtained by counting at least 10 images to
Fig. 3. Mechanical properties of various aging samples after exposure at 120 ◦ C for various times: (a) tensile strength, (b) yield strength, and (c) elongation, (d) the
variation of mechanical property.
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reduce the statistical error). Thin foils for TEM were subsequently
ground to less than 100 μm and punched into discs with 3 mm in
diameter, and prepared by twin-jet electro-polishing in a mixture of 30%
nitric acid with 70% methanol. The temperature is below -25 ◦ C with
liquid nitrogen.
For APT test, thin bars (0.6 × 0.6 × 12 mm3) were cut from rods
parallel to the extrusion direction and electro-polished. The APT anal­
ysis was conducted on a CAMECA 4000X HR instrument at a specimen
temperature of 25 K under ultrahigh vacuum conditions with a pulse
fraction of 15% and a detector efficiency of 38%. The reconstruction and
data analysis were performed using the Integrated Visualization &
Analysis software (IVAS) 3.6 package. In each data set, at least 107
atoms were collected for each condition, and the maximum separation
distance method was applied to identify the clusters and precipitates.
3. Results
3.1. Mechanical properties of various aged samples exposed at 120 ◦ C for
various periods
In order to investigate the thermal stability of different aging treat­
ment alloys, various aged samples are chosen to undergo further expo­
sure at 120 ◦ C for various times. Fig. 3 shows the tensile results of
different tempered alloy exposed at 120 ◦ C for various periods. The
dotted black line denotes the values of strength and elongation for the
alloy under T6, four-stage, three-stage and T74 state. In Fig. 3 (a) and
(b), the strength of four aged alloys gradually decreases as exposure time
increases. In Fig. 3 (c), the elongation of four tempers alloys increases
gradually as exposure time increases. In Fig. 3 (d), the tensile strength of
T6 alloy, four-stage aged alloy, three-stage aged alloy, and T74 alloy
decreases by 5.89%, 5.05%, 6.16%, 7.11% over the 0–500 h exposure
duration. Meanwhile, the yield strength decreased by 5.22%, 4.82%,
5.60% and 6.26%, respectively. It can be seen in Fig. 3 (d) that the
elongation of studied alloy in all aging conditions increases gradually as
exposure time increases. After exposing at 120 ◦ C for 500 h, the loss of
J. Zhao et al.
Fig. 4. Mechanical properties of various aging samples at 120 ◦ C.
the strength properties of four-stage aged sample is least in all aged
samples, indicating that four-stage aging can improve the thermal sta­
bility of the studied alloy.
3.2. High temperature tensile properties
In general, good high temperature mechanical properties are
required for Al-Zn-Mg-Cu series alloy because it is often used as oil
drilling serving at a temperature as high as 120 ◦ C. Fig. 4 displays the
high temperature mechanical properties of Al-Zn-Mg-Cu alloy carried
out at 120 ◦ C. There was an obvious difference in high temperature
mechanical properties for different aging samples. It can be seen that the
average tensile strength in T6, four-stage aging, three-stage aging and
T74 sample reached 583 MPa, 558 MPa, 543 MPa and 512 MPa,
respectively. Compared with T6 sample, the tensile strength of four-
stage aging, three-stage aging and T74 sample are decreased 25 MPa
by (4.3%), 40 MPa (6.9%) and 71 MPa (12.3%), respectively. However,
their elongations reveal higher values than that of T6 sample. Compared
to three-stage aging sample, the high temperature tensile properties of
four-stage aging sample are improved. This result proves that natural
aging for 24 h after regression is beneficial to improve the high tem­
perature tensile properties and elongation of Al-Zn-Mg-Cu alloy.
3.3. Hardness and conductivity of various aged samples exposed at
120 ◦ C for various periods
Hardness and conductivity properties of four aged samples after
exposing for various periods are shown in Fig. 5. The dotted black line
Fig. 5. Conductivity (a) and hardness (b) of the four aging samples after exposed at 120 ◦ C for various periods.
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denotes the values of conductivity and hardness for the alloy under T6,
four-stage, three-stage and T74 state. Fig. 5 (a) shows conductivity of
four aging samples gradually increases as exposure time increases.
Contrary to the variation of conductivity, Fig. 5 (b) shows hardness of
the four samples gradually decreases as exposure time prolongs. During
the entire thermal exposure, the hardness of four-stage aged alloy de­
creases slightly. The four-stage aged alloy exhibits excellent thermal
stability, as compared to other aging conditions.
3.4. APT analysis
Fig. 6 displays the atom maps for Mg, Zn, Mg + Zn and Cu distri­
butions, and the 15 at% Mg + Zn iso-concentration surfaces in four-stage
and three-stage aged samples. Precipitates with various size and dense
can be observed in Fig. 6. Using the method described Ref. [24],
different precipitates were defined according to the number of atoms
involved. The precipitates containing 100–1000 atoms are considered as
GP zones, those containing between 1000 and 5000 atoms are regarded
as ηʹ phase, and other containing more than 5000 atoms are regarded as
η phase. The proportion (54.8%) of GP zones in four-stage aged sample is
higher than that (46.5%) in three-stage aged sample, and the results are
obtained by analyzing 3DAP data. There is no significant difference in
the proportion of large ηʹ and η phases for four-stage and three-stage
aged samples.
Fig. 7 shows the composition profiles across the α/GP zone interfaces
in different aged alloys. It can be seen in Fig. 7 that the Mg concentration
of GP zones in four-stage aged sample is higher than that in three-stage
aged sample. Supersaturated vacancies are prone to combine with Mg
atoms instead of Cu atoms during natural aging process [25]. This will
accelerate the diffusion of Mg atom, and increase the nucleation rate of
GP zones because Mg-vacancy is the structural component of GP zones.
3.5. TEM analysis
The bright field TEM micrographs and corresponding selected area
electron diffraction (SAED) patterns of various aged samples after
exposure at 120 ◦ C for various times are shown in Fig. 8. Apparently, GP
zones is predominant in T6 sample, agreeing with the spots at the {1, 3/
4, 0}Al positions in corresponding selected SAED pattern. Besides, spots
at the 1/3 and 2/3 of {220}Al positions produced by ηʹ phase was also
found. Compared to Fig. 8 (a), the η phase in four-stage aged sample is
clearly revealed, agreeing with the spots close to the 2/3{220}Al posi­
tions. The SAED patterns in Fig. 8 (g) show that ηʹ and η phases exist in
three-stage aged alloy, while the diffraction spots at {1,3/4,0}Al in
<100>Al projection in Fig. 8 (g) correspond to G.P zones. According to
the diffraction spots in Fig. 8 (d) and (g), it is found that the diffraction
spot of GP zones in the four-stage aged sample are stronger than that of
three-stage aged sample, indicating that four-stage aged sample contains
more GP zones. This feature proposes that natural aging prior to re-aging
J. Zhao et al. Materials Science & Engineering A xxx (xxxx) xxx

Fig. 6. Atom probe analysis of (a) four-stage and (b) three-stage aged samples.

Fig. 7. The composition profiles across the α/GP zone interfaces in different aged alloys: (a) four-stage aging; (b) three-stage aging.

facilitates the formation of GP zones in four-stage aged sample. Based on
SAED patterns in Fig. 8 (j), the bright diffraction spots at the 1/3 and 2/3
of {220}Al positions suggested the existence of ηʹ and η precipitates. It
means that the grain interior precipitates in T74-treated alloy mainly
consist of ηʹ and ηʹ precipitates. Fig. 9 shows the HRTEM images of
various aged samples after exposure at 120 ◦ C for various times. When
the thermal exposure time is 0 h (Fig. 9 (a), (d), (g), (j)), for T6 sample,
fine and uniform precipitates are homogeneously distributed in the
matrix. In contrast, the precipitates of the four-stage, three-stage and
T74 aged samples both are coarse. As the thermal exposure time in­
creases, the average size of precipitates become larger for various aging
samples.
Corresponding statistical results of size distribution and average
radius of precipitates are given in Fig. 10. The size distribution and
average radius of precipitates are calculated by the method in Refs [26].
To verify the significance and ensure the accuracy, the results are ob­
tained by counting at least 1000 precipitates to reduce the statistical
error. When the thermal exposure time is 0 h (Fig. 10 (a)), it can be seen
that the average radius of T6 sample is smaller than that of other sam­
ples. The radius of most precipitates in T6 sample are smaller than 3 nm
with 70% of precipitates, and 30% precipitates in the range of 3–6 nm.
The calculated average radius of T6 sample is 2.31 ± 0.31 nm. The
average radius of precipitates in four-stage aged, three-stage aged and
T74 samples is 3.97 ± 0.27 nm, 4.42 ± 0.19 nm and 6.01 ± 0.22 nm,
respectively.
As the thermal exposure time increases to 300 h (Fig. 10 (b)), the
average radius of precipitate in T6, four-stage, three-stage aged and T74
samples become larger. The average radius of precipitates in different

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Fig. 8. Bright field TEM microstructures of different aged samples after exposing at 120 ◦ C for various times: (a) T6, 0 h; (b) T6, 300 h; (c) T6, 500 h; (d) four-stage
aging, 0 h; (e) four-stage aging, 300 h; (f) four-stage aging, 500 h; (g) three-stage aging, 0 h; (h) three-stage aging, 300 h; (i) three-stage aging, 500 h; (j) T74, 0 h; (k)
T74, 300 h; (l) T74, 500 h. All TEM images were taken near the <100> Al zone axis.

samples follows the sequence: T6<four-stage aging < three-stage aging
< T74. After thermal exposing at 120 ◦ C for 500 h (Fig. 10 (c)), the
average radius of precipitates in various samples are further enlarged.
The average radius of precipitates in different samples after exposing at
120 ◦ C for various times are summarized in Fig. 10 (d). It can be
concluded that the average radius of precipitates in different samples
increase with the increasing exposure time.
3.6. Grain boundary precipitates
Typical microstructures of grain boundary precipitates (GBPs) in
different aged samples exposed at 120 ◦ C for various times are present in
Fig. 11. The rod equilibrium η (MgZn2) precipitates distribute along the
grain boundaries (GBs). In addition, Tables 2 and 3 shown the width of
precipitation free zone (PFZ) and GBPs length. The narrowest PFZ and
shortest GBPs in T6 sample are observed. Without exposing, the average
widths of PFZ in different samples are 12.10 ± 0.87 nm (T6), 20.92 ±
0.72 nm (four-stage aging), 28.60 ± 0.51 nm (three-stage aging) and
32.30 ± 0.39 nm (T74), respectively. The average widths of PFZ in
different samples after 120 ◦ C/500 h exposure reaches 18.44 ± 0.76 nm
(T6), 28.72 ± 0.85 nm (four-stage aging), 39.98 ± 0.90 nm (three-stage
aging), and 50.40 ± 0.63 nm (T74). The widths of PFZ in T6, four-stage,
three-stage aged and T74 samples increase to 6.34 nm, 7.8 nm, 11.38 nm
and 18.1 nm, respectively. It can be seen that the change of PFZ width in

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Fig. 9. HRTEM images of precipitates for different aged samples after exposing at 120 ◦ C for various times: (a) T6, 0 h; (b) T6, 300 h; (c) T6, 500 h; (d) four-stage
aging, 0 h; (e) four-stage aging, 300 h; (f) four-stage aging, 500 h; (g) three-stage aging, 0 h; (h) three-stage aging, 300 h; (i) three-stage aging, 500 h; (j) T74, 0 h; (k)
T74, 300 h; (l) T74, 500 h. (a) image was taken near the <100> Al zone axis, (b-l) images were taken near the <110> Al zone axis. The precipitates of GP zone, η′ and
η phases are framed by yellow arrows or dotted lines, respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the
Web version of this article.)

T6 and four-stage aged samples are least than that of three-stage aged
and T74 samples. The length of GBPs in different samples also shows the
same trend. Moreover, the average widths of PFZ and lengths of GBPs in
different aging sample increase as the exposure time increase. Mean­
while, the η precipitates present a discontinuous distribution along GBs
with lower distribution density, which demonstrates higher corrosion
resistance properties [27]. Moreover, the rise of thermal exposure time
also leads to the increase of length of GBPs.
4. Discussion
4.1. Microstructure evolution of different aged samples during exposure
The general precipitation sequence in Al-Zn-Mg-Cu alloy is [28–31]:
supersaturated solid solution (SSS) →GP zones → metastable phase (ηʹ
phase) → equilibrium phase (η phase). Thermal exposure can be un­
derstood as the continuous aging for sample at a certain temperature.
The microstructural evolution of different aged samples during pro­
longed exposing at 120 ◦ C is shown in Figs. 8 and 9. As seen in Fig. 8 (a),

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Fig. 10. The size distribution of precipitates in different aging conditions after thermal exposing at 120 ◦ C for various times: (a) 0 h, (b) 300 h, (c) 500 h, (d) the
average radius of precipitates.

Fig. 11. Grain boundaries in different aging samples exposed at 120 ◦ C for 100 h, 300 h, 500 h: (a, b, c) T6, (d, e, f) four-stage aging, (g, h, i) three-stage aging and (j,
k, l) T74.

(d), (g), and (k), without exposing, the size of precipitates for all samples
are finer than that of samples after exposing. The main precipitates in T6
sample (Fig. 8 (a)) are GP zones and fine ηʹ phase. In present work, the
new four-stage aging is designed by adding natural aging for 24 h into
the traditional RRA (three-stage aging). For four-stage aging condition,
the first aging at 100 ◦ C for 24 h is applied to obtain GP zones and fine ηʹ
phase. The main change for microstructure during retrogression
(168 ◦ C/4 h) is the dissolution of the unstable precipitates (GP zones and
fine ηʹ phase) formed in first aging. Meanwhile, as the regression time
extends, ηʹ and η phases would grow. Then, the sample is quenched from
168 ◦ C to room temperature to preserve vacancies. During natural aging,
Mg atoms will combine with vacancy to enhance the nucleation of GP
zones [32]. Finally, in the re-aging stage (80 ◦ C/34 h), the GP zones are
precipitated again. Based on the above analysis, the main precipitates in

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Table 2 Table 4
The average PFZ width of different aged samples after thermal exposure at Precipitate characteristics of various samples after exposing at 120 ◦ C for
120 ◦ C. different times.
Tempers Exposure time/h Expose Tempers Precipitates Precipitate Dislocation
time type volume fraction mechanism
0 300 500
0h T6 GP zones + ηʹ 0.0916 28%
T6 12.10 ± 0.87 nm 19.60 ± 0.69 nm 18.44 ± 0.76 nm
bypass+72%
Four-stage aging 20.92 ± 0.72 nm 24.25 ± 0.36 nm 28.72 ± 0.85 nm
shear
Three-stage aging 28.60 ± 0.51 nm 37.30 ± 0.81 nm 39.98 ± 0.90 nm
Four-stage GP zones+ ηʹ 0.0899 45%
T74 32.30 ± 0.39 nm 41.27 ± 0.72 nm 50.40 ± 0.63 nm
aging +η bypass+55%
shear
Three-stage GP zones+ ηʹ 0.0712 60%
aging +η bypass+40%
Table 3 shear
The average length of grain boundary precipitates after thermal exposure at T74 ηʹ + η 0.0693 92%bypass+8%
120 ◦ C. shear
Tempers Exposure time/h 300 h T6 ηʹ + η 0.0493 99%bypass+1%
shear
0 300 500
Four-stage ηʹ + η 0.0326 Bypass
T6 9.60 ± 0.90 nm 17.18 ± 0.66 nm 27.50 ± 0.58 nm aging
Four-stage aging 12.41 ± 0.54 nm 22.16 ± 0.96 nm 30.27 ± 0.67 nm Three-stage ηʹ + η 0.0301 Bypass
Three-stage aging 28.23 ± 0.39 nm 39.84 ± 0.48 nm 47.37 ± 0.94 nm aging
T74 38.04 ± 0.86 nm 53.52 ± 0.61 nm 62.32 ± 0.76 nm T74 ηʹ + η 0.0282 Bypass

500 h T6 ηʹ + η 0.0251 Bypass

Four-stage ηʹ + η 0.0249 Bypass
four-stage aged sample are GP zones, ηʹ and η phases. The difference aging
between the four-stage aging and the three-stage aging is the introduce Three-stage ηʹ + η 0.0232 Bypass
of natural aging for 24 h before re-aging stage. TEM analysis proves that aging
natural aging enhances the nucleation of GP zones, which is consistent T74 η 0.0192 Bypass
with APT results in Figs. 6 and 7. For T74 sample, fine GP zones with
high density formed in the matrix during the first aging at 110 ◦ C/3 h.
For Al-Zn-Mg-Cu alloy, the precipitation strengthening include
The ηʹ phases nucleate and grow during the initial stage of second aging
shearing mechanism and Orowan bypass mechanism, it is mainly
(155 ◦ C/15 h), part ηʹ phase to η phase as aging continues at 155 ◦ C.
determined by the precipitate size [36]. When the size of precipitates
Therefore, the precipitates in T74 sample include ηʹ and η phases.
exceeds 3 nm, the strengthening mechanism of Al-Zn-Mg-Cu alloy
Compared to Fig. 8 (a), (d), (g), and (k), exposing for 300 h ((b), (e),
change from shear mechanism to bypass mechanism [37]. When GP
(h), and (k)) leads to a distinct growth of the precipitates in various
zones and fine ηʹ phase have been cut by dislocations, the strengthening
samples. The average size of precipitates in T6, four-stage, three-stage
effect of shear mechanism could be expressed as [38]:
aged and T74 sample, reaches 3.82 nm, 6.82 nm, 8.29 nm and 10.85 nm,
respectively. The relative frequency of the size distribution of pre­ Δτcut = αf 1/2 γ1/2 (1)
cipitates in different samples after exposing for various periods is plotted
in Fig. 10. The higher portion of large precipitates is usually observed in where f is the volume fraction of precipitates, r is the average radius of
three-stage aged and T74 sample. Such as, the η′ precipitates with a precipitates. According to previous Ref. [39], the αis about 364.4 MPa
diameter larger than 18 nm can be observed in three-stage aged and T74 nm-1/2 for aluminum alloy. Moreover, it is also a preferential choice for
samples but become absent in T6 and four-stage aged samples. After dislocation to bypass η phase with significantly large size. The
exposing for 500 h (Fig. 8 (c), (f), (i), and (l)), these precipitates in strengthening effect of bypass mechanism could be expressed as [40]:
various samples further coarsen. The average size of precipitates in T6,
Δτbypass = βf 1/2 γ− 1
(2)
four-stage, three-stage aged and T74 samples increases to 6.93 nm, 8.0
nm, 10.66 nm and 15.37 nm. During the whole exposure, the average
where β is constant, the value of β is 8.34 × 103 MPa nm for aluminum
coarsening rate of precipitate in T6, four-stage, three-stage aged and T74
alloy [41], f is the volume fraction of precipitates, r is the average radius
samples is 3.85 × 10-4 nm h-1, 3.41 × 10-4 nm h-1, 5.20 × 10-4 nm h-1 and
of precipitates. The volume fraction of precipitates for different samples
7.80 × 10-4 nm h-1. The coarsening degree of precipitates in four-stage
can be calculated by Ref. [14,42]:
aged sample is lower than that of other samples. As a result, the ther­
mal stability of the four-stage aged sample is higher than that of other Δp = Vsphere + 2Vplatelet − Vcor (3)
samples. /
Vplatelet = tD2 π 4 (4)

4.2. Effect of different aging treatments on strengthening mechanisms Δcor = (4π / 3)R3mean .Nplatelets (5)

As an age harden-able alloy, the strengthening mechanisms of Al-Zn-
Mg-Cu alloy include: solid solution strengthening, grain boundary
strengthening and precipitate strengthening etc. [33–35]. One of the
most effective methods of increasing the strength properties of
Al-Zn-Mg-Cu alloy alloys is precipitate strengthening, which is due to
the interaction between dislocations and precipitates. In present work,
the effects of solid solution strengthening and grain boundary
strengthening of four aged samples reveal no significant difference,
because the grain size and solid solution treatment are the same. The
difference in the strength properties is due to the different microstruc­
tures after various samples.
where Vsphere is the volume of observed round particles, Vplatelet is the
volume of observed edge-on platelets, Vcor is the volume of observed
round precipitates which actually are platelets, t is thickness of round
particles or platelets, D represents the diameter of round particles or
platelets, Rmean is the average radius of the precipitates, Nplatelets is the
density of platelets.
In summary, the detailed precipitate characteristics of different
samples after exposing at 120 ◦ C for various times are given in Table 4.
As seen in Table 4, the main phase transform in different samples form
GP zones, ηʹ and η to ηʹ and η. In addition, the volume fraction of pre­
cipitates continuously reduces as exposure time.

9
J. Zhao et al.
Fig. 12. Increase in yield strength of different samples after exposing at 120 ◦ C for various times.
The values of Δτ (increase in yield strength) can calculated by Eqs. (1)
and (2). Fig. 12 presents the calculated results of precipitate strength­
ening in different samples after exposing various times. It can be seen
that the strengthening effect of precipitates in all samples are weakened
with the increasing exposure time. Form 0 h–500 h, the average size of
precipitates increases while the volume fraction decreases, and the mi­
crostructures vary all the way. During exposure, the coarsening rate of
the precipitates in the four-stage aged sample is the lowest as compared
with other samples. Naturally, the four-stage aged sample has excellent
thermal stability. The results of thermal exposure indicate that the new
four-stage aged treatment can effectively improve the thermal stability
of Al-Zn-Mg-Cu alloy.
5. Conclusions
In this work, the influences of different aging treatment on the
thermal stability and microstructures of Al-Zn-Mg-Cu alloy were inves­
tigated. The results were summarized as follows:
(1) Natural aging for 24 h following retrogression has a positive ef­
fect on the strength properties and elongation of Al-Zn-Mg-Cu
alloy by forming GP zones.
(2) The width of PFZ and length of GBPs in all samples increase as the
exposure time increases. Meanwhile, the coarsening of pre­
cipitates gradually increases during the extended exposure.
(3) After exposing at 120 ◦ C for 500 h, the strength loss of the four-
stage aged sample is the smallest as compared with other sam­
ples. After exposure for 500 h, >94.95% of the tensile strength of
four-stage aged sample remained, indicating the four-stage aging
treatment could effectively improve the thermal stability of Al-
Zn-Mg-Cu alloy.
Data availability statement
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical or time limitations.
10
Materials Science & Engineering A xxx (xxxx) xxx
CRediT authorship contribution statement
Juangang Zhao: Methodology, Writing - original draft, Writing -
review & editing. Zhiyi liu: Conceptualization, Methodology, Valida­
tion, Formal analysis, Investigation, Resources, Writing - review &
editing, Visualization. Song Bai: Resources, Formal analysis, Writing -
review & editing. Tiantian Huang: Resources, Formal analysis, Writing
- review & editing. Jian Wang: Resources, Formal analysis, Writing -
review & editing. Haoyu Xie: Resources, Formal analysis, Writing -
review & editing. Diping Zeng: Resources, Formal analysis, Writing -
review & editing. Lei Luo: Resources, Formal analysis, Writing - review
& editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors are grateful for the financial support from the National
Key Research and Development Program of China (2016YFB0300900),
the National Key Fundamental Research Project of China
(2012CB619506-3), National Natural Science Foundation of China
(51171209).
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