Journal of Alloys and Compounds 775 (2019) 193e201

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

Tuning the microstructure features of in-situ nano TiB2/Al-Cu-Mg

composites to enhance mechanical properties
Jiwei Geng a, b, Gen Liu a, Tianran Hong c, Mingliang Wang a, *, Dong Chen b, d, **,
Naiheng Ma a, d, Haowei Wang a
a
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, No. 800 Dongchuan Road, Shanghai 200240, China
b
School of Materials Science & Engineering, Shanghai Jiao Tong University, No. 800 Dongchuan Road, Shanghai 200240, China
c
Aero Engine Corporation of China Commercial Aircraft Engine, No. 3998 South Lianhua Road, Shanghai 200241, China
d
Anhui Province Engineering Research Center of Aluminium Matrix Composites, Huaibei 235000, China

a r t i c l e i n f o a b s t r a c t

Article history: In the in-situ TiB2/Al-Cu-Mg composite, the dislocations are non-uniformly distributed after solution
Received 6 June 2018 treatment, where the localized dislocations with the higher densities around TiB2 particles have induced
Received in revised form the heterogeneous precipitation of S(Al2CuMg) phases and formed precipitation free zones (PFZs) during
1 October 2018
the aging process. These microstructure features have induced the inhomogeneously aging response on
Accepted 8 October 2018
the age hardening process, and strongly limited the further increment of mechanical properties of the
Available online 9 October 2018
composite. It has thus indicated the conventional aging treatment is inappropriate for the TiB2/Al-Cu-Mg
composite. In this work, we have introduced uniform dislocations into the composite prior to artificial
Keywords:
Metal matrix composite
aging by the pre-stretch method. Resultantly, the S precipitates can be refined to precipitate uniformly,
Nano TiB2 particles and the PFZs have been successfully eliminated through the aging treatment. Based on these improved
Aging behavior microstructure features, the homogeneous aging behavior has been achieved, and the strength and
Dislocations ductility are simultaneously enhanced for TiB2/Al-Cu-Mg composites. The underlying mechanisms
Mechanical properties related to the superior strength-ductility combination have been discussed in terms of microstructure
characteristics in the composite.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction During the T6 treatment of Al-Cu-Mg based composites, the

Recently, in-situ nano TiB2/Al composites have been investigated
and showed improved mechanical properties, including higher
modulus, yield/ultimate tensile strength and high cycle fatigue
limit strength [1e5]. As a result, these composites can be applied as
advanced aerospace materials. In the application of wrought Al-
based materials, the heat treatment is an essential step to
improve the mechanical properties of materials. Typically, the TiB2/
Al-Cu-Mg composites own similar heat treatments with their alloy
counterparts. For instance, the T6 treatment (Solution
treatment þ Peak aging) is a conventionally used method in Al-Cu-
Mg based materials, and the maximum strength can be achieved
[6e8].
* Corresponding author.
** Corresponding author.
E-mail addresses: mingliang_wang@sjtu.edu.cn (M. Wang), chend@sjtu.edu.cn
(D. Chen).
S(Al2CuMg)-type precipitates are the main strengthening phases
[8e11]. The aging responses of Al-Cu-Mg based composites have
been widely studied. Most researches showed that the reinforcing
particles can reduce the required time to achieve peak hardness in
comparison with their alloy counterparts, i.e., SiCp/2024 [9,12],
SiCp/2009 [13] and Ti3Al/2024 composites [14]. It was explained
that the strain caused by the difference in the coefficient of thermal
expansion (CTE) values between matrix and reinforcement was the
main reason for the accelerated S precipitation. This is because the
dislocations produced by the CTE difference can act as the het-
erogeneous nucleation site for the precipitate during aging treat-
ment [15,16]. In the composites, the S precipitates are acceleratory
formed with the improved aging kinetics, and found to aggregate
near reinforcing particles. All these factors can cause the inhomo-
geneous precipitation behavior for the S phase. Thus, the inho-
mogeneous precipitation behavior must affect the mechanical
properties. However, most of these studies only focused on the
aging kinetics, while the relationships among microstructures,

https://doi.org/10.1016/j.jallcom.2018.10.078
0925-8388/© 2018 Elsevier B.V. All rights reserved.
194 J. Geng et al. / Journal of Alloys and Compounds 775 (2019) 193e201
inhomogeneous precipitation behaviors and mechanical properties
were rarely studied [9,12e14].
For nano TiB2/Al-Cu-Mg composite, our previous works showed
two microstructural characteristics [4,17]: (I) Non-uniformly
distributed nano TiB2 particles; (II) Inhomogeneous distribution
of dislocations, i.e., the higher-density dislocations located in re-
gions approaching to TiB2 particles. The abundant dislocations are
mainly caused by two factors: (1) Geometrically necessary dislo-
cations (GND) induced by non-uniform plastic deformation in small
volume, such as the mismatch strain created by the CTE difference
during temperature fluctuation [2,9,18]; (2) Stored dislocations
from the plastic deformation process (extrusion). Indeed, the re-
covery and recrystallization may occur and consume a part of dis-
locations during heat treatment. Nevertheless, the dislocations can
be largely retained in the matrix due to the pinning effect by TiB2
particles [18]. Therefore, the TiB2 particles should have aggregated
the inhomogeneous distribution of dislocations prior to artificial
aging process. In this case, the precipitation behavior should
become much more inhomogeneous.
Currently, Hong et al. [19] reported the two-peak aging char-
acteristics in TiB2/2009 composite. It was found that the density of S
precipitates has increased in the TiB2 particle rich zones and
decreased in other zones. Clearly, the non-uniform dislocations
have aggravated the partial S precipitation in the regions around
particles. Therefore, the preferential precipitation at local regions
should lead to the formation of precipitation free zones (PFZs). The
PFZs are considered to be detrimental to mechanical and corrosion
properties [20e23]. Attributing to the inhomogeneous precipita-
tion of S phases and the formation of PFZs, the conventional arti-
ficial aging is unable to optimize the mechanical properties of TiB2/
Al-Cu-Mg composites. It has suggested that the improvement of
homogeneous precipitation behavior is significant for enhancing
the mechanical properties of the composite.
Since the dislocations can act as preferential nucleation sites for
S precipitates [15,16], homogenizing and increasing dislocations in
the Al-Cu-Mg matrix by the pre-deformation method should be
effective to tune the S precipitation behavior. Pre-deformation be-
tween the solution treatment and artificial aging process was
known to be used in the age-hardening Al alloys to tune micro-
structures and remove residual stress [24,25]. However, this
method has rarely been applied for the composites due to their
poor ductility. For the ex-situ particle-reinforced Al matrix com-
posites, the particle reinforcements are normally ceramic particles
(i.e., SiC, B4C and Al2O3) with the micro-size. Most of these com-
posites have little elongation [9,12e14,26]. Besides, the larger
reinforcing particle may produce microvoids at particle/matrix
interface, and even cause particle fracture during deformation
[27,28]. Therefore, the Pre-deformation method is not suitable to
these composites. For in-situ nano TiB2/Al alloy composites, they
generally have the comparable ductility with the alloy counterparts
[1e5], indicating that the pre-deformation method can be carried
out on them due to their much larger plastic-deformation ranges.
In this study, to homogenize S precipitation and eliminate the
PFZs in the in-situ TiB2/Al-Cu-Mg composite, a simple method of
pre-stretch aging treatment was applied to introduce homogenous
dislocations into the matrix. The underlying mechanisms related to
the superior strength-ductility combination have been discussed in
terms of microstructure characteristics in the composite.
2. Material and methods
The 2024 alloy and in-situ 5 wt%TiB2/2024 composite ingots
were fabricated by salt-metal reaction method [4]. Both the 2024
alloy and matrix alloy of 5 wt%TiB2/2024 composite had the same
nominal composition of Al-4.3Cu-1.7Mg-0.5Mn (wt.%). The as-cast
ingots were homogenized at 490  C for 24 h, and then extruded at
450  C with the extrusion ratio of 35: 1. Afterwards, the solution
treatment was performed at 505  C following by water quenching.
Subsequently, the solution-treated samples were immediately pre-
stretched by different strain. Finally, the artificial aging was carried
out at 180  C. For comparison, the samples without pre-stretch
were conducted with the same aging condition. The hardness
was measured using a Vicker‫׳‬s hardness testing machine with a
load of 20 kg and dwell time for 15 s. The tensile testing was carried
out on a Zwick/Roell machine at a strain rate of 6  104 s1.
Microstructures were examined by scanning electron micro-
scopy (SEM, NOVA NanoSEM 230) and transmission electron mi-
croscopy (TEM, JEOL 2100F and FEI Talos F200X). In detail, the TEM
(FEI Talos F200X) has been equipped with an energy dispersive X-
ray spectroscopy system with 4 Silicon Drift Detectors for superior
sensitivity and effective mapping capabilities. All the TEM micro-
scopes were operated at 200 kV. Electron backscattered diffraction
(EBSD) was conducted on NOVA NanoSEM 230. The beam step-size
and accelerating voltage were 0.15 mm and 20 kV, respectively. The
EBSD date was analyzed using the commercial software HKL
CHANNEL 5. The misorientations selected for high angle grain
boundaries (HAGBs, black lines) in the EBSD maps are >15 , while
the misorientations in 2 - 15 are defined as low angle grain
boundaries (LAGBs, gray lines). The spurious boundaries with
misorientation angles lower than 2 were not studied.
3. Results
3.1. Microstructures
Fig. 1a shows back scattering electron (BSE) micrograph of TiB2
particles in the TiB2/2024 composite after solution treatment. The
aggregated nano TiB2 particles can be found in the micro regions.
Obviously, the nano TiB2 particles are non-uniformly distributed in
the matrix. It is a common phenomenon in such composite due to
the particles pushed to GBs during solidification [29] and different
plastic flow during deformation [30]. According to the statistics
from SEM images, the size distribution of TiB2 particles is shown in
Fig. 1b, indicating most of the TiB2 particles are in the size of
30e500 nm.
Fig. 1c shows the dislocation distribution in the matrix after
water quenching. The dislocations are non-uniformly distributed,
greatly dependent on TiB2 particles. The higher density dislocations
are inclined to be formed nearby the TiB2 particles. In this case, the
non-uniformly distributed dislocations in the matrix have been
created prior to artificial aging.
Fig. 1d shows the EBSD analysis of the TiB2/2024 composite after
solution treatment. The EBSD map shows the typical 〈100〉 and
〈111〉 fiber texture along extrusion direction. It is noted that the
fractions of LAGBs and substructures are ~50% and 71%, respec-
tively. It may be due to the pinning effect of TiB2 particles on the
dislocation and LAGBs.
Therefore, the TEM and EBSD analyses suggest that the
numerous and non-uniformly dislocations and recovered sub-
structures have formed in the composite after solution treatment,
which should have great influence on the following artificial aging
process.
3.2. Two-peak age hardening response of the TiB2/2024 composite
Fig. 2a shows the evolution of Vickers hardness (HV) of 2024
alloy and TiB2/2024 composite. During the whole aging process, the
hardness of the composite is higher than the alloy. For the alloy, the
hardness reaches the maximum value after ~22 h. The maximum
hardening peak of the composite appears at ~20 h, which is shorten
 J. Geng et al. / Journal of Alloys and Compounds 775 (2019) 193e201 195

Fig. 1. Microstructures of in-situ TiB2/2024 composite after solution treatment: (a) BSE image showing nano TiB2 particles; (b) size distribution of TiB2 particles; (c) TEM image
showing the non-uniform dislocations and dislocation walls pinned by TiB2 particles, as indicated by arrows; (d) EBSD analysis showing high fraction of LAGBs and substructures.

Fig. 2. (a) Age hardening curves of 2024 alloy and 5 wt% TiB2/2024 composite at 180  C, (b) DSC curves of as-quenched 2024 alloy and 5 wt% TiB2/2024 composite.

by ~2 h than the alloy. Therefore, the age hardening kinetics of
composites are suggested to be accelerated by particulate re-
inforcements. Notably, an extra hardening peak at ~7 h is observed
from the curve of the composite before peak aging. This phenom-
enon is similar with that reported in TiB2/2009 composite [18]. It
should be related to the higher density dislocations approaching to
TiB2 particles (Fig. 1b). Although the age hardening is accelerated by
more dislocations, the two-peak age hardening response suggests
the inhomogeneous precipitation and distribution of S precipitates.
Fig. 2b shows the DSC curves of 2024 alloy and TiB2/2024
composite after water quenching. Generally, the heat flow curve for
the composite shows the similar pattern with the alloy. Four main
thermic effects are identified from DSC curves before 500  C.
(I) A weak exothermic Peak I between 50  C and 140  C is
attributed to the formation of Guinier-Preston-Bagaryatsky
(GPB) zones.
(II) An endothermic effect of Peak II at about 170e240  C is about
the dissolution of GPB zones (possibly along with some S00
phases).
(III) A strong exothermic effect containing two overlapping peaks
(III and III0 ) appears at about 200e350  C. The Peak III is due
196 J. Geng et al. / Journal of Alloys and Compounds 775 (2019) 193e201
to the formation of S-type precipitates, where the Peak III0 is
associated with formation of type II S phases. Type II S phases
have a weaker effect on strength since they are relatively
larger size [31].
(IV) An endothermic effect of Peak IV at 380e500  C stands for
the dissolution of S precipitates.
Compared with the alloy, the exothermic effect of S precipitates
of the composite shifts to lower temperature, leading to the sharper
shoulder peak III' in the composite. The formation peak area (Peak
I) of GPB zones of the composite is much smaller than the alloy.
Generally, the quenching vacancies can be annihilated by disloca-
tions, leading to the reduction of the nucleation of GPB zones [8,13].
The decreased GPB zones are responsible for the weaker hardening
response of the composite than the alloy before 10 min (Fig. 2a).
Then, the dissolution of GPB zones causes the slight decrease in
hardness after 15 min. Subsequently, the age hardening moves to-
wards to the peak hardness due to the S precipitation.
3.3. Inhomogeneous precipitation behavior of the TiB2/2024
composite
Fig. 3a shows the S phases precipitate firstly on abundant dis-
locations around TiB2 particles, which is responsible for the first
hardening peak at ~7 h. The S precipitates (~50e100 nm in length)
aggregated near TiB2 particles are clearly found in HAADF image at
a higher magnification (Fig. 3b). The distribution of TiB2 particles is
confirmed by corresponding element mapping (Fig. 3c and d).
Fig. 3e shows that both the density and size (~200e400 nm in
length) of S precipitates have largely increased after peak aging,
which should be responsible for the second hardening peak at
~20 h. The matrix near TiB2 particles can be regarded as the pre-
cipitation accelerated zones, while the other regions with few TiB2
particles form PFZs. Although the hardness reaches the maximum
Fig. 3. TEM images showing S precipitates in the non-stretched composite at different aging stages: (a) under aging, 7 h; (b) HAADF image at a higher magnification showing S
precipitates preferentially formed around TiB2 particles, (c) and (d) corresponding element mapping; (e) peak aging, 20 h; (f) over aging, 32 h.
value, the distribution of S precipitates is still very inhomogeneous.
As the aging time prolonging to 32 h (over aging stage), the S
precipitates have been obviously coarsening (>500 nm in length) in
zone “A” (sub-grain boundary) accompanying with the reduced
PFZs within grains (Fig. 3f). The S phases are preferentially coars-
ening on sub-grain boundaries and dislocations around TiB2 par-
ticles. Nevertheless, the PFZs are still evident in the over aged
sample, such as zone “B”. The plastic flow should occur preferen-
tially within the PFZs, since these regions are softer than the
precipitated matrix [20e23]. The evident PFZs can decrease both
the strength and ductility in the TiB2/2024 composites, because
they are soft to increase the possibility of premature fracture.
Both the age hardening and precipitation behaviors have
confirmed the inhomogeneous distribution of S precipitates
accompanying with the formation of PFZs. It is indicated that these
microstructure features are ineffective to improve mechanical
properties of TiB2/2024 composite.
3.4. Homogenizing precipitation behavior of the TiB2/2024
composite
Taking the 5% stretch aging as an example, the S precipitation of
the composite is shown in Fig. 4. Clearly, the homogeneous distri-
bution of dislocations are found after 5% stretch (Fig. 4a). After
aging for 1 h, the nano S precipitates are identified by the streaking
of the diffraction spots (Fig. 4b). In Fig. 4c, the uniform and coars-
ening S precipitates are clearly observed after aging for 5 h. It is
noted that the S precipitates are uniformly distributed, and thus the
PFZs are disappeared during the aging process.
The HRTEM images are shown in Fig. 4def. For the non-
stretched sample aging for 1 h, the S precipitates or its variants
(S-type phase having 12 equivalent variants [8]) are inhomoge-
neous with low density, mainly occurring on dislocations (Fig. 4d).
Comparatively, the 5% pre-stretched sample shows higher-density
 J. Geng et al. / Journal of Alloys and Compounds 775 (2019) 193e201 197

Fig. 4. TEM images of the 5% pre-stretched composite after aging for (a) 0 h, (b) 1 h, (c) 5 h. HRTEM images: (d) S precipitates non-uniformly precipitating on dislocations; 0% pre-
stretch aging for 1 h, 5% pre-stretch aging for (e) 1 h and (f) 5 h, showing the nano S precipitating uniformly.

of S precipitates with nano size (~1e2 nm in width and ~5e15 nm in
length), as indicated by arrows in Fig. 4e. However, the S pre-
cipitates are coarsening obviously after 5 h aging, especially in
width (Fig. 4f). The size of S precipitates is ~4e10 nm in width and
~15e25 nm in length. Even so, the size is still further smaller than
that precipitated in the non-stretched sample at peak aging, where
S is ~200e400 nm in length (Fig. 3e).
Distinctly, in comparison with the T6 treatment (Fig. 3), the
distribution of S phases is more homogeneous, and the size is finer
due to the increased nucleation sites. Attributing to these facts, the
microstructures related to S precipitates are apparently modified by
pre-stretch.
3.5. Effect of pre-stretch aging on the tensile properties
Fig. 5a presents the DSC curves of the composite experiencing
0%e10% pre-stretch after solution treatment. For pre-stretched
samples, only one exothermic peak exists between 200  C and
350  C. Compared with the non-stretched sample, the exothermic
peaks of S phase formation of all the pre-stretched samples are
sharper, and shift to lower temperatures with the increasing strain.
It has suggested that the precipitation kinetics of S phases in the
pre-stretched samples are enhancing.
Fig. 5b shows the evolution of HV as a function of aging time for
the composite experiencing 0% and 5% pre-stretch, respectively.
198 J. Geng et al. / Journal of Alloys and Compounds 775 (2019) 193e201

Fig. 5. (a) DSC curves of the composite experiencing different pre-stretch; (b) age hardening curves of the composite with 0% and 5% pre-stretch, respectively; tensile properties of
the composite as a function of aging time: (c) 0% pre-stretch, (d) 5% pre-stretch.

During the whole artificial aging process, the hardness of the 5% Conclusively, a better comprehensive mechanical properties of
pre-stretched composite is much higher than the non-stretch one. TiB2/2024 composite can be achieved by the pre-stretch aging
The higher initial hardness for the pre-stretched sample is directly method.
related to the enhanced dislocation density arising from the pre- The tensile properties of pre-stretched TiB2/2024 composites
deformation prior to aging. Similarly, the age hardening rate of after aging for 1 h at 180  C are summarized in Fig. 6 [7,12,13,32e43]
the 5% pre-stretched composite before ~10 min is lower than the Compared with T6 treatment (peak aging), both the strength and
non-stretched sample due to the reduction of GPB zones [8,13]. elongation are obviously enhanced by pre-stretch aging. For
For the non-stretched sample, two obvious peaks can be instance, after the composite undergoing 5% pre-stretch aging, the
observed on the age hardening curve. The first peak is at ~7 h, and
the second peak reaches the maximum hardness of ~160 HV at
~20 h. The two-peak aging response has indicated an inhomoge-
neous aging behavior of S precipitates. For the 5% pre-stretched
composite, the hardness reaches the maximum value (~189 HV)
after ~5 h, which is shorten by ~15 h than the non-stretched one.
Significantly, the single age hardening peak implies that the S
phases precipitate uniformly in the Al matrix.
The tensile properties of TiB2/2024 composite after T6 treatment
are depicted in Fig. 5c. The yield strength (s0.2) increases with aging
time before peak aging (20 h). After peak aging, the s0.2 decreases
clearly. Both ultimate tensile strength (sb) and elongation (d)
exhibit the decreasing tendency after aging for 1 h. Although s0.2
reaches the maximum value of ~438 MPa at peak aging, both sb and
d decrease to ~546 MPa and ~7.4%, respectively.
Fig. 5d shows tensile properties of the composite with 5% pre-
stretch aging. Clearly, sb has changed few, while s0.2 increases
apparently and reaches the maximum value of 626 MPa at peak
aging (5 h). The elongation decreases after aging for 1 h, but still
shows a reasonable value of ~7.6% at peak aging. Overall, after pre-
Fig. 6. Comparison of the tensile properties of TiB2/2024 composites after pre-stretch
stretch aging, both the strength and elongation of the composite aging with previously reported 2024 alloys and ex-situ particle reinforced 2024
are much higher than the conventional T6 treated one. composites [7,12,13,32e43].
 J. Geng et al. / Journal of Alloys and Compounds 775 (2019) 193e201
high strength (s0.2 ¼ 544 MPa, sb ¼ 643 MPa) and good elongation
(~11.7%) are simultaneously obtained. After 10% pre-stretch aging,
the composite shows ultrahigh strength (s0.2 ¼ 606 MPa,
sb ¼ ~676 MPa). The elongation (~7.6%) is still higher than the non-
stretch sample. After the peak aging, the s0.2 reaches the maximum
value, and sb is not decreased obviously in comparison with the
under aging state. Moreover, the mechanical properties of the 5%
pre-stretch aging samples are better than the T6 treated samples.
Resultantly, the strength can be remarkably enhanced by pre-
stretch aging, while the elongation has maintained at a high
level. In comparison with 2024 alloys and ex-situ 2024 composites
(Fig. 6), the pre-stretched TiB2/2024 composites have exhibited the
better strength-elongation combinations.
4. Discussions
The nucleation of S precipitates is greatly dependent on dislo-
cations and/or sub-grain boundaries in Al-Cu-Mg alloys [14e16].
For the non-stretched composite, a higher density of dislocations
and LAGBs have formed near TiB2 particles after solution treatment
(Fig. 1c). On one hand, a large amount of dislocations can be pro-
duced in the matrix during extrusion. Although dislocations can be
partially recovered during solution treatment, a number of dislo-
cations still exist near TiB2 particles. That is because that disloca-
tions or recovered dislocation walls can be pinned and stabilized by
nano TiB2 particles [17], as indicated in Fig. 1c. On the other hand,
the enhanced density of GNDs are created to accommodate the
plastic strain arising from the CTE mismatch after water quenching
[2,20], which can be approximately estimated by Ref. [44].
12DC DTf p
rCTE
G ¼

bdp 1  fp
where DC is the difference in the CTE values between Al and TiB2;
DΤ is the difference in temperatures between the solution
treatment and water, ~758 K
fp is the volume fraction of TiB2 particles, ~3.1%;
dp is the average particle size.
The CTE of Al and TiB2 are about 21  106 K1 and 8  106 K1,
respectively [2,26].
The value of rCTE 14 2
G is estimated to be 1.6  10 m . It means that
the matrix of the composite contains numerous dislocations and
substructures associated with TiB2 particles, and they are inho-
mogeneously distributed.
Therefore, the S phases precipitate firstly on abundant disloca-
tions around TiB2 particles (Fig. 3a), since the increased dislocations
serve as fast diffusion paths and traps for solute atoms during aging
[14e16,45]. Attributing to this fact, the accelerated S precipitation
near TiB2 particles has caused the formation of PFZs in the matrix.
However, the pre-stretch can not only increase the density of
dislocations, but also homogenize their distribution, for example
after 5% stretch in Fig. 4a. Resultantly, the phenomenon of S phases
preferentially precipitating near TiB2 particles has disappeared,
leading to the single-peak aging response and avoiding the PFZs
formation. The modified microstructures are key factors to improve
the mechanical properties.
For the good ductility, the strain energy and dislocation density
should be decreased dramatically after the incipient precipitations
nucleated on dislocations, i.e. the recovery or relaxation of internal
stress. The relaxation of internal stress should be in favor of the
dislocation accumulation before saturation under tensile stress.
Thus, it is beneficial to increase the ductility [31]. The elimination of
199
PFZs can be conducive to uniform deformation under tensile stress,
because the local stress concentration at PFZs is delayed.
Not only the elongation to failure is obviously increased by pre-
stretch aging, but also the uniform elongation (strain before
necking) of the composite is greatly improved. For example, the
uniform elongation of the composite after 5% pre-stretch aging is
~11.2% (Fig. 7a). In comparison, the uniform elongation of the
composite treated by T6 condition is only ~6.5%, showing obvious
necking. It is mainly caused by the PFZs and coarse S precipitates in
conventional T6 state. The uniform nano S precipitates can increase
the work-hardening rate by Orowan mechanism. The normalized
work-hardening rate Q can be described by Ref. [46].
1 ds
Q¼ (2)
s dε
where s and ε are the true stress and true strain, respectively.
As shown in Fig. 7b, the work-hardening rate of the sample with
pre-stretch aging is much higher than the sample aging without
pre-stretch. The higher work-hardening rate is essential for good
uniform elongation, because it can help to delay localized defor-
mation (necking) and increase the capability of dislocation accu-
mulation under tensile stress [46,47]. Nevertheless, the reduced
elongation at peak aging of T6 treatment is relative to its thicker
and longer precipitates.
However, for the T6 treated samples, the work hardening rate
within the PFZ should be different from the bulk materials. First, the
dislocations generated from suitable sources can readily move
through the soft PFZs until their motions are inhibited by pre-
cipitates at the PFZ-matrix boundaries, which cause back stress to
the oncoming dislocations within PFZs. As the applied stress
increasing, the number of dislocations piled up within PFZs is
(1)
increased. According to ABE et al. [23], the density of piled-up
groups (N) can be obtained
εPFZ
N¼ (3)
ðDPFZ  lÞb
ε
εPFZ ¼ (4)
VPFZ
For an ellipsoid grain, if the number of PFZs within a grain is n,
Eq. (4) can be written as:
L0 D20
εPFZ ¼ ε (5)
nD3PFZ
where D0 and L0 are the grain size at cross-section and extrusion
direction, respectively;
l is the critical width of the PFZ below which dislocations can
move out PFZs, approximately equal to inter-particle spacing;
DPFZ is the average width of PFZs;
b is the Burgers vector;
ε is the overall strain of the tensile sample;
εPFZ is the local strain of PFZ;
VPFZ is the volume fraction of PFZs.
Hence, the stress of PFZs can be expressed as:
pffiffiffiffi
sPFZ ¼ s0 þ DPFZ tc N (6)
where s0 is fractional stress to be constant;
tc is the shear stress; a is a constant;
G is shear modulus.
200 J. Geng et al. / Journal of Alloys and Compounds 775 (2019) 193e201

Fig. 7. (a) Tensile engineering stress-strain curves of in-situ TiB2/2024 composite under two typical aging conditions, squares mark the uniform elongation; (b) comparison of the
work-hardening rate curves of pre-stretch aging and conventional T6 treated samples (Using 5% pre-stretched sample as an example).

Then, Eq. (5) can be given as
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
L0 D20
sPFZ ¼ s0 þ tc ε (7)
nDPFZ bðDPFZ  lÞ
As shown in Fig. 3f, DPFZ is far larger than l. Therefore, the work
hardening rate of PFZs (QPFZ) is approximately expressed by
rffiffiffiffiffiffiffiffi
ds tc D0 L0
QPFZ ¼ PFZ ¼
dε 2DPFZ nbε
Therefore, the large size PFZs (~600 nm) in the T6 treated
samples should cause the lower work hardening rate than the
matrix with uniform S precipitates. This may be an important
reason for the lower work hardening rate in the non-stretch com-
posite than the composite with pre-stretch aging.
For the enhanced strength, it can be attributed to the coupling
effect of high-density nano S precipitates and dislocations. Due to
the pre-stretch, the dislocation density should be much higher than
the T6 treated sample in spite of dislocations recovered partially.
The tensile flow stress related to the dislocation density can be
given by Ref. [44].
pffiffiffiffiffi
Dsflow ¼ MaGb rS
where M is the Taylor factor;
rS is stored dislocations after aging treatments.
In comparison with T6 treatment, the shorter aging time may
reduce the dislocation recovery, and the pre-stretch can enhance
the dislocation density. Due to the more stored dislocations (Fig. 4),
the dislocation strength should be higher in the pre-stretched
samples.
The high-density nano S precipitates can provides effective sites
for trapping and accumulating dislocations, i.e. precipitation
strengthening (Dsp). It can be described by Ref. [48].
effective due to the decrease of precipitate particle size. Thus, it is
adequate to compensate for the loss of strength by dislocation re-
covery. For example, the sb of non-stretched and 5% stretched
sample after aging for 1 h are ~563 MPa and ~643 MPa, respectively.
Besides, the elimination of PFZs can reduce premature fracture and
improve strength.
As a result, the composites with pre-stretch aging can exhibit
not only the higher uniform elongation, but also higher strength
than the composite treated by the conventional peak aging.
(8)
5. Conclusions
(1) In the in-situ TiB2/Al-Cu-Mg composite, the age hardening
kinetics has been accelerated by TiB2 particles in comparison
with the alloy. Microstructurally, it has corresponded to the S
precipitation behavior, which has been enhanced around
TiB2 particles and impeded in other regions, leading to the
formation of PFZs.
(2) The inhomogeneous S precipitation has caused the two-peak
age hardening response in the composite. The non-uniform
distribution of the coarse S precipitates and PFZs signifi-
cantly limits the increment of mechanical properties.
(3) Pre-stretch can introduce uniformly distributed dislocations
(9) in the matrix, which is favorable to homogenize S pre-
cipitates and eliminate PFZs. Therefore, the homogeneous
and nano-sized S precipitates are obtained by pre-stretch
aging.
(4) Compared with T6 treatment, the pre-stretched composite
shows a single age hardening response. Both the strength
and ductility are simultaneously enhanced after pre-stretch
aging.
The higher-density dislocations, homogeneous S nano-
precipitates and elimination of PFZs are the key factors for the in-
crease in strength. Meanwhile, the homogeneous S nano-
precipitates and elimination of PFZs can also increase the work
hardening rate, and thus improve the ductility.

f
Dsp ¼ k (10) Acknowledgments
r

where r is the average diameter of precipitates; This work is sponsored by the project (Grant No. HT2R0076-
2014) sponsored by Aero Engine Corporation of China Commercial
f is the volume fraction of precipitates; Aircraft Engine (China), the project (Grant No. 2017WAMC002)
k is the constant. sponsored by Anhui Province Engineering Research Center of
Aluminium Matrix Composites (China), and the project (Grant No.
Apparently, the precipitation strengthening should be more GKJC010001) sponsored by the Collaborative Innovation Center for
 J. Geng et al. / Journal of Alloys and Compounds 775 (2019) 193e201
Advanced Ship and Deep-Sea Exploration, and Research Fund
(Project No. 15X100040018) at Shanghai Jiao Tong University
(China). Meanwhile, we would like to express our appreciate to Dr.
Yugang Li and Dr. Chou Zhou (Shanghai Jiao Tong University
(China)) for their great help in the experimental process.
References
[1] X.P. Li, G. Ji, Z. Chen, A. Addad, Y. Wu, H.W. Wang, J. Vleugels, J. Van Hum-
beeck, J.P. Kruth, Selective laser melting of nano-TiB2 decorated AlSi10Mg
alloy with high fracture strength and ductility, Acta Mater. 129 (2017)
183e193.
[2] M. Wang, D. Chen, Z. Chen, Y. Wu, F. Wang, N. Ma, H. Wang, Mechanical
properties of in-situ TiB2/A356 composites, Mater. Sci. Eng. A 590 (2014)
246e254.
[3] H. Yi, N. Ma, Y. Zhang, X. Li, H. Wang, Effective elastic moduli of Al-Si com-
posites reinforced in situ with TiB2 particles, Scr. Mater. 54 (2006) 1093e1097.
[4] J.W. Geng, T.R. Hong, Y. Ma, M.L. Wang, D. Chen, N.H. Ma, H.W. Wang, The
solution treatment of in-situ sub-micron TiB2/2024 Al composite, Mater. Des.
98 (2016) 186e193.
[5] J.W. Geng, G. Liu, F.F. Wang, T.R. Hong, J.C. Dai, M.L. Wang, D. Chen, N.H. Ma,
H.W. Wang, Microstructural correlated damage mechanisms of the high-cycle
fatigued in-situ TiB2/Al-Cu-Mg composite, Mater. Des. 135 (2017) 423e438.
[6] M.J. Styles, C.R. Hutchinson, Y. Chen, A. Deschamps, T.J. Bastow, The coexis-
tence of two S (Al2CuMg) phases in Al-Cu-Mg alloys, Acta Mater. 60 (2012)
6940e6951.
[7] N.D. Alexopoulos, Z. Velonaki, C.I. Stergiou, S.K. Kourkoulis, Effect of ageing on
precipitation kinetics, tensile and work hardening behavior of Al-Cu-Mg
(2024) alloy, Mater. Sci. Eng. A 700 (2017) 457e467.
[8] S.C. Wang, M.J. Starink, Review of precipitation in Al-Cu-Mg(-Li) alloys, Int.
Mater. Rev. 50 (2005) 193e215.
[9] S.M.R. Mousavi Abarghouie, S. Seyed Reihani, Aging behavior of a 2024 Al
alloy-SiCp composite, Mater. Des. 31 (2010) 2368e2374.
[10] G.E. Kiourtsidis, S.M. Skolianos, G.A. Litsardakis, Aging response of aluminium
alloy 2024/silicon carbide particles (SiCp) composites, Mater. Sci. Eng. A 382
(2004) 351e361.
[11] P. Jin, B.L. Xiao, Q.Z. Wang, Z.Y. Ma, Y. Liu, S. Li, Effect of solution temperature
on aging behavior and properties of SiCp/Al-Cu-Mg composites, Mater. Sci.
Eng. A 528 (2011) 1504e1511.
[12] V.K. Varma, S.V. Kamat, V.V. Kutumbarao, Tensile behaviour of powder met-
allurgy processed (Al-Cu-Mg)SiCp composites, Mater. Sci. Technol. 17 (2001)
93e101.
[13] R. Angers, M.R. Krishnadev, R. Tremblay, J.F. Corriveau, D. Dube, Character-
ization of SiCp/2024 aluminum alloy composites prepared by mechanical
processing in a low energy ball mill, Mater. Sci. Eng. A 262 (1999) 9e15.
[14] G. Chen, Y. Jin, H. Zhang, F. Han, Q. Chen, J. Xu, Z. Zhao, Microstructures and
mechanical properties of in-situ Al3Ti/2024Al composites after solution and
subsequent aging treatment, Mater. Sci. Eng. A 724 (2018) 181e188.
[15] G. Sha, R.K.W. Marceau, X. Gao, B.C. Muddle, S.P. Ringer, Nanostructure of
aluminium alloy 2024: segregation, clustering and precipitation processes,
Acta Mater. 59 (2011) 1659e1670.
[16] Z.Q. Feng, Y.Q. Yang, B. Huang, X. Luo, M.H. Li, M. Han, M.S. Fu, HRTEM and
HAADF-STEM tomography investigation of the heterogeneously formed
S(Al2CuMg) precipitates in Al-Cu-Mg alloy, Acta Mater. 59 (2011) 1843e1858.
[17] J.W. Geng, T.R. Hong, Y.W. Shen, G. Liu, C.J. Xia, D. Chen, M.L. Wang,
H.W. Wang, Microstructural stability of in-situ TiB2/Al composite during so-
lution treatment, Mater. Char. 124 (2017) 50e57.
[18] R. Arsenault, N. Shi, Dislocation generation due to differences between the
coefficients of thermal expansion, Mater. Sci. Eng. 81 (1986) 175e187.
[19] T.R. Hong, X.F. Li, H.W. Wang, D. Chen, K. Wang, Effects of TiB2 particles on
aging behavior of in-situ TiB2/Al-Cu-Mg composites, Mater. Sci. Eng. A 624
(2015) 110e117.
[20] T.F. Morgeneyer, M.J. Starink, S.C. Wang, I. Sinclair, Quench sensitivity of
toughness in an Al alloy: direct observation and analysis of failure initiation at
the precipitate-free zone, Acta Mater. 56 (2008) 2872e2884.
[21] Y.C. Lin, J.L. Zhang, G. Liu, Y.J. Liang, Effects of pre-treatments on aging pre-
cipitates and corrosion resistance of a creep-aged Al-Zn-Mg-Cu alloy, Mater.
201
Des. 83 (2015) 866e875.
[22] A. Zindal, J. Jain, R. Prasad, S.S. Singh, P. Cizek, Correlation of grain boundary
precipitate characteristics with fracture and fracture toughness in an Mg-8Al-
0.5Zn alloy, Mater. Sci. Eng. A 706 (2017) 192e200.
[23] M. Abe, K. Asano, A. Fujiwara, Influence of the precipitate-free zone width on
the tensile properties of an Al-6wt Pct Zn-l.2wt Pct Mg alloy, Metall. Trans. 4
(1973) 1499e1505.
[24] M. Gazizov, R. Kaibyshev, Effect of pre-straining on the aging behavior and
mechanical properties of an Al-Cu-Mg-Ag alloy, Mater. Sci. Eng. A 625 (2015)
119e130.
[25] B.L. Averbach, Cold Working of Metals, ASM, Cleveland, OH, 1949.
[26] D.J. Lloyd, Particle reinforced aluminium and magnesium matrix composites,
Int. Mater. Rev. 39 (1994) 1e23.
[27] V.K. Varma, S.V. Kamat, V.V. Kutumbarao, Tensile behaviour of powder met-
allurgy processed (Al-Cu-Mg)/SiCp composites, Met. Sci. J. 17 (2001) 93e101.
[28] S. Qin, C. Chen, G. Zhang, W. Wang, Z. Wang, The effect of particle shape on
ductility of SiCp reinforced 6061 Al matrix composites, Mater. Sci. Eng. A 272
(1999) 363e370.
[29] T. Wang, Z. Chen, Y. Zheng, Y. Zhao, H. Kang, L. Gao, Development of TiB2
reinforced aluminum foundry alloy based in situ composites e Part II:
enhancing the practical aluminum foundry alloys using the improved Al-5wt%
TiB2 master composite upon dilution, Mater. Sci. Eng. A 605 (2014) 22e32.
[30] X. Jiang, M. Galano, F. Audebert, Extrusion textures in Al, 6061 alloy and 6061/
SiCp nanocomposites, Mater. Char. 88 (2014) 111e118.
[31] S.C. Wang, M.J. Starink, Two types of S phase precipitates in Al-Cu-Mg alloys,
Acta Mater. 55 (2007) 933e941.
[32] C.Z. Nie, J.J. Gu, J.L. Liu, D. Zhang, Production of boron carbide reinforced 2024
aluminum matrix composites by mechanical alloying, Mater. Trans. 48 (2007)
990e995.
[33] A. Abdollahi, A. Alizadeh, H.R. Baharvandi, Dry sliding tribological behavior
and mechanical properties of Al2024-5wt.%B4C nanocomposite produced by
mechanical milling and hot extrusion, Mater. Des. 55 (2014) 471e481.
[34] Y.J. Huang, Z.G. Chen, Z.Q. Zheng, A conventional thermo-mechanical process
of Al-Cu-Mg alloy for increasing ductility while maintaining high strength,
Scr. Mater. 64 (2011) 382e385.
[35] Y.L. Zhao, Z.Q. Yang, Z. Zhang, G.Y. Su, X.L. Ma, Double-peak age strengthening
of cold-worked 2024 aluminum alloy, Acta Mater. 61 (2013) 1624e1638.
[36] R. Zheng, Y. Sun, K. Ameyam, C. Ma, Optimizing the strength and ductility of
spark plasma sintered Al 2024 alloy by conventional thermo-mechanical
treatment, Mater. Sci. Eng. A 590 (2014) 147e152.
[37] M.A. Sutton, B. Yang, A.P. Reynolds, J. Yan, Banded microstructure in 2024-
T351 and 2524-T351 aluminum friction stir welds: Part II. Mechanical char-
acterization, Mater. Sci. Eng. A 364 (2004) 66e74.
[38] Y. Xu, P.J. Gregson, I. Sinclair, Dispersoid and grain size effects on fatigue crack
growth in AA2024-type alloys, Mater. Sci. Forum 331e337 (2000)
1525e1530.
[39] H. Wei, F. Xia, M. Wang, Effect of ingot grain refinement on the tensile
properties of 2024 Al alloy sheets, Mater. Sci. Eng. A 682 (2017) 1e11.
[40] J.H. Shin, H.J. Choi, D.H. Bae, The structure and properties of 2024 aluminum
composites reinforced with TiO2 nanoparticles, Mater. Sci. Eng. A 607 (2014)
605e610.
[41] C.M. Cepeda-Jime
nez, P. Hidalgo, M. Carsí, O.A. Ruano, F. Carren ~ o, Micro-
structural characterization by electron backscatter diffraction of a hot worked
Al-Cu-Mg alloy, Mater. Sci. Eng. A 528 (2011) 3161e3168.
[42] M.J. Luk, F.A. Mirza, D.L. Chen, D.R. Ni, B.L. Xiao, Z.Y. Ma, Low cycle fatigue of
SiCp reinforced AA2009 composites, Mater. Des. 66 (2015) 274e283.
[43] A.H. Feng, B.L. Xiao, Z.Y. Ma, Effect of microstructural evolution on mechanical
properties of friction stir welded AA2009/SiCp composite, Compos. Sci.
Technol. 68 (2008) 2141e2148.
[44] M. Kouzeli, A. Mortensen, Size dependent strengthening in particle reinforced
aluminium, Acta Mater. 50 (2002) 39e51.
[45] D. Blavette, E. Cadel, A. Fraczkiewicz, A. Menand, Three-dimensional atomic-
scale imaging of impurity segregation to line defects, Science 286 (1999),
317-2319.
[46] G.E. Dieter, Mechanical Metallurgy, third ed., McGraw-Hill, New York, 1986.
[47] Y.H. Zhao, X.Z. Liao, S. Cheng, E. Ma, Y.T. Zhu, Simultaneously increasing the
ductility and strength of nanostructured alloys, Adv. Mater. 18 (2006)
2280e2283.
[48] T. Courtney, Mechanical Behavior of Materials, McGraw-Hill, New York, 1990.