materials

Article
Evolution of Microstructure, Texture and Mechanical
Properties for Multilayered Al Matrix Composites by
Accumulative Roll Bonding
Wen-Jing Wang 1,2,3, *, Kam-Chuen Yung 4 , An-Dong Tang 1 , Hang-Shan Choy 4 and Zheng Lv 5

1 School of Materials Science and Engineering, University of Science and Technology Beijing,
Beijing 100083, China; tangad1112@163.com
2 Institute for Advanced Materials and Technology, University of Science and Technology Beijing,
Beijing 100083, China
3 Beijing Laboratory of Metallic Materials and Processing for Modern Transportation, Beijing 100083, China
4 Department of Industrial and Systems Engineering, The Hong Kong Polytechnic University, Hung Hom,
Kowloon, Hong Kong 100077, China; wincokc.yung@polyu.edu.hk (K.-C.Y.);
choy.henry@polyu.edu.hk (H.-S.C.)
5 Advanced Electronic Materials Institute, GRIMAT Engineering Institute Co., Ltd., Beijing 101407, China;
lvzheng1988@126.com
* Correspondence: wendy_wang_7@hotmail.com






Citation: Wang, W.-J.; Yung, K.-C.;
Tang, A.-D.; Choy, H.-S.; Lv, Z.
Evolution of Microstructure, Texture
and Mechanical Properties for
Multilayered Al Matrix Composites
by Accumulative Roll Bonding.
Materials 2021, 14, 5576. https://
doi.org/10.3390/ma14195576
Academic Editor: Francisco Javier
Espinach Orús
Abstract: Carbon nanotubes (CNTs) reinforced aluminum matrix nanocomposites were fabricated by
Accumulative Roll Bonding (ARB). The surface morphologies, mechanical properties, grains texture
and orientation of the Al/CNTs nanocomposites were characterized, and the mechanisms and
influences of CNTs contents and ARB cycles on the mechanical performance and grain textures
of Al/CNTs were investigated and revealed. The strength of the composites rose with increase of
the CNTs content, and the ARB cycles showed a 26% improvement when the CNTs content varied
from 0 to 1 volume percent (vol.%). The increase in the mass fraction of the carbon nanotubes made
the grain distribution in the Al/CNTs nanocomposite samples more diffuse. Besides, the stable
texture of the hot rolled crystal grains on the α orientation are constantly turning to {011}< 011> with
the mass fraction of the reinforcing phase increased.
Keywords: accumulative roll bonding; metal matrix composites (MMCs); carbon nanotubes and
nanofibers; mechanical properties

Received: 23 July 2021

Accepted: 14 September 2021 1. Introduction
Published: 26 September 2021
Aluminum matrix nanocomposites have attracted considerable interest for structural
design due to their excellent mechanical and physical properties. The influence of the
Publisher’s Note: MDPI stays neutral
reinforcement is clearly present via high strength and high modulus than the sample with
with regard to jurisdictional claims in
no reinforcement [1]. The ceramic nanoparticles in the Al matrix could increase the porosity
published maps and institutional affil-
and decrease the density to fabricate lightweight composites [2]. These excellent properties
iations.
offer wide opportunities in applications such as aerospace and automotive structural
components. During the last decade, various types of nanosized reinforcements have been
used in an aluminum matrix to synthesize nanocomposites. Ceramic nanoparticles reduced
grain sizes at higher ARB cycles, which caused additional strengthening [3]. A recent study
Copyright: © 2021 by the authors.
showed the increased tensile strength and microhardness of the Al8011/SiC with only
Licensee MDPI, Basel, Switzerland.
up to ARB three cycles [4]. However, the elongation of the Al/MWCNT-Al2 O3 hybrid
This article is an open access article
composite is decreased by ten cycles of ARB [5].
distributed under the terms and
Carbon nanotubes (CNTs), which have engendered considerable attention as rein-
conditions of the Creative Commons
forcements in metal matrix composites, present high strength, high elastic modulus as
Attribution (CC BY) license (https://
well as high aspect ratio [6–8]. For structural applications, Al/CNTs composites have been
creativecommons.org/licenses/by/
4.0/).
successfully processed using different techniques, and most investigations have followed

Materials 2021, 14, 5576. https://doi.org/10.3390/ma14195576 https://www.mdpi.com/journal/materials

 Materials 2021, 14, x FOR PEER REVIEW 2 of 11
Materials 2021, 14, 5576 2 of 9

the powder metallurgy route, accompanied by the plastic deformation process. For in-
the powder
stance, metallurgy
ball milling route,plasma
and spark accompanied
sinteringbyfor
theconsolidating
plastic deformation process.
the composites Forbeen
have in-
stance,
applied ball milling
[9,10]. and sparkhave
Researchers plasma
alsosintering
exploredfortheconsolidating the composites
melt route (such as sprayinghave been
and liquid
applied [9,10]. Researchers have also explored the melt route (such as spraying and
infiltration) and the severe plastic deformation route (SPD, such as high-pressure torsion, liquid
infiltration)
ECAP, andand roll the severe To
bonding). plastic deformation
prepare compositesroute (SPD,
with highsuch as high-pressure
strength torsion,
and elastic modulus
ECAP, and roll bonding). To prepare composites with high strength and elastic modulus
offers a possibility of fabricating materials by using multi-laminates or introducing parti-
offers
cles ora possibility of fabricating
films with the materials of
repeated processes byaccumulating
using multi-laminates or [11].
and rolling introducing parti-
In theory, full
cles or films with the repeated processes of accumulating and rolling [11]. In theory, full
diffusion of particles could always be obtained with sufficient ARB cycles in the compo-
diffusion of particles could always be obtained with sufficient ARB cycles in the composites
sites fabricated. Furthermore, a metal matrix composite fabricated by the ARB process is
fabricated. Furthermore, a metal matrix composite fabricated by the ARB process is not
not necessary to process additional densification treatment. However, to date, few studies
necessary to process additional densification treatment. However, to date, few studies have
have been conducted on the investigation of Al/CNTs composites processed by the ARB
been conducted on the investigation of Al/CNTs composites processed by the ARB process.
process. The mechanism and influence of the ARB process on the microstructure and me-
The mechanism and influence of the ARB process on the microstructure and mechanical
chanical properties of Al/CNTs composite are limited and not clear.
properties of Al/CNTs composite are limited and not clear.
The present work aimed at preparing Al/CNTs composites using the ARB process
The present work aimed at preparing Al/CNTs composites using the ARB process
and in revealing the microstructures and mechanical properties of the composites. In ad-
and in revealing the microstructures and mechanical properties of the composites. In
dition, the morphologies of CNTs within the Al matrix, and the grain and macrotexture
addition, the morphologies of CNTs within the Al matrix, and the grain and macrotexture
of the Al matrix were analyzed using transmission electron microscopy (TEM), electron
of the Al matrix were analyzed using transmission electron microscopy (TEM), electron
back-scattereddiffraction
back-scattered diffraction(EBSD)
(EBSD)andandX-ray
X-raydiffraction
diffraction(XRD)
(XRD)methods.
methods.The
Themechanical
mechanical
properties of composites were investigated by tensile
properties of composites were investigated by tensile tests. tests.

2.2.Experimental
ExperimentalSection
Section
2.1.Materials
2.1. MaterialsPreparation
Preparation
Sheets
Sheetsofofcommercial
commercialpurepurealuminum
aluminumalloy
alloyAA1060
AA1060(H24,
(H24,GB/T
GB/T16475-2008)
16475-2008)werewere
used
usedas
as rolled
rolled samples, with
with dimensions 100× ×
dimensionsofof100 50 50 × mm.
× 0.6 0.6 mm. Multi-walled
Multi-walled carboncarbon
nano-
nanotubes (MWCNTs)
tubes (MWCNTs) withwith
outerouter diameters
diameters of 10–30
of 10–30 nm aand
nm and a nominal
nominal axial axial
lengthlength of
of 10–20
10–20 µm were
μm were used used as reinforcements
as reinforcements (Figure
(Figure 1). 1).

Figure1.1.TEM
Figure TEMmicrograph
micrographofofMWCNTs
MWCNTsused
usedininthis
thiswork.
work.

BeforeARB,
Before ARB,the thesurfaces
surfacesofofthe
theAlAlsheets
sheetswere
werescratched
scratchedwithwithaastainless
stainlesssteel
steelbrush
brush
andthen
and thendegreased
degreasedininacetone.
acetone. CNTs
CNTswere weredispersed
dispersedon onone-side
one-sideofofsix
sixraw
rawAl Alsheets
sheets
only.InInthis
only. thisstudy,
study,thetheaddition
additionofofCNTs
CNTswas wasobtained
obtainedby byultrasonic-assisted
ultrasonic-assistedliquid
liquidphase
phase
deposition. This deposition
deposition. deposition process
processconsisted
consistedofoftwo
twomain
main steps.
steps.The first
The step
first waswas
step to pre-
to
pare CNTs
prepare CNTs suspension
suspension liquids. Disperbyk-2150
liquids. Disperbyk-2150 was used
was in the
used CNTs
in the CNTssuspension
suspension to ob-
to
obtain theexcellent
tain the excellentcompatibility,
compatibility,flowing
flowing property
property and
and the increased content
content of of CNTs
CNTs[12].
[12].
Multipolymer
Multipolymer Disperbyk-2150
Disperbyk-2150 (BYK Additives Co., Co., Ltd.,
Ltd., Shanghai,
Shanghai,China)
China)was wasadded
addedto
toethanol
ethanol with
with a volume
a volume percentage
percentage of of about
about 40%,
40%, and
and then
then thethe CNTs
CNTs were
were mixed
mixed with
with the
the as-prepared solution by ultrasonicated treatment for 30 min. The second
as-prepared solution by ultrasonicated treatment for 30 min. The second step was to dis- step was to
disperse CNTs on the surfaces of the Al
perse CNTs on the surfaces of the Al sheets. The sheets. The prepared Al sheets
sheets were bathed inaa
were bathed in
 Materials 2021, 14, x FOR PEER REVIEW 3 of 11
Materials 2021, 14, 5576 3 of 9

suspension liquid filled with CNTs, and then the suspension solution was ultrasonicated
suspension liquid
again until the filledevaporated.
ethanol with CNTs, and then the suspension solution was ultrasonicated
againTheuntilroll
the bonding
ethanol evaporated.
process was performed without lubrication, and the prepared
The
sheets roll heated
were bonding toprocess
673 K forwas
30performed without
min and then lubrication,
operated a singleand thewith
pass prepared sheets
50% rolling
were heated to 673 K for 30 min and then operated a single pass with
reduction and speed of 1 m/min. Subsequently, the composite sheet was cut into two 50% rolling reduction
and speed
halves andof 1 m/min.
stacked Subsequently,
for next ARB cycle. the
Thecomposite
whole ARBsheet waswas
process cut repeated
into two forhalves
up toand
12
stacked for next
cycles. The ARB cycle.
monolithic The was
Al sheet whole ARB
also processusing
prepared was the
repeated
same for up toas12the
process cycles. The
contrast.
monolithic Al three
In this study, sheet compositions
was also prepared
were using the same
prepared throughprocess
the ARBas the contrast.
process: pureInaluminum
this study,
three compositions
and Al/CNTs were prepared
composites with 0.5through the ARB
and 1.0 vol.% process: pure aluminum and Al/CNTs
CNTs.
composites with 0.5 and 1.0 vol.% CNTs.
2.2. Materials Characterization
2.2. Materials Characterization
JEOL Model JSM-6490 (JEOL Ltd., Tokyo, Japan) and JEM2010 (JEOL Ltd., Tokyo,
JEOL
Japan) TEM Model JSM-6490
was applied (JEOL Ltd., Tokyo,
for microstructure Japan)
and grain and JEM2010
structure (JEOLand
observations Ltd., Tokyo,
analysis.
Japan)
The EBSDTEMsamples
was applied
were for microstructure
electrolytic and
polished in grain
a 10%structure observations
HClO4 ethanol solution andat analysis.
20 V for
The EBSD samples were electrolytic polished in a 10% HClO 4 ethanol
10 s. FE-SEM equipped with an HKL EBSD system was used to collect microstructure solution at 20 V for
10 s. FE-SEM The
information. equipped
overall with an HKL
texture wasEBSD systembywas
evaluated useddiffraction
X-ray to collect microstructure
(XRD, Rigaku
information. The overall texture was evaluated by X-ray diffraction (XRD, Rigaku Smart-
SmartLab, Rigaku Corporation, Tokyo, Japan). Incomplete pole figures of {1 1 1} {2 0 0} {2
Lab, Rigaku Corporation, Tokyo, Japan). Incomplete pole figures of {1 1 1} {2 0 0} {2 2 0}
2 0} were recorded, and the ODFs (Orientation Distribution Functions) were calculated
were recorded, and the ODFs (Orientation Distribution Functions) were calculated from
from the three incomplete pole figures using the series expansion method. A servohy-
the three incomplete pole figures using the series expansion method. A servohydraulic
draulic universal testing machine (CMT4105, Suns, Shenzhen, China) was used to test var-
universal testing machine (CMT4105, Suns, Shenzhen, China) was used to test various
ious ARB sheets at a nominal strain rate of 1.0 × 10−3 s−1 at ambient temperature.
ARB sheets at a nominal strain rate of 1.0 × 10−3 s−1 at ambient temperature.
3. Results
3. Results and
and Discussions
Discussions
3.1. Morphology
3.1. Morphology of of Al
Al and
and Al/CNTs
Al/CNTs Composites
Composites
Improvements in
Improvements in the
the mechanical
mechanical properties
properties of
of composites
composites prepared
prepared by
by the
the ARB
ARBpro-
pro-
cess, especially nanocomposites, depend on effective bonding of the sheets
cess, especially nanocomposites, depend on effective bonding of the sheets and uniform and uniform
distribution of
distribution of the
the reinforcements.
reinforcements. Figure
Figure 22 shows
shows the
the SEM
SEM micrographs
micrographs for
for the
the rolling
rolling
direction (RD) and normal direction (ND) of pure Al and Al/1.0 vol.% CNTs
direction (RD) and normal direction (ND) of pure Al and Al/1.0 vol.% CNTs nanocompos- nanocompo-
sitesprocessed
ites processedover
over12 12ARB
ARBcycles.
cycles.ItItcan
canbe
beseen
seenthat
that there
there were
were no
no obvious
obvious interfaces
interfaces in
in
thetwo
the two compositions
compositions after
after the
the 12
12 cycles.
cycles.

Figure2.
Figure 2. SEM
SEM micrographs
micrographs of
of (a)
(a) pure
pure Al
Al and
and (b)
(b) Al/1.0
Al/1.0 vol.%
vol.% CNTs
CNTs processed
processed by
by 12
12 ARB.
ARB.

Thetypical
The typicalTEM
TEMimages
images of of Al/1.0
Al/1.0 vol.%
vol.% CNTs
CNTs nanocomposites
nanocomposites processed
processed overover
12 ARB12
ARB cycles
cycles are shown
are shown in Figure
in Figure 3. Typical
3. Typical substructures
substructures (Figure
(Figure 3a) deformed
3a) and and deformed struc-
structures
tures (Figure
(Figure 3b)found
3b) were were found
in the in the composite.
composite. For
For the the deformed
deformed structures,
structures, lots oflots of aggre-
aggregative
gative dislocations
dislocations weretofound
were found be in theto be in the
form form of dislocation
of dislocation networks. networks.
Figure 3c,dFigure
shows3c,dthe
shows the CNTs distribution in the composite. The CNTs were found to
CNTs distribution in the composite. The CNTs were found to be singly dispersed in the Al be singly dis-
persed
grain in the3c),
(Figure Al grain
while(Figure
some CNT 3c), clusters
while somewereCNT clusters along
distributed were distributed along the
the grain boundaries
grain
(as boundaries
shown (as shown
by the black arrow by the black
in Figure 3d).arrow in Figurespacing
The interlayer 3d). Theofinterlayer spacing by
CNTs, calculated of
CNTs,a calculated
using by using a was
Digital Micrograph, Digital Micrograph,
0.345 was 0.345
nm, consistent nm,ideal
with the consistent withinterlayer
graphitic the ideal
space (0.34 nm). The distribution of CNTs at the grain boundaries exerted an effective
 reaction layers at the interface of CNTs and Al matrix in the composite. Al4C3 is one kind
of the interfacial reaction compounds, and excessive interfacial reaction compounds
would be detrimental to the interfacial bonding of the composites [13,14]. Al/CNTs com-
posites prepared by the PM route, and brittle phase Al4C3 at the interface of the CNTs and
Al matrix, caused severe impact damage to the CNTs during the long-time ball milling,
Materials 2021, 14, 5576 4 of 9
thereby the consolidation with high temperature (~870 K) led to the covalent bonding be-
tween the Al matrix and the defective CNTs [15–17]. In this work, the CNTs during one
ARB cycle were only subjected to a single force perpendicular to their axial direction at a
relatively
pinning on lower temperature
the grain process
boundaries, (673 K). Consequently,
contributing the CNTs
to the generation weredislocations
of many more stablein
in the Al matrix
the composites. and did not have some carbide formation.

Figure 3. Typical TEM images of Al/1.0 vol.% CNTs nanocomposites processed by 12 ARB cycles.
Figure 3. Typical TEM images of Al/1.0 vol.% CNTs nanocomposites processed by 12 ARB cycles.
(a) Substructures in Al matrix; (b) deformed structures in Al matrix; (c) individual MWCNT within
(a) grain;
Al Substructures in Alcluster
(d) MWCNT matrix;at(b) deformed
grain structures in Al matrix; (c) individual MWCNT within
boundary.
Al grain; (d) MWCNT cluster at grain boundary.
3.2. Mechanical Properties
From Figure 3d, the surfaces of the CNTs were covered with an amorphous carbon
The tensile strength
layer, as shown tests
by the blue results
arrow. with different
Careful inspectionCNTs content
indicated arethere
that shown in Figure
were 4a.
no obvious
The strength with CNTs content increasing from 0~1.0 vol.% decreased first,
reaction layers at the interface of CNTs and Al matrix in the composite. Al4 C3 is one kind then in-
creased sharply at 0.5 vol.% Al/CNTs. This is due to different mechanical properties
of the interfacial reaction compounds, and excessive interfacial reaction compounds would of the
constituent layers
be detrimental to [18]. It is evident
the interfacial that theofflow
bonding properties of[13,14].
the composites Al are Al/CNTs
different from those
composites
of CNTs. During the ARB process, the plastic instabilities such as necking
prepared by the PM route, and brittle phase Al4 C3 at the interface of the CNTs and Al and fracture
occur
matrix,ascaused
a resultsevere
of theimpact
difference between
damage to thethe flowduring
CNTs properties of the Alball
the long-time andmilling,
CNTs layers.
thereby
The necking and fracture of layers are affected by the strain hardening
the consolidation with high temperature (~870 K) led to the covalent bonding between exponents of thethe
constituent layers, strength coefficients of the constituents, and initial
Al matrix and the defective CNTs [15–17]. In this work, the CNTs during one ARB cycle thickness ratio of
were only subjected to a single force perpendicular to their axial direction at a relatively
lower temperature process (673 K). Consequently, the CNTs were more stable in the Al
matrix and did not have some carbide formation.

3.2. Mechanical Properties

The tensile strength tests results with different CNTs content are shown in Figure 4a.
The strength with CNTs content increasing from 0~1.0 vol.% decreased first, then increased
sharply at 0.5 vol.% Al/CNTs. This is due to different mechanical properties of the con-
stituent layers [18]. It is evident that the flow properties of Al are different from those
of CNTs. During the ARB process, the plastic instabilities such as necking and fracture
occur as a result of the difference between the flow properties of the Al and CNTs layers.
The necking and fracture of layers are affected by the strain hardening exponents of the
constituent layers, strength coefficients of the constituents, and initial thickness ratio of the
constituents [19]. The dimples of tensile fracture of pure aluminum laminated sheets are
 but both the strengths of the intermediate cycle pass show a saltation occasionally. How-
ever, the yield strength of pure Al shows a different trend. By increasing ARB cycles, the
thickness of the layers decreases, and the interface of the layers gradually tends to a wavy
shape. As necking extends, the shear bands are created in the composite after middle ARB
Materials 2021, 14, 5576 cycles. Thus, the presence of plastic instabilities in the fabricated composites at the final 5 of 9
ARB cycles decreases their tensile strength. Since CNTs and Al layers are forced together
during ARB process, a strain gradient is necessarily generated in their interface to fit the
different strains in these layers. By increasing the strain (increasing the number of ARB
obvious
cycles),and deep. However,
geometrically the dislocations
necessary elongation after fracture
(GNDs) decreases
are created andtopile-up
a certain extent
near with
the in-
terfaces
the of CNTs
increased volumeandfraction
aluminum layers.
of CNTs. In The dislocation pile-up
the meanwhile, it is alsoin the interface
shown reducedof the
dimples
CNTS
and and Alplastic
subdued layers fracture,
producesas a back
shownstress strengthening
in Figure 5. [20].

Materials 2021, 14, x FOR PEER REVIEW 6 of 11

Figure
Figure 4. Mechanical
4. Mechanical properties
properties of of Al/CNTsnanocomposites
Al/CNTs nanocompositeswith
with0,0,0.5
0.5and
and1.0
1.0vol.%
vol.% CNTs
CNTsafter
after 12
12 ARB
ARB cycles
cycles (a) and
and Al
Al with 0 (b), 0.5 (c) vol.% CNTs rolling different
with 0 (b), 0.5 (c) vol.% CNTs rolling different cycles. cycles.

Figure
Figure 5.
5. Tensile fracturemorphologies
Tensile fracture morphologiesofof Al/CNTs
Al/CNTs nanocomposites
nanocomposites withwith
0 (a),0 0.5
(a),(b)
0.5and
(b)1.0
and (c)1.0 (c) vol.%
vol.% CNTs CNTs
after 12after
ARB12cycles.
ARB
cycles.
The tensile strength test results of pure Al and Al with 0.5 vol.% CNTs content after
3.3. Texture
rolling 3, 6, Analysis
9 and 12 cycles are shown in Figure 4b,c. The tensile strength and yield strength
of AlThe
with 0.5 vol.%
rolling cyclesCNTs
with both
a high show an of
degree upward trend withhas
recrystallization increasing cycles,
a significant but both
decrease in
the strengths
strength. of the
On the intermediate
contrary, cycle of
the strength pass
theshow a saltation
material occasionally.
with fewer cycles is However,
lower. Addi- the
yield strength
tionally, of pure Al shows
the substructured a different (shown
grain frequency trend. By in increasing ARB cycles,
Figure 6) decreases withthethethickness
increas-
of the
ing layersofdecreases,
content CNTs, and and the
the interface of the effect
work-hardening layers caused
gradually
by tends to a wavygrains
substructured shape.out-
As
necking extends, the shear bands are created in the composite after middle
weighs the texture softening effect. The recrystallized, substructured and deformed fre- ARB cycles.
Thus, the
quency of presence of plastic for
pure Al hot-rolled instabilities
12 cyclesinwasthe14%,
fabricated
61% andcomposites at the final
25%, respectively. ARB
Mean-
cycles decreases
while, their tensile
those of Al/0.5 strength.
vol.% CNTs andSince
Al/1.0CNTs
vol.% andCNTs
Al layers are forced
hot-rolled together
12 cycles wasduring
48%,
ARB 14%
38%, process,
and a40%,
strain gradient
29%, is necessarilyThe
31%, respectively. generated in theireffect
strengthening interface to fit
caused bythethedifferent
disper-
strains
sion in these
of CNTs andlayers. By increasing
deformation, and thethe strain of
variation (increasing the number
the deformed of ARB cycles),
grain frequency shown
geometrically necessary dislocations (GNDs) are created
in Figure 6 has a consistent trend with the strength in Figure 4. and pile-up near the interfaces of
CNTs and aluminum layers. The dislocation pile-up in the interface of the CNTS and Al
layers produces a back stress strengthening [20].

3.3. Texture Analysis

The rolling cycles with a high degree of recrystallization has a significant decrease in
strength. On the contrary, the strength of the material with fewer cycles is lower. Addition-
ally, the substructured grain frequency (shown in Figure 6) decreases with the increasing
content of CNTs, and the work-hardening effect caused by substructured grains outweighs
the texture softening effect. The recrystallized, substructured and deformed frequency of
pure Al hot-rolled for 12 cycles was 14%, 61% and 25%, respectively. Meanwhile, those of
Al/0.5 vol.% CNTs and Al/1.0 vol.% CNTs hot-rolled 12 cycles was 48%, 38%, 14% and
40%, 29%, 31%, respectively. The strengthening effect caused by the dispersion of CNTs
Materials 2021, 14, 5576 6 of 9
Materials 2021, 14, x FOR PEER REVIEW 7 of 11

and deformation, and the variation of the deformed grain frequency shown in Figure 6 has
a consistent trend with the strength in Figure 4.

Figure
Figure 6.
6. EBSD
EBSDrecrystallization
recrystallization maps
maps of
of the
the pure
pure Al
Al (a)
(a) and
and Al/CNTs
Al/CNTsnanocomposites
nanocompositeswith
with0.5
0.5(b)
(b)and
and1.0
1.0(c)
(c)vol.%
vol.%CNTs
CNTs
after 12 ARB cycles. The blue, yellow and red grains are denoted as recrystallized, substructured and deformed grains,
after 12 ARB cycles. The blue, yellow and red grains are denoted as recrystallized, substructured and deformed grains,
respectively. RD-ND section with RD parallel to scale bar.
respectively. RD-ND section with RD parallel to scale bar.

The
The increase
increase of of carbon nanotubes content
carbon nanotubes contentincreases
increasesthe thenumber
numberofofgraingrain boundaries
boundaries in
in the composites. The number of grain boundaries directly
the composites. The number of grain boundaries directly depends on the grain size, depends on the grain size, so
so the
the increase
increase of tensile
of tensile strength
strength can becanexplained
be explainedby the byeffect
the effect
of grain of grain boundaries
boundaries on the on the
plastic
plastic
resistanceresistance of polycrystals.
of polycrystals. AccordingAccording
to the to the Hall–Petch
Hall–Petch effect,effect, the strength
the strength of poly-
of polycrystal
crystal increases with the increase of carbon nanotubes and
increases with the increase of carbon nanotubes and grain refinement. As the number grain refinement. As the num- of
ber of rolling cycles and CNTs content increases, the grains
rolling cycles and CNTs content increases, the grains transform from small-angle grain transform from small-angle
grain boundaries
boundaries to large-angle
to large-angle graingrain boundaries,
boundaries, and thisandtransformation
this transformation eventually
eventually con-
constructs
structs a thin layer structure, which can be seen from the delamination
a thin layer structure, which can be seen from the delamination of the grain structure. of the grain struc-
ture.
WhenWhen the number
the number of rolling
of rolling cyclescycles is further
is further increased,
increased, the thin the thinstructure
layer layer structure
is broken is
broken
and finallyandtransformed
finally transformed into fine grains.
into fine equiaxed equiaxed grains. According
According to the formula,
to the Hall–Petch Hall–Petchthe
formula,
smaller the thegrain
smallersizethe
of grain size of the
the material, thematerial,
greater the thestrength
greater of thethe
strength
material.of the material.
Additionally,
Additionally, the large strain results in the increase inside dislocation
the large strain results in the increase inside dislocation density and the defects, and density and the de-
the
fects,
dislocation slip movement is blocked, which is manifested as an increase in strength. in
and the dislocation slip movement is blocked, which is manifested as an increase
strength.Figure 7 presents the orientation distribution functions (ODFs) at ϕ2 = 0◦ , 45◦ , and
◦ Figure 7 presents
65 sections for the pure the orientation
Al and Al distribution
with 0.5, 1.0functions
vol.% CNTs, (ODFs) at φ2 = 0°, 45°,
respectively. and 65°
Compared
sections
with thefor the pure
typical Al and
preferred Al with 0.5, 1.0orientations
crystallographic vol.% CNTs,inrespectively. Compared with
rolled face-centered-cubic the
(FCC)
metals,preferred
typical the texture of pure Al was
crystallographic nearly randomly
orientations in rolleddistributed, and rotated
face-centered-cubic (FCC) cube and
metals,
copper
the components
texture of pure appeared
Al was nearly with relatively
randomlylow orientationand
distributed, density, as shown
rotated cube andin Figure
copper 7a.
There was no novel texture type developed in Al with 0.5,
components appeared with relatively low orientation density, as shown in Figure 7a. 1.0 vol.% CNTs, as shown in
Figurewas
There 7b,c.noHowever, the texture
novel texture density was
type developed in Alenhanced
with 0.5,from 7.5 to CNTs,
1.0 vol.% 18.9 with the CNTs
as shown in
content7b,c.
Figure increasing.
However, the texture density was enhanced from 7.5 to 18.9 with the CNTs
content Figure 8 shows the orientation density f(g) of Al with 0.5, 1.0 vol.% CNTs. With
increasing.
the mass fraction of the reinforcing phase increased from 0% to 1%, the grains on the α
orientation are constantly turning to {011}<011>, and the mass fractions have little influence
on the orientation density. The crystal grains gather toward the β orientation line, but there
is a certain degree of deviation from the standard position. The rolling texture is mainly
concentrated in the vicinity of the β orientation line and the copper (C) and brass copper (B)
orientations. As the mass fraction of the reinforcing phase increases, and the aggregation
extent on the β orientation line escalates. As the mass fraction is increased from 0 to
0.5%, the orientation of the grains turn from C orientation to the B orientation constantly.
As the mass fraction increases to 1.0%, both the C, S, and B orientations maintained at a
higher density.
During the rolling process, the orientation of the crystal grains moves along a certain
route to a stable orientation, and the final stable orientation of Al/CNTs is {011}<011>
orientation. In the ARB process,
(a) Pure Al—0° 45° the carbon nanotubes are second-phase 65° particles added
artificially. As the rolling deformation continues, the second phase particles added by
the ARB cycles and the moving dislocations will be blocked by the particles, making the
dislocations bend around the particles. This results in the accumulation of dislocations that
continue to increase, which produces a reaction force to the source of the dislocation and
increases the resistance to bypassing the dislocation, causing the leading dislocation to slip
Materials 2021, 14, 5576 7 of 9

or climb, making the dislocation loop interact and wrap around the particle. The increased
dislocation density in the material produces a work hardening effect. Meanwhile, due to
the incompatibility between the carbon nanotube particles and the surrounding aluminum
matrix particles, a large number of dislocations are generated around the particles. These
dislocations can ensure the geometric integrity of the material, but also produce a work
from 7.5 to 18.9 with the CNTs
hardening content
effect. increasing.
Both of these dislocations will hinder the activation of the sliding system.

(a) Pure Al—0° 45° 65°

(b) Al/0.5 vol.% CNTs—0° 45° 65°

(c) Al/1.0 vol.% CNTs—0° 45° 65°

Figure 8 The orientation distribution functions (ODFs) (φ =0°, 45°, and 65° sections) for rolling
Figure 7.Figure 8 The orientation
The orientation distributiondistribution functions
functions (ODFs) (ϕ2 =(ODFs)
0◦ , 45◦ ,(φ22=0°,◦ 45°, and 65° sections) for rolling
and 65 sections) for rolling textures of the pure Al
(a) and Al/CNTs nanocomposites with 0.5 (b) and 1.0 (c) vol.% CNTs after0.1,
textures of the pure Al and Al/CNTs nanocomposites with 0.6 and
12 ARB 1.0 wt.% CNTs after
cycles.
fourteen ARB cycles

Accordingly, Al with 1.0 wt.%CNTs has the minimum elongation resulting from the highest

content of the rotated cube and copper texture. Besides, the substructured grain frequency (shown

in Fig. 9) decreases with the increasing content of CNTs, and the work-hardening effect caused by

substructured grains outweighs the texture softening effect. The strengthening effect caused by the
Materials 2021, 14, x FOR PEER REVIEW 9 of 11

Materials 2021, 14, 5576 8 of 9

Figure 8.
Figure 8. Orientation
Orientation density
density ff (g)
(g) of
of Al with
with 0, 0.5, 1.0 vol.% CNTs
CNTs nanocomposites.
nanocomposites.(a)
(a)αα orientation
orientation
line (b)
line (b) ββ orientation
orientation line.
line.

Although
During thethe few second-phase
rolling additions make
process, the orientation of thethe crystal
crystal turning
grains to the
moves hard
along orien-
a certain
tation
route toand stop slipping
a stable after and
orientation, the slip system
the final is activated,
stable it will
orientation still causeissome
of Al/CNTs potential
{011}<011> ori-
slip system in the harder orientation previously activated. The movement
entation. In the ARB process, the carbon nanotubes are second-phase particles added ar- system results in
multiple slip occurring. In the ARB pure Al and Al/CNTs, because the strengthening
tificially. As the rolling deformation continues, the second phase particles added by the effect
of
ARBthecycles
second andphase particlesdislocations
the moving does not increase
will belinearly
blockedwith
by thetheparticles,
content of the particles,
making the dis-
the secondbend
locations phase particles
around the in the face-centered
particles. This resultscubic aluminum
in the accumulationmetal ofwill also affect that
dislocations the
activation
continue toofincrease,
the slip which
system. Moreover,
produces the composition
a reaction force to theand intensity
source of thevariation of and
dislocation the
rolling
increasestexture are affected
the resistance to by the dispersion
bypassing strengthening
the dislocation, effect
causing theand multi-slip
leading effect of
dislocation to
the second phase particles.
slip or climb, making the dislocation loop interact and wrap around the particle. The in-
creased dislocation density in the material produces a work hardening effect. Meanwhile,
4. Conclusions
due to the incompatibility between the carbon nanotube particles and the surrounding
The mechanical
aluminum properties
matrix particles, of thenumber
a large Al/CNTs nanocomposites
of dislocations are affectedaround
are generated by the the
content
par-
of CNTs and the ARB cycles. The increase of the strength of the composite
ticles. These dislocations can ensure the geometric integrity of the material, but also pro- is due to the
transformation from the small angle grain boundaries to the large angle
duce a work hardening effect. Both of these dislocations will hinder the activation of the grain boundaries
because of severe plastic deformation, and the eventual formation of ultra-fine grains and
sliding system.
the high densitythe
Although of dislocations
few second-phaseby ARB process and
additions make thethe
enhancement
crystal turningeffect
toof
thethehard
carbon
ori-
nanotubes enhanced phase.
entation and stop slipping after the slip system is activated, it will still cause some poten-
Thesystem
tial slip hot rolling
in thestable texture
harder is {011}<011>
orientation afteractivated.
previously 12 cycles.TheThemovement
increase insystem
the mass re-
fraction of the carbon nanotubes makes the distribution of grains in the sample more
sults in multiple slip occurring. In the ARB pure Al and Al/CNTs, because the strength-
diffuse. Under the combined effect of the strengthening of the second phase particles and
ening effect of the second phase particles does not increase linearly with the content of the
the multi-slip, the rolling texture strength of the nanocomposite increases with increase in
particles, the second phase particles in the face-centered cubic aluminum metal will also
the mass fraction of the phase.
affect the activation of the slip system. Moreover, the composition and intensity variation
The composition and distribution of the rolling texture can be improved by controlling
of the rolling texture are affected by the dispersion strengthening effect and multi-slip
the quality score of the enhancement item, and then controlling the microstructure and or-
effect of the second phase particles.
ganization of the material, and optimizing the comprehensive performance of the material,
according to actual application requirements. The study has laid a theoretical foundation
4. Conclusions
for the development of Al/MWCNTs nanocomposite materials, which is beneficial to the
The mechanical
development properties
and promotion of the Al/CNTs
of Al/MWCNTs nanocomposites
nanocomposites are aerospace
in the affected byfield.
the con-
tent of CNTs and the ARB cycles. The increase of the strength of the composite is due to
the transformation
Author Contributions:from the small angleW.-J.W.
Conceptualization, grain boundaries to the largeand
and Z.L.; investigation angle grain bound-
writing—original
ariespreparation,
draft because of severe
W.-J.W.plastic deformation,
and Z.L.; and the eventual and
writing and language—review formation
editing,of ultra-fine
K.-C.Y. grains
and H.-S.C.;
data
and supplement and analysis,
the high density A.-D.T. All by
of dislocations authors
ARBhave read and
process andagreed to the published
the enhancement version
effect of
of the
the manuscript.
carbon nanotubes enhanced phase.
The This
Funding: hot rolling
work was stable texture
supported byisthe
{011}<011>
National KeyafterResearch
12 cycles.andThe increase in
Development the mass
Program of
fraction
China of2018YFA0707300)
(No. the carbon nanotubes makes
and Beijing the distribution
municipal of projects
construction grains in theBJSJ2019007).
(No. sample more dif-
Partly
fuse. Under
funded by thethe
Hongcombined effect ofand
Kong Innovation the Technology
strengtheningFundof(ITF)
the second phaseNo.
under project particles and the
ITT/011/19GP
multi-slip,
and The HongtheKong
rolling texture strength
Polytechnic Universityofunder
the nanocomposite increases with increase in the
project No. P18-0361.
mass fraction
Institutional of theBoard
Review phase. Statement: Not applicable.
Informed Consent Statement: Not applicable.
Materials 2021, 14, 5576 9 of 9

Data Availability Statement: Not applicable.

Acknowledgments: The authors express their thanks to all members of the laboratory team for the
kind help on literature searching and technical support.
Conflicts of Interest: The authors declared no conflicts of interest.

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