Improvement of the Mechanical Properties of Al-Si Alloys

by TiC Nanoparticles
KONSTANTIN BORODIANSKIY, ALEXEY KOSSENKO, and MICHAEL ZINIGRAD
Al-Si alloy A356 was modied by TiC nanoparticles. First, the nanoparticles were mechano-
chemically activated together with aluminum powder. Next, the activated particles were hot
extruded in a home-made extruder. Finally, nanoparticles thus prepared in the aluminum matrix
were added to the liquid Al-Si alloy, which was then cast into sand molds. A comparison of the
microstructure and mechanical properties of the modied alloy thus produced with those of the
alloy without the nanoparticles demonstrated that the grain size of the modied alloy decreased.
The mechanical properties determined after T6 heat treatment indicated unusual behavior,
where the elongation of the modied alloys increased by 20 to 50 pct in dierent regions of the
cast, while the tensile strength remained unchanged and the hardness increased by 18 pct. An
electron microscopy study revealed concentration of dislocations near grain boundaries in the
modied alloy samples. These grain boundaries serve as obstacles to dislocation motion. It was
therefore concluded that the improvement in the mechanical properties of the aluminum alloy
modied by TiC nanoparticles was caused by the grain-size-strengthening mechanism.
DOI: 10.1007/s11661-013-1850-4
The Minerals, Metals & Materials Society and ASM International 2013
I. INTRODUCTION
METAL strengthening is one of the main challenges
encountered in materials technology. Traditionally, such
strengthening was achieved by alloying with other
chemical elements or compounds, but relatively high
fractions of relatively expensive materials were needed
to obtain the required technological characteristics, and
the results achieved were still far from satisfactory. The
growing interest in Al-Si cast alloys is due to their
widespread and extensive use in automotive, aerospace,
and transport systems. One of these alloys is A356 alloy,
which has excellent castability, mechanical characteris-
tics, and physical properties. The strength of the alloy
can be improved by alloying,
[16]
by means of master
alloys, by heat treatment, or by applying ultrasound that
aects the crystallization process.
[79]
There are reports
of TiB
2
particles being utilized, which serve as crystal-
lization nuclei and cause renement of the metal
grains.
[10,11]
Small addition of strontium and sodium
into Al-Si casting alloys enhance the formation of
rened eutectic colonies.
[12,13]
Another relatively new strengthening technology is
semisolid metal processing (SSM), which was initially
developed by researchers at MIT in the 1970s.
[14]
In the
SSM approach, metals are treated by a mixture of ne
solid nonmetal particles dispersed in the liquid.
[1518]
Nanotechnology is also used in the metal-strengthening
processes. It would be logical to expect that nanosized
particles would cause similar changes in mechanical
properties, but that their inuence would be milder
and more balanced. Indeed, it has been established that
the mechanical properties of Al A356 could be improved
by adding Al
2
O
3
nanoparticles in a minute concentra-
tion of 1 wt pct during casting.
[19]
In the current article, we report the inuence of
ceramic nanoparticles on the mechanical properties of
Al-Si alloy A356. One of the serious technological
problems associated with the introduction of these
particles into the molten metal is the poor wettability
of the former by the latter. We also report here a method
for solving this problem by severe mechanical loading of
the metal matrix with titanium carbide nanoparticles
pretreated by mechanochemical activation. The assump-
tion that the grain-size-strengthening mechanism acts in
the process is discussed in the current article.
II. EXPERIMENTAL
Al-Si alloy A356 (Rheinfelden Alloys GmbH) was
used as a bulk material. The composition of the alloy is
given in Table I.
Titanium carbide nanoparticles (Inframat

Advanced
Materials, 99.9 pct, crystallite size 20 nm) were
mechanochemically activated with aluminum powder
(Strem, 99 pct+, 20 to 40 mesh) in a Retsch PM 100
planetary ball mill. The milling speed was 400 rpm, and
the activation time was 5 minutes. The powder mixture
obtained was hot extruded at 623 K (350 C) in a home-
made extrusion container with an extrusion ratio of 17.4.
KONSTANTIN BORODIANSKIY, Researcher, is with the
Laboratory for Metal and Ceramic Coatings and Nanotechnology,
Materials Research Center, Ariel University, Science Park, 40700
Ariel, Israel, and also with Department of Chemistry, Bar-Ilan
University, 52900 Ramat Gan, Israel. Contact e-mail: konstantinb@
ariel.ac.il ALEXEY KOSSENKO, Researcher, and MICHAEL
ZINIGRAD, Professor and Head, are with the Laboratory for Metal
and Ceramic Coatings and Nanotechnology, Materials Research
Center, Ariel University.
Manuscript submitted March 17, 2013.
Article published online June 29, 2013
4948VOLUME 44A, NOVEMBER 2013 METALLURGICAL AND MATERIALS TRANSACTIONS A
To examine the eect of nanoparticle modication,
Al-Si alloy A356 ingots weighing 100 kg were melted in
an industrial electric resistance furnace and superheated
to 1033 K (760 C) and then subjected to a standard
industrial modication process using sodium and degas-
sing by FDU. After the degassing, a modier containing
0.03 wt pct of TiC nanoparticles (out of the total Al
mass) was added to the molten metal, and the mixture
was stirred for 10 minutes. The melt was poured into a
special sand mold (Figure 1), central part of which
solidied much more slowly than the outer perimeter.
The pouring temperature was controlled at about
1003 K (730 C).
Samples for a macrostructure investigation were
prepared by polishing and etching with Kallings
reagent. Microstructure studies were carried out using
a JEOL JSM 6510LV scanning electron microscope
(SEM). The phases were identied by XRD analysis
using a Panalytical XPert Pro X-ray powder dirac-
tometer at 40 kV and 40 mA. The XRD patterns were
recorded in the 2H range from 20 to 100 deg (the step
size was 0.03 deg, and the time per step was 3 seconds).
The chemical composition was determined by a Spec-
tromax optical emission spectrometer.
The specimens produced were T6-heat treated. First,
the solid solution was heat treated to dissolve the soluble
phases at 811 K (538 C) for 8 hours, after which the
solution was water quenched to develop supersaturation
in water, and then it was articially aged to precipitate
the solute atoms at 433 K (160 C) for 4 hours.
The mechanical properties were measured using an
Instron 3369 testing machine according to ASTM B 108-
01 after T6-heat treatment. The modied alloys pro-
duced were compared with the unmodied alloy cast
under the same conditions. Hardness tests were con-
ducted both on as-cast and heat-treated alloys by a
Rockwell hardness tester (Wilson Hardness Ltd.) before
and after modication. The results shown are averages
of three points in dierent regions of the alloys.
The aluminum-strengthening mechanism was deter-
mined from measurements taken on a JEOL JEM 2010
high-resolution transmission electron microscope (HR-
TEM). Specially prepared disks with a diameter of
3 mm were punched out of thinned Al and were
subsequently jet-polished using a solution of 30 pct
nitric acid and 70 pct methanol at 20 C (253 K) and
10 V.
III. RESULTS
Figure 2 shows the macrostructure of the as-cast Al-
Si alloy A356 before and after the modication process.
It can be seen that the modication process with
titanium carbide nanoparticles has a profound eect
on the structure of the cast alloy: the average grain size
of the modied alloy decreased, and the structure of the
material became ner.
Grain size measurements were conducted using the
SIAMS image analysis software. Grain size parameters
were determined for each zone in the eld of view. These
results are shown in Table II.
The calculated results showed that after nanoparticle
addition the grain size of the aluminum alloy decreased
by 44.5 pct.
SEM images of the microstructures of a modied alloy
sample vs an unmodied sample are shown in Figure 3.
Typical primary a-aluminum grains are observed in the
as-cast sample. In a modied casting sample, these
a-aluminum grains become smaller, and there are small
globular eutectic silicon crystals, which are uniformly
distributed between the grain boundaries (the white areas
around the aluminum grains in the image).
XRD measurements were used to reveal structural
changes in the alloys during the modication process.
XRD patterns of the modied and of the unmodied
cast Al-Si (A356) alloys are shown in Figure 4.
The XRD results indicate the presence of aluminum
(JCPDS 01-071-4624) and silicon (JCPDS 01-070-5680)
phases. No dierence caused by the modication is
observed; therefore, no new phase has been formed in a
detectable amount as a result of the modication
process. The very small quantity of the ceramic nano-
particles introduced in the modication stage is evenly
distributed and does not comprise any detectable phase.
The chemical compositions of the alloys before and
after modication were also determined by optical
emission spectroscopy and are presented in Table III.
After T6 heat treatment, two specimens cut from the
center and two from the perimeter of three dierent
modied casting parts were subjected to tensile strength
tests and compared with two specimens from the center
and the perimeter of one as-cast part. Cast part
perimeter crystallization rate was much higher as
compare to the crystallization rate at the central area
because of the dierent mold thickness.
Perimeter area average values of the tensile and yield
strength and the elongation of the as-cast and modied
alloys are presented in Table IV.
Table I. Chemical Composition of Al A356
Si Mg Fe Ti Others Al
7.020 0.354 0.121 0.125 0.1 bal.
Fig. 1Special sand mold used in the research.
METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 44A, NOVEMBER 20134949
The addition of a modier based on titanium carbide
nanoparticles increased the elongation by 20 and 50 pct
in the perimeter and in the central part of the mold,
respectively. The tensile strength of the parts remained
unchanged.
Fractographs of the alloys after tensile testing of the
specimens exhibit ductilebrittle fracture, as shown in
Figure 5. There are more dimples in the modied alloy,
which are characteristic of ductile fracture. The surface
also displays many smooth, at areas separated by
bright ridges. The at areas are cleaved silicon particles.
Hardness tests were conducted on the as-cast and
heat-treated alloys before and after modication. The
results shown below are averages of three points in
dierent regions of the cast ingots. The hardness of the
heat-treated as-cast alloy before modication was
42.3 1.7 HRB, and the hardness of the heat-treated
modied alloy was 49.8 0.3 HRB. The addition of
titanium carbide nanoparticles causes the hardness to
improve by 18 pct.
Electron microscopy observation was performed to
determine the mechanism of the strengthening which
occurs in A356 alloy because of the addition of the
Fig. 2Macrostructure of A356 alloy before (a) and after (b) the modication process. The average grain size of the modied macrostructure
(image b) profoundly decreased in comparison to the unmodied macrostructure (image a).
Table II. Grain Size Calculations of A356 Alloy Before and After the Modication Process Using the TiC Modier
Al Alloy Analyzed Area (mm
2
) No. of Grains on 1 cm
2
Average Grain Size (mm)
Al-Si Alloy Before Modication 82.0 1485 0.259
Al-Si Alloy Modied by TiC Nanoparticles 80.1 4810 0.144
Fig. 3SEM observation of the A356 microstructure before (a) and after (b) the modication process (200 times). The modied microstructure
contains small aluminum grains (black areas) with a high concentration of eutectic silicon crystals distributed between the grain boundaries
(white areas).
Fig. 4XRD patterns of the aluminum A356 alloy before and after
modication using TiC nanoparticles.
4950VOLUME 44A, NOVEMBER 2013 METALLURGICAL AND MATERIALS TRANSACTIONS A
ceramic nanoparticles. Figure 6(a) shows an electron
microscopy image of a grain boundary of the modied
alloy. A high dislocation concentration was observed
near the grain boundaries. On the other hand, no
titanium or titanium carbide was found near the grain
boundaries. Therefore, the particles act as crystallization
centers and can be found in the aluminum grains, as
shown in Figure 6(b).
Figure 7 shows an electron microscopy image of the
unmodied A356 alloy. As opposed to the modied
alloy, here dislocations are found in the Al grains, and
no TiC particles (Ti inclusions) are found in the sample.
IV. DISCUSSION
It is generally preferable to achieve a grain size in a
structure that is as small as possible, because a small
grain size signicantly improves the mechanical proper-
ties of metal castings. Signicant grain renement can be
achieved by adding inoculants to the liquid metal. These
inoculants are added in a suitable form to be uniformly
distributed throughout the liquid, and they act as
nucleating agents to increase the nucleation rate
throughout the casting.
In the current research, TiCnanoparticles were used as
nucleating agents. Because of their very small size, the
number of nanoparticles per unit volume is much greater
than the number of microparticles. These particles serve
as crystallization centers in the liquid aluminum and
cause the formation of a ne-structured aluminum alloy.
Nanoparticles have a very large surface-to-mass ratio
and are, therefore, highly surface active. To prevent
them from oating on the surface of the melt, the
titanium carbide particles were rst mechanochemically
treated with aluminum powder. The powder obtained
was pressed to remove the oxide layer. Total amount of
0.03 wt pct of TiC nanoparticles out of the total Al mass
was added to the molten metal.
Additional experiments were conducted to determine
the optimal concentration of added nanoparticles into
the melt. Total amounts of 0.1, 0.045, and 0.01 wt pct of
nanoparticles were added to the molten aluminum in
dierent experiments. It was found that the mechanical
properties in the additional experiments either were not
changed, or the changes were very slight. The addition of
0.03 wt pct was found as an optimal concentration in the
process. We assumed that the addition of a high quantity
of nanoparticles causes the formation of large aggregates
that are not eective in the metal-crystallization process.
At the same time, low quantity of nanoparticles has no
eect on the improvement of mechanical properties
because of their dissolution in the melt.
Normally, increasing the tensile strength reduces the
ductility and vice versa. Ductility is the ability of a
material to withstand plastic deformation without rup-
ture and is quantitatively expressed as the linear
elongation of a specimen in a tensile strength test.
Table III. Chemical Composition of Cast Alloys Before and After the Modication Process Using TiC Nanoparticles
State of the Cast Alloy Si Mg Ti Fe Cu Al
Before Modication 6.99 0.35 0.16 0.13 0.01 base
After Modication 6.96 0.34 0.16 0.13 0.01 base
Table IV. Mechanical Properties of A356 Alloy Before and After the Modication Process Using TiC Nanoparticles
State of the Cast Alloy Tensile Strength (MPa) Yield Strength (MPa) Elongation (Percent)
Center of a Cast before modification 268.3 225.0 1.9
after modication 280.9 1.0 221.7 4.0 3.8 0.7
Perimeter of a Cast before modification 311.0 233.0 6.5
after modication 310.4 3.1 226.9 2.2 9.0 1.3
Fig. 5SEM fracture micrographs of the unmodied (a), and modied cast alloy (b) (800 times).
METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 44A, NOVEMBER 20134951
Unusual behavior, under which the elongation increased
while the tensile strength remained unchanged, was
observed in our tests of the modied samples. Similar
results were found only in the study of Valiev et al.,
[20]
where the production of both high-strength and high-
ductility properties in an aluminum alloy by severe
plastic deformation (SPD) was demonstrated.
Existing data for aluminum indicate that, in the grain
size less than 1 lm, the material usually exhibits high
strength and low elongation and, in the grain size
greater than 10 lm, the material usually exhibits low
strength and high elongation. The phenomenon when
the elongation increases as the grain size decreases is not
well understood yet. This is also described in the study
of Li and Gui.
[21]
We found that the hardness of the modied alloy was
increased. Hardness is a very important mechanical
property, which indicates the resistance of the material
to localized plastic deformation, and can indirectly
indicate the tensile strength.
[22]
In our case, it is valuable
more for a resistance to the penetration of the surface
than an indication of the tensile strength; therefore, its
signicant improvement was not expressed by means of
UTS values.
Strengthening is dened as an increase in the resis-
tance of a material toward plastic deformation and
toward the formation and growth of cracks. Strength-
ening in aluminum alloys can be increased by several
mechanisms: (1) solid-solution strengthening when an
alloying element forms a solid solution with the metal so
that atoms of the solute prevent the motion of disloca-
tions in the lattice of the solvent; (2) grain-size strength-
ening expressed by the HallPetch equation.
[23]
r
y
r
0
Kd
1=2
; 1
where r
y
is the yield stress of the alloy, r
0
is a materials
constant for the starting stress for dislocation move-
ment, d is the average grain diameter, and K is the
strengthening coecient (specic to each material); and
(3) precipitation hardening or aging, which is the
Fig. 6Electron microscopy image of a modied A356 alloy with a high concentration of dislocations near a grain boundary of the alloy (a)
and Ti inclusions originating from TiC nanoparticles of the additive in an Al grain (b).
Fig. 7Electron microscopy image of the unmodied A356 alloy.
4952VOLUME 44A, NOVEMBER 2013 METALLURGICAL AND MATERIALS TRANSACTIONS A
process of xation of a high-temperature state of the
alloy at lower temperatures.
As can be seen in the electron microscopy images, in
the modied alloy, a large concentration of dislocations
are observed near the grain boundaries. TiC nanoparti-
cles were found only inside aluminum alloy grains. This
clearly indicates that they act as nucleation accelerators
in the crystallization process and cause the formation of
a ne-structured aluminum alloy. As a result, the
mechanical properties of the alloy are improved after
the modication. Based on the results of the testing of the
mechanical properties and the electron microscopy
investigation, it can be assumed that a grain boundary
mechanism is responsible for the process.
Evidently, the modication of Al-Si A356 alloy by
titanium carbide nanoparticles is an example of the
classical case, in which large numbers of grain bound-
aries impede the slip motion of dislocations from one
grain into another because of the dierence between the
orientations of the lattices of two neighboring grains.
As was shown in the microstructure images, the
uniformly distributed eutectic Si grains in the modied
alloy lead to some additional improvement in elonga-
tion. Lee et al.
[24]
showed that when the elongation is
improved, the fractographs display ductile fracture, and
the ductile metal matrix eectively prevents the crack
propagation. This claim is consistent with the SEM
fractographs presented in the current article.
It is noteworthy that the chemical and phase compo-
sitions of the modied alloy remained unchanged. This
is a very important achievement for the technological
process, because improved mechanical properties can be
obtained in this way without the need for an alloying
process that involves more expensive cast part. The
results were obtained using a specially prepared mod-
ier, which incorporates a very small amount of carbide
nanoparticles. They could neither dissolve in the melt
nor form a separate phase in the alloy, but they changed
the properties of the metallic structure.
V. CONCLUSIONS
The eect of modication by mechanochemically
activated TiC nanoparticles on the mechanical proper-
ties of Al-Si alloy A356 was investigated. The results
indicate that the grain size of the modied aluminum
alloy was reduced and that a ne structure formed in it.
Therefore, its mechanical properties were improved. In
particular, the elongation of the modied alloy increased
by 20 to 50 pct in dierent regions of the modied cast,
and the hardness of the heat-treated modied alloy
increased by 18 pct.
The strengthening mechanism that operates in the
modication process described was proposed. It was
found that TiC nanoparticles act as nucleation acceler-
ators during the crystallization process and do not cause
any changes in the phase or chemical composition. A
high concentration of dislocations was observed near the
grain boundaries of the modied alloy. Therefore, the
grain boundaries act as barriers to the motion of
dislocations, and, as a result, a grain-size-strengthening
mechanism operates in the Al-Si alloy modied by TiC
nanoparticles.
ACKNOWLEDGMENT
The current study was supported by the Chief Scientist
of the Israel Ministry of Industry, Trade, and Labor (The
MAGNET Program Grant No. 41889). The authors
would like to thank Ms. Natalia Litvak for her help in
the SEM studies.
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