materials

Article
Effects of Solidification Cooling Rate on the
Microstructure and Mechanical Properties of a Cast
Al-Si-Cu-Mg-Ni Piston Alloy
Lusha Tian, Yongchun Guo, Jianping Li *, Feng Xia, Minxian Liang and Yaping Bai
Materials and Chemical Engineering School, Xi’an Technological University, Xi’an 710021, China;
tianlusha51@163.com (L.T.); yc-guo@163.com (Y.G.); xiafeng0811@163.com (F.X.); dlmxian@163.com (M.L.);
jingpingxue2004@163.com (Y.B.)
* Correspondence: lijianping@xatu.edu.cn




Received: 25 May 2018; Accepted: 6 July 2018; Published: 18 July 2018


Abstract: The effects of cooling rate 0.15, 1.5, 15, 150, and 1.5 × 105 ◦ C/s on the microstructures
and mechanical properties of Al-13Si-4Cu-1Mg-2Ni cast piston alloy were investigated. The results
show that with an increase of solidification cooling rate, the secondary dendrite arm spacing (SDAS)
of this model alloy can be calculated using the formula D = 47.126v − 1/3. The phases formed
during the solidification with lower cooling rates primarily consist of eutectic silicon, M-Mg2 Si phase,
γ-Al7 Cu4 Ni phase, δ-Al3 CuNi phase, ε-Al3 Ni phase, and Q-Al5 Cu2 Mg8 Si6 phase. With the increase
in the solidification cooling rate from 0.15 to 15 ◦ C/s, the hardness increased from 80.9 to 125.7 HB,
the room temperature tensile strength enhanced from 189.3 to 282.5 MPa, and the elongation at
break increased from 1.6% to 2.8%. The ε -Al3 Ni phase disappears in the alloy and the Q phase
emerges. The δ phase and the γ phase change from large-sized meshes and clusters to smaller
meshes and Chinese script patterns. Further increase in the cooling rate leads to the micro hardness
increasing gradually from 131.2 to 195.6 HV and the alloy solidifying into a uniform structure and
forming nanocrystals.

Keywords: Al-13Si-4Cu-1Mg-2Ni alloy; cooling rate effect; solidification microstructure;

second phase; mechanical property

1. Introduction
Piston, known as the “heart” of the engine, is a key component of internal combustion engine.
Operating in a harsh environment, piston endure high temperature, high pressure, complex friction,
and coupled thermo-mechanical load. With the improvement of engine power density (kW/L),
demanding requirements imposed on the piston material increased greatly [1–4].
Among various piston alloys, near-eutectic Al-Si-Cu-Mg-Ni alloys, involving -13Si-4Cu-1Mg-2Ni
alloy, were widely used in high performance diesel engine piston since the near-eutectic alloys have a
better combination of light weight, high mechanical properties and a better castability combination
than other alloys. Up to date, intensive studies have been made on the heat treatment process and the
microscopic thermal characteristics of the Al-13Si-4Cu-1Mg-2Ni alloy [5]. Yongchun Guo, Tao Xu et al.
studied the precipitation phase in the Al-Si-Cu-Mg-Ni piston alloy and analyzes the five kinds of
Al-13Si-1Mg-2Ni-xCu (x = 0%, 2%, 3%, 4%, 5% (mass fraction)) of common liquid precipitation phase
composition and element Cu on its liquid phase precipitation formation regularity [6]. Manasijevic et al.
examined the thermal and microscopic features of the piston alloys and found that changes in the
concentrations of various alloying elements changed the composition and shape of the phases due
to segregation and redistribution [7]. The microstructure of Al-13Si-4Cu-1Mg-2Ni alloy is composed

Materials 2018, 11, 1230; doi:10.3390/ma11071230 www.mdpi.com/journal/materials

Materials 2018, 11, 1230 2 of 9
Materials 2018, 11, x FOR PEER REVIEW 2 of 9

1Mg-2Ni
of Al3 Ni, alloy
Al2 Cu, is composed
Mg2 Si, Al3of Al3Ni,
CuNi, AlAl 2Cu, Mg2Si, Al3CuNi, Al7Cu4Ni, Al5Cu2Mg8Si6 and Al9FeNi.
7 Cu4 Ni, Al5 Cu2 Mg8 Si6 and Al9 FeNi. The size and shape of
these phase changes are closely related to theare
The size and shape of these phase changes closely related
solidification to theThus,
process. solidification process.
solidification Thus,
control is
solidification control is very important to alter the microstructure of the alloy. However,
very important to alter the microstructure of the alloy. However, the research on the influence of the research
on the influence
solidification of solidification
cooling rate on thecooling rate on the
microstructure microstructure
and properties ofandthe properties of relatively
alloy is still the alloy islittle.
still
relatively little. This paper discusses the properties of the alloy under different solidification
This paper discusses the properties of the alloy under different solidification cooling rates, in pursuit cooling
rates,
of in pursuit
providing of providing
guidance for the guidance
design and formanufacture
the design and manufacture
of the of the piston alloy.
piston alloy.

2. Experimental
2. Experimental Methods
Methods and
and Processes
Processes
In the
In the experimental
experimental study,study, an an alloy
alloy model
model of of Al-13Si-4Cu-1Mg-2Ni
Al-13Si-4Cu-1Mg-2Ni (wt.%) (wt.%) waswas prepared
prepared in in an
an
intermediate frequency induction melting furnace. Pure aluminum ingot
intermediate frequency induction melting furnace. Pure aluminum ingot blocks were added into theblocks were added into the
graphite crucible
graphite crucibleand and
were were melted
melted firstly,
firstly, then thethen the ofpieces
pieces of pure
pure silicon, silicon,
Al-Ni Al-Niintermediate
and Al-Cu and Al-Cu
alloys were added into the melt, respectively. Furthermore, mischmetal, rich in elements Laelements
intermediate alloys were added into the melt, respectively. Furthermore, mischmetal, rich in and Ce,
La and Ce,
together withtogether
Al-P alloy with Al-P
as the alloy agents
modifier as the were
modifier
added agents were
into the added
molten into
alloy. the molten alloy.
Hexachloroethane as
Hexachloroethane
the degassing agentaswas theadded
degassing agent ◦was
at 720–740 C andadded
heldat
for720–740
15 min.°C ThenandMg held for was
block 15 min.
addedThen Mg
under
block
the meltwas added under
completely the melt
to keep it fromcompletely
contacting to oxygen
keep it from contacting
and burning. oxygen
After and burning.
skimming off the After
slags
skimming
covered onoffthethe
meltslags covered
surface, on the
the clean melt
melt wassurface,
pouredtheintoclean melt wasmolds
the different poured withinto the different
various cooling
moldsand
rates with variousto
solidified cooling rates and solidified to the ingots.
the ingots.
The cooling rate is calculated by by
The cooling rate is calculated recording
recording the temperature
the temperature and timeandpoint
time ofpoint of solidification
solidification process
process
with thewith the temperature
temperature paperless paperless
recorderrecorder in different
in different moldsmold,
molds (sand (sand metal
mold, mold,
metal mold,
coppercopper
mold
mold with water cooling). The solidification temperature range is from 650
with water cooling). The solidification temperature range is from 650 to 450 C as demonstrated in to ◦
450 °C as demonstrated
in Figure
Figure 1. 1. Three
Three setsofofdates
sets dateswere
weretested
testedforforeach
eachsample
sampleand and the
the approximations
approximations were were obtained.
obtained.
The preparation
The preparation methods
methods of of the
the test
test alloys
alloys with
with different
differentcooling
coolingrates
ratesareareshown
shownin inTable
Table1.1.

Figure 1.
Figure 1. The
The DSC (differential scanning
DSC (differential scanningcalorimetry)
calorimetry)curve
curveofofthe
thealloy
alloywith
withthe
thecooling
coolingrate
rateofof1515◦ C/s.
°C/s.

Table 1. The
Table 1. The preparation
preparation methods
methods of
of different
different cooling
cooling rate
rate alloys.
alloys.

Cooling Rate °C/s Casting Mold Mold Size Type of Furnace Cooling Rate Measurement
Cooling Rate ◦ C/s Casting Mold Ø50 mmMoldCylinder
Size Type of Furnace
induction melting Cooling Rate Measurement
paperless recorder
0.15 Sand mold
0.15 Sand mold
length:150
Ø50 mm
mm Cylinder furnace
induction melting thermocouple GZJ-800G
paperless recorder
Ø55length: 150 mm
mm Cylinder furnace
induction melting thermocouple
paperlessGZJ-800G
recorder
1.5 Metal mold
Ø55 mm Cylinder
length:150 mm induction melting
furnace paperless recorder
thermocouple GZJ-800G
1.5 Metal mold
length: 150 mm furnace thermocouple GZJ-800G
copper mold with Ø50 mm Cylinder induction melting paperless recorder
15 copper
15 water mold with
cooling Ø50 mm Cylinder
length:150 mm induction melting
furnace paperless recorder
thermocouple GZJ-800G
water cooling length: 150 mm furnace thermocouple GZJ-800G
copper mold with Ø4 mm Cylinder vacuum induction paperless recorder
150 copper
150 water mold with
cooling Ø4 mm Cylinder
length:10 mm vacuum
meltinginduction
furnace paperless recorder
thermocouple GZJ-800G
water cooling length: 10 mm melting furnace thermocouple GZJ-800G
vacuum induction
150,000 melt-spinning strip vacuum analog computation
150,000 melt-spinning strip meltinginduction
furnace analog computation
melting furnace
Materials 2018, 11, 1230 3 of 9

Materials 2018, 11, x FOR PEER REVIEW 3 of 9

The composition of the alloy was measured by a direct-reading spectrometer (model Bruker Q4
The composition
Tasman). of the
The results are alloyinwas
shown measured
Table 2. by a direct-reading spectrometer (model Bruker Q4
Tasman). The results are shown in Table 2.
Table 2. Element content in the test alloy (wt.%).
Table 2. Element content in the test alloy (wt.%).
Material Si Cu Mg Ni Al
Material Si Cu Mg Ni Al
Al-13Si-4Cu-1Mg-2Ni 12.76 4.03 1.06 2.17 balance
Al-13Si-4Cu-1Mg-2Ni 12.76 4.03 1.06 2.17 balance

The as
The as cast microstructures
microstructures of the Al-13Si-4Cu-1Mg-2Ni
Al-13Si-4Cu-1Mg-2Ni alloyalloy solidified
solidified with
with different
different cooling
cooling
rates were
rates were analyzed
analyzed using
using aa Nikon
Nikon EPIPHOT300
EPIPHOT300 optical
optical microscope
microscope (Nikon,
(Nikon, Tokyo,
Tokyo, Japan)
Japan) and
and aa
Quanta
Quanta 400F (FEI, Hillsboro, OR, USA) thermal field emission scanning electron microscope
Oregon, USA) thermal field emission scanning electron microscope equipped with equipped
with
an an INCA
INCA energyenergy dispersive
dispersive spectrometer.
spectrometer. The The
phase phase compositions
compositions contained
contained in the
in the alloy
alloy prepared
prepared at
at different
different cooling
cooling rates
rates were
were examined
examined usingananXRD-6000
using XRD-6000X-ray
X-raydiffract
diffractmeter
meter(Shimadzu,
(Shimadzu,Kyoto,
Kyoto,
Japan). Brinell
Japan). Brinellhardness
hardnesstested
testedwith
witha HB3000
a HB3000 hardness
hardness tester
tester (Shanghai
(Shanghai shangcai
shangcai testing
testing machine
machine co.
Co. Ltd.,
LTD, Shanghai,
Shanghai, China)
China) hashas a load
a load of 250
of 250 N.N. Vickers
Vickers hardnessload
hardness loadisis200
200NNwith
withaaWilsonV32D265
WilsonV32D265
Duisburg, Germany).
(Wilson, Duisburg, Germany). ItIt was
was utilized
utilized to
to measure
measure the
the hardness
hardness of of the
the three
three ingot
ingot samples
samples
prepared
prepared at different cooling rates. The tensile strengths
The tensile strengths of the cast Al-13Si-4Cu-1Mg-2Ni
Al-13Si-4Cu-1Mg-2Ni alloy wasalloy was
tested with
tested with the Instron 1195 mechanical testing machine (Instron, Shanghai, China).

3. Results
3. Results and
and Discussion
Discussion

3.1. Microstructural Analysis of the Samples at Different Cooling Rates

3.1. Microstructural Analysis of the Samples at Different Cooling Rates
Figure 2 shows the microstructures of the model alloy solidified with different cooling rates.
Figure 2 shows the microstructures of the model alloy solidified with different cooling rates. The
The solidification phase composition of alloy varies with cooling rate. The figure indicates that for
solidification phase composition of alloy varies with cooling rate. The figure indicates that for cooling
cooling rates in the range of 0.15–1.5 × 105 ◦ C/s, the microstructure of the alloy turns to be noticeably
rates in the range of 0.15–1.5 × 10 °C/s, the microstructure of the alloy turns to be noticeably refined
5
refined as the cooling rate increases, and dark gray eutectic silicon changes from continuous small strips
as the cooling rate increases, and dark gray eutectic silicon changes from continuous small strips to
to small granules. The size of white Ni- and Cu-rich alloy phase becomes smaller, and the distribution
small granules. The size of white Ni- and Cu-rich alloy phase becomes smaller, and5 the distribution
of the phases is more uniform in the structure. When the cooling rate exceeds 1.5 × 10 5 ◦ C/s, a uniform
of the phases is more uniform in the structure. When the cooling rate exceeds 1.5 × 10 °C/s, a uniform
granular α-Al grain formed, and the second phase which is small in size is distributed around the α-Al
granular α-Al grain formed, and the second phase which is small in size is distributed around the α-
grain, because the second phase produced during solidification is too fast to grow.
Al grain, because the second phase produced during solidification is too fast to grow.

Figure
Figure 2.2. SEM
SEManalysis
analysisininthe Al-13Si-4Cu-1Mg-2Ni
the Al-13Si-4Cu-1Mg-2Ni alloy solidified
alloy with
solidified different
with cooling
different rates:
cooling (a)
rates:
0.15 °C/s;
(a) 0.15 (b) 1.5
◦ C/s; (b)°C/s; (c) 15(c)
1.5 ◦ C/s; °C/s;
15 ◦(d) 150(d)
C/s; °C/s;
150 (e) 1.5 (e)
◦ C/s; × 101.5°C/s.
5
× 105 ◦ C/s.

It can be seen from Figure 2, as the cooling rate increases, the secondary dendrite arm spacing
It can be seen from Figure 2, as the cooling rate increases, the secondary dendrite arm spacing
(SDAS) obviously decreases. This is due to the fact that with the increased cooling rate, both the
(SDAS) obviously decreases. This is due to the fact that with the increased cooling rate, both the
critical nucleation radius and the nucleation activation energy decrease and the nucleation rate
increases [8–10]. The high cooling rate results in higher temperature gradient at the leading edge of
Materials 2018, 11, 1230 4 of 9

critical nucleation radius and the nucleation activation energy decrease and the nucleation rate
increases [8–10]. The high cooling rate results in higher temperature gradient at the leading edge of
the solid–liquid interface, thereby leading to more heterogeneous nucleation and inhibiting the grain
Materials The
growth. 2018, results
11, x FOR
ofPEER
SDASREVIEW
at different cooling rates are shown in Table 3. 4 of 9

the solid–liquid interface, thereby

Table leading
3. SDAS of the to more
alloy heterogeneous
ingot nucleation
at different cooling rates. and inhibiting the grain
growth. The results of SDAS at different cooling rates are shown in Table 3.
Cooling Rates/◦ C/s 0.15 1.5 15 150 1.5 × 105
Table 3. SDAS of84.1
SDAS/µm the alloy43.9
ingot at different
24.8 cooling
13.5 rates.
0.82
Cooling Rates / °C/s 0.15 1.5 15 150 1.5 × 105
SDASrelationship
The following classical / μm 84.1 the43.9
between 24.8 rate
metal cooling 13.5 0.82
and SDAS is derived from the
theory of heat transfer and mass transfer:
The following classical relationship between the metal cooling rate and SDAS is derived from
D = βv−1/3
the theory of heat transfer and mass transfer: (1)

where β is a constant related to the alloy D = βv−1/3

composition and cooling conditions. Using power (1) law
regression
where β isanalysis, a quantitative
a constant related to relationship between the
the alloy composition cooling
and rateconditions.
cooling (v) and theUsing
SDAS power
(D) of the
law
model alloy analysis,
regression can be obtained by fitting
a quantitative the data: between the cooling rate (v) and the SDAS (D) of the
relationship
model alloy can be obtained by fitting the data:
D = 47.126v−1/3 (2)
D = 47.126v−1/3 (2)
Figure 3 shows the XRD patterns of Al-13Si-4Cu-1Mg-2Ni alloy at different cooling rates.
Figure 3 shows the XRD patterns of Al-13Si-4Cu-1Mg-2Ni alloy at different cooling rates. The
The figure reveals that the composition of the alloy is similar to that of solidification under different
figure reveals that the composition of the alloy is similar to that of solidification under different
cooling rates, but the content of each phase is different. There is ε-Al3 Ni in the XRD analysis of a
cooling rates, but the content of each phase is different. There is ε-Al3Ni in the XRD analysis of a
sample at cooling rate of 0.15 ◦ C/s, and there is almost no ε-Al3 Ni phase in the alloy when the cooling
sample at cooling rate of 0.15 °C/s, and there is almost no ε-Al3Ni phase in the alloy when the cooling
rate is increased greatly, as demonstrated in the SEM analysis in Figure 4. It also indicates that there
rate is increased greatly, as demonstrated in the SEM analysis in Figure 4. It also indicates that there
are almost no other alloying phases forms in the Al alloy during solidification with the cooling rate of
are almost no other alloying phases forms in the Al alloy during solidification with the cooling rate
1.5 × 105 ◦ C/s except for α-Al phase. Because α-Al precipitated from under-cooling melt, the residual
of 1.5 × 105 °C/s except for α-Al phase. Because α-Al precipitated from under-cooling melt, the
melt did not have enough time to form other big second alloying phases, and therefore nanocrystal
residual melt did not have enough time to form other big second alloying phases, and therefore
exists in the alloy.
nanocrystal exists in the alloy.

Figure 3. XRD analysis in the Al-13Si-4Cu-1Mg-2Ni alloy solidified with different cooling rates.
Figure 3. XRD analysis in the Al-13Si-4Cu-1Mg-2Ni alloy solidified with different cooling rates. (a)
(a) 0.15 ◦ C/s; (b) 1.5 ◦ C/s; (c) 15 ◦ C/s; (d) 150 ◦ C/s; (e) 1.55 × 105 ◦ C/s.
0.15 °C/s; (b) 1.5 °C/s; (c) 15 °C/s; (d) 150 °C/s; (e) 1.5 × 10 °C/s.
Materials 2018, 11, 1230 5 of 9
Materials 2018, 11, x FOR PEER REVIEW 5 of 9

Al7Cu4Ni

20μm 20μm 20μm

(d) (e)

ɛ-Al3Ni δ-Al3CuNi

(f) (g)
γ-Al7Cu4Ni Q-Al5Cu2Mg8Si

Figure 4. SEM analysis in the Al-13Si-4Cu-1Mg-2Ni alloy solidified with different cooling rates:(a)
Figure 4. SEM analysis in the Al-13Si-4Cu-1Mg-2Ni alloy solidified with different cooling rates:
0.15 °C/s; (b) 1.5 °C/s; (c) 15°C/s; (d) EDS of ε-Al3Ni; (e) EDS of δ-Al3CuNi; (f) EDS of γ-Al7Cu4Ni; (g)
(a) 0.15 ◦ C/s; (b) 1.5 ◦ C/s; (c) 15◦ C/s; (d) EDS of ε-Al3 Ni; (e) EDS of δ-Al3 CuNi; (f) EDS of γ-Al7 Cu4 Ni;
EDS of Q-Al5Cu2Mg8Si6.
(g) EDS of Q-Al5 Cu2 Mg8 Si6.

Figure 4 presents an enlarged view of the SEM micrograph of the model alloy at: (a) 0.15 °C/s ◦
(b)
Figure
1.5 °C/s (c) 154 °C/s.
presents an enlarged
Energy dispersive view of the SEManalysis
spectroscopy micrographof theof the model
white phase hasalloy at: (a) 0.15
confirmed it toC/s
be
(b) 1.5 ◦ C/s (c) 15 ◦ C/s. Energy dispersive spectroscopy analysis of the white phase has confirmed it to
δ-Al 3CuNi phase and γ-Al7Cu4Ni phase. It has been reported that the major strengthening formed
be δ-Al3the
during CuNi phase and process
solidification γ-Al7 Cuin 4 Ni
thephase.
pistonItalloy
has been reported
are δ-Al that the major strengthening formed
3CuNi phase and γ-Al7Cu4Ni phase [7].
during the solidification process in the piston alloy
Figure 4a suggests that there are ε-Al3Ni phases in the solidified are δ-Al 3 CuNi phaseingot
and γ-Al 7 Cu
at the 4 Ni phase rate,
subcooling [7].
Figure 4a suggests that there
and there are few black M-Mg2Si phases. With are ε-Al 3 Ni phases in the solidified ingot at the
the increase in the cooling rate, the black M-Mg subcooling rate,
2Si
and there
phase risesare few black
slightly, M-Mg
and the δ and2 Siγphases. With thefrom
phases changed increase
largein the cooling
meshes rate, the
and clusters black M-Mg
to smaller meshes 2 Si
phase
and rises slightly,
Chinese script and the δ and
features. phases changed
At aγcooling rate of 15 from
°C/s,large
theremeshes and 5clusters
are Q-Al Cu2Mg8to Si6smaller
phasesmeshesin the
and Chinese script features. At a cooling rate of 15 ◦ C/s, there are Q-Al Cu Mg Si phases in the
microstructure of the ingot, and most of them are around the δ phase. However, no Q phase is found 5 2 8 6
microstructure
in of the ingot,at
the ingot microstructure and most ofrate
a cooling them ofare
0.15around the δ phase.
°C/s because Mg2SiHowever, no Q phase
is preferentially is found
precipitated.
in the ingot microstructure at a cooling rate of 0.15 ◦ C/s because Mg Si is preferentially precipitated.
The δ and Q phases both increase with rising cooling rate. Belov et al.2 studied the phase diagrams of
TheAl-Cu–Fe–Mg–Ni–Si
the δ and Q phases both system increaseofwith rising cooling
aluminum piston rate.
alloysBelov
[11], ettheal.Al-Si-Cu-Mg-Ni
studied the phase diagrams
alloy reported of
the Al-Cu–Fe–Mg–Ni–Si system of aluminum piston alloys [11], the
in the literature is the same as the alloy system studied in this paper, so the DSC curve is similar,Al-Si-Cu-Mg-Ni alloy reported
in the literature
which is shown in is the
the same as the
literature: thealloy
Q phasesystem studied
formed in thisLpaper,
through → (Al)so+ the (Si) DSC
+ θ +curve
Q + γisatsimilar,
about
which
503 °C.isWhen
shown theincooling
the literature: the Q phase
rate increases, formed through
the temperature decreases L →so(Al)fast+that
(Si)the
+ θhigh
+ Q temperature
+ γ at about
503 ◦ C. When
precipitates did thenot
cooling
have rate increases,
enough time to theprecipitate.
temperature Indecreases
this model so alloy,
fast that thethe high temperature
morphology of the
precipitates did not have enough time to precipitate. In this model alloy,
second phase is characterized by irregularity, which is generally attributed to the alterations in the the morphology of the second
phase is characterized
temperature gradientbyand irregularity,
the degree whichofis generally
overcooling attributed to the alterations
and composition in the temperature
changes during the
gradient and the degree of overcooling and composition changes during
solidification of the alloy. It is the cooling rate of the alloy in the solidification stage that influences the solidification of the
alloy.
the It is the cooling
microstructural rate of the of
morphology alloytheinalloy;
the solidification
it allows thestage that influences
secondary phase of the the microstructural
alloy to have a
morphology of the alloy; it allows the secondary phase of the
significant change in size and morphology [11–14]. When the cooling rate is accelerated, alloy to have a significant change in size
the energy
and morphology [11–14]. When the cooling rate is accelerated, the energy
fluctuation is larger and the nucleation rate increases. For the crystal grain, the liquid-solid phase fluctuation is larger and the
nucleation rate
transitions takeincreases.
place even Forbefore
the crystalthe grain,
crystalthe liquid-solid
grain grows up, phasethustransitions
producing takefine
place even and
grains before a
the crystal grain grows up,
deviation from the equilibrium state. thus producing fine grains and a deviation from the equilibrium state.
Figure 5 shows a high-magnification scanning microscopy image for the cooling rate of 150 °C/s
and a line scanning elemental profile. In the figure, the gray-colored region is the aluminum matrix,
and the fine white phase may be the γ-Al7Cu4Ni through EDS and XRD in Figure 6. From the line-
Materials 2018, 11, 1230 6 of 9

Figure 5 shows a high-magnification scanning microscopy image for the cooling rate of 150 ◦ C/s
and a line scanning elemental profile. In the figure, the gray-colored region is the aluminum matrix,
Materials 2018, 11, x FOR PEER REVIEW 6 of 9
and the 2018,
Materials fine 11,
white
x FORphase
PEERmay be the γ-Al7 Cu4 Ni through EDS and XRD in Figure 6. From the line-scan
REVIEW 6 of 9
distribution pattern, the complex compounds produce in a uniform symmetrical growth manner
scan distribution pattern, the complex compounds produce in a uniform symmetrical growth manner
scan distribution
during pattern, the complex compounds produce incooling
a uniform symmetrical growth when
manner
duringthe α-Alsolidification
theα-Al solidification process
process due
due to
to the
the excessive rate.
excessive cooling rate. Inthe
In themeantime,
meantime, when the the
during the α-Al solidification process due to 5
the◦ excessive cooling rate. In the meantime, when the
cooling
coolingrateratecontinues
continues to toincrease
increase to 1.5×× 10
to1.5 C/s(Figure
105 °C/s (Figure5),
5),the
theSDAS
SDASisistoo toosmall
smallto todistinguish
distinguish
cooling rate continues
gray-colored to increase to 1.5 × 105 °C/s (Figure 5),one
thecan
SDAS issee
toothat
small to distinguish
gray-colored regions from bright white-colored regions, and one can only see that the elements ofofthe
regions from bright white-colored regions, and only the elements the
gray-colored
alloy regions from bright white-colored regions, and one can only see that the elements of the
alloyare
areevenly
evenlydistributed
distributedtoto form
form aa solid
solid solution.
solution.
alloy are evenly distributed to form a solid solution.

10 μm
10 μm

Figure5.5.SEM
Figure SEManalysis
analysis with
with the ◦ C/s.
the cooling rate of 150 °C/s.
Figure 5. SEM analysis with the cooling rate of 150 °C/s.

Figure 6. SEM analysis in the Al-13Si-4Cu-1Mg-2Ni alloy solidified with cooling rate of 1.5 × 1055 °C/s.
◦ C/s.
Figure 6. SEM analysis in the Al-13Si-4Cu-1Mg-2Ni alloy solidified with cooling rate of 1.5 ××10
SEM analysis 105 °C/s.
Figure 7 shows the TEM image and EDS analysis of the sample at the cooling rate of 1.5 × 105 °C/s.
Figure 7 shows the TEM image and EDS analysis of the sample at the cooling rate of 1.5 × 105 °C/s.
It is clearly demonstrated that something like a polycrystalline ring or an amorphous ring is formed
It is clearly demonstrated that something like a polycrystalline ring or an amorphous ring is formed
around the [110] zone axis of Al matrix. EDS analysis of the matrix shows a small amount of Si and
around the [110] zone axis of Al matrix. EDS analysis of the matrix shows a small amount of Si and
Cu in the Al matrix, whereas the so-called grain boundaries are alloying elements in the states. Such
Cu in the Al matrix, whereas the so-called grain boundaries are alloying elements in the states. Such
Materials 2018, 11, 1230 7 of 9

Figure 7 shows the TEM image and EDS analysis of the sample at the cooling rate of 1.5 × 105 ◦ C/s.
It is clearly demonstrated that something like a polycrystalline ring or an amorphous ring is formed
Materials 2018, 11, x FOR PEER REVIEW 7 of 9
around the [110] zone axis of Al matrix. EDS analysis of the matrix shows a small amount of Si and Cu in
the Al matrix,
crystals whereas
are called the so-called
nanocrystals grain boundaries
because the matrixareAlalloying
contentelements in theto
is too high states. Such crystals
completely form
are called
amorphous. nanocrystals because the matrix Al content is too high to completely form amorphous.

(a) 1 (b)

(c) (d)

Figure 7. TEM analysis with the cooling rate 1.5 × 105 °C/s.
Figure 7. TEM analysis with the cooling rate 1.5 × 105 ◦ C/s.

3.2. Analysis of the Mechanical Properties of the Samples at Different Cooling Rates
3.2. Analysis of the Mechanical Properties of the Samples at Different Cooling Rates
As seen from Table 3, with the increase in cooling rate, the SDAS changes rather significantly.
As seen from Table 3, with the increase in cooling rate, the SDAS changes rather significantly.
Table 4 lists the test results of the cast model alloy solidified with different cooling rates. The results
Table 4 lists the test results of the cast model alloy solidified with different cooling rates. The results
show that as the solidification cooling rate accelerated, hardness changes from 80.9 to 125.7 HB and
show that as the solidification cooling rate accelerated, hardness changes from 80.9 to 125.7 HB and the
the micro hardness changes from 130 to 195 HV. Figure 8 shows the stress strain curve of different
micro hardness changes from 130 to 195 HV. Figure 8 shows the stress strain curve of different cooling
cooling rate of the alloy.
rate of the alloy.
Table 4. Mechanical properties of the cast model alloy solidified with different cooling rates.
Table 4. Mechanical properties of the cast model alloy solidified with different cooling rates.
Colling Rate °C/s Hardness Tensile Strength/MPa Elongation/%
Rate ◦ C/s
Colling0.15 Hardness
80.9 HB Tensile Strength/MPa
189.3 Elongation/%
1.6
1.5
0.15 118.6 HB
80.9 HB 213.3
189.3 2.2
1.6
1.5 118.6 HB
108.6 HV matrix 213.3 2.2
15 125.7 HB 108.6 HV matrix 282.5 2.8
15 125.7 HB 131.2 HV phases 282.5 2.8
131.2 HV phases
150
150 150.4 HV
150.4 HV -- --
15,000
15,000 195.6 HV
195.6 HV -- --
Materials 2018, 11, 1230 8 of 9

Figure 8. The stress strain curve of different cooling rate of the alloy.

Tensile strength at room temperature has also increased significantly by 49.2% and the elongation
increased from 1.6% to 2.8% since as the cooling rate increases, the grains become considerably finer,
and the various second phases dispersed more evenly, thereby giving rise to the dual effect of fine
grain strengthening and second phase strengthening.
It is evident from Figure 8 that the tensile strength is the point at which the premature failure
occurs. This means that the improved tensile strength at high cooling rates is related to the refinement
of secondary phases that delays the premature failure. Both the strengthening by fine phases and the
delay of premature failure contribute to the improved mechanical properties at high cooling rates.
The fine alloy phase size is the main reason for the reinforcement. With the strengthening in these
manners, there are improvements in the strength of the alloy material, the processing performance of
the material and the toughness of the alloy material.

4. Conclusions
By comparing the different cooling rate, the microstructure, hardness and tensile strength of the
alloy all changed obviously. The main findings are summarized as follows:
1. With the increase in the solidification cooling rate from 0.15 to 1.5 × 105 ◦ C/s, the SDAS
of Al-13Si-4Cu-1Mg-2Ni alloy is refined from 84.1 µm to 0.82 µm. With the increase in the
solidification cooling rate from 0.15 to 1.5 × 105 ◦ C/s, the main strengthening phases, δ-Al3 CuNi
phase and γ-Al7 Cu4 Ni phase, increased and the shape changed from the larger continuous mesh
and long chains into smaller clusters and granules. The formation of Q-Al5 Cu2 Mg8 Si6 phase
gradually increases while the ε-Al3 Ni phase decreases. There is a rapid change in alloy structure,
from different polymetallic phases to a single nanocrystal.
2. The mechanical properties of the as cast Al-13Si-4Cu-1Mg-2Ni alloy at room temperature
including hardness, tensile strength and elongation were noticeably improved due to the effect
of fine grain strengthening, fine second phase strengthening, and dispersion strengthening.
The hardness increased from 80.9 to 125.7 HB, the room temperature tensile strength enhanced
from 189.3 to 282.5 MPa and the elongation at break increased from 1.6% to 2.8%. Further increase
in the cooling rate leads to the micro hardness increases gradually from 131.2 to 195.6 HV.

Author Contributions: L.T. wrote the main part of the manuscript and took part in the planning and execution of
the experiments. Y.G. conceived and designed the study. J.L. participated in the coordination of the study and
reviewed the manuscript. F.X. carried provided experimental alloys and analytical samples. M.L. analyzed part of
experimental results. Y.B. performed performance tests and made a final examination of the article.

1
Materials 2018, 11, 1230 9 of 9

Funding: The authors would like to thank the National Basic Science Development Foundation of China
(613224), National Natural Science Foundation of China (Grant No. 51705391) and Creative Talents Promotion
Plan—Technological Innovation Team (2017KCT-05) for financial support.
Conflicts of Interest: The authors declare no conflicts of interest.

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