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Silicon (2018) 10:1979–1990

https://doi.org/10.1007/s12633-017-9710-2

ORIGINAL PAPER

Mechanical Properties and Wear Behavior of Zn and MoS2 Reinforced


Surface Composite Al- Si Alloys Using Friction Stir Processing
N. Saini1 · C. Pandey1 · S. Thapliyal1,2 · D. K. Dwivedi1

Received: 4 September 2017 / Accepted: 5 December 2017 / Published online: 17 April 2018
© Springer Science+Business Media B.V., part of Springer Nature 2018

Abstract
Friction stir processing (FSP) is a novel process for refinement of microstructure, improvement of material’s mechanical
properties and production of surface layer composites. In present investigation, composite reinforced with using Zn/ MoS2
powder in as-cast alloy were developed at tool rotational speed of 664 rpm and tool transverse speed of 26 mm/min using
FSP. Microstructural observation of MoS2 /Zn reinforced composites confirmed the fine and equiaxed grains in the stir zone
(SZ) and distribution of fine reinforced particles of MoS2 /Zn in SZ. Moreover, agglomeration of MoS2 /Zn particles were
not observed. The ultimate tensile strength was measured to be 113 ±9 and 82 ±7 MPa for MoS2 and Zn reinforced Al-
Si alloy, respectively. The sliding wear was studied using pin-on-disk tribometer and it was found that FSP enhanced the
wear resistance of the as-cast alloy. The MoS2 reinforced composite showed superior wear resistance than Zn reinforced
composite and base material. To understand the acting wear mechanism, the field emission scanning electron microscope
(FESEM) of worn out surfaces were performed.

Keywords Al-Si alloy · Composite · FSP · Wear · Microstructure

1 Introduction the addition of alloying elements or reinforcing agent


in the metal matrix [10]. Surface composites exhibit the
Hypereutectic aluminum-silicon (Al-Si) alloys are very enhanced characteristic of composites on the surface [11,
popular in the automobiles, aerospace and other engineer- 12]. Metal-matrix composites reinforced with metal exhib-
ing industries due to its less weight to strength ratio, high ited high strength, high resistance to wear, improved creep
thermal conductivity, low thermal expansion coefficient and and fatigue properties as compared with unreinforced met-
high resistance to wear [1]. In recent years, the applica- als [13, 14]. The surface composites have been developed
tion of Al-Si alloys in industries creates the need for study via friction stir process (FSP) in cast Al alloys, metal-matrix
of their mechanical and tribological performance [2–7]. composites and Al alloy substrate [15, 16]. Friction stir
The cast Al-Si alloys are commonly used for piston devel- welding (FSW) process is a precursor of FSP [17]. The tool
opment in automotive engines. The major disadvantage material and their design play a critical role during FSP.
observed with the addition of silicon was that it deteriorated FSP can locally modify the materials in terms of mechanical
the mechanical properties such as toughness and ductility and tribological performance such as enhance ductility and
[8, 9]. However, the disadvantage can be encountered by strength, reduces casting defects, refines microstructure and
enhance wear resistance [18–22]. In FSP, a non-consumable
 N. Saini rotating tool is responsible for microstructural modification
nit030078@gmail.com
[23]. Barmouz et al. [24] carried out FSP on the surface of
 C. Pandey grooved copper (Cu) filled by silicon carbide paper (SiC)
chandanpy.1989@gmail.com
particles and investigated effect of size and volume fraction
1
of SiC powder on mechanical properties. Increasing volume
Department of Mechanical and Industrial Engineering,
Indian Institute of Technology Roorkee, Uttrakhand 247667,
fraction and decreasing size of particles resulted in increase
India of hardness, and enhancement of wear behavior. Dolatkhah
2 School of Mechanical Engineering, Kalinga Institute
et al. [25] also performed FSP on 2 mm Al-groove
of Industrial Technology Bhubneshwar, Odhisha 751024, with SiC reinforcement and investigated effect of process
India parameters on microstructural and mechanical properties of
1980 Silicon (2018) 10:1979–1990

Al5052/SiC metal matrix composites. Decrease of SiC par- Al. FSP was used for composite fabrication in the top layer
ticles size and increase in number of passes enhanced the of the as-cast alloy substrate. The sample plate has been
hardness and wear properties of Al5052/SiC metal matrix prepared on the shaper machine and then made a drill holes
composites. Akramifard et al. [26] performed FSP on a net pattern as shown in Fig. 1b. The dimension of the drill hole
fine holes pattern filled with SiC particles. Designing a net pattern was in such a way that hole dia-2mm, hole depth-1.5
hole was very effective to prevent agglomeration of SiC parti- to 2 mm, transverse hole to hole distance-4mm, line-wise
cles and Cu/SiC composite showed higher hardness and better hole to hole distance-8mm. To decrease agglomeration of
wear behavior. A schematic of FSP is shown in Fig. 1a. The MoS2 /Zn particles, a net of fine holes (instead of groove)
FSP process has various benefits over other metal working was designed on the surface of cast Al-Si alloy sheets.
processes such as refined microstructure, densification, homo- Sathiskumar et al. [27] reported that the volume fraction of
geneity, and solid state processing process, environment- particles in the composites will be equal to the volume of the
friendly, energy-efficient process. The present investigation groove. The volume fraction of drilled holes (VG ) is given
deals with the fabrication of as-cast Al-alloy surface com- by Eq. 1;
posite via FSP route. The surface composite has been
developed by reinforcing MoS2 and Zn powder in the matrix
of cast Al-Si alloy. For reinforced surfaces, microstruc- (VG ) = 16(πd2 h1 /4) + 16(πd2 h2 /4) (1)
ture, mechanical and tribological characterization has been
performed. The wear surfaces were analyzed by using field- Where d is the hole diameter and h1 , h2 are the depth
emission secondary electron microscope (FESEM).
of drilled hole in the workpiece. The projected volume
of tool pin (VT ) is given by the product of pin diameter,
2 Experimental Details depth and the total length of drilled holes workpiece. The
volume fraction of drilled hole and projected volume of
Die casting method was used for the development of cast Al- tool pin were measured to be 211.12 mm3 and 6000 mm3 ,
17% Si alloy by mixing of cast Al-24% Si alloy with pure respectively. Based on the volume of drilled holes to the
volume of tool pin, the volume fraction of added particle
was calculated to be 3.51%. Hence, 3.51 wt % Zn and MoS2
was reinforced into two different 6 mm thick cast Al-17
(a) wt% Si alloy substrate.
The experiment was carried out on the modified vertical
milling machine (Friction stir welding machine). For FSP,
die steel tool was used. The tool material has distinctive
hardness, resistance to abrasion and ability to hold a cutting
edge at elevated temperature. The designed and fabricated
tool has dimensions such as shank dia-24.90 mm, pin dia-
7.90 mm, pin lenth- 3.50mm and shoulder dia-19.0 mm. The
process parameters were selected on the basis of a number
of experiments and with the help of literature such as root
rotational speed 664 rpm and welding speed 20 mm/min. A
pin-less tool was initially employed to cover the top of the
(b) drilled holes after filling with Zn/MoS2 particles to prevent
the particles from scattering during FSP. Then FSP is carried
out with threaded pin die steel tool. To characterize the
surfaces of composite fabricate using FSP, SEMQUANTA
200 Field emission scanning electron microscope (FESEM)
with energy dispersive X-ray spectroscopy (EDS) was used
with accelerating voltage of 20 kV, 10-nA probe current for
working distance of 8 mm. To perform the room temperature
tensile test, flat sub-size specimens were prepared with gage
length and width of 25.4 mm and 6.25 mm, respectively.
The test was performed on Vertical Tensile Testing Machine
(Instron 5982; Capacity: 100 kN) with a strain rate of 6.66
Fig. 1 a Schematic of friction stir processing and b Sample preparation ×10-4/s, as per ASTM standard B577-06 [28]. The average
in the form of drilled holes plate of three test samples have been reported. The microhardness
Silicon (2018) 10:1979–1990 1981

of specimens has been measured using Micro Hardness as shown in Table 1. The counter surface of the machine
Tester (Omnitech-S. Auto), at the load of 500 g and dwell after and before the test has been cleaned using emery
time of 10 s. To evaluate the wear performance of the paper and acetone solution. Before the sample fixed on the
specimens on the pin-on-disk tester at room temperature, machine, they should be weighed on the weighing machine
the samples were cut with 70mm×5mm×4mm from the and as well as after the test because wear rate is calculating
modified plates of composite fabricated using FSP. The using weight loss of the samples. The precision of weighing
wear test was performed as per ASTM G99 standard. For machine was up to third digits. The sample is fixed in the
wear test, EN31 steel was used as disk material for the job holder and mounted on the machine. Then set the time,
counter surface. First, the samples have been polished on rpm in the machine and set near zero value of wear and
emery papers up to 1000 grades. The sample holder has friction forces. After completing the experiment, unhold the
been prepared to hold the samples on the pin on disk sample from the machine and go to measure the weight after
machine. The dimensions of sample holder are as length: cleaning the surface with acetone solution. The wear rate is
60-70 mm, slot depth: 4-5 mm, slot width: 8- 9 mm. calculated from the equation: W=M/LD; where, W, M, L
The various process parameters such as sliding speed, and D are wear rate, weight loss, load, and sliding distance,
sliding distance and load have been selected on the basis respectively. This wear rate is helping in figure out the wear
of literature review and experience and performed on the resistance of the material and draws the graphs between
base material and composite fabricated using MoS2 and Zn wear rate variation with sliding velocity and the load.

Table 1 Calculation of weight


loss for varying load, varying Sample type Sliding velocity (m/s) Load (kg) rpm Time (min) Weight loss (g)
sliding velocity and fixed
sliding distance (1000 m) Base 0.5 1 119 33.34 0.0031
Base 0.5 2 119 33.34 0.0051
Base 0.5 3 119 33.34 0.0075
Base 0.5 4 119 33.34 0.0090
Base 0.5 5 119 33.34 0.0150
Base 0.2 2 48 83.34 0.0065
Base 1 2 238 16.47 0.0078
Base 2 2 476 8.235 0.0090
Base 4 2 952 4.117 0.0105
Base 6 2 1434 2.059 0.0285
FSPed with MoS2 0.5 1 119 33.34 0.0025
FSPed with MoS2 0.5 2 119 33.34 0.0035
FSPed with MoS2 0.5 3 119 33.34 0.0054
FSPed with MoS2 0.5 4 119 33.34 0.0080
FSPed with MoS2 0.5 5 119 33.34 0.0100
FSPed with MoS2 0.2 2 48 83.34 0.0031
FSPed with MoS2 1 2 238 16.47 0.0046
FSPed with MoS2 2 2 476 8.235 0.0064
FSPed with MoS2 4 2 952 4.117 0.0084
FSPed with MoS2 6 2 1434 2.059 0.0124
FSPed with Zn 0.5 1 119 33.34 0.0027
FSPed with Zn 0.5 2 119 33.34 0.0038
FSPed with Zn 0.5 3 119 33.34 0.0055
FSPed with Zn 0.5 4 119 33.34 0.0089
FSPed with Zn 0.5 5 119 33.34 0.0110
FSPed with Zn 0.2 2 48 83.34 0.0042
FSPed with Zn 1 2 238 16.47 0.0045
FSPed with Zn 2 2 476 8.235 0.0061
FSPed with Zn 4 2 952 4.117 0.0095
FSPed with Zn 6 2 1434 2.059 0.0169
1982 Silicon (2018) 10:1979–1990

(a) (b)
(a)

(c) (d)

(b)
(e)

Fig. 4 Elemental maps at the interface of modified surface with MoS2


reinforcement

Fig. 2 a Modified vertical milling machine setup and b Friction stir


3 Results and Discussion
processed zone and cross sectional view of macrographs for MoS2 and
Zn reinforced composites 3.1 Microstructural Characterization

The modified vertical milling machine (Friction stir welding


machine) setup is shown in Fig. 2a. The surface of cast

Fig. 3 a and b EDX maps for


MoS2 reinforced composite and
c and d EDX maps for
composite fabricated using Zn
Silicon (2018) 10:1979–1990 1983

Al-Si alloy was successfully modified using FSP. The


(a) (b)
macrographs and cross-sectional view of MoS2 and Zn
reinforced route are shown in Fig. 2b. Defects were not
found at polished surface validate that FSP is an effective
way for composite fabrication in cast aluminum-silicon
alloys. The porosity measured in as cast-state of Al-Si alloy
was about 0.24% [29].
The energy dispersive X-ray (EDX) spectroscopy of
MoS2 reinforced matrix revealed the presence of Mo and
(c) (d)
S in the MoS2 reinforced surface and distribution of Mo
and Si in the Al matrix, as shown in Fig. 3a-b. The EDX
maps of Zn reinforced matrix revealed the presence of Zn
in the Zn reinforced surface and distribution of Zn and
Si in the Al matrix as shown in Fig. 3c-d. The elemental
maps were required to describe the distribution and presence
of elements in the matrix. The MoS2 reinforced surface
in the fine distribution of particles at the interface in the (e)
matrix of the as-cast alloy. The fine distribution of particles
inside the MoS2 reinforced matrix is shown in elemental
mapping (Fig. 4). The Mo particle variation was found to be
uniform in the Al matrix as shown in Fig. 4e. The elemental
maps for Zn reinforced surface revealed the presence of
a various alloying element in the Al matrix, as shown in
Fig. 5. Figure 5e revealed the presence and distribution of
Zn particles in the Al matrix.
Fig. 6 Secondary electron micrographs of (a) as-cast Al-17% Si alloy,
(b) and (c) MoS2 reinforced composites for different magnification,
(d) and (e) Interface of MoS2 reinforced composites
(a) (b)
Secondary electron micrograph of the as-cast Al-17%
Si alloy is shown in Fig. 6a. It revealed the presence of
coarse primary Si and eutectic Si phase in the Al matrix.
Two different Si particle morphologies were observed for
as-cast alloy, the blocky coarse primary Si particle variety
and the needle/plate like eutectic Si variety. The existence
of porosities, big size and coarse/ irregular morphology of
(c) (d)

(e)

Fig. 5 Elemental maps at the interface of modified surface with Zn Fig. 7 Variation of tensile strength for as-cast alloy, MoS2 and Zn
reinforcement reinforced composites
1984 Silicon (2018) 10:1979–1990

Si crystals are responsible for poor ductility and strength


in cast Al-Si alloys. The microstructural refinement was
noticed from the surfaces of MoS2 and Zn reinforced Al-
Si alloy. The casting porosities were eliminated from the
matrix of as-cast alloy due to material movement from
the retracting side to the advancing side. The refined
microstructure after FSP is shown in Fig. 6b. The difference
in the morphology of primary silicon was noticed for as-
cast and FSP alloy as shown in Fig. 6a-b. The micrograph
of MoS2 reinforced Al-Si alloy was characterized with fine
silicon and MoS2 particles in the Al matrix at various
magnification, as shown in Fig. 6b-c. The presence of very
small primary silicon particles was noticed in the stir zone
of MoS2 reinforced Al-Si alloy as shown in Fig. 6c. The
interface micrographs of MoS2 reinforced Al-Si alloy are
shown in Fig. 6d-e. The difference in the size of primary Si
Fig. 9 Variation of microhardness for as-cast alloy, MoS2 and Zn
particles was noticed at the interface. Hence, FSP of as-cast reinforced composites
alloy resulted in significant break up of eutectic and coarse
primary Si particles. The Si particle size was measured
using Image J software from FESEM images of friction with Zn and MoS2 at tool rotation speed of 664 rpm and
stir processed (FSPed) surfaces. The size of Si particles a welding speed of 20 mm/min. The percentage elongation
was measured to be on average 195±40 µm, 3.5±0.85 µm was not affected very much in the case of composite
and 2.8±0.30 µm for as-cast alloy, MoS2 and Zn reinforced fabricated using Zn reinforcement in the as-cast alloy. The
composites, respectively. fracture surface morphology of tensile tested specimen is
shown in Fig. 8a-c. For an as-cast alloy, fracture surface
3.2 Tensile Test and Fracture Surface Morphology revealed the brittle mode of fracture. The fracture surface
consisted of cleavage facets with a negligible amount of
For as-cast alloy, the tensile strength and yield strength dimples. Composite fabricated with MoS2 shows the mixed
were measured 43 ±13 MPa and 116 ±8 MPa, respectively. mode of fracture. The fracture surface was characterized
After FSP the yield strength of composite fabricated using with the presence of cleavage facets, shallow dimples
Zn and MoS2 were found to be 39 ±6 and 23 ±1 MPa, and matrix cracking. Besides the ductile dimples, smooth
respectively. The ultimate tensile strength was measured intercrystalline areas were noticed at the fracture surface,
113 ±9 and 82 ±7 MPa for MoS2 and Zn reinforced Al- as shown in Fig. 8b. Zn fabricated composite also showed
Si alloy, respectively. Figure 7 shows the variation of the the mixed mode of fracture but the number of dimples was
tensile strength for as-cast alloy and composite fabricated found to be increased. The fracture surface revealed the

Fig. 8 Fracture surfaces


(a) (b)
morphology of (a) as-cast alloy,
(b) MoS2 reinforced composites
and (c) Zn reinforced composites

(c)
Silicon (2018) 10:1979–1990 1985

Fig. 10 Widthwise variation of


microhardness of composites
reinforced with a Zn and b MoS2
(a) (b)

presence of ductile dimples and cleavage facets, as shown Hence, microhardness value was observed to be enhanced
in Fig. 8c. For Zn fabricated composite, the area of ductile in the case of composite fabricated using Zn as compare to
dimples was found to be increased compared to MoS2 composite fabricated using MoS2 . The hardness in MoS2
fabricated composite. The size of dimples was also found to and Zn reinforced specimens was higher than that of as-
be reduced. cast alloy. This was due to (i) dispersion of the MoS2
and Zn particles as a harder phase in the Al-Si matrix,
3.3 Microhardness (ii) severe grain refinement with respect to as-cast alloy,
and (iii) quench hardening resulted from different thermal
The microhardness value was found on an average 63, 92.4 contractions between the MoS2 and Zn particles and the
and 89.3 HV in as-cast alloy and composite fabricated matrix.
using FSPed with Zn and MoS2 respectively. Hence, Fig. 9
shows the variation of microhardness of as-cast alloy 3.4 Wear Test
and composite fabricated with MoS2 and Zn. Fig. 10
shows the widthwise microhardness variation of MoS2 and Wear rate is calculated using weight loss method. A graph
Zn reinforced FSPed alloy. Based on microhardness data of sliding velocity versus wear rate at fixed load of 2
we can say that the microhardness has increased in Zn kg for as-cast alloy and composite fabricated with MoS2
reinforced as-cast alloy as compared to the base metal. But and Zn is shown in Fig. 11. Wear rate was found to be
it has not been affected so much for MoS2 reinforced as- more pronounced at higher speeds about 4 and 6 m/s
cast alloy in the transverse direction of processed region. in all samples. But in the case of composite fabricated
with MoS2 was found to be least. Hence wear resistance

Fig. 11 Wear rate versus sliding velocity at fixed load of 2 Kg for Fig. 12 Wear rate versus load at fixed sliding velocity of 0.5 m/s for
as-cast alloy, MoS2 and Zn reinforced composites as-cast alloy, MoS2 and Zn reinforced composites
1986 Silicon (2018) 10:1979–1990

Fig. 13 Comparison of
coefficient of friction and sliding
(a) (b)
distance for (a) as-cast alloy, (b)
MoS2 reinforced composites and
(c) Zn reinforced composites

(c)

is increases of both composites fabricated with Zn and and composite fabricated with MoS2 and Zn at fixed sliding
MoS2 as compare to the as-cast alloy. Figure 12 shows the velocity of 0.5 m/s. The wear rate was found to be increased
variation of wear rate with varying load for as-cast alloy with a load for fixed sliding velocity, but the effect of sliding

Fig. 14 Worn out surfaces of a


as-cast alloy, b MoS2 reinforced (a) (b)
composites and c Zn reinforced
composites at 0.2 m/s velocity
and 20 N loads

(c)
Silicon (2018) 10:1979–1990 1987

Fig. 15 Worn out surfaces of a


as-cast alloy, b MoS2 reinforced
composites and c Zn reinforced
composites at 6.0 m/s velocity
and 20 N loads

Fig. 16 Worn out surfaces of a


as-cast alloy, b MoS2 reinforced
composites and c Zn reinforced
composites at 0.5 m/s velocity
and 10 N loads
1988 Silicon (2018) 10:1979–1990

speed is more pronounced overload in all samples. Wear worn out surfaces of composite fabricated using FSP with
resistance is increased in the sequence such as composite MoS2 , and Zn reinforcement in the as-cast alloy. As seen
fabricated with MoS2 , composite fabricated with Zn and from Fig. 14a-c the micrographs of wear surfaces at 0.2
cast alloy. Hence, composite fabricated using FSP with m/s sliding velocity and 20N load, the hill and valley and
MoS2 has superior wear resistance in among all type of high deformed area seen in the worn out base metal sample
samples such as composite with Zn and base material. and the least wear occurs in the form of narrow grooves
Figure 13a-c shows the variation of the sliding distance in the case of composite fabricated using MoS2 . Narrow
versus coefficient of friction (COF) in base material, grooves and wedges are clearly seen from the Zn reinforced
composite fabricated using MoS2 and Zn, respectively at 0.5 composites as compare to MoS2 reinforced FSPed alloy.
m/s sliding velocity and 5 kg load, which clearly shows the At the higher sliding speed of 6 m/s and 20N load, the
coefficient of friction of composite fabricated with MoS2 cast Al-17% Si alloy lost their top surface completely as
has lesser variation with sliding distance. In the case of clearly seen from micrograph in Fig. 15a-c, the top surface
base material, the variation in the coefficient of friction was is stick with the counter surface. In the case of the higher
higher as compared to composite fabricated with Zn and load as 50N the hill and valley found, but not much higher
MoS2 . The average COF for surfaces of the as-cast alloy as in the case of higher speeds that means wear rate is
was measured as 0.435. However, the surface of composite more pronounced at higher speeds. In the case of 0.5 m/s
fabricated using FSP with MoS2 shows less scattering of sliding velocity and 10N loads, the wear rate is not much
COF (µ) as compared to other surfaces. In the case of high as other higher load samples. At the lower sliding
composite fabricated using MoS2 reinforcement, the COF speed of 0.5 m/s and 10N load the cast Al-17% Si alloy,
reduces up to 0.35 with least fluctuations. The reason for their top surface is not affected so much clearly seen from
the least fluctuation may be the formation of lubricant micrograph in Fig. 16a-c. Narrow grooves clearly indicate
film in between the contacting sliding surfaces. The COF the less deformed area as compare to the other condition.
(µ) reduces to 0.41 with fewer fluctuations in case of Zn The worn-out surfaces appeared relatively smooth with
reinforced surfaces as compared to for as-cast surfaces. some narrow grooves, which results the enhancement in
The FESEM study of worn out surfaces was done to find the wear resistance can be attributed to the MoS2 and Zn
out the nature of wear. Which shows the FESEM images of reinforcement and microstructural modification due to FSP.

Fig. 17 Worn out surfaces of a


as-cast alloy, b MoS2 reinforced (a) (b)
composites and c Zn reinforced
composites at 0.5 m/s velocity
and 50 N loads

(c)
Silicon (2018) 10:1979–1990 1989

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