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INFLUNCE OF MILLING TIME AND BALL-TO-POWDER RATIO OF
MECHANICALLY ALLOYED Fe-35Mn-5Cu ALLOY ON PARTICLE SIZE AND
GREEN DENSITY
S. SIVASANKARAN*, ABDULAZIZ S. ALABOODI, YASER A. ALSHATAIF, MOHAMMAD SAJID
Mechanical Engineering Department, Qassim University, Buraidah 51452, Saudi Arabia
ABSTRACT
In this research article, the development of Fe-35Mn-5Cu alloy (bio-degradable) through mechanical alloying was
discussed. The two key important parameters in mechanical alloying process, namely, milling time (1 and 10 h) and
ball-to-powder ratio, BPR (5:1 and 15:1) were taken as variable input parameters. The other parameter of milling
speedwas set at 200 rpm in all the samples. Elemental powders of iron (Fe), manganese (Mn), and copper (Cu) were
taken and mixed inside the high energy ball mill gravimetrically. The mechanical alloying was carried out under wet
milling method in which ethanol was used as a processing control agent. The particle size analysis on ball milled
powders were examined using laser light scattering technique. Them the milled powders were compacted (cold-uni
axial compaction) at 1100 MPa and green density was measured. The morphology of ball milled powders were also
examined using scanning electron microscope. The results revealed that both milling time and BPR were influenced
much on particle size reduction and green density of the consolidated samples. A 15:1 BPR with 1 h milled sample has
produced around 493.8 nm particle size. However, around 1630 nm particle size was obtained in a 5:1 BPR with 1h
milled sample. The more reduction in 15:1 BPR sample was attributed to more energy input in to the materials, sever
plastic deformation, and crystallite size refinement. Around 75% theoretical green density was obtained in 5:1 BPR
with 1 h milled sample whereas 66% theoretical green density was observed in 15:1 BPR with 10 h milled sample. The
drastic reduction of green density in 15:1 BPR with 10 h sample indicate more strain hardened in the milled powders
eventually the mechanical properties can be increased.
KEYWORDS: Fe-35Mn-5Cu Alloy; Mechanical Alloying; Powder Particle Size Analysis; Compaction; Green Density
Received: Jun 08, 2020; Accepted: Jun 28, 2020; Published: Sep 12, 2020; Paper Id.: IJMPERDJUN20201187
INTRODUCTION
Several materials are being used for implant products, namely, metallic materials (titanium-based alloys), ceramic
materials, and polymer-based materials. These materials are having some side effects/issue with the human organ
(osteoporosis, and thrombosis)[1]. To eliminate the side effects, recently several research works are being
conducted through the development of metallic based alloys, namely, iron-based alloys, and magnesium-based
alloys due to improved mechanical properties and corrosion resistance[2][3]. Iron based alloys are possessing high
value of ultimate strength with more amount of ductility compared to magnesium-based alloys. Further, more
degradation resistance can be obtained in iron based bio-degradable materials due to the formation of protective
iron oxide layer over the parts which inhibit the degradability [4]. It was proven by several authorsthat more safety
and high value of efficacy can be obtained from iron based implant parts[5]. It is well known that both iron (Fe)
and magnesium (Mg) are essential metabolic elements needed for human organs which are compatible with human
Orig
ina
lArticle
International Journal of Mechanical and Production
Engineering Research and Development (IJMPERD)
ISSN(P): 2249–6890; ISSN(E): 2249–8001
Vol. 10, Issue 3, Jun 2020, 12469–12478
© TJPRC Pvt. Ltd.
12470 S. Sivasankaran*, Abdulaziz S. Alaboodi, Yaser A. Alshataif, Mohammad Sajid
Impact Factor (JCC): 8.8746 SCOPUS Indexed Journal NAAS Rating: 3.11
cells [6].
Hermawan et al. [7] synthesized Iron-Manganese based implant materials through powder metallurgy process and
fabricated a cardiac stent. The author’s have found that the stent made by Fe-Mn implant materials exhibited enhanced
mechanical properties, metabolic activity in addition to improved corrosion resistance. Bagha et al. [8] discussed the
degradability of iron based biodegradable implant materials which was produced by means of ball milling and spark-
plasma sintering techniques. They reported that the corrosion rate of these materials was accelerated using appropriate
addition of Mn and Ag, as alloying elements. The examined alloy displayed high shear strength of around 420 MPa and
produced the average strain of 66%. Sotoudehbagha et al. [9] have studied various synthesizing method to produce iron-
based implant materials and further, the authors have varied different elemental composition. The authors have produced
novel Iron based materials which consisted of 30 weight fraction of Manganese and around 3 weight fraction of silver
using ball milling technique. They reported that the alloy contained 3wt% silver exhibited the best properties as compared
with the other alloys under their study. The properties studied included shear strength, micro-hardness, corrosion rate and
relative density. On the other hand, they reported that the optimal cytotoxicity and antibacterial behavior were obtained
when adding 1wt% silver.
Bagha et al. [6] studied the mechanical behavior, corrosion rate and biocompatibility of a nanocrystalline Fe-
35wt.%Mn biodegradable alloy. The alloy was synthesized by means of ball milling technique and traditional cold pressing
and sintering. The milled alloy exhibited higher hardness, enhanced compression strength, lower rate of corrosion,
improved cell adhesion, as compared to un-milled samples. Safaie et al.[10] successfully synthesized a solid solution of
nanostructured iron-based alloy mixed with 30 weight fraction of manganese using ball milling technique. The authors
have used the ball milling parameters of 10h milling time, and 30:1 ball-to-powder ratio. Sikora-Jasinska et al.
[11]developed Fe- Mg2Si composite for the applications of biodegradable implants with improved mechanical
characteristics and increased the corrosion resistance. The produced composite of Fe-Mg2Si were synthesized using ball
milling technique and then consolidated by hot rolling. They reported that the incorporation of one weight fraction of
magnesium silicide (Mg2Si) in the iron matrix was accelerated the corrosion resistance. Mouzou et al. [12] investigated the
biodegradability performance of Fe-20Mn-1.2C alloy in various corrosive solutions. The alloys were fabricated industrially
by casting process followed by hot rolling. The highest degradation rate was reported when using commercial Hanks
solution as a corrosion media while the lowest rate was found when using a corrosive media of Dulbecco's modified
solution.
Mandal et al. [13] developed a novel Fe-Mn-Cu alloy for fracture fixation with improved anti-microbial behavior.
The authors have developed different compositions of iron alloy with various percentage of Manganese and Copper in
which the maximum manganese content was 35 wt.% and the copper content was 10%. These alloys were manufactured
using high-energy mechanical alloying process followed by compaction and sintering. It was reported that adding up to
10wt% Cu resulted in increasing the corrosion rate with 6 times more than the base alloy. Furthermore, increasing the Cu-
level up to 5wt% resulted in a significant increase in the hardness of the investigated alloys. Additionally, increasing Cu-
content led to an improved anti-microbial property. Faruk Mert[14] has investigated the tribological behavior of
magnesium based biodegradable alloy (AZ1B hot rolled alloy) for implant applications. The sliding wear test was
conducted using pin-on-disc apparatus in which the author has varied the load starting from 10N to 80N, the sliding
velocity varied from 0.25 m/s to 2.5 m/s, and the maximum sliding distance was 5000 m. Finally, the author has found that
Influnce of Milling Time and Ball-to-Powder Ratio of Mechanically Alloyed 12471
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the hot rolled AZ1B magnesium-based implant materials was produced more wear resistance.
Based on several literature, there are limited studies explaining the development of iron-based implant materials.
Therefore, the main aims of the present research article are to synthesize the Fe-35Mn-5Cu alloy through solid state
mechanical alloying process, to study the effect of milling time (1 and 10h), to study the effect of BPR (5:1 and 15:1), to
examine the particle size analyses on the milled powders, and to investigate the green density with the function of milling
time and BPR.
EXPERIMENTAL PROCEDURE
Pure element metallic powders (iron-Fe, manganese-Mn, and copper-Cu) with a purity of more than 99.5% were purchased
from M/s Nanografi. The average particle size of all elemental powders was less than 45 m. The weight fraction of
developed Fe-35Mn-5Cu alloy was 0.6, 0.35, and 0.05 for Fe, Mn, and Cu respectively. The theoretical density, the
corresponding volume fraction, and the chemical composition are illustrated in Table 1. The theoretical density of Fe-
35Mn-5Cu was determined using rule of mixture in which the volume fraction of each incorporated elements was
accounted. The weighed powders were milled in a high-energy ball milling with different processes parameters as
illustrated in Table 1. The milled powders were then consolidated / compacted at 1100 MPa pressure with a strain rate of 1
mm/min to examine the densification behaviour. The schematic of two stations planetary high energy ball milling and cold
uniaxial pressing of powders were given in Figure 1. The powders were milled under wet medium in which ethanol was
used as a process control agent. Before green compaction, the die was lubricated with nano-graphene. The milled powder
particle size was measured using Zeta laser light scattering technique (M/s Malvern PANalytical, UK). The schematic laser
light scattering technique is illustrated in Figure 2. The powder morphology was also examined using electron microscope.
Table 1: Composition of various metallic elemental powders, weight fraction, volume fraction and theoretical
density of developed Fe-35Mn-5Cu alloy
Name of
Alloy
Name of elemental
powders
Theoretical
density of each
elemental
powders, g/cm3
Weight
fraction of
each
elemental
powders
Volume
fraction of
each
elemental
powders
Theoretical
density of
developed
alloy, g/cm3
Al-35Mn-5Cu
Iron (Fe) 7.874 0.60 0.5912
7.7587 Manganese (Mn) 7.430 0.35 0.3655
Copper (Cu) 8.960 0.05 0.0433
12472 S. Sivasankaran*, Abdulaziz S. Alaboodi, Yaser A. Alshataif, Mohammad Sajid
Impact Factor (JCC): 8.8746 SCOPUS Indexed Journal NAAS Rating: 3.11
Figure 1: Schematic of: (a) high-energy mechanical alloying process; (b) cold uni-axial compaction process, used to
produce Fe-35Mn-5Cu alloy
Figure 2.:Schematic of laser scattering technique used to measure the particle size of Fe-35Mn-5Cu alloy powders
Table 2: Experimentally measured laser particle size of milled powders, actual density and percentage relative
density of green compacts pressed at 1100 MPa of Fe-35Mn-5Cu alloy
Name of
alloy
Milling
time, h
Ball-to-
powder
ratio,
BPR
Particle size
of milled
powders, nm
Actual density of
green compacts at
1100 MPa
Percentage
relative density
of green
compacts, %
Fe-35Mn-5Cu
1 5:1 1630 5.8277 75.11
10 5:1 734.1 5.6430 72.73
1 15:1 493.8 5.7081 73.57
10 15:1 589.1 5.1288 66.1
RESULTS AND DISCUSSIONS
The powder surface morphology of as-received iron, manganese, and copper powders were given in Figure 3. Equiaxed
with roughly spherical powder particle shape was observed in iron powders (Figure 3a), polygonal shape with irregular
powder particles was observed in manganese powders (Figure 3b), and a dendritic with network powder particle topology
was observed in as-receive copper powders (Figure 3c). The processed milled powders morphology as per Table 1 was also
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examined. Figure 4a and Figure 4b are shown the powder surface morphology of Fe-35Mn-5Cu alloy with different
milling time (1 and 10 hr) and ball-to-powder ratio (5:1 and 15:1) as an example. From Figure 4a, the results explained that
the powder surface morphology was not changed to any considerable amount due to less milling time and lower value of
BPR. This was attributed to less energy was imported over the materials during 1 h milling time. Hence, homogeneous
alloy might not be formed. However, based on Figure 4b, 10 h milled powders with 15:1 BPR sample exhibited major
changes in the powder surface morphology in addition to particles size reduction. The changes in the powder
morphological shapes influences the mechanical properties of consolidated, and sintered preforms. The drastic reduction
was attributed to more energy was imported over the materials led to changes in the shape of powder surface morphology
which help to enhance the mechanical properties.
Figure 3: Powder surface morphology of as-received elemental powders to synthesize Fe-35Mn-5Cu alloy: (a) as-
received Fe; (b) as-received Mn; (c) as-received Cu[15].
In fact, more amount of kinetic energy, mechanical collisions, surface energy changes, crystallite size / structural
refinement would occur due to which the powder particle surface morphology was also getting changed. Almost, flake-like
flattened shape powder particles was obtained. The average powder particle size measured from laser scattering system are
illustrated in Table 2 and Figure 6. First sample |(Table 2) milled with 1 h and 5:1 BPR was exhibited the average particle
size was around 1630 nm, the 10h with 5:1 BPR sample produced the average particle size was around 734 nm. However,
1h and 15 h with 15:1 BPR samples have produced the average particle size was 494 and 589 nm respectively. These
results indicate that BPR has influence more compared to milling time. The drastic reduction of particle size with the
function of BPR was attributed to introducing more kinetic and mechanical collisions occurs in the ball mill. The powder
particle distribution for all the four samples were illustrated in Figure 5. From Figure 5a and Figure 5b, it is clear that both
the samples have got almost same distribution with two peaks. This was attributed to low energy imported on the Fe35Mn-
5Cu alloy. However, 15 h with 15:1 BPR sample exhibited a sharp peak with uniform particle size distribution as
illustrated in Figure 5d compared to 1h with 15:1 BPR sample. These results demonstrate clearly that BPR has influenced
more on powder surface morphological changes compared to %:1 BPR. Based on Figure 5c, there are two broadened peaks
was obtained in 1h with 15:1 BPR ratio due to cold welding and powder particles sticking together in early stages of
12474 S. Sivasankaran*, Abdulaziz S. Alaboodi, Yaser A. Alshataif, Mohammad Sajid
Impact Factor (JCC): 8.8746 SCOPUS Indexed Journal NAAS Rating: 3.11
milling. It was disappeared when the milling time was increased to 15 h. Hence, structural refinement with drastic powder
particle size reduction was observed when the milling time and BPR increased beyond 10 h and 10 BPR. Figure 6 shown
the variation of average powder particles with the function of milling time and BPR. In addition, two peaks were observed
in 1 h with 15:1 BPR sample due to the domination fo cold welding in early stage of welding. This is commonly occurring
in high-energy ball milling products. The observation of cold welding in early stage of milling was also observed
elsewhere [16]–[18]. It is obvious that BPR has influenced more on powder surface morphological changes compared to
milling time. This meant, more ball-to-powders-to-balls-vials collisions were expected to occur eventually drastic particle
size reduction, powder morphological changes, and structural refinement could obtain in the milled powder particles [19].
Hence, to obtained improved microstructures, BPR can be increased rather than increasing of milling time.
Figure 4: HRSEM images of powder surface morphology of Fe-35Mn-5Cu milled powders with different milling
time and BPR: (a) milling time 1h & BPR 5:1; (b) milling time 10h & BPR 15:1
Figure 5: Laser particle size of Fe-35-5Cu milled powders with different milling time and BPR: (a) milling time 1h
and BPR 5:1; (b) milling time 10h and BPR 5:1; (c) milling time 1h and BPR 15:1; (d) milling time 10h and BPR
15:1
Influnce of Milling Time and Ball-to-Powder Ratio of Mechanically Alloyed 12475
Fe-35mn-5cu Alloy on Particle Size and Green Density
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Figure 6: Variation of average particle size of Fe-35Mn-5Cu alloy powders after
milling with different time and BPR
The milled powders processed with different processing parameters (milling time and BPR) were compacted at
1100 MPa and the density of the green compacts were measured according to Archimedes principle. The relative density
was calculated from the ratio of actual density and theoretical density. The variation of obtained percentage theoretical
density with the function of milling time and BPR is shown in Figure 7. From Figure 7, it is clear that the percentage
density was decreased slightly when the milling time increased 1 h to 10 h for the same BPR, whereas, the percentage
density was decreased considerably when the milling time increased 1h to 10h in 15:1 BPR. The considerable reduction of
percentage theoretical density with 15:1 BPR results indicates the attainment of more strain hardening and strength in the
powder particles. The high value of percentage theoretical density in 1h with 5:1 BPR sample represent the lower amount
of strain hardening with low strength in the powder particles. The decreasing of percentage theoretical density in high
energy ball milled powders was also observed and explained elsewhere[20].Therefore, the strength of Fe-35Mn-5Cu alloy
can be enhanced by increasing of BPR compared to milling time which can be recommended for structural and automotive
applications.
12476 S. Sivasankaran*, Abdulaziz S. Alaboodi, Yaser A. Alshataif, Mohammad Sajid
Impact Factor (JCC): 8.8746 SCOPUS Indexed Journal NAAS Rating: 3.11
Figure 7: Variation of maximum percentage theoretical density of Fe-35Mn-5Cu
alloy with different milling time and BPR
CONCLUSIONS
Fe-35Mn-5Cu bio-degradable alloy was successfully synthesized through high-energy mechanical alloying
process with different processing parameters, namely, milling time and BPR.
Drastic powder morphological changes were observed in 10 hr milled with 15:1 BPR sample due to more work
hardening and structural refinement. SEM powder surface morphology has shown clearly the changes in particles.
The average powder particles were started to decreased with increasing of milling time and BPR in which
increasing of BPR has influenced more compared to milling time
The milled powders were successfully compacted at 1100 MPa with the strain rate of 1 mm/min and the actual
density was determined using Archimedes principle.
The percentage theoretical density was decreased slight with increasing of milling time due to less work
hardening whereas the percentage of theoretical density was decreased considerably with increasing of ball-to-
powder ratio. This indicates the attainment of more strength in the 15:1 BPR sample compared to 5:1 BPR sample
milled at 10h.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge Qassim University, represented by the Deanship of Scientific Research (SRD-QU), on
the material support for this research under the number (3535-qec-2018-1-14-S) during the academic year 1440-1441 AH/
2018-2019 AD.
Conflicts of Interest: The authors declare no conflict of interest.
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