influnce of milling time and ball-to-powder ratio of … · 2020. 9. 12. · influnce of milling...

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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

Fe-35mn-5cu Alloy on Particle Size and Green Density


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



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




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



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




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.



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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