Fabrication of Biodegradable Mg Alloy Bone

Scaffold Through Electrical Discharge µ-

Drilling Route

Neeraj Ahuja1, Kamal Kumar2(&), Uma Batra1,

and Sudhir Kumar Garg3
1
Department of Materials and Metallurgical Engineering,
Punjab Engineering College, Chandigarh 160012, India
2
Department of Mechanical Engineering, Punjab Engineering College,
Chandigarh 160012, India
kamaljangra@pec.ac.in, kamaljangra84@gmail.com
3
Department of Orthopedics, Government Medical College and Hospital,
Sector-32, Chandigarh 160030, India

Abstract. Magnesium alloys based materials are gaining popularity for bone
tissue engineering as they are biocompatible, bioresorbable and shows high
osteoblast activities in biological environment. In present work, perforated
structures are produced using electrical discharge drilling (EDD), with an
attempt to fabricate Mg alloy based biodegradable scaffold for bone tissue
engineering. Using appropriate EDD parameters and tubular electrode of
diameter 300 µm, micro holes of diameter 408 µm are produced in ZM21 alloy
and two different types of perforated structures are obtained with porosity of
22% and 34%. These two perforated structures are compared with solid sample
in terms of apatite formation, weight gain and loss of load bearing capacity after
immersion in simulated body fluid (SBF) media. After 21 days of immersion test
in SBF media, apatite formation in perforated structure with interconnected
holes (porosity 34%) is highest, resulting into highest weight gain of 6.23%, for
this sample, whereas, solid sample shows negligible weight gain of 0.58%. The
loss in mechanical load bearing capacity is found lowest at 5.58% in scaffold
having interconnected holes (with porosity 34%). Thus, interconnected perfo-
rated Mg alloy structures having well defined micro pores and pore density can
be designed and fabricated for biodegradable scaffold application.

Keywords: Mg alloy
ZM21
Biodegradable scaffold

Electrical discharge drilling
Micro holes
Apatite
Weight gain
Load bearing capacity

1 Introduction

Bone tissue engineering aims to improve the growth and differentiation of cells to form
functional tissues by developing engineered biomaterials that act as templates (also
called scaffolds) for acquisition of suitable source of cells, growth and proliferation of
cells, vascularization and cell and tissue storage [1, 2]. Scaffolds are made of porous

© Springer Nature Switzerland AG 2019

B. Gapiński et al. (Eds.): Advances in Manufacturing II - Volume 4, LNME, pp. 145–155, 2019.
https://doi.org/10.1007/978-3-030-16943-5_13
146 N. Ahuja et al.

structures, that provide three dimensional biological environments for cell growth and
proliferation during implantation, provide mechanical stability and facilitate in tissue
repair [3].
Scaffold material should be biocompatible, bioresorbable, having controlled
degradation rate and possess relatively low modulus of elasticity, good strength which
matches with that of bone [4]. Polymeric materials like poly lactic acid (PLA), polyg-
lycolic acid (PGA) are used for biodegradable scaffolds but due to fast degradation in
aqueous solution these polymeric material loses their mechanical integrity in two to four
weeks which is major limitation of these scaffolds [5, 6]. Recently, magnesium (Mg) has
come at the topmost priority for the application of biodegradable scaffolds since it
possesses good mechanical strength, low value of elastic modulus, good biocompati-
bility, bioresorbable and ability to allow osteoblastic activity [7, 8]. However, high
degree of degradation in physiological environment is a major concern of Mg that makes
it to degrade faster than the bone healing rate thereby reduces the necessary mechanical
stability till complete bone healing period [8–10]. This shortcoming of Mg-alloy based
scaffolds can be improved through suitable alloying with controlled composition,
modifying the surface characteristics, optimizing the scaffold geometry and selecting
optimal manufacturing route with best process parameters etc. [8].
Element alloying plays the vital role in the manipulation of corrosion resistance of
biomedical Mg alloys. Recently, a potential kind of Mg alloys such as Mg-Ca [11],
Mg-Zn-Ca [12, 13], Mg-Mn-Zn [14], Mg-Zn-Si-Sr [15] and Mg-Zn-Mn-Ca [16], have
been examined with the end goal of biomedical applications. Zn and Mn can be
endured in the human body. Zn is an essential element in the human body and it gives
strength to Mg alloys due to solid solution strengthening [17, 18]. Similar to zinc, Mn
is also important for human body, it helps to refine the grain size, enhancing the
ductility and to improve the tensile strength of Mg alloys [19]. Little addition of Mn
have been appeared to increase the corrosion resistance of the Mg alloy, which addi-
tionally lessens the effects of metallic impurities [20, 21]. Thus, studies on Mg alloys
having Mn and Zn as alloying elements are gaining significance.
While designing biodegradable bone scaffolds, pore density, pore size, surface to
volume ratio and interconnectivity plays vital role for bone growth and degradation of
scaffold. Various studies reported that the scaffolds having average pore size larger than
300 lm provide better conditions for bone formation [22, 23]. There have been several
known routes to produce metallic foams such as foaming of melts with blowing agents,
foaming melts by gas injection, powder metallurgy using a blowing agent or with space
holder, directional solidification, and vacuum foaming [24, 25–27]. Fabrication of
magnesium foam or scaffold remains a challenge because of high flammability of
Magnesium in liquid state. Also, using these traditional production routes, it is difficult
to accurately control the pore morphologies and thus affect the mechanical properties.
Using micro drilling, interconnected perforated structures can be fabricated to act as
a scaffold. Conventional twist drilling process is not capable to produce high aspect
micro holes in hard and composite materials. Electrical discharge drilling (EDD) is a
very popular and economical manufacturing process for machining conductive mate-
rials irrespective of its hardness. EDD is a special case of electrical discharge
machining (EDM) which is used for hole making only. In EDD, repeated spark takes
place that causes the high heat generation between the work material and tool electrode,
 Fabrication of Biodegradable Mg Alloy Bone Scaffold 147

as a result the material is removed through melting and evaporation [28, 29]. Using
Fast EDM µ-drilling process, perforated magnesium alloy structure having intercon-
nected open cell structure, controlled porosity and designed surface to volume ratio can
achieved [30]. In past extensive research work has been carried out in the field of EDM
drilling. Yan et al. [31] combined the EDM and ultrasonic machining to drill micro
holes with diameter of about 150 lm and depth of 500 lm in borosilicate glass. Liu
et al., [32] fabricated the micro holes in nickel alloy using micro EDM. Discharge
current was the most important parameter to achieve the optimum results. Kuppan et al.
[33] studied the EDM parameters such as peak current, pulse on time, duty factor, and
electrode speed in deep hole drilling of Inconel 718 using copper tube of 3 mm
diameter. Kumar [28] optimized the process parameters of electrical discharge drilling
for making high aspect holes of diameter 500 µm in die steel. Gill et al. [30] utilized
the EDD process to produce high aspect through holes in AZ31 Mg-alloy with
diameter 500 µm to vary the surface area. Apatite formation and weight loss study was
carried out in SBF solution at 7 days, 14 days and 21 days respectively for perforated
AZ31 alloy. Despite of many research works on electrical discharge drilling, no work
has been found on fabrication of biodegradable scaffold made of Mg alloys.
In present study, EDD has been utilized to produce perforated structure in
ZM21 Mg alloy, using brass electrode of 300 µm diameter. EDD is a thermal erosion
process which helps to achieve fine holes with surface roughness between 2 lm to
4 µm. This micro roughness would help to attract and grow the cell tissues in perfo-
rated structure. To demonstrate the potential of current machining process, two dif-
ferent types of scaffolds have been produced having fixed pore size and variable
porosity. Further, immersion test has been performed on perforated structures in sim-
ulated body fluid (SBF) at 37 °C for 7 days, 14 days and 21 days to study the apatite
formation, weight gain and loss in load bearing capacity in SBF.

2 Materials and Experimental Method

In the present work commercially available ZM21 Mg-alloy is used as a work material
in the form of extruded plate of thickness 6.5 mm. The chemical compositions of
supplied Mg-alloy (wt.%) is determined using XRF as Zn: 1.770%, Mn: 0.673% &
Mg: 97.55%. To examine the microstructure of Mg alloys sample of size 20  13
5 mm is polished using 400, 800, 1000 and 2000 grit paper, ultrasonically cleaned in
acetone and distilled water, then dried in open air. The samples were etched using an
etching agent solution of 5 ml HF, 20 ml Nitric Acid, 20 ml HCl and 60 ml water. The
microstructure has been observed using SEM (shown in Fig. 1a) and XRD analysis
(shown in Fig. 1b) has been carried out for the confirmation of the presence of phases
in the material.
EDD is a non-contact spark erosion machining process for producing holes (micro
to macro size) in metallic materials. Using EDD interconnected micro holes can be
easily fabricated in bio-metallic implants to produce perforated structure similar to
scaffold structures for better tissue growth and firm bone to implant fixation. In present
work 3- axis EDD machine (shown in Fig. 2) with tubular electrode of diameter
300 µm has been used to obtain micro holes in polished ZM21 Mg alloy.
148 N. Ahuja et al.

Fig. 1. (a) SEM micrograph of polished ZM21 Mg substrate, (b) XRD analysis of polished
ZM21 Mg substrate.

Fig. 2. Schematic representation of EDD set up.

Table 1. Experimental trials to select most appropriate EDD parameters

Exp. no. Tubular Discharge Pulse-on Pulse-off Hole Circularity Circularity
electrode current (Ip) time (Ton) time (Toff) Overcut entry (Cent) exit (Cext)
Material (lm)
1 Copper 5 40 60 105 0.882 0.924
2 Copper 5 60 40 124 0.908 0.962
3 Brass 3 40 80 114 0.859 0.968
4 Brass 3 50 40 121 0.918 0.962
5 Brass 3 60 50 108 0.921 1

Before fabricating scaffold, some trial experimentation has been carried out to
select optimal setting of parameters of EDD which produce the micro hole with
minimum diametric overcut and accurate hole circularity. Based on trial experimen-
tation (listed in Table 1), trial no 5 produced minimum diametric overcut of 108 lm
 Fabrication of Biodegradable Mg Alloy Bone Scaffold 149

and maximum hole circularity at entry and exit side. Therefore, micro holes of diameter
408 lm are drilled at parameters correspond to trial no 5 i.e., electrode material; brass,
electrode outer diameter; 300 lm, Ip; 3 amp., Ton: 60 ls, Toff: 50 ls. Simple tap
water is used as dielectric fluid which is supplied through tubular electrode at a pressure
of 6 bar.

3 Fabrication of Scaffold

An attempt has been made to fabricate scaffold by drilling through micro holes in
polished ZM21 samples of size 20  13  5 mm. Two types of scaffold designs are
fabricated to obtain different values of porosity. One having through micro holes on flat
side (i.e. on surface side of 20  13 mm) whereas in second design interconnected
holes are fabricated by drilling through micro holes on two sides (i.e. on side
20  13 mm and 20  5 mm). Using EDD, parameters correspond to trial no 5 i.e.,
electrode material; brass, electrode outer diameter; 300 lm, Ip; 3 amp., Ton: 60 ls,
Toff: 50 ls, scaffolds of pore size of diameter 408 lm has been obtained. Figure 3
shows the (a) polished solid sample (b) perforated sample (c) SEM micrograph of
micro hole drilled in ZM21. Figure 4(a) shows the SEM image of cut section of micro
hole and Fig. 4(b) shows that the hole surface has shallow morphology with micro
pores and micro cracks.

Fig. 3. (a) Solid polished ZM21 sample (b) Micro drilled polished sample (c) SEM micrograph
of a micro hole.

The detailing of sample weight, porosity and peak load bearing capacity of solid
and perforated ZM21 samples is listed in Table 2. Porosity is measured using the
formulation given in Eq. (1). The load bearing capacity in compressive is determined
using servo-controlled hydraulic universal testing machine (capacity 25 kN) at a strain
rate of 0.01 mm/sec.

d
P ¼1 ð1Þ
da

where d = density of perforated sample; da - density of the solid sample

150 N. Ahuja et al.

Fig. 4. (a) SEM image of cut section of drilled hole (b) zoomed image of hole surface.

Fig. 5. Apatite formation after immersion in SBF for 7 days, 14 days and 21 days.
 Fabrication of Biodegradable Mg Alloy Bone Scaffold 151

4 Immersion Test
4.1 Apatite Formation
All three types of ZM21 samples were immersed in the SBF solution kept in the
incubator at 37 °C. The SBF solution was replaced or refilled to maintain the pH value
of 7.4. Figure 5 shows the samples after 7 days 14 days and 21 days of immersion in
SBF. Solid sample show negligible apatite formation or ions deposition after 21 days of
immersion whereas perforated samples shows high apatite formation mainly in drilled
micro holes. In drilled micro holes, shallow surface having micro pores is generated
which results in more apatite formation as compare to flat surface of samples. Com-
paring solid and perforated samples, it is clear that the perforated structure attracts high
cells/tissues and forms high volume of apatite in biological fluid. Figure 6(a) shows the
SEM image of micro hole filled with apatite and Fig. 6 (b) confirms the presence of Ca,
P and Na ions in apatite deposit in micro holes.

Fig. 6. (a) SEM micrograph of micro hole with apatite formation (b) EDS of apatite deposition
in micro holes

Table 2. Sample description and their properties before and after immersion test
Sr. Sample Type of sample Porosity Before immersion test After immersion in
No. name (%) SBF for 21 days
Weight Peak load Weight Peak load
(gm) capacity in (gm) capacity in
compression compression
(kN) (kN)
1 A Solid ZM21 Nil 2.586 16.17 2.601 13.94
2 B Perforated sample having 22 2.563 14.02 2.692 10.60
micro holes on surface of
20 mm  13 mm
3 C Perforated sample having 34 2.467 12.18 2.620 11.50
micro holes on two surfaces
i.e. on side
20 mm  13 mm and
20 mm  5 mm
152 N. Ahuja et al.

4.2 Weight Gain and Loss of Load Bearing Capacity

After immersing in SBF at 37 °C, ions deposition on Mg alloys sample increases with
increasing immersion period as indicated in Fig. 7(a). In solid sample weight gain after
21 days of immersion test in SBF is minimum (0.58%) whereas interconnected per-
forated sample gives highest weight gain (6.23%). Due to interconnected micro holes,
more passage and surface to volume is available for cell attachment. Thus, intercon-
nected perforated ZM21 structure will provide better cell growth and bone growth
opportunity.
Table 2 shows that, before immersion test, peak load bearing capacity for solid
sample is better than perforated samples but after immersion in SBF for 21 days, the
percentage reduction of peak load capacity for interconnected perforated sample
(sample C) is lowest. Figure 7(b) and (c) shows the load bearing capacity and per-
centage reduction in load bearing capacity for three samples after immersion in SBF for
21 days.

AŌer 21 days of
C
immersion in SBF 12000
7 9000
30
6 6000
25
3000
5
Weight gain (%)

0
12000 B
20
4 9000
15
Load (N)

% loss

3 6000

2 3000 10
0
1 15000 A 5
12000

0 9000 0
A B C 6000

3000
A B C
Sample Type 0
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Sample Type
Displacement (mm)

(a) (b) (c)

Fig. 7. (a) Weight gain (%) after immersion in SBF for 21 days (b) Load bearing capacity and
(c) % reduction in peak load capacity of solid, perforated and interconnected perforated samples
after immersion in SBF for 21 days

5 Conclusions

An attempt has been made to fabricate perforated ZM21 structures for scaffold
applications using electrical discharge drilling with brass tubular electrode of diameter
300 µm. Two types of perforated structures with pore diameter 408 µm have been
produced with porosity of 22% and 34% from polished solid sample of size
20  13  5 mm. Fabricated scaffolds are analyzed for apatite formation, weight gain
and loss of mechanical strength after immersion in simulated body fluid at 37 °C for 21
days. The followings are the key finding of present work:
 Fabrication of Biodegradable Mg Alloy Bone Scaffold 153

• Increasing porosity increases the apatite formation and weight gain in ZM21 alloy
in SBF fluid.
• Electrical discharge drilling produces the hole surface with shallow and porous
morphology that attract and proliferate the cell growth.
• After 21 days of immersion test in SBF media, weight gain in perforated structure
with interconnected holes (porosity 34%) is highest; 6.23%, whereas solid sample
shows negligible weight change of 0.58%.
• Comparing with solid sample, load bearing capacity of perforated structure is lower
and it decreases with increasing porosity.
• The percentage loss of mechanical load bearing capacity after immersion in SBF for
21 days, is found lowest at 5.58% in scaffold design with interconnected holes.
This study indicate that interconnected perforated Mg alloy structures with well-
defined pores and pore density can be produced through Electrical discharge micro
drilling which are acceptable for scaffold application. Further, more detailed study is
required to explore the biocompatibility issues of EDM micro drilling, optimized
designs and degradation rate of scaffolds.

Acknowledgement. The funding for this work is sponsored by Science & Engineering Research
Board, Department of Science and Technology, New Delhi, India under the research project
entitled “Design and Development of biodegradable Mg alloy Implants for orthopedic applica-
tion” (File Number: EMR/2016/001581).

References
1. Lipi, M., Mahapatro, A., Gomes, A.S.: Fabrication of magnesium-based metallic scaffolds
for bone tissue engineering. Mater. Technol. 33(2), 173–182 (2018)
2. Yunhui, C., Frith, J.E., Manshadi, A.D., Attar, H., Kent, D., Soro, N.D.M., et al.:
Mechanical properties and biocompatibility of porous titanium scaffolds for bone tissue
engineering. J. Mech. Behav. Biomed. Mater. 75, 169–174 (2017)
3. Ratner, B.D., Hoffman, A.S., Schoen, F.J., et al.: Biomaterials Science. Academic Press,
London (2013)
4. Vats, A., Tolley, N.S., Polak, J.M., Gough, J.E.: Scaffolds and biomaterials for tissue
engineering: a review of clinical applications. Clin. Otolaryngol. Allied Sci. 28(3), 165–172
(2003)
5. Reed, A.M., Gilding, D.K.: Biodegradable polymers for use in surgery poly (glycolic)/ poly
(lactic acid) homo and copolymers: 2: in vitro degradation. Polymer 22(4), 494–498 (1981)
6. Ma, P.X., Langer, R.: Degradation, structure and properties of fibrous nonwoven poly
(glycolic acid) scaffolds for tissue engineering. MRS Online Proceedings Library Archive,
vol. 394 (1995)
7. Witte, F., Ulrich, H., Rudert, M., Willbold, E.: Biodegradable magnesium scaffolds: Part 1:
appropriate inflammatory response. J. Biomed. Mater. Res., Part A 81(3), 748–756 (2007)
8. Kumar, K., Gill, R.S., Batra, U.: Challenges and opportunities for biodegradable magnesium
alloy implants. Mater. Technol. 33(2), 153–172 (2018)
9. Staiger, M.P., Alexis, M.P., Huadmai, J., Dias, G.: Magnesium and its alloys as orthopedic
biomaterials: a review. Biomaterials 27(9), 1728–1734 (2006)
154 N. Ahuja et al.

10. Mahapatro, A., Kumar, S.S.: Determination of ionic liquid and magnesium compatibility via
microscopic evaluations. J. Adv. Microsc. Res. 10(2), 89–92 (2015)
11. Bakhsheshi-Rad, H.R., Idris, M.H., Abdul-Kadir, M.R., et al.: Mechanical and bio-corrosion
properties of quaternary Mg–Ca–Mn–Zn alloys compared with binary Mg–Ca alloys. Mater.
Des. 53, 283–292 (2014)
12. Nan, G.X., Zheng, Y.F.: A review on magnesium alloys as biodegradable materials. Front.
Mater. Sci. China 4(2), 111–115 (2010)
13. Yu, S., Zhang, B., Wang, Y., Geng, L., Jiao, X.: Preparation and characterization of a new
biomedical Mg–Zn–Ca alloy. Mater. Des. 34, 58–64 (2012)
14. Erlin, Z., Yin, D., Xu, L., Yang, L., Yang, K.: Microstructure, mechanical and corrosion
properties and biocompatibility of Mg–Zn–Mn alloys for biomedical application. Mater. Sci.
Eng., C 29(3), 987–993 (2009)
15. Mengqi, C., Li, Z., Liu, J., Li, S.: Effect of Sr on microstructure, tensile properties and wear
behavior of as-cast Mg–6Zn–4Si alloy. Mater. Des. 53, 430–434 (2014)
16. Xin, Y.J., Jiao, Y.P., Yin, Q.S., Zhang, Y., Zhang, T.: Calcium phosphate coating on
magnesium alloy by biomimetic method: investigation of morphology, composition and
formation process. Front. Mater. Sci. China 2(2), 149 (2008)
17. Witte, F., Hort, N., Vogt, C., Cohen, S., Ulrich, K., et al.: Degradable biomaterials based on
magnesium corrosion. Curr. Opin. Solid State Mater. Sci. 12(5–6), 63–72 (2008)
18. Boehlert, C.J., Knittel, K.: The microstructure, tensile properties, and creep behavior of Mg–
Zn alloys containing 0–4.4 wt.% Zn. Mater. Sci. Eng., A 417(1–2), 315–321 (2006)
19. Khan, S.A., Miyashita, Y., Mutoh, Y., Sajuri, Z.B.: Influence of Mn content on mechanical
properties and fatigue behavior of extruded Mg alloys. Mater. Sci. Eng., A 420(1–2), 315–
321 (2006)
20. Carlson, B.E., Jones, J.W.: The metallurgical aspects of the corrosion behaviour of cast Mg–
Al alloys. Light Met. Process. Appl. 833–847 (1993)
21. Polmer, I.J.: 2nd Mg Conference DGM Informationsgesellschaft, p. 201, Germany (1992)
22. Götz, H.E., Müller, M., Emmel, A., Holzwarth, U., Erben, R.G., Stangl, R.: Effect of surface
finish on the osseointegration of laser-treated titanium alloy implants. Biomaterial 25(18),
4057–4064 (2004)
23. Yoshinori, K., Jin, Q., Takita, H.: Geometry of carriers controlling phenotypic expression in
BMP-induced osteogenesis and chondrogenesis. JBJS 83, S1–S105 (2001)
24. Wen, C.E., Yamada, Y., Shimojima, K., Chino, Y., Hosokawa, H., Mabuchi, M.:
Compressibility of porous magnesium foam: dependency on porosity and pore size. Mater.
Lett. 58(3–4), 357–360 (2004)
25. Körner, C., Hirschmann, M., Bräutigam, V., Singer, R.F.: Endogenous particle stabilization
during magnesium integral foam production. Adv. Eng. Mater. 6(6), 385–390 (2004)
26. Lefebvre, L.P., Banhart, J., Dunand, D.C.: Porous metals and metallic foams: current status
and recent developments. Adv. Eng. Mater. 10(9), 775–787 (2008)
27. Carolin, K., Singer, R.F.: Processing of metal foams-challenges and opportunities. Adv. Eng.
Mater. 2(4), 159–165 (2000)
28. Kumar, K.: Optimizing the Electrical Discharge Drilling Process for High Aspect Micro
Hole Drilling in Die Steel, Book Chapter (2017). https://doi.org/10.4018/978-1-5225-2440-
3.ch006
29. Kumar, K., Rawal, S.K., Singh, V.P., Bala, A.: Experimental study on diametric expansion
and taper rate in EDM drilling for high aspect ratio micro holes in high strength materials.
Mater. Today: Proc. 5(2), 7363–7372 (2018)
30. Gill, R.S., Kumar, K., Batra, U.: Apatite formation and weight loss study in EDMed
perforated AZ31 Mg-alloy. J. Mag. Alloy 5(3), 362–367 (2017)
 Fabrication of Biodegradable Mg Alloy Bone Scaffold 155

31. Yan, B.H., Wang, A.C., Huang, C.Y., Huang, F.Y.: Study of precision micro-holes in
borosilicate glass using micro EDM combined with micro ultrasonic vibration machining.
Int. J. Mach. Tool Manuf. 42, 1105–1112 (2002)
32. Liu, H.S., Yan, B.H., Huang, F.Y., Qui, K.H.: A study on the characterization of high nickel
alloy micro-holes using micro-EDM and their applications. J. Mater. Process. Technol. 169,
418–426 (2005)
33. Kuppan, P., Rajadurai, A., Narayanan, S.: Influence of EDM process parameters in deep hole
drilling of Inconel 718. Int. J. Adv. Manuf. Technol. 38, 74–84 (2008)