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Article history:
Received 25 May 2013
Received in revised form 14 October 2013
Accepted 21 October 2013
Available online 1 November 2013
Keywords:
Porous magnesium
Sintering conditions
Powder metallurgy
Mechanical properties
a b s t r a c t
There has recently been an increased demand for porous magnesium materials in many applications, especially
in the medical eld. Powder metallurgy appears to be a promising approach for the preparation of such materials.
Many works have dealt with the preparation of porous magnesium; however, the effect of sintering conditions on
material properties has rarely been investigated. In this work, we investigated porous magnesium samples that
were prepared by powder metallurgy using ammonium bicarbonate spacer particles. The effects of the purity of
the argon atmosphere and sintering time on the microstructure (SEM, EDX and XRD) and mechanical behaviour
(universal loading machine and Vickers hardness tester) of porous magnesium were studied. The porosities of the
prepared samples ranged from 24 to 29 vol.% depending on the sintering conditions. The purity of atmosphere
played a signicant role when the sintering time exceeded 6 h. Under a gettered argon atmosphere, a prolonged
sintering time enhanced diffusion connections between magnesium particles and improved the mechanical
properties of the samples, whereas under a technical argon atmosphere, oxidation at the particle surfaces caused
deterioration in the mechanical properties of the samples. These results suggest that a rened atmosphere is
required to improve the mechanical properties of porous magnesium.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Magnesium and magnesium alloys have recently been studied for use
in many applications, such as in the automotive and aerospace industries
because of their low densities and good mechanical properties [1].
Many successful studies have been performed on biocompatible and biodegradable magnesium-based materials, which are considered suitable
materials for orthopaedic applications, such as for nails, screws, splints,
etc. [26]. For some applications, porous implants, called scaffolds, are
required because they possess mechanical properties, such as the modulus of elasticity, that are relatively similar to those found in natural bone
tissue [714]. The mechanical biocompatibility is important to aid in the
remodelling of new tissue [714]. Moreover, an interconnected porous
structure allows the transport of body uids to damaged or wounded
tissue and supports the incorporation of new tissue in the implant
[7,15,16]. Therefore, porous magnesium materials and their preparation
methods have been extensively studied in recent years [714].
Many methods have been developed for fabricating porous metallic
materials [17]. However, because biomaterials should contain interconnected pores [12] and should not be contaminated with harmful impurities [4], only a few of these methods are used for the production of
biomaterials. In the available literature, there are ve non-machining
Corresponding author. Tel.: +420 220444055.
E-mail address: Jaroslav.Capek@vscht.cz (J. apek).
0928-4931/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.msec.2013.10.014
22
Fig. 1. SEM micrographs (SE detector) of sample cross sections prepared under the following sintering conditions: (a) technical argon for 6 h, (b) technical argon for 24 h, (c) gettered
argon for 6 h and (d) gettered argon for 24 h.
Table 1
The inuence of sintering conditions on sample porosity (in vol.%).
Atmosphere/sintering time
0h
3h
6h
12 h
24 h
Technical argon
Gettered argon
29 2
29 2
28 1
28 1
28 2
27 2
29 3
25 3
31 4
24 2
23
compacts were annealed for 4 h at 130 C in a mufe furnace in air. During this step, the decomposition of ammonium bicarbonate and the
evaporation of hexane occurred. Afterwards, sintering was performed
at 550 C in a tube furnace. The green compacts were sintered for 0, 3,
6, 12 and 24 h. The sintering process was performed under two types
of owing atmosphere at a ow rate of 0.1 l/min: (1) argon with technical purity (99.996 vol.%) and (2) argon puried by a 55-mm-thick
layer of Mg chips (250500 m in size), which was placed around the
sintered material and acted as a getter. After sintering, the average material porosity was determined according to Eq. (1) [8,13]:
P 1=Mg 100%;
2. Experimental
A purchased Mg powder (purity of 99.6 wt.%, mesh 100 + 200,
Alfa Aesar) and NH4HCO3 powder (p.a. purity, 250500 m) were
used as starting materials. An Mg/NH4HCO3 volume ratio of 90:10 was
used because, according to our previous work [19], this ratio imparts a
good combination of strength and corrosion resistance to the resulting
material. Materials prepared using this ratio have been shown to possess better mechanical properties that are more comparable to natural
bone tissue than porous biomaterials, which have recently been used
for medical applications [19]. To avoid segregation, the powders were
intensively blended with 30 vol.% hexane for 30 min. Subsequently,
pre-weighed mixtures were pressed into cylindrical green compacts
(10 mm in diameter and 30 mm in length) at a pressure of 265 MPa
using a LabTest 5.250SP1-VM universal loading machine. The green
compacts were then subjected to a two-step procedure. First, the
Fig. 4. SEM micrographs (BSE detector) and elemental maps determined by EDX of samples sintered 24 h under (a) technical argon atmosphere and (b) gettered argon atmosphere. Scale
bar 50 m.
24
Fig. 5. Microstructure of powder particles during the material fabrication process: (a) the initial powder, (b) compacted powder after annealing at 130 C for 4 h, (c) compacted powder
after annealing at 130 C for 4 h and sintering at 550 C for 3 h under technical argon and (d) compacted powder after annealing at 130 C for 4 h and sintering at 550 C for 24 h under
technical argon.
25
Fig. 8. Fracture surfaces of samples after exural testing under the following sintering conditions: (a) technical argon for 6 h - overview, (b) technical argon for 6 h - detail, (c) technical
argon for 24 h and (d) gettered argon for 24 h. The white arrow in Fig. 8c denotes oxide particles. In Fig. 8d, the arrow indicates traces of plastic deformation.
Fig. 10. The compressive yield strength versus sintering time of prepared samples.
26
Fig. 11. The ultimate compressive strength versus sintering time of prepared samples.
27
Table 2
Mechanical properties of porous biomaterials.
Material
Porosity (vol.%)
UFS (MPa)
CYS (MPa)
UCS (MPa)
Reference
Natural bone
Porous Mg
Porous Mg
Porous Mg
Porous Mg
Porous Mg
Porous Mg
Porous Mg
Porous Mg
Porous Ti
Porous hydroxyapatite
Porous hydroxyapatite
Porous composite (poly-L-lactide + 2050 wt.% of bioglass)
Porous polycaprolactone
Porous polycaprolactone
Porous polycaprolactone
Porous polylactide-co-glycolide
Porous composite of polylactide-co-glycolide and 45S5 bioglass
2931
2338
1444
3655
5270
50
28
3555
78
5077
7788
4877
3755
5556
31
43
250500
250500
250500
200400
~1250
200500
170
100400
200500
200400
366444
~100
116
89
2150
315
417
25
1427
27
14
1353
23
23
2180
2070
1531
414
2
24
1217
35
117
30
~0.4
23
[13]
This study
[19]
[22]
[13]
[8]
[14]
[7]
[11]
[14]
[13]
[25]
[13]
[25]
[25]
[26]
[27]
[27]
0.5
0.4
28
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