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Materials Science and Engineering C 35 (2014) 2128

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Materials Science and Engineering C


journal homepage: www.elsevier.com/locate/msec

Effect of sintering conditions on the microstructural and mechanical


characteristics of porous magnesium materials prepared by
powder metallurgy
Jaroslav apek , Dalibor Vojtch
Department of Metals and Corrosion Engineering, Institute of Chemical Technology, Prague, Technick 5, 166 28 Prague 6, Czech Republic

a r t i c l e

i n f o

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

approaches that have been reported for the fabrication of porous


magnesium materials: (1) injection of an inert gas into a melt [4], (2) directional solidication of the metalgas eutectic (the GASAR process)
[9], (3) plaster casting [4], (4) negative salt pattern moulding [12] and
(5) powder metallurgical techniques [11,13,14]. However, the rst
two methods mentioned above do not necessarily produce open-cell
structures, and the following two methods may contaminate or corrode
the nal product during pattern removal [18]. Suitable modications to
powder metallurgy (PM), for example, using space-holder particles,
allow the fabrication of materials with interconnected pores. This
modication consists of preparing a green compact that contains a
powdered mixture of magnesium and a space-holder material, which
is later removed by leaching or thermal decomposition. Subsequently,
the porous green body is sintered at high temperatures [8,10,13,14].
In principle, any solid matter may be used as the space-holder material;
however, in practice, this selection is limited because the spacer
material has to be removed without contaminating the product. In the
literature, urea and ammonium bicarbonate have been successfully
used as spacer materials in the preparation of PM porous magnesium
[8,11,13,14,19]. Hao et al. [8] removed the urea by leaching the material
in a NaOH-water solution, whereas other authors removed the spaceholder particles by thermal decomposition [10,11,13,14]. The majority
of these authors used urea as the spacer material, even though its
complete decomposition occurs at temperatures above the melting
point of magnesium. Because urea only partially decomposes at lower

J. apek, D. Vojtch / Materials Science and Engineering C 35 (2014) 2128

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.

temperatures, contamination may occur [20]. For example, Zhuang et al.


[13] found traces of carbon and oxygen on pore walls, which they attributed to contamination by urea residues. Ammonium bicarbonate, which
decomposes at signicantly lower temperatures (36 C60 C), appears
to be a more suitable spacer material for the preparation of PM porous
magnesium. In addition, leaching the spacer material has the disadvantage of possibly hermetically enclosing some of the spacer particles in
the magnesium matrix, which prevents their dissolution. Moreover,
water-based dissolving agents are corrosive to magnesium [21].
The mechanical properties of PM porous magnesium are inuenced
not only by the total porosity but also by the pore size, distribution and
shape and the connection between magnesium particles [8,10,13].
These structural characteristics can be adjusted by selecting the optimal
sintering time and temperature, compacting pressure and size, shape
and volume ratio of the starting material powders [8,11,13,19,22].
Grain coarsening within each magnesium particle, which is expected
during the sintering process, may also affect the mechanical properties
of the nal material [23,24].
In our previous work [19], we showed that porous magnesium can,
in principle, be successfully prepared by PM using ammonium bicarbonate as the space-holder material. Although several works on the preparation of porous magnesium have been reported, to the best of our
knowledge, no systematic study on the inuence of the processing

parameters, namely, the sintering time and atmosphere purity, on the


microstructure and mechanical properties of porous magnesium is
available. Therefore, our study focused on sintering kinetics and the
effect of the sintering atmosphere on the important characteristics of
PM porous magnesium.

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

Fig. 2. XRD patterns of samples sintered for 6 h.

J. apek, D. Vojtch / Materials Science and Engineering C 35 (2014) 2128

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%;

Fig. 3. XRD patterns of samples sintered for 24 h.

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

where P is the porosity, is the density of the porous sample (calculated


from the dimensions and weight) and Mg is the density of pure magnesium (Mg = 1738 kg/m3). This approach for determining porosity was
used because it describes the volumetric 3D porosity more precisely
than analysing 2D micrographs.
The material mechanical properties were characterised by exural,
compression and Vickers hardness tests that were performed at room
temperature. Samples 26 mm and 15 mm in length were used for exural and compression testing, respectively. Five samples of each series
were used for the exural tests, and three samples of each series were
used for the compression tests. The average hardness was calculated
from ten values. Standard deviations for all tests were calculated and
are shown as error bars in the gure plots. The deformation rates during
the exural and compression tests were 0.5 mm/min and 1 mm/min,
respectively. A LabTest 5.250SP1-VM universal loading machine was
used for these tests. After exural testing, the fracture surfaces were
observed by a TESCAN VEGA-3 LMU scanning electron microscope
(SEM). Metallographic cross sections were also prepared and examined
by SEM. Afterwards, the metallographic cross sections were etched (2 g
of picric acid, 10 ml of 99% acetic acid, 10 ml of water and 70 ml of ethanol), and the microstructures of the powder particles were observed
using an Olympus PME 3 light metallographic microscope. The phase
composition and elemental distributions were examined by X-ray diffraction using a PANalytical X'Pert PRO X-ray diffractometer equipped
with a Cu anode (XRD) and a TESCAN VEGA-3 LMU SEM equipped
with an Oxford Instruments INCA 350 EDX analyser (SEM-EDX). The
Vickers hardness was measured for each series with a load of 3 kg (HV 3).

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.

J. apek, D. Vojtch / Materials Science and Engineering C 35 (2014) 2128

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.

3. Results and discussion


3.1. Microstructure and porosity
The microstructures of samples sintered under two types of atmospheres for different periods of time are shown in Fig. 1.
In the magnesium matrix, two types of pores were observed:
(1) pores approximately 250500 m in size that were formed from
the decomposition of spacer particles (Type I in Fig. 1) and (2) smaller
pores that most likely originated from imperfect compaction during
pressing and the expansion of trapped gas during sintering (Type II
in Fig. 1). No signicant difference in microstructure was observed for

Fig. 6. Flexural stressstrain curves of selected samples.

samples sintered for 6 h under the different atmospheres. A prolonged


sintering time caused annihilation of Type II pores under the gettered
atmosphere, whereas under the technical argon atmosphere, the
amount of these pores did not signicantly change. The sample porosity
was measured, and the effects of the sintering conditions on porosity
are shown in Table 1. This table indicates that samples sintered under
the gettered argon atmosphere became more compact with longer
sintering times, i.e., contained less pores. In contrast, the technical
argon atmosphere produced materials whose porosities appear almost
the same.

Fig. 7. Ultimate exural strength of prepared samples versus sintering time.

J. apek, D. Vojtch / Materials Science and Engineering C 35 (2014) 2128

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.

This phenomenon suggests that sintering under the gettered argon


atmosphere enhanced the diffusion connection between the magnesium
particles, which led to annihilation of some Type II pores (Fig. 1). In
contrast, the use of technical argon caused a slight increase in total porosity. As shown below, porosity is directly related to the presence of oxides
in the material.

The XRD patterns of the samples sintered under various conditions


are shown in Figs. 2 and 3.
The XRD patterns indicate that there is no signicant difference in
the amount of magnesium oxide in the samples sintered for 6 h, regardless of the atmosphere type (Fig. 2). In this gure, the peaks that are
assigned to MgO are similar for both samples sintered for 6 h. However,

Fig. 9. Compressive stressstrain curves of selected samples.

Fig. 10. The compressive yield strength versus sintering time of prepared samples.

26

J. apek, D. Vojtch / Materials Science and Engineering C 35 (2014) 2128

samples that were sintered for 24 h in technical argon (Fig. 3) contained


signicantly higher amounts of MgO than those sintered in gettered
argon. No traces of ammonium bicarbonate or the reaction products of
magnesium and ammonium bicarbonate were found by the XRD
analysis.
To determine the difference between the samples sintered for 24 h,
EDX analysis was performed. The results are shown in Fig. 4. The X-ray
elemental maps show the presence of Mg particles surrounded by oxide
layers. Comparing Fig. 4a and b reveals that more extensive oxidation
occurs at the grain boundaries during sintering under the technical
argon atmosphere than under the gettered atmosphere. This difference,
which is observed after sintering for more than 6 h, is in good agreement with the results acquired from XRD analysis (Fig. 3). Traces of
oxygen and water are present in technical argon and cause surface
oxidation, which weakens the diffusion connection between the
magnesium particles. Thus, annihilation of the smaller Type II pores
is slowed during longer sintering periods (Table 1). Moreover, oxides
on the sample and particle surface may spall off and increase the measured porosity. In contrast, a lower extent of oxidation was observed
under the gettered atmosphere, which supports the annihilation of
some Type II pores because of the diffusive processes of the magnesium particles, as shown in Table 1.
The presence of nitrogen and carbon was also investigated as
contamination by either ammonium bicarbonate or its decomposition
products. No traces of these elements were found; therefore, their
distribution is not shown in the XRD elemental maps.
Grain coarsening within magnesium particles during sintering
was also investigated because it may have an impact on sample
properties. Fig. 5 shows detailed views of the microstructure of individual powder particles.
The initial powder (Fig. 5a) possesses a relatively ne microstructure
(grain size up to 13 m). After compaction and annealing at 130 C for
4 h (Fig. 5b), the grain size slightly enlarged; however, the microstructure remained ne (approximate grain size of 15 m). The grain size
signicantly increased after sintering at 550 C for 3 h in technical
argon (approximate grain size of 45 m) (Fig. 5c). Sintering for longer
periods did not cause any further signicant grain growth. The average
grain size after sintering for 24 h at 550 C was approximately 48 m
(Fig. 5d). The type of atmosphere did not inuence grain growth during
sintering.

Fig. 11. The ultimate compressive strength versus sintering time of prepared samples.

A study of the fracture surfaces helped to explain this behaviour. The


fracture surfaces of samples after exural testing are illustrated in Fig. 8.
For all the samples, the fracture surfaces were similar (Fig. 8a); however, slight differences were observed at higher magnications. Generally,
the fracture surfaces were brittle, but traces of plastic deformation were
observed, especially in samples sintered under gettered argon for longer
time periods (12 and 24 h) (Fig. 8d). The fracture surfaces were nearly
identical and oxide free after sintering for up to 6 h, independent of
the atmosphere (Fig. 8b). After longer sintering times, some differences
were observed between the fracture surfaces of samples prepared
under the different atmospheres. Samples sintered in gettered argon
had nearly oxide-free fracture surfaces with features of plastic deformation (Fig. 8d), whereas a large amount of oxide was present on the
fracture surfaces of samples sintered in technical argon (Fig. 8c). This
observation conrms the XRD and EDX results that were mentioned
above (Figs. 24).

3.2. Mechanical properties


The exural stressstrain curves of selected samples are shown in
Fig. 6.
Samples sintered in technical argon had a signicantly lower modulus of elasticity than samples sintered under the gettered atmosphere.
This result can be explained by the increased amount of oxygen at the
interface between powder particles, which results in decreased cohesiveness between the particles. Oxides also impact exural strength,
which will be shown and discussed below.
The exural stressstrain curves of all the materials contained only
elastic regions; no regions of macroscopic plastic deformation were
observed (Fig. 6). The ultimate exural strength (UFS) as a function of
sintering time is plotted in Fig. 7.
The ultimate exural strength increased with longer sintering times,
up to 6 h, independent of the atmosphere. The samples attained
approximately the same UFS, 12 MPa, after 6 h of sintering under
both atmospheres. For longer sintering times under the gettered argon
atmosphere, the UFS increased to approximately 15 MPa. The difference
between samples sintered for 12 and 24 h under the gettered argon
atmosphere is negligible. In contrast, prolonging the sintering period
to more than 6 h under technical argon had a completely opposite
effect. The UFS rapidly decreased to 5 MPa after 12 h of sintering and
continued to decrease to approximately 3 MPa after 24 h of sintering.

Fig. 12. The HV 3 versus sintering time of prepared samples.

J. apek, D. Vojtch / Materials Science and Engineering C 35 (2014) 2128

27

Table 2
Mechanical properties of porous biomaterials.
Material

Porosity (vol.%)

Pore size (m)

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]

Fig. 9 shows the compressive stressstrain curves of selected samples.


From the gure, the trends of the compressive and exural behaviour of
the material are similar, with the exception of the effect of atmospheric
condition on the compressive modulus of elasticity, which is not as strong.
The compressive yield strength (CYS) and ultimate compressive
strength (UCS) as functions of the sintering time are plotted in Figs. 10
and 11.
Under the gettered argon atmosphere, both the yield strength (CYS)
and the ultimate strength (UCS) increased with longer sintering times.
The maximum CYS and UCS values after sintering for 24 h are 53 and
69 MPa, respectively. These high strength values result from a low
amount of oxide, decreased porosity and good contact between the
particles in the samples (Figs. 24, Table 1). In contrast, for samples
sintered under technical argon, the maximum CYS and UCS were
attained after 6 h of sintering. Prolonging the sintering period under
this atmosphere led to a signicant decrease in compressive properties.
This nding can be attributed to the extended oxidation that occurs during sintering, which weakens the diffusion bonds between particles. An
interesting observation in Figs. 10 and 11 is that the CYS of samples
sintered in gettered argon increased almost linearly with sintering
time, whereas the UCS increased for up to 6 h of sintering and then increased signicantly more slowly. These results indicate that the Type
II pores, which decrease in quantity during long sintering periods
(Table 1), inuence the yield strength rather than the ultimate strength.
The ultimate compressive strength is probably more inuenced by the
larger Type I pores, whose amount is almost constant for all samples.
The reason may be that the large pores concentrate the stress in their
vicinity and initiate the crack nucleation and subsequent collapse of
the porous structure. On the other hand, the small Type II pores concentrate the stress to a smaller extent and plastic deformation takes
place in their surroundings. Therefore, their partial vanishing during
longer sintering times seems to increase the stress needed for the plastic
strain to begin.
Fig. 12 reveals the effect of sintering time on sample hardness.
Samples sintered in gettered argon possessed a higher hardness
than those sintered in technical argon. The effect of sintering time on
hardness was small for samples sintered in technical argon. However,
prolonging the sintering period in the gettered argon led to an increase
in hardness, with a peak hardness occurring in samples sintered for
12 h. Sintering up to 24 h slightly decreased sample hardness. This
result may be caused by oxidation beginning at the grain boundaries
and decreases the cohesiveness of the magnesium particles.
A comparison of our results with previously reported results is difcult because of differences in the porosities and pore sizes of the studied
materials. Nevertheless, we conducted a small review that summarises
the mechanical properties of natural bone tissue and porous materials

0.5
0.4

that are considered suitable biomaterials. The results of this research


are summarised in Table 2.
From this table, it is clear that porous magnesium-based metallic
materials exhibit mechanical properties similar to those of natural
bone tissue. However, non-metallic porous materials (especially
polymer-based materials) have weaker mechanical properties compared to natural bone tissue. It is also important to note that the materials prepared in our study have higher UFS and UCS values than porous
magnesium materials that have been prepared in the majority of other
works and non-metallic porous materials. Moreover, the materials prepared in this work possess mechanical properties that are comparable
to natural bone tissue.
4. Conclusions
Magnesium samples with porosities of 2931 vol.% were prepared
by powder metallurgy under different sintering conditions. When compared to non-metallic biomaterials, the samples exhibited enhanced
mechanical properties that were similar to human bone tissue. After
sintering for up to 6 h, no signicant effect of atmosphere purity on
sample microstructure or mechanical behaviour was observed. Under
the gettered argon atmosphere, longer sintering times decreased porosity but enhanced the mechanical properties of the sample. Under the
technical argon atmosphere, the opposite trend was observed, which
can be attributed to oxidation of the powder surface. These results
suggest that when sintering is longer than 6 h, the purity of the argon
atmosphere plays an important role in determining the mechanical
properties of PM magnesium.
Acknowledgements
The authors would like to thank the Czech Science Foundation
(project no. P108/12/G043) for supporting this research.
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