Materials Science and Engineering C 33 (2013) 434–439

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Materials Science and Engineering C

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

Effect of sintering atmosphere on properties of porous stainless steel for

biomedical applications
Agata Dudek a,⁎, Renata Włodarczyk b
a
Technical University of Czestochowa, Materials Engineering, Poland
b
Technical University of Czestochowa, Department of Energy Engineering, Poland

a r t i c l e i n f o a b s t r a c t

Article history: This study discusses manufacturing of metallic biomaterials by means of powder metallurgy with consideration
Received 11 May 2012 for their unquestionable advantages, i.e. opportunities of obtaining materials with controllable porosity. The
Received in revised form 27 July 2012 paper focuses on properties of 316L stainless steel obtained using the method of powder metallurgy with respect
Accepted 17 September 2012
to compacting pressure and sintering atmosphere. All the specimens were compacted at 700, 400 and 225 MPa,
Available online 25 September 2012
and sintered at 1250 °C. In order to analyze the sintering atmosphere, three different media were used: dissoci-
Keywords:
ated ammonia, hydrogen and vacuum. The study covered sintering density, porosity, microstructure analysis and
Sintered stainless steel corrosion resistance. The proposed method of powder metallurgy allowed for obtaining materials with predict-
Biomaterials able size and distribution of pores, depending on the parameters of sinter preparation (compaction force,
sinter atmosphere). High corrosion resistance of the materials (sintering in the atmosphere of hydrogen
and in vacuum) and high porosity in the sinters studied offer opportunities for using them for medical
purposes.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Besides unquestionable progress in development of ceramic materials
and composite materials [4–6], there is ongoing search for a broader
range of metallic implants, particularly those used in orthopedics and
surgical interventions (e.g. joint endoprostheses, bone loss) and dentistry
(prosthesis replacements) [1–4].
Long-lasting implants, made typically of metals and their alloys, are
characterized by improved mechanical properties, but their corrosion
resistance and biocompatibility remain at a relatively low level.
Development of implants for the purposes of bone surgeries is
considerably determined by the progress in biomaterial engineering.
The attempts are being made to obtain biomaterials which would
meet demanding biofunctionality criteria such as mechanical strength,
corrosion resistance or biocompatibility [5–7].
In recent years, metallic porous materials have attracted much interest
as candidates for biomedical applications. Porosity of materials used is an
essential parameter in implantology since it ensures ingrowth of the
vascularised soft tissue and in consequence guarantees a firm connection.
This concerns mainly the improvement in implant osseointegration with
surrounding bone tissue [8].
The porous metallic biomaterials should be considered as very
attractive implant materials due to their elastic modulus which is
similar to this in the bone as well as the opportunities for bone tissue
⁎ Corresponding author. Fax: +48 343250721.
E-mail address: dudek@wip.pcz.pl (A. Dudek).
ingrowth into pores, which provides good stabilization of the implant.
High requirements are set though to ensure proper durability.
One group of biomaterials which raises great expectations is porous
materials obtained by means of compaction and powder sintering
technologies. During the past three decades, powder metallurgy (P/M)
methods have significantly contributed to the development of more
effective surgical implants. Sintering process is regarded as an important
procedure in P/M technology because furnace atmosphere affects the
process and the parameters of the obtained materials. The final properties
of the material using P/M technology largely depend on the atmosphere
where sintering is performed [5,6].
Some investigations have been carried out to fabricate porous 316L
stainless steel [9–12]. Corrosion resistance of the currently used 316L
stainless steel depends on their passivation by a thin surface layer of
oxide. Studies presented in [13] have demonstrated that corrosion
resistance decreased with porosity, which was attributed to the
small, isolated pores that trap ionic species and restricts the access of
oxygen, which in turn limits available oxygen and allows for formation
of corrosion resistant passive layers. In highly porous compacts with an
open and interconnected pore morphology, free flow of species resulted
in a material with increased corrosion resistance.
The investigations of opportunities for development of new materials
for medical applications have been a very popular domain of research
works.
The aim of this paper is to study the effect of compacting pressure,
sintering temperature and sintering atmosphere on the properties of
porous 316L stainless steel compacted. The microstructure, density and
porosity were comparatively analyzed to understand the mechanisms of

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http://dx.doi.org/10.1016/j.msec.2012.09.010
 A. Dudek, R. Włodarczyk / Materials Science and Engineering C 33 (2013) 434–439 435

Table 1 • D — Axial compression at 225 MPa and sintered at T = 1250 °C for

Chemical composition of the powder used for sintering.
Powder grade C [%] Mo [%] Ni [%] Cr [%] Si [%] Mn [%]
316 L 0.025 2.2 12.3 16.7 0.9 0.1
sintering. Behavior of materials in tissue environment is a fundamental
determinant of biocompatibility and thus it determines opportunities
of using materials for bone implants. Corrosion in metallic implants
might have an unfavorable effect on the processes which occur at
the interface of bone tissue/implant phases. The aim of this study is
to examine the behavior of sintered stainless steel used for materials
in Ringer and artificial solution under corrosion conditions and also
to compare their specific electrochemical properties. Biocorrosion
has been considered as a problem that limits durability of implants
present in human body while the release of metal ions might cause
adverse physiological effects, toxicity, carcinogenicity and metal
allergies.
2. Material and methods
Water-atomized 316L steel powder (Höganäs, Sweden) was used
for the investigations. The shape of particles was irregular, which is
typical of this manufacturing method.
Chemical composition of the powder is presented in Table. 1.
The powder of 316L steel was compacted with the following load:
• A — 700 MPa and sintered at T = 1250 °C for 30 min in ammonia
medium, denoted by 700/DA,
• B — 400 MPa and sintered at T = 1250 °C for 30 min in ammonia
medium, denoted by 400/DA,
• C — 400 MPa and sintered at T = 1250 °C for 30 min in hydrogen
medium, denoted by 400/H2,
120 min in vacuum, denoted by 225/V.
Fe [%]
DA (Dissociated Ammonia) atmosphere containing 75% hydrogen
Balance
and 25% nitrogen (75% H2/25%N2) is designed for producing an
economical source of pure, dry, highly reducing atmosphere.
The obtained sinters of austenite alloy steel were used for micro-
structural testing by means of Axiovert optical microscope.
The density of the sintered parts was measured by Archimedes'
immersion method.
The aim of this work was also to carry out an analysis by means
of computer software (Image-Pro Plus) that helps determine po-
rosity occurring in sintered steels. The software, based on different
statistical parameters, allows for classification of pore shape and
quantity.
The polarization tests were carried out in order to measure corro-
sion in sintered stainless steels. Diagnostic experiments included
measurements of open circuit potential with exposure time, and
potentiodynamic measurements. Electrochemical measurements
were carried out in three-electrode arrangement by means of CH In-
strument (USA) measurement station. Sintered steel was used as a
working electrode, whereas comparative electrode was provided by a
saturated calomel electrode. Platinum wire was used as an auxiliary
electrode.
Prior to the measurements, sintered materials had been polished
with sandpapers with 250, 600, 1200 grit and then finished with
a diamond paste. Electrochemical measurements, at the temperature
of 37 °C were taken in the solution known as Ringer solution with
the following composition: NaCl — 8.6 g/dm 3, KCl — 0.3 g/dm 3,
CaCl2 — 0.48 g/dm 3 (pH = 5.0) and the solution of artificial saliva:
NaCl — 0.7 g/dm 3, KCl — 1.2 g/dm 3, Na2HPO4 — 0.26 g/dm 3,
NaHCO3 — 1.50 g/dm 3, KSCN — 0.33 g/dm 3, urea — 1.3 g/dm 3
(pH = 6.7). Deionised and demineralised water was used in order
to obtain the solutions. Potentiokinetic curves were registered within
the range of potentials of −0.8 do 2.0 V vs. SCE, scan rate 10 mV s−1.

Fig 1. Microstructures in the sintered materials: a) 700/DA; b) 400/DA; c) 400/H2; d) 225/V.

436 A. Dudek, R. Włodarczyk / Materials Science and Engineering C 33 (2013) 434–439

Table 2 Despite higher compression force in 700/DA sinters, porosity of

Properties of the obtained sintered materials. 18.6% was obtained, whereas in 400/DA sinters this value was 11.82%.
Sintered materials Grain size [μm] Sinter density [g cm−3] It is remarkable that the shape of the obtained pores changed and, for
higher compaction forces, pores tended to adopt a more regular
700/DA ~50 6.70
400/DA 6.19 shape. Furthermore, they were more evenly distributed across material
400/H2 6.36 core.
225/V 5.70 The hydrogen sintering atmosphere used in the study caused a re-
duction in dynamics of phenomena which occur during the process of
sintering. The sinter was characterized by elevated porosity of 34.19%.
Hydrogen has been known to be the most effective reducing atmo-
3. Results and discussion sphere that allows for enhanced oxide removal, which necessitates
longer sintering times. Small hydrogen atoms diffuse into the metal
3.1. Microstructural testing lattice and inhibit elimination of final porosity [6,8].
In the case of 225/V sinters, the analysis focused on the objects
Microstructures in each sinter are presented in Fig. 1. which were characterized by the shape factor up to the value of 3.
Microstructural testing revealed differences in grain size in austenitic Above this value, the biggest non-analyzed particle which takes the
phase and in porosity of each sinter, and a sufficient degree of sintering. greatest volumetric fraction (53.08%) can be observed (marked
The micrographs of parts sintered in nitrogen exhibit an austenitic black in the photograph presented in Table 6). It provides a specific
microstructure with Cr2N regions created as a consequence of nitrogen skeleton formed by the pores to promote ingrowth of tissue, and
absorption. the resultant processes of osseointegration, which represents an
extremely important functional advantage.

3.2. Investigations of density and porosity of sinters

Apparent density was determined in the studied sinters. Their results
are presented in Table 2. The density of the used powder 316L was
2.67 g cm−3, grain size ≅50 μm.
Sintering atmosphere has a significant effect on sinter density.
Higher density was obtained when sintering in hydrogen compared to
nitrogen atmosphere. The major cause is the formation of Cr2N, which
is absorbed from the nitrogen atmosphere, which in turn reduces the
diffusion rate, resulting in a lower sinter density.
Development of an effective biological connection of biomaterial
and bone depends on pore size and their spatial arrangement. The
focus of further analysis was on pore shape and fraction in the sinters
obtained at different compaction pressures and different sinter at-
mosphere. The shape of pores was analyzed in terms of roundness,
fraction of each size class and surface in the obtained pores. The results
are presented in Tables 3–6.
3.3. Electrochemical testing
As results from the data available from the literature [6–13], steels
with austenitic structure are characterized by a relatively high corrosion
resistance. Assessment of corrosion resistance in metallic biomaterials
was assessed based on potentiokinetic measurements.
Polarization curves were recorded in order to determine the effect
of sintering and compaction atmosphere.
Based on aggregate polarization curves, the authors determined the
rate of partial processes (corrosion potential was used for determina-
tion of corrosion rate). Corrosion current density was determined
through extrapolation of linear sections in anode and cathode curves.
If Tafel linearity was observed only in one partial curve, it was extrapo-
lated with a single straight line. This principle ensures higher measuring
accuracy (while extrapolating with one straight line allows for minimi-
zation of corrosion current error). If Tafel's sections could not be found

Table 3
Distribution of shape factor and statistical parameters of surface area in 700/DA sinters.

Class Class ranges shape Frequency, %

No. factor
Beginning End of the
of the range
range
1 1 3 83.14
2 3 6 11.49
3 6 10 3.06
4 10 > 2.31

Volumetric share of
Pore surface area, µm2
pores, %
Min 10.62

Max 2496.28 18.63

Mean 232.60
 A. Dudek, R. Włodarczyk / Materials Science and Engineering C 33 (2013) 434–439 437

Table 4
Distribution of shape factor and statistical parameters of surface area in 400/DA.

Class Class ranges shape factor Frequency, %

No. Beginning End of the
of the range
range
1 1 3 20

2 3 6 22.85
3 6 10 25.71
4 10 20 17.14
5 20 > 14.3

Volumetric share of
Pore surface area, µm2
pores, %

Min 8.35

11.82
Max 2747.88

Mean 310.82

in either of the curves, the tangents (for partial curves with slopes that
were consistent with the theory of electrode processes) were extrapo-
lated to corrosion potential [7].
Open circuit potential tests were used to measure free corrosion
potential in different environments (Ringer solution and artificial
solution).
Regions of active solubilisation and passivation can be observed in
polarization curves (Fig. 2). Comparison of the registered potentiokinetic
curves reveals that the materials sintered in the atmosphere of 75%
H2/25% N2 and in the atmosphere of H2 are characterized by similar
corrosion potential in the environment studied. Corrosion potential of
the material sintered in the atmosphere of vacuum is shifted towards
positive values and amounts to −0.187 V vs. SCE (in artificial saliva).
The lowest value of corrosion current density was measured in the
sinter obtained in the atmosphere of hydrogen 5 ∙ 10 − 3 mA cm − 2
(in Ringer solution). The data are presented in Table 7. The lowest values
were found for the material sintered in hydrogen (0.002 mA cm − 2).
As results from the shape of polarization curves, current densities

Table 5
Distribution of shape factor and statistical parameters of surface area in 400/H2.

Class Class ranges shape factor Frequency, %

No. Beginning End of the
of the range
range

1 1 3 64.95
2 3 6 19.65
3 6 10 5.13
4 10 20 6.83
5 20 > 3.44

Volumetric share of
Pore surface area, µm2
pores, %

Min 3.79

Max 4044.17 34.19

Mean 381.26
438 A. Dudek, R. Włodarczyk / Materials Science and Engineering C 33 (2013) 434–439

Table 6
Distribution of shape factor and statistical parameters of surface area in 225/V.

Class No. Class ranges shape factor Frequency, %

Beginning End of the
of the range
range
1 1 1.6 73.1
2 1.6 2.3 14.94
3 2.3 3 8.90

Volumetric share of
Pore surface area, µm2
pores, %
Min 0.54
Max 199.11 2.1
Mean 32.15

observed in passive range, regardless of the compaction pressure, are was found for 400/H2 sinter, whereas its highest values were measured
comparable. for 225/V.
Fig. 3 presents the open circuit potential versus time for sintered Tafel curves presented in Figs. 2 and 4 show a particularly long
stainless steel in Ringer solution. Under conditions of open circuit, passivation range in 400/H2 sinter for the potential range from
lowest value of potential was found in a sinter obtained in the atmo- 0.6 ÷ 2 V. Despite the lowest corrosion potential compared to other
sphere of hydrogen. This reflects the effect of compaction pressure. specimens, this sinter is characterized by a stable passive layer and
The material compacted at the pressure of 700 MPa, with higher is resistant to pitting corrosion.
density (6.70 g cm − 3) exhibits lower potential compared to the sin- The effect of structural properties of the material on corrosion resis-
ter compacted at lower pressures (at 400 MPa, sinter density is tance is presented in Fig. 6.
6.19 g cm − 3), with the potential ranging near − 0.1 V. The highest As results from the figure above, in order to obtain the highest cor-
potential in OCP (Open Circuit Potential) conditions was found for rosion resistance, one should optimize the parameters of manufacturing
the specimen 225/V. of 316L sintered steel.
At the next stage, in order to examine the effect of sintering param-
eters and compaction atmosphere on corrosion resistance in materials Table 7
used for implants (e.g. used in dentistry), polarization curves were reg- Electrochemical parameters for polarization curves.
istered in the atmosphere of artificial saliva (Fig. 4). Regardless of the Solution Parameters 700/DA 400/DA 400/H2 225/V
compaction pressure, the potentiokinetic curves recorded for the
Ringer Ecorr [V] −0.444 −0.432 −0.460 −0.158
compacted sinters in the atmosphere of 75% H2/25% N2 have similar solution icorr [mA cm−2] 0.008 0.042 0.005 0.052
shapes. The values of current densities and corrosion potentials differ (ipass) vs. SCE [mA cm−2] 0.065 0.165 0.050 0.100
insignificantly (Table 7). The highest value of corrosion potential is Artificial saliva Ecorr [V] −0.482 −0.456 −0.571 −0.180
observed for 225/V sinter. Fig. 5 shows curves representing potential icorr [mA cm−2] 0.007 0.022 0.002 0.064
−2
(ipass) vs. SCE [mA cm ] 0.042 0.120 0.027 0.088
vs. time in open circuit. Under these conditions, the lowest potential

103 0.2
102 700/DA 0.1
Current density/mA cm-2

10 1 400/DA 0.0
OCP/V vs. SCE

10 0 -0.1
225/V 700/DA
400/DA
-0.2
10-1
-0.3
10-2 400/H2
-0.4
10-3
225/V -0.5 400/H2
10-4
-0.6
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 0 400 800 1200 1600 2000
Potential/ V vs. SCE Time/s

Fig. 2. Potentiokinetic curves obtained for sintered stainless steel obtained in Ringer solution. Fig. 3. Open circuit potential in sintered materials in Ringer solution.
 A. Dudek, R. Włodarczyk / Materials Science and Engineering C 33 (2013) 434–439 439

103 60 0.5
Ringer Porosity/%
Current density/mA cm-2 10 2 400/DA Artificial saliva
50
0.4
10 1 700/DA
40

ipass vs. SCE

Porosity/ %
0.3
100
30
10-1 0.2
20
10-2
400/H2 225/V 0.1
10
10-3

10-4 0 0.0
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 700/DA 400/DA 400/H2 225/V
Potential/ V vs. SCE
Fig. 6. Relationship of material porosity and passivation current density.
Fig. 4. Potentiokinetic curves obtained for sintered stainless steel obtained in artificial saliva.

0.1 with respect to compacting pressure and sintering atmosphere. The

results presented in this study lead to the following conclusions:
0.0
• Appropriate manufacturing parameters (compaction pressure and
-0.1 sintering atmosphere) of 316L steel allow for obtaining a material
OCP/V vs. SCE

225/V 700/DA with functional properties required for successful implantations in

-0.2 400/DA human body.
-0.3 • Application of hydrogen atmosphere results in 2.5-time rise in porosity
in compacted sinters at comparable pressures (400 MPa).
-0.4 • Despite the lowest corrosion potential measured for 400/H2 specimens,
these sinters exhibit the lowest values of corrosion current and, impor-
-0.5
400/H2 tantly, a passive layer is created on their surface within the whole range
-0.6 of potentials from 0.6÷2 V.
0 400 800 1200 1600 2000 • High corrosion resistance measured in Ringer solution and a solution
Time/s of artificial saliva (sintering of material in hydrogen and vacuum atmo-
Fig. 5. Open circuit potential in sintered materials in artificial saliva. sphere) and high porosity in the sinters studied open up the opportu-
nities to use them in medicine.

The values of porosity above 30% and adequate manufacturing condi-

tions (sintering atmosphere) are likely to guarantee high corrosion resis-
tance, measured both in Ringer solution and in artificial saliva solution.
Passivation current densities found within the passive range
presented in Figs. 2 and 4, correlated with the results obtained for porosity
(Fig. 6), show insignificant differences. However, the scope of passivation
for individual specimens is significant. This is caused by the build-up of
passive layer on the material surface. Thus, open porosity values will
affect changes in surface properties.
4. Conclusions
The focus of this paper was on changes in properties of 316L stain-
less steel obtained by means of the method of powder metallurgy
References
[1] J.F. Shackelfortd, R.H. Doremus, Ceramic and Glass Materials, Springer, 2008.
[2] U. Schulz, H-Tay Lin, Andvanced Ceramic Coatings and Interfaces II, Wiley-Interscience,
2007.
[3] K.A. Khalil, S. Kim, H.Y. Kim, Mater. Sci. Eng. 456 (2007) 368–372.
[4] A. Dudek, J. Eng. Mater. Technol. 133 (2011) (021006–1 - 021006–50).
[5] A.R. Vaccaro, Ortop. 25 (2002) 571–578.
[6] M.M. Dewidar, H.C. Yoon, J.K. Lim, Met. Mater. Int. 12 (2006) 193–206.
[7] M.U. Kamachi, T.M. Sridhar, et al., Corros. Rev. 21 (2003) 2–3.
[8] N. Chawla, X. Deng, Mater. Sci. Eng. 1 (390) (2005) 98–112.
[9] W. Moreira-Lima, N. Candela, in: , 1998, pp. 413–418.
[10] W.M. Lima, F. Velasco, J.M. Torralba, Mater. Sci. Forum 299–300 (1999) 431–438.
[11] I.B. Halil, Scr. Mater. 55 (2006) 203–206.
[12] M.M. Dewidar, K.A. Khalil, J.K. Lim, Trans. Nonferrous Met. Soc. China 17 (2007)
468–473.
[13] K. Seah, R. Thampuran, S. Teoh, Corros. Sci. 40 (1998) 547–556.