Materials Science Forum Vol.

782 (2014) pp 499-502 Online: 2014-04-09

© (2014) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/MSF.782.499

Effect of Silver Content on Microstructure and Corrosion Behavior of

Material Prepared from Silver Coated Iron Powder
Monika Hrubovčáková1, a, Miriam Kupková1, b, Andrea Fedorková2, c,
Renáta Oriňáková2, d and Adam Zeleňák1, e
1
Institute of Material Research of SAS, Watsonova 47, Košice, Slovakia
2
Institute of Chemistry, Faculty of Science, P. J. Šafárik University in Košice, Košice, Slovakia
a
mhrubovcakova@imr.saske.sk, bmkupkova@imr.saske.sk, candrea.fedorkova@upjs.sk,
d
renata.orinakova@upjs.sk, eazelanak@imr.saske.sk

Keywords: iron powder, coating, microstructure, corrosion behavior

Abstract. Iron was considered a good material candidate for temporary implants in cardiovascular
and orthopedic surgery. Mechanical properties of iron are attractive, however, a higher degradation
rate is required. The contribution deals with the effect of silver content on microstructure and
corrosion behavior of materials prepared from Ag coated iron powders. Using electroless
deposition, Fe-powders with 0.29 and 2.1 wt.% of silver were prepared. Cylindrical specimens
compacted at a pressure of 200 MPa were isothermally sintered at 1120°C for 60 min. The
microstructure of the sintered specimens consisted of iron matrix with Ag-precipitates. The
corrosion behaviour of sintered compacts was studied using the potentiodynamic polarization
technique in Hank’s solution and complemented with SEM analysis. It was found out that corrosion
resistance of material decreased with an increase in silver content.

Introduction

At present, Mg and Fe based alloys are two classes of frequently researched biodegradable
metallic materials [1-3]. Poor mechanical properties of magnesium, higher degradation rate in
physiological environments and significant hydrogen evolution limit the application of Mg based
alloy materials, especially in orthopedic surgery [3]. When a higher load is required, the use of iron
based materials appears to be a good alternative [4]. The results of the first in vivo animal test of
pure iron stents showed suitability of iron as a biodegradable material. No marks of local or
systemic toxicity, local inflammations or early restonsis due to trombotic processes were detected
and degradation products were very well absorbed [5]. However, the degradation rate of pure iron
was shown to be too low. Schinhammer et al. [6] proposed that a good chemical alloying concept of
iron can not only increase degradation rate, but also achieve desired mechanical properties.
Hermavan et al. [7] presented Fe-Mn alloys with a significantly higher degradation rate than that of
pure iron and with mechanical properties similar to those of stainless steel 316, which is widely
considered as the gold standard for stent implants. Degradable iron based imlpants are attractive in
bone surgey, since they offer high strength at a medium corrosion rate. At the beginning of the
healing process, the implant serves as a stabilizer. Then, during the remodeling process, the implant
is resorbed and the entire load is gradually transferred to the bone. Here, the Young's modulus must
not exceed the bone implant stiffness, so that an optimal bone remodeling can be achieved. This can
be done by using cellular metals. Porosity of the material allows bone cells and veins to grow
throughout the implant, which is essential for regeneration of the bone tissue [4].
Silver has a unique position among metals. This is because of its high biological activity and
antibacterial effects. The objective of this research was to study the impact of silver content on the
microstructure and corrosion resistance of sintered materials prepared from silver coated iron
powder.

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500 Metallography XV

Experimental procedure and method

Water atomised iron powder ASC 100.29 (Höganäs AB, Sweden) grade > 63µm was used as a
starting material. Using electroless deposition, the powder particles were coated by silver coating.
15 g of iron powder was added to the plating electrolyte. Powders with 0.29 wt.% and 2.1 wt.% Ag
were prepared using the plating electrolyte consisting of:
1. 20 ml 2% AgNO3, 40 ml 26% NH3 and 30 ml 35% glucose,
2. 20 ml 6% AgNO3, 8 ml 26% NH3 and 8 ml 35% glucose.
Coating was carried out at 70°C for 30 minutes. The silver content was analyzed using ICP-MS
AGILENT 7700 inductively coupled with plasma mass spectrometer. Cylindrical specimens of
Ø10x10mm3 were compacted at 200 MPa and sintered at 1120ºC for 60 minutes in a tube laboratory
furnace Marsh. The mixture of 10%H2-N2 was used as a protective atmosphere. Corrosion
behaviour of materials was studied electrochemically. Cyclic voltammetry measurements were
performed by Autolab Potentiostat PGSTAT 302N. A conventional three-electrode system with
Ag/AgCl served as a reference electrode, platinum as a counter electrode and our specimen was
used as a working electrode. In Hank's solution, three cycles of anodic potentiodynamic polarization
were registered for each specimen. Polarisation curves were obtained by varying the applied
potential from -1000 mV up to +100 mV at a scan rate of 25 mV/s. The morphology of powder
surfaces was studied by scanning electron microscopy with Tesla BS 340. The microstructure was
observed using light (Olympus GX 71) and scanning electron microscopy (Jeol JSM 7000F
equipped with INCA EDX analyzer).

Results and discusion

Figs. 1a, b show SEM micrographs of iron powder particles coated with 0.29 wt.% (Fig. 1a) and
2.1 wt.% of silver (Fig. 1b). The surface morphology of the coated iron powder particles was
determined by the silver content.

a b

Fig. 1 SEM micrographs of silver coatings iron powders particles with

a) 0.29 wt.% , b) 2.1 wt.% of silver

The surface of iron particles with 0.29wt.% of silver were covered with small, randomly distributed
"islands" of silver coating; the surface morphology of particles with 2.1 wt.% Ag was significantly
changed, Fig. 1b. The powder particles were covered with a discontinuous layer of rough coating. In
rare cases, a dendridic structure of silver was observed.

Table 1 Green and sintered density of compacts of the starting iron powder and the powder coated
with Ag

Green density [g/cm3] Sintered density [g/cm3]

Fe 5.64 5.73
Fe+0.29 wt.% Ag 5.56 5.63
Fe+2.1 % wt.% Ag 5.47 5.49
 Materials Science Forum Vol. 782 501

The compresibility of powder was affected by the presence of coating; the addition of silver causes
a decrease in density. (Table 1).
In order to analyze the microstructure of the powder-metallurgical samples, micrographs were
prepared. Figs. 2a, b show the cross-section of the sintered compacts with 0.29wt.% and 2.1
wt.%Ag . In the metallographic cross section, silver is visible as bright regions distributed mainly
along the boundary of former powder particles. In the microstructure with lower silver content, the
precipitates have nearly spherical shapes, sized up to 5 µm; at a higher silver content, the number
and the size of precipitates increase.

a b

Fig. 2 Metallographic cross section of compacts sintered at

1120°C for 60 min with a) 0.29 wt.% Ag , b) 2.1 wt.% Ag

Degradation of metals in vivo occurs due to various corrosion processes, where the main
processes are surface corrosion, intergranular corrosion and pitting corrosion [4]. The corrosion of
sintered compacts in Hank´s solution which simulates human body fluid environment was examined
by anodic polarization curves at 25°C. Three cycles of anodic potentiodynamic polarization were
attested for every specimen. Generally it was observed that the corrosion resistance of compacts
decreases with the number of cycles.

Table 2 The determined values of Ecorr, icorr and corrosion rates

Ecorr [mV] icorr [µA/cm2]

1. cycle 2. cycle 3. cycle 3. cycle
Fe-0.29 wt.%Ag -299 -385 -467 1.069
Fe-2.1 wt.%Ag -432 -480 -519 1.286

The passive layer on the compacts top-surface, which to some extent protected the material, was
dissolved during the first cycle of anodic polarization. Subsequently, in the next cycle, specimens
showed a higher tendency to corrode. Compared to compacts with 0.29 wt.% Ag, the corrosion
potential of compacts with 2.1 wt.% Ag was shifted to more negative. This negative shift indicates
that specimens with higher silver content have a higher tendency to corrode. The polarization curves
are shown in Fig. 3. The values of corrosion potential (Ecorr) and the estimated corrosion current
densities (icorr) are summarized in Table 2.
Fig. 4 shows SEM micrographs of compacts with 2.1 wt.% of silver after the corrosion test.
A high potential difference between Fe and Ag made corrosion occur via contact corrosion. Since
silver does not dissolve in iron, silver precipitates acted as local corrosion spots.
502 Metallography XV

-2
log i
-4

-6
2.1 wt.% Ag
0.29 wt.% Ag
-8
-1000 -700 -400 -100 200
Potential [mV]
Fig. 3 Anodic polarisation curves of Fig. 4 SEM micrograph of Fe-2.1 wt.%
specimens in Hank´s solution Ag after the corrosion test

Conclusion

Iron powders with 0.29 and 2.1 wt.% Ag coatings were prepared using electro-less deposition.
Produced coating is of bad quality with low adhesion to the powder surface. This means that the
emphasis of future research has to be laid on the development of alternative coating technniques. In
the microstructure of compacts sintered at 1120°C, silver was present in the form of bright
precipitates; the size and amount of precipitates were determined by silver content. Corrosion
resistance of sintered compacts was studied by electrochemical potentiodynamic polarization in
Hank´s solution. The results showed that, compared to compacts with 0.29 wt.% Ag, the corrosion
potential of compacts with 2.1 wt.% Ag was shifted to more negative values. This indicates that
specimens with higher silver content have a higher tendency to corrode.

Acknowledgement
This work was supported by the Project APVV-0677-11 of the Slovak Research and Development
Agency and Projects VEGA 1/0211/12, 2/0168/12 of the Slovak Scientific Grant Agency.

References

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Metallography XV
10.4028/www.scientific.net/MSF.782

Effect of Silver Content on Microstructure and Corrosion Behavior of Material Prepared from Silver
Coated Iron Powder
10.4028/www.scientific.net/MSF.782.499

DOI References
[1] M. Moravej, D. Mantovani, Biodegradable metals for cardiovascular stent application: Interest and new
opportunities, Int. J. Molec. Sci. 12 (2011) 4250-4270.
http://dx.doi.org/10.3390/ijms12074250
[2] H. Hermawan, D. Dubé, D., Mantovani, Development in metallic biodegradable stents, Acta Biomat. 6
(2010) 1693-1697.
http://dx.doi.org/10.1016/j.actbio.2009.10.006
[4] B. Wegener, at al., Microstructure, cytotoxicity and corrosion of powder-metallurgical iron allloys for
biodegradable bone replacment materials, Materials Sci. and Eng. B 176 (2011) 1789-1796B.
http://dx.doi.org/10.1016/j.mseb.2011.04.017
[6] M. Schinhammer, A. C. Hanzi, J. F. Loffler, P. J. Uggowitzer, Desing strategy for biodegradable Fe-based
alloys for medical applications, Acta Biomat. 6 (2010) 1705-1713.
http://dx.doi.org/10.1016/j.actbio.2009.07.039