Surface and Coatings Technology, 34 (1988) 209 - 217 209

EFFECT OF SILICON ADDITION ON THE MICROSTRUCTURE

AND CORROSION BEHAVIOR OF SINTERED STAINLESS STEEL

WEN-TA TSAI, YING-NAN WEN, JU-TUNG LEE and HON-YEE LIOU

Department of Metallurgy and Materials Engineering, National Cheng Kung University,
Tainan (Taiwan)

WEN-FUNG WANG
Department of Mechanical Engineering, Nan-Tai Institute of Technology, Tainan
(Taiwan)

(Received November 4, 1986)

Summary

The influence of silicon addition on the physical properties and the

corrosion behavior of sintered austenitic 304L stainless steel was evaluated.
The density of the sintered stainless steel changed depending upon the
amount of silicon added. A “pseudo-peritectic” reaction developed during
the sintering of high silicon content alloys and resulted in an increased sin-
tering rate and enhanced densification. The corrosion resistance of the various
sintered stainless steels was evaluated from the results of potentiodynamic
polarization curves and corrosion rate measurements and from the appear-
ance of the corroded surfaces. The results indicated that the corrosion resis-
tance was improved with the addition of more than 2 wt.% Si.

1. Introduction

The corrosion resistance of sintered stainless steel is generally inferior

to that of its wrought counterpart mainly owing to a high surface area
(porosity) and the use of unsuitable sintering processes. It is generally
believed that the corrosion resistance of powder metallurgical (PM) alloys
increases with increasing density [1]. In a recent study, Itzhak and Harush
[21 found that the addition of 0.5 3 wt.% Sn enhanced the densification of
-

~itered 316 stainless steel (SS) and improved its corrosion resistance in
sulfuric acid. Similarly, Wang [3] found that the addition of silicon increased
the density of sintered 304L SS.
Since silicon acts as a ferrite stabilizer in austenitic stainless steel, its
addition will produce duplex microstructures (austenite and ferrite). The
corrosion resistance of wrought ingot metallurgical (TM) silicon-stabilized
duplex stainless steel has not yet been thoroughly explored. In a recent
study, Wilde [4] reported that the addition of silicon to an (l8Cr—8Ni)-

0257-897 2/88/$3.50 © Elsevier Sequoia/Printed in The Netherlands

210

base IM alloy increased its resistance to pit initiation. Meanwhile, the alloy
with a 4.45 wt.% Si content had a corrosion rate approximately 20-fold
lower than that observed for AISI 304 SS in an acidic FeCl3 solution.
Whether or not the addition of silicon to the PM stainless steel will improve
its corrosion resistance is of great interest. In this study the microstructure
and the corrosion behavior of sintered 304L SS containing various amounts
of silicon were investigated.

2. Experimental details

An AISI 304L SS powder with the composition (wt.%) 0.02 C, 0.9 Si,
18.9 Cr, 10.9 Ni and balance iron was used. The apparent density and 145
3 and the
average particle size
pm respectively. The of thesilicon
pure stainless steel
used powder
in this studywere
had 2.7 g cm
an apparent density
of 2.3 g cm3 with an average particle size of 40 pm. Samples were prepared
by adding 0 5wt.% Si powder to the base metal powders. They were mixed
-

and compacted at a pressure of 600 MPa. These samples were then sintered
in a hydrogen atmosphere at 1200 °Cfor 45 mm. The sintered sample had a
disc shape with a diameter of 11 mm and a thickness of 5 mm.
Metallographical examinations were performed on the cross-sections of
the sintered specimens. The cross-section of each specimen was polished with
600 grit SiC paper and then etched in Emmanuel’s reagent at 95 °Cfor 25 S.
The etched microstructure was examined by optical microscopy.
Potentiodynamic polarization measurements were conducted in 3.5
wt.% NaCl and 6 wt.% FeC1
3 solutions (pH 1.6) at 25 °C.The exposed cross-
section surface of the sintered specimen was polished with 600 grit SiC
paper, washed in distilled water and rinsed with acetone prior to use. The
polarization curve was1,with
determined using areferenced
all potentials PAR 273 to potentiostat
a saturatedatcalomel
a scan
rate of 60(SCE).
electrode mV min~
Immersion tests were also conducted to measure the corrosion rates of
the sintered stainless steels in a 6 wt.% FeCI
3 solution. The weight losses
during a testing period of 3 days were used to calculate the corrosion rates.
In other immersion tests an extended test period was employed so that the
microstructural change in the corroded surface could be clearly differen-
tiated by optical microscopy and scanning electron microscopy (SEM).

3. Results and discussion

Figure 1 and Table 1 depict the influence of silicon addition on the

density of the sintered (in a hydrogen atmosphere at 1200 °Cfor 45 mm)
stainless steel. The results show that the density decreased as the amount of
added silicon increased from zero to 2 wt.%. With more than 2 wt.% Si, the
density increased almost linearly with the amount of silicon added. With the
 211

I I I I I

6.6 - ,~.._-. -

64 /

Z58 - -

a
5.6 - ‘-.~ -

54 .

I I I I I
0 1 2 3 4 5 6
Si ADDITION, (wt!.)
Fig. 1. Variations in the green density (A) and the sintered density (•) of PM stainless
steel (sintered at 1200 °Cin a hydrogen atmosphere) with silicon content.

TABLE 1
Apparent density of the PM stainless steels with various amounts of added silicon

Silicon Average sintered3) Average green

density (g cm3)
added (wt.%) density (g cm~
0 641 6.14
1 6.27 5.98
2 6.20 5.81
3 6.30 . 5.70
4 6.47 557
5 6.61 5.44

addition of more than 4 wt.% Si, the density was greater than that of plain
sintered 304L SS. The variation in sintered density as a function of silicon
content is explained as follows. The green density of the powder compact
decreases with increasing amount of silicon addition (also depicted in Fig. 1)
owing to the difference in both elastic and plastic behavior between silicon
and stainless steel powders. However, the presence of silicon lowers the
liquidus and the solidus temperatures of the austenitic stainless steel. In the
sintering of a PM austenitic stainless steel at 1200 °C,the addition of silicon
would cause, at an early stage, the formation of a liquid phase at the inter-
face between the silicon and stainless steel powders. The formation of a
liquid phase would improve the sintering rate and enhance the densification
of the sintered parts [5]. With small additions of silicon, however, the
amount of liquid phase formed was probably not enough to induce efficient
liquid phase sintering. Thus, there was no significant increase in the sintered
density. As the added silicon content was increased to more than 2 wt.%, a
very large amount of the liquid phase was formed and liquid phase sintering
212

became important. Therefore enhanced densification was observed by the

increase in the sintered density as shown in Fig. 1.
Metallographical results are given in Fig. 2. Duplex structures were
observed when the amount of added silicon was greater than 1 wt.%. The
volume percentage of the ferrite phase increased on increasing the silicon
addition up to 4 wt.%, as illustrated in Fig. 2. At 5 wt.% added silicon, a
transient liquid phase existed and the PM alloy underwent a “pseudo-
peritectic” reaction during sintering at 1200 °C.The reaction could be div-
ided into two stages. Firstly, silicon powder plus austenitic stainless steel
powder gave a transient liquid phase. Secondly, the transient liquid phase
plus austenitic stainless steel powder reacted to form ferritic stainless steel.
During cooling from the sintering temperature, a secondary austenitic phase
precipitated again in the ferrite matrix. The resulting microstructure is given
in Fig. 2(d), and depicts a phase inversion as compared with the micro-
structures in Figs. 2(a) 2(c). -

Potentiodynamic polarization curves of sintered stainless steels with

various amounts of silicon in 3.5 wt.% NaC1 and in 6 wt.% FeCl3 solutions
are shown in Fig. 3. For the 3.5 wt.% NaCl solution, the shapes of the polar-
ization curves of the PM alloys were similar except that the solution
containing 5 wt.% added silicon had a more negative corrosion potential (see
Fig. 3(a)). The polarization curve for wrought IM 304L SS is also shown in
Fig. 3(a). The existence of passive behavior is apparent in the potential range

C’ ~ .• ~ ‘I~~L~
;.. J— .~.. ~ ~ ~

¶ 1”! ~ ~ ‘(~i4:’
~ ~)~t’II_

~ ~ d~Ø :~
\~f ~

~ ~

~ 4
~~%~?44i~¼ ~
p. ~ (~ ~ . ~

Fig. 2. Optical m icrograph.~ of PM stainless steels sintered in a hydrogen at mosphere at

1200 °C for 45 mm: (a) 304L SS; (b) 304L SS + 2 wt.~ Si; (c) 304L SS + 4 wt.% Si;
(d) 304L SS + 5 wt.% Si.
 213

I I I I

106 I I I I I I I

2 . e
io
I I I I _1~I I 100 I I I I I I
—800 —400 0 400 —800 —200 200 600 1000 1400

(a) POTENTIAL EscE I mVI (b) POTENTIAL ESCE I mV)

Fig. 3. Potentiodynamic polarization curves for sintered stainless steels in (a) 3.5 wt.%
NaC1 solution (pH 5.8) and (b) 6 wt.% FeCI
3 solution (pH 1.6) at 25 °Cand at a scan rate
of 60 mV min’: curve a, IM 304L SS; curve b, PM 304L SS; curve c, PM 304L SS + 1
wt.% Si; curve d, PM 304L SS + 3 wt.% Si; curve e, PM 304L SS + 5 wt.% Si.

from —650 to —200 mV(SCE). The PM alloys do not show passive behavior
because of the existence of porosity. Figure 3(b) shows the polarization
curves of various PM alloys tested in 6 wt.% FeC13 solution. In such a strong
acidic oxidizing environment none of the specimens tested exhibited passive
behavior.
Corrosion rates of the sintered specimens tested in a 6 wt.% FeCl3 solu-
tion as a function of silicon content are illustrated in Fig. 4 and Table 2.
Except for the specimen containing 1 wt.% added silicon, the corrosion
resistance of the PM stainless steel increased with increasing silicon content.
The improvement in the corrosion resistance was probably due to the forma-
tion of an Si02 film on the specimen surface [61 and to the increase in
sintered density. The results of metallographical examinations of the surface
appearance of the corroded specimens were consistent with the corrosion
rate measurements, as will be discussed later.
Surface appearances of the sintered specimens after immersion for 496
h are shown in the optical micrographs in Fig. 5. In order to differentiate the
relative corrosion resistance of ferrite and austenite microscopically, the
specimens were lightly etched before being immersed in the 6 wt.% FeC13
solution. The micrographs in Fig. 5 show that the cross-section surface of the
plain sintered austenitic stainless steel was corroded more uniformly than
those of other specimens. At an addition of 2 wt.% Si, the ferrite phase was
preferentially attacked, as can be seen in Fig. 5(b). It has long been recog-
nized that increasing the ferrite content in ferrite—austenite duplex stainless
steel is beneficial to corrosion resistance [71. Dundas and Bond [81 have also
pointed out recently that preferential corrosion of the austenite phase in
wrought duplex stainless steel in 10 wt.% FeCl36H20 would occur because
214

350 I I I I
-~ 6’!. F,C1
3
uS 300 - • 72h s

250 ///\\\ OU~

~200 \.. -

S
150 -
‘0

~ 100 I I I I I
‘0 0 I 2 3 1. 5 6
5~ADDITION, (wt’f,)

Fig. 4. Effect of silicon content on the corrosion rate of sintered stainless steel in 6 wt.%
FeCl3 solution (average for two coupons).

TABLE 2
Corrosion rates of sintered stainless steels in 6 wt.% FeC!3 solution (pH 1.6 at 25 °C)

Silicon added (wt.%) 2 ratea

Corrosion per day)
(mg dm
0 237
1 293
2 228
3 212
4 167
5 187

aAverage for two coupons.

the austenite contained less chromium than ferrite. The ratio of the
chromium content of ferrite to that of austenite, as analyzed by an electron
probe microanalyzer (EPMA), was 1.18 for the sintered 304L SS + 2 wt.% Si
alloy. The corrosion behavior was, however, contrary to that of TM duplex
stainless steel. It is not yet clear, however, whether the porosity, chemical
composition or other factors are responsible for this controversial behavior.
The sintered 304L SS + 4 wt.% Si alloy had the lowest corrosion rate
observed in the FeCl
3 solution (see Fig. 2). The corresponding micrograph
obtained in the extended immersion test (Fig. 5(c)) shows that the cross-
section surface of this alloy was not severely corroded except for the ferrite—
austenite grain boundary. Previous results of Wilde [4] have indicated that
increasing the silicon content from 1.01 to 4.45 wt.% r~ulted 2 perinday
a progress-
for the
ive decrease in the corrosion rate from 2170 to 50 mg dm
corresponding TM l8Cr—8Ni alloys. In the present study, the experimental
results indicated that the addition of 4 wt.% Si had the same beneficial
 215

~•Q~~ ~(.r ~

c ~ : ~ ~ d ~ -. - ,.~j ~

Fig. 5. Optical micrographs showing the cross-section surface appearance of various

sintered stainless steels (after immersion in 6 wt.% FeC!
3 solution for 496 h): (a) 304L
SS; (b) 304L SS + 2 wt.% Si; (c) 304L SS + 4 wt.% Si; (d) 304L SS + 5 wt.% Si.

effect on the corrosion resistance of sintered stainless steel as the IM

wrought counterpart.
Figure 5(d) shows the optical micrograph of the corroded surface of the
sintered 304L SS + 5 wt.% Si alloy. In this case, the austenite phase was
attacked while the ferrite phase remained almost unaffected in 6 wt.% FeCI3
solution. The selective attack of the austenite phase occurred because its
chromium content was lower than that of the ferrite phase.
SEM micrographs of the sintered stainless steel after its immersion in
6 wt.% FeC!3 solution for 496 hare shown in Fig. 6. These specimens were not
etched before immersion, and the results are consistent with the corrosion
rate measurements and the optical examinations shown in Fig. 4 and Fig. 5
respectively. It may be noted that only minor attack was found for the alloy
containing 4 wt.% added silicon. Without the addition of silicon, severe
pitting corrosion occurred on the austenitic 304L SS, as seen in Fig. 6(a).
However, the ferrite phase seemed much more resistant to pitting corrosion
in the acidic FeC13 solution as illustrated in Fig. 6(d). The results were
similar to those found for IM stainless steel [4, 8].
216

___ :i~’~-~c~___
- ~ ~~5Qf~m ‘~,—~-‘~

Fig. 6. SEM rnicrographs showing the cross-section surface appearance of various sintered
stainless steels (after immersion in 6 wt.% FeC!
3 solution for 496 h): (a) 304L SS; (b)
304L SS + 2 wt.% Si; (c) 304L SS + 4 wt.% Si; (d) 304L SS + 5 wt.% Si.

4. Conclusions

1. The density of the sintered stainless steel was influenced by the

amount of silicon added. Enhanced densification due to liquid phase
sintering occurred at a higher silicon content.
2. A ferrite—austenite phase inversion was observed for the silicon-
stabilized sintered stainless steel with the addition of 5 wt.% Si.
3. The corrosion resistance of the sintered stainless steel was improved
by the addition of more than 2 wt.% Si. With a lower silicon content, ferrite
corroded more readily in an acidic oxidizing chloride solution. In the case
where ferrite was the major phase, however, the secondary austenite phase
was preferentially attacked.

Acknowledgments

The authors gratefully acknowledge the support for this work provided
by the Materials Research Laboratories of the Industrial Technology
Research Institute, Taiwan.
 217

References

1 R. M. F. Jones, Proc. mt. Powder Metallurgy Conf., Princeton, NJ, 1974, p. 25.
2 D. Itzhak and S. Harush, Corros. Sci., 25 (1985) 883.
3 W. F. Wang, Metals Industries, 16 (1982) 20.
4 B. E. Wilde, Corrosion (Houston), 42 (1986) 147.
5 R. M. German and K. A. D’Angelo, Int. Metall. Rev., 23 (1984) 249.
6 D. H. Ro and E. Kiar, in H. H. Hausner and P. W. Taubenblat (eds.), Modern Develop-
ments in Powder Metallurgy, Vol. 13, Metal Powder Industries Federation, Princeton,
NJ, 1980, p. 247.
7 J. W. Flowers, F. H. Beck and M. G. Fontana, Corrosion (Houston), 19 (1963) 196t.
8 J. J. Dundas and A. P. Bond, Mater. Perform., 24 (10) (1985) 54.