Materials Science and Engineering A 472 (2008) 324–331

Microstructure and property evolution during the sintering

of stainless steel alloy with Si3N4
Akhtar Farid a,b,∗ , Peizhong Feng c , Xueli Du b , Askari Syed Jawid b , Jianjun Tian b , Shiju Guo b
a Department of Metallurgical and Materials Engineering, University of Engineering and Technology, Lahore, 54890, Pakistan
b Institute of Powder Metallurgy, School of Materials Science and Engineering, University of Science and Technology, Beijing 100083, China
c School of Materials Science and Engineering, China University of Mining and Technology, Xuzhou 221116, China

Received 21 May 2006; received in revised form 8 March 2007; accepted 11 April 2007

Abstract
This paper describes the sintering of a martensitic stainless steel alloy with addition of Si3 N4 . Sintering behavior was studied at different sintering
temperatures ranging from 1250 to 1400 ◦ C with different holding times (20–80 min) and with varying Si3 N4 . Results showed that the samples
were densified rapidly via liquid phase sintering mechanism. Nearly full density was obtained at 1300 ◦ C after 60 min of holding time with 5 wt%
Si3 N4 . Temperature above 1350 ◦ C and Si3 N4 content 10 wt% caused slumping of the samples. Two weight percent Si3 N4 was found chemically
stable in steel alloy. Above 2 wt% Si3 N4 dissolved in the steel matrix. The distribution of dissolved Si and N was characterized by XMAP. When N
content reached much above its solubility limit in steel alloy it diffused out leaving pores in steel alloy with considerable decrease in the sintered
density. The mechanical properties of the sintered product with varying Si3 N4 were measured. A maximum ultimate tensile strength of 1011 MPa
was achieved with 2 wt% Si3 N4 sintered at 1300 ◦ C after 60 min of holding time. Fracture morphologies of tensile samples are also reported.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Stainless steel; Sintering; Si3 N4 ; Mechanical properties; Microstructure; XMAP

1. Introduction
Stainless steels produced by powder metallurgy are candi-
dates for automotive and structural applications. P/M stainless
steels are produced by enhanced densification that involves
liquid phase sintering. High density of P/M stainless steels is
imperative for better mechanical properties. Several investiga-
tions have reported the enhanced sintering of stainless steels
by incorporating sintering additives like FeB, NiB and Cu3 P
[1–5]. The sintering additives activate the sintering process of
iron powders by the formation of the liquid phase. The liquid
phase has very low solubility in iron and remains favoring the
classical phenomenon of liquid phase sintering, as an almost
continuous network between solid grains [4]. So far, not much
research is reported on enhanced sintering of P/M stainless
steels–particulate composites. Effect of YAG on the sintering
∗ Corresponding author at: Department of Metallurgical and Materials Engi-
neering, University of Engineering and Technology, Lahore 54890, Pakistan.
Tel.: +92 42 5171852; fax: +92 42 6822566.
E-mail address: faridmet22@hotmail.com (F. Akhtar).
behavior of 316 L stainless steel was studied by Jain et al. [6].
Research on sintering of 316 L stainless steel powders with upto
10 vol.% YAG addition has been reported. It was concluded that
the sintering porosity was more homogeneous for 5 wt% YAG
containing composite than with only 316 L stainless steel under
identical sintering conditions. 316 L stainless steel sintered with
SiC reinforcement was studied by Patankar and Tan [7]. They
reported that the addition of SiC to the 316 L stainless steel
resulted in higher sintered density. This was attributed to the
interaction of SiC with 316 L stainless steel matrix, resulting
in the formation of a low melting Fe–SiC phase. Mukherjee
and Upadhyaya investigated the effect of Al2 O3 on sintering
behavior and mechanical properties of 434 L ferritic stainless
steels [8].
This present work is aimed to investigate the effect of Si3 N4
addition on the sintering behavior, mechanical properties of
P/M 465 stainless steel. Custom 465 stainless steel is a premium
melted, martensitic and age hardenable alloy. Due to its high
strength, excellent notch tensile strength and fracture toughness,
465 stainless steel has wide spread applications especially
in automotive and aerospace industry [9]. It is assumed that
the presence of Si3 N4 will result in greater densification.

0921-5093/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2007.04.032
 F. Akhtar et al. / Materials Science and Engineering A 472 (2008) 324–331 325

Table 1 stainless steel powders were prepared with 0–10 wt% Si3 N4 as
Composition of 465 stainless steel used in current study additive. The powders were poured into a tensile specimen die
Element wt% and uniaxially pressed at a pressure of 600 MPa. Sintering of
Aluminium 0.25
all prepared specimens was performed within a high temper-
Silicon (maximum) 0.75 ature vacuum furnace at a vacuum level of 1 × 10−2 Pa. The
Nickel 10.70 sintering cycle applied to the specimens was as follows: the spec-
Titanium 1.55 imens were heated to 1000 ◦ C at a rate of 10 ◦ C/min and held at
Chromium 12.00 1000 ◦ C for 15 min, then the specimens were heated to various
Molybdenum 1.10
Iron Balance
sintering temperatures of 1250, 1300, 1350 and 1400 ◦ C at a
Si3 N4 0–10 rate of 5 ◦ C/min and held at each temperature for 20, 40, 60 and
80 min. The densities of the sintered specimens were measured
Metallographic techniques were employed to investigate the by Archimedes water immersion method. Samples presintered at
effect of sintering temperature and Si3 N4 addition on the 800 ◦ C were prepared for dilatometer study. A vertical push rod
microstructure evolution of P/M 465 stainless steel. XMAP dilatometer was used to quantify the dimensional changes during
was used for the mapping of Si3 N4 in stainless steel alloy. the process of sintering. A heating rate of 10 ◦ C/min, 1300 ◦ C as
sintering temperature and 60 min as holding time was selected
2. Experimental for dilatometry. For metallographic examination, the specimens
were cut and metallographically prepared to 0.5 ␮m diamond
The composition of prepared stainless steel powders is given finish. The microstructure of sintered specimens and XMAPs
in Table 1. The mixed powders were dry milled for 6 h. 465 were observed on Kevex LEO-1450 SEM. All tensile tests were

Fig. 1. (a) Effect of Si3 N4 addition on the sintered density at 1300 ◦ C for 60 min. (b) Effect of sintering temperature on the sintered density (sintering time 60 min)
with 0–10 wt% Si3 N4 addition. (c) Effect of sintering time on sintered density with 0–10 wt% Si3 N4 addition at sintering temperature of 1300 ◦ C. (d) Variation in
shrinkage with time of 465 stainless steel containing 2 wt% Si3 N4 and 5 wt% Si3 N4 .
326 F. Akhtar et al. / Materials Science and Engineering A 472 (2008) 324–331

Table 2
Effect of Si3 N4 addition to 465 stainless steel on the green, ideal and sintered density
Number 465 steel (wt%) Si3 N4 (wt%) Green density at Ideal Sintered density Percentage of relative
600 MPa (g/cm3 ) density (g/cm3 ) density (g/cm3 )
(g/cm3 )

1 100.0 0.0 6.41 ± 0.03 7.840 6.50 ± 0.03 82.97

2 98.0 2.0 6.42 ± 0.03 7.747 7.34 ± 0.03 94.75
3 95.0 5.0 6.32 ± 0.02 7.608 7.50 ± 0.04 98.50
4 90.0 10.0 6.27 ± 0.04 7.376 6.88 ± 0.05 93.30

performed using Instron mechanical tester at constant crosshead
speed of 0.5 mm/min (25 mm gauge length). The hardness test
was performed at HRC scale. At least four tests were conducted
under the same conditions for reliability of the results.
3. Results and discussions
The densification during liquid phase sintering is analogous
to viscous flow sintering. Rapid sintering takes place with the
increase in liquid volume fraction and decrease in the liquid
viscosity with increasing temperature. The influence of Si3 N4
concentration, temperature and time on the sintering behavior
of loose maraging steel is shown in Fig. 1. Fig. 1a shows the
effect of Si3 N4 addition on the final sintered density at 1300 ◦ C
for 60 min. The sintered density increases with Si3 N4 content up
to 98.5% of the theoretical density (with 5 wt% Si3 N4 addition)
and then decreases to 93.8% of theoretical density with 10 wt%
of Si3 N4 addition. Fig. 1b shows the variation of sintered density
with temperature. Nearly full density, 98.5% of theoretical was
obtained at 1300 ◦ C for 60 min holding time with 5 wt% Si3 N4 .
The effect of Si3 N4 addition to 465 stainless steel on the green,
ideal and sintered density is summarized in Table 2.
Si3 N4 activates the sintering process of iron powders by for-
mation of liquid phase. The liquid phase has very low solubility
in iron and remains favoring the phenomenon of liquid phase
sintering. Ten weight percent Si3 N4 content and temperature
1350 ◦ C caused slumping of the samples depicts the presence of
large amount of liquid phase. The results of the effect of sinter-
ing temperature, time and Si3 N4 content on the resultant sintered
density is given in Fig. 1c. The samples containing 5 wt% Si3 N4

Fig. 2. Sintered microstructures of stainless steel: (a) 465 stainless steel without Si3 N4 addition sintered at 1400 ◦ C for 60 min, (b) with 2 wt% Si3 N4 addition sintered
at 1300 ◦ C for 60 min, (c) with 5 wt% Si3 N4 addition sintered at 1300 ◦ C for 60 min and (d) with 10 wt% Si3 N4 addition sintered at 1300 ◦ C for 60 min.
 F. Akhtar et al. / Materials Science and Engineering A 472 (2008) 324–331 327

Fig. 3. (a) Steel sintered with 2 wt% Si3 N4 at 1300 ◦ C for 60 min, (b) XMAP of Si, (c) XMAP of N, (d) steel sintered with 5 wt% Si3 N4 at 1300 ◦ C for 60 min, (e)
XMAP of Si, (f) XMAP of N, (g) steel sintered with 10 wt% Si3 N4 at 1300 ◦ C for 60 min, (h) XMAP of Si and (i) XMAP of N.
328 F. Akhtar et al. / Materials Science and Engineering A 472 (2008) 324–331
Fig. 3. (Continued ).
reached to a maximum sintered density after sintering for 60 min,
however higher sintering times do not increase density. Where
as, with 10 wt% Si3 N4 maximum sintered density (94% of theo-
retical density) was achieved in first 20 min, and higher sintering
times caused decrease in the sintered density (93.8% of theoret-
ical density). Fig. 1d shows the variation in the shrinkage with
time obtained from dilatometry. It shows that effective sinter-
ing takes place between 1170 and 1300 ◦ C. The higher sintering
shrinkage (around 15%) is associated with the sample containing
5 wt% Si3 N4 as sintering additive.
Fig. 2 shows the microstructure of the samples containing
0, 2, 5 and 10 wt% Si3 N4 , respectively, sintered at 1300 ◦ C for
60 min. Fig. 2a shows the Si3 N4 free sintered maraging stainless
steel alloy. The microstructure shows the sintered grains and
pores inside, similar findings are reported in literature [4,10–12].
Fig. 2b shows the presence of Si3 N4 particles embedded in steel
matrix. A maximum sintered density 95% of theoretical was
achieved with 2 wt% Si3 N4 . This may be due to the segregation
of Si3 N4 to grain boundaries and surfaces to form a layer at
particles contact areas or the grain boundaries that provide a
path of high diffusivity and allows the densification. With 2 wt%
Si3 N4 the number of pores is reduced and the pore shape is
smoothed. This indicates that a layer of high diffusivity is formed
at the grain boundaries resulting in fast densification and reduced
the number and size of pores at the grain boundaries that can
retard the densification process by pinning grain boundaries.
Fig. 2c shows the microstructure of the maraging stainless
steel with 5 wt% Si3 N4 addition sintered at 1300 ◦ C for 60 min.
This composition has shown the maximum sintered density
(98.5% of theoretical). It is interesting to note that Si3 N4 parti-
cles are absent in the microstructure. The dissolution of Si3 N4
has been taken place in steel alloy. This dissociation can take
place according to following reactions [13].
Si3 N4 = 3Si + 4N (1)
Si3 N4 + 4Cr = 3Si + 4CrN (2)
 F. Akhtar et al. / Materials Science and Engineering A 472 (2008) 324–331 329

According to reaction (2) the Si3 N4 has been dissociated in steel

alloy and Si will form liquid phase with Fe and cause densifica-
tion (98.5% of theoretical). Where as nitrogen will go to the steel
matrix as the solubility of nitrogen in higher in Cr containing
steel alloys as compared to pure iron [13]. It has been previ-
ously predicted that dissociation would proceed by the reaction
of Si3 N4 with Cr as given in reaction (2).
The reaction between Si3 N4 and Cr is proposed to happen
around 1000 ◦ C. In our case no precipitates were present in sam-
ples sintered at 1300 ◦ C for 60 min as shown in Fig. 2c. This
shows that if the dissociation mechanism of Si3 N4 is accord-
ing to the reaction (2) then the product CrN is not stable at
1300 ◦ C. On the other hand, the sintering is carried out in a
high vacuum furnace at a vacuum of 1 × 10−2 Pa, it is very less
likely to form SiO2 . Also, during the study of microstructure
and in XMAPs no evidence of SiO2 is found. Fig. 2d shows
the microstructure of steel alloy sintered with 10 wt% Si3 N4 .
Absence of Si3 N4 particles in Fig. 2d confirms the complete
dissociation of Si3 N4 in steel alloy. Fig. 3 shows the distribution
of Si and N in steel alloy determined by XMAP. Fig. 3a shows
the sintered microstructure of steel alloy with 2 wt% Si3 N4 . The
sintered microstructure contains Si3 N4 particles embedded in
steel matrix. Fig. 3b and c shows the XMAP of Si and N in
steel alloy. Comparing Fig. 3a–c, it can be concluded that Si3 N4
particles are embedded and no dissociation of Si3 N4 has taken
place. It can be speculated that lower amounts such as 2 wt%
Si3 N4 are stable with stainless steel alloy. It might be because
of the small amount of Si present in steel alloy that can hinder
the dissociation Si3 N4 in steel alloy and is confirmed by XMAP
of Si and N in Fig. 3. It has also been previously reported that
addition of Si to ferrous alloys can hinder the dissociation of Fig. 4. (a) Variation of hardness (HRC) with Si3 N4 content and (b) variation of
Si3 N4 [13,14]. ultimate tensile strength with Si3 N4 content.
Fig. 3d–f shows the microstructure of 465 stainless steel con-
taining 5 wt% Si3 N4 and XMAP of Si and N, respectively. The
figures describe that Si3 N4 is not stable and has been dissolved density. With decrease in density the hardness varied inversely.
in the steel alloy. Same results can be observed in Fig. 3g–i. This clearly indicates that Si3 N4 acted as stabilizer for other
Comparing XMAPs of Si in Fig. 3e and h it can be seen that soft phases (ferrite and austenite) instead of martensite and due
Si has segregated at the grain boundaries. This depicts that the to that the hardness has been decreased. This is independent of
liquid phase formed during sintering is rich in Si. Contrary to the increase in sintered density of the steel alloy. With 5 wt%
that, from the XMAPs of nitrogen (Fig. 3c, f and i) it is visible addition, the hardness of steel dropped further to 17 HRC. With
that with 2 wt% addition of Si3 N4 to steel nitrogen is present 5 wt% addition, the Si3 N4 has been dissociated. The Si is ferrite
in the form of Si3 N4 , with 5 wt% addition the nitrogen has dis- stabilizer and N is austenite stabilizer. So, less or no martensite
persed in the steel alloy and 10 wt% addition the nitrogen has will occur that causes decrease in hardness at maximum sintered
left the steel alloy. This may be the possible cause of decrease in density of 98.5% theoretical. With 10 wt% Si3 N4 addition the
sintered density of steel alloy with 10 wt% Si3 N4 addition. The sintered sample showed higher hardness 32 HRC. This is due to
nitrogen diffused out of steel alloy and had left the secondary the diffusing out of nitrogen from the steel alloy during sintering
pores responsible for the decrease in the sintered density. process. It causes decrease in density and increase in hardness
The overview of the mechanical properties in given in Fig. 4. of the alloy.
Fig. 4a shows the variation of hardness of sintered steel alloy Fig. 4b shows the variation of the strength of maraging stain-
with Si3 N4 addition. Without Si3 N4 , the steel sintered at 1350 ◦ C less steel alloy with Si3 N4 content. The maximum ultimate
showed hardness as high as 33 HRC. This high hardness is due to tensile strength of 1011 MPa is achieved with 2 wt% Si3 N4 .
the presence of martensite phase in sintered maraging stainless This high strength is shown at 95% of theoretical density. Si3 N4
steel alloy. The lower hardness of Si3 N4 free steel is due to is responsible for such high strength with 95% of theoretical
higher amount of porosity present at the sintering temperature density because these second phase particles hinder the move-
1300 ◦ C. It is worth interesting to note that with the addition ment of dislocations and increase the ultimate tensile strength
of 2 wt% Si3 N4 the hardness decreased to 23 HRC where as, of the steel alloy [15,16]. Gradually with the increase in addi-
the sintered density has improved from 91 to 95% of theoretical tion of Si3 N4 content, the decrease in UTS happens as shown
330 F. Akhtar et al. / Materials Science and Engineering A 472 (2008) 324–331
Fig. 5. (a) Fracture morphology of stainless steel alloy sintered at 1400 ◦ C for 60 min without Si3 N4 addition, (b) fracture morphology of stainless steel alloy sintered
at 1300 ◦ C for 60 min with 2 wt% Si3 N4 addition and (c) fracture morphology of stainless steel alloy sintered at 1300 ◦ C for 60 min with 5 wt% Si3 N4 addition.
in Fig. 4b. With 5 wt% Si3 N4 the density was the highest but
Si3 N4 hard particles have been dissolved in steel matrix. So, no
toughening mechanism by hard Si3 N4 is operative, due to that
UTS decreased to 980 MPa with 98.5% of theoretical density.
Samples containing 10 wt% Si3 N4 showed less ultimate ten-
sile strength (517 MPa). This is due to the diffusion of nitrogen
out of stainless steel alloy that causes decrease in sintered den-
sity to 93.8% of theoretical and secondary pores. The fracture
morphologies of samples are shown in Fig. 5. Fig. 5a shows the
fracture surface of sample sintered without Si3 N4 addition; there
are a number of pores between the particles, although the parti-
cles have fused together. The fracture surface of sample sintered
with 2 wt% addition of Si3 N4 is shown in Fig. 5b. The fracture
morphology shows the dimpled rupture, particles and pores. The
dimpled rupture corresponds to ductile fracture. The fractograph
of sample containing 5 wt% Si3 N4 is given in Fig. 5c. It shows
that the fracture morphology has obvious inter grain boundary
fracture characteristics. Austenite and ferrite that occur during
the sintering process increases the sintered density to 98.5 wt%
of theoretical and exhibits ductile fracture.
4. Conclusions
The effect of Si3 N4 addition on the sintering behavior,
microstructural development and mechanical properties was
investigated. The stability of Si3 N4 in stainless steel matrix was
also examined. With increasing Si3 N4 content, the sintered den-
sity increased and a maximum sintered density of 98.5% of
theoretical was achieved with 5 wt% Si3 N4 additions. It was
found that Si3 N4 particles were stable up to 2 wt% Si3 N4 in the
stainless steel matrix at sintering temperatures. More Si3 N4 was
dissociated in steel alloy in Si and N. Higher Si3 N4 addition
to steel alloy caused decrease in sintered density and ultimate
tensile strength. It was because of dissociation of higher amount
of Si3 N4 that gave the nitrogen content much higher than its
solubility limit in steel. So, nitrogen diffused out of steel matrix
leaving behind the pores. The best combination of mechanical
properties was achieved with addition of 2 wt% Si3 N4 addition
after sintering at 1300 ◦ C for 60 min (21 HRC hardness and
1011 MPa ultimate tensile strength).
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