Effect of the Length of Soaking Time on the Properties of Si

3
N
4
Ceramics Prepared from Low
Cost -Powder

Nirut Wangmooklang
1
, Kuljira Sujirote
2
and Shigetaka Wada
1
1
Department oI Materials Science, Faculty oI Science, Chulalongkorn University, Bangkok 10330
Phone 0-22185555, Fax. 0-22185561 E-mail: nirutw77yahoo.com
2
National Metal and Materials Technology Center, Pathumthani 12120
Phone 0-2564-6500, Fax. 0-2564-6501-5, E-Mail: kuljirasmtec.or.th


Abstract
The present study investigates the eIIect oI the length
oI soaking time on the microstructure and the mechanical
properties oI Si
3
N
4
ceramics. The low cost -Si
3
N
4
, MgO
and Al
2
O
3
powders, were used as starting materials.
Sintering was conducted at temperature oI 1850 C with
varying soaking time oI 0.5, 2 and 6 h. Density and mass
loss oI sintered specimens increased as a Iunction oI
soaking time. Grain size was increased by prolonging
soaking time; however, the grain aspect ratio was still
low. The specimen with soaking time oI 2 h showed the
highest values oI the mechanical properties: 544 MPa Ior
Ilexural strength, 16 GPa Ior Vickers hardness, and 5.9
MPa m
1/2
Ior Iracture toughness.
1. Introduction
Silicon nitride (Si
3
N
4
) ceramics are well-known as
engineering structural ceramics. They exhibit excellent
mechanical strength, high wear resistance, good oxidation
resistance and thermal shock behavior at both room and
high temperature. These ceramics are usually used Ior
several applications such as cutting tools, bearing balls,
gas turbines or valves Ior automotive engines. However,
the uses oI these materials were inhibited by their high
costs. Some research on the low cost Si
3
N
4
ceramics have
been investigated by using low cost starting materials and
sintering process (sintering in air atmosphere Iurnace)
|1|. However, the mechanical properties oI this material
are still not high enough Ior engineering applications. The
causes oI low mechanical properties are the low aspect
ratio oI microstructure and much amount oI glassy phase
in sintered body. The mechanical properties oI Si
3
N
4

ceramics are strongly depending on their microstructures
|2-4|. ThereIore, it is necessary to improve the
mechanical properties oI Si
3
N
4
ceramics with retaining
low cost.
In the present study, the eIIect oI soaking time on the
sintering behavior, the resultant microstructure and
mechanical properties oI Si
3
N
4
ceramics prepared Irom
low cost -powder was investigated Ior an additive Irom
the MgOAl
2
O
3
system.
2. Experimental procedure
-Si
3
N
4
powder (SN-F2 grade, Denki Kagaku Kogyo
K.K. Co.,Ltd., Japan) was used as starting material. It
includes 1.18 wt oxygen and about 0.2 wt Fe. The
average particle size (D
50
) was 29 m. The powder was
mixed and milled with 2 wt MgO (99.9 pure, Iwatani
Chemicals Co.,Ltd., Japan) and 2 wt Al
2
O
3
(99.99
pure, Taimei Chemicals Co., Ltd., Japan) by modiIied
attrition mill |5| and Si
3
N
4
balls with 5 mm in diameter.
The rotation speed and milling time were 500 rpm and 4
h, respectively. Then, the slurry was dried at 80 C in an
oven. The dried powder was sieved through 100 mesh.
The sieved powder was Iormed into rectangular bar with
dimension oI 40 x 4 x 6 mm
3
by mechanical pressing oI
20 MPa Iollowed by cold isostatic pressing (CIP) with a
pressure oI 200 MPa.
Green specimens were placed in BN sagger and then
BN sagger was put in graphite crucible. Sintering was
perIormed using N
2
gas Iurnace with graphite heating
element (HIGH MULTI-5000, Fujidempa, Japan) at 1850
C Ior 0.5, 1 and 2 h under a N
2
gas pressure oI 1 MPa
and a Ilow rate oI 2 lit/min. The properties oI the sintered
specimens were characterized as Iollows: mass loss by
comparing the mass beIore and aIter sintering, bulk
density by Archimedes` method, Vickers hardness and
Iracture toughness by indentation method, and Ilexural
strength by three-point bending method in conIormity
with JIS R1610-1991 using a universal testing machine
(Instron 5844, USA). Microstructure oI the specimens
C04
was observed under scanning electron microscope (SEM)
(FE-SEM, S-4800, Hitachi, Japan).
3. Results and Discussion
(1) Mass loss
As seen in Fig. 1, mass loss oI the sintered specimens
increased as a Iunction oI soaking time. The major mass
loss reaction oI Si
3
N
4
may be related to the reaction oI
surIace silica (SiO
2
) covered on Si
3
N
4
particles and Si
3
N
4
.
The chemical reaction can be written as Iollows: |6-7|
Si
3
N
4
(s) 3SiO
2
(s,l) 6SiO (g) 2N
2
(g)
Soaking time (h)
0 1 2 3 4 5 6 7
M
a
s
s

l
o
s
s

(

)
2
3
4
5
6
7
8
9
10

Fig. 1 Mass loss oI specimens sintered at 1850 C as a
Iunction oI soaking time
(2) Densitv
The eIIect oI soaking time on the density oI sintered
specimens is shown in Fig. 2. From the result, bulk
density oI specimens sintered with soaking time oI 0.5, 2
and 6 h are 3.14, 3.16 and 3.20 g/cm
3
, respectively, which
correspond to the relative density oI approximately 98, 99
and 100 theoretical density. The soaking time oI 0.5 h
led to the lowest density, suggesting that 0.5 h is
kinetically insuIIicient Ior completion oI sintering
process.
3.10
3.12
3.14
3.16
3.18
3.20

Soaking time (h)
97
98
99
100
Bulk density
Relative density
0.5 2 6
B
u
l
k

d
e
n
s
i
t
y

(
g
/
c
m
3
)
R
e
l
a
t
i
v
e

d
e
n
s
i
t
y

(

)
Fig. 2 Bulk density and relative density oI specimens
sintered at 1850 C as a Iunction oI soaking time

(3) Microstructure
The microstructure oI specimens sintered with
soaking time oI 0.5 and 6 h is shown in Fig. 3. The 0.5 h
specimen has equiaxed grains with monomodal size
distribution, uniIorm microstructure and some amount oI
porosity. The porosity and small grain size are attributed
to insuIIicient soaking time at the maximum sintering
temperature; thereIore, its density is lower than that oI 6 h
specimen. For the 6 h specimen, it shows bimodal size
distribution with large grains dispersed in small grain
matrix due to the longer soaking time and Ostwald
ripening |2,8|. No porosity was observed in this
specimen. It means that the soaking time is enough to get
high density specimen and much grain growth oI large
grain. However, there was not so much amount oI needle-
like grain (high aspect ratio) occurred in this specimen
because oI the sintering temperature was too low |8|.

(a) 0.5 h

(b) 6 h
Fig. 3 SEM micrograph oI specimens sintered at 1850 C
with diIIerent soaking times
(4) Mechanical properties
As seen in Fig. 4, the Ilexural strength oI specimens
C04
(M2A2) with soaking time oI 0.5, 2 and 6 h was 491,
544 and 528 MPa, respectively. The strength oI 2 h and 6
h specimens is insigniIicantly diIIerent, but the strength
oI 0.5 h specimen is quite lower than that oI the others
due to the lower density and much higher porosity.
Vickers hardness (Hv) and Iracture toughness (K
IC
)
oI specimens (M2A2) sintered with diIIerent soaking
times are shown in Fig. 5. Hv and K
IC
oI 0.5, 2 and 0.6 h
specimens were 12, 16 and 14 GPa, respectively. The 0.5
h specimen exhibited lower Hv than that those oI 2-h and
6-h sintered specimens because its density is lower.
Although the density oI 2 h specimen is similar to 6 h
specimen, Hv oI 6 h specimen is lower than 2 h
specimen. It was supposed that the decreasing oI Hv is
due to the enlargement oI grain size, because a decrease
in grain size is accompanied by an increase in hardness as
the dislocations generated by the indenter are blocked by
the grain boundaries |9|. For the K
IC
, the K
IC
oI 0.5 h, 2 h
and 6 h specimens were 5.2, 5.9 and 5.7, respectively.
The values are similar in all oI the specimens.
Soaking time
0.5h 2h 6h
F
l
e
x
u
r
a
l

s
t
r
e
n
g
t
h

(
M
P
a
)
0
100
200
300
400
500
600
700

Fig. 4 Flexural strength oI specimens sintered at 1850 C
with diIIerent soaking times
0.5 h 2 h 6 h
0
2
4
6
8
10
12
14
16
18
Vickers hardness (GPa)
Fracture toughness (MPa m
1/2
)

Fig. 5 Hardness (Hv) and Iracture toughness (K
IC
) oI
specimens sintered at 1850 C with diIIerent soaking
times

4. Conclusion
Mass loss and density oI sintered Si
3
N
4
ceramics
increase as a Iunction oI soaking time. The rod-like shape
(high aspect ratio) microstructure could not be achieved
by prolonging the soaking time. The mechanical
properties oI specimens decreased when the soaking time
is prolonged (6 h). The highest mechanical property
values: Ilexural strength, 544 MPa, Vickers hardness, 16
GPa and Iracture toughness, 5.9 MPa m
1/2
are in the
specimen sintered at 1850 C Ior 2 h with 2 wt MgO
and 2 wt Al
2
O
3
additives.
Acknowledgements
The authors would like to express our gratitude to
Thailand Graduate Institute oI Science and Technology
(TGIST) Ior the Iinancial support oI Mr. Nirut
Wangmooklang, under contact TGIST 01-47-010 and
express to Mr. Thanakorn Wasanapirnpong Ior his kindly
help with the SEM observation.
References
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Department oI Materials Science, Faculty oI Science,
Chulalongkorn University, 2004.
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(2000).
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rd

Thailand Masterials Science and Technology
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|7| Yokoyama, K. and Wada, S. J. Ceram. Soc.
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(1988).
|9| McColm, I. J., Ceramic Hardness., Plenum Press,
New York and London, 1990.

C04