Synthesis of dense mullite/MoSi

2
composite for high
temperature applications
Z.I. Zaki
a,b,
, Nasser Y. Mostafa
a,c
, Y.M.Z. Ahmed
b
a
Chemistry Department, Faculty of Science, Taif University, P.O. Box: 888, Al-Haweiah, Taif-Saudi Arabia
b
Advanced Materials Division, Central Metallurgical R&D Institute (CMRDI), P.O. Box: 87, Helwan, Cairo, Egypt
c
Chemistry Department, Faculty of Science, Suez Canal University, Ismailia 41522, Egypt
a b s t r a c t a r t i c l e i n f o
Article history:
Received 12 December 2013
Accepted 6 March 2014
Available online 18 March 2014
Keywords:
Synthesis
Mullite
MoSi
2
Oxidation
Electrical characters
This work is aimed at producing a dense mullite/MoSi
2
composite froma reactive blend of MoO
3
, SiO
2
and Al by
under load-combustion synthesis. Thermodynamic analyses proved the development of the entire combustion
product in molten state with an adiabatic temperature of 2340 K. Diluting the reaction mixture with 25 vol.%
of the combustion product was necessary to produce homogeneity between the obtained phases. The sample
porosity was reduced to ~3.0 vol.% by controlling the pressing load, Al particle size and the delay time. The coef-
cient of thermal expansion of the obtained product was 5.968.93 10
6
K
1
. The obtained dense composite
exhibited good oxidation resistance at 1300 C and a low electrical resistivity (1.80 cm).
2014 Elsevier Ltd. All rights reserved.
Introduction
Due to its unique properties (thermal, electrical and chemical) in
addition to its moderate density, MoSi
2
has received the attention of
many research groups. Despite its weak mechanical properties and
pest oxidation problems, MoSi
2
composites are becoming important
elevated temperature structural materials for application in oxidizing
and aggressive environments specially as heating elements in high
temperature furnaces [1]. On the other hand, mullite (3Al
2
O
3
2SiO
2
),
a typical solid solution oxide, combines high melting point, lowthermal
expansion, low electrical conductivity, good mechanical strength and
resilience at elevated temperatures. Therefore, it is considered as a
potential candidate material for structural applications such as kiln
furniture, protection tubes, and heat insulation parts [2].
MoSi
2
is thermodynamically stable with mullite and a variety of
other ceramic reinforcements, including TiC, ZrO
2
, Al
2
O
3
, TiB
2
, SiC and
Si
3
N
4
[311]. MoSi
2
has also been employed as a conducting phase in
Si
3
N
4
MoSi
2
particulate composites [10]. Alumina composites with
20 vol.% and higher MoSi
2
are electroconductive due to the formation
of a three-dimensional percolating network of the conductive MoSi
2
phase [7,12]. Other composites of MoSi
2
with Mo
5
Si
3
[13], WSi
2
[14],
and ZrB
2
[15,16] were also reported. A composite between MoSi
2
and
mullite is rarely mentioned in the literature. In a trial to improve the
mechanical properties of MoSi
2
by the powder metallurgy route, some
authors used mullite and mullite whisker as reinforcement [17]. Mullite
containing 20 vol.% MoSi
2
was synthesized by hot pressing a mixture of
mullite and MoSi
2
powders at 1650 C with 69 MPa for 2 h. The product
was found to have a K
lc
and strength values up to two times that of
monolithic mullite [18].
Various starting materials and preparation methods have been used
to prepare synthetic mullite and MoSi
2
ceramics. These include reaction
sintering of mechanically mixed powders [1924], hydrothermal treat-
ment of mixtures of sols [2527], and chemical vapor deposition
[2831] for synthesis of mullite. On the other hand, mechanical alloying
[4,32], hot pressing [16], reactive sintering [33], plasma-spray processing
[34] and self-propagating high-temperature synthesis (SHS) are used for
synthesis of MoSi
2
[13,35,36].
Self-propagating high-temperature synthesis (SHS) is one of the
rapidly emerging cost-effective technologies used to synthesize
monolithic and composite in situ ceramics [35,37]. The principle of
this technique is that the initial reagents, when ignited, spontaneously
transform into products due to the exothermic heat of the reaction.
The major problem to overcome in the SHS processing of refractory
ceramics is the high-retained porosity of the synthesized products.
However, applying sudden mechanical pressure during the reaction
has resulted inhighly dense materials [38,39]. The densicationbehavior
inthat case is only due to the compactionand is favored by the formation
of liquid phases during the reaction [39]. The very short processing time
of typical SHS reactions limits the diffusion phenomena responsible for
the material shrinkage in other processes [40]. Therefore SHS under the
load process represents a one-step manufacturing route capable of
Int. Journal of Refractory Metals and Hard Materials 45 (2014) 2330
Corresponding author.
http://dx.doi.org/10.1016/j.ijrmhm.2014.03.006
0263-4368/ 2014 Elsevier Ltd. All rights reserved.
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Int. Journal of Refractory Metals and Hard Materials
j our nal homepage: www. el sevi er . com/ l ocat e/ I JRMHM
producing highly dense composites with a homogeneous distribution of
the different phases. Another serious drawback of SHS is it's limitation to
a highly exothermic reaction. Recently, successful management of the
heat evolved from the common SHS reactions have enabled carrying
out side endothermic reactions [36,41,42].
In a previous work, we have successfully prepared a MoSi
2
/mullite
composite in a self sustaining manner without applying external
mechanical pressing. The product unfortunately was highly porous,
cracked and was non-homogeneous [42]. The aim of the current work
is to in-situ develop a high density and homogeneous composite of
MoSi
2
and mullite starting from relatively low cost raw materials
(MoO
3
, SiO
2
and Al) by applying sudden external mechanical pressing.
Designing a composite of MoSi
2
and mullite will result in the fabrication
of a new low cost ceramic conductor that can be easily shaped using an
electric discharge machine and can be used as a heating element. Both
MoSi
2
andmullite resist oxidationat hightemperature andare thermody-
namically stable with each other. The mullite phase will be the matrix
while the MoSi
2
phase will be responsible for conducting the electricity
through that matrix. SHS under load methodology is chosen to perform
simultaneous synthesis and densication of MoSi
2
and mullite where
the technical parameters controlling the process are studied. These
parameters include: diluent vol.%, pressing load, Al particle size and
delaying time. To the best of our knowledge this composite did not syn-
thesize before as a dense object by SHS methods especially from these
starting materials.
Experimental
The materials used in this study were molybdenumtrioxide of 99.5%
purity and 15 m average particle size (Atlantic Equipment Engineers,
NJ, USA), aluminummetal powder of 99.5% purity and different average
particle sizes of 52.3, 37, 18.5 and 5.6 m(GFS Chemicals, Inc., USA) and
silica of 11 m average particle size with 99% purity (Riedel-de Haen,
Germany). Particle size distributionof the rawmaterials was investigated
using Microtrac Bluewave particle size analyzer operated with FLEX soft-
ware (Microtrac S3500). The wet samples were inserted as a suspension
with double distilled water. Ultrasonic waves were used for making the
suspension more homogenous. The powders were mixed in the required
molar ratio to form MoSi
2
-7/9 mullite composite and dry blended in a
slow rotating mill with alumina ball for 5 h. The powder mixture was
uniaxially pressed without a binder at 78 MPa into a cylindrical compact
of 15 mm height and 20 mm diameter with an approximately 55% rela-
tive density. The compact was transferred into a combustion reactor
andplacedintoa steel die lledwithsandwhere the mechanical pressure
was applied on the movable punch. The pressure was transferred to the
green compact through a sand medium. Ignition of samples is carried
out in thermal explosive mode using a resistance coil placed around the
compact. All the work was conducted under vacuum. A detailed proce-
dure of carrying out combustion reactions was provided elsewhere [39].
The electricity was supplied from an AC power source (3040 A). Linear
thermal expansion (LTE) and the coefcient (CTE) of its dense product
were measured using dilatometery (Linseis Inc., Germany, Model L76/
1550) in the temperature range of 200 up to 1250 C with a heating
rate of 10 C/min. The electrical resistivity investigation was carried
out in air under one atmospheric pressure from a room temperature
of up to 900 C with a heating rate of 2 C/min. The data (temperature
vs resistivity) were recorded every 2 min. Oxidation resistance of the
combustion product was investigated in open atmosphere at 1300 C
for 3 hinorder to determine the thermodynamic stability (compatibility)
between the obtained phases of MoSi
2
and mullite. Weight changes
during oxidation were measured by means of an automatic weight re-
cording balance.
Different phases of the combustion products were identied by
X-ray diffraction analysis using an X-ray diffractometer (D8 Advanced
Bruker AXS, GMbH, Karlsruhe, Germany). The microstructure of speci-
mens was investigated using a scanning electron microscope (SEM,
Model JSM-5410, JEOL, Tokyo, Japan) equipped with electron dispersive
spectroscopy (EDX). SEM investigation is conducted on polished
surfaces coated with gold to ensure good electrical conductivity of the
entire components of the sample. Sample porosity was measured via
Archimedes' method (submersion in water).
Results and discussions
Adiabatic temperatures and molten factions
The combustion process of this work is based on the following reac-
tions:
MoO
3
2SiO
2
14=3Al MoSi
2
7=3Al
2
O
3
H 1470kJ 1
7=3Al
2
O
3
14=9SiO
2
7=9 3Al
2
O
3
2SiO
2
H 52:6kJ 2
MoO
3
2SiO
2
14=3Al 14=9SiO
2
MoSi
2
7=9 3Al
2
O
3
2SiO
2
H 1417:4kJ :
3
It could be easily noticed that reaction (1) is highly exothermic while
reaction (2) is endothermic in its nature. However, according to the
endothermic nature of the reaction (2) it could not proceed alone in a
self-sustaining manner. Meanwhile, the addition of SiO
2
to the reactant
of reaction (1) in a stoichiometric amount (14/9 mol) equivalent to the
quantity of liberatedalumina (7/3 mol) generates the overall reaction(3).
This reaction (3) was found to be highly exothermic in which the heat re-
leased by the progress in reaction (1) will support reaction (2). On the
other handreaction(3) seems to be a complicatedone whichcanbe com-
posed of many reactions. The possible reactions that can compete to yield
reaction (3) and their thermodynamic properties are organized in a con-
secutive manner according to its expected order and given in Table 1.
Regarding reaction (3), the adiabatic combustion temperature and
the fractions of molten phases of the products can be calculated from
the following equation:
H
r;298

Z
To
298
C
p
MoO
3
2SiO
2
14=3Al 14=9SiO
2
dT

Z
2303
298
C
p
MoSi
2

s
dT 7=9
Z
2123
298
C
p
3Al
2
O
3
2SiO
2

s
dT
H
f;MoSi2
7=9H
f;3Al2O32SiO2
4
where, H
(r,298)
is the enthalpy change of reaction (3), C
p
is the specic
heat capacity, H
(f,MoSi2)
and H
(f,3Al2O32SiO2)
are the enthalpies of
fusion [42], and and are the molten fractions of MoSi
2
and mullite
respectively.
Fig. 1 shows the adiabatic temperatures and the molten fractions of
mullite and MoSi
2
phases calculated from Eq. (4) as a function of initial
temperatures. It is found that the adiabatic temperature at 298 K is
equal to 2340 K. This temperature exceeds the melting points of mullite
(2123 K) and MoSi
2
(2303 K). This means that both phases will be
produced in the molten states. This could be a good point in order
to produce a highly dense mullite/MoSi
2
structure via compaction
during the reaction progress.
Table 1
Expected sequence of the reactions involved in the combustion process.
Reaction H, kJ G, kJ
1 MoO
3
+ 2Al = Mo + Al
2
O
3
927.5 911
2 3SiO
2
+ 4Al = 3Si + 2Al
2
O
3
614.1 589
3 Mo + 2Si = MoSi
2
131.3 115
4 3Al
2
O
3
+ 2SiO
2
= (3Al
2
O
3
2SiO
2
) 67.6 56.0
24 Z.I. Zaki et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 2330
Synthesis of mullite/MoSi
2
composite
The work is started using a sample having aluminum with an
average particle size of 37 m and ignited by a thermal explosion
mode. A compaction pressure of 82 MPa is suddenly applied during
the reaction. The combustion product was characterized by phase
identication using XRD analysis, shown in Fig. 2. The pattern
revealed that MoSi
2
and mullite appear as the main phases while alu-
mina appears as a minor one. On the other hand no peaks character-
istic for the starting materials are detected. This indicates that the
reaction between the starting precursors have been going to comple-
tion according to reaction (3) using thermal explosion mode under
applied pressure. However the microstructure homogeneity of such
a composite is regarded as one of the highly important parameters
that have a direct impact on its physicmechanical properties. Ac-
cordingly the microstructure of the produced composite has been in-
vestigated via SEM analysis. Fig. 3a presents the SEM micrograph of
the produced composite. It could be noticed that there is almost a com-
plete separation between the different phases such that one big MoSi
2
ball is developed at the center of the specimen and other small ones
are found embedded into the mullite matrix. This could be attributed
to the fact that the combustion temperature of reaction (3) is very
high (T
ad
= 2340 K) as shown in Fig. 1. This temperature exceeds the
melting points of MoSi
2
(2303 K) and that of mullite (2123 K) causing
a high agglomeration of the melting MoSi
2
phase especially during
compaction. This inhomogeneous microstructure is responsible for de-
teriorating all the physicalmechanical properties of the produced
composite.
Fig. 1. Adiabatic combustion temperatures and molten fractions of MoSi
2
& mullite as a function of initial temperature and dilutions.
Fig. 2. XRD of combustion product prepared by using samples having 37 m Al particle size pressed during the reaction at 82 MPa.
25 Z.I. Zaki et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 2330
According to the previous investigation, the vigor of the reaction (3)
should be inhibited to some extent for preventing the agglomeration of
the molten MoSi
2
during compaction. One solution is the addition of
diluents which could compensate some of the heat evolved from re-
action (3) and decreasing the probabilities for agglomeration of the
molten MoSi
2
phase. In this regard and in order to keep the sample
Fig. 3. SEMimages of combustion products containing: a) no diluents b) 20 vol.% dilution c) 25 vol.% dilution and BES images of d) 30 vol.% dilution pressed during the reaction at 82 MPa.
Fig. 4. Effect of dilution amount, pressing load and Al average particle size on the combustion product porosity.
26 Z.I. Zaki et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 2330
composition without changes the combustion product of reaction (3) is
crushed, pulverized to pass a 20 m sieve and used as a diluent. In this
case the combustion reactions will be proceeding as follows:
MoO
3
2SiO
2
14=3Al 14=9SiO
2
x MoSi
2
7=9 3Al
2
O
3
2SiO
2

1 x MoSi
2
7=9 3Al
2
O
3
2SiO
2
H 1417:4 kJ
5
where x, is the weight percentage of the diluents.
Regarding reaction (5), the adiabatic combustion temperature and
the fractions of molten phases of the products can be calculated from
the following equation:
H
r;298

Z
To
298
Cp

MoO
3
2SiO
2
14=3Al 14=9SiO
2
x

MoSi
2
7=9 3Al
2
O
3
2SiO
2

dT 1 x

Z
2303
298
Cp MoSi
2

s
dT

Z
Tad
2303
Cp MoSi
2

1
dT 7=9 1 x

Z
2123
298
Cp 3Al
2
O
3
2SiO
2

s
dT

Z
Tad
2123
Cp 3Al
2
O
3
2SiO
2

1
dT

1 x H
f;MoSi2
7=9 1 x H
f;3Al2O32SiO2
6
where, x is the number of moles of the product which is added to the
reaction media as a diluent.
For comparison, the adiabatic temperatures and the molten frac-
tions of mullite and MoSi
2
phases as a function of initial temperatures
and dilution volume percentage are assembled in Fig. 1. It is clear that
increasing the amount of diluents in the reaction medium at any value
of the initial temperature leads to a parallel decrease in adiabatic tem-
perature. This could be highly useful in controlling the microstructure
of the produced product. The XRD of all samples produced with different
dilution amounts varied from 10 to 30 wt.% (not shown) and revealed
that the target composite of mullite/MoSi
2
is the main phase without de-
tection of any peaks for the reactant precursors. The addition of dilution
did not affect the phase composition of the produced sample according
to the fact that it is one of the products during the reaction between the
starting precursors. The microstructure of the sample produced with dif-
ferent dilution percentages (20, 25, and 30 wt.%) are investigated and
compared with that of the sample without dilution, Fig. 3. It reveals a reg-
ular decrease in the particle size of MoSi
2
(from several mm to few m)
with a signicant improvement in the homogeneity among sample
phases with an increasing diluent volume percentage. At 20 vol.% dilu-
ents (Fig. 3b), although a large agglomerate of MoSi
2
phase is still present
in the combustion product, its amount as well as particle size are largely
reduced compared with one without a dilution (Fig. 3a). However, a
complete disappearance of agglomerated phase is achieved at 25 vol.%
diluents (Fig. 3c). This could be attributed to the continuous decrease in
the combustion temperatures and the molten fractions of mullite and
MoSi
2
phases by increasing the amount of diluents. With a further in-
crease in the dilution addition to 30 vol.% (Fig. 3d), although a homoge-
neous microstructure is also produced, a higher degree of porosity
could be clearly noticeable. The behavior of increasing sample porosity
with dilution addition was clearly observed in all samples. The porosities
of these samples were measured and given in Fig. 4. These measured
porosities conrmed the observation from SEM images that the porosity
of the sample increased with an increase in the amount of diluents.
Although the sample having a 25 vol.% diluent has a higher porosity
than the 0, 10 and 20 vol.% diluents' samples, it has the highest degree
of homogeneity among its phases. Accordingly, a trial was made for
enhancing the densication parameter of such sample via varying the
pressing load during the reaction.
The effect of different pressing loads (82292 MPa) on the sample
open porosity is investigated using the sample having a 25 vol.% dilution
and the results are shown in Fig. 4. It is found that the pressing load has a
strong effect on the sample porosity such that a sharp decrease in
the sample porosity is achieved. The sample porosity is reduced to
~3.65 vol.% upon applying a mechanical pressure of 117 MPa and
falls to 2.09 vol.% at 234 MPa. While with further increase in the
pressing load (at 292 MPa) there is not much of an enhancement in
sample porosities noticed. On the other hand SEM investigation of the
microstructure of the sample pressed at 234 shows homogeneous
distribution of the different phases such that no collection of phases is
formed due to pressing (Fig. 5a). This is a conrmation that increasing
the pressing load enhances the densication parameter of such com-
posite without any changes in both phase formation as well as the
microstructure homogeneity.
However, it is well known that the Al particle size usually plays a very
important role during the combustion synthesis process. Accordingly,
the effect of reducing Al particle size (52.3, 37, 18.5 and 5.6 m) on
the porosity and microstructure of the product is investigated under
Fig. 5. BES images of combustion product containing 25 vol.% diluent pressed at 234 MPa,
a) using 37 mparticle size Al, b) 5.6 mparticle size Al, and c) 37 mparticle size Al after
20 s of reaction.
27 Z.I. Zaki et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 2330
the mechanical pressing of 234 MPa with the sample containing
25 vol.% diluent. This trial was made in order to reduce the sample
porosity of the produced sample as much as possible. Fig. 4 illustrates
the effect of Al particle size on the porosity of the samples. This gure
shows that reducing the Al particle size to 5.6 m leads to an increase in
the porosity of the sample. This is because ner Al particle size usually
leads to vigorous reactions. On the other hand, increasing Al particle
size from 37 to 52.3 m does not affect the porosity of the sample. Al-
though the sample produced using Al 5.6 m still has a low porosity
(~4.6 vol.%), it suffers from non-homogeneity between phases such that
agglomerations of MoSi
2
are noticed as it can be seen from the SEM
image (Fig. 5b). These results revealed that although the particle size of
Al could play an important role during the reaction between the starting
precursors, it did not affect the densication parameter of the sample
using the modied SHS technique.
Another trial for enhancing the sample porosity is to control the
delay time at which the pressing load is applied. Delaying the time of
pressing is important in some cases in order to give enough time for
the gases evolved during combustion to release. This may help in reduc-
ing the sample porosity. Therefore the pressing loadis investigatedbefore
the beginning of the reaction, during the reaction, and 5, 10, 15 and 20 s
after the reaction has nished. The effect of delay time on the porosity of
the samples is given in Fig. 6. It is concluded that pressing the sample at
any time after starting the reaction and up to 10 s after the reaction has
nished leads to almost the same sample porosity. Delaying the pressing
time for more than 10 s leads to an increase in the sample porosity due to
a dramatic reduction of the combustion temperature with time. This
behavior is also noticed during SEM investigation (Fig. 5c).
Composite properties
Coefcient of thermal expansion
Althoughoptimizing the controlling parameters lead to a highdensity
composite, it suffers fromthe existence of microcracks. The coefcient of
thermal expansion (CTE) as a function of temperature (2001250 C) is
Fig. 6. Effect of delay time on the sample porosity.
Fig. 7. Coefcient of thermal expansion and electrical resistivity behavior of the dense product at different temperatures.
28 Z.I. Zaki et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 2330
given in Fig. 7. It can be seen that the presence of MoSi
2
(~18.96 vol.%) as
a second phase increases the CTE of the mullite matrix (5.968.9310
6
K
1
) compared with CTE of pure mullite in the same temperature range
(4.46.510
6
K
1
). This means that during cooling, the mullite matrix
will suffer from thermal stress that causes the development of such
cracks. On the other hand, a simple calculation of volume changes
shows that reaction (3) is accompanied by a decrease in volume equal
to 18% due to the conversion of the reactants to the product. The fast
reaction and sudden cooling behavior of combustion synthesis and the
mismatch in the thermal expansion coefcient between MoSi
2
and
mullite may contribute to the formation of cracks.
Electrical resistivity
The electrical resistivity behavior at different temperatures is given in
Fig. 7. The measured electrical resistivity of this composite is 1.8 cmat
room temperature. This reects its good electrical conductivity at room
temperature which will facilitate its machining into complex shapes by
using the economical electrical discharge machining (EDM) technique.
This technique essentially needs the component tobe electrically conduc-
tive (resistivity b 100 cm) [33]. By increasing the temperature, the
electrical resistivity slightly increases as a common behavior for resis-
tance heating elements.
Oxidation resistance investigation
Oxidation resistance of the dense combustion product was carried
out in open atmosphere at 1300 C for 3 h. No weight gains or weight
losses were noticed. This ensures that this composite has good resistance
to oxidation within the investigated temperature range. XRD pattern of
the oxidized specimen at 1300 C, Fig. 8, shows the existence of a SiO
2
cristobalite phase and a weak diffraction pattern of alumina. There is no
evidence for the decomposition of MoSi
2
to the Mo-rich phase (Mo
5
Si
3
)
as commonly reported for samples containing MoSi
2
[31,32]. This could
be attributed to the embedding of MoSi
2
grains in the mullite matrix
which prevents direct contact between MoSi
2
grains and atmospheric
oxygen.
Conclusion
Combustion synthesis under load methodology has been successfully
used to produce a high density mullite/MoSi
2
composite having less than
3.0 vol.% porosity. The sample treated without dilution was totally
inhomogeneous. The addition of a 25 vol.% combustion product as a
diluent was necessary to produce a homogeneous product. The lowest
sample porosity was achievedupon applying 234 MPa mechanical pres-
sure during the combustion reaction. Using Al with an average particle
size less than 37 mwas found to increase sample porosity. The obtain-
ed high density composite has good oxidation resistance at 1300 C and
low electrical resistivity (1.8 cm) at room temperature. The mea-
sured coefcient of the thermal expansion of this product was 5.96
8.93 10
6
K
1
in the temperature range of 2001250 C.
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