j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 5 ( 2 0 0 8 ) 224–231

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Carbothermal synthesis of silicon nitride (Si3 N4 ):

Kinetics and diffusion mechanism

A. Ortega ∗ , M.D. Alcalá, C. Real

Instituto de Ciencias de Materiales de Sevilla, Centro Mixto C.S.I.C./Universidad de Sevilla,
Av. Americo Vespucio no. 49, 41092 Sevilla, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Sample controlled reaction temperature (SCRT) has been used for the first time to study the
Received 4 May 2006 kinetics of the carbothermal reduction of silica in nitrogen to obtain silicon nitride (Si3 N4 ).
Received in revised form It is noteworthy to point out that SCRT method allows both a good control of pressure in the
26 April 2007 sample surroundings and the use of reaction rates low enough to keep temperature gradi-
Accepted 3 May 2007 ents at a negligible level to avoid any heat or mass transfer phenomena. It has been shown
that the carbothermal synthesis of silicon nitride is best described by a two-dimensional
diffusion kinetic model with an activation energy of about 306 kJ/mol. Effects of experimen-
Keywords: tal parameters on the activation energy has been investigated. By using SCRT it has been
Sample controlled reaction possible to obtain ceramic powder with a determined phase composition and a controlled
temperature (SCRT) microstructure.
Diffusion mechanism © 2007 Elsevier B.V. All rights reserved.
Kinetic mechanism
Silicon nitride carbothermal
reduction
Kinetic model

1. Introduction the carbothermal reduction and nitridation of silica, direct

Silicon nitride Si3 N4 is an advanced ceramic compound suit-
able for structural applications at high temperature. Important
progress has been made in the development of ceramic mate-
rials, especially those which are expected to be widely used
in structural applications. Silicon nitride is one of the most
promising materials in this class and has attracted much
attention in material engineering due to their technologically
interesting properties (Liang et al., 1999; Segal, 1991; Gogotsi
and Andrievski, 1999). Small dense sintered silicon nitride
components are used in both automobile and truck engines
for applications where stresses and temperatures are rela-
tively low and the consequence of failure is not catastrophic.
The most prevalent methods of silicon nitride preparation are
nitridation of silicon, and thermal decomposition of silicon
diimide (Van Dijen and Vogy, 1992; Ekelund and Forslund, 1992;
Barsoum et al., 1991; Pigeon et al., 1993; Lange et al., 1991;
Moulson, 1979; Ziegler et al., 1987; Ziegenlag et al., 1999; Segal,
1986; Hashishin et al., 1999; Weimer et al., 19972853; Komeya
and Inoue, 1975; Siddiqi and Hendry, 1985; Durham et al., 1991;
Hanna et al., 1985; Alcala et al., 2002). The carbothermal reduc-
tion takes place according to the following overall reaction:
3SiO2 + 6C + 2N2 = Si3 N4 + 6CO (1)
It is generally accepted in the literature (Komeya and
Inoue, 1975; Siddiqi and Hendry, 1985; Durham et al., 1991;
Yoshimatsu et al., 1989; Sanyal et al., 1991) that this reac-

∗
Corresponding author.
E-mail address: aortega@us.es (A. Ortega).
0924-0136/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2007.05.004
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 5 ( 2 0 0 8 ) 224–231 225

tion occurs through the formation of an intermediate SiO essary to promote the formation of Si3 N4 from SiO2 . This
vapour phase. Moreover, the competitive formation of sili- excess influences the temperature of reaction and the prod-
con carbide has been reported at temperatures higher than uct composition. The optimum amount of carbon depends on
1500 ◦ C. Si3 N4 occurs in two phases ␣ and ␤. The ␣ phase pow- the composition of reactants and on the system developed
der is the generally preferred raw material for manufacturing for performing the carbothermal synthesis. The percentage of
compacted bodies because of the favourable microstructural ␣-Si3 N4 and ␤-Si3 N4 were determined from the intensities I␣
characteristics obtained during the ␤ transformation at high and I␤ of the (2 0 1) ␣-Si3 N4 and (1 0 1) ␤-Si3 N4 X-ray diffraction
temperatures (Wild et al., 1972; Mitomo et al., 1990; Wendel peaks, respectively, applying the direct comparison method
and Goddard, 1992). This fact explains that a number of (Cullity, 1978). The following expression was calculated for
authors have paid attention to study the influence of the determining the fraction x␣ of the ␣-Si3 N4 phase:
experimental conditions on the structure of the final products
of reaction (Liang et al., 1999). Ekelund and Forslund (1992) 1
x␣ = (2)
have investigated this reaction at temperatures up to 1550 ◦ C 1 + 0.688(I␤ /I␣ )
and have concluded that ␣ formation is promoted by increas-
2.2. Methods
ing the synthesis temperature, contrarily to what would be
expected considering that ␤-Si3 N4 is the most stable phase at
The kinetic experiments were carried out by SCRT method.
high temperature. However, it is necessary to take into account
The SCRT equipment is constituted by a high temperature
that the higher the CO formation rate according to Eq. (1) the
tubular furnace of mullite of 25 mm of inner diameter and a CO
higher is the partial pressure of this gas in the close vicin-
IR sensor interfaced to the furnace temperature controller. The
ity of the sample. Thus, the increase of the percentage of
sample, constituted by a mixture C/SiO2 , was located into an
␣-Si3 N4 reported by Ekelund perhaps could be explained by
alumina boat. Both the flow rate of nitrogen and the concen-
considering that the formation of this phase is promoted by
tration of hydrogen was regulated by means of two mass flow
increasing the CO concentration around the sample (Alcala
controllers The flowing gas sweeps the CO generated in the
et al., 2002). The PCO during synthesis has been found to be
reaction through the CO IR detector ADC, model SB 300, with
of great importance for the conversion achieved in carbother-
a single range 0–2% associated to a linear analogical output of
mic experiments (Ekelund and Forslund, 1992; Durham et al.,
1 V f.s.d. This electrical signal was interfaced to the furnace
1991; Alcala et al., 2002; Higgings and Hendru, 1986; Kormeijer
through a PID (Proportional,Integral,Differential) controller in
et al., 1990). Monitoring low values of CO around the sample
such a way that the CO concentration was maintained con-
is very difficult, since the gas is a reaction product. Thus heat
stant at the value previously selected by the user. Since the
treatment is a critical step in the preparation of these materi-
CO pressure was maintained constant and that the reaction
als from the precursors, a careful study of the heat treatment
rate is proportional to the gas pressure generated, the reaction
would help to clarify the relation between the preparation
rate will be constant in the entire process. The reaction rate at
method and the properties.
every particular concentration of CO can be chosen by properly
Previous investigators show that the process of preparing
selecting the nitrogen flow rate. This instrument allows one
Si3 N4 from SiO2 or Si is complicated (Vlasova et al., 1995;
to maintain constant pressures in the range 10−3 to 130 Pa.
Beruto et al., 2003; Liou and Chang, 1996). Therefore a suit-
The temperature was measured with precision because the
able method for controlling external parameters (PCO , etc.) is
thermocouple was placed very near to the sample.
needed. To overcome this problem we use a new and pow-
erful experimental arrangement that permits a precise and
2.3. Characterization
independent control of both the reaction rate and the con-
centration of CO self generated in the reaction. The sample
The XRD diagrams of the final product was recorded with a
controlled reaction temperature (SCRT) (Perez-Maqueda et al.,
difractometer Philips, model 1060 equipped with a scintilla-
1999), is a method that implies to use the own sample for
tion counter using Cu K␣ radiation and a primary graphite
controlling the reaction temperature and it provides the pos-
monochromator, the scanning rate of the goniometer was
sibility of producing powders with controlled particle size,
0.4◦ min−1 . The estimated standard deviations (ESD) was <5%.
morphology and crystalline structure. It has higher sensitivity
The SEM pictures were recorded with a Philips XL30 micro-
and resolution than conventional methods (TG, etc.). Our aim
scope at 30 kV.
is to present a contribution to the knowledge of the mecha-
nism of this reaction and to calculate its activation energy.
3. Synthesis and characterization of silicon
nitride
2. Experimental
Four samples of silicon nitride was synthesized by employ-
2.1. Materials ing SCRT method through carbothermal reduction of SiO2 in
nitrogen atmosphere. Fig. 1 shows, by way of example, a plot
Silica and carbon from Aldrich with a specific area of 280 m2 /g of the evolution of the temperature and partial pressure of CO
and 1500 m2 /g, respectively were used. A mixture of 95% nitro- for the carbothermal synthesis of Si3 N4 recorded, as a func-
gen and 5% hydrogen was used, as reaction gas. As raw tion of time at a reaction rate of C = 0.0007 min−1 and a partial
material, a SiO2 /C mixture in a molar ratio 1/5.5 was used. pressure of CO of 0.0050 atm. The CO generated in the reaction
We use this molar ratio because an excess of carbon is nec- was maintained constant all over the experiment. The reacted
226 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 5 ( 2 0 0 8 ) 224–231

results seem to show that the reaction temperature has not

influence on the phase composition of the final product.
On the other hand, to evaluate the morphology of the differ-
ent samples, a study by scanning microscopy was performed;
the results are shown in Fig. 3. The micrographs show that the
sample 1, obtained at the lowest reaction rate, is constituted
by ribbons (long cylinders) while the sample 4, obtained at the
highest reaction rate, is constituted by hexagonal crystallites
(two-dimensional conformation) with homogeneous size. The
higher crystal size of the sample 4 would be explained by tak-
ing into account that this sample was obtained at a higher
temperature than sample 1.

4. Kinetics
Fig. 1 – Evolution of the temperature and partial pressure of
CO recorded, using SCRT, as a function of time for the If we use ˛ to denote the extent of reaction, then the basic
carbothermal synthesis of Si3 N4 at 0.0050 atm of CO. kinetic rate equation is usually taken as:

d˛
= K(T)f (˛) (3)
dt

where T is the temperature and K(T) is the temperature-

dependent rate constant:
 E

K(T) = A exp − (4)
RT

A and E are the pre-exponential factor and activation energy,

respectively, and f(˛) is the kinetic model function in differ-
ential form, which describes the dependence of the reaction
rate on the extent of reaction. If the process is carried out at
a constant reaction rate C (SCRT method) from Eqs. (3) and (4)
we get:
 E

C = A exp − f (˛) (5)
RT

Fig. 2 – X-ray diffraction diagrams of final products of four Eq. (5) can be written as:
samples (Table 1) from the reaction of SiO2 with C and N2 .
1 A E
The estimated standard deviations (E.S.D.) is <5%. ln = ln − (6)
f (˛) C RT

fraction ˛ at the time t is given by the ratio between the area
enclosed by the CO trace, at this time t, and the total area when
the reaction is over.
The phase compositions (as determined from XRD analy-
sis, Fig. 2) of the series of silicon nitride samples, obtained at
different reaction rate and the same partial pressure of CO,
are shown in Table 1. The results point out that the fraction
of ␣-Si3 N4 does not changes when the constant reaction rate
decreases and, consequently, the reaction temperature. These
The plot of the left-hand side of Eq. (6) against the reciprocal
of the temperature gives the values of the activation energy E.
Fig. 4 illustrates the temperature ranges at which the reaction
takes place.
4.1. Kinetic mechanism
The carbothermal reduction, involving the reaction of solids
and gases, exhibits a certain degree of complexity. Here a
model was proposed where the system is considered to be

Table 1 – Experimental conditions and characterization compositional of final product prepared using the SCRT method
at different reaction rate and 0.005 atm of CO
Sample Sample weight (g) Flow rate N2 (cm3 /min) C (min−1 ) % ␣-Si3 N4 % ␤-Si3 N4

1 2 50 0.0003 100 0
2 2 100 0.0007 99 1
3 2 200 0.0014 98 2
4 2 300 0.0022 98 2
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 5 ( 2 0 0 8 ) 224–231
Fig. 3 – SEM micrographs of silicon nitride obtained from carbothermal reduction of silica. Samples 1 and 4.
an agglomerate of small grains, and the reaction occurs at
the surface of the silicon dioxide/carbon grains. Silicon diox-
ide is in intimate contact with carbon and these reactants are
uniformly dispersed at the molecular level. SiO2 reduction ini-
tiates in the contact region of silica and carbon aggregates,
during heat treatment. Ribbons of very fine silicon nitride pow-
der cover the surface of silicon dioxide/carbon grains.
It is generally accepted in the literature that the car-
bothermal reduction occurs through the formation of an
intermediate SiO vapour phase (Vlasova et al., 1995; Lencart-
Silva and Viera, 1999). The physical contact between carbon
and silicon dioxide is essential for SiO gas formation:
SiO2 (s) + C(s) → SiO(g) + CO(g)
Once SiO is formed in accordance with reaction (7) it will
continue to react, with nitrogen, to form silicon nitride ribbons
in accordance with reaction (8):
3SiO(g) + 3C(s) + 2N2 (g) → Si3 N4 (s) + 3CO(g)
Fig. 4 – Reacted fraction ˛ as a function of T for four SCRT
curves carried out at different reaction rates C (min−1 ) for
the carbothermal synthesis of Si3 N4 .
227
After nuclei are formed, more SiO and nitrogen will be
transported to the reaction site to form the Si3 N4 thin layer
(the growth reaction). The thickness of the layer gradually
increases, and the nitridation rate decreases, consequently,
the reaction will be mainly controlled by the diffusion of
the gaseous reactants through the product layer. Diffusion
through the pore will be necessary for reactant gas to react
on the solid grain surface. The diffusion of the gaseous
reactant becomes the rate limited step. The mathematical cal-
culation, which is similar to Jander equation in the case of
three-dimensional particles, is based on two-dimensional par-
ticles. The approximation of the quasi-steady-state method
was assumed. The discussion was restricted to the diffu-
(7) sion through the layer of the reaction product. The product
grows from each contact to form a shell which advances
from the outside toward the interior as the reaction proceeds.
The following assumptions were made for the derivation of
the diffusion kinetic equations which takes account of the
topochemical character of s–s reactions by considering a state
of packing of reactant particles:
(8)
• The diffusion coefficient of the species being transported is
a constant.
• The product phase is not miscible with any of the reactant
phase. The concentration (activity) of the reactant remains
constant on both side of the reaction interface.
• Molar volume of the two components is assumed to be inde-
pendent of concentration. The schematic representation of
this case is given in Fig. 5.
Assuming that the quantity of diffusing material which
passes per unit time through an unit area normal to the direc-
tion of diffusion is proportional to its concentration gradient
we can write (Fick’s law) following Delmon (Delmon, 1969) pro-
cedure:
dCn
˚ = ±D (9)
dx
where Cn is the concentration per unit volume of diffusing
species, ˚ the diffusive flux of nitrogen, the quantity per unit
time per unit area, D the diffusion coefficient of nitrogen and
defines the quantity diffusing in unit time through a cross-
228 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 5 ( 2 0 0 8 ) 224–231

obtains (Delmon, 1969):

2xh˚x = 2ri hKi (14)

After rearrangement, integration and taking into account

the boundary and initials conditions (CB = 0 at r1 and CB = 1 at
r2 ) we obtain:

 0  r1
dx
DB dCB = Ki r1 (15)
1 r2
x

Fig. 5 – Schematic representation of the diffusion After substituting Eq. (10) this leads to:
mechanism of a single particle.
1
DB dt = r1 (ln r1 − ln r2 ) dr1 (16)
VA

If we take into account the balance of matter, following the

section when the concentration gradient is unity, and finally x
procedure of Fevre and Murat (1975), the total volume of the
is the distance of diffusion (the thickness of product layer). The
particle is equal to the volume of the reacted material plus the
conditions are such that steady-state diffusion is maintained
volume of the unreacted material:
(Delmon, 1969).
On the other hand we define the interfacial specific rate Ki
r22 h = (r02 − r12 )hZ + r12 h (17)
as the number of moles of solid reactant A (SiO2 /C agglom-
erate) transformed per unit time per unit area. The diffusion
And we find that:
proceeds, in accordance with Delmon theory (Delmon, 1969),
at a rate which is proportional to the reaction surface:
r22 = Zr02 − r12 (Z − 1) (18)

1 dr Substitution of Eq. (18) into Eq. (16) followed by rearrange-

Ki = (10)
VA dt ment and integration gives:

where VA is the molar volume of the solid reactant, r is radial  t  r1

1 r1
distance and the subscript ‘i’ refer to the interface. If the vol- DB dt = r1 ln dr1 (19)
0
VA r0 [Z(r02 − r12 ) + r12 ]
1/2
ume of the reacting particles expanded by moving the reaction
interface from the original surface, the value of the reacted
On the other hand from Eq. (11) one obtains:
fraction, ˛, at a time t, is defined as (Fevre and Murat, 1975):

r12 = r02 (1 − ˛) (20)

volume of the particle A reacted at t r2
˛= = 1 − 12 (11)
volume of particle A at t = 0 r0 Substituting Eq. (20) into Eq. (19) followed by integration
gives:
The diffusion kinetic equations can be improved by
accounting for differences in the volume of the product layer 1 2 1−˛ 1 r02
DB VA t = r0 (1 − ˛) ln + Z ln [1 + ˛(Z − 1)]
with respect to the volume of the reactant consumed. Thus we 4 1 + ˛(Z − 1) 4 (Z − 1)
introduce in the equation the parameter Z of Scriven (Scriven, (21)
1959) to account for the change in volume:
After rearrangements we finally obtain:
volume of product formed (Si3 N4 ) r22 − r12
Z= = (12) 1−˛ Z
volume of reactant consumed r02 − r12 (1 − ˛) ln + ln[1 + ˛(Z − 1)] = Kt (22)
1 + ˛(Z − 1) Z−1

To satisfy conservation of matter, under quasi-stationary where K = 4DB VA t/r02 or in the general kinetic form g(˛) = Kt,
conditions, the quantity of material transformed per unit time where
in the reaction interface equals the quantity of material dif-
fusing through any surface of radii x (Delmon, 1969). This 1−˛ Z
g(˛) = (1 − ˛) ln + ln[1 + ˛(Z − 1)] (23)
1 + ˛(Z − 1) Z−1
statement can be conveniently expressed as:

A correction of the Ginstling–Brounshtein (Ginstling and

Area(x) · ˚x = Area(ri ) · Ki (13)
where Area(x) is the cylindrical area of diffusion path at a radii
x, and Area(ri ) refer to the same area at the reaction interface.
The reactant B (nitrogen) diffuses inward through the prod-
uct layer AB (Si3 N4 ) from the outer interface. From Eq. (13) we
Brounshtein, 1950) model has been put forward by Valensi
(1935) in a similar treatment. The mathematical f(˛) function of
Eq. (3) is obtained, by definition, from the following equation:
1 dg(˛)
= (24)
f (˛) d˛
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 5 ( 2 0 0 8 ) 224–231 229

Thus, substituting Eq. (23) into Eq. (24) one obtain: sponding value of the activation energy E was calculated, for
different values of the constant reaction rate C.
1 Fig. 6 shows the plots of the left-hand side of Eq. (26) against
f (˛) = (25)
−ln((1 − ˛)/((Z − 1)˛ + 1)) the reciprocal temperature for the four experiences of Fig. 4,
a Z-value of 1.5 was chosen (the theoretical Z-values can be
The f(˛) function obtained is a mathematical function depend-
determined according to the molar ratio between reactants
ing on the reaction model here proposed. This fact allows the
and products and their mole volumes, but the true Z-value is
activation energy to be obtained from Eq. (6).
hard to achieve owing to a lack of high temperature density
data for computing the Z-value, usual densities are in a range
4.2. Effect of the constant reaction rate C on the
of values, the 1.5 value here reported is only an approximated
activation energy
value). This figure shows the effect of C on the activation
energy E. It can be seen that the relationship is linear and
Substitution of Eq. (25) into Eq. (6) yields:
indicates that diffusion of nitrogen through the product layer
 1−˛
 A E
is probably the rate controlling step. When, for example, the
ln −ln = ln − (26) spherical model was assumed, the left-hand side of Eq. (26)
(Z − 1)˛ + 1 C RT
(using the corresponding f(˛) function) is not a linear function
By using the experimental values of the reacted fraction ˛ of the reciprocal temperature, thus, the spherical model, was
obtained from Fig. 4, for each reaction temperature, the corre- discarded.

Fig. 6 – Effect of the constant reaction rate C on the activation energy.

230 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 5 ( 2 0 0 8 ) 224–231

Table 2 – Activation energy of the carbothermal

synthesis of silicon nitride for different values of the
reaction rate C (for Z = 1.5)
C (min−1 ) E (kJ/mol)

0.0003 289
0.0007 288
0.0014 308
0.0022 339

Table 2 shows the values of the activation energies calcu-

lated from Eq. (26).
From Table 2 and Fig. 6 it can be seen that the constant reac-
tion rate C causes a slight increase in the activation energy
of this reaction. The results here obtained shows that when
SCRT was used, the good control of pressure in the sample
surrounding and the use of reaction rate low enough to keep
temperature gradient at a negligible level to avoid any heat
or mass transfer problem, the activation energy obtain was
nearly independent of the reaction rate. On the other hand
the mean value of the activation energy (E = 306 kJ/mol) dif-
fer form the value of 115 kJ/mol obtained by Liou and Chang
(1996). The difference can be explained if we take into account
that these authors have used pyrolyzed rice husk pellet and
a kinetic model based on spherical particles. Moreover, the
pellet was made by compacting the powder and the thermal
analysis have been carried out using conventional method
(TGA), in these conditions, the literature data (Ortega, 2002;
Gotor et al., 2000, 1998) have shown that, the experimental
parameters, such heating rate, mass and heat transfer effect,
thermal gradients, etc., can affect significantly the calculated
values of the activation energy.
To confirm that the diffusion kinetic model control the car-
bothermal synthesis of silicon nitride, we take into account
the conclusion established in previous finding (Criado et al.,
1990) which demonstrated that the shape of SCRT curves pro-
vide valuable information for elucidating the actual kinetic
model obeyed by the reaction. Thus a mere glance at the shape
of master plots of the SCRT curves provides an easy way of
discriminating between the different families of kinetic reac-
tion models. Fig. 7 shows the characteristic shape of the set
Fig. 7 – Shapes of the theoretical SCRT curves in
normalized temperature scale (Dn = unidimensional
diffusion, D1 ; two-dimensional diffusion, D2 and
three-dimensional diffusion, D3 ; Rn : interface reaction; An :
Johnson–Mehl–Avrami law).
of isokinetic theoretical SCRT curves and we can see that the
experimental SCRT curves in Fig. 4 are similar in shape to those
given in Fig. 7 for the Diffusion family of kinetic models, Dn .
4.3. Effect of the volumetric Z parameter on the
activation energy
In order to obtain the effect of the change in volume of prod-
uct formed per unit volume of solid reactant on the activation
energy of the carbothermal reduction of SiO2 we have used
Eq. (26) for different values of Z (0.5, 1.0 and 1.5). Fig. 8 shows
the plots of the left-hand side of Eq. (26) against the reciprocal
temperature for three values of the Z parameter.
From Fig. 8 and Table 3 it can be seen that the activation
energy decreases by increasing the volumetric parameter Z for
the same value of the reaction rate C (C = 0.0014 min−1 ). The
same trends are obtained for the other C-values.

Fig. 8 – Effect of the volumetric parameter Z on the activation energy.

 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 5 ( 2 0 0 8 ) 224–231
Table 3 – Effect of Z on the activation energy (kJ/mol) for
C = 0.0014 min−1
Z E
0.5
1 320
1.5
4.4. Discussion
The diffusion mechanism proposed in this paper perhaps
could be supported by considering an approach analogous to
the Pilling-Bedworth rule (Kubaschewski and Hopkins, 1962)
widely used by metallurgists to explain and predict the corro-
sion of metals. This criterion states that oxide layers that form
on reactant metals during oxidation are protective if the oxide
to metal volume ratio is greater than one. The same hypothe-
sis is used during the natural weathering of silicate minerals
(Velbel, 1993). The presence or absence of protective surface
layers and the rate determining mechanism of the weather-
ing reactions are determined by the stoichiometries and molar
volumes of reactant minerals and their weathering products.
In the present investigation the reactant to Si3 N4 volume ratio
is greater than one and, consequently, diffusion through layer
is the rate determining step. If the volume ratio is smaller
than 1, the product does not totally cover the reactant sur-
face, permitting free access of the nitrogen atmosphere to the
agglomerate SiO2 /C on certain locations. In this case the prod-
uct layer is too porous or otherwise unable to be transport
(diffusion) limiting.
The result obtained was interpreted by a reaction mech-
anism that involves instantaneous nucleation on the surface
of the particles with subsequent advance of the reaction inter-
face. From the SEM micrographs in Fig. 3 it can be clearly noted
the hexagonal form of the crystallites and ribbons (long cylin-
ders), thus this advance is controlled by the bidimensional
diffusion of nitrogen through the cylindrical layer of prod-
uct, because this advancement is faster than the diffusion of
gases through the layer formed (i.e. the chemical reaction at
the phase boundary is considerably faster than the transport
process), thus the bulk-diffusion reaction can become the rate-
determining step. This conclusion would be in agreement with
the above observation that when the carbothermal reduc-
tion of silica take place, at higher temperature, the number
of bidimensional crystallites is higher and the bidimensional
diffusion is promoted, because diffusion is an “activated”
process, that is, it becomes more favoured with increasing
temperatures.
references
Alcala, M.D., Criado, J.M., Real, C., 2002. Adv. Eng. Mater. 4 (7), 478.
Barsoum, M., Kangatkar, P., Koczak, M.J., 1991. J. Am. Ceram. Soc.
74, 1248.
Beruto, D.T., Ferrari, A., Giordani, M., Marino, F., 2003. Mater. Sci.
Eng. A 355, 286.
231
Criado, J.M., Ortega, A., Gotor, F., 1990. Thermochim. Acta 157, 171.
Cullity, B.D., 1978. Elements of X-ray Diffraction. Adisson-Wesly
Publ. Co., London, p. 397.
Delmon, B., 1969. Introduction a la Cinetique Heterogene.
Technip, Paris.
353
Durham, S.J.P., Shanker, K., Drew, R.A.L., 1991. J. Am. Ceram. Soc.
74, 31–37.
308
Ekelund, M., Forslund, B., 1992. J. Am. Ceram. Soc. 75, 532.
Fevre, A., Murat, M., 1975. J. Therm. Anal. 7, 429.
Ginstling, A.M., Brounshtein, B.I., 1950. Concerning the diffusion
kinetics of reactions in spherical particles. J. Appl. Chem.
USSR 23 (12), 1327.
Gogotsi, Y.G., Andrievski, R.A. (Eds.), 1999. “Materials Science of
Carbides, Nitrides and Borides” NATO ASI Series. High
Technology, vol. 68.
Gotor, F.J., Macias, M., Ortega, A., Criado, J.M., 1998. Int. J. Chem.
Kinet. 30, 647.
Gotor, F.J., Macias, M., Ortega, A., Criado, J.M., 2000. Phys. Chem.
Miner. 27, 495.
Hanna, S.B., Mansour, N.A.L., Taha, A.S., Abd-Allah, H.M.A., 1985.
Br. Ceram. Trans. J. 84, 18–21.
Hashishin, T., Kaneko, Y., Iwanaga, H., Yamamoto, Y., 1999. J.
Mater. Sci. 34, 2193.
Higgings, I., Hendru, A., 1986. Br. Ceram. Trans. J. 85, 161.
Komeya, M., Inoue, H., 1975. J. Mater. Sci. Lett. 10, 1243.
Kormeijer, E., Scholte, C., Blömer, E., Metoelaan, R., 1990. J. Mater.
Sci. 25, 1261.
Kubaschewski, 0., Hopkins, B.E., 1962. Oxidation of Metals and
Alloys, second ed. Butterworths, London, p. 319.
Lange, H., Wötting, G., Winter, G., 1991. Angew. Chem. Int. Ed.
Engl. 30, 1579.
Lencart-Silva, F., Viera, J.M., 1999. J. Mater. Process. Technol. 92,
112.
Liang, Y.N., Lee, S.W., Park, D.S., 1999. Wear 225–229, 1327.
Liou, T.H., Chang, F.W., 1996. Ind. Eng. Res. 35, 3375.
Mitomo, M., 1990. In: Somiya, S., Mitomo, M., Yashima, M. (Eds.),
Silicon Nitride-1. Elsevier, London, pp. 1–11.
Moulson, A.J., 1979. J. Mater. Sci. 14, 1071.
Ortega, A., 2002. Int. J. Chem. Kinet. 34 (4), 223.
Perez-Maqueda, L.A., Criado, J.M., Real, C., Subrt, J., Bohacek, J.,
1999. J. Mater. Chem. 9, 1839.
Pigeon, R.G., Varma, A., Miller, A.E., 1993. J. Mater. Sci. 28, 1919.
Sanyal, A.S., Mukerji, J., Bandyopadhyay, S., 1991. J. Am. Ceram.
Soc. 74, 2312.
Scriven, L.E., 1959. Chem. Eng. Sci. 10 (1), 1.
Segal, D.L., 1986. Br. Cream. Trans. J. 85, 184.
Segal, D., 1991. Chemical Synthesis of Advanced Ceramic
Materials. Cambridge University Press.
Siddiqi, S.A., Hendry, A., 1985. J. Mater. Sci. Lett. 10, 3230.
Valensi, G., 1935. Kinetic of oxidation of metallic wires. CR Acad.
Sci. Paris 201, 602.
Van Dijen, F.K., Vogy, J., 1992. J. Eur. Ceram. Soc. 10, 273.
Velbel, M.A., 1993. Am. Mineral. 78, 405.
Vlasova, M.V., Bartnitskaya, T.S., Sukhikh, L.L., Krushinskaya,
L.A., Tomila, T.V., Artyuch, S.Yu., 1995. J. Mater. Sci. 30, 5263.
Weimer, A.W., Eisman, G.A., Susnitzky, D.W., Beaman, D.R.,
McCopy, J.W., 19972853. J. Am. Ceram. Soc. 80.
Wendel, J.A., Goddard III, W.A., 1992. Chem. Phys. 97, 5048.
Wild, S., Grieveson, P., Jack, K.H., 1972. In: Popper, P. (Ed.), Special
Ceramic 5. British Ceramic Association, Stoke-on-Trent, pp.
385–395.
Yoshimatsu, H., Kawasaky, H., Miura, Y., Osaka, A., 1989. J. Mater.
Sci. 24, 3280.
Ziegenlag, G., Focke, T., Holldorf, H., Brinkand, R., Lang, H., 1999. J.
Mater. Sci. 34, 2199.
Ziegler, G., Heinrich, J., Wötting, G., 1987. J. Mater. Sci. 22, 3041.