A Kinetic Model for Metal + Nonmetal Reactions

A.M. KANURY

In attempts to mathematically model the process of gasless self-propagating high-temperature

synthesis (SHS) of materials, the existing chemical kinetic rate relations are found to be unable
to explicitly account for the dependence of the reaction rate on reactant particle size, reactant
proportions in the supply mixture, and presence of an inert. A rate expression is developed in
this article based on the following mechanism: the metal melts and flows around the nonmetal
particle; an intermediate (liquid) complex is formed; the metal ions diffuse from the melt, across
the complex, to readily react with the nonmetal at its surface; the product of reaction is the
complex itself, which dissolves on the metal-melt side at such a rate that the thickness of the
complex is proportional to the instantaneous diameter of the nonmetal particle. As the concen-
tration of the metal in the outer melt decreases with time, the nonmetal particle gradually be-
comes smaller. Coupling these two temporally varying quantities, a relation is obtained for the
instantaneous rate as dependent on temperature, supply particle size, compaction density, reac-
tant proportions, and the inert content.

I. INTRODUCTION of reaction in a homogeneous mixture of particles of a

C O N V E R S I O N of chemical energy into thermal en-
ergy is the main objective of ordinary combustion pro-
cesses. The products of combustion then are of concern
only in the contexts of combustion efficiency, thermal
radiation from the flames, and pollution effects of the
exhaust. Turning the problem around, certain reaction
processes which behave much like ordinary combustion
may very well be suited to economically produce certain
desired products. Combustive synthesis or self-
propagating high-temperature synthesis (SHS) is just such
a method of producing a solid product. Transition met-
als, as well as other metals, such as magnesium, man-
ganese, iron, cobalt, and nickel, are now well known to
react with nonmetals, such as boron, carbon, silicon,
phosphorus, and sulfur, in a self-sustainingly exothermic
manner to produce numerous important products. For
obvious reasons, SHS reactions of the type [solid +
solid ~ solid] are also termed gasless combustion, al-
though truly gasless systems are indeed rare. Self-
propagating high-temperature synthesis reactions in which
gaseous reactants are involved to produce nitrides and
hydrides are also possible. The present article deals only
with gasless combustion.
The concept of SHS has been formulated and proven
by Merzhanov l~] and co-workers with efforts spanning
over two decades. Over the past few years, there is a
great deal of SHS research activity in this country and
elsewhere, t2] Both the science and technology of com-
bustive synthesis, however, are but in an emerging stage
to date. A number of important issues remain to be re-
solved. One such issue is related to the very definition
and nature of a reaction in solid state.
A theoretical model describing the chemical kinetics
A.M. KANURY, Professor, is with the Department of Mechanical
Engineering, Oregon State University, Corvallis, OR 97331-6001.
This article is based on a presentation made in the symposium
"Reaction Synthesis of Materials" presented during the TMS Annual
Meeting, New Orleans, LA, February 17-21, 1991, under the auspices
of the TMS Powder Metallurgy Committee.
melting solid and a nonmelting solid is presented in this
article. The model reaction considered is that of titanium
reacting with carbon to form titanium carbide. It appears
that the present development can be easily extended to
other similar reactions. We specifically seek to develop
an equation for the intrinsic reaction rate (kilograms or
kmoles of carbon consumed per unit time per unit vol-
ume of the compact) as dependent on the temperature,
particle size, compaction density, reactant proportions,
and dilution with the inert product. Such a rate equation
is necessary as a constitutive relation for inclusion in the-
oretical models seeking to predict the rate of propagation
of the SHS reaction wave in a reactant compact of any
arbitrary configuration.
The reasons for the unavailability of such an intrinsic
rate equation in the existing literature can only be sur-
mised. For reactions involving only gaseous reactants,
the concept of collision frequency offers a reasonable
starting point to arrive at a rate equation. For solid-state
reactions, however, this concept is of little or no use.
Whereas gas molecules are of the order of angstroms in
size and are relatively free to translate in space, solid
particles are generally of the order of tens of microns in
size, usually constrained in a crystal matrix which can
be excited vibrationally but not translationally.
The rate of an SHS reaction is intuitively expected to
be higher at higher temperature and to become zero when
either of the reactants is completely depleted. Most of
the existing theoretical analyses of the SHS process con-
trive a rate equation to account for these trivial depend-
encies on the basis of the extensive experience either with
gas reaction kinetics or with metal tarnishing and rusting
reactions. The temperature dependency is usually taken
to be described by an Arrhenius-type exponential. This
turns out to be correct, since diffusion in condensed phase
follows an exp [-E/(RT)] type of temperature depen-
dence. [3'4'5] The influence of reactant concentrations C~
is taken, again based on the experience with gas reac-
tions, as: rate ~ CTC'~or C'~, where n and m are positive
constants known as the orders of the reaction with re-
spect to species 1 and 2, respectively. Since the particles

METALLURGICAL TRANSACTIONS A VOLUME 23A, SEPTEMBER 1992--2349

are large compared to typical gas molecules, the defi-
nition of carbon concentration is itself prone to some
ambiguity.
The concentrations are replaced in some works with
(1 - r/), where ~/is called the extent of reaction, which
is zero at the start of the reaction and unity upon com-
plete reaction. The expression (1 - 7/) may be defined
in a number of ways; it may be the ratio of the particle
diameter to its initial diameter; the particle volume to the
initial volume; the particle mass to its initial mass; the
metal mass to its initial mass; or the metal concentration
in the melt to its initial concentration. The term ~7 may
also be defined as the mass or concentration of the prod-
uct in the melt normalized by its final value. Not all
investigators appear to use the same definition of 77. We
will note later in this article that there is no single def-
inition of the extent of reaction which would serve well
under all conditions. Even more importantly, the exist-
ing literature appears to shed little light on the depen-
dence of the intrinsic reaction rate on variables such as
the reactant particle size, the degree of dilution with the
inert product, the excess reactant in the initial mixture,
and the density to which the compact is compressed.
Perhaps the most elegant available experimental study
of the chemical kinetics of a reaction involving a melting
reactant and a nonmelting one is that of Aleksandrov and
Korchagin.161 Employing an electron microscope and X-ray
phase analysis with a synchrotron radiation diffracto-
meter, these authors have witnessed that the metal melts
and flows around the nonmetal particle (Figure 1). A
layer of low-melting-point intermetallide complex is pro-
duced by reaction at the nonmetal surface. This inter-
metallide is presumably some form of a distinct metastable
phase. Reference 6 contains experimental evidence in-
dicating that the layer of intermetallide complex, diffu-
sional transport across which is an essential element of
the reaction process, arises not only in the thermite re-
action of Fe203-A1 and intermetallic reaction of Ni-A1
but also in reactions involving Ti, Nb, or Ta with C and
Ti, Nb, Ta, and Hf with B.
It is assumed that metal ions and atoms diffuse from
the outlying melt across the shell of the intermetallide
complex to the nonmetal surface. Reaction at this sur-
\
TI * TIC mixture melt in which the
concentration of titanium gradually
decreases with time.
C-Ti liquid complex of thickness ~"
across which titanium cations diffuse
to the carbon surface.
Carbon particle whose diameter gradually decreases
with time due to reaction at its surface.
Fig. 1 - - S c h e m a t i c o f the Aleksandrov/Korchagin model.
2 3 5 0 - - V O L U M E 23A, SEPTEMBER 1992
face is assumed to produce the intermetallide at the same
rate as it is dissolved at the outer surface into the metal
melt. The intermetallide thus quickly attains a quasi-
stationarily constant thickness. As the reaction pro-
gresses gradually, the diameter of the nonmetal decreases
with time; in the outlying melt, the metal concentration
decreases, and the product concentration increases with
time.
Assuming that the rate of reaction at the nonmetal sur-
face is far higher than the rate of metal diffusion across
the intermetallide complex, Aleksandrov and Korchagin t61
heuristically infer that the reaction rate is proportional to
the instantaneous surface area S of the nonmetal particle
and to the instantaneous concentration C of metal in the
outlying melt. For a stoichiometric mixture in which the
nonmetal particles are spherical, if ~7 is the extent of re-
action, based on the carbon particle volume or mass,
S oc (1 - ,/)2/3 and C ~ (1 - r/) so that the rate dTi/
dt oc (1 - r/) 5/3. The proportionality constant is set to
be a function of temperature, t is time. By extension,
for any mixture composition and particle shape, drl/
dt ~ (1 - /zT/) (1 - ~7)t(i-~)/jl. The t e r m / x is the ratio
of the metal's stoichiometric molar coefficient to its ac-
tual molar coefficient such t h a t / z r / - 1. The indicesj =
1, 2, and 3, respectively, stand for planar, cylindrical,
and spherical nonmetal particles. It is obvious that if
/z < 1, the mixture is metal-rich, all the nonmetal gets
consumed, and ~/goes from 0 to 1. I f / z > 1, the mixture
is nonmetal-rich, and r/goes from 0 to 1//z. The mean-
ings of both 7/ and /z in this later case are not entirely
clear. The effect of possible dilution of the initial mix-
ture with the inert product is not addressed by the heu-
ristic model of Aleksandrov and Korchagin. t61
II. THEORY
A. Stoichiometry and Thermodynamics
If only for clarity of this presentation, let the metal be
titanium and the nonmetal be carbon. Thus, the reaction
of concern is
1 kmol of C + a kmol of Ti + b kmol of TiC
--->(b + 1) kmol of TiC
+(a- 1)kmolofTi: ifa->l
--->(b + a) kmol of TiC
+(1-a) kmolofC: ifa-<l
[1]
a < 1, = 1, and > 1 represent carbon-rich, stoichio-
metric, and titanium-rich initial mixtures, respectively.
(We note that a is the inverse of Aleksandrov's/z.) The
expressions b = 0 and > 0 represent mixtures undiluted
and diluted with the product, respectively. The present
manner, evident from the left side of Eq. [1], of de-
scribing the starting mixture composition in terms of the
mole numbers a and b is desirably unambiguous.
Assuming complete conversion of Ti and C to TiC,
METALLURGICAL TRANSACTIONS A
the adiabatic reaction temperature can be obtained from
the first law of thermodynamics as follows:
Tr,ad : To + {hc/[(a - 1)CpT i
+ (1 + b)CpTiC]}: if a--> 1
= To + {ahr - a)Cpc
+ (a + b)CpTiC]}: i f a -< 1
where To is the supply temperature, hc is the enthalpy of
combustion, and Cpi is the specific heat of ith species.
B. Kinetics
Although based on an experiment which is perhaps the
most elegant and detailed available, the rate equation has
been obtained by Aleksandrov/Korchagin in a rather
qualitative way. The description of the starting mixture
and the definition of the extent of reaction have been left
with some clarity desired. In the following, we construct
a simple theory based on Aleksandrov/Korchagin ex-
perimental observations. Our development follows the
fundamental principles of conservation of species and
overall mass in a system involving diffusional transport
of the metal to the nonmetal surface at which the reac-
tion takes place. The reaction itself is assumed to be much
faster than the diffusion process. This appears to be a
reasonable assumption in many solid-state reactions aris-
ing in SHS, intermetallic alloying, metal + gas, as well
as semiconductor processes.t7.8.9]
In the context of Figure 1, let us denote the radial
coordinate by r, the instantaneous spherical carbon par-
ticle diameter by dp, and the intermetallide thickness by
6. Let Cri be the concentration of titanium at any radial
location in the complex, CTim the concentration in the
by kmols
C [ 7rd3/6] [pc/Mc]
Ti [Zrpc/(6Mc)] [(a - 1)d~o + d3]:
TiC [rrpc/(6Mc)] [(b + 1)d~o - d3]"
[(a
C T i m o r CTiCm
[(a - 1) + (dJdpo) 31 ( M T i / P r i )
melt. d e and CTim are unknown functions of time. Let
D = Do exp [ - E / ( R T ) ] be the coefficient of diffusion
of titanium across the intermetallide complex, T tem-
perature, E activation energy, and R the universal gas
constant. If the diffusion of titanium across the complex
occurs much slower than the reaction at the carbon sur-
face, CT~(r) is governed by
( 1 / r 2) (d/dr) [Dr 2 dCxi/dr] = 0
METALLURGICAL TRANSACTIONS A
The boundary conditions stipulate that the titanium con-
centration is zero at the particle surface due to the fast
reaction: r = dp/2, Cvi = 0. It is assumed that titanium
remains uniform at all times in the outlying melt so that
its concentration is CTim (a function of time yet to be
determined). Thus, at the outer edge of the melt product
complex, r = (6 + dpl2), CTi = CTi m.
Solution of Eq. [3] gives the molar diffusion rate of
[2] titanium across the melt complex to the carbon surface
to be
Ti molar diffusion rate
(for spherical carbon particles)
= 7rdp(dp + 26)DCTim/6 [4]
The carbon molar consumption rate can be written in
terms of the rate of decrease of the particle volume as
C molar consumption rate
(for spherical particles)
= - ( 1 / M c ) (d/dt) [pcTrd3/6] [5]
where Mc and Pc are the molecular weight [kg/kmol]
and density of carbon [kg/m3], respectively. The stoi-
chiometry indicated in Eq. [1 ] dictates that the two rates
given by Eqs. [4] and [5] be equal, thus leading to one
of the two equations needed for the two unknown func-
tions of time CTim(t ) and dp(t).
(1/Mc) (d/dt) [pcrrd3/6] = - rrdp(dp + 26)DCr~m/8
[6]
At time t = 0, the carbon particle diameter is dpo and
the mixture composition is [1 kmol C + a kmol Ti + b
kmol TIC]. At any time t > 0, the mixture contains
by m 3
[~rd3/61
[(7r/6) (pc/Mc) (MTffPTi)] [(a -- 1)d~o + d3] '
[(7r/6) (pc/Mc) (MTic/RTic)] [(b + 1)d~o - d 3]
With the kmols of Ti and volumes of Ti and TiC melts
thus known, the concentrations can be easily found in
terms of dp(t) to close the problem with Eq. [6].
- 1) + (dJdpo) 3] or [(b + 1) - (dpldpo) 3]
[7]
h- [(b + 1) - (dp/dpo) 3] (MTic/Pl-iC)
We can also find the melt diameter d m a s a function of
time.
(dm/dpo) 3 = (dp/dpo) 3 + (pe/Mr
9{[(a -- l) + (dJdpo) 3] (MTi/Pri)
+ [(b + 1) - (dp/dpo) 3] (Mvic/Pnc)}
[3] [8]
VOLUME 23A, SEPTEMBER 1992--2351
With the nondimensional variables and parameters
defined as
A =--dp/dpo; r ~ CTim/fTimO; * =-- D/Do
/3 =- 6/dp; "r* =- D o t / d ~
Eqs. [6] and [7] transform to the following form:
dA3/d~ * = - { ( 6 M c / P c ) [(1 + 2/3)/fl]CT~.,o}A6A
~) : (l/CTimO) [(a - 1) + A31
"- {[(a - l) + A31 ( M T i / P T i )
+ [(b + 1) - A3I (MTic/PTic)}
The initial concentration of Ti in the melt is simply
CTim0 -m- a/[a(MTi/PTi ) "-b b(MTic/P.ric) ]
Solutions of Eqs. [9] and [10], with the initial conditions
A(0) = 1 and ~b(0) = 1, give A and ~b as functions of
It*; A, a, b,/3]. The molar volumes (M/p)i are, of course,
constants. Before proceeding further with the theory of
spherical particle, let us digress briefly to examine the
effect of particle shape.
If the particles are cylindrical pellets of length ~ and
diameter dp rather than spheres of diameter dp, Eq. [3]
can be written in cylindrical coordinates and solved (with
the assumption of negligible length-wise diffusion) to
obtain the molar diffusion rate of titanium across the
complex as 27r~DCTim/ln [(dp + 2~)/dp]. For ~ < d p ,
this rate relation can be safely simplified to
Ti molar diffusion rate
(for cylindrical carbon particles)
= r + r162
Thus, while Eq. [4] gives the titanium diffusion rate per
unit area of the particle surface as [1 + (28/dp)]DCTim/~
when the particles are spherical, Eq. [ 12] gives this rate
as [1 + (~/dp)]DCTim/~ when the particles are cylin-
drical. The effect of curvature is, thus, clearly more se-
rious when the particles are spherical. If the curvature is
vanishing, i.e., ~/dp ---> O, both these rate relations lead
to the planar particle limit in which the diffusion rate per
unit area is DCTi,n/t% The equations corresponding to
Eqs. [7] through [11] can be easily derived for the cy-
lindrical and planar particles. Since no new concepts are
involved, we shall not carry out this derivation. Instead,
we return to the spherical particle considerations.
The physical meaning of the nondimensional variables
A, ~b, and r* and parameters h and/3 needs to be men-
tioned here. The definition of nondimensional time r*
is trivial in that the physical time t is measured in units
of the diffusional time (d2po/Do). We note that the initial
size of the carbon particle is embedded in the definition
of nondimensional time. The parameter A, being of the
form of the well-known Arrhenius exponential, embod-
ies the temperature dependency of the diffusion rate.
The particle diameter A is unity at time ~* equal to
zero. If the supply mixture is titanium-rich, i.e., the mole
number a > 1, all the carbon will be consumed in due
time so that A ---> 0 as ~-* ---> ~. As such, an extent of
2352--VOLUME 23A, SEPTEMBER 1992
reaction can be defined as proportional to (1 - A3) so
that it varies from zero initially to unity finally. Such an
extent of reaction represents the volume fraction or mass
fraction of carbon yet to be consumed at any given time.
In this case of a > 1, some titanium will remain uncon-
sumed at infinite time.
The titanium concentration ~b is unity at time r* equal
to zero. If the supply mixture is titanium-deficient, i.e.,
[9] the mole number a < 1, all the titanium will be con-
sumed in due time so that ~b ~ 0 as r* ---> o0. As such,
an extent of reaction can be defined as proportional to
(1 - ~b) so that it varies from zero initially to unity fi-
nally. Such an extent of reaction represents the concen-
[10l tration fraction of titanium yet to be consumed at any
given time. In this case of a < 1, some carbon will re-
main unconsumed at infinite time.
In order to see the conditions under which the extent
[l 1] of reaction defined on the basis of A above is equal to
that defined on the basis of th, differentiate th(t) given
by Eq. [10]. If the molar volumes of Ti and TiC are
equal, we obtain
dqb/dT* = ( i / a ) dA3/d'r * [13]
independent of the dilution coefficient b. The solution
of this equation is th = (A 3 + a - 1)/a. If a = 1,
~b = A3, so that the two foregoing definitions of the ex-
tent of reaction are equivalent only when (1) the molar
volumes of Ti and TiC are equal and (2) the initial mix-
ture is stoichiometric.
Finally, /3 is the thickness of the intermediate melt
complex measured in units of the instantaneous diameter
of the carbon particle. The thickness of the intermediate
complex itself has been observed by Aleksandrov and
Korchagin t6j to be about 0.1 /xm when the carbon par-
ticle is 40 /zm in diameter. Thus, under the observed
[12] conditions of titanium + carbon reaction,/3 is of the order
of 0.0025. It is assumed that/3 is an experimentally de-
termined characteristic of the reaction mechanism. Since
/3 is quite small, the factor [(1 + 2/3)//3] in Eq. [9] may
safely be approximated as equal to [1//3]. Thus,
dA3/dt o: qbA//3 o~ qbA2. This result is entirely consistent
with the argument that the rate is proportional to the
product of the instantaneous titanium concentration and
carbon particle surface area. This consistency motivates
us to set/3 =- 8/dp = a constant for a given reaction so
that as dp decreases with time, so also does & Aleksandrov
and Korchagin appear to suggest that 8 itself is probably
a constant characteristic of the studied reaction.
III. RESULTS AND DISCUSSION
A. Thermodynamics
If Ti and TiC are in solid state, the JANAF tables give
hc = 183.3 -+ 8.4 MJ/kmol. The specific heats depend
on temperature. However, for approximate estimation of
the reaction temperature, they can be taken to be about
55, 40, and 25 kJ/(kmol K), respectively, for TiC, Ti,
and C. Thus, for undiluted stoichiometric mixtures with
To = 300 K, Eq. [2] gives the adiabatic reaction tem-
perature to be roughly 3630 K. Mixtures with a r 1 and
b ~ 0 obviously lead to lower reaction temperatures.
METALLURGICAL TRANSACTIONS A
B. Kinetics
Numerical integrations of Eqs. [9] and [10] are pre-
sented in Figures 2 through 5. In each of these figures,
the top graph gives the variation of the carbon particle
volume and of the titanium concentration in the outer
melt as functions of time, all nondimensionally. The graph
at the bottom gives the history of the derivative of the
top graph.
Figure 2 presents the influence of temperature. The
mixture is stoichiometric and undiluted. The/3 value of
0.0025 is typical of TiC reaction. Recall that A -=
D/Do = exp [-E/(RT)]. Since A appears as a mere
multiplier, the time coordinate could have been rescaled
as (7*A) so that the indicated A = 1 curve also repre-
sents histories for any arbitrary value of A provided the
x-axis is viewed as ( z ' A ) . This scaling effect merely
confirms the intuitively obvious fact that the reaction
characteristic time is inversely proportional to
exp [-E/(RT)]. The A3 and ~b histories are observed to
differ little. This minor difference is due to differences
in the molar volumes. The time dependence of the rates
of disappearance of carbon and titanium, i.e., the deriv-
,0\, , , , , /
O.6 ~ ~ I~ ~
o.,_
0 I a 11
I - b.o ,.0002, I
2.104
104
103
102
0 0.001 0.002 0.003
r*
Fig. 2--Effect of temperature on the histories and rates of consump-
tion of carbon and titanium. Undiluted stoichiometric mixtures with
the intermetallide thickness parameter/3 = 0.0025.
METALLURGICALTRANSACTIONSA
atives of the histories presented in the top graph, is shown
in the lower part of the figure for three values of A. Dif-
ferences in molar volumes of various involved species
exert only negligible influence on these rate histories as
well. The higher the temperature, the higher the rate(s).
In this rate graph, too, the time coordinate could have
been changed to (~-*A) to make the single curve per-
taining to A = 1 embody the effect of different
values of A.
The influence of the magnitude of the intermetallide
complex thickness fl on the histories and rates of carbon
volume and titanium concentration, for an undiluted
stoichiometric mixture at a temperature corresponding to
A = 1, is shown in Figure 3. It is clear that a smaller/3
will facilitate faster diffusion to result in a faster overall
reaction. It is important to notice that although the his-
tories of the particle volume and titanium concentration
appear to differ only in a minor way, their slopes (i.e.,
the rates) may differ dramatically, especially at small
values of/3. Note also that, at any given/3, the rate of
titanium concentration decrease is larger at small times
O.6
0.4
[ a=l b--0 I--1[
2.10s
0 0.001 0.002 0.003
r*
Fig. 3--Effect of the intermetallide complex thickness/3 on the his-
tories and rates of consumption of carbon and titanium. Undiluted
stoichiometric mixtures with the activation exponential
parameter A = 1.
VOLUME 23A, SEPTEMBER 1992--2353
and smaller at large times than the rate of carbon volume
decrease. Whether or not this crossover of the rates has
1.0 I ~ 1 I I
any significant meaning is not now clear. $
The effects of reactant mole ratio a on the histories 0.8
and rates of decay are presented in Figure 4 for an un-
diluted mixture with A = 1 and/3 = 0.0025. If a < 1,
then a kmol of TiC is formed and (1 - a) kmol of the 0.6
excess carbon remains unconsumed. If a > 1, then
1 kmol of TiC is formed and (a - 1) kmol of the excess
titanium remains unconsumed. In the excess titanium case,
the rates approach zero quite abruptly.
Finally, the effect of dilution with the inert product is
shown in Figure 5 for a stoichiometric mixture with 0.2 -- -- 0 ~ ' - - ~,,,~,-,~,-,~,-,~
_
A = 1 and/3 = 0.0025. One would expect that the rate
would be smaller when the content of the inert is larger.
This expectation is found to be valid only in the early 0 I I I I I
stages of the reaction. In later stages, the presence of the
inert results in an increase in the rate(s). Neither the rea- a= 1 A= 1 B = 0.0025
sons for this peculiarity nor the significance of the cross-
over point are clear. 2.10 s
Calculations show that the melt diameter decreases with I I I I I
time as the reaction proceeds. Table I gives the calcu-
lated initial and final values of dmett/dpo under various 10s ~ -dAS/dr --
9 . . . . . d,,.

l.o ~ I 9 I I I I

0.8 ~-~ As--

~

X N~, _ " ~ . ~ . ~ 4.10 z I 1 I I I "

0.2 -- ~ ",-~- "" ~~~ " ~ . . . ~ -- 0 0.001 0.002 0.003

T~

Fig. 5 - - E f f e c t of dilution with the inert product on the histories and

rates of consumption of carbon and titanium, Stoichiometric mixture
with A = 1 and 13 = 0.0025.
b= 0 ,~= 1 f l = 0.0025 ]

2.10 s conditions. The decrease in the melt diameter lies in the

k~\ I I I I I
lOs range of about 14 to 25 pct, so that volume decrement
will be in the approximate range of 36 to 58 pct. The
temperature factor A has no apparent effect on the extent
of melt volume decrease. A decrease in the intermetallic
thickness parameter/3 notably enhances the volume dec-
rement. An increased inert content dampens the volume
10 2 decrement. Increase in the amount of titanium leads to
- .0..~,~ a reduction in the extent of volume decrement. Self-
propagating high-temperature synthesis experiments in-
dicate that the volume of a compact generally changes
~. % o _ -~r very little due to the reaction and that the product is po-
101 rous at about 25 pct porosity. Our melt volume calcu-
0.001 0.002 0.003 lations appear to overestimate this porosity. The
l-,k mechanism of pore nucleation and growth under various
mechanical conditions of constraint imposed on the sam-
Fig. 4 - - E f f e c t of excess reactants on the histories and rates of con-
sumption of carbon and titanium. Undiluted mixtures with A = 1 and ple is yet to be studied.
13 = 0.0025. The foregoing result of per particle analysis for the

2354--VOLUME 23A, SEPTEMBER 1992 METALLURGICAL TRANSACTIONS A

 Table I. Variation of the Melt Diameter with Stoichiometry,
Inerting, lntermetallide Complex Thickness, and Temperature

dmelt/dp~ Percent
a b /3 A at ~'* = 0 at z* --~ ~ Decrease
1 0 09 1 2.84 2.13 25.0
1 0 0.0025 10 2.84 2.13 25.0
1 0 0.0025 100 2.84 2.13 25.0
1 0 0.0250 1 2.84 2.37 16.5
1 0 0.00025 1 2.84 2.12 25.3
1 0.5 0.0025 1 3.91 3.20 18.1
1 1.0 09 1 4.97 4.28 13.9
0.5 0 09 1 1.92 1.56 18.8
1.5 0 0.0025 1 3.76 3.06 18.6

rate of reaction, when multiplied by the number of car-
bon particles in a unit volume, yields the macroscopic
reaction rate as follows:
9 rr!
(-We) = 6[mc//mmix] [Pmix//Pc] [(1 -t- 2/3)///31
9{ M c C ~ i m o D o / d ~ } exp [-E/(Rr)] 6 a
in units of [kg of carbon/(m 3 s)]. The diffusivity factor
A = D/Do has been written out as exp [-E/(RT)] for
an explicit indication of the effect of temperature 9 Writ-
ten in terms of volumetric molar consumption rate, the
rate is simply3 ( - N ~ ) =- ( - ~ ' ~ / M c ) in units of [kmol
of carbon/(m s)l.
9 trt
(-Nc) = 6 [mc//mmix] [Pmix//Pc] [(1 -t- 2/3)///3]
9{CTimoOo/d~} exp [-E//(RT)] q~A
This is the intrinsic reaction rate equation we set out to
obtain. In this equation: [mc/mm,x] is the mass fraction
of carbon in the compact, a function of a and b; [P~x/Pc]
is the ratio of compacted density to the carbon density;
and Cv~mOis the initial concentration of titanium in the
melt, also a function of a and b. It is evident that the
reaction rate is higher at higher temperatures in undiluted
(i.e., b = 0) stoichiometric (i.e., a = 1) mixtures of
finer particles compacted densely.
IV. CONCLUDING REMARKS
Consideration of the reaction mechanism involving
various phases is scheduled for our future research. Ex-
tension of the model for reactions with the stoichiometric
coefficient different from unity is also now in progress
in our laboratory 9
Efforts to validate the model are also now in progress 9
These efforts fall into two the following aspects: (1) an
electron microscopy study of the progress of an iso-
thermal reaction in a differential thermal analysis ap-
paratus, fashioned after the work of Aleksandrov/
Korchagin, 161 is being initiated9 (2) An experiment to
measure the propagation rate of an SHS reaction wave
along a cylindrical compact is developed 9 The measure-
ments are being compared with predictions from a tran-
sient conduction moclel employing the present reaction
kinetic scheme 9 The goodness of this comparison will
validate the kinetic model 9 Although our findings to date
are encouraging, there exist certain other unresolved
problems, such as the dependency of thermal conductiv-
ity on the degree of compaction and on temperature.
Research in this area is now in progress.
[14a] The research reported in this article can be summa-
rized by the following two conclusions:
1. An SHS reaction kinetic model, for C + aTi + bTiC,
has been presented to unambiguously describe the de-
pendency of the reaction rate on the mixture ratio,
dilution with the inert product, temperature, com-
paction density, and particle diameter 9 The details of
reaction mechanism postulated by Aleksandrov and
Korchagin 161 are indeed revealing and profound 9 Our
quantification of this mechanism, based on the first
[14b] principles of mass and species conservation, is sim-
ple; yet, the final results appear to be powerful and
important.
2. The thickness of the intermetallide complex ~ is an
empirical constant, a characteristic of the reactant
system, typically of the order of dp/400. If this thick-
ness is a constant during the reaction, the reaction
rate will be proportional to the instantaneous surface
area of the particle. In view of the fact that diffu-
sional mass transfer is intensified as the particle be-
comes gradually smaller, it appears reasonable to take
to be proportional to the instantaneous diameter of
the particle. Such an assumption additionally leads to
disappearance of the intermetallide complex upon
complete consumption of carbon.
A change in the constant/3 = 8/dp is expected to act
merely as a multiplying constant correction to the rate.
Any uncertainties in its magnitude are almost certain to
be overshadowed by variations in the thermochemical
and thermophysical properties.
NOMENCLATURE
a moles of titanium per mole of carbon in the
initial mixture
b moles of inert diluent (TIC) per mole of
carbon in the initial mixture

METALLURGICAL TRANSACTIONS A VOLUME 23A, SEPTEMBER 1992--2355

Cpi specific heat of species i [kJ/(kmol K)] 0 initial (or reference)
Ci molar concentration of species i [kmol/m 3] m in the melt
carbon particle instantaneous diameter [m] mix compacted initial mixture
carbon particle initial diameter [m] p carbon particle
dm diameter of the outlying melt [m] Ti titanium
D coefficient of diffusion of Ti ions and atoms TiC titanium carbide
in the intermetallide [m2/s]
Do reference diffusivity [m2/s]
E activation energy [kJ/kmol] ACKNOWLEDGMENT
J = 1, 2, and 3 for planar, cylindrical, and
spherical particles, respectively This research has been partially supported by NSF/
Mi molecular weight of species i [kg/kmol] CBTE under Grant No. CTS-8913556.
F radial coordinate [m]
R universal gas constant [kJ/(kmol K)]
t time Is] REFERENCES
T temperature [K]
-W c
9 tsr
volumetric reaction rate [kg/(m 3 s)] 1. A.G. Merzhanov: in Combustion and Plasma Synthesis of High-
Temperature Materials, Z.A. Munir and J.B. Holt, eds., VCH
--~/dp Publishers, New York, NY, 1990, pp. 1-53.
thickness of the intermetallide complex [m] 2. Z.A. Munir and U. Anselmi-Tamburini: Mater. Sci. Rep., 1988,
=-d#do vol. 3 (7-8), pp. 279-365.
extent of reaction 3. P.G. Shewmon: Diffusion in Solids, J. Williams Book Co., Jenks,
OK, 1983.
A D / D o -- exp [ - E / ( R T ) ]
4. B.I. Boltaks: Diffusion in Semiconductors, Academic Press, New
the Aleksandrov/Korchagin composition York, NY, 1963.
factor 5. S. Sarian: J. Appl. Phys., 1969, vol. 40 (9), pp. 3515-20.
Pi density of species i [kg/m 3] 6. V.V. Aleksandrov and M.A. Korchagin: Fiz. Goreniya Vzryva,
T* nondimensional time 1987, vol. 23 (5), pp. 55-63; translated in Combustion Explosion
and Shockwaves, 1988, vol. 23 (5), pp. 557-64.
6 -- C rim/ C TimO 7. R.E. Carter: J. Chem. Phys., 1961, vot. 34 (6), pp. 2010-15.
8. N.L. Wu, T.C. Wei, S.Y. Hou, and S.Y. Wong: J. Mater. Res.,
Subscripts 1990, vol. 5 (10), pp. 2056-65.
9. R. Pampuch, J. Lis, and L. Stobierski: in Combustion and Plasma
c combustion Synthesis of High-Temperature Materials, Z.A. Munir and J.B.
C carbon Holt, eds., VCH Publishers, New York, NY, 1990, pp. 211-18.

2356--VOLUME 23A, SEPTEMBER 1992 METALLURGICAL TRANSACTIONS A