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Abstract
Recent progress on understanding fundamental mechanisms governing the Self-propagating High-temperature Synthesis
(SHS) process, which is characterized by the flame propagation through a matrix of compacted reactive particles and is
recognized to hold the practical significance in producing novel solid materials, is reviewed. Here the focus is not only on
the theoretical description of the heterogeneous nature in the combustion wave, which has not been captured by the conven-
tional premixed-flame theory for a homogeneous medium, but also on the extensive comparisons between the predicted and
experimental results in the literature. Topics included are the statistical counting procedure used for deriving governing
equations of the heterogeneous theory, flame propagation in the adiabatic condition, flame propagation and extinction under
heat loss conditions, effects of bimodal particle dispersion on the combustion behavior, those of external heating by electric
current, the transition boundary from steady to pulsating combustion, and the initiation of the combustion wave by use of the
external heating source. The importance of heterogeneity in the combustion wave, that is the particle size of the nonmetal or the
higher melting-point metal, has been emphasized for fundamental understanding of such combustion behavior as flame
propagation, extinction, and initiation. Potentially promising research topics are also suggested. 䉷 2000 Elsevier Science
Ltd. All rights reserved.
Keywords: Combustion synthesis; Self-propagating high-temperature synthesis; Flame propagation; Burning velocity; Range of flammability;
Extinction; Ignition; Ignition delay time
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. The SHS process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1. General characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2. Scope of the present survey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3. Phenomenological description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3. Formulation of the heterogeneous theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1. Surface regression rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2. Statistical counting procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.1. Change of distribution function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.2. Conservation equations in general form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.2.1. Overall continuity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.2.2. Species conservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.2.3. Momentum conservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.2.4. Energy conservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
* Tel.: ⫹ 81-53-478-1050.
E-mail address: tmaki@eng.shizuoka.ac.jp (A. Makino).
0360-1285/00/$ - see front matter 䉷 2000 Elsevier Science Ltd. All rights reserved.
PII: S0360-128 5(00)00004-6
2 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Nomenclature
A Reduced surface Damköhler number Da exp
⫺Ta =T
a Parameter
a3 f ⫺ 1 in Section 4; length of the rectangular cross section in Section 6; thermometric
conductivity in Section 8.1; radius of heating area by radiative heat flux in Section 8.2
a0 Leading term of the normalized mass burning rate
m=ma in Sections 5 and 7
B Frequency factor for the surface reaction in Section 3; constant in Section 7
B~ Frequency factor for the “reaction” term in the conventional homogeneous theory
b Parameter
b3 f ⫹ 2g ⫹ 1 in Section 4; width of the rectangular cross section in Section 6
C Constant; maximum temperature in Section 7
c Specific heat
D Mass diffusivity in Sections 3–7; constant in Section 8.
Da Surface Damköhler number;
BR=D
E Electric field in Section 6.4; energy for establishing combustion wave in Section 8
F Thermal runaway criterion in Section 8.2
f Distribution function
fst Stoichiometric mass ratio
G Size distribution function
H Heat-input parameter in Section 6.4
h Enthalpy
hrad Radiative heat-transfer coefficient
I Integrated quantity
Jn Bessel function of the first kind of order n in Section 8.2.2
K Constant in Section 7; derivative of temperature in nondimensional form in Section 8.1.2
k Inverse of the arithmetic mean of melting point and adiabatic combustion temperature in nondimensional form
k~ Over-all transverse wave-number in Section 7.3; nondimensional parameter related to normalized mass burning
rate in Section 8.1
L Volumetric heat loss
Le Lewis number
M Melting parameter
m Mass burning rate for deflagration
n Number of N particles
p Static pressure in Section 3; perimeter of rectangular cross section in Section 6.3
P Size ratio defined in Eq. (143) in Section 6.1.1
Q Heat flux
q0 Heat of combustion per unit mass of N species
R Average radius of N particles
R_ Rate of change of particle size R
dR=dt
r Radius of compacted specimen
S Cross-sectional area of compacted specimen
s Variable which represents a change of particle size in Section 3; stretched variable of time in reactive/diffusive
region in Section 8.2
s~ Stretched variable of time in transient/diffusive region in Section 8.2
T Temperature
T0 Standard temperature
Ta Activation temperature for the reaction
Td Activation temperature for the condensed phase mass diffusivity
t Stretched variable of temperature in Section 5.6.1; time in Sections 7 and 8.
U Diffusion velocity of species
u Heterogeneous burning velocity
v Velocity of a particle
W Molecular weight
X Normalized heat loss, defined as X exp
⫺2bC=a 02 exp
⫺C1 in Sections 5 and 7; stretched variable of
location in reactive/diffusive region in Section 8.2
x Physical spatial coordinate
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 5
Y Mass fraction
y Stretched variable of mass ratio of fluid in Section 5.6.1
Z Mass ratio of fluid
Greek symbols
a Normalized temperature rise
b Spalding transfer number in Section 3; Zeldovich number in Sections 4–8
G Mass ratio of small particles to large particles in Section 6
g Mass ratio of fluid to solid
D Damköhler number for flame initiation in Section 8
d( ) Delta function
d Thickness of combustion wave
e Emissivity
z Normalized mass fraction
h Variable which represents a change of particle size in Section 3; inner variable of length in Section 5.6.1
u Normalized temperature
k Degree of dilution defined as the initial mass fraction of the diluent
L0 Mass burning rate eigenvalue
L Heat penetration coefficient in Section 8
l Thermal conductivity
l u, l d Exponents which represent temperature distribution in Section 6.4 and Section 7
m Mixture ratio defined as the initial molar ratio of nonmetal, N, to metal, M, divided by the corresponding
stoichiometric molar ratio
n Stoichiometric coefficient
j Normalized mass ratio of fluid
1⫺j Normalized mass ratio of solid
r Density
s Nondimensional coordinate
sc Electric conductivity in Section 6.4
s ST Stefan–Boltzmann constant
s Stretched coordinate in the downstream in Section 5.6.1.
t Nondimensional time
t xx xx component of the viscous stress tensor in Section 3.
f Inverse of the mixture ratio m in Section 4.6 and 5.6; heat loss in Section 8.2.
w Function which represents dependence of the “reaction” term on reactants
w~ Nondimensional parameter related to heat loss in Section 8.1
x Surface regression rate
C Heat-loss parameter
c Variable for particle size distribution in Section 3; stretched variable for temperature in Section 8
V Constant
v Mass rate of production by homogeneous chemical reaction in Section 3; stretched variable of location in
transient/diffusive region in Section 8.2
6 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Subscripts
a Adiabatic condition
c Initiation of the combustion wave
cr State of extinction
d Downstream
E Equivalent
e Edge of boundary
f Fluid
I Inert heating
ig Igniter
in Material flow to the fluid from particles
L Large particles
M Metal or lower melting-point metal
m Melting point
max Maximum
N Non metal or higher melting-point metal
P Combustion product
p Perturbed term
r Representative value in Section 6.4; radial direction in Section 8.2
rel Relative
S Small particles
s Solid or surface
sb Neutral stability boundary
sp Specimen, that is, medium to be ignited
TMD Theoretical maximum density
t Differentiation with respect to time
u Upstream
z Differentiation with respect to location in the axial direction
j With respect to mass fraction of fluid Z
u With respect to temperature
t Ignition delay
0 Initial or unburned state
∞ Final or burned state in the adiabatic condition
Superscripts
t Nondimensional
— Average over all velocities in Section 3.
Synthesis (SHS) process. In the present review, emphasis is compacted reactive particles (cf. Figs. 1 and 2). From the view-
put on the latter, because of its various advantages, to be point of combustion science and/or technology, as shown in
examined. Fig. 2 photographically, the SHS process falls into a category
of the flame propagation, because a reaction initiated at one
end of a compacted medium self-propagates through an
2. The SHS process unburned medium, in the form of a combustion wave.
The velocity of the combustion wave, depending on
2.1. General characteristics systems, varies from 1 to 250 mm/s. The high temperature
needed for synthesis (perhaps more than 2000 K for inor-
Among various types of combustion synthesis, wide ganic compounds and more than 1000 K for intermetallic
attention has been given to the SHS process, proposed by compounds) can be supplied by the self-sustained exother-
Merzhanov and co-workers [1–3] in Russia in the late mic chemical reactions. The potential advantages of this
1960s, because not only bulk processing of materials, but process are as follows [4–9]: rapid synthesis; self-heating;
also formation of some elemental combinations not energy savings; self-purification due to enhanced impurity
previously synthesized, can be performed [4–9] by initiat- outgassing; near-net-shape fabrication, etc. In addition,
ing and passing a combustion wave through a matrix of more than 500 kinds of materials, including carbides,
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 7
Fig. 2. A sequence of the advance of a combustion wave in the SHS process for Ti–C system; stoichiometric mixture without dilution; diameter
is 18 mm and length is about 50 mm; the initial temperature T0 is 300 K and radius R0 of the carbon particle is 5 mm; the maximum temperature
is about 3200 K and the burning velocity u is 17 mm/s. (a) Just after the ignition; (b) 1 s; (c) 2 s; and (d) 3 s.
8 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
FeSi2, CoSi2
Fe4N, Fe8N
NiS, Ni3S2,
profiles in composition) was considered because of its rapid-
CoS, CoS2
FeB, NiB
ity in production. Although it has proven effective, it was
VIII
also recognized that in order to control the manufacturing
process, dependence of flame propagation speed on various
dominant parameters is indispensable. In addition, range of
MoB–Al2O3,
flammability with respect to various parameters is urgently
MnB, MnB2
MnSi
MnS
VII
MoSe2, WSe2
CrSi2, MoSi2,
Mo3Si, WSi2
Cr3C2, MoC,
MoS2, WS2, have pursued. That is, researchers in the field of combustion
Mo2B5, WB
WC–Al2O3,
CrB2, MoB,
Mo2C, WC
B4C–Al2O3,
TaN, Ta2N
VC, Nb2C,
VN, NbN,
NbC, TaC
VB, NbB,
TiSi, TiSi2,
ZrB2, HfB2
TiH2, ZrH2
ZrSi, ZrSi2
TiS2, ZrS2,
PbS, TiSe2
ZrN, HfN
ZrC, HfC
SiC, TiC,
PrH2, NdH2
B4C, Al4C3
TiC–ZrO2,
BN, AlN,
only of interest for its own sake, but also of great use for
potential improvement in the manufacturing process.
CeB2
NdN
CeS
III
Mg2Si, CaSi2
MgB6, CaB6
Mg3N2, SrN
ZnSe, CdTe
CaC2
BaN
Cu2S,
CsH2
CuN
Hydride
Carbide
Table 1
Silicide
Nitride
Boride
Fig. 3. Laminated structure in the combustion products; Ti–C system for stoichiometric mixture without dilution; the initial temperature T0 is
300 K. (a) Radius of the carbon particle R0 is 0.5 mm and the relative density r rel is 0.56. (b) R0 0:5 mm and rrel 0:63: (c) R0 0:5 mm and
rrel 0:72: (d) R0 2:5 mm and rrel 0:47: (e) R0 2:5 mm and rrel 0:64:
2.2. Scope of the present survey medium of compacted reactive particles. Again we are
required to construct an appropriate model which can prop-
Although much work has been conducted both experi- erly represent the combustion situation in the SHS process,
mentally and theoretically, a general lack of consistency by taking its heterogeneity into account in an essential
has been noted [25] in the combustion data and no firm manner.
understanding of the combustion mechanism has been The present paper, restricted to theoretical accomplish-
achieved. This may be attributed to the fact that compari- ment, aims to complement the extensive reviews by Fran-
sons between experimental and theoretical results have been khouser et al. [5], Munir and Anselmi-Tamburini [7],
rare, regardless of their importance for comprehensive Merzhanov [8] and Varma and Lebrat [9] regarding the
understanding of various combustion characteristics. experimental accomplishment, and those by Merzhanov
Through agreement between theoretical and experimental [4], Merzhanov and Khaikin [23] and Margolis [24] regard-
results over wide range of parametric quantities for various ing the theoretical accomplishment. Indeed, because of the
combinations of metal and nonmetal (or another metal of a broad coverage of some of these reviews, a narrow range of
higher melting point) systems, appropriateness of theories topics will be discussed here, focused on the heterogeneity
should therefore be examined. in the SHS process, to which little attention has been paid,
When such comparisons are conducted with conventional although it is indispensable for realistic descriptions of
models in the homogeneous premixed-flame theory, there combustion behavior. The present survey also emphasizes
exists an inherent deficiency that cannot account for size understanding of the fundamental mechanisms govern-
effect of particles, while experiments have firmly estab- ing the flame propagation, extinction, and/or initiation in
lished that the flame propagation speed increases with the SHS process, by being restricted to the solid–solid
decreasing particle size in a sensitive manner [26–28]. systems. It is also suggested that the reader refers to
This inherent deficiency comes from insufficient treatment, Ref. [31] for topics about the SHS process for the
based on the homogeneous premixed-flame theory. Even if gas–solid systems, which are not covered in the present
fine powder is used, for example 0.1 mm in particle review.
diameter, each particle contains more than 10 8 atoms. This In the next section, a phenomenological description of the
situation is far from that to which the homogeneous flame propagation in the SHS process is presented. In
premixed-flame theory can be applied. That is, we cannot Section 3, the statistical counting procedure is reviewed
regard the SHS process as a homogeneous phenomenon. and its usefulness is assessed. In Section 4, theoretical
Therefore, we are urgently required to re-examine the approaches are primarily aimed at studying the SHS flame
appropriateness of describing the SHS process as the propagation in the adiabatic condition. Following this,
premixed flame propagation in the homogeneous medium. several important effects on the SHS flame propagation
In another mathematical model for the SHS process, it is (such as the heat loss, size distribution of particles, and
proposed to assume the compacted medium as laminae of external heating by electric current) are discussed in relation
reactants [29,30]. The combustion situation for the usual to flame extinction. In Section 7, the transition boundary
SHS process, however, is quite different from this model between steady and pulsating combustion, which is indis-
because the combustion wave propagates through the pensable in bulk processing, is discussed. Up to this point,
10 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 4. Schematic flame structure in the heterogeneous flame (crystallization not described) [32].
discussion is confined to the flame propagation and extinc- consideration strongly suggests that a satisfactory formula-
tion. In the next section, initiation of combustion wave is tion must take into account the nonpremixed mode of par-
discussed for two different ignition methods: igniter and ticle reaction.
radiative heat flux. Here, it may be of great importance to recognize that the
flame propagation in the SHS process is actually quite simi-
2.3. Phenomenological description lar to that in fuel spray combustion, if we identify the fuel
droplets as the nonmetal (or higher melting point metal)
In order to recognize differences between the hetero- particles and the oxygen in air as the molten metal, restrict-
geneous flame in the SHS process and the homogeneous ing ourselves to the flame zone in the combustion wave. It is
premixed flame, let us first make a detailed phenomenolo- also appropriate to recognize that across the combustion
gical consideration for the SHS flame propagation. It can be wave, dozens of nonmetal particles [33] can exist in the
considered that the SHS process typically involves reaction “reaction” zone in which the temperature is higher than
between particles of a metal and a nonmetal (or another the melting point of metal. This can easily be confirmed
metal of a higher melting point). Generally speaking, before by comparing a representative particle size, for instance
the arrival of the combustion wave, the effects of the reac- 10 mm, to the approximate “flame thickness” d of about
tion cannot be remarkable due to the low temperature and 0.3 mm, evaluated from a relation d ⬇ l=
rcu derived by
small area of contact between particles. However, as this the phenomenological analysis for gaseous premixed flames
particle matrix is heated by the approaching combustion [34], with representative values of thermometric conductiv-
wave, the lower melting point metal melts first, resulting ity l /(r c) of 3 × 10⫺6 m2 =s and the burning velocity u of
in slurry consisting of the higher melting-point nonmetal 0.01 m/s for Ti–C system. This recognition further suggests
particles suspended in the molten metal. In addition, due that a statistical counting procedure for spray combustion,
to an increase in the area of contact, as well as that in explained in Ref. [35], is indispensable and of great use in
temperature, the reaction between nonmetal particles and describing the combustion behavior of the heterogeneous
molten metal is greatly enhanced. Then, it is anticipated flame in the SHS process. The degree of similarity is achiev-
that the subsequent reaction between them will take place able if we restrict ourselves to fundamental principles with-
mainly over the surface of the nonmetal particles; this situa- out probing too far into specific details of the physical
tion is schematically shown in Fig. 4 [32]. Provided that the processes.
nonmetal particles do not dissolve in the molten liquid, and Another important factor that can influence the SHS flame
that they are not too small, compared to the thickness of the propagation is the mass diffusion in liquid phase, which is
combustion wave, it is easily seen that the flame propagation closely related to the nonpremixed reaction of nonmetal
through the compacted medium is basically heterogeneous particles in the combustion wave. Since the mass diffusivity
in nature, involving a premixed-mode of propagation for the in the SHS process is anticipated to increase markedly over
bulk flame supported by the nonpremixed reaction of the a relatively thin, high temperature combustion wave, use of
dispersed nonmetal particles in the liquid metal. Therefore, the temperature-dependent liquid-phase mass-diffusivity in
it is reasonable to anticipate that the resulting flame struc- Arrhenius fashion [22] is appropriate and indispensable.
ture and response should be quite different from those As for the surface reaction on each nonmetal particle,
obtained by assuming a premixed-mode of reaction at the related to the nonpremixed reaction in the combustion
molecular level. That is, the present phenomenological wave, it is recognized to be quite similar to the combustion
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 11
of a single solid particle, having been examined in the field Ta;s
A Das exp ⫺ ; b exp
x~ ⫺ 1;
5
of solid combustion, if the oxygen in air is identified as the Ts
molten metal. This recognition further facilitates inclusion
of the finite-rate reaction at the particle surface when formu- by solving the quasi-steady liquid-phase conservation equa-
lation is conducted. tion in spherical coordinates
!
Finally, in closing this section, it may be informative ~ ~
to describe a simplified model [32] which has been ~ d r~2 dY M ⫹ x~ dY M 0;
⫺
r~ D
6
d~r dr~ dr~
adopted for investigating combustion behavior of the
heterogeneous flame in the SHS process. As shown in under the isothermal condition, with the boundary condition
Fig. 4, the combustion situation modeled is the planar, at the particle surface
~r 1
heterogeneous flame in an infinite domain of a !
~
compacted medium, originally consisting of a mixture ~ s dY M ⫹x~ Y~ M;s ⫺x~ ;
⫺
r~ D x~ ⬅ r~ vr r~2 AY~ M;s ;
of particles of nonmetal N, metal M, and an inert which dr~ s
can be the product P of the reaction according to
7
nM M ⫹ nN N ! nP P; where n i is the stoichiometric coef-
ficient. For simplicity, it is assumed that there is no and that at the outer edge
~r ! ∞ of the boundary layer
reaction until the mixture has been heated to the melt- around the particle
ing point Tm of the metal, at which all the metal par- Y~ M Y~ M;e :
8
ticles melt instantly. The reaction that follows is assumed to
take place at the particle surface at a finite rate and proceed In the above, A is the reduced surface Damköhler number,
until all of the nonmetal (or higher melting-point metal) parti- Das the surface Damköhler number ( B·R/D), b the Spald-
cles, or metal species, are consumed. ing transfer number, and other variables and parameters are
defined as
r vR Y n W
3. Formulation of the heterogeneous theory r~ ; vr r ; Y~ M M ; fst M M ;
R De fst nN WN
3.1. Surface regression rate rM D
r~ ; D~ :
rM;e De
Before describing the statistical counting procedure used
in spray combustion, let us first confirm the description of a where r is the radial coordinate, vr the radial velocity, Y~ M the
single solid particle undergoing combustion. Since it is stoichiometrically weighted mass fraction, fst the stoichio-
unnecessary to consider the velocity difference between metric mass ratio, W the molecular weight, D the mass
particles and molten metal in the SHS combustion wave, diffusivity, and the subscript s and e designate, respectively,
only combustion behavior in a quiescent fluid will be exam- the particle surface and the outer edge of the boundary layer.
ined. For a single, spherical, nonpermiable, solid particle of An introduction of the isothermal condition, which
radius R in a quiescent fluid, the rate of change of its mass enables us to put r~ 1 and D~ 1; can be justified when
caused by the surface reaction nM M ⫹ nN N ! nP P is the thickness of the bulk flame is much larger than the
expressed as particle size because we can anticipate that both a nonmetal
solid particle and molten metal around the particle are
M_ ⫺ d rN 4 pR3 ⫺rN 4pR2 R; _
1 heated equally as the combustion wave arrives. The use of
dt 3 the conventional constant property assumption can also be
which yields justified if attention is confined to a restricted region around
the single particle. Note that changes in thermophysical
rM D M_ properties in the bulk during the flame propagation can be
⫺RR_ x~ ; x~ ⬅ :
2
rN 4prM DR incorporated.
The analytical expression in Eq. (4), however, is an im-
Here, x~ is the surface regression rate, which coincides with plicit expression with respect to the surface regression rate,
the definition of the nondimensional combustion rate, which is difficult to have a clear image of its dependence on
commonly used in the conventional solid combustion. other parameters. Therefore, an attempt has been made to
Then, we have obtain an explicit, approximate expression [32,36] as
x rM D
R_ ⫺ ; x x~ :
3 x~ ⬅ ln
1 ⫹ b ⬇ ln 1 ⫹
A ~
Y M;e ;
9
R rN 1⫹A
The specific form of x~ can be obtained as [32,36] by use of the approximate relation
Y~ M;e ⫺ b b
x~ A ;
4 1 ⫺ exp
⫺x~ ⬇ x~
10
1⫹b 1⫹b
12 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
for small x~ ; as is the case for most solid combustion. Note the overall continuity equation for the fluid is given as
that the expression in Eq. (9) for the surface regression rate 2rf ZZ
has the same form as that commonly used in droplet ⫹ 7 x ·
rf u ⫺ _ dR dv;
rN 4pR 2 Rf
12
2t
combustion. The error between Eqs. (4) and (9) is within
2% for Ti–C system. It may be informative to note that Y~ M;e where r f is the fluid density defined as the mass of fluid per
in Eq. (9) can change as the combustion wave propagates, unit volume of physical space. Note that the fluid and liquid
being governed by the species conservation equations, to be densities are related by the expression
mentioned in the next section.
ZZ 4
rf rM 1 ⫺ pR3 f dR dv :
13
3.2. Statistical counting procedure 3
equation is given as and the bar denotes an average over all velocities, that is
" !# " !#
1 Z_ 1 Z
2
r h ⫹
u2
⫹ 7 x · rf u hf ⫹
u2 R_ Rf dv; v vf dv:
20
2t f f 2 2 G G
Eq. (18) can be further simplified as
2p XN
⫺7 x ·q ⫺ 7 x ·
T·u ⫹ ⫹ rf Yk
u ⫹ Uk ·f k 2 _ 1 2
2t
RG ⫹ 0;
SvG
21
k1 2R S 2x
ZZ 4
⫺ rN pR 3
F·vf dR dv when the local cross-sectional area S(x) only depends on the
3 variable x. Here, v is the x component of v ; and the quantities
! _ v;
R; and G are averages over the cross section, independent
ZZ v2
2_
⫺ rN 4pR R hin ⫹ f dR dv;
17 of the spatial coordinates normal to x.
2 By using a relation that R_ ⫺x=R in Eq. (3), Eq. (21)
becomes
where hf is the total enthalpy per unit mass of the fluid, q the
heat flux vector, and hin the total enthalpy per unit mass of 2c 2c
⫺x
⫹ vR 0;
22
material flowing from the vicinity of a particle to the fluid. 2R 2x
In the above, the last two terms accounts for the work done where
on the fluid by particle and the energy added to the fluid by
the material from the surface.
SvG
c⬅ :
23
R
3.3. Heterogeneous theory for the SHS process Upon transformation to the new independent variables
Zx x Zx x
In the SHS process, it is usual to consider a situation in s 2 R2 ⫺ 2 dx; h2 R2 ⫹ 2 dx;
which a reaction, initiated at one end of a matrix of ⫺∞ v ⫺∞ v
compacted reactive particles, moves through the adjacent
24
unburned matrix in the form of a self-sustained combustion Eq. (22) becomes 2c=2s 0; which means that c only
wave. In this situation, even a quasi-one-dimensional treat- depends on h . Letting the subscript 0 identify conditions
ment has practical importance, and its simplicity is favor- at the unburned state, we have c c 0(h ). Since h R0
able for clarifying dominant parameters that influence the as x ! ⫺ ∞, we see from Eq. (23) that the expression
flame propagation.
S 0 v0 R
G G
h
25
Sv h 0
3.3.1. Size distribution function in quasi-one-dimensional
form determines the size distribution G(R, x) at any position x in
The velocity dependence of the distribution function f, terms of the distribution G0(h ) at the unburned state
x !
which is not of primary interest, can be eliminated from ⫺∞:
the governing equations by integrating Eq. (11) over all
velocity space. Since f ! 0 as 兩v兩 ! ∞ for all physically 3.3.2. Conservation equations for steady, one-dimensional
reasonable flows, the integral of the last term in Eq. (11) form
is zero. As for the unsteady change of the distribution func- When we restrict ourselves to steady, one-dimensional,
tion f, it is of considerable significance in spray combustion, constant-area flows in which all particles travel at the same
in relation to such phenomena as diesel-engine combustion velocity, the distribution function f is expressed as
or combustion instability in liquid-propellant rocket motors.
f
R; x; v G
R; xd
v ⫺ v;
26
However, in the SHS process it may be excluded from our
consideration, because a matrix of compacted reactive par- where x is the flow direction, v the velocity of all particles,
ticles through which a combustion wave propagates is and d (·) the delta function.
expected to have a certain distribution of particles when it
is produced by compaction, as far as the distribution of 3.3.2.1. Overall continuity The integral over v in Eq. (12)
particle sizes is concerned. Then, we have yields
2 _ d Z∞
RG ⫹ 7 x ·
vG 0;
18
rf u ⫺ _ dR;
rN 4pR 2 RG
27
2R dx 0
where the number of particles per unit volume per unit range where u is the x component of u. The RHS in Eq. (27) also
of radius is appears in
Z d Z∞
G f dv;
19
r v
_ dR;
rN 4pR2 RG
28
dx s 0
14 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 5. Representative flame structure for the temperature u , the carbon concentration
1 ⫺ j; and the reaction rate dj /ds , along the
nondimensional coordinate s , for the stoichiometric mixture
m 1:0 without dilution
k 0 when the initial temperature T 0 450 K;
the Lewis number Le0 100; the initial Damköhler number Da0 10 9 ; and the adiabatic mass burning rate eigenvalue L0 6:109 × 10⫺5 :
Dashed curves are the results in the adiabatic condition [32] and solid curves are those in the nonadiabatic condition [64].
4.4. Theoretical and experimental results for Ti–C system nature of the heterogeneous flame structure supported by
particle reaction, so that the region of the particle consump-
Eqs. (67) and (68) have been numerical integrated to tion in the combustion wave can be called the “consumption
determine the mass burning rate eigenvalue for Ti–C system zone.” For the prescribed conditions with R 0 10 mm; the
[32]. Values of the physicochemical parameters are: q flame thickness and burning velocity are predicted to be
15 MJ=kg; c 1 kJ=
kg:K; rM 4:50 × 103 kg=m3 ; rN about 1 mm and 10 mm/s, respectively.
2:25 × 103 kg=m3 ; WN 47:9 × 10⫺3 kg=mol; WM 12:0 × Fig. 6 shows mass burning rate eigenvalue L 0 as a func-
10⫺3 kg=mol; Td 1973 K; Ta 3 × 104 K: For the mass tion of the initial surface Damköhler number Da0
diffusivity D D0 exp
⫺1:66 × 104 =T m2 =s is used, B·R0 =D0 for an initial temperature T~ 0 0:03
T0
following Hardt and Phung [29]. Since apparent thermo- 450 K; with the Lewis number Le0 and the mixture ratio
metric conductivity l /(r tc) is of the order of 10 ⫺5 m 2/s at m taken as parameters. With increasing Da0, L 0 initially
3000 K [41], the Lewis number Le0 is estimated to be 50 or increases and attains a constant value for Da0 ⬎ 10 5.
more. Total densities before and after combustion are This implies that for higher values of Da0, the reaction,
assumed to be equal. Note that the thermophysical proper- and hence the mass burning rate, becomes diffusion
ties used here implicitly account for effects of compact limited, herein A=
1 ⫹ A ! 1 in x~ which appears in
density, gases in void spaces, gas evolution, etc. Eqs. (67) and (68). Since Da0 is closely related to B·R0,
Fig. 5 shows a representative flame structure with profiles its value is also shown in the abscissa. Fig. 6 further
of temperature u , carbon mass fraction, 1 ⫺ j; and the par- shows that due to the very large value of Le0, L 0 is insen-
ticle consumption rate dj /ds , along the nondimensional sitive to Le0. It is, however, significantly increased with
distance s m a
1 ⫺ Z0 =
l=cx: The dashed curves rep- increasing m because of the increased amount of
resent the results in the adiabatic condition, while solid volumetric heat generation.
curves are those of the nonadiabatic condition, to be Since L 0 is basically independent of Le0, in order to
discussed in Section 5. Position at which u u m is set at determine appropriate values of B and Le0, numerical results
s 0: With the monotonic increase in the temperature u are compared with the experimental results [33] for various
from the melting point u m to the adiabatic combustion radii (from 0.5 to 12.5 mm) of specimen and it is confirmed
temperature
u 1; the mass fraction of carbon 1 ⫺ j [32] that close correlation can be obtained for Le0 100
rapidly decreases from 1 to 0. The particle consumption and B ⱖ 10 3 m=s when the relative density r rel is about 0.6.
rate dj /ds exhibits the initial increase due to carbon deple- Note that the value of B ⱖ 103 m=s implies that the combus-
tion and consequent decrease due to reactants depletion, as tion is diffusion-controlled. Fig. 7 shows the effect of the
R ! 0: Its profile spans approximately the same range over initial radius R0 of carbon particle on the burning velocity u0
which the temperature increases. Compared to the typical of the stoichiometric mixture
m 1 for various B. The
premixed flame structure, characterized by a narrow, highly comparison between the predicted and experimental results
peaked reaction rate profile located close to the maximum [26–28,33,42] demonstrates the importance of heterogen-
temperature, the present result demonstrates the diffusive eity in the flame propagation process, and shows the fact
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 19
Fig. 7. Burning velocity u0 for Ti–C system as a function of the Fig. 8. Burning velocity u0 for Ti–C system as a function of the
initial radius R0 of carbon particle, with the frequency factor B taken mixture ratio m , with the initial particle radius R0 and the frequency
as a parameter [32]; the Lewis number Le0 100; the initial factor B taken as parameters [32]; the Lewis number Le0 100 and
temperature T~ 0 0:03 (T0 450 K), and the mixture ratio m the initial temperature T~ 0 0:03 (T0 450 K). Data points are
1:0: Data points are experimental [26–28,33,42]; solid curves are experimental [33]; solid curves are calculated with Arrhenius diffu-
calculated from theory. sivity; dashed curves are calculated with representative diffusivity.
20 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 9. Burning velocity multiplied by particle radius (SHS rate-constant) u0·R0 for Ti–C system as a function of 2m=
1 ⫹ m; with the degree of
dilution k taken as a parameter [40]; the initial temperature T0 450 K: Data points are experimental [33,43] for different particle radii of
R0 5 mm and 12.5 mm.
parameter. Introduction of 2m=
1 ⫹ m; which is a harmonic gradually decreases until k reaches the dilution limit given
mean of m and 1=m; enables us to discuss the effect of m , by Eq. (78), due to reduced volumetric heat generation.
which can change from zero to infinity, in a finite domain. Experimental results shown in Fig. 11 are those by
With increasing 2m=
1 ⫹ m; the SHS rate-constant u0,a·R0 Bloshenko et al. [44] at T0 973 K and those by Makino
first increases, reaches the maximum, and then decreases. et al. [33] at T0 450 K; the experimental results
The increase in u0,a·R0 is attributed to an increase in the [26,45,46] with carbon particles of 0.1 mm in diameter are
volumetric heat generation, as well as an increase in the excluded because steady propagation cannot be expected.
heat generation rate in the combustion wave, related to the Fig. 12 shows u0 as a function of the relative density r rel
total surface area of N particles. The peak of u0,a·R0 occurs for m 1:0; with 2R0 taken as a parameter; u0 gradually
on the rich side
m ⬎ 1 of N particles, because of the decreases when 2R0 is larger than 10 mm and the steady
increase in the total surface area of N particles, in spite of
the decrease in volumetric heat generation. Further increase
in 2m=
1 ⫹ m results in a decrease in u0,a·R0, because of the
reduced volumetric heat generation. It is also observed that
u0,a·R0 decrease with increasing k , and that dilution moves
the position of the maximum u0,a·R0 towards the stoichio-
metric mixture. Experimental data [33,43] for two different
particle sizes are also shown in Fig. 9 and fair agreement is
observed as far as the general trend and the approximate
magnitude are concerned. It is pointed out, however, that
discrepancies near the maximum u0,a·R0 may be attributed to
the assumption of constant thermophysical properties
throughout the combustion wave. Overestimation of the
range of flammability by Eqs. (77) and (79) is attributed to
the heat loss to be discussed in Section 5.
Fig. 10 shows u0 as a function of the initial temperature
T0, for m 0:6 and 1.0. The trend of increasing u0 with
increasing T0 is as expected, as the preheating effect. The
comparison with experimental data [33,44] is again satisfac-
tory.
Dilution by the final product (TiC), to control the burning
velocity and/or combustion temperature has also been inves- Fig. 10. Burning velocity u0 for Ti–C system as a function of the
tigated; in the field of material processing, this corresponds initial temperature T0, with the mixture ratio m and the frequency
to controlling grain size in materials through control of the factor B taken as parameters [32]; the Lewis number Le0 100 and
maximum temperature. Fig. 11 shows u0 as a function of k the initial radius R0 10 mm: Data points are experimental [33,44];
for m 1:0; with T0 taken as a parameter. It is seen that u0 solid curves are calculated from theory.
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 21
Fig. 12. Burning velocity u0 for Ti–C system as a function of the relative density r rel, with particle diameter 2R0 taken as parameters; the Lewis
number Le0 100 and the mixture ratio m 1:0: Data points are experimental [26,33]; open symbol designates the steady propagation and
half-open symbol the pulsating combustion.
22 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
ing.
Borovinskaya et al. [51]
Borovinskaya et al. [51]
Borovinskaya et al. [51]
The intermetallic compounds such as titanium cobaltide
Azatyan et al. [46]
3:00 × 104
3:83 × 104
3:73 × 104
4:79 × 104
1:68 × 104
4:28 × 104
5:61 × 104
1767
1728
934
12:0 × 10⫺3
10:8 × 10⫺3
10:8 × 10⫺3
10:8 × 10⫺3
58:7 × 10⫺3
47:9 × 10⫺3
47:9 × 10⫺3
Mol. wt. of
4:50 × 103
4:50 × 103
6:53 × 103
13:09 × 103
2:69 × 103
8:90 × 103
8:85 × 103
Density of
M-species
Co ⫹ Ti ! TiCo
Zr ⫹ 2B ! ZrB2
Al ⫹ Ni ! NiAl
Ti ⫹ 2B ! TiB2
Graham [63]
Graham [63]
The comparison between predicted and experimental
and Td
500
10
10
4
1:66 × 104
1:54 × 104
1:74 × 104
2:40 × 104
9:01 × 103
1:87 × 104
1:92 × 104
2:0 × 10⫺7
8:9 × 10⫺9
1:3 × 10⫺8
5:0 × 10⫺7
4:8 × 10⫺6
1:1 × 10⫺5
2:9 × 10⫺5
System
Ni–Ti
Hf–B
Zr–B
Ti–C
Ti–B
b
a
Fig. 13. Burning velocity u0 as a function of the mixture ratio m , with the initial temperature T0 taken as parameters [47]; solid curves are
calculated from theory. (a) Ti–B system for Le0 103 and R0 0:5 mm; (W) data from Hardt and Holsinger [45]; (A) from Kirdyashkin et al.
[49]; ( ) from Zenin et al. [50]; (K) from Borovinskaya et al. [51]; (S) from Novikov et al. [52]. (b) Zr–B system for Le0 500 and R0
0:5 mm; (A) data from Merzhanov and Borovinskaya [3]; (W) from Hardt and Holsinger [45]; ( ) from Zenin et al. [50]; (K) from Borovinskaya
et al. [51]; (S) from Novikov et al. [52], (c) Hf–B system for Le0 4 and R0 0:5 mm; (K) data from Borovinskaya et al. [51]; (S) from
Novikov et al. [52]. (d) Co–Ti system for Le0 10; R0 30 mm and 50 mm; ( ) data from Itin et al. [53]; (A, W) from Itin et al. [54].
Fig. 14. Burning velocity u0 as as a function of the degree of dilution k , with the initial temperature T0 taken as a parameter [47]; stoichiometric
mixture
m 1:0; solid curves are calculated from theory. (a) Ti–B system for Le0 103 and R0 0:5 mm; (W) data from Hardt and
Holsinger [45]; (K) from Borovinskaya et al. [51]; (S) from Novikov et al. [52]; ( ) from Shcherbakov and Pityulin [55]; (L) Maksimov
et al. [56]. (b) Zr–B system for Le0 500 and R0 0:5 mm; (A) data from Merzhanov and Borovinskaya [3]; (W) from Hardt and Holsinger
[45]; ( ) from Zenin et al. [50]; (K) from Borovinskaya et al. [51]; (S) from Novikov et al. [52]. (c) Hf–B system for Le0 4 and R0
0:5 mm; ( ) from Zenin et al. [50]; (K) from Borovinskaya et al. [51]; (S) from Novikov et al. [52]. (d) Al–Ni system for Le0 10 and R0
10 mm; (A, S) data from Maslov et al. [57] for T0 298 K and 740 K. (e) Co–Ti system for Le0 10 and R0 30 mm; (W) data from Itin et al.
[53] for T0 873 K:
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 25
26 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
4.6. Approximate expression for the burning velocity 4.6.1. Derivation of the approximate expression for m ⱕ 1
To this aim, we should first note that for the usual SHS
Mass burning rate eigenvalue L 0, the square root of process the diffusion-controlled reaction prevails, as
which is the nondimensional burning velocity, has been mentioned in the previous sections, and the Lewis number
obtained numerically [32,47] and hence presented is very large, say, Le ⬎ 104 in the consumption zone. By
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 27
assuming diffusion-controlled limit and infinite Lewis and the complementary error function
number, we have
2 Z∞
x~ ⬇ ln
1 ⫹ Y~ M
81 erfc
z p exp
⫺t2 dt
89
p z
T~ d
T~ ∞ ⫺ T~ 0
b
85
T~ ∞2
T~ d T~ n o
d 1 ⫹ a
1 ⫺ u ⫹ a2
1 ⫺ u2 ⫹ …
T~ T~ ∞
" #
b 3 1 2
⬇ ⫹ a2
1 ⫺ u ⫹ ;
86
a 4 2a
we have
p
p 3b
Iu ⬇ p exp ⫺
2b a=b 4a
1 1 ⫹ 2a
1 ⫺ um
erfc p ⫺ erfc p
87
2 a=b 2 a=b
where Fig. 17. Temperature profile in the reaction zone, with the mixture
ratio m taken as a parameter [37]. Solid curves are numerical results
T~ ∞ ⫺ T~ 0 and dashed curves the assumed profiles to obtain the approximate
a ;
88
T~ ∞ analytical expressions for the mass burning rate eigenvalue L 0.
28 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
p
Fig. 18. Nondimensional burning velocity L0 for Ti–C system [37]; (a) as a function of the mixture ratio m ; and (b) as a function of the degree
of dilution k . The initial temperature T0 is taken as a parameter. Solid curves are numerical results and dashed curves are those with analytical
expression.
the integral Ij in the RHS of Eq. (83) is expressed as initial temperature T0, the mixture ratio m , and the degree of
! " dilution k are operating parameters when the experimental
1 ⫹ um 1
f ⫺ 1
Ij ⬇
f ⫹ g 2 ⫺ ⫹ conditions are specified.
2 5
f ⫹ g 2a Keeping only the leading terms in Iu and Ij in Eqs. (87)
( ! p ) and (92), respectively, the functional dependence of L 0 on
1 ⫹ a 3 p ⫺1 2 ⫺ a 3
ln ⫺ 2 3 tan p ⫺ p the system parameters can be displayed as
f 3a 3
m 2
1 ⫺ k2 exp
⫺b=a
f ⫹ 2g ⫹ 1 L0 ⬃
94
⫹
m ⫹ fst
1 ⫹ fst ⫺ k
1 ⫺ mb
1 ⫹ um
6b
( ! p )# As far as m and k are concerned, L0 ⬃ m2 =
m ⫹ fst for
b ⫺ 13 p ⫺1 2 ⫹ b 3
× ln ⫹ 2 3 tan p ⫺ p ; k 0; and L0 ⬃
1 ⫺ kp 2
for m 1: That is, the nondimen-
f ⫹ 2g 3b 3 sional burning velocity L0 decreases with decreasing m
92 and 1 ⫺ k: Its quantitative dependence on m and 1 ⫺ k;
however, is more complicated because volumetric heat
where a3 f ⫺ 1; and b3 f ⫹ 2g ⫹ 1:
generation, which is a function of m and 1 ⫺ k; also influ-
Then, from Eqs. (87) and (92), we have
ences a and b through T∞. The effect of T0, which deter-
r Iu I
L0 t;0
1 ⫺ Z 0 u ;
93 mines T∞, may also be significant because T∞ can
rt
1 ⫹ gIj Ij exponentially influence L 0 through a and b . Note that b
also depends on the choice of the mixture components.
which is found to be surprisingly close to that obtained by a
When we compare L 0, Ti–C for Ti–C system with L 0, Ti–B
numerical calculation. This good agreement further demon-
for Ti–B system, (L 0, Ti–B/L 0, Ti–C) 1/2 is about 4 for m
strates the importance of the describing processes well at the
1; k 0; and T0 450 K; because of the smaller value of
hot boundary, rather than the cold boundary (cf. Fig. 17).
b for Ti–B system.
Since Eq. (93) is relatively simple, its use could facilitate
analysis and interpretation.
4.6.3. Comparisons with numerical results
4.6.2. General behavior Applicability of the analytical expression has been exam-
An explicit form of L 0 provides useful insight into the ined by comparing it with the numerical results [32,47] for
effects of the reduced parameters (a , b , u m, f , and g ), TiC, TiB2, ZrB2, HfB2, and TiCo systems in Sections 4.4 and
which depend on the system parameters (fst, Td, Tm, T0, m , 5.5, and a fairpagreement
has been reported in Ref. [37]. Fig.
and k ) used in the experiments. Among these parameters, 18(a) shows L0 for Ti–C system as a function of m , with
the stoichiometric mass ratio fst, the activation temperature T0 taken as a parameter. Solid and dashed curves are respec-
Td in the mass diffusivity, and the melting point Tm of the tively numerical and analytical results.pExcept
near stoichio-
lower melting-point metal are physicochemical parameters metry
m 1; both results show that L0 decreases until m
when the two components of the mixture are specified. The reaches the limit given by Eq. (77), and that they mostly
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 29
p
Fig. 19. L0 for Ti–B system. Notation is the same as that in Fig. 18.
agree well with each other. Although the trend in the analy- then, we have
tical expression near m 1 is opposite to that of the numer-
r I fI u
ical result, the quantitative comparison can be considered to L 0 t;0
Z∞ ⫺ Z0 u ;
96
be fair (⬍7% error). This discrepancy is attributed to the rt Ij
1 ⫹ gIj
overestimated temperature profile given by Eq. (90), which
causes an overestimation of Ij , and hence an underestima- where the relation has been made use of in Eq. (61). The
tion of L 0. Fig. 18(b) shows the similar comparison with integral Iu is the same as that in Eq. (87), while the integral
respect to k . The analytical expression again agrees well Ij is expressed as [40]
with the numerical results, to be within 7%. Figs. 19 and ! !
1 ⫹ um f⫹g
20 show similar comparisons for Ti–B and Co–Ti Ij ⬇
systems. The extent of agreement is similar to that for 2 f2
Ti–C system. "
3 ⫺ 5f ⫺ 3
1 ⫺ fa2
f ⫹ g
× 2
1 ⫺ a2 ⫹ ⫹
10
f ⫹ g 3b
4.6.4. Approximate expression for m ⱖ 1 ( !3 !
2
f ⫹ g b⫺1 p 2⫹b
When the mixture ratio is over-stoichiometric, the ln ⫹2 3 tan⫺1 p
normalized concentration z of M-species is f ⫹ 2g a⫹b 3b
!)#
Z∞j p ⫺2a ⫹ b
z⬇ ;
95 ⫺ 2 3 tan⫺1 p : (97)
Z 0 ⫹
Z∞ ⫺ Z0 j 3b
p
Fig. 20. L0 for Co–Ti system. Notation is the same as that in Fig. 18.
30 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
p
Fig. 21. L0 for Ti–C system as a function of m when T0 450 K; with k taken as a parameter. Solid curves are numerical results and dashed
curves are those with analytical expressions.
p
Dependence of L0 for Ti–C system on m in its wide range this aim, it is required to extend the adiabatic theory to allow
is shown in Fig. 21, with k taken as a parameter. The extent for the volumetric heat loss, to properly describe flame
of agreement in m ⱖ 1 is similar to that in m ⱕ 1: extinction and the various parameters that characterize it.
It will be emphasized here that not the reaction, but the
4.7. Some remarks on the flame propagation in the adiabatic temperature sensitive Arrhenius liquid-phase mass-diffusion
condition is responsible for the flame extinction, because in the SHS
process, combustion is basically diffusion controlled.
Calculated results for several ceramics and intermetallic
compounds, such as Ti–C, Ti–B, Zr–B, Hf–B, Al–Ni, Co–
5.1. Governing equations and boundary conditions
Ti, Ni–Ti systems, using consistent sets of physicochemical
parameters, respectively, show satisfactory agreement with A one-dimensional model with heat loss has been used to
experimental results in the literature, if we use the hetero- discover the dominant parameters which determine the limit
geneous theory in the adiabatic condition. An important of steady flame propagation. Although heat loss perpendi-
relation, that the burning velocity is inversely proportional cular to the propagation direction might lead to the curva-
to the nonmetal particle size, has been discovered. In ad- ture of the combustion wave, a choice of this model
dition, these comparisons suggest that the nonmetal (or simplifies the formulation and hence meets the present
higher melting-point metal) particles in these systems purpose. Therefore, regardless of the existence of heat
react in the diffusion-controlled limit, indicating that finite loss, the governing equations (except for the energy conser-
rate chemical reaction is not the controlling factor in the vation equation) have the same form as those in the adia-
propagation of the bulk flame. Furthermore, it has been batic condition, that is Eq. (46) for N-consumption and Eq.
suggested that concentration of the molten metal is mainly (49) for M-conservation [64]. The energy conservation
affected through consumption, because of the excessively equation is now not Eq. (57), but Eq. (58).
slow rate of diffusion compared to the thermometric Defining the nondimensional variable and parameter
conductivity and reaction rate, due to excessively large
Lewis number in the combustion wave. These identifica-
Z ∞ ⫺ Z0 ma
l=cL
s x; F
u 2 0
98
tions further enable us to obtain an approximate expression
l=c m a q
T~ ∞ ⫺ T~ 0 ;
for burning velocity, which can show clear dependence of
in addition to those in Eqs. (66), (71) and (72), we have the
the burning velocity on the dominant parameters.
governing equations as
" #
dz ~ m
Le 0
rt;0 =rt exp
T~ d =T
5. Flame propagation in the nonadiabatic condition
ds Z0 ⫹
Z∞ ⫺ Z0 j ma
The heterogeneous theory [32] described in Section 4 is
Z∞ Z0z
an adiabatic one, and hence is incapable of describing the z⫺ j⫹ ;
99
experimentally observed phenomena of flame extinction due Z∞ ⫺ Z0 Z∞ ⫺ Z0
to heat loss from the high-temperature combustion process.
From a practical point of view, extinction is to be properly d2 u m d u⫺j F
u
⫺ ;
100
described and hence controlled in the SHS process. Toward ds 2 m a ds Z ∞ ⫺ Z0
Z ∞ ⫺ Z0 2
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 31
" #
dj x~
ds
m=m a L0
rt;0 =rt exp
T~ d =T
~
1=3
Z∞ ⫺ Z0
1⫺ j :
101
1 ⫺ Z0
Eqs. (99)–(101), together with the mass burning rate m, are
to be solved subject to the boundary conditions
s0: u u m ; z 0; j 0;
102
du F
u dz dj
s!∞: ⫺ ; 0; 0:
ds
m=m a
Z∞ ⫺ Z0 ds ds
103
In the same manner as that in the adiabatic flame propa- Fig. 22. The representative profiles of the diffusion, consumption,
gation, the cold boundary difficulty is eliminated by speci- convection, and loss terms in the energy conservation equation,
fying that the reaction is initiated at the melting point of M. along the nondimensional distance [64]. Conditions are the same
The downstream boundary condition for u , based on as those in the nonadiabatic situation in Fig. 5; m=ma 0:6 and C
convection-loss balance, requires a short domain of integra- 3:347 × 10 ⫺2 :
tion, and is preferred over the statement of T T 0
u 0;
which would require an excessively large domain of inte-
gration. If we further assume the heat loss to be Newtonian,
it is expressed as F
u C·u; where C is called the heat Here, ma,st is the mass burning rate for the stoichiometric
loss parameter. mixture in the adiabatic condition. Results exhibit the char-
acteristic extinction turning point behavior, with the upper
5.2. Characteristics in the nonadiabatic condition branch being the stable solution and the turning point desig-
nating the state of extinction. With decreasing m or increas-
Values of the physicochemical parameters employed are ing k , the mass burning rate is gradually reduced, until
those for Ti–C system and the Lewis number Le0 is set to be extinction occurs. Since not only m/ma,st but also (ma/
100 [32] as described in Section 4.4. Representative flame ma,st) 2·C strongly depends on the mass burning rate m, the
structure for the stoichiometric mixture
m 1 without parameters m/ma and C are usually used to obtain the
dilution
k 0 has already been shown in Fig. 5 by solid extinction condition; the values of (m/ma)cr corresponding
curves, when the nonadiabatic situation is close to the to flame extinction ranges from 0.57 to 0.70, depending on
extinction state. In contrast to the adiabatic case in which m and k .
temperature increases monotonically to the adiabatic flame Here it may be informative to note the significant impli-
temperature, the temperature gradually decreases to the cation of Eq. (81). Since extinction is frequently associated
ambient value after the maximum flame temperature. with the nonlinear, highly temperature-sensitive nature of
Decrease in the temperature u reduces the particle consump- the Arrhenius kinetics, the disappearance of its influence in
tion rate dj /ds and hence the normalized burning-rate m/ma. the diffusion-controlled limit implies that extinction as
The reactant consumption zone is then broadened due to shown in Fig. 23 is actually caused by an alternate
heat loss. factor, which also has a nonlinear influence on flame
By obtaining profiles of the four terms constituting Eq. propagation. This factor is the liquid mass-diffusivity
(100), which, respectively, represent diffusion d 2u /ds 2, D D 0 exp
⫺Td =T which varies in a sensitive, nonlinear,
convection ⫺
m=ma =
Z∞ ⫺ Z0
du=ds; consumption Arrhenius manner with temperature. Thus in the SHS
m=ma =
Z∞ ⫺ Z0
dj=ds; and heat loss ⫺F
u=
Z ∞ ⫺ process, even in the diffusion-controlled limit, combustion
Z0 2 ; a further examination has been made to identify the behavior, as well as the particle regression rate, is still an
flame structure for the nonadiabatic case in Fig. 5. As shown Arrhenius function of temperature, with the large activation
in Fig. 22, the combustion wave consists of a relatively thin temperature for diffusion, Td, exerting the dominant
zone of diffusion and consumption/convection, which is temperature sensitivity.
followed by a much thicker zone of convection and heat Fig. 24(a) and (b), respectively, show the effect of m and
loss. The existence of an extended zone of downstream k on the critical heat loss parameter Ccr ; with the initial
heat loss is similar to the nonadiabatic homogeneous temperature T0 taken as a parameter. The change in Ccr is
gaseous flame. gradual when either m or k is away from the flammability
Fig. 23 shows the variation of the normalized mass burn- limit, while Ccr decreases rapidly as this limit is approached.
ing rate m/ma,st as a function of the normalized heat loss It is also seen that Ccr increases with increasing T0 for a given
C ⴱ
m a =ma;st 2 ·C with m and k taken as parameters. m or k . This suggests that even if a heat loss exists, flame
32 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 23. Normalized mass burning rate m/ma,st as a function of the normalized heat loss C ⴱ
m a =ma;st 2 ·C; with the mixture ratio m and the
degree of dilution k taken as parameters when the initial temperature T 0 450 K [64]. The values of numerically obtained (m/ma,st)cr
corresponding to the turning point are indicated by the horizontal solid lines; those of analytical ones are indicated by the dashed lines.
propagation can be sustained when T0 is high. Note that Eliminating s from Eq. (104) with Eq. (101) and conducting
there exists a maximum in C cr at high T0. integration, we have
!
exp⫺b
1 ⫺ u m 2 rt;0 T~ d
L0 exp
5.3. Turning-point determined by the thermal theory b ma rt T~ ∞
The heterogeneous SHS flame propagation has some Zj
105
u⫺j
special features, as shown in Eqs. (81) and (82), which × 1=3 dj;
0 Z∞ ⫺ Z0
can be contrasted with the homogeneous gaseous flame
Z ∞ ⫺ Z0 1 ⫺ j x~
1 ⫺ Z0
propagation. Nevertheless, an explicit relation for the state
of extinction can be derived [64] in the same manner as that where the relation has been used in Eq. (86), retaining up to
for the homogeneous premixed flame [65]. the first term. When je ⬇ 1 at the downstream edge of the
In the thin diffusion consumption/convection zone, consumption zone, by taking account of the adiabatic con-
contribution of the heat loss term is very small, such that dition, that is u j 1 and m m a ; we obtain the follow-
Eq. (100) becomes ing relation to the lowest order:
du m u⫺j m 2
⬇ :
104 exp⫺b
j e ⫺ ue :
106
ds ma Z ∞ ⫺ Z0 ma
Fig. 24. Critical heat loss parameter C cr [64]: (a) as a function of the mixture ratio m when the degree of dilution k 0; and (b) as a function of
k when m 1:0: The initial temperature T0 is taken as a parameter.
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 33
Fig. 25. Comparisons between numerical and analytical solutions for the critical value of the mass burning rate ratio (m/ma)cr [64]; (a) as a
function of m ; and (b) as a function of k . The initial temperature T0 is taken as a parameter.
by the use of the upstream relation
du=ds
m=m a Note here that C depends not only on the physicochem-
u=
Z∞ ⫺ Z0 and the downstream boundary condition ical parameters, but also on the particle radius R0 and the
(103). compact diameter 2r. It is also inferred that R 02 =
2r; which
Combining Eqs. (106) and (108), we obtain the relation is sometimes called the “Heat Loss Index”, can be a useful
parameter in correlating size effects related to the heat loss,
m 2 m 2 from a practical point of view. This parameter R20 =
2r can be
ln ⫺V;
109
ma ma understood as follows, from a physical point of view; the
increase in R0 decreases the total surface area of N particles
from which we have
m=m a cr e ⫺1=2 0:6065 at the turn-
in the combustion wave, thereby reducing the volumetric
ing point, corresponding to the state of extinction. Fig. 23
heat generation rate; the decrease in r increases the
shows that this analytical extinction state fairly represents
surface-volume ratio of the compact, thereby enhancing
the numerical value, as the first approximation.
heat loss rate.
Fig. 25(a) and (b) further show (m/ma)cr as functions of m
and k , with T0 taken as a parameter. Although the numerical
and analytical solutions for (m/ma)cr differ by 15%, this 5.4.1. Range of flammabilty and extinction limit
difference is reduced to less than 4% in determining C cr. Predicted results are compared with experimental data for
A more precise treatment will be given in Section 5.6. Ti–C system [64]. In addition to the values of physicochem-
ical parameters, described in Section 4.1, use has been made
of l=
rt c 10⫺5 m2 =s [41], e 0:4 [41], and s SB
5.4. Experimental comparisons for Ti–C system 5:67 × 10 ⫺11 kJ=
m2 :s:K4 : The compact radius is set to be
r 9 mm and its relative density 0.6, in accordance with the
There exist several sources of experimental data which
experiments [33,43]. As for the heat loss parameter C , it is
can be compared with the calculated results, as in
evaluated at the maximum temperature of the combustion
Refs.[64,66], by keeping as many parameters as fixed
wave.
possible. For the heat loss, only thermal radiation is consid-
Fig. 26(a) shows the range of flammability when T 0
ered, because of the high temperature in the consumption
450 K; the abscissa is the mixture ratio m and the ordinate
zone, say, higher than 2000 K. Then the lateral heat loss for
the particle radius R0. Extinction is anticipated to occur
a cylindrical compact with radius r can be expressed as
when C in Eq. (112) reaches the critical heat loss parameter
4h rad C cr in Fig. 24(a). We see that while the range of flamm-
L
T ⫺ T0 ;
110
2r ability spans from 0.448 to 1 when R 0 ! 0; it contracts with
34 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 26. Nonadiabatic combustion behavior for Ti–C system [64]; Fig. 27. Nonadiabatic combustion behavior for Ti–C system [64].
solid curves are calculated from theory; data points are experimental (a) Range of flammability with respect to the degree of dilution k
[33,43]. (a) Range of flammability with respect to the mixture ratio and the particle radius R0; notation is the same as that in Fig. 26(a).
m and the particle radius R0; (W) designates the steady propagation, (b) u0·R0 as a function of k , with R0 taken as a parameter.
(Z) the pulsating combustion, (K) the flame extinction during the
propagation, and ( × ) the non-ignition. (b) SHS rate-constant u0·R0
as a function of m , with R0 taken as a parameter. dilution k is shown in Fig. 27(a), and Fig. 27(b) shows u0·R0
as a function of k . The same comments as those for Fig.
26(a) and (b) can be made.
increasing R0. It also shows that the combustion wave Fig. 28(a) shows the range of flammability for various m
cannot propagate through a compact when R0 is larger and k , with R0 taken as a parameter [66]. The range of
than 20.9 mm. Experimental results [33,43] are also shown flammability becomes narrow with increasing R0. Exper-
in Fig. 26(a). Outside the range of flammability, even if the imental results [33,43] in Fig. 28(a) are those of R0
flame propagation might be initiated by a powerful ignition 5 mm: Fig. 28(b) shows a similar comparison [40] for the
source, it loses its self-sustained nature and is extinguished dependence of the range of flammability on m in its wide
in the course of the propagation. Fair agreement is demon- range when R0 12:5 mm: In the range from m 1 to 2, the
strated for particles smaller than 7.5 mm, while discrepancy range of flammability with respect to k is wider than that for
becomes large for R0 12:5 mm: This discrepancy is attrib- the stoichiometric mixture. This is attributed to the increase
uted to the effect of smaller particles, because of the exis- in u0,a·R0 (cf. Fig. 9), which reduces C , and hence retards the
tence of particle-size distribution. It is also pointed out that flame extinction. Discrepancy between the predicted and
the extinction limit obtained here corresponds to that for the experimental results for the under-stoichiometric mixtures
steady flame propagation. When the process occurs in an
m ⬍ 1 is attributed to the effect of smaller particles
unsteady mode, due to disappearance of stability of the because of the existence of particle size distribution. Dis-
steady propagation, the limit of self-sustained combustion crepancy for the over-stoichiometric mixtures
m ⬎ 1
could be modified accordingly. Fig. 26(b) shows the SHS might be attributed to an initiation of a radial crack, which
rate-constant u0·R0 in the adiabatic condition as a function of inevitably appears in pulsating combustion [1–3] resulting
m . The agreement is again fair, as far as the trend and in a laminated structure with separable layers.
approximate magnitude are concerned, suggesting that Munir and Lai [67] measured the boundaries of the SHS
u0·R0 is one of the important parameters in correlating for Ti–C system at several ambient (or initial) temperatures.
experimental results. Their test specimen (19 mm in diameter and 0.65 in relative
The range of flammability with respect to the degree of density) is composed of tens of layers (5 mm in thickness)
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 35
because the heat loss rate is enhanced due to an increase in constant u0·R0 and the heat loss index R20 =
2r is demon-
the surface-to-volume ratio. Fair agreement is demonstrated strated, as the correlating parameters for experimental
between the experimental and predicted results. results.
Extinction of the combustion wave in the SHS process Here, b is the Zeldovich number defined in Eq. (85),
has been obtained numerically and hence presented par-
s m a a
ametrically. An approximate analytical expression for the s ; a0 ⫹ 1 ⫹ 22 ⫹ …;
115
extinction criterion [72] which explicitly displays its func- b ma b b
tional dependence on the various system parameters, is also
and C1 ; C2 ; … are constants.
obtainable by referring to an analytical criterion for the
As for the inner solution, with the inner variables being
“premixed” SHS flame propagation obtained by Kaper et
al. [73] by the use of matched asymptotic expansion method. t1 t y y
u1⫹ ⫹ 22 ⫹ …; j y 0 ⫹ 1 ⫹ 22 ⫹ …;
The analysis and results presented herein is an extension of b b b b
those described in Section 5.3.
116
h
s ;
b
5.6.1. Asymptotic expansion analysis
Following Ref. [73], we have the following expressions we obtain the following equations for the first-order inner
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 39
structure have
!
d 2t1 a0 dy0 2bC
⫹ 0;
117 exp ⫺ a20 k
1 ⫺ M ⫹ M;
125
dh2
Z∞ ⫺ Z0 dh a 02
" # which has nearly the same form as that presented by Kaper
r dy 3b b 1 at 2 et al. [73] except for the factor k. The parameter M identified
bL0 t;0 a0 0 exp ⫺ ⫺ ⫺ 1
rt dh 4a a 2 b in Ref. [74] is called the melting parameter because it corre-
2 3 sponds to the energy to heat the unburned mixture from T0 to
Z∞ ⫺ Z0 Tm. Consequently, 1 ⫺ M is the normalized driving force for
1=3 f ⫺ y
Z∞ ⫺ Z0 6 1 ⫺ Z0 0 7
× 1⫺ y0 ln 6
41 ⫹ 7;
5
the adiabatic flame propagation. The turning point
1 ⫺ Z0 Z ⫺ Z0
g⫹ ∞ y0 corresponding to the flame extinction, then, appears at
1 ⫺ Z0 dC=da 02 0; which yields
118
Xcr
1 ⫹ ln Xcr M;
126
where a is defined in Eq. (88) and f 1=m: where ln Xcr ⫺2bC cr =
a0 cr2 ;
as well as the following rela-
Matching the outer and inner solutions in the limit of h ! tions for the critical parameters at extinction:
^∞; we have
⫺Xcr ln Xcr X
ln Xcr 2
a0
a0 2cr ; C cr cr :
127
h ! ⫺∞ : t1 ! C1 ⫹ h; y0 ! 0;
119 k
1 ⫺ M 2bk
1 ⫺ M
Z∞ ⫺ Z0
Note that hte maximun flame temperature is given by
h ! ∞ : t1 ! C1 ; y0 ! 1;
120 umax 1 ⫹
ln Xcr =b:
Knowing the critical heat loss parameter C cr and the
where the constant C1 is given by the second-order inner maximum flame temperature u max, the critical size of N
problem as particles and the critical compact diameter for the extinction
are determined through
2bC !
C1 ⫺ :
121
a 02 R 02 C cr
rt c
u0;a R0 2
;
128
2r cr l=
rt c4es SB
Tmax 2 ⫹ T 2
T
0 max ⫹ T0
By using the matching conditions, Eq. (117) can be inte-
grated once to yield derived from Eq. (112) when only the thermal radiative heat
loss from the cylindrical surface of a compact with radius r
dt1 a0
1 ⫺ y0 :
122 is considered [64,66]. It is informative to recall that R20 is
dh
Z∞ ⫺ Z0 closely related to the heat generation rate in the consump-
Eliminating h from Eq. (122) with Eq. (118) and conducting tion zone and 2r the heat loss rate. In addition, the SHS rate-
integration, we have constant in the adiabatic condition, which is the product of
" the burning velocity u0,a and the initial radius R0 of N
#
Z∞ ⫺ Z0 ZC1 3b b 1 a t1 2 particles, is expressed as
exp ⫺ ⫺ ⫺ dt1 !
bL0
rt;0 =rt a20 ⫺ ∞ 4a a 2 b
2 rM 1 ⫺ Z0 Iu
u0;a ·R0 3Le0 D0
2
;
129
Z1
1 ⫺ y0 rN Z∞ ⫺ Z0 Ij
2 3 dy0 :
Z∞ ⫺ Z0
0
1=3 f ⫺ y0 by combining Eqs. (75) and (96).
Z∞ ⫺ Z0 6 7
1⫺ y0 ln 6
41⫹ 1 ⫺ Z0 7 5
1 ⫺ Z0 Z∞ ⫺ Z0
g⫹ y0 5.6.2. Correction term for the heat loss parameter
1 ⫺ Z0
123 Predictions based on Eq. (126) have been found to deviate
substantially from the numerical results shown in Section
If we note here that L 0 is expressed in Eq. (93), that Iu in Eq. 5.4. The discrepancies are at least 50% for the heat loss
(87), and that Ij in Eq. (92) for m ⬉ 1 and Ij in Eq. (97) for parameter C cr, and are even more for the critical particle
m ⱖ 1; then Eq. (123) becomes size and/or compact diameter. Since this discrepancy is
" !# expected to be caused by ignoring the O(b ⫺1) term in
2a 02 b
1⫺ bIu exp obtaining the RHS of Eq. (118), which would have modified
1 ⫹ um a the RHS of Eqs. (125) and (126) by an amount ⫺O
1 ⫺
Z0 M=b; we are therefore required to add the term (1 ⫺ M)/b
at
exp t1 1 ⫺ 1 dt1 ⬇ 1 ⫺ exp
C1 :
124 to Eq. (126) as
C1 b
1⫺M
X cr
1 ⫹ ln Xcr M ⫺ :
130
Putting k 2=
1 ⫹ um and 1 ⫺ M bIu exp
b=a; we b
40 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
( ! )
1 1 e⫺2 1
C cr ⬃ 1⫺
m ⱖ 1
Fig. 38. Critical value of the normalized heat loss, Xcr 2eT~ d m ⫹ fst T~ d m ⫹ fst
exp⫺2bC cr =
a0 cr2 ; as a function of the melting parameter M,
137
with the measure of activation energy relative to thermal energy,
b , taken as a parameter [72]. Solid curves are numerical results and when there is no dilution
k 0; when the mixture is
dashed curves are results by the explicit approximate analytical stoichiometric
m 1; we have
expression. ( ! )
1 1⫺k e⫺2 1⫺k
C cr ⬃ 1⫺ :
138
2eT~ d 1 ⫹ fst T~ d 1 ⫹ fst
With this modification, the discrepancies can be reduced
to less than 20%. Furthermore, Xcr is now explicitly That is, C cr increases with increasing m when m ⱕ 1; while it
expressed in terms of M as decreases with increasing k or m when m ⱖ 1; although with
progressively diminishing rate. The effect of T0, which deter-
1=2 p !
1 1⫺M 1 ⫹ 2e mines T∞, also appears because T∞ influences C cr through a
Xcr 1 ⫹ 2e M ⫺ ⫹ 1⫺ M2; and b .
e b e
131
5.6.4. Applicability of the analytical expression
which yields a discrepancy of less than 1% (cf. Fig. 38), in Applicability of the analytical expression has been exam-
the range of practical values of M. ined by comparing it with the numerical results for the
syntheses of TiC, TiB2, ZrB2, HfB2, and AlNi, because of
fair agreement between numerical and experimental results,
5.6.3. General behavior of the heat loss parameter as shown in Sections 5.4 and 5.5. Fig. 39(a) shows the
An explicit form of C cr provides useful insight into the critical value of the heat loss parameter C cr for Ti–C system
effects of the reduced parameters (a , b , and u m), which as a function of m , with k 0 and T0 taken as a parameter.
depend on the system parameters (fst, Td, Tm, T0, m , and Solid and dashed curves are respectively numerical and
k ), in the same manner as that for the mass burning rate analytical results. Fig. 39(b) shows C cr as a function of k ,
eigenvalue L 0 in Section 4.6.2. Keeping only the leading with m 1 and T0 taken as a parameter. The analytical
terms, the functional dependence of C cr on the system par- result mostly agrees with the numerical result, within 17%
ameters can clearly be displayed as error.
Fig. 40(a) shows the critical value of the heat loss index
R 02 =
2rcr as a function of m , with k 0 and T0 taken as a
1 ⫹ um 2a
e ⫺ 1 ⫺ e
C cr ⬃ 1⫺ :
132 parameter. The agreements between the numerical and
4eb b
analytical results are generally good, except near the stoi-
Here the following relations chiometric state at which the analytical result shows a
reverse trend, resulting in about 18% under-prediction at
m 1: The discrepancy here is attributed to the overestima-
b 2a
1 ⫺ M bIu exp ⬃1⫺
133 tion in Ij in obtaining the approximate expression of L 0, as
a b
mentioned in Section 4.6. Fig. 40(b) shows R 02 =
2rcr as a
and function of k , with m 0:95 and T0 taken as a parameter.
When m is 0.95 or less, agreement is good, with less than
1 e
2a ⫺ 1 14% error.
Xcr ⬃ 1⫹
134 Figs. 41 and 42 show similar comparisons for Hf–B and
e b
Al–Ni systems, as examples, when the degree of dilution is
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 41
Fig. 39. Critical heat-loss parameter, C cr, for Ti–C system [72]; (a) as a function of the mixture ratio m , with the initial temperature T0 taken as a
parameter when the degree of dilution k 0; and (b) as a function of k , with T0 taken as a parameter when m 1: Solid curves are numerical
results and dashed curves are those with the analytical expression.
varied. The extent of agreement, including Ti–B and Zr–B features of the heterogeneity in the SHS process. A useful
systems, is similar to that for Ti–C system. parameter called the “heat loss index”, which is defined as
the square of the nonmetal particle size divided by the
5.7. Some remarks on the flame propagation under heat loss compact diameter, has also been identified. Furthermore,
condition under the appropriate and realistic assumptions of diffu-
sion-limited reaction and infinite Lewis number, an approx-
A nonadiabatic, heterogeneous theory for the SHS process imate criterion for the extinction has been derived, which can
with heat loss has been formulated and the range of flammabil- yield useful insight into manipulating the flame extinction.
ity can be determined from the characteristic extinction turn-
ing-point. A particularly significant identification is that the
process responsible for its temperature sensitivity and ultimate 6. Other aspects of the nonadiabatic flame propagation
extinguishment is the Arrhenius liquid-phase mass-diffusion.
Fair agreement between predicted and experimental results In this section, several other important effects, such as the
for the extinction limits, in trend and in approximate magni- bimodal particle distribution, representative length of the
tude, suggests that this theory has captured the essential cross-section of a compacted medium, on the SHS flame
Fig. 40. Critical heat-loss index [R02/(2r)]cr for Ti–C system [72]; (a) as a function of m , with T0 taken as a parameter when k 0; and (b) as a
function of k , with T0 taken as a parameter when m 0:95: Notation is the same as that in Fig. 39.
42 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 41. Critical values of parameters for stoichiometric Hf–B system as a function of k , with T0 taken as a parameter: (a) C cr; (b) [R02/(2r)]cr.
Notation is the same as that in Fig. 39.
propagation and/or extinction are described. Also described possibly more desirable, packing. Since not only the
here is the correspondence between the heterogeneous increase in the burning velocity but also the extension
theory and the homogeneous premixed-flame theory, from of the flammability limit is anticipated by reducing the
the analytical point of view. Effects of the electric field on particle size, for a fixed amount of the dispersed phase,
the flame propagation and/or extinction are also described in it is considered to be desirable to have small particle
this section. size for the propagation of the combustion wave.
However, preparation of the small particles can be
6.1. Bimodal particle dispersion quite energy intensive. Therefore, preparation of the
bimodal mixture, with only a fraction of the N particles
Analyses of the heterogeneous flame, hitherto having small sizes, can be less energy intensive without
described, have assumed a monodisperse distribution substantially affecting the burning intensity. Further,
of the nonmetal particles. However, there exist practical since SHS processes have been observed to possess a
interests in having a bimodal particle distribution. For variety of flame instability phenomena, which are invari-
example, such a distribution would allow smaller par- ably dependent on the burning intensity and hence the
ticles to fill in part of the inter-particle spacing between particle size, such instabilities could be modulated for
large particles, hence allowing for a denser, and bimodal mixtures. In view of the above considerations,
Fig. 42. Critical values of parameters for stoichiometric Al–Ni system as a function of k , with T0 taken as a parameter: (a) C cr; (b) [R02/(2r)]cr.
Notation is the same as that in Fig. 39.
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 43
formulation has been extended to bimodal systems the mass burning rate eigenvalue becomes
under nonadiabatic situations [75,76]. " #
Z∞ ⫺ Z0 2 m2a
L0
4p
rM D0
l=c
n0 R0 E
6.1.1. Equivalent particle radius
" #
The problem of interest is basically the same as that Z∞ ⫺ Z0 2
1 ⫺ Z0 u20;a
RL;0 =F2
described in Section 5.1. The bimodal system for N particles
145
1 ⫺ Z0 3Le0 D20
rM =rN;L
is considered to consist of small particles of density r N,S,
initial radius RS,0, and number density nS,0, and large parti- where RL,0/F is the equivalent particle radius and
cles with the corresponding parameters r N,L, RL,0, and nL,0. ! !2
In spite of the existence of the bimodal particle distribution, rN;L RL;0
1⫹ PG
the governing equations and boundary conditions are iden- rN;S RS;0
F
2
:
146
tical to those for the monomodal case, if we introduce the
1 ⫹ G 2=3
1 ⫹ P3 G 1=3
equivalent particle radius and number density as (n0R0)E and
express the conservation equation for the N-Consumption We see that u0,a·(RL,0/F) is independent of the bimodality,
formally as [75,76] and that Eq. (143) suggests P O
R S;0 =RL;0 : Note that
G=
1 ⫹ G is the mass fraction of small particles and can
d
1 ⫺ Z 4prM D u 1 ⫺ Z 1=3 be called the degree of small particle content. As for the
⫺
n0 R0 E 0 x : heat loss parameter C , it is given as
dx m u 1 ⫺ Z0
139 " #" 2 #
l 4es SB
T 2 ⫹ T02
T ⫹ T0
RL;0 =F2
C :
Thus, our primary concern is to find out the specific form of rtc
rt c
u20;a
RL;0 =F2 2r
(n0R0)E in Eq. (139), as a function of the bimodal par-
147
ameters. The description for the bimodal system has first
been made for the system with the same kind of N particles It depends not only on the physicochemical parameters but
[75] and then extended for the system with different kinds of also on the equivalent particle radius RL,0/F and the compact
N particles [76]. diameter 2r.
The parameter (n0R0)E can be obtained by using the size
distribution function 6.1.2. Experimental comparisons for spherical carbon
particles
rN G0
R rN;S nS;0 d
R ⫺ RS;0 ⫹ rN;L nL;0 d
R ⫺ RL;0 ; There exist several sources that can be compared with the
140 numerical results. Makino et al. [43,77,78] using various
radii of spherical carbon particles, measured the range of
where d (·) is the delta function. By substituting it into the flammability and the burning velocity of the SHS process
general N-consumption equation in Eq. (45), we have for Ti–C system. The representative Lewis number of Le0
" ! !2 # 25; which corresponds to l=
rt c 5 × 10⫺6 m2 =s and has
rN;L RL;0 been determined through correlation similar to that in
n0 R0 E 1 ⫹ PG
rN;S RS;0 Section 4.4 with experimental results [43,77,78] (0.6 rela-
1=3 tive density) of monomodal system, has been used in numer-
1⫹G ical calculations [75] because of the fair correlation for
n L;0 RL;0
141
1 ⫹ P 3G various radii of spherical carbon particles and various
compact diameters, as shown in Figs. 43 and 44.
where
Fig. 43(a) shows the range of flammability for the mono-
r N;S nS;0 RS;0
3 modal system with respect to the mixture ratio m and the
G
142 heat loss index R20 =
2r; with T0 taken as a parameter [79].
rN;L nL;0 R3L;0
Experimental results [43,77,78] for various particle radii
is the mass ratio, P
hS =RS;0 =
hL =RL;0 the size ratio, and (1.5, 2.5, 5, 10, and 15 mm) and various compact diameter
hi =Ri;0
i S; L the normalized particle size defined as (5, 7, 10, and 18 mm) at T0 300 K show that not only the
range of flammability but also the range of pulsating
!2 combustion extends with decreasing R20 =
2r: Fig. 43(b)
hi 2 Zx x
1⫺ 2 dx
i S; L:
143 shows the similar comparison with respect to the degree
Ri;0 Ri;0 ⫺ ∞ u
of dilution k and R20 =
2r: Fair agreement is demonstrated
If we further take account of the relation for the mass frac- between the predicted and experimental results.
tion of N particles as The choice of Le0 25 for the spherical carbon particles
requires further comments because Le0 100 has been used
4 in comparisons in Section 4.4 and 5.4. As a remarkable
rt;0
1 ⫺ Z0 prN;L
1 ⫹ G
n L;0 RL;0
3
144
3 difference, compared to the irregular particles in Refs.
44 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 43. Range of flammability for Ti–C system with monomodal particles; (a) with respect to the mixture ratio m and the heat-loss index R02/
(2r), with the initial temperature T0 taken as a parameter [79]; and (b) with respect to the degree of dilution k and the heat-loss index R02/(2r).
Data points are experimental at T0 300 K [43,77,78]: (W) designates the steady-propagation; (Z) the pulsating combustion; (S) the quasi-
steady, multipoint combustion; (K) the extinction during the flame propagation, and ( × ) the non-ignition.
[33,43], the spherical particles are reported to have smooth function of G=
1 ⫹ G for T 0 300 K and m 1; with k
surfaces and very narrow size distribution [77]. This taken as a parameter. Owing to the decrease in the equiva-
suggests that the value of Le0 100 for the irregular par- lent particle radius, u0,a increases first gradually and then
ticles implicitly accounts for the effects of surface roughness rapidly with increasing G=
1 ⫹ G : At a certain G=
1 ⫹ G ;
and the relatively wide size distribution because these u0,a decreases with increasing k because of the reduced
effects, which appear in (n0R0)E in Eq. (139), are grouped amount of chemical heat generation. The dashed curve is
into l /c when only the particle size is known. the extinction limit under heat loss conditions. A fair degree
Fig. 44(a) shows the SHS rate-constant u0·R0 for the of agreement is shown.
monomodal system as a function of the inverse of the heat The appropriateness of the equivalent particle radius can
loss index R20 =
2r at T0 300 K; with m taken as a para- further be shown in Fig. 46. It is, however, important to note
meter [79]. The trend is the same as that in Fig. 31(a). Data that since the present formulation is based on the statistical
points are experimental [43,77,78] and the agreement is analysis, a few tens of large particles should exist at least
again considered to be satisfactory. Fig. 44(b) shows a simi- across the consumption zone, even for the bimodal system.
lar comparison, with k taken as a parameter. Violation of this restriction results in the breakdown of the
Having confirmed the appropriateness of the choice of present formulation, such that discussion with the equivalent
several physicochemical parameters, comparisons for the particle radius becomes less useful.
bimodal system have been conducted, with the size ratio
P taken to be P RS;0 =RL;0 : Fig. 45(a) shows the range 6.1.3. Experimental comparisons for diamond particles
of flammability for the bimodal system with respect to the There exists another source for the bimodal system.
degree of small particle content G=
1 ⫹ G and the degree of Makino et al. [77] measured the range of flammability and
dilution k , for T 0 300 K; m 1; RS;0 1:5 mm; RL;0 the burning velocity of the SHS process for Ti–diamond
10 mm; and 2r 18 mm: It is seen that the range of flamm- system, as a basic research to fabricate the diamond
ability, which spans from k 0 to 0.178 when G=
1 ⫹ G embedded TiC/Ti composites by the SHS process, to
0; gradually extends with increasing G /(1 ⫹ G ) and finally achieve advanced cutting tools and/or abrasives. In this
spans from k 0 to 0.400 when G=
1 ⫹ G 1: Extension fabrication, the SHS flame must propagate through a
of the range of flammability is attributed to the decrease in medium of compacted particles of titanium, carbon (or
the equivalent particle radius RL,0/F. The limit of dilution graphite), and diamond, without participation of the
k 0:446 without heat loss suggests that even at G=
1 ⫹ diamond particles in the SHS process.
G 1: the heat loss affects the range of flammability. It is By comparing the predictions [76] with the experimental
seen that as far as the trend and approximate magnitude are results [43,77] it has been determined to use the physico-
concerned, we can fairly predict the experimentally chemical parameters, described in Sections 4.4 and 5.4.1,
obtained extinction limit [43,77]. except for r N 3:51 × 10 3 kg=m3 : A Lewis number of
Fig. 45(b) shows u0,a in the adiabatic condition as a Le0 100 is used because of the fair correlation with the
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 45
Fig. 45. Combustion behavior for Ti–C system with bimodal par-
ticles [75]; (a) Range of flammability with respect to the degree of
small particle content G=
1 ⫹ G and the degree of dilution k , for
T 0 300 K; m 1; RS;0 1:5 mm; and RL;0 10 mm; data points
are experimental [43,77] and notation is the same as that in Fig. 43.
(b) Burning velocity u0,a in the adiabatic condition as a function of
G=
1 ⫹ G ; with k taken as a parameter; notation is the same as that
in Fig. 44.
Fig. 44. SHS rate-constant u0·R0 for Ti–C system with monomodal
particles, as a function of the inverse of the heat loss index R02/(2r) at
to k . Data points are experimental [43] and the same
T0 300 K [79]; (a) with m taken as a parameter and (b) with k
taken as a parameter. Data points are experimental [43,77,78]; open
comments as those for Fig. 47 can be made.
symbol designates the steady propagation and half-open symbol the Having confirmed the fair agreement for the monomodal
pulsating combustion. system, it was intended to make experimental comparisons
for the bimodal system. Fig. 49(a) shows the range of
flammability with respect to G=
1 ⫹ G and k , and Fig.
49(b) shows u0,a as a function of G=
1 ⫹ G ; for the stroichio-
experimental results [43,77] (0.6 relative density) for the metric mixture
m 1 at T 0 300 K with RS;0 3 mm;
various radii of diamond particles, as shown in Figs. 47
and 48. The compact diameter 2r is 18 mm in accordance
with the experiments.
Fig. 47(a) shows the range of flammability for mono-
modal compacts with respect to m and R0, for T0
300 K and k 0: Experimental results [43,77] for the
steady propagation, quasi-steady multipoint combustion,
extinction, and non-ignition show that the range of
flammability extends with the decreasing R0. Fig.
47(b) shows u0,a·R0 as a function of m , with R0 taken
as a parameter. Compared to the Ti–C system, the burn-
ing velocity for Ti–diamond system is reduced because
of the increase in the nonmetal density r N, as shown in
Eq. (76), which suggests that u0,a is inversely propor-
tional to (r N) 1/2. The increase in r N, thus, reduces the Fig. 46. SHS rate-constant u0,a·(RL,0/F) in the adiabatic condition as
total surface area of particles in the combustion wave, a function of the degree of dilution, with T0 taken as a parameter.
and hence, suppresses the volumetric heat-generation Data points are experimental [43,77] and notation is the same as that
rate. Fig. 48 shows a similar comparison with respect in Fig. 44.
46 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 47. Combustion behavior for Ti–diamond system with mono- Fig. 48. Combustion behavior for Ti–diamond system with mono-
modal particles [76]. (a) Range of flammability with respect to m modal particles [76]. (a) Range of flammability with respect to k
and R0, for T0 300 K without dilution
k 0; data points are and R0, for stoichiometric mixture
m 1 at T0 300 K; data
experimental [43,77] and notation is the same as that in Fig. 43. points are experimental [43,77] and notation is the same as that in
(b) u0,a·R0 as a function of m , with R0 taken as a parameter. Fig. 43. (b) u0,a·R0 as a function of k , with R0 taken as a parameter.
Fig. 49. Combustion behavior for Ti–diamond system with bi- Fig. 50. Combustion behavior for Ti–C–diamond system [76]. (a)
modal particles [76]. (a) Range of flammability with respect to Range of flammability with respect to G=
1 ⫹ G and k , for m 1 at
G=
1 ⫹ G and k , for m 1 at T 0 300 K with RS;0 3 mm; T 0 300 K with RS;0 2:5 mm; RL;0 15 mm; rN;S 2:25 × 10 3
RL;0 15 mm; and rN;S rN;L ; data points are experimental [77] kg/m 3, and rN;L 3:51 × 103 kg/m 3; data points are experimental
and notation is the same as that in Fig. 43. (b) Burning velocity u0,a [77] and notation is the same as that in Fig. 43. (b) Burning velocity
in the adiabatic condition as a function of G=
1 ⫹ G ; with k taken u0,a in the adiabatic condition as a function of G=
1 ⫹ G ; with k
as a parameter; notation is the same as that in Fig. 44. taken as a parameter; notation is the same as that in Fig. 44.
expressed as es ST
T 4 ⫺ T04 pd: Then, we have Fair agreement is again obtained, as far as the trend and
approximate magnitude are concerned.
es ST
T 4 ⫺ T04
L ;
148 6.3. Correspondence between the heterogeneous theory and
S=p
the homogeneous theory
by which the heat loss parameter is expressed as
Much of the theoretical analyses on the flame propagation
" # !
l 4es SB
T 2 ⫹ T02
T ⫹ T0 R20 in SHS, as reviewed in Ref. [24], are based on the classical
C :
149
rtc
rt c
u0;a R0 2 4S=p treatment of the premixed flame propagation, characterized
by a large activation energy Arrhenius reaction rate and
When the cross-sectional area is circular with radius large Lewis number heat and mass diffusion. Although
r, we have S pr2 and p 2pr; which yields 4S=p these analyses have successfully captured the temperature-
2r: When the cross-sectional area is rectangular with a sensitive nature of the flame propagation, and consequently
in length and b in width, we have S ab and p 2
a ⫹ have been able to describe such empirically observed
b; which yields 4S=p 2ab=
a ⫹ b: It may be informa- phenomena as abrupt flame extinction due to heat loss,
tive to note that this is a harmonic mean of a and b, and instability of the combustion wave in the form of pulsat-
and is called the equivalent diameter in the field of the ing and spinning propagation, as explained in Refs. [4–9],
heat-transfer engineering. there are several fundamentally unsatisfactory aspects as
Fig. 51(a) and (b) shows the range of flammability for Ti– mentioned in the previous sections. While it is pleasing
C system as a function of m and k , respectively. Values of that the heterogeneous theory has been successful in
the physicochemical parameters are as those in Sections 4.4 explaining the experimental results, especially the tempera-
and 5.4.1 Data points are experimental [80] at T0 450 K ture sensitivity, one must nevertheless confront the some-
with various a and b, as well as the various radii of (irregu- what curious result that the characterization of an Arrhenius
lar) carbon particles. Appropriateness of the choice of the diffusion process can be similar to that of an Arrhenius
representative length is demonstrated. Fig. 52(a) shows u0 as reaction process. To resolve this interesting correspondence,
a function of m , with k taken as a parameter, and Fig. 52(b) we shall demonstrate [81] that the governing equations for
shows u0 as a function of k , with m taken as a parameter. the heterogeneous theory can indeed be cast in a form which
48 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 51. Range of flammability for Ti–C system, with T0 taken as a parameter; (a) with respect to m and R20 =2ab=
a ⫹ b; and (b) with respect to
k and R20 =2ab=
a ⫹ b: Data points are experimental [80] and notation is the same as that in Fig. 43.
can be considered to be functionally identical to that The boundary conditions are as follows:
describing the large activation-energy premixed-flame
x 0 : T Tm ; 1 ⫺ Z 1 ⫺ Z0
156
propagation in a condensed medium.
To this aim, the N-consumption equation (46) must first
d L d
1 ⫺ Z
be rewritten as x!∞:
cT ⫺ ; 0:
157
dx
rt u dx
d
1 ⫺ Z T
rt u ⫺rt B~ w exp ⫺ d ;
150 We see that a set of governing equations and boundary
dx T
conditions is exactly the same as that for the conventional
where homogeneous theory (cf. Ref. [4]). Although differences are
! ! minor from a mathematical point of view, this identification
3 rM rt
B~
1 ⫺ Z0 D0 ;
151 is valuable for the physical interpretation of the combustion
R20 rN rt;0 behavior. First, it should be noted that w in the “reaction”
1=3 term is a function of the mass fraction of solid N particles,
1⫺Z A ~
w ln 1 ⫹ YM ;
152 1 ⫺ Z: In addition, if we note that the SHS proceeds under
1 ⫺ Z0 1⫹A diffusion-controlled situation, as is the case for usual SHS,
we have A=
1 ⫹ A ! 1; which suggests that the mass diffu-
1⫺m
1 ⫺ Z0 ⫹
1 ⫺ Z sivity in the Arrhenius fashion exerts nonlinear influence on
m
Y~ M :
153 flame propagation and/or extinction. That is, the activation
1 ⫺
1 ⫺ Z temperature which can influence the nonlinear, highly
In deriving Eq. (153), the following relation has been used temperature-sensitive nature of the SHS flame propagation
is not the activation temperature Ta for the reaction, but Td
Z
1 ⫹ Y~ M
1 ⫹ Y~ M;0 0 ;
154 for the liquid-phase mass-diffusivity. As for the effect of
Z particle size, it has been incorporated into the frequency
~ tacitly.
factor B;
derived from Eq. (49) under the assumption of the negligible
Since it has been confirmed that the set of the governing
diffusion effect. The particle consumption term in the RHS
equations and boundary conditions in the heterogeneous
of Eq. (150) therefore corresponds to the “reaction” term in
theory is identical to that in the conventional homogeneous
the homogeneous premixed-flame theory, with B~ being the
theory, results of theoretical analyses hitherto obtained by
“frequency” factor, w the “reactant concentration”, and Td
the homogeneous premixed-flame theory, as reviewed in
the “activation temperature”. As for the energy conservation
Refs. [23,24], can be anticipated to be qualitatively valid
equation, from Eq. (58), we have
if we take note of the differences involved.
d l d d T
cT ⫺ rt u
cT ⫹ q0 rt B~ w exp ⫺ d
dx c dx dx T 6.4. Field activated SHS
scE 2
P
1 ⫺ Z ;
159
2
l=cs c E 2
H ;
160
m2a q0
Fig. 52. SHS rate-constant u0·R0 for Ti–C system as a function of
the inverse of the heat loss index R20 =2ab=
a ⫹ b at T0 450 K;
in addition to other variables and parameters in Sections 4.2
(a) with m taken as a parameter; and (b) with k taken as a parameter.
and 5.1, Eq. (158) becomes
Data points are experimental [80] and notation is the same as that in
Fig. 44. !
d du m=m a m=ma
⫺ u⫹ j
ds ds Z∞ ⫺ Z0 T~ ∞ ⫺ T~ 0
C·u H
1 ⫺ j
⫺ ;
161
propagation, it is usual to heat a compacted medium exter-
Z ∞ ⫺ Z0 2
Z ∞ ⫺ Z0
T~ ∞ ⫺ T~ 0
nally by preheating and/or by applying an electric field.
Since preheating in a long period of time could induce where H can be called the heat-input parameter. The other
production of undesired compounds which might inhibit governing equations are the same as those in Eqs. (99) and
initiation of the combustion wave, it is reported to be prefer- (101). The boundary conditions are also the same as those in
able [82,83] for low exothermic systems to apply the electric Eqs. (102) and (103).
field, which can also exert a great influence on the flame
propagation [84,87] especially when the electric conductiv-
ity in the combustion wave is much higher than those in the 6.4.2. Temperature profiles outside the combustion wave
unburned and burned states. Although there exist several As mentioned in Section 5.2, in the limit of large Zeldo-
analytical [88] and/or numerical [84,86] works on this vich number, melting, diffusion, and consumption/convec-
subject based on the homogeneous premixed-flame theory, tion are confined to a thin layer in the neighborhood of the
heterogeneity involved has not been explored. In this combustion wave. Outside this layer, the diffusion and
section, focusing on the effect of the electric field on the consumption/convection terms are exponentially small. If
burning velocity, let us examine it by use of the heteroge- we consider the situation that the combustion wave locates
neous theory. at s s f and that the electric field exerts influence only in
the region 0 ⬍ s ⬍ s f ; temperature profile outside the
combustion wave is expressed as
6.4.1. Heat-input parameter
The problem of interest is basically the same as that s ⱕ 0 : u A u exp
lu s; j 0;
162
50 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Relations among constants Au, Ah, Bh, and C are deter- 6.4.3. Effective range of electric field
mined by use of the continuities of temperature and heat flux In order for the electric field to be effective for increasing
at s 0; respectively, the continuity of temperature at the combustion temperature, the flame location must be posi-
combustion wave
s s f ; and the jump condition of du / tive, which requires that the logarithmic term in Eq. (173)
ds in the combustion wave as must be positive. From this requirement, the range in which
the heat-input parameter H can exist is determined as
du du m=ma
⫺ ;
166 T~ m ⫺ T~ 0
ds s f⫺ ds s f⫹ T~ ∞ ⫺ T~ 0 0ⱕH⬍ ⬍ 1:
174
Z∞ ⫺ Z0
which is obtained by integrating Eq. (161) and evaluating at
s s f : Then, we have In the same manner, when there exists heat loss, we have
from Eq. (171) the following relation between C and H.
1 m=ma ( )
Au exp
⫺lu s f
lu ⫺ ld T~ ∞ ⫺ T~ 0 1
m=m a 2 H
Z∞ ⫺ Z0
⫺ ⫺
2 4 T~ m ⫺ T~ 0
ld H
Z∞ ⫺ Z0
⫺ 1 ⫺ exp
⫺lu s f ;
167 v
( )
lu ⫺ ld C
T~ ∞ ⫺ T~ 0 u
u
m=ma 2
m=ma 2 H
Z ⫺ Z
⫺t ⫹ ∞ 0
1 m=ma ld H
Z∞ ⫺ Z0 8 8 T~ m ⫺ T~ 0
Ah ⫹
lu ⫺ ld T~ ∞ ⫺ T~ 0 lu ⫺ ld C
T~ ∞ ⫺ T~ 0 ( )
1
m=m a 2 H
Z∞ ⫺ Z0
⬍C⬍⫺ ⫺
exp
⫺lu s f ;
168 2 4 T~ m ⫺ T~ 0
v
( )
lu H
Z∞ ⫺ Z0 u
Bh ⫺
169 u
m=ma 2
m=ma 2 H
Z ⫺ Z
lu ⫺ ld C
T~ ∞ ⫺ T~ 0 ⫹t ⫹ ∞ 0
:
175
8 8 T~ m ⫺ T~ 0
1 m=ma Note that when C has the value of the limit, length between
C exp
⫺ld s f
lu ⫺ ld T~ ∞ ⫺ T~ 0 the location of melting and that of the combustion wave
becomes infinite.
lu H
Z∞ ⫺ Z0
⫺ 1 ⫺ exp
⫺ld s f :
170
lu ⫺ ld C
T~ ∞ ⫺ T~ 0 6.4.4. Experimental comparisons for Si–C system
Values of physicochemical parameters employed are
If we further note that the temperature at s 0 is the
those for Si–C system: q 0 6:23 MJ=kg; c 1 kJ=
kg=K;
melting point, we can determine the flame location s f as
r M 2:34 × 103 kg=m3 ; rN 2:25 × 103 kg=m3 ; WM
2 m ld 3 28:1 × 10⫺3 kg=mol; WN 12:0 × 10⫺3 kg=mol; Tm
6 ⫹ H
Z ∞ ⫺ Z 7 D 3:3 ×
1 ma C 0 1681 K: For the mass diffusivity,
sf ln 6
4
7;
5 10⫺5 exp
⫺3:39 × 104 =T m2 =s is used [90]. As for the
lu ~ ~ l
T m ⫺ T 0
lu ⫺ ld ⫹ d
H
Z ∞ ⫺ Z0 representative Lewis number, Le0 1; because experimen-
C
171 tal results [85] have been correlated for this value.
Fig. 53 shows the SHS rate-constant u0·R0 for stoichio-
which is obtained from Eq. (167) by setting Au um : The metric Si–C system, as a function of the square root of the
flame temperature in the adiabatic condition, which is indis- heat-input parameter H. A solid curve is u0,a·R0 in the adia-
pensable for nondimensionalization, is obtained from Eq. batic condition and a dashed curve is that at the extinction
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 51
physicochemical parameters, but also of the operating par- 7.2. Linear stability analysis
ameters, such as the mixture ratio, degree of dilution, parti-
cle size, and initial temperature. From this identification, 7.2.1. Basic solution for planar propagation
operating parameters at which steady flame propagation is Prior to the linear stability analysis, let us first confirm the
maintained, even at the adiabatic condition, are obtained, to governing equations and boundary conditions. By introdu-
elucidate the necessary condition for pulsating combustion, cing the nondimensional time defined as
in order to identify the useful parameter in suppressing
Z∞ ⫺ Z0 2 m2a t
pulsating combustion. Finally, transverse effects related to t ;
178
l=crt
heat loss from the side surface of the compact are examined
to assess the range of steady combustion. in addition to the other variables and parameters introduced
in Sections 4.2 and 5.1, the energy conservation equation
7.1. Criterion for the appearance of cracks and the N-concentration equation are expressed as
197
8 s9
< =
1 a0 1 Z∞ ⫺ Z0 2
pd 1⫺ ⫹4
iv :
2 Z∞ ⫺ Z0 : C 2 a0 ;
198
Having obtained the perturbation quantities u p(s ,t ) and
ap(t ), we can now evaluate the perturbed term in Eq. (176)
as
" !2 !
1 a0 B
a 0
Z∞ ⫺ Z0 exp
ivt ⫺
2
iv Z∞ ⫺ Z0 a0
( !2 ! )
1 a0 B
⫹ 1⫹ C
199
2
iv Z∞ ⫺ Z0 a0 Fig. 54. Location of the neutral stability boundary [92].
v
!2 #
u
u 1 Z ⫺ Z0
t 2 ⫹ 4 ∞
where Xsb is determined by solving the neutral stability
iv :
C a0 condition
Since the jump condition with respect to 2u=2s at s 0 b X
gives iv as [73] 2 X⫺M
8 s 9
! 2" ( !2 ! )
< 2=
1 a0 1 B B 2 1 2
iv ⫺ ⫺ ⫹4 C s 1 ⫹ 1 ⫹ 1 ⫺ ln X ;
206
8 Z∞ ⫺ Z0 C2 a0 a0 2 : 4 b ;
1 ⫺ ln X
!v
u
!2 ! # b
1 B u t 1 B B
^ ⫺ ⫹ ⫺8 C ; with X ⬅ exp
⫺2bC=a 02 a20 k
1 ⫺ M ⫹ M: In obtaining
C a0 C a0 a0
Eq. (206), use has also been made of Eqs. (187) and (194).
200 Fig. 55 shows the neutral stability boundary in the b –M
we see that the perturbed term attenuates in the regime plane, with X being taken as a parameter.
0 s1 p ! Once the critical values of the heat-loss parameter C sb,
B 1 A 1 6 and the flame temperature u sb, are obtained, the critical size
0ⱕ ⬍ 2C@1 ⫹ 1 ⫹ ; 1 ⱕ ⬍ ;
a0 4C4 C 2 of N particles and compact diameter for steady combustion
201
p !
B 1 6 1
0ⱕ ⬍ ; ⬍ ;
202
a0 C
1 ⫺ C2 2 C
a0 sb2
C sb ⫺ ln Xsb ;
204
2b
ln Xsb
usb 1 ⫹
205
Fig. 55. Neutral stability boundary in the b –M plane [92].
b
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 55
Fig. 57. Ranges of flammability and instability for Ti–C system as functions of m and k , for T0 300 K and 2r 18 mm [95]. The solid curve
is the limit of flammability [64], the dashed curve the numerically obtained boundary [92] for R0 1:5 mm; and the dotted curve the predicted
result [95] in the adiabatic condition. Data points are experimental [77] for R0 1:5 mm and notation is the same as that in Fig. 43.
be close to the adiabatic condition, as shown in Fig. 56(a) Since T∞ ⫺ T0 is related to the system parameters as [40]
and (b), heat-loss effect on this boundary is relatively small. 8
>
> m
1 ⫺ k
>
< m ⫹ fst
m ⱕ 1
7.2.4. Boundary at the adiabatic condition T~ ∞ ⫺ T~ 0 Z∞ ⫺ Z0 ;
210
>
>
1 ⫺ k
In the SHS process, reduction of particle size, which >
:
m ⱖ 1
reduces heat-loss effect, facilitates the occurrence of pulsat- m ⫹ fst
ing combustion when the system parameters, such as the when there is no external heating, we can obtain the critical
physicochemical and operating parameters in Sections values for these operating parameters.
4.6.2 or 5.6.3, are given. However, even if we use small Fig. 58(a) shows the boundary between steady combus-
particles, there is a possibility that steady combustion is tion and pulsating combustion in the adiabatic condition, as
maintained because appearance of pulsating combustion functions of the mixture ratio m and the initial temperature
also depends on the operating parameters, such as the T0, when there is no dilution
k 0: The solid curve is the
mixture ratio m , degree of dilution k , and initial temperature limit of flammability numerically obtained [64] and the
T0, through the heat of combustion when the physicochem- dashed curve for k~ 0 is the boundary obtained with Eq.
ical parameters for a specific system are given. Such that, (208) [95]; the chain curve for k~ k~lower is the boundary
operating parameters at which steady combustion proceeds when the transverse effect is the largest, which will be exam-
even at the adiabatic condition (i.e. X 1) has been ined in the next section. We see that the pulsating combus-
obtained in order to elucidate the necessary condition for tion regime expands with increasing T0, and that the steady
pulsating combustion, under which the only way effective in combustion regime contracts. Experimental results
suppressing the appearance of pulsating combustion is [33,43,77] for small carbon particles, with diameters less
increasing size of N particles. In order for Xsb to be unity, than 3 mm, are also shown because these data are considered
the critical values of b and M must satisfy to be influenced very little by the heat loss (cf. Fig. 57). Fair
p agreement is demonstrated as far as the general trend is
b=2
2 ⫹ 5;
208 concerned. Fig. 58(b) shows the transition boundary as func-
1 ⫺ M sb
tion of k and T0, when the system is stoichiometric. The
which has already been identified in the field of stability extent of agreement is similar to that in Fig. 58(a).
analysis. If we recall the expression 1 ⫺ M
bIu exp
b=a in Section 5.6.1 and Iu in Eq. (87), we can 7.3. Transverse effects on the range for steady combustion
obtain
T∞ ⫺ T0 sb because a and b are defined by use of
T∞ ⫺ T0 : Note that when the normalized melting-point u m is The transition from steady combustion to pulsating
smaller than about 0.7, the following equation fairly rep- combustion is in general accompanied by the appearance
resents the relation between a and b . of nonplanar spatial perturbations. Through various analyses
p p for examining the transition boundary by use of the multi-
5 ⫹ 2 p exp
y2 erfc
y b=a dimensional media with cylindrical [74,96,97] or rectangu-
a⬇ p ; y⬅ :
209
2 y 2 lar [98–100] shapes, it is reported that this kind of
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 57
Fig. 58. Ranges of flammability and instability for Ti–C system [95]; (a) as functions of m and T0; (b) as functions of k and T0. The solid curve is
the limit of flammability [64] numerically obtained, while the dashed curve for k~ 0 and the chain curve for k~ k~lower are the numerically
obtained boundaries [95] between steady and pulsating combustion; k~ 0 means that there is no transverse effect, while k~ k~lower means the
transverse effect is the largest. Data points are experimental [33,43,77] when R0 is less than 1.5 mm; notation is the same as that in Fig. 43.
and using the Laplace transformation, we have diffusive region near the contact surface, stretched variables
!
us s2 c b
u ⫺ u I ; X ⫺bKz
s ⫺ s c ;
224
uI exp ⫺ ~
⫺ w~ k t
1 ⫹
Lsp =Lig 4t are introduced, where b is the Zeldovich number defined as
( ! " ! 2#
1 L sp s p T~ d
Z∞ ⫺ Z0
× 1⫹ p ⫹ k~ t b :
225
2 Lig
exp
2 t T~ c2
! ! Retaining only nonvanishing terms on the exponential, we
s ~
p 1 L sp
× erfc p ⫹ k t ⫺ 1⫺ have
2 t 2 Lig
d2 c D
" ! 2# ⫺ t ec⫺X ;
226
s p dX 2 2
× exp ⫺ p ⫹ k~ t
2 t !
! 2 x~ c
Dt ;
227
s ~
p bKz2
Z∞ ⫺ Z0 L0
rt;0 =rt exp
T~ d =T~ c
× erfc ⫺ p ⫹ k t
2 t
which is subject to
" s! 2 #
s a ig dc
⫹ exp ⫺ p ⫹ w~ t
c X0 0; 0:
228
2 t asp dX X!∞
s!) Eq. (226) can be solved analytically and we have
s a ig
" ( !2 )#
× erfc ⫺ p ⫹ w~ t : (221)
2 t asp 1 ⫺1 ⫹ C e ⫺X
c X ⫹ ln 1⫺ ;
Dt 1 ⫹ C e⫺X
Here, L ig and L sp are the heat penetration coefficients. In the p
229
following, temperature rise in the inert, heating stage is 1 ⫺ 1 ⫺ Dt
C p
designated with the subscript I. Note that temperature 1 ⫹ 1 ⫺ Dt
response for a finite size of the igniter can also be obtained
(e.g. Ref. [111]). Since there is no solution for Dt ⬎ 1; the
in the same manner, as shown by Strunia et al. [106]
critical condition is as follows:
!
8.1.2. Transition stage 2 x~ c
Dt ⬅ 1;
230
In analyzing the transition from inert heating to vigorous bKz2
Z∞ ⫺ Z0 L0
rt;0 =rt exp
T~ d =T~ c
reaction, temperature deviation must be taken into account
because the heat generation term becomes important as where
!
temperature rises. Since departure from the inert heating is 2uI us
anticipated to occur at time and position such that uI ⫺
uI c Kz exp
⫺w~ k~tc
2s c
1 ⫹
Lsp =Lig
is close to zero, we have the lowest order solution as
(
uI
uI c ⫹ Kt
t ⫺ tc ⫹ Kz
s ⫺ s c ;
222 p
× k~ exp
k~ 2 tc erfc
k~ tc
by expanding Eq. (221), where Kt
uI =utc ; Kz
s ! s!)
2uI =2s c : Note that (·)c designates the condition corre- aig aig aig
sponding to the rapid increase in temperature, which occurs ⫺ w~ exp w~ 2 tc erfc w~ t : (231)
asp asp asp c
at t tc and s s c ;
uI c is the maximum temperature in
the inert heating. Since temperature at a certain position in
Recalling definitions of parameters, we see that the ignition
the specimen first increases and then decreases, the most
delay time can be expressed as functions of not only physi-
plausible condition for the ignition is that for 2uI =2t 0;
cochemical parameters, but also operating parameters char-
at which the position has its maximum temperature.
acteristic to the SHS process, such as the mixture ratio,
The inner problem for the asymptotics is then as
degree of dilution, initial temperature, and particle radius,
2u 2 2u x~ through the eigenvalue L 0 and Z∞ ⫺ Z0 :
⫹ :
223
2t 2s z2
Z∞ ⫺ Z0 L0
rt0 =rt exp
T~ d =T
~ It may be informative to note that the criterion used by
Averson et al. [104] and/or Strunia et al. [106] was Dt 2
Here, reactant consumption and heat loss are ignored, as is which was obtained by Enig [112] by the use of the so-called
the case for usual ignition phenomena. Identification of Eq. integral method by equating a transient–reactive relation at
(223) infers that the present problem parallels the earlier the flame initiation and a transient–diffusive relation in the
development [104–110]. In analyzing the reactive– inert heating. Such that, compared to the criterion in
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 61
Fig. 63. Ignition delay time tc for e 1, with (R0)sp in the specimen taken as a parameter [103]; (a) as a function of the mixture ratio m sp; and (b)
as a function of the degree of dilution k sp. Data points are experimental [113].
62 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 65. Ignitable range with heat loss taken as a parameter [103]; (a) as functions of the mixture ratio m sp and the heat loss index R20 =
2rsp ; and
(b) as a functions of the degree of dilution k sp and the heat loss index R20 =
2rsp : Data points are experimental [113]. (W) designates the flame
initiation and ( × ) the non-ignition.
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 63
It may be informative to note that the expression of Ec when the propagating SHS flame in the igniter locates at
obtained by Strunia et al. [106] is slightly different from s s f
⬎0: After that by assuming constant speed of the
that of Eq. (234) because their expression was derived flame propagation, the following relation has been used
under an assumption that there is no temperature distribu-
rt sp
s f ⫺k~ t
242
tion in the compacted medium, although they have taken the
rt ig
temperature distribution into account in obtaining the igni-
tion delay time. which is equivalent to xf ⫺
uig t:
As for the energy E0, supplied before the arrival of the
SHS flame, although it has not been taken into account in the 8.1.6. Results for the ignition energy
literature [106] is expressed as In numerical calculations, the situation considered is the
same as that in Section 8.1.4. Fig. 66 shows the ignition
s! energy E as a function of m ig in the igniter, with e taken
1
rt ig 4w~ us
E~ 0 1⫹ 1⫹ as a parameter. It is seen that with decreasing m ig, the igni-
2
rt ig k~ CB tion energy E increases first gradually and then rapidly until
" ! ( s!⫺1 )# the ignition limit, and that the contribution of E0 supplied
X∞
CA
n
2 4w~
× ⫺ 1 ⫹
2n ⫹ 1 1 ⫹ ; before arrival of the SHS flame is relatively large. In ad-
n0
CB k~ig k~ig dition, in spite of the decrease in the heat of combustion in
236 the igniter, the energy E0 increases with decreasing m ig. This
64 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 67. Ignition energy E under heat loss condition
e 1; with (R0)sp in the specimen taken as a parameter [114]; (a) as a function of m sp in the
specimen; (b) as a function of k sp in the specimen. The mixture ratio m ig in the igniter is 0.8.
A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74 65
Fig. 69. Model used for analyzing the SHS flame initiation by use of
radiative heat flux [124].
2u 22 u 22 u 1 2u
⫹ ⫹ ⫺ fu;
243
2t 2s z2 2s r2 s r 2s r
I:C: t 0; u 0; 244
2u ~
B:C: s z 0; 兩s r 兩 ⱕ a;
~ ⫺Q;
245
2s z
2u
s z 0; 兩s r 兩 ⬎ a;
~ 0;
246
2s z
s z ! ∞; s r ! ∞; u 0;
247
Fig. 68. Ignition energy E as a function of
R0 2sp ; with e taken as a
parameter [114]; (a) the mixture ratio m ig in the igniter is 0.8; (b) where
mig 0:65:
Z∞ ⫺ Z0 ma xi Q
si ;
i z; r; Q~ ;
l=c
Z∞ ⫺ Z0 2 q0 ma
8.2.1. Model definition and inert stage
The problem of interest is the radiative heating of the
Z∞ ⫺ Z0 ma a
a~ ;
front surface of an axisymmetric semi-infinite compacted
l=c
medium (Fig. 69), originally consisting of a mixture of N
particles, metal M, and an inert I that can be the product P of
the reaction nM M ⫹ nN N ! nP P. The front surface of the C
f ;
compacted medium is subjected to a partial, stepwise heat-
Z ∞ ⫺ Z0 2
ing with a constant heat flux Q for time t ⬎ 0; the diameter " # 2!
of heating area is 2a. Monodisperse size distribution is l 4es SB
T 2 ⫹ T02
T ⫹ T0 R0
C :
considered for N particles, with an initial radius R0 and rtc
rt c
u0;a R0 2 2r
number density of n0.
As described in Section 8.1.1, in the ignition processes Noted that the inert problem described has a known solution
66 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 71. Ignition delay time tc for Ti–C system of the stoichiometric
mixture
m 1; as a function of R0, with Q taken as a parameter
[121]. Data points are experimental [126].
Fig. 73. Ignition delay time tc for Ti–C system with R0 5 mm; as a
function of k , with Q and a taken as parameters [122]; (a) as a
function of m ; and (b) as a function of k . Data points are exper-
imental [126].
Fig. 75. Behavior of the thermal runaway criterion on the heat loss [123], for the stoichiometric mixture of Ti–C system with R0 5 mm; heated
by the radiative heat flux of 3.3 MW/m 2, with 10 mm in heating diameter.
70 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
Fig. 76. Ignition delay time tc for Ti–C system, with the radiative
heat flux Q and the emissivity e taken as parameters [123]; (a) as a Fig. 77. Ignition delay time tc for Ti–C system of the stoichiometric
function of the mixture ratio m ; (b) as a function of the degree of mixture
m 1; as a function of the particles radius R0, with Q and
dilution k . Conditions are the same as those in Fig. 70.
e taken as parameters [123].
conductivity and reaction rate (suggested by the excessively differences are minor from the mathematical point of
large Lewis number in the combustion wave), it has been view, important identification which has already been
clarified that concentration of the molten metal is mainly pointed out for the physical interpretation has been recon-
affected through consumption. firmed. So that qualitative validity of theoretical results
A nonadiabatic, heterogeneous theory for the SHS based on the homogeneous premixed-flame theory has
process with volumetric heat loss, has further been formu- been shown, if the differences involved are noted.
lated and shown that the characteristic extinction turning The field activated SHS, which is effective especially for
point exists in the same manner as that in the premixed low exothermic systems to sustain flame propagation, can
flame. It has also been found that the range of flammability also be examined by use of the heterogeneous theory, by
under heat loss conditions can well be described, in terms of introducing an additional term due to external heating by
its dependence on stoichiometry, dilution, initial tempera- electric current. It has been shown that the external heating
ture, particle size, and compact diameter. A particularly enhances the burning velocity and extends the range of
significant identification is that the process responsible for flammability, as expected. Significant identifications
its temperature sensitivity and ultimate extinguishment is obtained are that extent of these effect is strongly influenced
the Arrhenius liquid-phase mass-diffusion. The fair agree- by the particle size, as well as the physicochemical par-
ment between predicted and experimental results for the ameters, and that the range of flammability is still restricted
extinction limits in trend and in approximate magnitude even under external heating conditions, neither of which
suggests that this theory has captured the essential features have been captured by the homogeneous premixed-flame
of the nonadiabatic heterogeneous flame propagation in the theory. In this context, the heterogeneous theory is indeed
SHS process. A useful parameter called the heat loss index, viable in examining the field activated SHS.
which is defined as the square of the nonmetal particle size The study for the transition boundary from steady to
divided by the compact diameter, has also been found. pulsating combustion by use of the neutral stability analysis,
Based on these identifications, not only an approximate has also been conducted and it has been shown that there
expression for burning velocity in the adiabatic condition, exists a limit in the use of small particles, which is an
but also for extinction criterion in the nonadiabatic con- important suggestion for near-net-shape fabrication by use
dition, has been derived under the appropriate and realistic of the SHS process. As for the effects of transverse wave
assumptions of diffusion-limited reaction and infinite Lewis number, which are related to heat loss on the side surface, on
number. Effects of the dominant parameters on the burning the location of the boundary, it has been found to be rela-
velocity and/or extinction criterion have been clarified, tively small from a practical point of view.
yielding useful insight into manipulating the SHS flame In addition to the flame propagation and/or extinction,
propagation and extinction. Since a fair degree of agreement initiation of the combustion wave has been examined
with numerical results has been demonstrated by examining because energy required is basically that for initiating
applicability of these expressions, these expressions are SHS flame and effects of various parameters on the flame
expected to have general, qualitative and quantitative utility, initiation are indispensable for practical utility. It has been
in each case. found that the ignitable range is limited by heat loss during
Bimodal particle dispersion for the nonmetal particles has flame initiation when the particle size is large and/or
also been taken into account in the nonadiabatic heteroge- compact diameter is small; while it is heat loss during
neous theory. It has resulted that the mathematical problem flame propagation that confines the ignitable range when
can be rendered identical to the monomodal case by intro- the particle size is small and/or compact diameter is large.
ducing an equivalent particle radius expressed as a function This identification provides useful insight to controlling
of the bimodal parameters. This identification has further ignition phenomena in the SHS process by varying particle
provided useful insight into manipulating the flame propa- size, which is expected to make various contributions in
gation and/or extinction by making the system bimodal, practical applications.
especially in recognizing that because of the increase in
the total surface area of particles in the combustion wave, 9.2. Area for further research
the reduced equivalent particle size in the bimodal system
increases the burning velocity and broadens the range of In view of the recent interest to produce Functionally
flammability. Furthermore, flame instability, usually caused Graded Materials (FGMs) by use of the SHS process, a
by the high energy-release rate in the combustion wave candidate for research is the examination of flame
when the preparation is made with small particles, can propagation in a medium with distributed reactant concen-
even be suppressed by increasing the equivalent particle trations, not only in the longitudinal direction but also in the
size in the bimodal system. lateral directions. In this situation, contour of the combus-
The heterogeneous theory which has succeeded in captur- tion wave is no longer planar and the combustion wave
ing the essential feature of the heterogeneity in the SHS spreads two-dimensionally, because of the distributed heat
process has further been examined to elucidate differences generation rate and/or two-dimensional temperature distri-
from the homogeneous premixed-flame theory. Although bution, caused by the distributed reactant concentrations.
72 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
[21] Boddington T, Cottrell A, Laye PG. Combust Flame [52] Novikov NP, Borovinskaya IP, Merzhanov AG. Combust
1989;76:63. Explos Shock Waves 1974;10:157.
[22] Margolis SB, Williams FA. Flame propagation in solids and [53] Itin VI, Bratchikov AD, Merzhanov AG, Maslov VM.
high-density fluids with Arrhenius reactant diffusion. In: Combust Explos Shock Waves 1981;17:293.
Sandia Report, SAND90-8508, Sandia National Labora- [54] Itin VI, Bratchikov AD, Merzhanov AG, Doronin VN.
tories, 1990. Combust Explos Shock Waves 1982;18:536.
[23] Merzhanov AG, Khaikin BI. Prog Energy Combust Sci [55] Shcherbakov VA, Pityulin AN. Combust Explos Shock
1988;14:1. Waves 1983;19:631.
[24] Margolis SB. Prog Energy Combust Sci 1991;17:135. [56] Maksimov YuM, Merzhanov AG, Raskolenko LG, Pak AT,
[25] Dunmead SD, Readey DW, Semler CE, Holt JB. J Am Lepakova OK. Dokl Akad Nauk SSSR 1986;286:911 (in
Ceram Soc 1989;72:2318. Russian).
[26] Shkiro VM, Borovinskaya IP. Study of combustion mechan- [57] Maslov VM, Borovinskaya IP, Merzhanov AG. Combust
ism for mixtures of titanium with carbon. In: Merzhanov AG, Explos Shock Waves 1976;12:631.
editor. Combustion processes in chemical technology and [58] Naiborodenko YuS, Itin VI. Combust Explos Shock Waves
metallurgy. Akad. Nauk SSSR, OIKhF, 1975. p. 253–8 (in 1975;11:293.
Russian). [59] Naiborodenko YuS, Itin VI. Combust Explos Shock Waves
[27] Nekrasov EA, Maksimov YuM, Ziatdinov MKh, Shteinberg 1975;11:626.
AS. Combust Explos Shock Waves 1978;14:575. [60] Bratchikov AD, Merzhanov AG, Itin VI, Khachin VN,
[28] Deevi SC. J Mater Sci 1991;26:2662. Dudarev EF, Gyunter VE, Maslov VM, Chernov DB. Sov
[29] Hardt AP, Phung PV. Combust Flame 1973;21:77. Powder Metall Met Ceram 1980;19:5.
[30] Armstrong R. Combust Sci Technol 1990;71:155. [61] Itin VI, Khachin VN, Bratchikov AD, Gyunter VE, Chernov
[31] Merzhanov AG. Combust Sci Technol 1995;105:295. DB. Inorg Mater 1980;16:1337.
[32] Makino A, Law CK. Heterogeneous flame propagation in the [62] Samsonov GW, Vinitskii IM. Handbook of refractory
self-propagating high-temperature synthesis (SHS) process: compound. New York: Plenum Press, 1980.
theory and experimental comparisons. In: The 24th Sympo- [63] Graham D. Summary of impurity diffusion in the beta phase
sium (International) on Combustion. The Combustion Insti- of titanium. In: Wheeler Jr. JA, Winslow FR, editors. Diffu-
tute, Pittsburgh. 1992. p. 1883–91. sion on body-centerd cubic metals. Metals Park: American
[33] Makino A, Araki N, Kuwabara T. Trans JSME Ser B Society for Metal, 1965. p. 27–34.
1992;58:1925 (in Japanese); JSME Int’l J Ser. B (English [64] Makino A, Law C K. Propagation and diffusion-limited
Translation) 1994;37:576. extinction of nonadiabatic heterogeneous flame in the SHS
[34] Williams FA. Theory of laminar flames. Combustion theory. process. In: The Twenty-Fifth Symposium (International) on
2nd ed. Menlo Park: Benjamin/Cummings, 1985. p. 130–81. Combustion. The Combustion Institute, Pittsburgh, 1994, p.
[35] Williams FA. Spray combustion. Combustion theory. 2nd ed. 1659–67.
Menlo Park: Benjamin/Cummings, 1985. p. 446–84. [65] Williams FA. Ignition. Extinction, and flammability limit. in
[36] Makino A. Combust Flame 1992;90:143. combustion theory. 2nd ed. Menlo Park: Benjamin/
[37] Makino A, Law CK. Combust Flame 1995;101:551. Cummings, 1985. p. 265–93.
[38] Kanury AM. Metall Trans A 1992;23:2349. [66] Makino A, Law CK. J Am Ceram Soc 1996;79:3097.
[39] Huque A, Kanury AM. Combust Sci Technol 1993;89:27. [67] Munir ZA, Lai W. Combust Sci Tech 1992;88:201.
[40] Makino A. Ann Chim Fr 1995;20:143. [68] Munir ZA, Sata N. Int J SHS 1992;1:355.
[41] Touloukian YS. Thermophysical properties of high tempera- [69] Touloukian YS, DeWitt DP. Thermophysical properties of
ture solid materials. Thermophysical properties research matter, vol. 8. New York: IFI/Plenum Press, 1972.
center, Purdue University, vol. 5, New York: MacMillan, 1967. [70] Itin VI, Bratchikov AD, Doronin VN, Pribytkov GA. Sov
[42] Kirdyashkin AI, Maksimov YuM, Merzhanov AG. Combust Phys J (English translation) 1981;24:1134.
Explos Shock Waves 1981;17:591. [71] Itin VI, Naiborodenko YuS, Bratchikov AD, Butkevich NP,
[43] Makino A, Kita K, Araki N. Nensho no Kagaku to Gijutsu Korostelev SV, Sholokhova LV. Sov Phys J (English trans-
(Combust Sci Technol, Jpn) 1993;1:165 (in Japanese). lation) 1975;18:408.
[44] Bloshenko VN, Bokii VA, Borovinskaya IP, Merzhanov AG. [72] Makino A, Law CK. Int J SHS 1995;4:25.
Combust Explos Shock Waves 1984;20:676. [73] Kaper HS, Leaf GK, Margolis SB, Matkowsky BJ. Combust
[45] Hardt AP, Holsinger RW. Combust Flame 1973;21:91. Sci Technol 1987;53:289.
[46] Azatyan TS, Mal’tsev VM, Merzhanov AG, Seleznev VA. [74] Margolis SB, SIAM. J Appl Math 1983;43:351.
Combust Explos Shock Waves 1977;13:156. [75] Makino A, Law CK. Combust Sci Technol 1995;106:193.
[47] Makino A, Law CK. J Am Ceram Soc 1994;77:778. [76] Makino A. SHS flame propagation and extinction for titanium
[48] Touloukian YS, Powell RW, Ho CY, Nicolaou MC. Thermal and diamond system: theory and experimental comparisons. In:
diffusivity, Thermophysical properties of matter, The TPRC Chan SH, editor. Transport phenomena in combustion, vol. 1.
Data Series, vol. 10. New York: IFI/Plenum Press, 1973. Washington: Taylor and Francis, 1996. p. 678–88.
[49] Kirdyashkin AI, Maksimov YuM, Merzhanov AG. Combust [77] Makino A, Yamada T, Araki N. Nensho no Kagaku to
Explos Shock Waves 1981;17:591. Gijutsu (Combust Sci Technol, Jpn) 1995;3:41 (in Japa-
[50] Zenin AA, Merzhanov AG, Nersisyan GA. Combust Explos nese).
Shock Waves 1981;17:63. [78] Makino A, Sugiyama K, Araki N. Nensho no Kagaku to
[51] Borovinskaya IP, Merzhanov AG, Novikov NP, Filonenko Gijutsu (Combust Sci Technol, Jpn) 1996;4:93 (in Japanese).
AK. Combust Explos Shock Waves 1974;10:2. [79] Makino A. Energy Convers Mgmt 1997;38:1043.
74 A. Makino / Progress in Energy and Combustion Science 27 (2001) 1–74
[80] Makino A, Izumi H, Araki N. Nensho no Kagaku to Gijutsu [104] Averson ÉA, Barzykin VV, Merzhanov AG. Dokl Phys
(Combust Sci Technol, Jpn) 1998;6:65 (in Japanese). Chem, Acad Sci USSR 1968;178:1.
[81] Makino A, Law CK. Submitted for publication. [105] Strunina AG, Martem’yanova TM, Barzykin VV, Ermakov
[82] Knyazik VA, Merzhanov AG, Solomon VB, Shteinberg AS. VI. Combust Explos Shock Waves 1974;10:449.
Combust Explos Shock Waves 1985;21:333. [106] Strunina AG, Vaganova NI, Barzykin VV. Combust Explos
[83] Yamada O, Miyamoto Y, Koizumi M. J Mater Res Shock Waves 1977;13:707.
1986;1:275–9. [107] Strunina AG, Ermakov VI, Barzykin VV. Combust Explos
[84] Feng A, Munir ZA. Metall Mater Trans B 1995;26:581. Shock Waves 1978;14:441.
[85] Feng A, Munir ZA. Metall Mater Trans B 1995;26:587. [108] Strunina AG, Ermakov VI, Averson ÉA. Combust Explos
[86] Feng A, Munir ZA. J Am Ceram Soc 1996;79:2049. Shock Waves 1979;15:484.
[87] Munir ZA. Int J SHS 1997;6:165. [109] Strunina AG, Ermakov VI, Kostin SV, Barzykin VV.
[88] Filimonov IA, Kidin NI. SHS-process in external electric Combust Explos Shock Waves 1981;17:351.
fields. In: The 24th Symposium (International) on [110] Strunina AG, Firsov AN, Kostin SV. Combust Explos Shock
Combustion. The Combustion Institute, Pittsburgh, 1992. Waves 1981;17:500.
p. 1893–8. [111] Law CK. Int J Heat Mass Transfer 1978;21:1363.
[89] Makino A. Investigation of effects of electric field on the [112] Enig JW. Proc R Soc A 1968;305:205.
combustion behavior in the SHS process by use of the hetero- [113] Yamada T, Makino A, Araki N. Measurement of ignition
geneous theory. In SHS-99, Moscow, Russia, 1999. energy in the SHS process for Ti–C system. In: Proceedings
[90] Thermophysical Properties Handbook. Japan Society of of the 32nd Japanese Symposium on Combustion. The Japanese
Thermophysical Properties, editor. Tokyo: Yokendo, 1990. Section of the Combustion Institute, Sendai, 1994. p. 579–81.
p. 232 (in Japanese). [114] Makino A. Initiation of SHS flame induced by another SHS
[91] Touloukian YS. Thermophysical properties of high tempera- flame—determination of the ignition energy. In: Proceedings
ture solid materials, vol. 1. Thermophysical properties of the Second International Symposium on Advanced Energy
research center, Purdue University. New York: Macmillan, Conversion Systems and Related Technologies, RAN98,
1965. p. 85 1998. p. 242–3.
[92] Makino A, Law CK. Pulsating instability in the nonadiabatic [115] Kanury AM, Hernandez-Guerrero A. Combust Sci Technol
heterogeneous SHS flame: theory and experimental compar- 1995;104:181.
isons. In: The 26th Symposium (International) on Combus- [116] Liñán A, Williams FA. Combust Sci Technol 1971;3:91.
tion, The Combustion Institute, Pittsburgh, 1996. p. 1867– [117] Linan A, Williams FA. Combust Flame 1972;18:85.
74. [118] Liñán A, Crespo A. Combust Sci Technol 1972;6:223.
[93] Shkadinsky KG, Shkadinskaya GV, Matkowsky BJ, Volpert [119] Niioka T, Williams FA. Combust Flame 1977;29:43.
VA. Combust Sci Technol 1992;88:271. [120] Niioka T. Combust Sci Technol 1978;18:207.
[94] Butakov AA, Vaganov DA, Leont’ev SN. Combust Sci [121] Makino A. Initiation of the heterogeneous flame in the self-
Technol 1995;106:137. propagating high-temperature synthesis (SHS) process
[95] Makino A, Law CK. On the transition boundary from steady induced by radiative heat flux. In: ASPACC99, Taiwan,
to pulsating combustion in SHS flames. In: The 27th Sympo- 1999.
sium (International) on Combustion, The Combustion Insti- [122] Makino A. Initiation of the heterogeneous SHS by radiative
tute, Pittsburgh, 1998. p. 2469–76. heat flux. In: Proceedings of the 37th Japanese Symposium
[96] Margolis SB, Kaper HG, Leaf GK, Matkowsky BJ. Combust on Combustion. The Japanese Section of the Combustion
Sci Technol 1985;43:127. Institute, Chiba, 1999. p. 395–6.
[97] Margolis SB. Matkowsky. SIAM J Appl Math 1988;48:828. [123] Makino A, Law CK. Transient radiative initiation of the
[98] Margolis SB. Proc R Soc London A 1991;433:131. heterogeneous flame in SHS: theory and experimental
[99] Margolis SB, SIAM. J Appl Math 1991;51:693. comparisons. In: The 28th International Symposium on
[100] Margolis SB. Combust Sci Technol 1993;88:223. Combustion, The Combustion Institute, Edinburgh, 2000
[101] Barzykin VV, Merzhanov AG, Strunina AG. Ignition of (submitted for presentation).
heterogeneous systems containing condensed reaction [124] Niioka T, Hasegawa S. Ignition time of locally heated reac-
products. In: The 23rd Symposium (International) on tive materials. In: Rep. Inst. Fluid Sci., vol. 1, Tohoku
Combustion, The Combustion Institute, Pittsburgh, 1990. p. University, 1990.
1725–31. [125] Carslaw HS, Jaeger JC. Conduction of Heat in Solids. 2nd ed.
[102] Barzykin VV. Pure Appl Chem 1992;64:909. Oxford: Clarendon Press, 1959. p. 264.
[103] Makino A. Dependence of the ignition delay time on various [126] Kaise T, Makino A, Araki N. Effects of Various parameters
parameters in the SHS process initiated by another SHS flame. on the ignition delay time in the SHS process for Ti–C
In: Proceedings of the 5th ASME/JSME Joint Thermal Engi- system. In Proceedings of the 34th JSME Conference in
neering Conference, AJTE99-6321, San Diego, CA, 1999. Tohoku Section, Sendai, 1999. p. 127–8.