COMBUSTION SCIENCE AND TECHNOLOGY

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A Simplified Theoretical Model for the Vapor-Phase

Combustion of Metal Particles

C. K. LAW

To cite this article: C. K. LAW (1973) A Simplified Theoretical Model for the Vapor-Phase
Combustion of Metal Particles , COMBUSTION SCIENCE AND TECHNOLOGY, 7:5, 197-212, DOI:
10.1080/00102207308952359

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Combustion Science and Technology © Gordon and Breach, Science Publishers Ltd.
1973, Vol. 7, pp. 197-212 Printed in The United Kingdom

A Simplified Theoretical Model for the Vapor-Phase Combustion

of Metal Particlest
c. K. LAW
Department of Applied Mechanics and Engineering Sciences, University of California at San Diego,
La Jolla, California 92037

Abstract-An analytic model for the vapor-phase combustion of single metal particles is proposed. The condensa-
tion of vaporized oxides on the droplet surface and the motion of condensed oxides are properly accounted for.
Three modes of vapor-phase combustion are possible depending on the direction of motion of the condensed
oxides formed at the flame. Additional solutions, valid in dilute or enriched atmospheres, are obtained by allowing
the flame temperature to decrease or increase, respectively. Flammability limits are also determined. Sample solu-
tions are obtained for the combustion of Al and Be with O 2 , It is shown that the mass burning rate and the flame
stand-off distance are substantially increased by allowing for surface condensation. Be is found to burn much
slower than AI, in addition to its tendency to accumulate substantial condensed oxides on the droplet surface.
When results of the model are compared with available experimental observation, the agreement is reasonable, both
qualitatively and quantitatively.

NOMENCLATURE Yo Yo/Y
T, p,p temperature, density, pressure. & ()(1 + v)
k,C,D thermal conductivity, heat capacity, Subscripts
diffusion coefficient. f, s, 00 flame, droplet surface, infinity.
enthalpy. s, I, g solid, liquid and gaseous phases.
mass flux. I, 2 inner and outer diffusion zones, respec-
specific heat of vaporization at T s • tively (except as subscripts for Q).
heat of reaction/condensation at T, for F, 0, v, fuel, oxidizer, vapor product, condensed
oxide vapor per unit mass of fuel. c, p product, all products.
Q Ql + Q2'
r radial distance. I. INTRODUCTION
T; boiling point of oxide.
V bulk velocity. Metal powders have long been used as an ingredient
Y, r, mass fraction, mass fraction per unit in solid propellant formulation, both to increase
mass of gaseous components. the specific impulse and to suppress certain modes
() fraction of oxide vaporized at flame. of combustion instability. Due to the desirability
'YJ fraction of () diffusing inward. to keep the combustion chamber small, it is
v stoichiometric mass ratio of oxidizer to essential that the powders burn rapidly in order to
fuel. achieve complete combustion before being ex-
hausted. Thus, the study of the combustion
Nondimensional Parameters mechanism and the burning rate of a single metal
a t, - t; particle in various atmospheres is of paramount
b Tf - T aJ
importance.
~1 {I - 8'YJ,,- (1 + v - 8)~1} .- Several theories (Brzustowski and Glassman,
~2 {-v+e(I-'YJ)+(1+y-e)~2} 1964; Kuehl, 1965; Kuehl and Zwillenberg, 1968;
fz hlL Wilson, 1969; Klyachko, 1969) have been ad-
Le kl(CpD) vanced attempting to describe single metal particle
M m/(4TfpDrs) combustion. A comprehensive summary on the
C?t.2 Q121L(1 + y) t This work has been sponsored by the Air Force Office
f rlr: . of Scientific Research, Office of Aerospace Research, U.S.
t CT/L Air Force under Grant AFOSR-72-2333.
2
198 C. K. LAW
results of vapor-phase burning, which is relevant
to the present work, can be found in the paper by
Wilson (1969).
Based on Godsave's theory of hydrocarbon drop-
let combustion (see, for example, Williams, 1965),
Brzustowski and Glassman (1964) constructed a
simplified model for metal particle combustion.
This model deviates from that for the hydrocarbon
droplet mainly by limiting the flame temperature,
T f , to the boiling point of the metal oxide, T;, and
by allowing the oxide to vaporize only partially.
Both deviations stem from a consideration of the
total energy available.
The model of Brzustowski and Glassman was
modified by Kuehl (1965) and by Kuehl and
Zwillenberg (1968) by allowing for the inwardly-
directed transport of vaporized products and their
subsequent condensation on the droplet surface.
They have, however, assumed the vaporized frac-
tion, (j, of the product to be the same in the
presence of surface condensation as it is with
surface condensation inhibited. Furthermore, the
heat released from surface condensation was in-
corporated into the analysis in only an approximate
manner.
Wilson (1969) experimentally observed the ac-
cumulation of condensed product at the flame and
proposed a model to describe it. This model,
however, is only applicable for the special case
when T, is not constrained to T; and that all
products exist in condensed phase at the flame.
Recently, the problem with surface condensation
was also solved by Klyachko (1969), but at the
expense of selecting an arbitrary constant value for
the fraction 'YJ of (j that diffused inward. The heat
release due to surface condensation also was not
accounted for properly.
It is felt that to go one step further than the
contributions of Brzustowski and Glassman, the
following salient features of metal particle com-
bustion will have to be taken into account. A
proper treatment for the surface condensation of
vaporized products is essential. The condensation
heat release at the droplet surface is to be included
in the overall heat-balance equation. The values of
(j and 'YJ are to be found as eigenvalues] of the
problem, The, condensed products at the flame,
instead of being gas-like as some of the models have
t The term "eigenvalue" is used in its broad sense,
meaning a parameter whose value is determined in the
course of solution of a set of differential equations. The
strict interpretation within the context of Sturm-Liouville
theory is not intended here.
assumed, are to be convected away by the bulk
gaseous motion. The present model attempts to
introduce these improvements.
The complete model developed in Sections II and
and III henceforth will be called Model A. It
includes all the improvements proposed in the
previous paragraph, always restricting the flame
temperature to the boiling point of the oxide.
Section IV describes a modification of Model A in
which surface condensation of vaporized oxides is
inhibited, this will be called Model B. In Section V
solutions for Model A are extended into regions of
dilute atmospheres (low YOcrJ by allowing the
flame temperature to decrease and complete con-
densation of the products at the flame; and into
regions of enriched atmospheres (high Y O CXJ ) by
allowing the flame temperature to increase and
complete vaporization of the products at the flame.
The above two extensions are designated Models C
and D respectively. Sample solutions for Al and
Be reacting with O 2 will be discussed in detail for
all models in Section VI. Theoretical results are
compared with experimental observations in Section
VII.
II. THE MODEL
Several features of the familiar hydrocarbon droplet
combustion model (Williams, 1965) are adopted
here. Thus, it is assumed that the burning process
is steady-state, spherically symmetric and isobaric.
The coefficients of thermal conductivity and the
heat capacities of the various species are constant
and equal to each other. Unity Lewis number is
also assumed in order to obtain explicit expressions
for the final results.
The molten metal droplet is at its boiling point,
T s • Williams (1960) has shown that such an
assumption will cause .significant errors in the
computed burning rates only for low energy fuels
which probably will not ignite in the first place.
Since the transport of mass and heat are the
rate-limiting processes, evaporation of the fuel
takes place instantly and diffusion through any
condensed oxides on the droplet surface is assumed
to be sufficiently fast. The outwardly diffusing
fuel vapor and inwardly diffusing oxidizer gas
react instantaneously and completely at a surface
detached from the droplet where the mass flux
ratio 'V of the oxidizer to the fuel is in stoichiometric
proportion. At the flame, to satisfy Glassman's
criterion (Glassman, 1960) that the flame temper-
ature, T f , be limited to the oxide's boiling point,
T;, a fraction (j of the product formed at the flame
 MODEL FOR THE VAPOR-PHASE COMBUSTION OF METAL PARTICLES
is vaporized with the rest (1 - (j) in condensed
phase. Furthermore, a fraction 'YJ of the vaporized
products diffuses inward and condenses instantan-
eously and completely upon contacting the droplet
surface. The rest (1 - 'YJ) diffuses outward and
may condense eventually at infinity. The heat
generated at the flame, and at the droplet surface
when oxide vapor condenses, is used to vaporize
the fuel as well as to heat up the fuel vapor and
oxidizer gas. It is also required that T, > T, to
ensure vapor-phase burning (Glassman, 1960).
Condensed species do not diffuse, hence con-
densed products formed at the flame can only be
convected away by the bulk gaseous motion.
Since the bulk gaseous velocities, VI and V2 , in the
inner and outer region can both be directed either
inward or outward, four possible motions for the
condensed products can result: (i) they will be
completely dispersed to infinity if VI > 0 and
V 2 > 0; (ii) they will be trapped at the flame if
VI > 0 and V 2 < 0; (iii) they will be swept inward
and accumulated on the droplet surface if VI < 0
and V 2 < 0; (iv) it will be shown later the: case
VI < 0 and V2 > 0 is non-existent. The transition
among various models as proposed here is dis-
continuous due to the step change in mass flux in
either the inner or outer region.
Radiation effects are neglected in the present
formulation. Brzustowski and Glassman (1964)
found that for particle sizes less than 100 It, the
burning rates of Al and Mg were influenced to less
than 20 per cent by radiative effects. Wilson (1969)
also estimated that for a 60 ft particle, radiation
effects were less than 10 per cent. Since metal
particles encountered in the combustion chamber
are usually less than 100 ft in size, the neglect of
radiation is justified. The above assumption,
however, renders the present solutions to be inde-
pendent of the particle size. The influence of
ambient pressure enters only through the variations
of various thermochemical constants with pressure.
The inclusion of surface condensation of the
vaporized products, to account for the experi-
mentally observed phenomenon of the gradual
accumulation of condensed oxides on the droplet
surface, is an essential feature of the model. It
not only provides an additional heat source for the
vaporization process, but also allows for the
possibility of inwardly directed bulk gaseous vel-
ocities to bring the condensed oxides from the
flame to the droplet surface.
The assumed processes for the transport of
vaporized products in the inner region and their
199
subsequent condensation on the droplet surface
deserves further elaboration. During their migra-
tion from the flame to the droplet surface, con-
densation of vaporized products is prohibited.
This assumption is reasonable since the temperature
in the inner region is quite elevated, hence not
conducive for rapid nucleation to occur, at least
not until the vaporized products are near the
droplet surface. However, if this assumption is
not made, the formulation of the model will be
greatly complicated. A distributed condensation
heat release zone with continuous formation of
condensed oxides will exist. If VI > 0 at the flame,
then these condensed oxides will be continuously
swept towards the flame. If VI < 0 at the flame,
then it is possible that, under certain conditions,
VI > 0 occurs at some distance away from. the
droplet surface. Under this situation the condensed
oxides formed at the flame as well as in the gaseous
phase in region 1 will be trapped at the location
where VI = O. These potential complications will
not be analyzed.
The statement that complete condensation occurs
on the droplet surface, i.e.,
Y v ,I = 0 at r = rs (1)
requires that the condensation process occurs much
faster than the rates of transport of mass and heat.
This is assumed to be true in the present formula-
tion, since on physical grounds it appears most
realistic. If this assumption were not made, then
a rate expression for condensation would have to
be introduced. Such an expression would involve
additional (kinetic) parameters whose values are
unknown.
As condensed oxides slowly build up on the
droplet surface, if the rate of diffusion of the fuel
vapor through them is comparable with the rates
of heat and mass transport, then several of the
fundamental assumptions of the present model
break down. First, since the diffusion rate of fuel
vapor through the condensed oxides is expected to
decrease as the amount of oxide increases, the
burning process ceases to be steady state. When
the accumulation of the oxides on the droplet
surface is uneven, evaporation and the subsequent
combustion will be more rigorous in certain
directions, resulting in the commonly observed
phenomena of jetting and spinning. This destroys
the assumption of spherical symmetry. Finally,
when the oxide coating becomes increasingly non-
permeable to the fuel vapor, vapor-phase com-
bustion may be reduced to surface burning. In
200 C. K. LAW

severe cases chemical reaction may terminate alto- can now be expressed, in non-dimensional form:
gether and the burning process is said to be M I = {I - Or; - (1 +y - O)~I}MF
quenched. In all of the above situations the
=~IMF (7)
"d 2-law" , which is a consequence of spherically
symmetric vapor-phase burning with heat and Mg,1 = {I - &r;}MF (8)
mass transport being the rate-limiting process, lYf2 = {-y + &(1 - r;) + (1 + y - &)~2}MF
becomes invalid. The resulting exponent for d is =~2MF (9)
expected to lie between 1 and 2. The burning time
for a particle is substantially prolonged. M g,2 = {-y + &(1 - r;)}MF (10)
The presence of trapped condensed oxides in the B. Directions of Bulk Gaseous Velocity
flame zone is not expected to influence the burning The directions of V I , 2 are given by the signs of
process to any significant extent. This is because, Mg,1 and M g,2' Since M F is always flowing outward
first, they are distributed over a larger area at the and hence positive, the following criteria are
flame, and secondly, it has been suggested (Wilson obtained:
and Williams, 1971) that under certain conditions
VI ~ Oo¢:? r; ~ 1/0 (11)
they can be intermittently ejected outward by
acquiring significant thermal diffusion velocities; V 2 ~ Oo¢:? r; ~ (1 - y/O) (12)
thus it appears unlikely that there will be enough The direction of transport of the condensed
condensed oxide accumulated to form an effective oxides formed at the flame depends on VI and V2 •
non-permeable shell to slow the burning process Suitable combinations of the directions of VI and
substantially. V2 , produce four possible motions for the condensed
It can, therefore, be concluded that the present oxide.
model is expected to be able to provide a very
i) Dispersed to infinity (~I = 0, ~2 = 1). This
general qualitative description of the vapor-phase
occurs when VI > 0, V2 > 0. The combined
combustion of a metal particle in a prescribed
criteria on 0 and r; can be shown to be:
atmosphere. The reliability of the quantitative
prediction on the eigenvalues of the solution (e.g.,
mass burning rate and the flame stand-off distance),
°< r; < (1 - y/O); y < 0 < (1 + y) (13)
ii) Trapped at the flame (~I = ~2 = 0). "This
however, decreases when the detrimental effect of occurs when VI > 0, V2 < 0. The values of () and
surface oxide becomes serious as burning progresses. r; are now restricted by the inequalities:
Nevertheless the model does indicate, in a relative
max {O, (1 - y/O)} < r; < min {I, I/O};
manner, the conditions under which the accumu-
lation of surface oxides are expected to be serious. °< 0 < (1 + y) (14)
iii) Accumulated on the droplet surface (~I = 1,
III. FORMULATION ~2 = 0). This occurs when VI < 0, V 2 < 0. The
A. Stoichiometric Mass Flux Relations possible values of &and r; are given by:
From stoichiometry, the mass fluxes of various 1/& < n < 1; 1 < &< (1 + y) (15)
species, which are conserved quantities in the
respective regions where they are present, can all iv) The conditions for VI < 0, V >
2 are
mutually exclusive. Hence this regime does not
°
be expressed in terms of that of the fuel as:
exist.
MV,I = -{&r;}MF (2)
Equations (13) to (15) indicate thatthetransitions
Me,1 = -{(1 + y - &)~I}MF (3) between modes (i) and (ii), and between modes (ii)
Mo = -{y}MF (4) and (iii), occur at the limits - y + &(1 - r;) = 0
M V,2 = {&(1 - r;)}MF (5) °
and I' - Or; = respectively.
The regimes given by equations (13) to (15) are
M e,2 = {(1 + y - &)~2}MF (6)
'shown in Figure 1 for the metals Al and Be re-
where (~b ~2) is equal to unity when the condensed acting' with 02' It is to' be noted that the above
products formed at the flame are convected (in- criteria are by no means sufficient conditions for the
ward; outward), and is equal to zero otherwise. existence of various modes of combustion. Addi-
The bulk mass fluxes m = 47Tr 2 pV and the bulk tional restrictions, ensuring that the solutions
gaseous fluxes m g = 47Tr 2 pg V in each of the regions obtained are physically realistic (e.g. , Too > 0) will
 MODEL FOR THE VAPOR-PHASE COMBUSTION OF METAL PARTICLES 201

I.0 r-----r---..-----'T'--r---..-----r----.--..........--..,...,..--~-____,

0,8

0.6
7]
0.4

0,2

0,0 ~.....lo.-:.-J-~~~"---1.... _ _.l--_L_----I...~~~~~~~~......:::..__:::..I~___J

0,0 0,2 0.4 0.6 0.8 0.0 0,2 0.4 0,6 0.8 1.0
B B
FIG. 1. Regions in the O-'Y} space where solutions exist for various combustion modes for (a) Al and (b) Be.

have to be investigated for each combustion mode Furthermore, it can be shown that P and pg are
as well as for each metal. related by
It may be emphasized that while the results pg= p(1 - Yc)/(1 - R) (20)
obtained here depend on the assumption of
where R is the fraction of the total volume of
spherical symmetry, they are independent of most of
physical space occupied by the condensed particles.
the other simplifications, such as neglect of radia-
By making the realistic "dilute spray" approxi-
tion, constant transport coefficients, etc.
mation (Williams, 1965) that R «
1, equation (20)
C. Conservation of Species becomes
The mass flux of the i t h species in a gaseous flow (20a)
with condensed products can be expressed as Equation (16) can now be reduced to the familiar
m, = 47Tr 2{p
VYi - pg D dYi,g/dr} (16) diffusion equation for the i t h gaseous species:
In equation (16) whereas the convective term is m, = 47Tr 2p{VYi - D dYi/dr} (21)
evaluated for all the species present, the diffusive
In non-dimensional form, equation (21) can be
term is dependent only on the gaseous components.
written as
The binary diffusion coefficient D is assumed to be
M, = MYi - f2 d Y'[d? (21a)
a constant for all pairs of gaseous species in each
region. Integrating equation (2Ia) from the flame to any f
For the condensed species, the diffusive term is gives the general expression for the distribution of
absent. Equation (16) becomes, in non-dimensional the i t h gaseous species:
form,
r; = Mc/M (17) sur: - r;l) = In {(MJ:,f - Mi)/(MJ: - M i )}
Equation (17) shows that the mass fraction of the (22)
condensed products is a constant in each region. D. Conservation of Energy
That constant always will be zero in at least one of The non-dimensionalized energy equation, valid
the two regions. in a region free of energy sources or sinks, is
From the definitions of Y i andYi,g, viz.
Y i = pJ p, Yi,g = Pi/(P - Pc) (18) (23)
where Pi is the partial density of the i t h species, the where HI and H 2 represent the total amount of
following relation is obtained: energy flux in the inner and outer regionsrespec-
Yi = (1 - Yc)Y i. g (19) tively.
202 C. K. LAW

In obtaining equation (23), it has been assumed Inner Region:

that a constant heat capacity C is used for all
species and that the Lewis number Le = k/(CpD) c: Ye.1 = -(1 + v - (j);I/g;'1 (29)
is unity. Neither of these assumptions is essential v: M 1U- 1 - r-;I)
in obtaining a solution.· They are nevertheless
imposed so that explicit analytical results can be = --In {(g;'IYv,1 + (j'f))/(g;'IYV,t + B'f))} (30)
derived. F: M 1U- 1- 'i1) = -In {I - g;IYF} (31)
By taking the reference temperature to be the
droplet surface temperature T s ' the enthalpies for T:M 1U- 1 - r-;I)
the various species are: = --In {1-g;I(Tt - T)/(g;l a -(PI)} (32)
ho = (T - Ts ) hF = (T - Ts) Outer Region:
hv = - Ql + (T - Ts) he = - Q + (T - Ts)
(24)
c: Ye,2 = (1 +v- B);2/g;'2 (33)
where Q = Ql + Q2' v: M 2U-
1
- 'i1)
Evaluating equation (23) at t; and by applying
= --In{[g;'2 Yv,2- B(I-'f))]/[g;'2Yv,t-B(1-'f))]}
the boundary condition that
(34)
{,2 dT/df}s = M F + M v,I(Q2)
= MF{I - B'f)Q2} (25) 0: M 2U- 1 - 'i 1) = -In {1 + g;'2 YO} (35)
HI is found as
T: M 2 U- 1 - r-/)
HI == MF{(B'f)Q - I) + (1 + v - B)Q;I} (26a) = -In {I - ,:FiTt - T)/(g;'2a - 9?2)} (36)
Furthermore by noting that in crossing the flame where
from region I to region 2, an amount of heat flux,
M F(1 + if - B)(-Q + a)(1 - ;),associated with 9?1 = (B'f)Q2 - 1) (37)
the condensed oxides trapped at the flame during 9?2 = (O'f)Q - I) + 0(1 - 'f))Ql
mode (fi)burning, is lost. Hence H 2 can be found + (1 + v - B)[Q - a(1 - ;)] (38)
as
H 2 = HI - MF(I +v- O)(-Q + a)(1 - ;) F. Eigenvalues
(26b) Applying the boundary conditions that at f =
P, = I; Yv.1 = 0, YF = YF,s, T = t; to equations.
where ; = ;1 + ;2' Integrating equation (23)
from the flame to any', the general expression for
(30) to (32), respectively, and that at
YV,2 = 0, Yo = Yoro, T = r:
00;
to equations (34)
,=
temperature distribution is found as to (36), respectively, we obtain
MU- 1 - 'i1) = -In {1 - g;'(Tt - T)/(g;'a - 9?)}
MF'-~I(1 - 'i 1) =
In {I + g;'IYv,t/(B'f))} (39)
(27)
where 9? is given by 1
M Fg;I(1 - Pi ) = -In {I - g;'IYF.s} (40)
1
MF,-~il - 'i ) = In {I + g;'l a/(1 - B'f)Q2)}
9? = (MvQl + MeQ + H)/MF (28)
Equations (17), (22), and (27) are the general (41)
solutions to the present problem. When applied to
1-:#'2 Yv,t/e(1-'f))
-In {O;:
A

0 ; ; ; ' 'rt=
M F:#'2/ ' }

the inner and outer regions separately, the entire

flow field can be obtained. (42) 1

E. Distributions of Species and Temperature

M FG;2/'t = In {I + g;'2YOro} (43)

Noting that at, = 't, YF = 0, Yo = 0, Y v = Yv.i' M FG;2/'t = In {I - ,-c.F2b/(~2a - 9?2)}

and by using equations (2) to (6), the distributions (44)
of species and temperature in both the inner and
outer regions can be obtained from equation (17), The six equations, (39) to (44), are used to solve-
(22) and (27) as: for the: six eigenvalues M F, 't, 0, 'f), Yv.t, YF •s' It:
 MODEL FOR THE VAPOR-PHASE COMBUSTION OF METAL PARTICLES
is worth noting that in the classical hydrocarbon
droplet combustion model Yv,s and T, are eigen-
values of the problem instead of being given as
boundary conditions in the present formulation.
Hence, we are now able to determine instead two
alternate eigenvalues 8 and» which do not exist in
the hydrocarbon droplet case.
Eliminating M F , 'f' YV,f' and YF,vfromequations
(39) to (44), we obtain,
Y OaJ = {(1 - 'Y))(1 - 8'Y)Q2)/(a'Y)) - ~2}-1 (45)
b = Y OaJ(<fJ2 - ~2a) (46)
There are eight parameters in equations (45)
and (46), namely, the fuel characteristics a, v, Q1'
and Q2; the oxidizer characteristics band Y oaJ;
and the combustion characteristics 8 and 'Y)" For
a given fuel oxidizer system there are two ways to
solve the problem.
I) Inverse problem. Given 8 and 'Y), Y OaJ and b
are expressed by equations (45) and (46). The
mode of combustion can also be determined from
the inequalities in equations (13) to (15). For the
solutions to be physically realistic, we further
require that 0 < Y OaJ <
I and 0 <
T aJ ~ r.. The
upper limit in T aJ is placed because when the
ambient temperature exceeds T f , the true flame
temperature is expected to be greater than T f ,
hence invalidating the assumption that T, be equal
to the boiling point of the metal oxide.
2) Direct problem. Given Y OaJ and b, and by
assuming one of the three combustion modes
prev~ils (i.e., assuming values for ;1 and ;2), solve
for e and 'Y). A quadratic equation in 'Y) results,
C1'Y)2 + C 2'Y) + c; = 0 (47)
where C1, C 2, and c, are functions of v, Q1' Q2'
a, b, and Y oaJ' For all the cases studied that will
be presented later, there is at least one root to
equation (47) that is physically unrealistic. There-
fore, it seems that multiple solutions do not exist
for equation (47), although it has not been proven
analytically. " eigenvalue to be found from the problem. By
When 'Y) is known, e is given by,
8= YoaJ{(1 1:, v)[~ - a(1 - ;1)] + av - I} - b
Y ocx,{Q2(1 - 'Y)) -a('Y) - ;1)}
(48)
The () and 'Y) thus found not only have to be bounded
by zero and unity, they should also satisfy one of
the criteria in equations (13) to (15) so as to be
consistent with the initially assumed values of ;1
and ;2'
203
When b, Y o aJ, 8, and 'Y) are known, the rest of
the eigenvalues are given by:
~,f = a8'Y)j(1 - 8'Y)Q2) (49)
YF •s = {~1 + (1 - 8'Y)Q2)/a 1 t (50)
M F = {In [1 + ~laj(1 - 8'Y)Q2)]}j~1
+ {In [1 + ~2YOaJ]}j~2 (51)
~ {~21n [1 + ~la/(l- 8'Y)Q2)]}
r. = 1 + {~11n [1 + ~2 Y oaJ]} . (52)
Equations (47) to (52) are the general expressions
describing vapor-phase combustion with surface
condensation. It may be noted that although a is
assumed to be a constant in Model A, it can also
be treated as a variable if the flame temperature is
allowed to change. The results of Models B, C
and D proposed in the next two sections are special
cases of equations (39) to (44). In particular,
most of the analytic results can be obtained through
simple algebra by solving either equations (45) and
(46), or equations (48) to (52) without going into
equation (47).
IV. MODEL B: COMBUSTION WITH
SURFACE CONDENSATION INHIBITED
It has been observed occasionally (Prentice, 1970;
Wilson and Williams, 1971) that during the
combustion of Al particles in O 2/ Ar atmosphere
there does not seem to be any accumulation of
condensed oxides on the droplet surface. It is not
inconceivable that for some fuel-oxidizer systems
surface condensation of vaporized products is not
favored under special conditions. The model
postulated in previous sections needs only slight
modification to describe the present case, which is
similar to that put forth by Brzustowski and
Glassman (1964).
All the equations derived through equation (44)
remain valid except equation (39), which is to be
abandoned since now Yv,s is not zero but is an
setting 'Y) = 0, and ;1 = 0, explicit expressions are
derivable for all the eigenvalues of interest. The
expressions for 8, YF,s, M F , and r, can be obtained
simply by setting 'Y) = 0 and F 1 = 1 in equations
(48), (50), (51), and (52) respectively; whereas
YV,f is now given by
YV,f = Y oaJ8/(1 + ~2 Y o aJ) (53)
Equation (50) shows that YF,s is now a function
of the fuel properties only. Furthermore, for the
204
complete dispersion mode, ~2 = 1, .:F2 = 1, then
equations (51) and (52) show that M F and Pf are
independent of &, and hence the ambient tempera-
ture T CXJ' This interesting result illustrates the
"shielding" nature on the fuel evaporation process
when the assumptions of constant flame tempera-
ture and 'YJ = 0 are made. Variations in T co
cause: changes in & in such a way that M F and Pf
remain undisturbed.
The transition between modes (i) and (ii) occurs
at () = v/(I + v) when V2 = O. In the model by
Brzustowski and Glassman the stoichiometric
molar ratio of oxidizer to fuel was used instead of
v in defining this transition limit.
By setting () = I and letting T, be an unknown
in the present problem instead, the classical
hydrocarbon droplet burning results can be re-
covered.
V. COMBUSTION IN DILUTE AND
ENRICHED ATMOSPHERES
In Models A and B proposed in the previous sec-
tions, the flame temperature was always held at the
boiling point of the metal oxide as a result of the
high heats of vaporization or dissociation of metal
oxides upon vaporization (Glassman, 1960). This
constraint on the flame temperature, however, is to
be removed after complete condensation «() = 0)
or complete vaporization «() = 1) of the oxides
occur. Physically it is expected that combustion
with complete oxide condensation or vaporization
will be most relevant during burning in dilute or
enriched atmospheres respectively.
A. kIodel C: In Dilute Atmospheres «() = 0)
First we note that during combustion in dilute
atmospheres results from Models A and B should
agree with each other. This is because with () = 0,
surface condensation of oxide vapor is irrelevant
since oxides do not exist in the vapor phase. This
reasoning is found to be true from the analytic
solutions obtained.
The lower limit of Models A and B, where
combustion with Tf~ = Tfo is still possible, is
obtained by setting 8 = 0 in equation (48). At
this limit the combustion is expected to be ex-
hibiting mode (ii) behavior (~1 = ~2 = 0). A
linear relation in (Ico s YOrfJ) is obtained as,
t: = If - [(1 + v)Q - I - a]YOrfJ (54)
where If = I;. Equation (54) will be termed the
flammability limit for a metal particle burning
with T, = T; in a prescribed atmosphere.
C. K. LAW
As the atmosphere is further diluted (or cooled),
combustion with T, = T; is not possible. Inorder
to sustain further vapor-phase burning, it is
reasonable to assume that the flame temperature
starts to decrease so that less heat will be lost to the
ambient. This assumption was also made in the
models by Brzustowski and Glassman (1964),
Kuehl and Zwillenberg (1965,1968), and Klyachko
(1969). Recently, Law (1973) has also observed
that when magnesium particles burn in "dilute
atmospheres (YOrfJ as low as 0.031), the flame
intensity becomes progressively weaker as YOrfJ
decreases.
The general expressions of Model A (or Model B)
for T/).!, YF,s, M F, and Pf [equations (49) to (52)]
similarly apply to the present case by setting
() = 0, :#1 = 1, and :#2 = -v. The flame tem-
perature T f , which is built into the definitions of a
a.,nd b, is treated as a variable. An expression for
T, is obtained by rearranging equation (54) in the
form
If = {IrfJ + [Is+(1 +v)Q-I] YorfJ}/{1 + YOrfJ}
(55)
When T rfJ < T s ' as T, is reduced to T s ' further
vapor-phase combustion is not possible according
to Glassman's criterion (1960). This extended
flammability limit is obtained by letting T, = T;
in equation (54), viz,
r: = Is - [(I + v)Q - 1] YOrfJ (56)
At this limit equations (50) to (52) show that
YF,s = 0, M F = -{In (1 - YOrfJ)}/v, and Pf = 1.
Equation (56) illustrates the important result
that in order to support combustion in very dilute
atmospheres, a fuel-oxidizer system is desired to
have small values of v and T, and large value of
T rfJ and (Q - L). These results are, of course,
expected physically.
The extended flammability limit as given by
equation (56) does not exist when Ti; > T s . The
limit YOrfJ = 0 is reached first as YOrfJ decreases.
When YOrfJ = 0 and a > 0, equations (50) to (52)
give
YF,s = a/(1 + a); MF = In (1 + a); Pf = 00
(57)
Equation (57) illustrates the phenomenon of pure
evaporation, as would be expected physically.
Model C is identical to the flame structure model
(with complete accumulation ofcondensed products.
 MODEL FOR THE VAPOR-PHASE COMBUSTION OF METAL PARTICLES
at the flame) put forth by Wilson (1969). The
present analysis in addition indicates that this
model is only valid for burning in very dilute
atmospheres. When T, is increased to T; (as Yow
increases), partial dissociation of condensed prod-
ucts at the flame is an essential process. Models
A or B should be used instead.
B. Model D: In Enriched Atmospheres (0 = 1)
In the model by Brzustowski and Glassman where
surface condensation is inhibited, it was found a
fraction of the oxides formed at the flame are
always in condensed phase so that enough heat is
liberated at the flame to sustain combustion.
When surface condensation is allowed, con-
densation of oxide vapor occur both at the flame
as well as at the droplet surface. It is reasonable to
expect that under certain conditions (i.e. high
Yow, high Too atmospheres) enough condensation
heat is evolved at the droplet surface to support
combustion such that condensation at the flame is
not necessary (i.e. 0 = 1). The flame temperature
can now be allowed to increase. It may be empha-
sized that although complete oxide vaporization at
the flame is assumed, the present case differs from
the classical hydrocarbon droplet model in allowing
for the addition process of surface condensation.
Results obtained for Model A specialize to
Model D by restricting 0 = 1 and by treating T,
as an unknown in the problem. Values of j7 and
T f for Model D can be obtained by solving equa-
tions (45) and (46); YV.f' YF,s' M F , and Yj are
then given by equations (49) to (52) respectively.
Finally we note that Models C and D respectively
resemble modes (ii) and (i) [or (iii)] burning of
both Models A and B, in that in the former case
the bulk motion in the inner and outer regions are
directed towards the flame whereas in the latter
case their motions are in the same direction.
VI. SAMPLE SOLUTIONS
Since six free parameters are needed to specify
the problem, a thorough parametric study of the
theoretical results would be extremely tedious. We
will instead present solutions for Al and Be re-
TABLE I
Thermochemical constants evaluated at one atmosphere for the AI-Q 2 and Be-02 systems.
TiOK) T;COK) L(Kcalfgm)
Al System 2767 3850 2.58
Be System 2757 4060 7.90
3
205
acting with O 2 in detail to illustrate the nature of the
theory.
The selection of these two metals for study is
not random. The boiling points for Al and Be,
and also the boiling points for their respective
oxides, are very close (see Table I). They also have
similar values for the (molar) heats of vaporization.
However, despite these similarities in some of
their thermochemical constants, experimental evi-
dence obtained by Prentice (1970, 1971) and by
Macek et al. (1967, 1969) have conclusively
demonstrated that their combustion mechanisms
are quite different. It is thus of interest to investi-
gate . their combustion characteristics from a
theoretical basis. Another additional advantage in
choosing Al and Be for study is that in the experi-
mental research on single metal particle combustion,
they are two of the most thoroughly studied. The
large amount of reliable experimental observations
would be helpful in interpreting the theoretical
results.
The reactions assumed for Al and Be are:
2Al(g) +. to'~Al,O,(g)}
(58)
AI20 3(g) ~ AI20 3 (l)
Be(g) + 10, ~::. BeO(g) } (59)
BeO(g) ~ BeO(s)
In equation (58), AI 20 3(g) is a generic repre-
sentation of the gaseous combustion products
arising from the first reaction. These may include
AIO(g) , AI 20(g), 02' 0, etc. It is generally
accepted that AI 20 3(g) does not exist, although
this point has not been unassailably established
(Markstein, 1966). In computing Ql and Q2:> it is
assumed that AI20 3(g) consists of 2AIO(g) -+- !02
and that frozen chemistry prevails within region 1.
An alternate representation for AI 20 3(g) is
AIO(g) + AI0 2(g), in which case the values of Ql
and Q2 adopted in this work will be slightly
changed.
A summary of the thermochemical data, which
A A
Ql(Kcal/gm) Q2(Kcal/gm) v Ql Q2
2.10 7.31 0.886 0.432 1.50
5.45 18.2 1.773 0.249 0.834
206
were all taken from the JANNAF Thermochemical
Tables (1971), is listed in Table I. In non-
dimensionalizing the temperature from T to the r,
value C = 0.25 caI./gmtK is used throughout.
This value represents a reasonable average for the
various species evaluated at the extremes in
temperatures.
The only pressure effects in the present model
arise through the dependence of the various
thermochemical constants on pressure, and are
usually not significant enough to affect the com-
bustion behavior qualitatively. We have thus
evaluated all the thermochemical constants in
Table I at I atm. pressure for simplicity.
A. Solutions for Models A, C and D
Knowing the fuel-oxidizer characteristics v, T" T;,
Q[ and Q2, complete solutions for Al and Be were
obtained by using equations derived in the previous
sections. Regions of existence for Model A with its
three possible modes of combustion, and also for
Models C and D, are mapped out in the 1/-0 plane
in Figure I and in the Too - Yooo plane in Figure 2.
The non-dimensionalized mass burning rate M F
and flame stand-off distance Pf are plotted as
functions of Yooo for the ambient temperatures
Too = 300 OK, 2500 OK, and 3000 OK in Figures 3
and 4.
Figure 2 indicates that solutions for Model A are
bounded by the limits IJ = 0 and IJ = I. Between
0.4 0,6
Yoco Yo00
FlG. 2. Regions in the Too - Y ooo space where
solutions exist for various combustion modes for
(a) AI and (b) Be.
C. K. LAW
the flammability limit of equation (54) and the
extended flammability limit of equation (56) (or the
Yo oo = 0 limit if Too > T,) solutions for Model C
exist; whereas between IJ = I and Yo oo = I
solutions for Model D apply.
It may also be noted that in the Too - Yo oo plane,
a gap exists during transition between modes (i)
and (ii) whereas an overlapping region exists
during transition between modes (ii) and (iii).
These void or over-lapping regions are so small
that they cannot be distinguished in Figure 2. All
the eigenvalues also change discontinuously during
transitions among various modes. The above
behaviors have no physical significance and are
mathematical difficulties caused by the initially
assumed locations of the condensed products
(formed at the flame) during transition. For
example during transition from mode (i) to mode
(ii) these condensed products are relocated dis-
continuously from infinity to the flame. The
enthalpies of the condensed oxides change by an
amount C(Tf - Too) and C(Tf - T,) during tran-
sitions between modes (i) and (ii), and between
modes (ii) and (iii) respectively. Since these
changes are smaIl when compared with the total
enthalpies of the condensed oxides, the differences
of the eigenvalues at the points of transition are
usually not large. This is especially true when the
temperature differences (T', - Too) and (Tf - T,)
are small, as during transitions either at high Too
or between modes (ii) and (iii).
From the above observations it can also be
concluded that the quantitative results of the theory
are not influenced significantly by accounting
properly for the motion of the condensed products.
To facilitate the mathematical derivations the
condensed products formed at the flame can be
effectively treated as gas-like. The error resulting
from such an approximation would be less than
(I + v)CTf/Q when compared with unity. After
complete solutions have been found, the location
of the condensed oxides can then be determined
from the respective values of IJ and 1/.
Figure 2a shows that for AI combustion mode
(iii) does not exist whereas modes (i) and (ii)
behavior occur for relatively richer and leaner
oxidizer concentrations respectively. During com-
bustion in an atmosphere with more oxidizer,
relatively less oxide vapor are needed to condense
1.0
at the flame to support burning. The higher oxide
vapor concentration at the flame results in a larger
outwardly-directed oxide-vapor mass flux in the
outer region, hence favoring the occurrence of mode
 MODEL FOR THE VAPOR-PHASE COMBUSTION OF METAL PARTICLES 207

(0) AI (b) Be
2

-·ffi~~nil MODEL A
. ·--······..·. (
.---------model,ill
- - - MODELC
- - - - MODEL D

0,6 1.0
~m YOm
FIG. 3. Nondimensionalized mass burning rate M F as function of Yo", with various T",'s for (a) AI and (b) Be.

(i). Similarly as ambient oxidizer concentration is
reduced, more condensed oxide will be formed at
the flame, producing a net inwardly-directed
gaseous mass flux in region 2. Since the gaseous
velocity in region I is usually directed outward in
the case of AI [i.e. (1 + lI)O"YJ < I], mode (ii) is
favored.
For Be combustion (Figure 2b) in low T",
atmospheres, modes (iii) and (ii) occur for richer
and leaner ambient oxidizer concentrations re-
spectively. The occurrence of mode (iii) is due to the
large stoichiometric oxidizer to fuel ratio 11 such
that VI = I - (I + lI)O"YJ < 0. As T", increases
and Yo", decreases, mode (iii) changes into mode (i).

I I I I I I I I

(0) AI (b) Be
5 - -
•.......... mode (1)1 MODEL .............. modes
or(iii) ti) } M~DEL
------ mode(ii) A
4 I - - MODEL C
\. Teo" 3000'K _ . - MOOEL D
V Tm" 3000'K
------ mode (ii)
- - MOOEL C
- - - - MODEL P
-
"rf .." ./
<: , (il
,;' .. _...~-::.-
3 -j 2500'K --....~
,,---
' .......
'-"1"-._.- - - - - - - - --l -~

1<·~·;t.·K--~~·/~~~~.--
-
, - /, , , , / , 250:" ,
I
I
0,0 0.2 0,4 0,6 0,8 0,0 0,2 0.4 0,6 0.8 1.0
~co ~m
FIG. 4. Nondimensionalized flame stand-off distance " as function of Yo", with various T", 's for (a) Al and (b) Be.
208
This is caused by the increased amount of con-
densation at the flame needed to sustain burning
in these dilute atmospheres.
It is interesting to note that except for the
directions of motion, mode (i) of Al resembles
mode (iii) of Be under similar circumstances. This
is caused by the symmetrical nature of the fuel and
the oxidizer in these two modes. In fact by inter-
changing the locations of fuel and oxidizer, mode
(iii) can then be called mode (i), and vice versa.
We can further suggest that for a fuel-oxidizer
system (a) if v < I, then the bulk motion tends to
be directed from the fuel to the oxidizer; and (b)
if v > I, the bulk motion tends to be directed from
the oxidizer to the fuel. The larger v deviates from
unity the stronger the respective tendency will be.
The above observation, of course, is only a very
crude criterion which is to be modified strongly by
the particular values of 0 and 1] existing under vari-
ous atmospheres of Too and Yo",.
It may also be emphasized that, again due to the
larger value of v, in the Be-0 2 system more oxide
vapor condenses on the droplet surface per unit
mass of Be consumed than, say, in the AI-0 2
system. This situation is further aggrevated during
mode (iii) burning when additional condensed
oxides formed at the flame are transported to the
droplet surface by the bulk gaseous motion.
It is instructive to discuss the variations of 0 and
"/ with T", and Yooo. For Too < T" as Yo oo
decreases. 0 decreases whereas 1] increases. The
decrease in 0 increases the heat generated at the
name whereas the increase in '1 supplies relatively
more condensation heat at the droplet surface.
Both of these effects are beneficial to burning in a
dilute atmosphere. When Too > T" however, 0
and '1 both decrease as Yo oo is reduced. The
reduction in 1] suggests the system is now actually
receiving energy from the ambient and less surface
condensation is needed to sustain burning. As was
discussed previously the extended flammability
limit does not exist when Too > T, and fuel evap-
oration can still take place in the absence of any
chemical heat release at Yo oo = O.
Figure 3 shows that M}<' increases approximately
linearly with Yooo. It is also quite insensitive to
variations in Too. It has also been found that Ml<'
for AI is higher than that of Be by a factor between
1.5 and 2. This is in agreement with the analysis
of Kuehl and Zwillenberg (1965, 1968) that the
mass burning rate of Al is usually higher than Be
by approximately a factor of 1.5.
Figure 4 shows that when Too < T" ;1 increases
C. K. LAW
rapidly with increasing Yooo for combustion with
condensed oxides trapped at the flame (Model C
and mode (ii) of Model A), but does not vary too
much as Yooo further increases. When Too > T"
;1 first decreases very rapidly from infinity at
Yo", = 0, and is followed by a more gentle
decrease afterwards. It is also shown that at higher
ambient oxidizer concentrations the values of the
flame stand-off ratio only weakly depend on varia-
tions in the ambient temperatures.
Finally it may be noted that Model D breaks
down when Zybecomes too high. At Too = 300 "K,
the computed T 1 at Yo oo = I for Al and Be are
about 6100 OK and 9050 OK respectively. These
values are unrealistic. Further dissociation of the
vaporized products would have already taken place
and kept T 1 to a much lower value. The burning
rate, however, might not be affected much by
dissociation. This situation is similar to the
treatment usually extended to the classical hydro-
carbon droplet burning case, where the flame
temperature obtained from the solutions assumes
frozen equilibrium of the products instead of the
more realistic limit of dissociation equilibrium.
The mass burning rate so obtained is nevertheless
used frequently, and favorable agreement can
usually be found with experimental data (Law and
Williams, 1972).
B. Solutions Jor Model B
Solutions for Models Band C are plotted for M p
and ;1 versus Yo oo in Figures 5a and 5b respectively.
Only solutions for Al are presented because
experimental evidences have conclusively demon-
strated that in Be combustion there is always a
large amount of condensed oxide accumulated on
the droplet surface, hence invalidating the basic
assumption of Model B. Theoretically, however,
solutions for Be combustion do exist .and are
found to be qualitatively similar with those of AI.
Qualitative agreements exist between results for
Model B and those obtained earlier by Brzustowski
and Glassman (1964). Solutions for the complete
dispersion mode (i) depend on T", only through
the location where this mode terminates and changes
into mode (ii) burning. The transition between
modes (i) and (ii) is again discontinuous as in the
solutions of Model A. Mode (i) burning occupies
the entire oxidizer-rich regime and some oxides
still exist in condensed phase when Yo", reaches
unity. This is to be contrasted with results from
Model A where complete vaporization of the oxides
 MODEL FOR THE VAPOR-PHASE COMBUSTION OF METAL PARTICLES
I.0 , - - - - - , - - - , - - - , - - - - - - , r - - - - - ,
0.8 (0)
0.6
- - mode (il MODEL 1
----- mode (i i) B
.........._- MODEL C
0.2 i 2.0
f
J.:J.-
0.0 v--- 3000· K
2500·K
" ' - - - - ' - _ - - - L_ _.l..-_--I..-_--.J
0.0 0.2 0.4 0.6 0.8 1,0
YOet>
FIG 5. (a) M F and (b) ; f as functions of Yo", with various T", 's for AI burning without surface condensation.
at the flame occurs at a relatively low value of Yo""
It may also be noted that at high T", some solutions
for mode (ii) are so close to the curves representing
mode (i) that the differences are imperceptible in
the figures.
A comparison of Figures 3a and 5a ind icates
that the lack of surface condensation has the effect
of greatly reducing the mass burning rate. For
example, the values of M F are reduced by a factor
of 1.7 and 2.5 at Yo", = 0.2 and 0.5 respectively.
Figure 5b shows that, except in an atmosphere
with low Yo", and high T"" P, is very close to unity
and is usually much smaller than the corresponding
values obtained from Models A and D. Finally, it
has been found that M F of AI again exceed those of
Be by approximately the same factors obtained for
combustion with surface condensation inhibited.
The comparisons between combustion with and
without surface condensation cited above are in
qualitative agreement with the analysis of Kuehl
and Zwillenberg (1965,1968). They have, however,
underestimated the effect of surface condensation
by using a smaller value of f) obtained from
combustion without surface condensation. It has
been found here that under similar conditions the
values of f) from Model A exceed those from Model
B by a substantial amount.
VII. EXPERIMENTAL EVIDENCE
A large body of experimental observations on Al
and Be have been documented. In particular we
209
6.0 1'1'~ -----,--..,-------,---,-----,
5.0 To:> =3000 0 K (b)
;
\
4.0
- - mode lil
_____ rnodelii]
1MODEL
B
............... MODEL C
1.0 Ll::::L:=I==:::r==:::::::r:::::::d
0,0 0,2 0.4 0,6 0.8 \,0
YOo:>
have found results on Al by Wilson and Williams
(1969, 1971), and on Al and Be by Macek and
Semple (1967,1969) and by Prentice (1970, 1971)
most systematic, useful, and relevant to the present
models. Experimental evidence cited below are
mainly abstracted from the works by the above
groups of investigators.
The assumption that the molten droplet is at its
boiling point is further supported by Macek's
(1967) conclusion that ignition of AI particle
occurs when the surface oxide melts (at about
2300 OK). Since thermal equilibrium is established
rapidly (compared with the total vapor-phase
burning time) within the droplet due to the small-
ness of the particle and the large thermal conduc-
tivity coefficient of AI, it is expected that the entire
droplet will be near or at its boiling point soon
after ignition. Similar arguments can be said about
Be combustion.
As was discussed in Section II, the most serious
detrimental agent in destroying the steady-state
behavior, as well as several other fundamental
assumptions in the models, is expected to be the
accumulation of condensed oxides on the droplet
surface. Model A predicts Be combustion will
result in more accumulated surface oxides that AI.
This is conclusively confirmed by experiments
(Prentice, 1970, 1971; Macek and Semple, 1969).
In fact when Al burns in O./Ar atmosphere there
is usually no noticea ble amount of oxide present on
the droplet surface. Based on this observation
alone it seems Al is best described by Model B,
210 C. K. LAW
a Ithough some other evidences cited below tend to
suggest otherwise.
The statement that M F and TI are constants in a
burning process is equivalent to the "d 2-law", that
is the rate of decrease of the droplet diameter
squared is constant. Wilson and Williams (1971)
concluded the exponent of d is between 1.5 and 2
for Al combustion after surveying experimental
data from many sources. They have also established
the constancy of TI for Al burning in 02/Ar.
Steady-state assumption does not hold in Be
combustion. Both Prentice and Macek have
found that vapor-phase combustion of Be usually
reduces to surface reaction, due to the accumulation
of condensed oxides on the droplet surface, in
the later stage of the burning process at room as
well as at elevated ambient temperatures. If the
onset of surface reaction does not occur too early,
results from Model A can still be approximately
utilized. Otherwise a surface reaction model would
be more appropriate to use. Model B, which
does not take into account surface condensation,
is totally inadequate to describe Be combustion.
For AI combustion, theoretical results from all
models show that the condensed products formed
at the flame are continuously being swept outward
at high Yo", but are trapped at the flame at low
Yo"" At T", = 300 "K the transition occurs at
Yo", ~ 0.24. It is expected that the oxides trapped
at the flame will grow rapidly in size once nucleation
is started, and hence will probably be observable
experimentally. To this effect the dual-mode
combustion behavior, observed under identical
ambient conditions by Wilson and Williams (1971),
may be significant. AI particles were ignited in
02/Aratmosphere withp", = 5 atm, T", = 300 OK,
Yo", = 0.167. In one experiment a large oxide
fragment, which is thought to be a result of the
incomplete removal of the oxide film during the
ignition process, was found to be moving about in
the flame zone. This behavior is consistent with
the mode (ii) description, and also agrees with the
analytic predictions (Figure 2a). However, in
another experiment conducted under identical
ambient conditions but with increased incident
laser flux for ignition, mode (i) burning seems to be
taking place. Since there is no overlapping region
in the T", - Yo", plane where solutions for modes
(i) and (ii) can exist simultaneously, this dual-mode
behavior is not predicted from the present models.
It is, however, possible that due to the uncertainties
in the transport coefficients used and the generic
representation of AI 20 3(g) selected, the true tran-
sition point lies close to Yo", = 0.167 instead of the
presently computed values of Yo", ~ 0.24. Then
it is reasonable to assume that slight variations in
the ambient conditions can shift the combustion
behavior from one mode to the other. It has been
found that if a value of C = 0.175 cal/gmrK is
used in place of C = 0.25 cal/gmr'K, then the
computed transition point is shifted to Yo", ~ 0.17,
which is much closer to the experimental condition
observed for the dual-mode bahavior. Alterna-
tively it can also be argued that multi-mode be-
havior is mathematically possible and hence
perhaps physically realistic. With different initial
conditions to the time-dependent differential equa-
tions for the combustion process, various steady-
state solutions can emerge. In that case the
present models may represent only some of the
several possible solutions.
Wilson and Williams (1971) have in addition
observed a sunburst effect at Yo", = 1 and p =
0.5 atm. Here groups of light emitting particles
intermittently move outward from the flame, their
tracks producing a sunburst pattern during the
open shutter time. The presence of condensed
oxides at the flame when Yo'" = I is within the
description of Model B but not Model D, which
assumes I) = I throughout. This sunburst effect,
however, occurs only at low ambient pressures;
and therefore could be a peculiar effect associated
with combustion near the ignition limit, which
was found to be at Po", = 0.2 atm.
Strong jetting phenomenon was also observed at
high Yo", atmospheres. This is thought to be
caused by the high rate of influx of the oxide vapor
(proportional to Yu.tl) 'f) such that an uneven
distribution of condensed oxides is formed on the
droplet surface in a very short time.
For Be burning in room temperature atmosphere,
Prentice (1971) has observed that the predominant
combustion mechanism is vapor phase at low Yo""
but changes to surface reaction at high Yo",. This
is not in agreement with the present models which
indicate that as Yo", increases, the amount of
surface oxide accumulated per unit mass of fuel
consumed (i.e. 6'f) should decrease. However, it
is also possible that due to the fast rate of de-
position of condensed oxides on the droplet surface
at high ambient oxidizer concentrations, the
diffusion flame is quenched before steady-state
burning can be established. The ensuing surface
reaction produces the excessive surface oxides
observed.
Macek and Semple (1969) burned single Be
 MODEL FOR THE VAPOR-PHASE COMBUSTION OF METAL PARTICLES 211

particles in high temperature environment and
observed rapid vapor-phase burning at high Yo""
As the oxidizer concentration was gradually
lowered the flame intensity was found to decrease
and vapor-phase combustion gradually changed
over to surface reaction. All these observations are
in qualitative agreement with the present theory.
The theoretical burning rate M F from Models A,
B, C and D for Al burning in Too = 300 OK are
plotted in Figure 6 together with the experimental
data reported by Wilson and Williams (1971). To
convert the mass burning rate data f3 = (d/dt)(d'f)
as reported by them to our dimensionless mass
burning rate M p = mF /(41T pDr,), the relation
M F = (p,f3)/(8(pD» is used, where p, is the
density of liquid Al at T,. Wilson (1969) has
discussed in detail the averaging procedure of (pD)
over both composition and temperature. We have
chosen values obtained from using the arithmetic
average [Table 3 of Wilson (1969)] because they
give better fit to the theoretical curve (the experi-
mental~M/o' is too large when geometric averaged
values are used). Law and Williams (1972) have
also found arithmetic averaged values give good
agreement between theory and experiment for
hydrocarbon droplet combustion. The error bars
associated with the data in Figure 6 are the un-
certainties in least-square fitting the experimental
data in determining f3. Uncertainties in (pD) are
not indicated. Wilson (1969) estimated that they
can be as large as 75 per cent.
Figure 6 shows that the experimental data agree
well with predictions of Models A, C and D.
Values' for M F from Model B will lie within the
4.----,-----,,.----,-----,,.-----,,
I I J I I
METAL: AI
...._.... MODEL A possible the transition in behavior has not taken
Ta:i' 300 0 K
3f- ---- MODEL 8 -
-
---
MODEL
MODEL
° Data from Wilson
C
D I
----1
and Williams (1971) __ -
error bounds of the data only when generous
allowance for the uncertainties in (pD) is made.
Macek (1967) observed that under similar con-
ditions Al burns faster than Be by less than a
factor of two. By assuming the factor (pD) does
not vary much between mixtures of AI/AIO and
Be/BeO, the present study indicates that this
factor is between 1.5 and 2.
The insensitivity of the burning rates to variations
in ambient temperatures have not been tested due
to the lack of sufficient experimental data.
The ignition limit for AI (T", = 300 OK) ob-
served by Wilson and Williams (1971) are Yo", =
0.17 and 0.08 atp", = I atm and 5 atm respectively.
The extended flammability limit obtained from
Model C is at Yo", = 0.06, which does provide a
lower bound for the ignition limits since ignition
limits are expected to be higher than the extended
flammability limits.
The variation of if with Yo", has been docu-
mented by Wilson and Williams (1971) for AI. It
was found that if increases from about 3 at
Yo", c:::' 0.08 to 4 at Yo", c:::' 0.12 and remains
around that value as Yo", further increases. This
initial increase in if and its subsequent constant
behavior is in qualitative agreement with results
from Models A and D, but not with Model B.
The experimental values of if are higher than
predictions from all models. However, their
differences with Model B (if < 1.35 for Yo", > 0.3)
seem too great to be consequences from either
uncertainties in transport properties or other funda-
mental assumptions.
Macek (1967) did not observe the dilatation of the
flame as Yo", --->- 0 (when Too > T,). However,
since the ambient temperatures encountered in his
experiments are only slightly greater than T" it is
place. An ideal metal to study this flame dilatation
phenomenon (or the lack of it) is Mg, which has a
boiling point of only 1378 OK at J atm. A simple
burner can provide an ambient temperature
T", »T,. We mention in passing that complete

If-
. ....1./...-- solutions have also been obtained for Mg reacting
with 0.. The results were found to be qualitatively

.
.........~...........
----
--------------- similar with those of the AI-O. system.
From the above observations it can be said that
.·b _ - - -
0;'0'--1
I I I for Al burning in O./Ar atmospheres, Models A
O'-----'---.L-----'----'--_---L.I 1

and D, which take into account of surface con-

0.0 0,2 0.4 0.6 0.8 1.0 densation, seem to provide a closer description of
Yo CD the physical process than Model B, in which
FlO. 6. Comparison of theory and experiment on surface condensation is inhibited. There are,
M p • however, certain qualitative observations [e.g.
212
apparent absence of oxide accumulation on droplet
surface; presence of condensed oxides at the flame
at Yooo = I (but at low POl)] that do seem to be ex-
plicable best on the basis of Model B.
For AI burning in, say, N./O. atmosphere, as
well as for Be combustion, Models A and D
intrinsically provide a more complete description
since surface condensation is an experimental fact
in these cases.
CONCLUDING REMARKS
Models were developed to describe the vapor-phase
combustion of metal particles. It was shown that
the inclusion of surface condensation greatly in-
creases the mass burning rate and the flame stand-
off distance. Complete oxide vaporization at the
flame is also possible with surface condensation.
It was found that mass burning rates are in-
sensitive to variation in ambient temperatures.
The condensed oxides formed at the flame can be
effectively treated as gas-like in the formulation
without losing much accuracy in the eigenvalues
obtained.
It was shown that Be burns much slower than AI
in an O.flnert atmosphere. In addition, accumula-
tion of condensed oxides on the droplet surface
was also more substantial during Be combustion.
This is due to the large stoichiometric oxidizer to
fuel mass ratio v of the Be-a. system.
Fair agreement is obtained when results of the
models are compared with available experimental
observations.
This problem was suggested by my thesis adviser,
Professor F. A. Williams. Its completion would not
have been possible without his invaluable advice and
criticism.
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diffusion flame in the combustion of magnesium and
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ill Aeronautics and Astronautics: Heterogeneous Com-
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Inc., New York, Vol. IS, pp. 75-116.
C. K. LAW
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Revised manuscript received May 15, 1973