VOL. 5, NO. 6, NOV.-DEC. 1989 J.

PROPULSION 665

Aerothermochemical Analysis of Carbon-Carbon Nozzle

Regression in Solid-Propellant Rocket Motors
V. Borie,* J. Brulard,* and G. Lengellet
Office National d'Etudes et de Recherches Aerospatiales, Chatillon, France

An aerothermochemical analysis for the process of carbon-carbon composite material regression in large
advanced solid-propellant rocket motors has been conducted. The analytical approach is similar in spirit to the
approach of Klager, Keswani, and Kuo, with the main idea of the nozzle regression being due to the carbon
chemical attack by H2O. The different steps of the work have consisted of the development and applications of
several numerical codes substantiated by experimental results concerning the regression rate and the surface
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roughness of a carbon-carbon material. The calculated results show good agreement between measured data and
the predicted regression when a flow transition is assumed, in the model, between a laminar boundary layer
existing on the "smooth" virgin carbon-carbon material at the firing start and a turbulent boundary layer
existing on the very rough ablative carbon-carbon surface during stabilized motor operation.

Nomenclature e = edge of boundary layer

B = convective transfer parameter g =gas
E = activation energy / = species /
h — roughness height k = kinetic
K = constant / = liquid
k = kinetic energy of turbulence m = mass
Le = Lewis number s = surface or sand grain
M = Mach number or molecular weight T = transition
Pr = Prandtl number t = throat
p = pressure w = wall
q = heat flux density 0 = initial
R = radial distance 30 = 30% excess
Re = Reynolds number
r = regression Superscript
r' — regression rate * = reference
Sc = Schmidt number
St = Stanton number I. Introduction
T = temperature
Tu
U
- turbulence intensity ratio
= voltage
W ITH the development and use of high-energy, solid-pro-
pellant, and harder firing conditions in large advanced
solid rocket motors, carbon-carbon materials have found in-
u - gas velocity along nozzle surface creasing application as nozzle materials because of their high-
ur = friction velocity temperature, thermal and physical properties, and low densi-
v = gas velocity normal to nozzle surface ties.
X = mole fraction But in spite of the advantages of these composite materials,
Y =mass fraction because of the attack of carbon-carbon nozzle surface by the
z = axial distance products of the propellant combustion during motor opera-
e = dissipation rate of turbulence kinetic energy tion, the nozzle surface regresses by loss of material, and the
0 = momentum thickness nozzle throat area increases. Hence, the nominal performance
v = kinematic viscosity of the rocket motors decrease, and the resulting performance
p = density reduction must be evaluated to be taken into account by the
cb = mass production rate per unit surface designer of motors.
The classical way to measure performance reduction is to
Subscripts test full-scale motors, but this takes a long time and is very
expensive because tests must be repeated for every new motor.
c = convective
A complementary method is to establish regression models
ch = chamber
that can accurately predict the regression rates of nozzle
d = diffusion
throats, but these models require a fundamental knowledge of
the major mechanisms that drive the regression rate.
This paper describes an aerothermochemical analysis devel-
oped at ONERA over the past ten years that has led to build-
ing a comprehensive model of carbon-carbon regression of
Presented as Paper 88-3346 at the AIAA/ASME/SAE/ASEE 24th large advanced solid-rocket nozzle throats.
Joint Propulsion Conference, Boston, MA, July 11-13,1988; received
June 2, 1988; revision received Dec. 7, 1988. Copyright © 1988 by the II. Background
American Institute of Aeronautics and Astronautics, Inc. All rights
reserved. The identification and description of the major significant
* Scientist, Energetics Department. mechanisms happening in the nozzle regression constitute a
fSenior Scientist, Energetics Department. Member AIAA. relatively recent field of study in solid rocket technology. It
 666 BORIE, BRULARD, AND LENGELLE
has been the subject of many investigations,1"11 first, because
of the numerous parameters to take into account: chemical
propellant composition, chamber pressure, duration of firing,
type, geometric form and properties (density, thermal conduc-
tivity, chemical reactivity) of the nozzle material, among oth-
ers; and, second, because of the complexity of the description
of the driving phenomena, such as geometric and temperature
history of the nozzle, rates of diffusion of the species through
the boundary layer, and chemical kinetics of the surface reac-
tions.
The activities and the state of the art relevant to research in
this field have been well discussed in the thesis of Keswani,8
and it appears that several previous studies have shown the
influence of some of the important parameters, as well as
some of the major mechanisms.
Swope and Berard1 studied the effects of 15 aluminized
solid-propellant formulations on ZTA graphite erosion in a
subscale rocket motor. A direct correlation between the total
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concentration of the oxidizers capable of forming CO with the
insert material and the rate of graphite erosion was found;
water appeared to be the major contributor to graphite ero-
sion.
Delaney el al.2 developed a simple model for the erosion of
graphite throat nozzles in aluminized or nonaluminized pro-
pellant exhausts on the basis of a chemical mechanism, taking
into account the chemical composition of the exhaust stream,
the geometric and temperature history of the insert, the rates
of diffusion of the molecular species through the boundary
layer, and the chemical kinetics of the surface reactions. The
mass- and heat-transfer coefficients were based on fully devel-
oped pipe flow formulas. The results showed that ATI
graphite nozzle erosion was limited by both processes of diffu-
sion and chemical surface reactions (C-H2O, C-CO2, and C-
H2) and that pressure was an important parameter involved in
erosion.
McCuen et al.3 developed four computer programs for the
prediction of thermochemical erosion rates of charring and
noncharring materials exposed to high-temperature, chemi-
cally active gases, and they conducted an arc-plasma generator
rocket-simulation test program to study the effects of chemi-
cal and mechanical erosion of these materials. One of the
major results of the study was the demonstration of the impor-
tance of heterogeneous reaction kinetics, which were, when
available, seriously questionable when obtained in a static or
near-static gas environment or with diffusion not taken into
account as a rate-limiting condition.
McDonald and Hedman,4 on the basis of the results of an
analytical study and analysis of short-duration test data with
high-density bulk graphite nozzles and aluminized propel-
lants, found that the erosion of graphite is primarily the result
of a chemical surface reaction that is rate-controlled during
the transiently heated period, and diffusion-controlled when
surface temperature exceeds about 2000 K. They also found
that the erosion decreased with an increase in the aluminum
content in the propellants and that the hydrogen-carbon reac-
tion was not significant with the studied propellants.
Lewis et al.5 investigated the interactions of various carbons
(pyrolytic graphite, vitrous carbon, and an erosion-resistant
synthetic graphite) with CO2, H2O, and O2 in kinetically con-
trolled conditions with pressures of 1-3 atm and surface tem-
peratures of 1500-2000 K. The results showed that the effects
of the type of carbon and also the effects of the reactant gases
are less pronounced at high temperatures than at lower tem-
peratures and that, for high-temperature propellants, the con-
tributions due to their amount to the overall erosion rate are
H20>C02>02.
Tong et al.6 conducted a combined experimental (use of an
arc-plasma generator) and analytical (development of codes)
program to obtain required data and develop improved proce-
dures for predicting the ablation performance of different
graphitic materials (bulk and pyrolytic graphites and carbon-
carbon composites) in large advanced rocket nozzles. A signif-
J. PROPULSION
icant conclusion of this program was the critical importance of
appropriate estimations for the mass-transfer coefficients and
for the kinetic constants of surface reactions in the evaluation
of ablation. The reactions C-H2O and C-CO2 were found to
play a major role for surface temperature in the range
2200-3100 K, and the reaction C-H2 was found to play a
dominant role for surface temperatures above 3100 K.
Klager7 found, on the basis of data obtained by experimen-
tal firings on small aluminized solid rocket with AT J and ZTA
graphite nozzles and of thermodynamic analysis, that graphite
removal in solid rocket nozzles depended principally on pres-
sure and on chemical attack by H2O and CO2, which react
with the surface to give CO. The chamber flame temperature
was found not to affect the graphite removal directly, and the
recession rates were found, as in McDonald and Hedman,4 to
decrease when the aluminum content in the propellant in-
creases. A good correlation was observed between the reces-
sion rates and the mole fraction of H2O.
Keswani8 conducted theoretical studies to predict recession
of graphitic nozzles in different rocket motors (HIPPO,
Bates, MERM, ORE), with different nozzle geometries and
materials (carbon-carbon composites and bulk graphites), at
different operating pressures and temperatures, and in a wide
range of propellant formulations. Recession was found to be
strongly influenced by propellant composition, chamber pres-
sure, and motor geometry, and the analysis showed that reces-
sion is due primarily to the oxidation of carbon to carbon
monoxide by H2O and CO2. The analysis also showed that
the influence of chemical kinetics is predominant only when
the surface temperature is low and that the recession rate is
largely determined by the diffusion rate of oxidizing species
when the nozzle surface temperature has reached about 2500
K. The heterogeneous kinetic expressions with constant inhibi-
tion coefficients and kinetic constants with wide variation in
activation energy, pre-exponential factors, and inhibition fac-
tors from one carbon to another, given by Tong et al.,6 were
found to be inaccurate because of the wide range of tempera-
tures studied and the very small number of data points from
which the kinetic constants were determined. The disagree-
ment concerning the importance of the hydrogen reaction
obtained between Tong et al.6 and other investigators4'7 was
resolved by studying the thermodynamics and the chemical
kinetics of the C-H2 reaction; and, on the basis of kinetic data
of Chi and Landahl,12 it appears that ignorance of the C-H2
reaction as a significant contributor to the recession process is
justified. An accurate modeling of the mass- and heat-transfer
processes by the use of a k, e turbulence model in the descrip-
tion of the turbulent reacting boundary layer and a careful
evaluation of heterogeneous kinetic data (use of Libby and
Blake13 and Golovina14 data) were carried out to clarify view-
points expressed in the literature concerning the relative im-
portance of diffusion and of heterogeneous chemical kinetics.
The papers of Keswani and co-workers9'11 have recently
completed the thesis of Keswani.8 The other major conclu-
sions of these works were: the total recession increases as
material density decreases, as surface roughness increases, or
as carbon thermal conductivity decreases. By comparison be-
tween concentration profiles of H2O across the boundary layer
under frozen and equilibrium assumptions, it was also shown
that the graphite recession process is relatively independent of
gas phase reactions.
III. Summary of Method
The analytic approach is similar in spirit to that of Klager7
and Keswani and co-workers8'11 (when the ONERA work was
initiated 10 years ago, the results of these authors were not
known), with the guiding idea that the nozzle regression is
principally due to the chemical attack by gases such as H2O
(C-H2 reaction unimportant, mechanical erosion and carbon
sublimation, unsignificant under motor operating conditions).
The overall description for the regression phenomena is as
follows: as the propellant burns in the rocket chamber, the
 NOV.-DEC. 1989 AEROTHERMOCHEMICAL ANALYSIS OF CARBON-CARBON ROCKET MOTORS 667

INSULRTING MRTERIRL resulting hot combustion gases flow in the nozzle and form a
CHRMBER EQUILIBRIUM boundary layer (laminar or turbulent, depending on the condi-
CRLCULRTIONS tions) over the lower-temperature nozzle surface. The aggres-
sive chemical species, principally H2O, present in large quan-
CRLCULRTIONS tity in the core flow, diffuse across this boundary layer to the
nozzle surface, where heterogeneous reactions with carbon-
BOUNDRRY LRYER carbon material occur, inducing regression. At the beginning
CRLCULRTIONS of the motor operation, the surface temperature is low, the
surface reaction rates are lower compared to the aggressive
species diffusion rates across the boundary layer, and the
JC/C RTTRCK DESCRIPTION! (5 overall regression phenomenon is controlled by the kinetics of
T————————— heterogeneous surface reactions. When the motor progres-
REGRESSION RRTES sively reaches its equilibrium operating conditions, the surface
and SURFRCE ROUGHNESS temperature increases, the surface reaction rates become of
EXPERIMENTRL DETERMINRTIONS the same order as the diffusion rates, and the regression phe-
HERT TRRNSFER and
nomenon becomes controlled by both mechanisms, with a
REGRESSION CRLCULRTIONS major influence for the process that has the slower rate.
Figure 1 presents a summary of the different steps of the
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Fig. 1 Summary of carbon-carbon nozzle regression approach.
analysis, consisting of several calculations and a carbon-car-
bon attack description substantiated by experimental results
concerning the regression rate and the increase of transfer
coefficients due to the surface roughness for one carbon-car-
bon material.

40 r
IV. Chamber Equilibrium Calculations
Poh - 5 MPa
Because all previous studies have confirmed that propellant
I/WI NITHOUT composition greatly influences nozzle regression, it is vital to
identify the major products that constitute the propellant ex-
2 30 -
7 Y R12031 - 0.35 haust gases. Hence, the first calculations of the analysis have
1- been made to provide the characteristics of typical propellant
\ ] WITH RlzOag exhaust gases in the combustion chamber.
^ 7 Toh « 3387 K Figure 2 shows the theoretical gas composition, tempera-
d 20 - Y R12031 - 0.21 ture, and mass fraction of a typical aluminized propellant
under the assumption of equilibrium in the rocket chamber at
a chamber pressure of 5 MPa. As can be seen, two calculations
7-
have been made: a classical one without gaseous alumina and
10 -
a nonclassical one with gaseous alumina, by use of the data of
^ 1 I Stull.15 Taking into account gaseous alumina, as a species

Gl
'
/ n 3i
1 1 \A \ I7h c/n
existing in propellant exhaust gases, makes the chamber tem-
perature decrease by 198 K and the mass fraction of liquid
alumina decrease by 14%, but we see that the gas composition
H2 CO HC1 H20 N2 RlaOag H Cl CO 2
has no significant differences because, for about 90%, the
Fig. 2 Calculated propellant exhaust compositions in combustion major species are in both cases in decreasing order: H2, CO,
chamber. HC1, H2O, and N2.
The results without gaseous alumina have been confirmed
by several thermochemistry codes. In accounting for the un-
certainty of the existence and the contribution of gaseous
alumina, the following calculations have been made without
any gaseous alumina.
i V. Nozzle Inviscid Flow Calculations
a 1.0 The calculation for the hot combustion gas flow in the
nozzle is carried out through division of the flow into two
zones: the flow-wall interaction zone (boundary-layer flow),
en
n
where the viscous force action and the heat- and mass-transfer
p processes are concentrated, and the nonviscous zone (inviscid-
core flow).
The calculation of the nonviscous nozzle flow was carried
Q
(C
out in subsonic and transonic parts of the nozzle in two steps:
1) Calculation of the two-dimensional velocity field of the
0.5 flow by use of a pseudo-unsteady method of transonic poten-
tial flow developed at ONERA.16
2) Calculation of other thermodynamic flow properties
(pressure, temperature, density) at the outer edge of the
M - 0.6
boundary layer by use of a numerical procedure allowing for
equilibrium composition effects between motor chamber and
i-i geometric throat of the nozzle.
Q With the assumptions of one-phase equivalent flow and a
0 value of the specific heat ratio of 1.17, Fig. 3 shows a typical
-0.85 -0.50 0 0.35
Mach number distribution for studied nozzles in dimension-
DIMENSIONLESS RXIflL DISTRNCE, z/Rt less diagram R/Rt(z/Rt) where Rt represents the throat ra-
Fig. 3 Calculated iso-Mach contours of nonviscous nozzle flow. dius. At the geometric throat section (z = 0), we see a Mach
 668 BORIE, BRULARD, AND LENGELLE J. PROPULSION

(Teh - 3585 K, p o h - 5 MPa, Tw - 3080 K) 14

9 hs - e q u i v a l e n t sand g r a i n
* 5 12 roughness h e i g h t
8
i 10
8- 7
8
£ 6
6

i' 3
—«--*--*-
— ----
—— —— —
k,E METHOD, Tuo = 3*4
k,E METHOD, Tuo = 7%
k,E METHOD, Tuo - 9*
4

2
...r*. FULLY ROUGH
I —————— INTEGRRL METHOD
2 10 100 1000
Rehs ur hs/ •? u>
19
Fig. 6 Dirling correlation for compressible flow
-1.2 -1.0 -0.5 0 0.3
DIMENSIONLESS RXIRL DISTRNCE, z/Rt the temperature, and the turbulent Prandtl number was 0.9
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Fig. 4 Calculated heat flux density on smooth nozzle wall. classically.

1000
h30 - c h a r a c t e r i s t i c (30*< exceedance)
roughness h e i g h t
CD
& sity (Tu0 = 3%), the boundary layer does not transition and
100
(Rn = body curvature radius)
40
0. 1 1.0 10
X = h30/9 Te/Tu 1/C1 + h30/Rn)
Fig. 5 Batt and Legner correlation for transition.18
number of 1.15 at the wall and, therefore, an increase in
velocity of about 15% over one-dimensional flow, resulting
from the two-dimensional flow effects.
The calculation of other thermodynamic flow properties at
the outer edge of the boundary layer gives, for a chamber
pressure of 5 MPa, a throat pressure of 2.5 MPa and a throat
temperature of 3400 K. For these conditions, it is verified that
the freestream species concentrations are little affected by the
pressure and Mach number changes between chamber and
nozzle and that the major species are always in the order: H2,
CO, HC1, H2O, N2.
The corresponding transport properties calculated for the
mixture give, for the laminar Prandtl number, the value 0.4 at
the chamber or at the throat.
Figure 4 shows calculated typical heat flux densities on a
nozzle smooth wall obtained by the (k,e) method for the
conditions indicated: chamber temperature = 3585 K, cham-
ber pressure = 5 MPa, wall temperature = 3000 K and, for
several initial turbulence intensity ratios in the nonviscous core
flow, Tu0 = 9, 7, 3%. We see that, for small turbulence inten-
remains laminar at the nozzle throat but, for larger turbulence
intensity (7w 0 = 7, 9%), the boundary layer is turbulent at the
nozzle throat, with turbulent convective heat flux density
about four times the corresponding laminar heat flux density
value. We also see, on Fig. 4, the small differences between
turbulent results (TuQ = 9 or 1%) at the nozzle throat. These
small differences are also verified for other conditions (differ-
ent boundary-layer initial thickness or macroscale of turbu-
lence).
From the results of (k,e) calculations for several wall tem-
peratures, correlations were obtained for, first, friction coeffi-
cient as a function of Reynolds number based on integral
momentum thickness and, second, Reynolds analogy coeffi-
cient. These correlations were used in an integral boundary-
layer solution based on the resolution of the momentum inte-
gral equation by a classical fourth-order Runge-Kutta method
where the shape parameter was calculated by assuming power
laws for velocity and total enthalpy.
In this integral boundary-layer solution, a segregation effect
of the liquid alumina particles (AL2O3/ = 0) was assumed, and
there was a possibility of transition between assumed initial
laminar flow at the stagnation point of the profile and turbu-
lent flow in the rough nozzle. The beginning of the flow tran-
sition due to the roughness was detected by use of the Batt and
Legner correlation18 summarized in Fig. 5:

where Re6T represents the transition Reynolds number based

VI. Boundary-Layer Calculations
Because of the complexity of the problems, the boundary-
layer calculations giving the heat and mass convective flux at
the wall have been made by a two-step process:
1) Reference (k,e) boundary-layer calculations on a smooth
wall.
2) Practical integral boundary-layer calculations with coef-
ficents adjusted on the results of the (&,e) reference solutions.
The (£,e) reference method used the classical numerical
algorithm17 of London Imperial College. The flow was as-
sumed frozen, that is, without chemical reactions between
combustion products. The boundary conditions were given, at
the outer interface, by the results of the nonviscous flow
calculations and, at the wall, by the no-slip condition for the
velocity, frozen total enthalpy, and zero transport for k and e.
The initial conditions were laminar at the stagnation point of
the nozzle profile, the viscosity law was to the power of 0.7 of
on integral momentum thickness 6 and /*30 the characteristic
(30% excess) roughness height defined by Batt and Legner.18
The calculation of the transfer coefficients on rough walls was
made by the Dirling method19 using the compressible rough-
ness correlation:
ue/UT=f(Rehs)
shown on Fig. 6. The transition description was made by use
of a global intermittency factor, which was assumed to be
accelerated by the appearance of the roughness height. The
value of the roughness height /*3018 at the end of the firing was
obtained by a statistical treatment of several afterburning
nozzle throat fragments of interest, and the value of the equiv-
alent sand-grain roughness hs19 during stabilized motor opera-
tion was chosen to agree with the experimental results ob-
tained in the next section.
 NOV.-DEC. 1989 AEROTHERMOCHEMICAL ANALYSIS OF CARBON-CARBON ROCKET MOTORS
VII. Experimental Work
The first objective of the experimental work was to obtain
the characteristics of the kinetics of the attack of carbon-car-
bon material under experimental conditions existing at nozzle
throats of advanced rocket motors to permit the regression
calculations in the final step of the analysis. In the course of
the analysis, this first objective has been completed because of
the need to obtain experimental data concerning the increases
of transfers due to the material surface roughness.
The experimental setup used to obtain experimental carbon-
carbon rates and surface roughness coefficients is schemati-
cally represented in Fig. 7. This setup consists of cylindrical
(12-mm-diam) carbon-carbon test specimens exposed to the
hot product stream produced by a combustion chamber. Feed
gases were essentially O2 and H2 to form H2O, but it was
possible^ to form CO2 and HC1 by using CO and C12. In the
water test series, the-fefed rates were chosen to provide maxi-
mum H2O (with small amounts of OH necessarily resulting
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from dissociation at high temperatures), except for several
tests in which the composition was adjusted to provide a large
excess of H2. The maximum heat flux density on the carbon-
carbon surface specimens was achieved when the samples were
placed typically at 42 mm of the throat of the combustion
chamber.
The carbon-carbon regression was detected by a laser opti-
cal system (or camera); the other principal measurements to
,CRMERR
|WRTER COOLEDI
I^CRLORIMETER^J
PHOTO-ELECTRIC
DETECTOR
Fig. 7 Experimental setup for carbon-carbon rates and surface
roughness (schematic diagram).
EXPRNSION and HOMOGENEIZRTION
He/Ne LRSER OPTICRL UNIT
RECTRNGULRR / j\
NINDOW
PHOTO-ELECTRIC DETECTOR
Fig. 8 Carbon-carbon regression measurement by laser beam.
669
characterize the material response were
1) Carbon-carbon surface temperature and emissivity histo-
ries measured with a two-wavelength optical pyrometer.
2) Total pressure recorded by a piezoelectric pressure trans-
ducer.
3) Heat flux density measured at the end of tests by a
water-cooled calorimeter.
The carbon-carbon regression measurement details are
given in Fig. 8, where the boxed drawing indicates the surface
structure of the sample during the regression. After expansion
and homogenization in an optical unit, a He/Ne laser beam
was diaphragmed by a rectangular window of known area,
and the resulting rectangular laser beam was directed perpen-
dicularly to the carbon-carbon sample. A part of the light
energy was intercepted by the sample, and the other part of the
light energy was received, via an optical filter and an integra-
tion sphere, by a photoelectric detector. The sample mean
regression r was thus proportional to the measured voltage,
and the regression rate r' was given by the derivative of the
voltage evolution. In order to insure good measurements, it
was verified that the sample spectra had not interfered with
the receptor sensibility.
Figure 9 shows the surface temperature and regression rate-
time traces obtained in a typical carbon-carbon regression
experiment. This experiment was conducted with a four-direc-
tional carbon-carbon sample and lasted about 6 s, with a
chamber pressure of 1.54 MPa and a chamber temperature of
3457 K. We see that both traces are continuous curves, from
which it has been possible to obtain the kinetic correlation law
used in the last step of the analysis.
The form of the regressed kinetic correlation law used in the
analysis has been selected to be
r' =K exp (-E/R°TS)pH2Os
where K and E represent, respectively, the pre-exponential
factor and the activation energy of the heterogeneous kinetic
reaction between water vapor and carbon material and/?H2O5
the partial pressure of water vapor at the surface. The choice
of this form, valid at low pressure when regression is limited
by the number of collisions between water vapor gas and
surface carbon and by the level of available energy to form
adsorbed water and to create the reaction between the ad-
sorbed water nd the carbon surface, is justified by the descrip-
tion8'20 of the attack mechanism involving the elementary steps
of diffusion of water vapor in the boundary layer, adsorption
on an active site, reaction between adsorbed water and carbon
(pch - 1.54 MPa, Teh - 3457 K, GRMMRch - 1.2,
qc - 4 3 . 4 MW/m2, ps - 0.35 MPa)
r - 1-2
.3000 0.9
u
QL
(E
U2000 h * 0.6
U o
M
in
y 1000 in
h|0.3
U
o:
0)
0 0 1 2 3 4 5 6
TIME, t (s)
Fig. 9 Carbon-carbon surface temperature and regression rate-time
traces (experiment 344).
 670 BORIE, BRULARD, AND LENGELLE J. PROPULSION

(YH20ch - 0.767, YH2ch - 0.021, YOach - 0.072, 1.0

LIBBY-BLflKE KINETICS <C PflRTICLES)
kr - 3, EQUILIBRIUM RNRLYSIS)

~ 4

O.
a 3
O
\ 0.1

u
a
GEISLER
ooo (B.G.) TONG ET
(PYROCRRB
a: +++ H2
a.
xxx CO

0.01
3E-4 4E-4 5E-4
5
en *** • 1 / Ts (K-l)
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Fig. 12 High-temperature kinetics of water-carbon reaction.

0 1 2 3 4 5 6
TIME, t (s)

Fig. 10 Calculated surface pressure evolutions on carbon-carbon (STRGNRTION POINT SURFRCE EXPERIMENTS)
sample (experiment 344).
100 - t 2000 -

~ 1.0
£ 80 r- ,:1600
REGRESSED DRTR
r'/pHaOs - 4.07 exp(-9200/Ts)
E 60 - a 1200

40 800 -
I
0. 8
0.1
£ 20 400
x
— SMOOTH REFERENCE SURFflCE

ooo EXPERIMENT 346 (H 2 EXCESS)

xxx EXPERIMENT 344
+++ EXPERIMENT 323 Fig. 13 Heat flux density and surface temperature time traces for
0.01 roughness coefficient evaluation.
3E-4 4E-4 5E-4
1 / Ts (K-l)

Fig. 11 Carbon-carbon regression rate kinetic evaluation in

(equilibrium analysis).
surface, desorption of the surface, and diffusion of the pro-
duced species.
The partial pressure of water vapor at the surface has been
calculated from the measured total pressure and from the
calculated mass fraction of water vapor at the surface. This
latter quantity has been obtained from the mass fraction of
water vapor in the hot stream by utilization of the same
reduction process as the one explained in Sec. VIII by using
calculations of the heat- and mass-transfer coefficients on the
heated rough ablative sample wall. In this process, the evalua-
tion of the species laminar Lewis number at a reference tem-
perature has been carried out using an exact model of species
diffusion in the sample boundary layer (Stefan-Maxwell equa-
tions).
With the assumption of an equilibrium boundary layer on
the sample, Fig. 10 gives the calculated surface pressure evolu-
tions for H2O, H2, and CO species in experiment 344, for
which the mass fractions of H2O, H2, and O2 in the combus-
tion chamber were, respectively, 0.767, 0.021, and 0.072 and
the measured roughness coefficient was 3. We see an evolution
of the water vapor surface pressure, which indicates the transi-
tion from a completely kinetic controlled regime at the begin-
ning of the experiment to a mixed kinetic/diffusive controlled
regime at the end of the firing.
For three tests obtained with the four-directional carbon-
carbon material, the evolutions of the ratio r'//?H2O5, from
which were deduced the final regressed kinetic correlation law,
are presented in Fig. 11. We see that the results for the H2
excess experiment are close to the other results and, thus,
confirm the assertion of most authors that H2 is not a signifi-
cant contributor to the recession process.
In Fig. 12, the available data obtained for the carbon-steam
reaction at high temperatures (above 2000 K) are regrouped in
the diagram r '/pH2O5 (l/Ts). The Libby and Blake data13 are
those given by Keswani and co-workers,8'10 the King data21 are
those given for PO3 and CFZ bulk graphites (E.G.), the Lewis
et al. data5 are those obtained for b5890 bulk graphite, the
Tong et al. data6 are those given for carbon-carbon pyrocarb
901 in pure H2O, the Golovina data14 are those given for low
pressure, and the Geisler result is given by Jones et al.22 for
bulk graphite and corrected by taking into account the esti-
mated difference between partial pressures in the stream and
at the surface. As can be seen, there is a rather wide scatter in
the data due, in part, to the different carbon materials used
(bulk graphites and carbon-carbon materials) and, in part, to
the difficulty of obtaining good measurements at high temper-
atures. We see that the results for the four-directional carbon-
carbon are in good agreement, within this scatter, with the
other available data.
 NOV.-DEC. 1989 AEROTHERMOCHEMICAL ANALYSIS OF CARBON-CARBON ROCKET MOTORS
Because of the very rough ablative carbon-carbon surfaces
obtained during the regression-rate measurements, a second
objective of the experimental work has appeared in the course
of analysis: the determination of empirical multiplying rough-
ness coefficients that are representative of increases in trans-
fers resulting from the material surface roughness. These em-
pirical multiplying roughness coefficients, measuring the
increase of transfer coefficients for both stagnation-point and
nozzle experiments, have been obtained by comparison be-
tween heat flux densities measured, first, on an ablated cold
carbon-carbon surface and, second, on a "smooth" surface of
the same material in the same conditions, that is, at the same
surface temperature.
For stagnation-point surface experiments, Fig. 13 shows,
in discontinuous lines, the evolutions of the heat flux density
and the surface temperature measured on a "smooth" refer-
ence surface and, in continuous lines, the corresponding
evolutions measured on the ablated surface (high rate
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of regression). From these results, it is possible to obtain,
at the same surface temperature, the values of empirical
roughness coefficients of interest. For example, in Fig. 13, at
a surface temperature equal to 1200 K, the heat flux density on
the smooth reference surface is about 35 MW/m2 and the
corresponding heat flux density on the ablated surface is about
90 MW/m2: the multiplying roughness coefficient is, at this
temperature, 90/35 = 2.6. On the average, for the experiments
with a sample ablated in the stagnation point, a value of about
3 has been found and, for a sample ablated in the nozzle, a
value of about 1.7. These results have been obtained whatever
the rate of ablation (rf — 0.18-0.46 mm/s), whatever the at-
tack angle of aggressive flow on the sample (incidence angle of
10-90 deg) and whatever the orientation angle of the sample in
the flow (angle of 0-270 deg). All in all, the values of empirical
coefficients have been found to depend only on the way the
surface has been ablated.
VIII. Carbon-Carbon Attack Description
The fifth step of the analysis is a description of the carbon-
carbon wall nozzle attack by water vapor, which 23
has been
established by utilizing the early works of Lees and Dor-
ranee.24
In the adopted description, the general conservation equa-
tions of a flowing system written with the frozen boundary-
layer approximations are resolved with the following
boundary conditions: at the edge of the boundary layer (e),
velocity, total frozen enthalpy, and mass fraction of species
are given by corresponding values calculated in the external
flow and at the wall (w), velocity and total frozen enthalpy are
given by the no-slip condition, and the mass fraction of the
species is unknown.
In the classical assumption: Pr = Lei = Sc{ = 1, by taking
account of conservation of species at the surface and by use of
the convective heat-transfer parameter
B = (pV)w/(peUeSt)
the expression for the surface mass fraction of species / is
given by
v. — Yie
•*• iw —
\+B
where Yie represents the external mass fraction of species i and
uiw the mass production rate of species i at the wall. In this
expression, if we take into account that the production rate of
species / at the surface is a function of pressure, surface
temperature, and surface mass fraction of species /, we obtain
a second-degree linear equation system for the injection mass
flow rate (pv)w and the mass fraction of species / at the surface
Yiw. It is then possible to obtain limiting cases of practical
interest: carbon attack controlled by heterogeneous kinetic
reaction, carbon attack controlled by species diffusion across
671
the boundary layer and, finally, the mixed mode with small
mass injection in the boundary layer for which we find that the
injection mass flow rate is given by8"10
1 1 1
(pv)wk
where (pv)wlc and (pv)wd represent, respectively, kinetic-limited
injection mass flow rate and diffusion-limited injection mass
flow rate.
In the more general assumption Pr j* Let ^ Sci9 by uncou-
pling the enthalpy and momentum conservation equations
with respect to species continuity equation, a similar expres-
sion is obtained for species / mass fraction at the wall where B
is replaced by the convective mass-transfer coefficients
where Le* is the species / reference laminar Lewis number
calculated by an exact model of diffusion (Stefan-Maxwell
equations).
The net heat flux entering in the surface is calculated by the
sum of the convective flux, the ablation flux given for the
reaction water vapor-carbon, and the radiative flux exchange
represented by a parallel plate model.
In the parallel plate model, the effective emissivity is given
as a function of the gas surface and of the surface emissivity.
The surface emissivity has been obtained from the experimen-
tal results at about 0.9, and the gas emissivity has been evalu-
ated from the gas radiative properties at the nozzle throat
given by Pearce.25
IX. Heat-Transfer and Regression Calculations
The final step in the analysis of carbon-carbon regression
has been the calculation of the thermal response and the
regression of the nozzle throat material.
This step has been carried out using a monodimensional
heat-transfer model in the material in the radial direction, with
integration of the unstationary heat-transfer equation between
moving ablating surface material and insulating material with
material thermophysical properties (heat capacity and heat
conductivity) variable with respect to temperature.
The initial condition was constant ambient temperature,
and the boundary conditions were heat flux density calculated
after the preceding description at the surface and heat flux
density at the interface to the insulating material as a function
of the interface temperature.
The numerical resolution of the heat-transfer equation has
been made using a variable transformation, to avoid oscilla-
tions at the surface, and an explicit finite-difference method
with respect to time and direct approximation of conservation
law in the nodes. The time step has been calculated using the
classical Courant-Friedrichs-Levy stability criterion, and the
rate of regression has been calculated at every time step by an
iteration process because of its dependence on the water vapor
pressure at the surface, which is itself a function of the regres-
sion rate.
According to two-phase nozzle flow calculations,26 alumina
does not penetrate the boundary layer. This assumption of
alumina particle segregation in the boundary layer has been
made in the calculation.
The further assumption of a flow transition between a lam-
inar boundary layer existing on the "smooth" virgin carbon-
carbon material at the firing start and a turbulent boundary
layer existing on the very rough ablative carbon-carbon sur-
face during stabilized motor operation has been made. This is
because an important delay has been observed on the start of
the regression, not explainable by several other assumptions:
thermal dilatation of the nozzle throat, giving only a few
tenths of a millimeter, two-dimensional heat transfer, giving
only a few degrees of difference at the nozzle throat, and the
 672 BORIE, BRULARD, AND LENGELLE J. PROPULSION

(pch =4.9 MPa, EQUILIBRIUM KINETIC DRTfl,
MERSURED ROUGHNESS COEFFICIENT » 1.7 ,
RLUMINR SEGREGRTION, ROUGHNESS TRRNSITION)
~ 7
EXPERIMENTS DRTR (SEP):
• POST-FIRING MERSURED DRTR
M3
I RVERRGED POST-FIRING DRTR
TJUL MERSURED EVOLUTIONS
DURING FIRINGS
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presence of a protective alumina coating, not seen in large-
scale nozzle tests, interrupted at about 13 s.
Figure 14 shows the experimental regression data obtained
by SEP under DEN contracts and the corresponding predicted
regression as a function of time for a carbon-carbon nozzle
throat of interest and for the indicated conditions (A* = 4.9
MPa, use of carbon-carbon regression rate kinetics given in
Fig. 11, alumina segregation, and roughness transition as-
sumptions). We can observe the large delay at the beginning of
the recession and the agreement between measured and pre-
dicted recession at all times.
Figure 15 shows the corresponding calculated heat flux den-
sity evolutions at the nozzle throat. The convective nozzle heat
flux density decreases in the initial phase of the motor firing,
then increases rapidly in response to the roughness transition,
and then decreases again as a result of the increase in the
surface temperature, and the sum of convective and radiative
nozzle heat fluxes is quite similar to that of the convective heat

flux evolution. At the start of firing, the ablative nozzle heat

flux is zero, and its absolute value increases during the firing
Fig. 14 Carbon-carbon regression evolutions at the nozzle throat. in response to the increase in the rate of regression. The result
is that the total calculated nozzle heat flux has a decreasing
general behavior, except during roughness transition.
Finally, Fig. 16 shows the corresponding calculated major
mechanism percentage of regression as a function of time. The
chemical percentage, defined as proportional to the ratio be-
(pch - 4.9 MPa, EQUILIBRIUM KINETIC DRTR, tween the water vapor mass fraction at the wall and the
MERSURED ROUGHNESS COEFFICIENT - 1.7 , corresponding value at the external edge of the boundary
RLUMINR SEGREGRTION, ROUGHNESS TRRNSITION) layer, is 100% at the start of firing because there is a zero rate
~ 14 of regression, decreases rapidly during the initial phase of the
— — CONVECTION motor firing, and stabilizes at about 30% during the rest of the
12 ——— CONVECTION + RRDIRTION motor operation. The physical percentage, defined as indi-
cated and representative of the H2O diffusion process in the
cr 10 boundary layer, has an opposite evolution to that of the
chemical percentage.
I- o
1-1 »
O)
X. Conclusions
I.
X
According to this analysis, carried out over the past ten
3 4
years, the following major conclusions can be made:
1) A comprehensive model of carbon-carbon regression of
—— TOTRL
large advanced solid rocket nozzle throats, which turned out
(CONVECTION + RRDIRTION + RBLRTION)
to be similar in spirit to the approach of Keswani and co-work-
———I_______I_______I_______I______ ers,8"10 has been developed.
10 20 30 40 50 2) An improved new technique using an expanded laser
TIME, t (s) beam for measuring instantaneous averaged carbon-carbon
regression has been put in place and used.
Fig. 15 Calculated heat flux density evolutions at the nozzle throat. 3) The assertion of Keswani and others that H2 is not a
significant contributor to the regression process is confirmed
by the obtained experimental results.
4) The experimental kinetic correlation for the four-direc-
tional carbon-carbon material of interest is found to be in
(pch - 4.9 MPa, EQUILIBRIUM KINETIC DRTR,
good agreement with the other available high-temperature
MERSURED ROUGHNESS COEFFICIENT - 1.7 , data for carbon materials.
RLUMINfl SEGREGRTION, ROUGHNESS TRRNSITION) 5) The predicted regression, using the assumptions of alu-
* 100 mina particle segregation in the boundary layer and flow
transition between a laminar boundary layer existing on the
8 PHYSICRL
"smooth" virgin material at the firing start and a turbulent
JE 80 boundary layer on the very rough ablative surface during
YH20u> + MH20 / MC stabilized motor operation, compared well with experimental
I 100 BmHaO data for the nozzle of interest.
u 60 YH20e
6) The increase in convective heat-transfer flux by a factor
of 1.7 resulting from the large surface roughness of the abla-
40 tive carbon-carbon material plays a significant part in the flux
received by the material.
7) The calculated results show that, at the end of the firing,
20
CHEMICRL 100 YH20u» / YH20e the controlling phenomenon is intermediate: 30% chemical
and 70% physical.
10 20 30 40 50 Acknowledgments
TIME, t (s)
This work was carried out under contract from the Direc-
Fig. 16 Calculated major mechanism percentage evolutions of re- tion des Engins (DEN) and in relation with the Societe Euro-
gression at nozzle throat. peene de Propulsion (SEP). The authors wish to thank D.
 NOV.-DEC. 1989 AEROTHERMOCHEMICAL ANALYSIS OF CARBON-CARBON ROCKET MOTORS
Lambert and Y. Maisonneuve for experimental work during
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the analysis.
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