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UNCLASSIFIED AD740720

Ablation

ADVISORY GROUP FOR AEROSPACE RESEARCH AND DEVELOPMENT

MAR 1972

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UNCLASSIFIED
AGARD-AG-161

NORTH ATLANTIC TREATY ORGANIZATION

ADVISORY GROUP FOR AEROSPACE RESEARCH AND DEVELOPMENT

(ORGANISATION DU TRAITE DE L'ATLANTIQUE M0«D)

AGARDograph 161

ABLATION
VETD C
by
V* MAY 2 W
lliiaibu u £
H.Hurwicz, K.M.Kratsch and J.E.Rogan Q_*~-~
-
Edited by

R.E.Wilson

Naval Ordnance Laboratory


White Oak, Silver Spring. Maryland, USA.

This document was prepared at the request of the Fluid Dynamic. Panel of AGARD
THE MISSION OF ACARD

The mission of AGARD is Jo bring together the leading personalities of the NATO nations in the fields of
science and technology relating to aerospace for the following purposes:

- Exchanging of scientific and technical information;

- Continuously stimulating advances in the aerospace sciences relevant to strengthening the common defence
posture;

- Improving the co-operation among member nations in aerospace research and development;

- Providing scientific and technical advice and assistance to the North Atlantic Military Committee in the
field of aerospace research and development;

- Rendering scientific and technical assistance, as requested, to other NATO bodies and to member nations
in connection with research and development problems in the aerospace field.

- Providing assistance to member nations for the purpose of increasing their scientific and technical potential;

- Recommending effective ways for the member nations to use their research and development capabilities
for the common benefit of the NATO community.

The highest authority within AGARD is the National Delegates Board consisting of officially appointed senior
representatives from each Member Nation. The mission of AGARD is carried out through the Panels which are
composed for experts appointed by the National Delegates, the Consultant and Exchange Program and the Aerospace
Applications Studies Program. The results of AG/ RD work ?<-e reported to the Member Nations and the NATO
Authorities through the AGARD series of publications of which this is one.

Participation in AGARD activities is by invitation only and is normally limited to citizens of the NATO nations.

The material in this publication has been reproduced


directly from copy supplied by AGARD or the author

Published March 1972

629.7.023.225

i i
\ \
*
Printed bv Technical Editing and Reproduction Ltd
T-r

PREFACE

Ablating heat shields have successfully protected many hypersoruc vehicles during
atmospheric re-entry. Detailed knowledge of the characteristics of many materials and of
the interaction mechanisms between materials and high-temperature environments exists.
Using this information, very reliable passive heat shields can be designed.

There is an extensive literature containing the results of both analytical and experi-
mental investigations of ablation. Although the technology has reached a mature status,
new materials arc continually being developed and passive ablating systems are of great
interest to heat-shield designers. The well-developed literature and ccntinuing interest
in ablation technology make this a particularly suitable subject for an AGARDograph. The
intimate coupling between the fluid mechanics of high-temperature boundary layers and
ablating materials makes sponsorship by the Fluid Dynamics Panel very appropriate.

This AGARDograph review the advances in ablation technology, the present status,
and indicates possible future directions. Ablation analyses are discussed starting with the
original simple model in which the amount of material removed is computed from the heat
transfer to a non-ablating body and the effective heat of abiation. Analytical methods are
carried through the development of the most sophisticated approach which considers the
coupling between the boundary layer, the ablating materials, and includes complets non-
equilibrium chemistry. The behavior of various materials is compared. The status of today's
experimental facilities used to determine ablation behavior is reviewed, inctuding test tech-
niques and instrumentation. Finally, the shape changes and changes in surface roughness
which result from ablation are discussed. These changes obviously interact with vehicle
performance, flow fields, and aerodynamic characteristics.

The authors have covered, with remarkable completeness, atargecomplex subject. The
bibliography, as well as the material covered here, should be of considerable use to those
interested in ablation technology and the design of ablating heat shields.

Dr.REWILSON
Fluid Dynamics Panel Member

'

The AGARD Fluid Dynamics Panel wishes to thank Dr. Wilson for his contribution in under-
taking the renew and editing of this AGARDograph.
•TT"~''' ip—'in ».—.-^

ABLATIO*

Henry* Rurvlci
Chief Advance Technology Engineer

Kenneth H. Kratsch
Advanced Themal Protection Syatema

Jaaes E. Rogao
Branch Chief
Heat and Mass Transfer

Aero/Thermodynamics _ad N u c l e a r E f f e c t s Department J


P e a e a r c h and Development J
Advance Systems end Technology
McDonnell Douglas Aatraaautlca Company i
5301 Boll* Avenue .
Huntington Beech, California 92617 ?
1
J
BUMMAFTt

Tvo decades of advances in ablation technology are revieved vith particular enphasle on
developMntt of the laat eight yeara. Leveling off of research a c t i v i t i e s ie noted reflecting both the
apace eysterna r*quire_ents end acceptance of ablation aa an estebliehed near.a of the>_»l protection.

Phyalco-_athe_eticel approaches to analysis of ablation processes ere brought out ranging


fron simplistic heat of ablation concept to the sophisticated analysis of laminar end turbulent flov, non-
equilibrium ablation ie chemically reacting flov fields including surface reactions and radiative heat
transfer. Particular emphasis i s given to the synergistic aechenlama occurring during the ablation j
process. £xe_plee of noaetip interaction vith aero/thcrmodynaaic environment at the aurface and In depth
pheuomena i s given, ea v e i l aa etriatioii phenomena on the afterbody are discuseed. ,

Graphite i s used aa an example of aynerglstic ablation phenomena and effects because of the
interest noted in the literature and because o'.ner materials may be treated in a similar fashion. '
Graphite erosion mechanises ej.d i t i mlcroetructur* eh«rmCteritati*>n are reviev»d. The »ffe»*f of f i l l e r s , J
binders, porosity, and other parametere are diacuaeed a» v e i l aa the synergistic effecte of the above
parameters are also approached in e novel reahion.

Material property and environmental effacta on material performance are also revieved aa veil
aa the teet simulation requirements. Requirements for further etudiee of mechanical erosion, other
synergistic affects, and extension of f a c i l i t i e s range of performance are also noted.

LIST OF 8YMB0_3

C^ Local (dlmeealonless) pure convectlve beat transfer coefficient or


Stanton numbers including dissociation. Miss injection and surface
reectloni

C LceaX (dlmenelonlees) diffusion (mass transfer) Stanton number


M
d

C Local (dimeneionlees) cold vail heat transfer coefficient or Stanton


o number uncoupled from species solution

j C. Specie maaa fraction or concentration of ith specie, p.lo


, I
i C Specific heat for comprslte mixture of boundary l*yer apecles at
p
f constant pressure
i
C Specific heat for ith epeciea at constant pressure
P
• i
I
C Specific heat of condtmeed phase in the decomposing ablator
p
s
C* Specific heat of mixture of bourdary layer epeciee, C
p p
} atmos f
\ c" Specific heat for eompo-lte mixture of gaseous products of
p
I * depolymeritation at constant pressure

f
I
r '1
Activation energy used in Arrhenlu,' rate expression for ths
representative solid phase resin component o

*12 Activation energy used in Arrheniu8• rate expre.eion for the


repre.entatlve completely volatile re.ln corponant o

Activation energy used in Arrheniua' rate expression for the


representative completely v o l a t i l e nylon reinforcementJ

*C, ^ _ J » * i i 0 n ! D e r g y f ° r A r r n M l « ' rate expression describing rete


limited aurfaee ero.ion or removal by oxidation of graphite C

r o r ^ r ^ ! _ ? I F T d l 0 A r r h t n l u « ' « * • «pre««ion describing a


fern of depoeltion interaction or coking for the ablation model

Ratio of char denaity to virgin plastic density of model ablator

number fraction of particles eroded

Mass fraction of particles

Solid fraction mechanically eroded

Melt or evaporation fraction, y . ^ , - l v l 0 f the n t i o of tne m . of

evaporation to the total ablation rate in the liquid layer equation

External radiation potential from gloving" internal ablation


reactiona as a result of char tranaparency

g(n>
Reduced (dimension-..,) total enthalpy function, refers »o I/I
in the laminar boundary layer solutions «
g f (n) Reduced (dlmenaionl.s.) total "sensible" enthalpy ^ i ,
c t c n
t n e lM| D
f fe l «J" boundary layer solutions

Enthalpy function defined aa \ c (I c dt • h°;


i 'o i l

Sensible enthalpy function defined ae J C | C At


o *i
Specie enthalpy function, [ c At • h°
Jo p i »

Chemical enthalpy of formation of the 1th apecles

niiTi^r ista*-**if not o t h —"«~—« *» -


Combined heat of melting end vaporisation (alao lncludea combu.tlon

Wall anthalpy (at ablator-boundary layer Interface)

Lumped enthalpy of me., transfer and vaporisation or sublimation


verm

Total enthalpy at boundary layer edge, aaae as 1


e
Total enthalpy function defined as [ Cj (f C dt • h°)* u 2 /?

-otal "sensible" enthalpy function derlned ai j C f C 2


1 » J 0 Pt dt • uV2

ss riS-_.ii
r
J Variable la the "glowing" expression

k Frequency factor used in Arrhenlus' rate expression


Also exponent of Y^ to signify tvo dimensional ( K T ) or a_l-
symmetrlcsl (kel)
I Also volume ftactioo
I
r *11 frequency coefficient uivd In Arrhenlus' rate expreealon for the
representative solid phase resin component o
i;
J *12 Frequency coefficient used in Airhenics" rate expression for the
representative complelely v o l a t i l e reein component o . j i

k
i 2 frequency coefficient used in Arrhenlus' rate expression ror the
representative completely v o l a t i l e nylon reinforcement p.
<
I *c Frequency coefficient uaed in Arrheniue* rate expression describing ]
a form of depoaltlon interaction or coking for the ablation model

Mans fraction of oxygen at the outer edge of the boundsj-y layer


«
& Binder mass fraction

» Geometric mean mass flux


E Mass flux
r due to surface erosion or removal by oxidation of graphic
1 C vfctn ir the rate limited temperature regime

c • \g Mass flux due to aollJ surface eroalon


.
m , ffl
& g Coapo.lte aase flux of gasecue products of decomposition

flu
f \ **•• * of ablation gas products, includee both sV , and _ . ,

\ **• Mass flux of solid specie, of surface material


I

} •_" M-1" flux of lndepth pyrolysis gas apeclea j

-v Total ipjected pass flux fr^a, the ablating eurface

*r **>• flux due to mechanical erosion (liquid or solid)

M
\ l e»r; molecular veight of boundary lays- species

M M
jnj «»r. nole<.«_,_r .eight of Injected species

"c Molecular veight of atomic oxygen

M
0 Molecular veieht of molecular o>/gen
2

n
l l rressure exponent appearing in rate lav expression

n
ll Reaction order exponent used In rate lav expres.ion for the
representative .olid phaae ream component o

n
I j l2 Reaction orJer exponent uaed in rate lav exprea.lon for the
repreaentatlve completely volatile renin component o , .

" i
B-B-ri-B-M-B-B_HBi_a-a-fc-a-M_^_B_a-M-M II inm.ii i •),., . .. ---»
!-tt»NPP BH

Peactiox orlar exponent used in rate lav expression for the


representative completely v o l a t i l e nylon reinforcement p g .
Also reaction order exponent for oxidation of graphite by 0 in
rate lev expression
Reaction order exponent for oxidation of graphite by 0 2 in rrte
°3 lav expression
Local partial pre».ur« of char depoaltlon exponent in coking rate
lav expreasion
Reaction order exponent for a rate lav expreaelon describing a for*
of deposition for the ahlation model

Local pressure
Local partial pressure of coking char material

Local boundary layer edge pressure

Generalized presaure

Molecular Prandtl Number

r Eddy (turbulent) Prandtl Number


T
heat traaafer rate contribution due to "heat blockade" by mass
blocking transfer

q Heat transfer rate contribution due to chemical reactions ie


chemlcal surface energy balance equation

Cold vail pure convectlve heat transfer rate evaluated by Eckert'e


reference enthalpy method.
Also stagnation point neat transfer rate

Padiative plus convective heat transfer rate


* R
*r Net radiative heat transfer rate Into surface q -q or
-c vOTv • o v q^rai

Radiative heat flux to surface free environment


S-ad

1, Net heat transfer rate or flux through surface to the interior of


ablator • -(< dt/dy)

Aerodynamic heat tranafer rate to the surface of the ablator from


the boundary layer

Recovery factor, • P 1 / ? (for lam. B . l . ) , • P 1 / 3 (for t-irb. B.L.)

Universal gas constant


Reflectivity of the char at the aurface of the ablator appearing in
"gloving" term
Reflectivity of the char material In depth at location of
evaluation of dP/dy appearing In "gloving" term

Steady state receselon rate

Time
t Binder bridge thickness

T Local temperat _re

Ty Local "vail" or surface temperature )

u Streasviae component of flov f i e l d velocity vector v parallel to s


direction '

v Transverse component of flov f i e l d velocity vector v normal to a 4


direction and parallel to y direction ,J
I
v. Annihilation or creation of species (i.e., mass rste of change of i
soecie) through chemical reactione vithin the boundary layer \
1
y Special curvilinear c ordinate normal to s coordinate and transverse ^
to ablator surface, also depth into material |
s Transformed dep-h into miterial (Eq *1)

a Absorptance In depth used in "gloving" expression.


Also viscous resistance coefficient
a
v Absorptance of surface of the ablator

S* Laminar and turbulent boundary layer ness injection parameter

Y Specific heat r a t i o , C /C , for Heal gas; also given as the char


ttass fraction of pyrolyting material

r Volume 'ractlon of a degradation polymer in a virgin ablator


composite (repre.ented as Phenolic Nylon for the ablator aodel)

' Char depth measured from the outer surface of an ablation t e s t


model

Ab Ablator nodal thlciwee. uaed in transient heat conduction solution

AE Energy released by combustion reactions betveen the gaseous jurface

•saterlal. pyrolysis products and environment combined Into one tenc

AH Boundary layer enthalpy potential for the free stream gas

AH Enthalpy of deposition
AH Enthalpy of depolymerltatlon and p y r o l y . i s
AIL Energy absorbed by p y r o l y s i s

AQ .Net energy of decomposition plus sensible enthalpy vith original


temperature and state aa reference

t Foroaity

c^ Ablator surface emisslvity


1 Parameter defined by Eq 38

0 Similarity traneformed (Lee's Dorodnitsyn) or reduced body


coordinate y use! in laminar boundary layer aoiutions, alao
transpiration coefficient used in liquid layer eouatlon

V viscosity

< Molecular (for gas epecies) thermal conductivity

x- iddy (turbulent) thermal conductivity

i Parameter defined by Eq 39

0 Loral composite density of a l l species Iga.eous-both boundary iayer


and pyrolysis products)

J
li Instantaneous condensed phase density of the representative solid
phase reein component of the model ablator
.J
_s> usmss

Instantaneous condensed phase d e n s i t y of the r e p r e s e n t a t i v e


°12 depolymcrlted and completely v o l a t i l e ret in coupon~nt of the model
ablator

Inatantaneous condenaed phase d e n s i t y of the r e p r e s e n t a t i v e


°2 depolymerlsed and completely v o l a t i l e nylon reinforcement component
of the model ablator

Inatantaneoua condensed phase d e n s l ' y due t o a form of d e p o s i t i o n


! •.
p Instantaneous velghted sua of l o c a l polymer condenaed phase ;
dp d e n a l t l e a ( o , . , o . . . D.)

p Density of t h e Ith species in the boundary l a y e r of the same unit


i volume a. p

C Density of o r i g i n a l a b l a t i v e material before decomposition


o

p Total instantaneous condensed phase d e n s i t i e s of l o c a l p o l y c e r and


. depoaltlon contribution. '

Maas flux of p y r o l y s i s gaaes


rp

(PT)¥ Total a b l a t i o n mesa flux

0 Stefen-Bclttmann constant

0" Eroded surface depth a

T Aerodynamic shear . t r e . . m
V

Subscripts

b Binder •

e Denotea boundary layer edge v a l u e .


Alao eno s f f e c t region properties jfl

f Denote, a e n s i b l e enthalpy term

i Denotea i t h s p e c i e s , i n i t i a l v a l u e ; or i t h nodal laminar S

k' twnotea a b l a t o r char s o l i d phase s p e c i e s fl

k
tg " Denotes ablator p y r o l y s i s can s p e c i e . 9

J . k. 1 Refers t o orthogonal rectangular c o o r d i n a t e s ( 3 dim.)

Refera t o stagnatiou point value or v i r g i n material M


r i °
i

r Denoter recovery value

rp Pyrolyala product fl

s Denote, condensed phase; or net .urface value jH

th Thensochemical

V Pore volume H

V Denotes " v a i l " or ablator aurface value

• Denote, free atreaa value. 9


Alao thick aample properties £•

L I

i J
1
1.0 LITRODUCTIOB

r . . . t r » « ! , « . . It r « o « . L . 4 t k . - . « . « . of . « « ! < > » " _ " " ? " "J"^ '.J ^ ^ ' h J S U 1

:_n«Mir_r_^^^
. b l . to p r ~ l c t tk. g r o . . o.k«»lor of » ! « » • • " J ? * * ™ - * \ ! T _ U r t _ , 4«<.lop.«« r . o u i r . a to . . t l . f y

:r_n r ^:^-;r-o^^T^.s"p~":.:" 1 ^"o v, . - £ « - ; « - * « • — «


pirMp. J _ t t k . . u r f c . „ l » t l « i . . lo t o . c u e of . r . p t l t . . lo K M M » l r e _ « t . .

Ik. purpo.. of t k l . i _ J - « ~ » 1 . to r . v l « t k . J j « . . . >»- » J « _ J * ^ ; ^ S J - ! -

Many rtviev papers (vith extensivs blbliogrepa-.s) have u t « " * T ~ ' . v 1 . l l v / n D t a 0 m e - e . Some of the
J T l H .ech'vith so_«bat different . _ , * £ . « various asp. U ^ ^ S ^ ^ t interact lec
review, stressed - M l « mechaniema or « - t . r i a l *J S **;_» 2 J_e_a_eM i n f l i g h t . In the l a t t e r part of
S S ablative s y . W . .ad experimental • i - * * * ' * * f { * * £ J j ^ j % ? £ £ t e s t i n g nev aspect, of
the s i x t i e s production of revi.v paper, nearly " ^ £ ^ J ^ £ vjfch may be due to satisfactory
1
ablation pi.enom.ne. This indicate, a } * ^ ^ ' ^ " • . " J ^ j S contemplated space mission. - or in
.OIUUOM of angl-ecring problem. M J O C ^ * " ! 2 » £ L ' K _ - « i r t S u t a l - • • « of t M r i Pro-
other vorda attainment of maturity by • * * « * • vn.ch nov m t « « r e . e arch and develcp-
f . c t l c e and found i t . vey into handbook.. This ^ M M » M M £ ^ h £ u l r e o e n t . r a t h e r then
- n t a c t i v i t i . . . but i t d o . , orient .uch « " * * ' « ^ w o T - i x t i . - . This decreased e ^ h a s i . cn ablation
bread t h . o r e t i c . l studies so typical of t h , f i f " * " * * _ J J J J O M . " t o l l * < - • « • * • * * • < i t h « r l 0
researcH pe-.M »ay be caused by the ' " * * * ; J * * * ™ ! * J " S S L . oT-cm_-d reus* of the surface vith
, ,
M viremm_^. vhich i n v i t . stuu, of non-receding p M M t a £ ? £ d e M l t p o l v a e r U . cannot be undere.ti-
stl11
minim-s or refurbi.h-«it. ^Tne a t t r a c t J J J J j J J J ^ J g " ^ ^ ^ . * b U U o D i8
mated _r. thus studies of "near" * l m t ' ^ • ^ L . ^ ^ ^ t r y vehicles. A previous AOAPDcgraph (c)
on. of th. meet affective and « ^ % ~ £ c ^ . £ C ^ U t I o n by one of the author, of t h i s >ublice-
raviev of the r e l a t e .ubject of ^ ^ " ' J ^ i S l . a L d i i l l b e treated here a. t departing >i_t to
tion carried the advance, in ablation ^ t o t h . J ^ " ^ « * J ^ e ( 1 3 l U ) « t h e i U b J e c t . of a l . t i o n
avoid repetition. Also the euthor. * £ « £ * * £ ' ! * * _ _ be useShere vhere required, S t . * . b: require-
i S t i w r E : s s s rrSJSToSd as.is t s u * , .«* *« ** *.* bee»«.
last five year., concentrated in the following »re_«:
1. Internal pyrolysis pbe&ose-a for low lensity ablator..
2. Behavior of graphite, in high pressure and temperature environments including i n t e i - a l
pyrolyais and aechsnlcal erosion.
3 Empirical .valuation of _ecb_nical erosion of ablator, and analysis of shape c anges
due to ther-ochemical/tber-omechanical forces.
U. Respona. of material, in environment vith h>gh radiative f l u x . . . « * including pre.ence
of massive ablation.
Better und.rst«ding of surface and boundary layer chemistry,
5.

6.
. " f a c e ' « T f l o V field chemistry for laminar and turbulent flov.

T,
pn
me di.cus.ion of the environment ^ ^ lo out of the ~ £ ^ J * Z ^ » * rHpcn.e'and
referred to (15. l6) for .uch reyi.v. . ^ ^ ^ t 2 1 2 T S S _ - « - - a T - u e h will be revieved here,
vehicle performance 1. c r i t i c a l in .velum ion ^ ^ X S S S s % \ ^ i« * * * * • « - ^ » " . ••»-«*•»•
It i . hoped that t h i . ^AP^ogr.ph vith J ^ S ^ ^ f ^ n t l p t e t h e . c l e n t i . t and engineer

S S £ r d ? . l g r i n g , t . p r c . 1 e r i : . 1 ^ d C d . v e l 0 P l n g material, used for thermal protection.

F t t rt.er vork in - — - J - ^ U S r S - S l ^ ^d
sira .uxncrntiorT^^^ — - - -"*—
2.0 ABUT!OB ANALYSES

2.1 General Conalderatlona

«. -HM_-«M t - --,--;;- i s a r r r - _^s r^rnrurkStTM..


affecting ablation m«cbaoia_. are: • M 1 ^ t 9 T ~ * * * r Jhe e u l s . external and Internal pressure forces,
P . ^ heating rate, shape of ^ S ^ l S ^ S ^ ^ £ - i « 5 - S S S . . i - r t i a l mnd dynanic
aarodyn-alc shear ^ • J J j ^ ^ J j . ' T S l i J concern 1. the mean, of accomodating the energy
' c o v e r t o t e t ^ e f . S T £ S l PriUeti-X s r ^ « . This 1. accc-pli.ned in three vay. : (al . - . • - p t l e , .

M__-m
r H
(b> radiation, and (c) reduction of the aerodynamic heat prior to l t reaching the vehicle (18).

The requirement to minimise body veight has often l . d to the choice of materials purpoeely
designed to undergo internal .ndothermie reaction. Lading tc t h . formation or a eerbooeuceoua char vhen
h.ated and to vaporise at t h . .urfae. .xpossd •© t h . oypereooic environment. The energy absorption
a*.eclated vith auch p r o c e s s . . , tog.tb.r v%n i • reduction of t h . heat t r a e s f . r coefficient aa a result
of injection of the products of degradation and the vaporised species Into the boundary layer have proved
to be extremely e f f e c t i v e in providing tellable thermal protection systems (19).
T
.t has been found necessary (20) for efficient design to have an --.curate . . t h e m a t i c !
description of the complex heat and mass transfer phenomena associated vith .uch proce.se. inside the
material and an e f f i c i e n t numerical procedure for implementing these calculations baa.d on t h . mathematical
nodel. In practice, the ablation pheuonena are meet often encountered in situations vhere t h . environmental
parameters are nonlinear functions of time. This fact, coupled vith the heat shield physically b.lng of
f i n i t . thickne.. make, i t nece..ary t o perform trenaien*. rather than eteady state calculation. (19). Th.
fully tran.isnt solution includ.. the decomposition in d.pth vith t h . .ttendent density and temper.tur.
gradients, internal transpiration and radiation g.n.ration, material rede roe l t ion, .ovrc. t.rma for
convactive and/or radiative input, and provides for a variety of boundary conditlona or i-urfae. phenomena
(20). With the aid of present day computers the .olutlon 1. practical .ven for q u i t , complex, sys.ems.

It has been shown (19, 2 1 , 22) that an intricate relatlom between the environment end . _ t e r l a l
response indeed e x i s t s and that the solution of the problM must account for them.
Although the trsnsleat problem can be solved vith a certain degree of r e l i a b i l i t y fur certain
combinative of environment and materials, or for steady state «xperlM_ts, . steady state .olu\ Ion Is
deemed adequate end Is l e . s expensive in terms of cemputi-s time. Often, in preliminary design phases, a
combination of transient and .t.ady . t a t . aoluticm. 1. uaed .« cause the e o . t s eeeoeiated vith a comprehen-
sive traneient analysis cannot be Justified.
One such condition where a steady .tate analysis ( I . e . , neglecting Indeptb phenaaena) can be
effectively u t i l i t e d la In the lnveatlgatloo of the ablation requirements Tor l i f t i n g vehicles vhich enter
from orbit and eu-teln long con.tsnt altitude trajectories and minimal decelerations. Here the ablative
process resaina in the diffusion-limited -eglme and Involvee t h . least i n t r i c a t e of mechanisms. In lov
heating environments ( i . e . , heat fluxes less than 75 Btu/ft2-see), the surface recession Ua. been shown
experimentally to be insignificant. The formation of the char and the influence of pyrolysis on material
properties may ajeo be considered inconsequential vith respect t o a material ineulating capability. An
aaju-sptlcv. of thie nature inherently postulates an energy balance of the contradicting effects of pyrolysis
vnervby blockage or heat transfer by gaseoua mass flux Is compensated for by neglecting the increase of
•her-al conductivity due t o char formation. Hence, based on these premises in lov heating envlranments,
a simplified steady . t a t e mod.l nay b . utilised for estimating ablation requirements,
wnere .imiiar approacue. can be t a x . - to reduce the prcbies to a steady state s«>»»5~> lori *r» dlseu.SMd in
(20. 23, 2M.
2.2 Surface Mech.nl.ms - Transient Ablation
The several energy tran.Ier mechanisms betveen t h . boundary layer gas and the ablating .urfaee
are shown in Figure 1. The energy balance at toe surf.ee extaLUshes the boundary condition for eolution
of the boundary layer equations. The energy balacc. y l s l d s .

(1)
i, - - ^ - \ \ • I, t V » ¥ « \ . > v * $„ ( V > v (
V > v * V « t * °v V o i - *T\

vhere the mass balance across the surface is given by,

a • a • m •m ii)

vith

v.. 1 ^ ' \mtll^Ki^


and

• - *s

The dependency of both CH sod CH on m^ and i a p l i c i t l y cm hw 1. .sen in the boundary layer


d
expressions. ?OT the surface energy bslaacs l t la sxp.di.nt to define.

13)
p u C
. e H

I . us i II i

—•*-*——wt-- -m*r~ —~MF—» - —wmpge M-»• -»a!a
_-2
• -.
55 "O o
5_
C 3
.3 J
t _ .__-s~
3.
x, O * t « a

a —.
S 6
o
—' 9
—> • —
— _ 3 _ •
• - -

3
-

i
e _. c
— «
9 _ s J .. . « _
• • I - . O
•»
- • —
^T -»
3

_> _>
9S — — t-25-M. « a - . - — r:
«•
=
• J3
— 3a—
-3 - — • 3 - — o o -•
:. s 1_5 r— - o _•?C
O
" w 3 v
C — »-
3 a

— o w
c • —. 3 - M C
• or- C •
5-. * • V •
— 3 •
_ •
-» «• •§! -. — o «
s a ee
- 2-. S - £
c -
-•i
hi
e « —• - o.
»"• • g ._ « • o a — •
t-j-_ r
_ • -« _• ~ 3 S • aj
?_s •—<—•
ills • - m •
i S3- • -> •» —
j-lf • *>
—• c
• • _
• - 5- a*.*
-a. ^
a _
C

u
_

•—
M


_.
M -•

c

5* fk o »<
S "« _ M M
i JC m
o -
• - •
-

o
5*.-

— •» c 5 3 —1 o _
»• » — i
O • -J 3

t
5
*-
'•
•< e - -1 - V T - 6
• - :s c -
- • r
— o •_
_. M •.
•a
.1
>> M M M
5- •- -••
o — — 3 -
•Si —> - _
1?
is 8 ill a :
•a
o - « • _ - .
- -o m _
— o
^i o
• • •» I?: . S " "r_
= a£
o — a
— •* c
•» •
P -
V

I - x. •

3
^
Q
_
: ^ 5

• ._
c •»

O

_s 3 a^.s
3
»» »-
« O .

a e- M .-
<J M
_, 3
• H »
>• _ o • • _ . o c o -

C
^ _ _> •M _M
M 3
• S <7
M
5 _ -
^> • u i_ 36_ • c • _ « _- - . o —
•s • k. 3 o Q A
../ -- { - _ p
35_
* o -. « M »• c S
^r 3 - M
•o o m
_r- " a t - S S .
C M M « M
. -5 « 52 * ** _ S Hf
-. 3
s 8 6 • •-* a *•
_> A o • _
1- -_ « -_ • a • —• - •
J O B
a>? . 3 ^ = ; ^
fi"3 3 _%. 3 5
• M O M O M Ik.
10
^
The equations for eonisrvatlon of slsmentil sperles coma directly from ths roni erratic* of
s p s . i . equation, and too s . t a l y t i c surfe,. rotation rounder? . . e d i t i o n (15. 2 5 ) . 'ltk'ltT2gtV
tttuMd In order to iemons.rsv. ths same solution form In t h . turbulent CMS (21). However, at e l l times
the S^miary i * , , r t t t t M t t are as.used to rt wtergoing tlmultMseut . o u l l l b r l . . dli.o.i.tlon-
S , a £ r _ ! ! _ ? i ^ o _ - * \ ' * ? 1 ? f # r , , i y t - * l t h # , u r f * " ' Xn f M l » 4 - « « » - - • » • " • • * t h . two . i t r e - N
of diffusion limited ttd r . t . iiaitsd relation, may be s f f . o t . d M long as t h . p r o o . s . . . are eonfln.d to
i 7 _ . ! a _!?: * • _ » • ' " • • rstoticn. ».tw.en some ablator spec Its and ths boundary r.aotMts may b. diffuolon.
l l i l t o d vniie .there are slmu}tM.ou.Iy r t t . - U m i t i d (ft, 2 1 , 26). -**-•*- »«r *• « r r u . i o n .

Th. ebl.tlor, mefhani.M vanously termed sublimation, vtporls.tltm anl/or smiting with
! _ S f fl" * " • n * r , f t , r J - W - t U r M p w M t t r ' . . i h M i s phae. r t « t i l o o t with en.rgy tbsorptlon. Tli.
t-.3im.tiso or v s p o T l s s t l a l i gtn.ra.iy u i o s i . t . d with the sbeidsal rotations b.tveon ambient boundary
l s r o r . o o i t U u . n l e , p y r o l / . U gas., ond th. subliming surfs*. M t t r l . 1 . Cond.,u.ntly, t h . he.ts of p h u t
« * . # . - f - « o . t o f l M in.ludsd with .h.mls.1 enthmlple. of formation of th. s u r f . . . on.r sond^I.^pnast
• r e . l . . . The., anas, fhango r.aetlMi . f f . s t l v o l y aeeraae. the shsnloel resetter, . n t h a l p l . . .

Tne ablation as.nset.s t.nwd M.hanloal •roeion include, liquid I v o r flow. Mohonio.)
. . - l i . t en, SM M a j M i i h w of surf.sc _4 U r i e l . Uguid l ^ . r _ . . . . i t n . iUrniliin 5 1 J .«
• U . . . . U . . Mt.ntflld.t spall.tiur, of .h.frir.1 t U t t o r . can U caused by ths Ut.ftigl • ! • • -re of !ho
. « . . s o r . s u t l n g through t h . .har (17). Th. s t r e s . . . can . . . . . 4 t h . t i n . i l e streo.th of JhTcJ.r for
_?-L - f _! , l f f _ ! _ ! • " • * • » • *• » -«.so«uo.no, • tart or soft of th. .her car, s t p t r . t . froe tho
v rgtH M t . r l a l . Hoa.Mi.ei suoar Elation is charaotsri.,rt h- s e a l ! . s l i d oh.r partiolss le.vTni ths
•UffM. duo to s u r f u . sh.tr f o / . s s . tnth of t h . . . proosss.s o „ b . «»p.dlt.d by th. l-plngwmnt of
• • a l l solid part i s l e t i . th. Sound* ry laysr as frequently occurs in tho ronk.v r.ot.1. oro.lon. Meihanloal
.hoar l i m i « id mof-ell/ Ms.sUtOd with moro s.v.rs .nrlronm.nt.1 condition, snd thinner oh.r l l / . r .

.... . * **! l f . l W r f t 4 l i * r r t M P t i i W i I" tht form mt pr.s.nt.d .ut OM be rearrange to ar


• i t . m a t . fort. An alternate ohole. for ths surfeoe .n.rgy L I M B S Is th. following . x r r e . i t 01. (19, U)t

%/Alcv - t v 1 *x M m * Shorn! t . l H
v*. *b looking (3)

ruro SMV.stlM term MM» irvi»ftr, vsporlsatler blooking


with -* b.arlr.g no Md surf.ee ohstistry t.rm t.rm
rt.rend.no. en a cr h

vhere

Uvmlsml' V , U , ( l k h " I ( C i ) . " U f l - ) { C


iV * K,"r-Jtfl'- U^MMC,, ) ))
•w w

tfld

(6:

Wing' V \ •%"(Vr'ur,J
vb.rs

(7

with

Ths b'ssklBi term v i s e , from sxprssslng i to term, of Ck ln.t.od of 0 . wh.r. r u is th.


n
BtMtom n « * e r , o H , with sero . a s . mjsotion ( l . . . , i y • 0 ) . Thla r . H . v e s the rttpttittblUty of

s-flrlssa rs 1st 1MS fr.4u.ntly r . o l l l t . t . d . t . r - i u . t l M ef t h . bleekliig term.

In meet es.es t^, 0. Md ^ er. .MStMts while 4 , ^ ( 1 ) Is . tabl. t r riving from ths .hook
)V#r solution.. At fitted ea/Jler, gultt frequently qfi t . e v a l u a t e by E t t t r t ' t r . f . r e n e . onthtlpf
•sthed for . few slmpl. . h a s . * , both for turbul.nl end laminar environments (IV, ?(>),
11
2.3 tt-tllon with Llould Lever tUWto

•me. traa.r.I h _!L B f J!*_i'* !_- J* c o " - M - r - - - • •» intormedi.t. proo.tt to tn. t b l t t i o n with only . u r f e e .
- ! ! ! t ^ I l I u l J l J i r J E - J S ^ ? " " • " J r ° 1 V l n 4 * • • • > • • * « • • I" 4-Pth. The o . . . of . l . p l / . I u i ^ *
lat-rf_a- 1 2 IJUfZA ! w t a n w u s l y .wtpt from tho surface or total vaporisation at the l i q u i d - . . .
S S i V S i S - 2 ! J J _ , ^ _ _ *, Y%f -t rP4 arii t l"0 ^n V #f t r m * *t l1h # 1 • f t n { > d i o f t h - vr-vlou. . . o U o n * How-
r y s iroind t h e ^ J y I t T i l r U m i f ° ° f ^ - " - - ' * • " the liquid l . y . r p a r t i . l l y
. . e n arouna i n . tody and partially evaporate, r.qulrs a nor. eoapl.x modal of t n . m-ehaniam r,.„,

«*- .i«^t.fjk.rj_;^-jrrpo^ii-5;;'r.^!^,o;\;rPji;ri. ira_*£\5r" *


SW^^Ev5^ ~ ;
*"-=- "-.-'rC:^::^233.-
d i . p l V i n g liquid l t y . r flow around t h . body and not Just gli ..y m t t t r i t l l Th. i e o o r t e n c . a f th-
4 th
t _ ^ - w a y n r a -M-^sfflLd-! -- - - • » - - - - "---*. -
-»• Ineoeth Msoh_r^H«

. _ _ « _ ~ £ - _ _ v «::.:u,.."tt„:,i'8:,!9";1r:i.:'3;!!,rrtu • » - w - * » - »*-«-«*
. . . .e /°lMtliv' tn
- -urftto equations And t h . coupled boundary lay.r solutions n-r.lv reni-m-at .

~:.;«}nri_s»'Sk_s.^ xr ,or *• °-'1" —s^ —}" a"s_S4_rs_._-


k

•>. • • « « & > , «.)

The usual assumption, oon.tralnlng tn. ind.pth solution ar. as follows.

l
' 2 ! o ! r . _ 2 ° U _ . I 2 _ a _ ? e " c a P P r l M " " V J** ***** * t U t 0 P t 0 l M l u , U » t h * <-f»Wltltn.
porous ohar, decomposition (or rsMtl^n) and virgin mat.rlal regions.
'' M _ S _ ? ^ d ? £ ; _ • " " I f T l 1 ooepl.teiy i„to g . . . o u . s p . d e , or leave.
# m,ltln
t ! . l-Jr-o.. "" " ° ' t n t - r l n < i f t t 0 h - t " » « " o u . r s . o t i o n . at

3. Tne mass flux of ind.pth pyrolysis gas sous product, s r . . . n s . d Inettnt.n.ously . t ths
surfeo. t f t e r - . p o s i t i o n Md/or deoompoeltfon r . a « » l , n i , - • - * * « . . - . . . y at ths

*. Th. p>rolysls g s . s s o r . . W a y . m thsrmal .Oulllbriue vith the porou. char.


y
2La^ l is! llf,l- M,#- •* -** ~u in otmp4ri,on uth- * - » ' °f «•
6 ,nth
' rTlJturi! " " * l p l M •»• " « • • • • ' • - hnom function, or l o c i t . « p . r . t u r . and . x t . r n . l

I. Th. th.rmtl conductivity and tmetiflo hs.t of th. . o l i d , oan b. r.pr.lsnt.d e . linear
funotlon. of tho eondonioo phots density .nd functions of t.mpsraturs.

'' •o\!!.bi..rr.or'1 t
"U"M th# 0
" ' *lmW§i9«*1 ir
*»ilw* h
" ' •*> • • • • «--" to be normal

'r 2 . nsglcoted
e»o S i l - a t L In __*T , U °h.at
^ St hl *. !trmn.l.nt h t n
° " flu# t eolutlon.
" oond>--!tlen 0 Vl-C0
"' itr
« M « rWftlOfi, mixing, e t c . .

10. The abl.tlr-g s u r f . . . w i n s s r v . . . t h . f t f . r e . o t 'rem for tho moving coordln.t. . y . t - .

"' I . J r T l . l J " 0 " P O ' U l 0 f t *"d " r u . l t l o n «rs t.tumsd to follow simpls Arrh.nius' r a t . j
j

1 1 0 b,0n>tl ln
"' il^IIntld" .; . - .^Tl«r °? • • - » - * " " « H ' t m slllcloun char 1. u.utlly j
rspr.s.ntsd as s g-adl.nt eiprssnon add.d to th. heat transfer squstlon. .
ahl.tiftn . - l ! K J r M H _ _ _ . * r # • • n , P - U y ••••Pt.d .S ths .tsnd.rd .snunpMon. .ccoupanyln. an tnd.nth

L J
12

OC g n 2»
S P, st *y *y
°.57
Sensible energy pure Energy exchange Energy exchange
exchange conduction due to naaa due to moving
transfer and coordinate system
cracking

(9)
4 !___ • dh
^'dp i t 2 3y

Energy exchange due to Energy exchange External radiation


decomposition ( i . e . , due to deposition .xehang. due to char
pyrolysis and ( i . e . , coking) transparency
dspolym.rlt.tlon

vith the auxiliary equations


3o 3m
—_ . -.A and o. • o • o. (10)
3t 3y dp c i

Lnthelpy of decomposition, _H , and enthalpy of u.posttlon, &H , are f(P .T). Typically, an
exampl. decomposition reaction might be i 3 , ii) •

T(L FL P ) • (l«D(i(_ Rv * ) &H. e(T)F •f(T)EF,-»g(T)E.P.,*l('l)P


C % C 2 U 2 2
•l \ l „ 2 \ 2 . **
(11)

Vlrxln Composlts Pyrolysls gsseous product.

soils char

such that p., • r ( o , , • o,.,) • ( l - r ) o . and T being the volune rr.ctlon -here o,_ and o„ are coaplet.ly
dp 11 14 2 Id <
converted into g . i . o u . producte.

Then the Aovernlna Arrhenlu. rate expree.lon mlxht be, for Instance,

»-{
•ii __*
r» o„(o)
°ii ( t ) - -ho RT
p
iil0)

E t2 1.1
ro.,(tj "l2 12 0,(0
e "* • (1-Dk DglO)
* rVl2(0)
(12)

whor. f_ m - enar
o o
virgin
Similarly •'or a typical deposition reaction which ml,rht be 21. H (pyrolysis ga.) ^e EP
(furthsr pyrolysis gas) • 3fc (solid char) the governing Arrhenius rete expression would probably be

E
i n. o_(t) c
__ • -k 0 (0; o
-Z- ' ' (0 ) C
( C
(13)
ot c c c 0(0]
c
Note the arrov In the »bov« deposition reaction .hov. «oln« to completion a. atated in the
approximations. A reverse reaction vcild Involve equilibrium constanta and partial pressure dependence.

Considering this as the complete picture then conservation requires, as seen by the auxiliary
enuatlor.s, that
bit 30 3i), dO
_ _ „ _ _ _ . __X , __. (1.)
3y 3t 3t 3t
r f i n a l l y t h e char transparency r a d i a t i o n term as proposed in ( 2 ) would be q u i t e a d . q u s t s f o r
13

t h l . t y p i c a l a n a l y s i s , namely

. - ( y - f l ) • R «••*»•»••)
£.a<j-je)*a<i-po)ro (15)
-2A (X-o]
l-R R e
o y

vhere J i s solved from t h e a u x i l i a r y s e t of equations

3 2 J - e 2(J -V (16)
h2

3J
(17)
3y"" a

J • .yV (18)

with boundary c o n d i t i o n s J ( y - o ) • a^o . (19)

and
l-R
(20)
V^'-.I-R o
Vr-ed
and

J(y-x) • P1(l) • o (21)

A l l of t h . . . equation, are thence aeaembled in f i n i t e d i f f e r e n c e form and . o l v e d numerieally


on t h s computer ( 2 1 , 3 6 ) . Th. s o l u t i o n s provide accurate thermal h i s t o r i e s and p r o f i l e , throughout t b .
ablator as w e l l a . a r e a l i s t i c p r e d i c t i o n of t h e d e c - s p o s l t l o n and d e p c . l t l o o p r o c e s s .

2.5 Mechanical R

I t i s known that some a b l a t i o n m a t e r i a l , under certain external or I n t e r n a l h l g h - p r . . . u i


c o n d i t i o n , amy e i t h e r experience mechanical o p e l l a t l o n of the aurfac. or o t b . r f a i l u r e , r e s u l t i n g i n
• . c h a n i c a l removal of m a t e r i a l . The mechanisms or f a i l u r e c r i t e r i a for aueh a b l a t i o n p r o c e s s e s have been
studisd ( 2 7 , 3 7 ) , c r i t e r i a assumed and p o s t u l a t e d , inC t b . l r r e s u l t s Incorporated in t h e thermal a b l a t i o n
models, further d e t a i l v i l l be provided in Section 3 . 0 .

2.6 S p e c i a l i s e d Ablation Modell

The sample model of a b l a t i o n material exhibited e a r l i e r t o represent t h e t y p i c a l lndeptb


decomposition and - x>sitlon aecnar.i.ma v a s symbolically t h a t or phenolic nylon in absence of mechanical
removal. The symbolic p y r o l y s l s g e s e s r e l e a s e d by decomposition of t h i s model were a four component
e l x t u r e , namely KP^, l y i , R 2 , and P r e p r e s e n t i n g r e s p s c t l v e l y aethsne (CH^), a c e t y l e n e ( C . H . ) , hydrogen
i i i j , and a combination of assumed n o n p a r t l c l p a t i n g gases ( i . e . , non-rsaetlng v i t h boundary l a y e r a p e c l s s )
such as nltrogsn and hydro/tn cyanide ( 3 5 ) • In t h i s model the completely v o l a t i l e nylon reinforcement vas
r s p r s s . n t e d by o v h e r e a . the 0 . . (completely v o l a t i l e ) and o.. combination r e p r . a e n t e d t h e d e n a i t y of the
phenolic r e . l n with T being the volume f r a c t i o n of phenolic resin In tne e n t i r e v i r g i n p l a s t i c composite
( 3 . 2 1 , 3 0 ) . The l a . t reference t r e a t , a rather t o p h i . t i r a t e d coupled chemically r e a c t i n g boundary l a y e r /
charring ablator problem with i n t e r e s t i n g r e . u l t a , but unfortunately not quite t r a c t a b l e oy a p r a c t i c i n g
engineer. With t h e equilibrium a u r f a c . r e a c t i o n s betveen these p - r o l y s i s ga.eoua product, and t h e
boundary layer apeelea in mind, t b . c h o l c . of vhlch components are r e p r e s e n t a t i v e o r most s i g n i f i c a n t
becomes l a r g e l y aa a r t depending on t h e range of surface temperatures ( a ) . The problem of hmndling
c o n . e c u t l v e equilibrium surface r e e c t l o n s i n v o l v e s no sore then writing ons combined s t o i c h i o m e t r i c e x -
pression and the a s s o c i a t e d e f f e c t i v e equilibrium c o n . t a n t . On the other hand, simultaneou. s q u l l l b r l u a
• urfacts r e a c t i o n , momentarily appearing as primary, secondary and t e r ' i a r y in some o r d e r , only t o have
t h e i r r o l e s reversed or permuted as t h . temperature change., p r . s s n t . t h e only r e a l c h a l l e n g e f o r c h o i c e
of o r i g i n a l p y r o l y s i s components. This c e r t a i n l y vould seem t o preclude the four component nodal from
even representing the a b l a t i o n of p h e n o l i c nylon <ruch l e s s the general a b l a t o r .

Hovever, knowledge of t h e thermocheslcel properties of s a t . r i a l , .uch a . t . f l o n or carbon and


t h . g r . p h l t . s and t h t l r r e s p e c t i v e a b l a t i o n r-ecevior, in auch v e r i t a b l e d e t a i l permits s p s c l a l l t e d
handling. T h l . g r e a t l y s i m p l i f i e s t h e a b l a t i o n equations lurther f a c i l i t a t i n g i n c l u s i o n of more d e t a i l e d
chemistry ( 3 9 ) - f o r I n s t a n c e , carbon ( g r a p h i t e ) can form ths r e l i e v i n g a b l a t i o n products l i m i t e d In t h e
oxidation and sublimation regime.: ( a , MO, e l , . 2 ) c , C , C , C. C , and C J _ . ror q u . r t i
5 ' C C C 0 2, - ' *
the chemistry i e auoh simpler a . t h e only reaction requiring consldsratlon 1 . ( 2 « ) .
Ik
1
8i02(t) „ 3iO^0 2

where (1) deootee liquid.

Intermediate .tops can Include:

8iO g (l) * 3iOg

8i02 _ 8l40 2

8iO_ 810*|o?

for graphite where the surface reactions and henc. .blation i s reaction rate limited the
following heterogenous completion react lens are representative, namely:

C (s) • 0 • CO
Simultaneous completion
(reaction rate limited)
C (s) 4 ± o 2 * CO

The maas tl'%% of C (a) leaving the surface by interaction with 0 and 0? being represented by
the combli d rate lav and Arrhenlua exp.-easlon:

n
fl 2 fl
m • const P [-(cj ) p (C0 ) ) exp (22)
PL °v ?.

Similarly for teflon vho.e ablation and surface erosion occurs at the surface, the folloving
r a t . dependant formation of the teflon monomer and a subsequent oxidation reaction can be expressed
a. U 3 ) .
( C r ) (s) - N(Cf ) (s) HlCF } (?) „ 2N(CP )(g)
N 2 2
K,10 (23)

(cr 2 )(g) • o cor.


(with arrows in both directions for diffusion l i _ i t e d and forward direction only for rate United
reactions).
The basic advantage of considering the teflon, quartz, and carbon models separately from the
generalised model l i e s in the feature of having to consider only indepth transient heat conduction
Internally. All reactions are confined to the surface area.

The ailicone ele.tooera conversely pursue the opuo.ite rout.. Ablation occur, primarily
through the indepth decompo.itior. m.chanisms vith relatively . p . r . e surface erosion reactions. The porou.
• i l l c e char produced provides e highly lnoulative layer that primarily reradi.ter. energy back to the
environmental flov f i e l d (kk). The ba.lc indepth reactions consist of unzipping of the highly cross-
linked bonds of the elastomer with the releaae of a few basic pyrolyai. gaaes such as vater vapor, carbon
monoxide and methane (7). A highly ptrou. s i l i c a char, S10 2 may reduce to s i l i c a carbide and carbon
monoxide later capable of entering into re.etion vith the boundary layer constituent, and forming the
dioxide sgaln (7. - 5 . - 6 ) .
The s i l i c a - r e s i n composite, present the combined complexities of the silicone •la.tomerlc
indepth reactions with the phenolic-nylon', phenolic reslr. decomposition (1*6) and quartz's surface
reaction characteristics (2U).
The carbon-graphlts resin composites essentially proceed with the s u e or comparable indepth
reaction kinetics a. the phenolic nylon model vith char erosion surface reactlona aiailar to the pure
graphite model (39, - 7 ) .

2.7 S t r o n g Radiating Shock Layers


At entry v e l o c i t i e s above .5.000 rps, stagnstion point heating can be primarily caused by
strong atomic line and continuum radiation. Under theee condition., ablation ratea result In maoa fluxes
from the heat ahield on the order of 20 pareent of the air riux through the ehock (U8. - 9 ) . Claealeally,
eueh conditiona result In "blown-orr" .hock layers with the convectlve heating reduced many ordera or
magnitude below the value that vou.'d occur without bloving.

81nce moat of the coupling radiation occur. In the ultraviolet .pectrum, ablation-products in-
jection will not offer any significant alteration or theae phenam na, although they will be somewhat

rt-a-a J
r • _ . _ — . - — -r—r s , _ - .... .-

accentuated. Ttttto conclusions v . - e borne out by Coleman, Ufferdo. Hearne, and Vojvodieh (k8) vhere
radiative coupling to ablating beat shields were studied; reductions In radiative heating from ablation-
-•• •• ••< - - • •• > . . . — . • • • - .

»
i . ... I W W M • — M M

1
products i n a c t i o n for the cases conaidered by Rigdon, Dirliag, and Thome. (k9) r.»ch 30 p a r e n t .

Th. r.cent decrease in emphasis on msaned entry missions at v e l o e i t l e a in . x c . s s of 36,000 fp.


have vitnessed a corresponding decreaae in the attempt, to further und.r.tand and analytic!Ay model the ;
phenomena.

3.0 SYNERGISTIC ABUTI0N MECHAKI3MS '


It is known that some ablation materials under certain external or internal high pressure con-
ditions nay either experience mechanical spallation of the surface material ttrmt. or other f a i l u r e . $
resulting in mechanical removal of material. The mechanlama or failure c r i t e r i a for such ^ " i o n pro- ,
cesses have boon studied, ',27, 37) c r i t e r i a a.eumed and postulated, and their results incorporated In the
thermal ablation models. Although these materlala have been studied analytically vith some vig»r, recently ,
developed hlgn pressure test f a c i l i t i e s have revealed a large deficiency In analytical p r e d i c t i o n of the
obse.-ved mass-loss data. As a consequence, analy.ts have resorted to empirical and eemi-eop rical i
correlations of the t e . t data vith rather questionable results when extrapolated to actual flight environ- ,
menta.
Understandably, empirical c o r r e c t i o n s or test data _re at best provisional; l l t t . e insight
«nto the actual mechanises ope.-etive during the ablation processes i s g.ined (50, 51). conversely rather
sophi.tic.ted analy.es of the ther-ochemical eroalon of a variety of carbon-based notorial, hnt evolved
(3 52 53) Development of these analyaea t a . been closely rolloved by a number of papers dealing with
various asp-cts of the thermomechanlcal ablation problem (37. 27. 35) and are specialized to the carticular
material unaer study. The composite of these analyses ha. failed t o provide repetitive correlation of the
test data - obviating their generality. It Is now evident that a large number of disciplines are required
to effectively .pproach the analytical description of even whet previouely vas describee as homogeneous
notorial.; e . g . , graphite.
Oraphlte reaponse mechanisms v i l l be used here as a typical example. Analogous response would
occ_r in some other aateriala.

3.l Environmental-Ablation Interaction.

3.1.1 Typical No.e Tip Interaction


The definition of material response that is required to account appropriately for the inter-
action of the local aerodynamic environment at the expoaed material surface and for the resulting indepth
Phenomena la complex. To illustrate this behavior in an applied situation, a nccc t i - .a tr.alyie- .or a
ballistic entry flight case perturbing f i r s t the extent, of mechanical erosion and then tranaltion
criteria. The results are prerented in Figure 2.

Tho results of the s e n s i t i v i t y analyala Tor the eaaea examined are:

Case 1. The basis for the nose shape change reaults in t h i s flight simulation e*.e I . • t i l . --ous
nose t i p materiel. A nominal transition criterion neglecting roughness and blowing
vaa employed to determine transition to turbulent heating. Mechanical erosion vas
deduced from ground test data report In (5»).

Case 2. This case shov. the sensitivity or mechanical erosion erfects on nose shape change (55)
and recession. The case is Identical to Case 1 with the exception that the mechanical
correlation u t i l i s e d v s . for a factor of 3 increase greater In receaaion over that
employed vith the sllaceous material in Case 1 at a stagnation pressure of 100 ata.

Case 3. This case retains a l l assumptions of mechanical erosion for the allaceous material
used in Cass 2. Th. enly exception is that laminar flov le. assieed to p e r e i . t
throughout tr.t reentry f l i g h t .

Caee . . This caae employe the aame material assumptions as Csses 2 and 3, with the exception that
turbulent flov 1. pre.umed to exist from the start of reentry throuRhout the flight perioa.
The all-turbulent run Indicated here simulated a fully turbulent atagnatlon point through-
out the flight. 1
In summary, the results reflected in figure 2 show large changes in spatial and temporal nose
* ... —.a •*—•_,_ _v_. ( _ . 1 1 \ . « ( n a r — r- H A I 1 _, j

.rth?o e p-r^rrpTlmi-y - t t e n U o n \ e focGsed"on~mechanleei erosion and* the relatively nrw approachea used
to analyse end gain Insight into the mechanisms promoting t h i s erosion.

3.1.2 Afterbody Response


Recently differential ablation patterns have been obaerved or. afterbody surfaces. Previously,
intriguing ablation patterns on meteorites and t . k t i t e . had been noted and studied ( e . g . . References 56,
57 58). Later, attention vas focused on cross-hatching and related roll torque, by the advent of email

- . - I I ' i msaMsr--- --• _.___ . . * _


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,__..*....._*__. «/.
_ _ _

hyperveloelty vehicles and their erratic r o l l behavior. Ler.on and Meteor noted ths development of cross-
hatching on camphor models Into a pattern resembling that observed on many aeteorltes (59). Canning
Wilkin, end Teuber have reported on turbulent wedges, s t r e e m . l t . grooves, and cro».-h.t:h«d pattern. r*oa
IT
1
their b a l l i s t i c rang, and vind-tunn.l tests and proposed . phyeioel flow mod.l to explain th.ee patterns
(60. 61. 68).

Legenelll and . . . t i e r have reported the results of t e s t s in the Malt, rocket exhaust f a c i l i t y
and the Lengley 6-ft structures tunnel on a vide variety or material., ranging from vood to carbon
phenolic (63). Particular amphasl. we. placed on char-forming materials.

Williams i6.) (flgurs 3) obtained cross-hatching in . hypersonic vind-tunn.l on .everal lov


temperature ablators, mostly subliming camphor and Korotherm. He shoved the scale of cross-hatching
decreasing with increasing pressure for camphor and the pattern of melting-vaporizing naphthalene to be
similar to that of subliming camphor. A unique feature of t h e . , t . s t . was the direct rn.esur.nent of roll
torque, during the ablation process. Later teete (65) extended this work to a more r e a l l . t l c simulation
of the reentry vehicle flight regime and geometry. Similar reeulte v»re o b t a i n s In camphor and wax by
Stock and Qlnoux (66). McDevltt (67) Investigated ths coupling between roll dynamic, and ablatio, pattern.
by tasting .pinning Korotherm and lun chloride models in e hypersonic vind tunnel.
Reproduced (rem
beii . v e i l . b l . copy.
©

I i

figure 3. Cross-hatching oe * 20° Camphor Cone at Hach 6

j n 11 _ n »
10

Various analyse, her. been mad. to explain the phencweoc* of cross-hatching, only a few earn be
mentioned bore. Tobax (W) suggested vortices as the origin Of e.-oas-faatehir-g. lechtabelm (69) believes
a tbln liquid layer i s essential. Probsteln, Oold mod Scullen (TO) believe that crcaa-hetohiag occurs
because of a resonance betveea boundary layer disturbances end t suitabls inelastic deformable eurfaee.
la OB U v e e t l f t t l o n of the pressure end temperature distributions over a two-dUeeneleenl neneblatlng wevy
v t l l , - i l l i t _ e and Inger (71) have theoretically proved end experimentally confirmed e v e i l tenpereture
phot lag correi t>on den ce to boundary layer pressure disturbances. Will lax. tad Inger (71) also report that
a pre-oroae-hetehed nonablatlng model confirmed cross-hatching experience by Indicating higher heat trans-
fer t o the valleys then to the ridges; t h i s i s diametrically opposed to normal super.onle beat t r t n e f . r
experience wbieh .bow. peek beating on protuberances.

3.2 Qrenhlte -melon Mechanism.


It has been obo.rred by . auaber of investigators (12, 73. 7k), that under certain pressure-
temperature environment, bulk polycrystallice graphite undergoes l o t . of solid material of minute quantity
oh erect e r i s t i c of the constituent s i z e of the materiel components. la a closer •xaminetloo of the type of
behavior that occurs whoa graphite, are subjected t o high-temperature environments, e cross section or a
tested specimen i s shown In figure k. The figure r e f l e c t , an Indepth degradation of materiel, ehowing e
rather open irregular structure proceeding into the material mad t h . eppearaace of an interface showing a
lose porou. structure with Increased mateTial mete. A view of t h . .urface demoo.trate. lerge differencee
la materiel strueture end preferential loss of n e t e r l e l revealing irregular rectangular appearing
particles.

CROSS seer ION SUMACS

figure k. high Tenpereture Expoeed Croee Section and Surface Photomicrograph of Graphite ( T J - S )

Some perepective can be focuaed on the reaulte of the ablated pattern illustreted in
Figure a. Graphite, by i t s very nature, is en lnhomogeneous ma- trial composite consisting of f i l l e r
pmrticlee and binder structure with * high degree of poro.ity. The differential n.ture of the constituent
material, used in febrleatias of the graphite i s believed to result in preferential eroeion giving rise to
an Irregular, roughened eurfece that interacts eloeely to the environment at the heeted surface of the
materiel. This interaction involves a complex association of the local environment and the material
benevlor.

3.2.1 Physical Characterletlea


An understanding of the nlcroetructure of graphite requires some knovlsdge of the proeeeees by
which graphite ie formed. The commercial graphite, used in aerospace appllcetlons can be described as
synthetic or manufactured, Tbeee bulk graphite, are manufactured by miming ta organlo binder, ueually ,
a coal tar pitch, with careen f i l l e r particles end molding or extruding t h . mixture t o form a "eyeon"
b i l l e t . The binder 1 . them carbonised by beating to temperature, on the order of 1300*P, followed by
further heating t o temperature, up t o JkOO'P, t o produce t> more ordered nicroetruoture. The f i l l e r
material may be any particulate g r t p h i U or carbon, tueh a. natural graphite, omrboa black, coke. a t e .
Per economic rettoma, f i l l e r materiel 1 . moot oo—only made fran the coked residue of the petroleta
refislag process. Tat coke matt I t crushed tad groxmd t o ollmlaate grces poroeity, and screened l a t e
con trolled particle e l i e e . Beoauae of unavoidable intercryatalUa. mloropores, tho particles retain <
n l a l w porosity of 5 to 6 percent ( 7 5 ) , r e t u l t l a g la epparant d e n . l t l e . of tbout 2.0 t o 2.2 gm/cc.

figure 5 provides . schematic of tho proposed bulk graphite arrangement after grephltlsatloe
(the deeorlptlon given here abets tho excellent discussion of graphite by Pi ley (76]). The f i l l e r
perticlee eppeer as en array of looealy peeked irregular-shaped coke eleneat. cemented together by the
cerbc-ieed binder. The ratio of b l n d e r - t o - f i l l . r veight may be varied over wide U n i t e , with normal
practice being between 20 t o ko percent. In the baking cycle (1500*f) the pitch binder Is pyrolyeed,
leelag about kO t o 50 percent of i t e initiel.wmlght. During the baking cycle, end upon subsequent graph!.
tiseticm, the binOer shrlnXa. Since ahrinxage le const rained by t h . f i l l e r p a r t i c l e s , the volume nominally
occupied by the bicaer h e . a large void e c a t e - t . The resulting necroporee la the binder allow for eaay
paaeege of evolved go.ee through the binder matrix and eevount for the relatively high porotity of bulk
graphite. Saab f i l l e r particle l e held in the resulting matrix by a network or binder bridges occasionally
interrupted by Interconnected mecroportt. The maeropore diameter varies, but Is about the same a. t h .
diameter of t h . f i l l e r p a r t i c l e . . A l i a . of latoreonnected necroperee may propagate a mechaaleal failure
•lace t h i . 1. th. path of minianmt croee section. The ale restructure evidenced in figure 5 erpoees the
Heterogeneous qualities or graphite in d e t a i l , f i l l e r particles consist of closely packed e r y s t e l l l t o e
and intercryetalline micropores. Significantly, t h . c r y s W l l t e e are cot completely ordered; the binder
c r y s t a l l i t e , ere even l e s s ordered, which account, for the ninlnal anieotropy exhibited lo the thei
physical properties of bulk graphite.

BINDER
MACROPORES
FILLER PARTICLE

BINDER COKE CRYSTALLITES

MICROPORES

FILLER COKE CRYSTALLITES

MACROPORE

FILLER COKE PARTICLE

figure 5. Schematic of Graphite Mierestructure

"i.2.2 freferentlal Eros lorn

Bather extensive l n v e . t l g e t i o c . or the preferential er slon aapecta of graphite have occurred


in recent literature. Mann, and Oehryer (72) obaerved l o e . of particle . o l i d of graphite no.e t i p
-a;^g
EXPER.MEOTAL MASS FLUX
.If. J 1!
THERMOCHEMICAL MASS FLUX ss5**!e
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In air tnYlrocnenta, the boundary layer c o a . t i t u . n t s ohemically react vith the carbon structure resulting
la theraoeamau.al eroalon by oxidation end eublimatloc of the carbon structure. The porosity inhsrent in
graphite efforda a means of sub.urfae. chemical eroaion to oecur. Th.s. effects enccspass subsurfacs
oxidation end sublimation that are cloeely related to the material', macro and microporosity. Porosity
sicca Is not oonflned to that open to attack by the boundary layer constituents but includes closed pores
vhich may, at sufficiently elevated temperatures, ect es miniature pres.ure vessels as sublimation occurs
vltbin the enclosed internal pore surface area.

Coneequently, the differential microstructure betveen f i l l e r particles and binder material


holding the p a r t i c l e s , through a labyrinth of binder vails connected and interlaced throughout the pores
may have significant effect en the micromechsnical erosion observed by graphitic materials. The prefer-
ential removal of either binder or f i l l e r particle material leads to a differential recession rate cauaing
en irregular aurfaca, promoting surface rojghness and increased heat transfer. Material protruding about
an aerodynamic surface le subject to aerodynamic shear and pressure forces vhich, depending on the material
atrength, extent of expoeure, and bonding, may be sufficient to erode solid from the surface. If the
material pore structure i s small and ronstricted, a pressure differential may exist across the material
causing local failure of the partially eroded material.

To quantite material ccr.position and variables vhich nny be significant in isolating individual
erosion mechanisms contributing to the total performance of graphite, necessitates an approach vhich f i r s t
dissociates material variables interactions from the applied environment. With the material quantities
characterised, auch as binder content, f i l l e r particle size and distribution, pore distribution and shape,
e t c . , coeciee statements can be made about the material variables influences in aerodynamic environments.
These material variables can then be related to the observed eroaion occurring and developmental goals
for improved graphitic materials atated.

3.2.j Surface Roughness Effect on Heat Transfer

The materiel characteristics are though to directly Influence heat transfer to the material
ablating eurface. Surface roughness elements can o c r from material impurities and preferential erosion;
or they can be inherent in the material f i n i s h , even when highly polished. The effects of surface rough-
ness en heat tranefer have been treated by numerous investigators (80 through 93) vith varying objectives.
The bulk of the reported studies have been concerned either vith singular roughness elements (both tvo-
end three-dimensional) on symmetrical bodies or vith roughness elements on flat p l a t e s . The u t i l i t y of
t h e . , d . t . in . high-pressure environment, end as related to heat transfer, has yet to be determined.
The date of Bertram, et al. (91, 92, end 93) vould appear to be useful in that the effects of the
sinusoidal variation can be directly r e l a t e l to some of the irregularities existing on graphite materials.
More recently, Walsh (91*) end Akin and Marvin (95) have investigated the effects of surface roughness
on spherical geometries in representative high-pressure environments. Reference 95 presrnte results
obtained in a combustion-driven shock tube. These results shov an anomalous behavior of tne convective
heat transfer in that the data deviate from the laminar theoretical predictiona, increasing directly vith
increasing stagnation presslre (Figure 8 ) . The deviation from theory i s as high as 60 percent. It has
been postulated that this deviation i s due to the flov being in a transitional state (from laminar to
turbulent).
P0 A I M
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1.0 -Q29 — J3

0.8

' 2 3 4 5
RATIO OP BOUNDARY LAYER* THICKNESS TO ROUGHNESS THICKNESS (<S/K)
figure 8. Heat Transfer as a Function of Boundary Lrvycr Thicunees (05)
•8

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3
«3 Qraphlte Mlcroatructure Chorecterliotl-a

- M * - . _ . . . ?_?____*_**_* * • • " • * • » . Serial-environmental interaction poetuleted in eeetlon 3.2 a nev


S . 1 S - L - , l _ n e _ ! . _ 0 f ^ t 1 1 " ? J* 1 I * 1 " 1 * " r f o ™ " * h.t.rogenJou. m e t e r l S . I . i T p r o g r . . . !
to t - - _ I m ^ J . _ S ? f ! charect.ri.lng t h . material microetructural q u a n t i t l . . and employing t h T r e . u t .
P^en_eint ***** •»-•*•« mechenl.m. end finally their combined effect on h l g h i r e a . u r e tf.laT.an

meth-d-K--- 1 - i ^ r . 0 0 ! _ T " * U ! ' > e , , % r - 1 o f the .alient features or t > i s approach and lllustratea the
-rounl u T v S o r L J . M . l ' v a r r a . r . ^ K ^ 1 0 ' 1 • * » « « * - - " - " • - " • • ^ l l u - t r a t l i n . ^ a r e c « t rid
VhlCb m
•rSlti. T T T ^ . ^ ! ! M ^ K T * 0t e o n ««»'" n e - l« **• t « s l ablation ben.vior of
^ ! ^ ; - - ! ° * * * ^ t a taebnlo.met n . c . s t r y t o ensure a self-cone 1 stent eet of characterisation parameter.

_ssr*rs_s asirs »._&_ ""• - - ••«- w-h *^_tsar_r


3.3.1 Micro- Hecroporoaltv

t h . v w - . r h . f ° r ? * U y f f evephitic materials may play an important role in determining thermochemlcal and


thermoeechanlcal erosion. Conaldereble effort to develop reliable method, of characterising the norelitv
- L 2 ^ _ _ T _ _ I r _ f e T U t : i ! r e ; U l N d ' T h U , f f ° n l B « - ^ t a . t . d bec.ua. S ^ J T S S - l f « r j £ o f '
pcres that nay occur io a alngle material. In particular, t e e type, of poroeity are apparent ThTrirat

as sas i p ^ ^ w s s i s s . SI^AISE'S sssrJS


i?ra_J5sff^yr Mo4- f- mut *-*«- ™* *-** * *£&%»
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* ** r c u r * b - t h — « - . » • r r t l J deterSneri. only
a qualitative measure of pore radius . i n c . photomicrograph, .how that pores are generally of a relatively
soo-n I!. S g u r f " **"+ * * ' U " ° p , D l D « ' A t f p l c a l *>*<**"*** « - u r e . e n t of ATJ J r S - l S U

tvo - a - S r f ! f ! ° S J 1 ! « r a » h i t i c - - t e r l a l s the accessible volume distribution, are characterised by

K ^ J . : ^:.n- SE -_s-ra_r_^,_s_5_-,is_.,ai: r^'r,:?1*


3.3.2 f i l l e r Pertlclea

in the n e _ e _ 2 ! j S L S -\" F - r t i c l e . used in the manufacture of aero.pece-gr.de graphite are Important


oceurl _eea_!. 2 X ?° S " , ° , • r - » ' h * t e - X t h " >•«" PO.tul.ted that mech_iical ero.lon cf graphite

a-T-vTa^rT^ti!. Jif!c_ r c h t n cal reB0Vdl f filler


? > t r t l c l M fr* "h* °"1-1-«« •nd ••*»»•« •-?'•«.
U r i l L r ! f - ! P r O c " V t 0 "rotnermal environment have generally aseumed that the r i l l * , partlclee
n ? . i t _ - ! ^ I C T U , d y ' TJ" 1 * M % n " " ( ? 8 ' 9 6 ) i h o v e v e r » : t i - ^ llk
« ^ t h * * Preferential r e - o v ^
- . i M _ ? f - n e t 1 n _ T m _ r e J t f * S t T * ^ " l n r " P ° n ' e t 0 t h * * P P l l e d P " ' 3 u r ' M<1 P " " " " « S " » t i T
I l T b J r ? S u L - - * P S - t S L _ J* -" P , r h * P : " h , P *- H e n C e ' t h e "•triMUtlon of particle s i z e . (Figure lol
SJlreaeUS -overnlng the mechanical eroeion of graphite In high pre.sure
F i l l e r particle s i t e distribution, n(d p ) denotes the number density of probability of occur-enc
? n / t ^ " ! < " 1 ! t f i U , r p M , t l c l f t ' A ' i T 1 " 1 c - ^ * ^ r . fine-gram graphite Is pre.ented In Flgur. U .
Cl

Fox tela particular r.raphit. the dletributic- 1. n.arly normal. However" larse aep.r-.ures fro- cllusslar,
daaw.-a .ens may be .xpectcd for coarser-grain f i l l e r p a r t i c l e . . The mean particle diameter, d , and
2 ft
varleoce, o p , can be obtained from these data free tne following eq-j.tior.ct

d„d a
I •• V P P (2a)

• | n(d ) !dp - dp ) d dp
'25)

- H . - e li i miimgn
KRCENT ABOVE SIZE INDICATED
3 fe S
o»rrcmiMTuu. mCOB—»t voxi
I* SULK VOLUM_m-CmOM»

o
i

i
1
5
I

o
§
SJ
i
i
o 1 ^>i
* ! i
S «/^
1
• 1
i
• ~t
i i
/ !
1
i
i
• 1
I i

- i

i -ar-i i .-. .___d_H


f ••
]

4 0 B 10 12
•ARTICLI D I A M I T I - (MICRONS)

Figure 11. Numb.r Density of Plll.r P.rtlel.a

'/h. M - sroj....« area. A , and velum., vr , of . filltr pertlalt esn si.o t . or t.m.d fro-,
• o
in. •tiers an. thlrrt aemsnts of ths tletrllution tastier. | thtt i s ,

(P6)

(P7I

for Oautslsn dlstrlbutlorif A MI V art siaply r.l.t.d iw d and o 7 by

(.-«)

tad

!»v)
4 /
P„

«„•« „.£.::"£ s s i s r i : - -?_.", >4ri'"" * • -- *—• A «-«• -


i "(#) T7TT77 < V))
.% *

m-_n i-M-m
-hart

i :
k naaber of particles per gr a
t ! p • f l l l . r particle density
a • partiol. projected ar.. p.r gram
These properties mutt be measured prior to tht binder-filler mislng process. Attempts hsve
been aadt to us. th. shape factor a. defined above In . relation of tho Ton
A.SC-t (31)

vhere a end t are toaotant. to determine the filler particle packing d.n.ity that could b. aehi.v.d in
t dry ttate (that i s , unalMd vith blnd.r). It appear, clear that no euoh simple relation . - l e t s to deter-
mine th. porosity of th. gr.phltio materials oansidered for Mrotp.ee appHoatlon. In particular, eddl-
tlemal p-reitt.r. .curing into an ..pv.s.lea for c vould iaolude the binder SMI ratio, the verlano. of
IBs filler particle tlto dietrlbution, and th. gr«phltl».tion tenper.tur.. Oth.r th.n through influencing
the porosity of th. gr-phitio eats rial, i t Is clear at thit tiat that tht shape factor is an important
influence oc erosion mechanisms.

3.3.3 pfrdar Proe.rtl.s


The primary binder properti.s of Interest for Mrothermal eroeion pr.dletlon. ar. blnd.r
bridge thiokn.se Ml deo.ity. -elth.r of those properties osm b. ee Mured dir.ctly, htnot aaalyttt have
eeeadeveloped to predict the., prop.rti.. from available character! tatlon data. Some aablguity ua.nl2y
•lists In the definition of those quaotlti.s,
Th. blneer brldg. thiokaoss l t ac i-portant paramet.r in deterainlog eroeion rete due to
subliaatlna and/or oald.tlon of bind.r mat.rlal lmn.di.t.ly bale, the turfaca. Thl. can b. defined at
tht new thiokntis of blndtr aattrial turrouading f i l l . r partition, madrepores, end micropore., la keeping
vith the model of large mscroporss reached by itail optr.in|S (nicropor..) both ths f i l i . r partlol.s and
Ilorepor.rtr. nodal.? M epbere. of _ . « volum. V M g Vy , r.tptotiv.ly, obt.in.d ft*, th. rs.p.ctlv.
'o o
dlstrlvutioo fuaotione. Tho aloroporss ar. modeled M oyilndrlcl tunn.l. of neen radius r_ lflro . Th.
o
intoett.lbls void volum. is inolud.d lo th. Mosssibl. maoropors volum.. For this modsl th. a.sn bridg.
thickness, t^ . is given by

(32)

vh.rt
133)
l.e-d-Vpf
Mg p is th. .pparent deoeity of tho graphitto a.teri.1, Pfl,ls th. bind.r material density, end g_ l o r p i .
th. fr.stlon of bulk volw. eon.istlng of mioropores.
The variation io aeon binder bridgt tmcnn.ss is snovn in Figure li for tev.rel value, cf
tht blndtr nass fraction, K., typiotl of various grsphlts.. Significantly, tb. man binder bridge
tnTtkMM i r t - i t t thin, -tin a . - t i l degrad.tion in thl. thlckn... by oalamtlon/ttthii-atljn a v free the
othervlee soostralnsd partlol.s rt.ulttng In their being e « i l y dislodged from the net.rlaJ surf.o. by
MrodynsnU tstrM,
3.3.. Surface nolle, tuorostrait
Th. influ.no. of str.ss.s on th. thsrmomsehsnlosl .ro.ion car, b. consid.rsd from both th.
aecro-sohtnloal and _lcro-.ohenicel point of view. Ths r.sults of i t r t t t enelyses can be used to .stebll.h
tbs astro- or ml ..•.failure of ths material sj.d r . l . t . lt to th. ohenlo.l -nd mechanical .ro.loo.
In Edition t© th. poro.lty vhlch 1. pr.a.nt.d In th. net.rlal l n l t l s l l y , additional surface
and .ubsurf.o. porosity nsy oocur. At or n.ar ths surf.o. th. internal miorostruoturs ohsj.gea Critically
with tins. ismpereture. mod .nvlronaent. Corr..pondlngly any ehangee In th. a . t . r i . l properties .t or
near the surface also affect th. a s c r o . t r . . . . . , not only the surfMO stresses but aleo the strsstes vithln
ths body Itself.
The naaaltude of poro.lty eon be estln.t.d by ths s u i -nd h.st balance relation. To i count
for porosity, thTSttrial prop.rtle. «ttd for oath tie-eat in a finite -l.aent - t e l y . l . can be properly i
nodlflsd. -.ll-Meahln (97) suggsetsd ths following modlfioatloni

..rVrj (3»)
• a " * * (35)
vhere

(1 • v >(13 - I5v )

(36)

2(1* - 5v )

S-rrrsJr (37)

:. M o s s aTTJ: ^TT&L- _? *5_ssr - -—-—

8
X
h
UJ

cc
0)
z
<

PARTICLE RADIUS FOR MEAN PARTICLE VOLUME. ( — ) <M>

W i - r t 12. VtriatKa, of Binder Bridge Thickness

reduction due to weight Iocs (caused by Increeatu7oM-it»T-r'_. ST e , * e r i » - l - l results . the strength


Thi. .tr«gth reduction 1. p r . d i c t ^ l . ^ h . o r e t . : ^ ^ ; 1 ^ $ £ £ g S S S 1 5 , ^ " '" ^ *» ^ '

6 k v 2/3 i
1 -
w(l - k")
27

the same trends—a marked reduction in strength due t o porosity. The results may be used t o correct t h .
physical propertiee entering In the maeroetreee analysis. With the ebove information a v a i l a b l e , l t i s
possible to predict surface macroetreeeee and macro-failure M affected by the varying pore content vhich
i s a function of time mad temperature.

3,000

O A-ORIENTATION

tn
2,600
• 0-ORIENTATION

<v£f^
t
g 1,800
o.

1,400
{////%&

1,000
6 8 10 12 14 16
WEIGHT LOSS (%)

Figure 13. Change in Transverse Strength of AJIL Graphite vith Weight


Los. Caused by Oxidation in Dty Air (96)

* - VOLUME FRACTION OF INCLUSIONS


\ • VOLUME FRACTION OF PORES (SPHERICAL)
02 - - STRENGTH OF SOLIO BODY (NON-POROUS)
- STRENGTH OF POROUS BODY

BINOER
i L-
6 8 10 12 14 16
VOLUME FRACTION OF PORES - V l%)

Figure 1U. Strength Reduction of an Inclusion-Reinforced Solid Due


to Porosity (99)
88

3.3.5 S m . r _ l . t l c gffeet.

The erosion behavior of graphitic material, entails ao Mse.sment of t b . competing ebemloal


mod meehaolcsl mechanism* of graphite troelon end their synergistic a f f e c t s . The preceding he. illustrated
•evernl of the phenomena of consequence in tb/- analytical performance description j i t remains t o formulate
end experimentally verify the complete analytical model. At t h l . . t a g s , i t le clear that a more thorough
epproech l e neeeeeery in analytical modeling of hetergeneoue materials. The benefit i s twofold; a
rigorous ablation analysis which includes t h . material micrestructure! ebaracterlotlcs results end a
r e a l i a t l c insight t o the material characteristics which eentribute t o the observed ebletlon date le
obtained enabling material formulation, to be aade, aimed at reducing or alleviating t t e enhance, eroeion.

3.b Oranhlte TbornochsmJ sal Erosion

Thermochemlcal erosion of graphitic materials, both in the laboratory and in ground teet
f a c i l i t l e e , DM been the eubject of some considsreble study for the p u t decade. At present, en incomplete
tmderetanding e x i s t s of the detailed effacte of materiel etructure cm oxldetlce and sublimation. It i s
known, however, that the surface reactivity of the material i s important in determining oxidetlon rates
in the kinetic-controlled regine.

Several studies shoving the effect of graphite solid structure on oxidation kinetics hare
been eccoasplished. For the moot part, result, are Incomplete because the investigator, have f a i l . d to
includ. a l l p c . i b l e influences on their experiments in a controlled mennor. For example, both the
o . i e n t . t i o n and also of graphite cryetailltea have been negleeted in performing reduction of oxidation
data,

The diffusion controlled oxidation eroeloe of graphitic materials in hyperthermal environments


i s relatively w e l l eetabllebed. The oxldatico kinetic regime has been fomul.ted by several investigators
with various degree, of .ophleticatlon. The work by Welsh end Chung (100), Hearne et a l . (1C1), and
Seals (52) provides results reflsctlng state of the art determination of the reaction rate regime descrip-
tion for graphitic materials. The diffusion controlled oxidation regine aod trsnsition to thle regine b u
been deecrlbed employing both equal and unequal olffueion c o e f f l c l e n t s , u t i l i s i n g similar boundary layer
Msuaptlons of Lees, the approximations of Scale and, more receatly, the unequal diffusion coefficient
approximation by Kendall (38). It remains that significsnt differences existing between the several eets
of s o l J t i o n . , vb.n using Identical thermodynamic properties, have yet to be demonstrated.

The hlgb-tempereture tbermochemical eroeion regime of graphite le leee v e i l understood because


of the limitation in obtaining the nigh teaperaturee required and Maocleted temperature aeMurement
error.. E f f e c t , of lnport.nc. are vapor pressure of ths carbon species evolved, the p o e s i b l l l t y of
departure frcm p h u . equilibrium, incomplete definition of the experimente In term, of such considerations
M reaction times, e t c . The question a r i s e s , however, M to the total effect of tne idealisation, that
are made presently on the chemical oroelon of graphite. Conclusively, i t can be . a i d that ths material
structure hes a definite effect an the chemical erosion and the importance of l t e detailed structure
remains undetermined.

3.-.1 Vepor Properties

Considerable interest aod reeearch have been fecused oo ths identification and thermodynamic
characterisation of high-temperature carbon vapor species, and elucidation of the carbon vapor equation
of state in the l u t several years. Up until then, the thermodynamic properties of a l l polyatomic carbon
vapor species larger than C have been calculated (102, 103, 10.) from the free energy lscremente of
Pitaer end Clementl (102), vhich vera fitted to yield e triple-point pressure of 100 ata at t0OOaK (105).
Likevise, the equation of state calculations (103, 10*. 106, 107, 108) have failed to include the heavier
molecular . e i g h t epecles C to C , despite evidence of their existence (109, U0) and likelihood of
'17 '30
their prominence at high preeeuree and temperetures. Ths carbon ring noleculee have alao been excluded.

An extenalw study of the carbon vapor thermodynamic, and thermochamlcal ablation performance
of graphite in high-pressure environments VM given in reference 77. The r e . u l t . (77) lneluled t h .
thermodynamic characterisation of high-temperature carbor.-rapor specie, and the elucidation of the carbon-
vapor equation of . t a t e . Heate of formation end thermodynamic properties v.re calculated for both the
linear end monocyclic polygonal ring conformations of C up to C - over the temperature range 100°K to
5,000*K. The thermodynamic propertias of the linear and cyclic molecules C- t o C vere calculated by
quantum and s t a t i s t i c a l mechanical techniques. The resonance energy of each molecule v u cewputed from
the electronic veve functiooe by the extended Huckel method of Hoffmenn (111), end the eorreepondiag
vibrational frequencies vere determined by a normal coordinate analyela of the molecular structure. The
theoretical procedures employed vere . . l f . c c e e l s t e e t and did not resort to t h . empirical increments
adopted by P l t t e r and Clementl (102) and used by other. (103, 10k). Figure 15 deplete the logarithms of
the partial pressures of the linear molecules in phMo equilibrium vith graphite. The plot shows linear
C3 i s the moot . t a b l e speciee and linear C^ sonevhat more atable than C. and C,, in agreement vith
previous mess spsctrometrie finding. (109, 112). It i s also apparent that the contribution of ring
molecules l e n e g l i g i b l e (77), end that larger linear molecules became very importent at t500°K, and ahould
be included in calculations performed above «000°K, Io Figure 15, an even-odd alternation is evidenced
ebove C1Q at -0OO°Ki the affect appear, to propagate to smaller values of n vith increMiog temperature.

Figure 16 reflecta the present state of affairs in regard to tote, carbon vapor pressure and
aaverel caleulatlone thet have been made in the p u t s.vsraJ yeare. Aa obaerved, large differences in
vapor p r e . . u r . « x l . t In the teaper.ture range 3000 to -500°K. The calculated total vapor p r e . . u r . (77)
1. in good agreement with the experimentally determined eublimation point of Thorn and Wlnelov (112) and
11*. b.tv.en the recent triple-point temperature, of Schoessov ( l i t ) and Fateev. (115). The calculated
w

10 20 30 40
NUMBER OF CARBON ATOMS

Figure 15. Partial Pressures of Linear Carbon Vapor Speclea

UNCERTAINTY INAFJ? • -20% 0+20*

PITZERAND
CLEMENTl/

/ 'DUFF AND
s o
—f BAUER

LO
UU
QCL
Q.
O -2
O
EXPERIMENTAL DATA
OTMORNANDWINSLOW
-4 OSCH0ESS0W
-.FATEEVA
0 BASSET

-6
2,000 3,000 4,000 5,000
TEMPERATURE <°K)
Figure 16. Graphite Equilibrium Vapor Pressure
i

s.M "m -nfr"r»_sae_g

(38)

^sife«?^avvrrtr»-^
- o l c normel to tb. »al- oy i e f l B p f l M B t. cowistlng of th.

iot.mel gas ^
c_n..rvatloo ^ ^ ' are
.tatenent. J i ma*.
r S Jh. vail (77),
(30)

I PD«
PD«CC V (UO)
(pv)c - pvv • p \ c - K
\ -sr
sr*' ¥
pD«K (tl)
f ______r 1^
(pv) - o - PVV K 0 - i t — s ? - j v
v *

(ov)^ -o -**,*,„- r " " ^


* , gradient of th. individual chemical . 1 — -t the veil 1. 1 - by. e.g.. carb-

it V-V (-3)
(ft Hof^)^\
«• , »« ths wall by conduction and diffusion

(..)
w-ll-S) "'•u-c« (\ • "•)
Ser "* w

._-_, _-"_5-?- f 5-!- - -• - " " •w" "


\>
(U5)

Where for graphite la « air boundary lay.r

(U6)

iiasassisii date
1
ev
w • m • n . n
v g s r

V V1 (W)
_„ - 0.768 tc • 1

K - 0.232 *c - 1
e r

lhe fraction of solid entering t h . control volume vhich ie l o . t at the eurface as particulate
•olid ie defined from Eq. «6

P\ n. • KK
(t7)

Inspection of Eq. »5 shows that ths mass fraction of the element carbon at the v a i l ie deter-
mined solely by the s u i flux of elemental carbon injected et ths surface M vapor, reflected by the
difference in fluxes entering and leaving the control volume. Equations similar to Eq. «5 for the element
oxygen end nitrogen provide the neceesary relation, satisfying Eq. 39. A stoichiometric statement then
directly r e l a t e , the elemental s u i fractions to the chemical composition of the combustloe.subllmatlon
speciee at the ablating surface

v. H.
k-I-Ht'H <.8)


Suaarical solutions to the governing equation, vere given in (77) invoking the chemical
e q u i l i b r i a constraint. The chemical reaction eystea included eubllmaticc apeciaa for the ring and chain
molecules, end in addition air species, and carbon-air reaction product, l i s t e d below

KG co.

"2° cw
K02 C
2R2
CO

Graphite sublimation rates over a large preaaure range are ehovn in Figure 17 normalised to
the feailar diffusion-controlled oxidation rate (m^ 0.17t 0 u Io the f i r s t several decades cf
preeeure the tbreahold sublimation temperature Increase, v l t b IncreMing pressure reflecting the carbon-
vapor-pressure diegrea ehovn in Figure lb. The 101 to 10^ ata preeaure range i s of special Interest; the
threshold sublimation tempereture i s compree.ed due to sublimation of large quantitla. of polyatomic
carbon-vapor apeclee. Thua, the hlgh-preeeure subllaetlon regime of graphite occur, over a fairly narrow
eurfaee temperature range (circa 7O0O-8o0O°R) Hi ccntrwt to Scale's (52) results (7000-10000°R) which
CBlt carbon molecules larger that C > Upon definition of a surface-energy balance and the Indepth heat
conduction, sublimation rata, are directly coupled to surface tempec.tur. and pressure and the local
Mrodynamic heating.

Ecargy transfer to a eurfaee undergoining material consumption via thermocbemical erosion and
tbcmemeeoanlcal loee of eolld i s given by an energy balance, Figur. 1. The beat conducted by the solid
•way from the surface r e f l e c t , the energy fluxes leaving and entering the control VOIWM expressed in the
followingi
l H m (-9)
*conv- • S m i * «re- - "K V ' r \ ' *cond " \ "t " \ \
in out

vbere
_ • Y K, H,
v _M J J (50)
J
Ij - / Cpdt • 4Kf
The aiamatioo in Eq. 50 le ends over a l l species in the gM at the vail vith concentration,
defined by the mM.-trensfer rates end epplicatlon of the squillbrium constant. For the c u t of Le • 1 the
net heal transfer to the surface may he . x p r . s . . d M (at this time m i s act equal to sero)

-.11-- I II •
SURFACE TEMPERATURE ( R)

Figure 17. Graphits Sublimation Rat.

(51)
H 14B } H Vad - err
l
cond
I*'y »; . - < * *J in
.

* _ _, — 1 - M M - - - — " — """"' " "*


(52)

*. u. - -*- - : SMrMlM^f-^H^^«"H,.1,,

£=tt?5i_i-i?f-£«_--!S_s-

- r j s a-sraasr- *— <«>• _, _, *-*-_


5.000 6.000 7,000 9,000
4.000
SURFACE TEMPERATURE (°R>

Figure 18. Enthalpy of Combvation-Bubllmation Product, . t Ablating Crepbite 8urface

0.001
7.000 7,200 7.400 7,600 7.800
SURFACE TEMPERATURE (°R)

Figure 19. Chemical Composition at 3rapr.it. 8urfae.

_*•»_
fl
emd ev-anaeai only a ea-11 neee of carbon i s a b l a t e because of tbeee reaction ProOucte. « * _ J * t l > #
I !
_ ^ ^ S t r a t - r t ( « J o S o contribution, due to Cj to C3 occur, lacreaalng the meat fructloo of ablated
ea-aom With increased temperature larger carbon vapor species subline frcs. the eurface appearing flret
I f l t ^ l e m _ _ v S _ ^ r o T u t o l O c-rbon a t e - , and t h . n i n spmci.. having froa 11 to 20 carbon atoms.. For
S e i r ^ ^ u r T t c m d l u o n . n W , l i t t l . contribution f r o . vapor . p e c ! . , vith greater I M « N M >
_ n _ - ^ u r . r ! l _ r r a l 5 - r l y than indicated in Figure 19. i t It apparent that t h . additive .mall eonceo-
tratlona of the polyatomic carbon vapor opeclee le quite appreciable.

8.500
6.000 6.500 7.000 7.500

SURFACE TEMPERATURE ( R>

Figurm 20. Partition of Elemental MMS Fraction of Carbon vith Surface Temperature

3.».3 Baneltlvltr Analysis


The uncertainty l i m i t . established for t b . carbon-vaprr specie. M a f f e c t . mat. tramafer and

!
_SSni__S__-?S _-SS^' II
! 1
• 1

H i t _ 2 l « . « « r - , r . . . a r . .o»t,lb„tlo» of t h . kl.b _ t e « _ w - 1 * 1 ~ p o r 1 , - l u r t J . £ " " " ; £ » « „


r . . u l t / « o v l _ 5 . • « • « «f »k. t « h u . t l « - . « . b l l _ t l o » p r o . « t . « . U I - t k _ ~ , hx. - ~ > J" " « ™ »•
S T l ^ E f o f t h . . . r . . u l t . _ ! . . M . . . — k t of t h . unc.rtklot, « . u r f . . . r . c . l o . r . t . t o M '• •

_-__*. r_S3=««'-nspjtr _ ^ » ^ ^ - ^ r £ »
SSS_a_S-fc-r^^

I
-""•IT

r
' " S ^ Q . NORMALIZED SUBLIMATION RATE
_nO
ENTHALPY (BTU/LB J
1
«
§2
«2
«•.-
•A I
*,*<
B *
•P t/» cr
cz
1X3
tel -*>

matl
M
S5 > O
o
m 3 rn
n o
_>
m
r* §.
3 IS
51 _r "O
&6 m
m 73
a t* I
>• • ^
*f 1*

;rj A
c
NJtl- "~b
O TO

sr*
*•"
^ o
1*

M
tT
e
a
P

J!
H s • 10,000 BTUA.B

STAGNATION PRESSURE (ATM)

Figure 23. Thermocbemical Surface recession Fete

. ...» ...._-*_itif. . i v i t y o surface rec.esion 1" comparable


thermodynamic properties vith Msoclated uncertainty -i f
to t n e T e u r e c y for vhich local Mrodyneelc heating c_ :on. can be define .
3,5 Graphite f e h e a l c e l Erosion

S-T=S_SKJ-"-S:_^«5_SSt_-»r&ts_=j^-
ssr_*_i_i-S--'i-U-7--iru-2i=s5 _S-i__r_«...-»*— —
3.5.1 tblatlon Data
-_-r.aa_t.tlve ar-phite plaama arc ablation data «lveo in (7T) ie preeented for c c s p l a t s s i H .
Bepre.smtetiv. grspns*- ?* . m _ - 4 « - « t * i rece.elon dete are plotted agaio.t apperent
A typical blocs of * ^ ^ * £ ^ % £ £ SScS. bovn are data taJen <» the stegnetion
•tagaatloo enthalpy. Tvo . e t a of d e t . ere given as * £ » " , - , c b „ t o f a _ t a VM
pressure rang, of 83.5 to 8A.6 a t . and data gathered betveeo WjO ana i ^ ^ ^ ^
correlated (77) using a L o t .quare. curve f i t of the data PJJ-*J- f t h e _ , « . „ . . « a«.t. „.ae...
obtained f„r -onlaal atagnetioe * * * " « * «_J I J o - T l a £ g u r T n H.re experimental recession r s t .
cc_.truction of the esperimentel rece.eion ^ ^ ^ Z ^ S S T M p - » ^ P r m t t l the total picture

- M ^ M - S F S S S S S ^ S - : " -—=••="•—'

-j
• ••! HI —I I . J — H — — -
o o o o
(03S/-NI) liV_ N0ISS3D__ TVlN3WI_3dX3
03S/-NI. HIVM N0ISS333_ TV_re3WI_3dXB
3.5.1

tarn K t y to •boo. the departure fro. thtr-o.nt_l.tl rot. ion if. more meaningful terms. Fram

-B^f__^St_s^-__@_#M- i J

40 60
STAGNATION PRESSURE (ATM)

figure 26, Fr.qtIon of Hoi11 Eroded From taperlaeat-1 Det.


f
afftttt.
nrrsoisa sr
ey S ^oT
lesi ofs esolid
J ! ! fro.
tZ^lLll K-*.surface,
ths heeled * 7 ***** 1. %h9
. " * " _lotsvorthy, the *rather
• * « • §Mali
- • « "l u
- «r s temper.turs
u * 1. ( u r r .a.
..
1 U%iW9 f , o X U #r0d#a
i S T S ! f" - I - - iff * " ° ' * ' ' < « • t«sptr.t_r iot . f f ^ # e j eoH

-at. I. th. fsjs^^ a s a r . a t w a K s ;_«


be gffgjj of p r . . . u r . on surr.e. tt.pe-.ture 1. ..all at th. I 5 H . U V ? V £ ^
(olUln th. pre.sur. ran., eev.red). Thu., eaeh value of tt.gn.tloo .athalpy oan be vulee In u J i s ^ f
2-!:.! _ -f?)* ° f • t *«"- t l o n P r t "- r «« "»• ™n.al foree Mtmg on the heated aurf.cV A. the
_l_.ll r " / 4 0 ' r _ ! - ! a , i r t l , _ i i 9 f t 4 f l 0 U ' - l M m ••"""-•-•If •Sottd. Los. of binder btlov ths
heated i-rfeo< and by direct thtraviahMle.l erosion st the surfeee tondo to free the _._mm«i-- _ ! - - . I . . - . .
tad ttMVnai lattrltOtd p.rtiol... Th. larg.r filler panio^Mar. Jhin J.ther I t l 2 _ til. Jr
?«I^f. . l M r _ M , d Pr-ti-r- Mtlat to free the . . . H e r partlol.s, Also, almit. saounts bf binder
- m t l l i i ^ - - . - * " *' M h f d * t h # '***« " " • ' Petioles. A. Udloatsd In' n«_-s JTJS effeot of
# , 1 hi
Jn.^.1. J ^ l . - .
th. loss of paitloulat. solid I S _ i ? T * Int.rsetlngly. "th.
. T ' 'Ji ": * , r freotio..
pr#Mur
"-fW.olid t0
- eroded
«•»».•" • "tomE£
appear, dominate,
be sWrn-emlmeV.

_!E-_i .# J - M L ! _ ! ***•' r i B - i l * r - t b - - t l e f of ttrodynuie tns.r tad prtstur. .radiant.


typieaJ 0 f position, removed from th. stagnation point Is to indues lnereessd pertlole l o . . Tout, . . .

--A1 _____!
I 59
1

f $ , FRACTION OF SOLID ERODED

figur. 27. Influ.no. of Solid Fraction Eroded oo Surface Temperature

i s faced wltb loes of partloulate graphlt. ©v.r a rather broed rang, of aerodynamic conditions, perhaps
even extending Into the relatively moderete super-orbital . n t i y environment.

3.6 Ccnojuj tfiii-tt


A aodel lnoerporatlng the allotroplo feature, of bulk graphite has beeo postulated and used to
deseribe t b . uo-tlauou. removal of partloulate graphite from the heeted surface. Although Hypothetical in
Its formation, sufflcisct laboratory dat. are advanoed to ostabllah the c r s d i t . b l l l t y of removal of f i l l e r
partieles In the .olid state. The key role of the different form, of carbon In graphite oo nurfao. aro.loo
has bean established. Theraodyaealo propertie. of the linear end cyclic molecule. C3 to C30 were calculated
by quantum and s t a t i s t i c a l aeobanloal techniques. The resonanos energy of each molecule v u computed from
the reepeotlva electronic were function., and the correepcndlcg v i t r a t l . d frequencies vere detomlned by e
normal coordinate analysis or ths molsoular structure. The theoretical procedures are . e l f - c o o . i e t . n t ,
resort to the empirical Increment, adopted by Pltsor and Clenentl and us.d by oth.rs nas been avoided. The
egreemeat of the oalculatsd vspor pressure vith the triple-point and subllaation data le excellent. By
purely analytical means, the uncertainty In the free energy of formation he. ..en established; the effect
on oelouleted tbemoohealoal our face recession vat found to be s a a l l . Significantly, this result hM en-
eblod Identification of the solid fraction of graphite eroded in hlgh-preesure ground teste vith confidence.

To establish the solid fraction of particulate graphite eroded ablation ''.ate encompassing
fin. to e o e r s . g r . l * graphlt•• h.ve be.n corral at ad. The l o s s of mat«rlei in tbe solid stats b u been
determined over e range of environmental conditions (in tern, of stagnation pressure snd enthalpy)
evidencing lerge fraction, of solid removal. u » . of particulate solid initiates at rather lov stagnation
pr.s.ur.s ; the actual threshold is dependent on heetlng rate a. veil M procure. Th. n . e h a n l n . by
vhloh lose of partioulat. graphite occurs eppeere to be by preferential eurfece receeslon end subsurface
loss of binder matrix. Filler particles are then e e s l l y dislodged from tbe surface by even moderate
f o r c e ( 1 . . . , pressure, ehe.r). Surprisingly, the loss of solid at the heated aurfac. doea not appreciably
depress surfao. temperature., even for r.ther large fraction, of solid loss.

Tbe reeults preeeeted le this revlev (77) open several Interesting avenues for pursuit.
Clearly, the role of graphite alerostruotur. In dictating aurfac. .roslon oannot be dismissed. Closely
related to the nlerostrueture of ti.e binder and f i l l e r phase, are the thermophyslcal, mechanical, and
ebenleal properties which individually, cr in combination, affect ablation performance. Future analyses
employing s t . t l s t l o a l distributions of particle s i t s , void s i t . and spacing, and account!ng for the
teapereture-tlM course of the c r y s t a l l i t e grovth v l l l be necessary before e completely analytical per-
formanoe description of graphite can b. achieved. Finally, nev grephltee overcoming the evident dla.lmila.-
obaracterl.tle. of the constltuant materials appear to afford a means of rsduclng or ellevistlng
preferential erosion, hence, loss of solid material.
a

_ . -Mil — as J
bo

fc.O KATETUAW BBUVIOP. AID TESTTgO

The lnportancs of mat.rlal. characterisation in t h . .tudy of ablation phenomena cannot be over


empbulsed. since aoet application, require specialised a e t e r i a l e end . i n c . sach environment interects
d l f f t r e a t l y vith tbe ablator, l t nay be .aid that .ach ablation theory 1. fath.red by development of en
T r T _ . * b I ' t ° r * X t ** d , , l r - b l e t 0 revlev factore vblch affect the sblatlon perfomancs of material
sen . I t i n ty of ablation to variou. material and environment parameters and mesas of ablation t c t l n g .

The material c l c s e s of lLtere.t a r . :

1> Refractories and ceramics

2. PlMtice

3. ElMtomere

*». Composites.

Energy of decomposition, s u i trenefer blocking of convectiv. nesting, thermal diffusivity


and eurfece E l a t i o n tempereture ere some of the ablation parameter. Influencing the ablative material'
s e l e c t i o n . Table 3 summarise, application of ablative materials and the general importance of M i c t i o n
C lt
* !a!'*.' T h " , u r f - c * " l a t l o n tempcr&cures are Indicated to be high, moderate, or lov as c h a r c t e r l s t l c
of o f f i i i c t ablative materials for the application. The heating expoeure time strongly influence,
insuletive requirements.

The folloving paragraphs identify the s e n s i t i v i t y of ablation par. s t e r . to materiel properties


•nvlronmental e f f e c t e , and thensoetructural con.ideretlon..
».l Met.rlel Property Effect.

Material propertlee bev. a broad influence on ma., .blatlon (and aurface receeelon) and on
theme- ineuletlve efficiency. The therms: ineuletion requirements are defined by the temperature vhich
the structure end heat ehleld bend are capable of withstanding. Total veight requirements result from
the anticipated aeee lose and insulation demand.

The s u i ablation comparisons in Figure 28 shov t h e t , although a cmrbonMcoue material lo


more susceptible to oxidation, total mass l o s s 1 . greater for the s i l i c e materials. The major reason Is
that surface eblation temperatures are greater for carbons, thus increasing surface raradiation and
reducing the convactlve nesting - also r - 0.9 for eerbon base materials and c - 0.5 for . i l i c a D M .
aateriale. " >
TABLE
-1 1
ABLATIVE MATERIAL APPUCATIOl- AID 8ELBCTIOI CRITERIA

Heating
Exposure Weight Per Has. Thermal Surface
Time Unit SvirfMe Ablation Ineulatlve Ablation Surfac.
Application (Second.) Arc note Properties Temperature Receseioo

1. iligh-Performance 15 to -0
Conloal Rooatry
Vehicle.
(v/c_A > 1500
r
per):
e. So.ecap Unimportant Leoe Unimportant High Important
La port ant
b. Conical Important Important High Lea
Section Important Important
o. Aft Cover Important Important Lov to Unimportant
Unimportant Moderate

2. Lov-Bellletlc 20 to 100
Coeffiolent
Reentry Vehicle.
(-/c_A < 1500
r
pef):
Leee Important Leas High Important
a. Bo.ecap Important Important
Important Important Moderate Unimportant
b. Other Region. Important to High
Important UnlsrDortant Lov Unimportant
e. Aft Cover Important
3. Lov to Inter- 10 to 50
mediate Range
Ballistic
M1..11..
Less Important Use Moderate Lena
a. Bo.ecap Important Important to High Important
Important Important Important Lov to Unimportant
b. Oto.r Region. Moderate
Important Unimportant Important Lov Unimportant
c. Aft Cover
.. Lifting, 300 to Important Unimportant Important Moderate important
S a t e l l i t e and 2000
Planetary Entry
5. Launch and 5 to 200 Important Unimportant Important Lov Unimportant
Booster
Insulation

o. Rocket flotzles 1 to 100


a. Throat Less Unimportant Less High Important
Important Import ant
b. Other Regloos I-portant Leee Important High Lett
Important Important

Hypersonic Inter- 5 to 100


ceptor Hieelles
a. losecap and Unimportant Less uesa High Important
Control Fin Important Important
Lending Edges
b. Control Fins Important Important Important Moderete Unimportant
Forvard 8ur- to High
fac. Region.
c. Otb.r R.gion. Important Less Important Lov to Unimportant
Important Moderate

1 l-lll I f l - H i iSSiai • Ss
n bt

OS 1

SILICA . M I N O t P C

o_ -

C.2

CARSON PHaNOLiC

10 » 30 .0
TIME t ROM 300. 0O0 f f E T ALTlTJOC ISEO

Con-ipiriion of Mam Ablation Rates Bstwen Sitics Phenolic snd Carbon Phsnolic

Figure 28

K M . ablation rate, are enhanced by liquid flov ablation, apallation of the char layer, and
mechanical removal of the char layer. S i l i c a baae materlale are eusceptlble to liquid flov surface
reeeeslon. Movever, l t l e only important for noeecep application, and other reglone subjected to signi-
ficant pressure aad shear gradient.. A detrimental characteristic of many charring ablators i s lov-char
strength. The application of eblatlve material., .uch as the epoxlee end elaetomerics. Is consequently
restricted to lov-.hsar end l o v - p r e c u r e region, or to v e h i c l e , subjected to l e s s . . v e r s heating environ-
ments. Shear or spallation of the char is also an important consideration to high .tr*ngth charring
abletore.

Mce ablation may not be c r i t i c a l for .om. applications. Ablative material selection le
strongly sensitive to material properties vhich Influence thermal ineulatlve performance. A numerical
description of tbe traneleet beat conduction relationship indicates tbe a e n . i t l v i t y to material properties
with tbe dominant material property being the thermal conductivity . l a c e tbe epeelfic heats for most
ablative materlale bev. nearly identical value..

Heat ooadueted into the ebletlve material 1. abeorbed by pyroly.l. decomposition and by the
mass transfer toward t h . surface. Tb. o.crsassd density due to internal pyrolysis r.sults in t h . thermal
conductivity shifting from lov-uadcomposed material values to higher values for the char. An example of
the Influence of higb-ebmr thermal conductivity on phenolic-nylon ablation le ehovn In Figure 29. Tbe
thermal conductivity data are from (117). Although surface recession is lov, the buildup of the char
thlckaees near the end of flight i s about 0.5 inch. The char density Is about 0.30 time, ths original
density of 72 l b / f t 3 ; conssquently, internal s i n trenefar remove s elgnificant fraction of best con-
ducted in et tbe surface.

uaaata. U
n •3

so so
TIME FROM 4OO.0OU F££T !S£C

Figure 29. Surface-F.eceesion, Pyrolyele-Depth, and Surfce-Tempereture


Historia. for Phenolic Rylon Abletlon

.•en i* e ^ - _ ^ _ ! _ ! ! s ^ ' ' - - T ? . ^ o f • b l » t l o n - * t e r i e l s i s a strong function of thermal conductivity


M eeen in the above example and (118). The thermal conductivities of severs/ .M.t<„„ „ • . ,
presented in figure 23 M function, of tempereture. The ^ . ^ ^ • ^ a i . ^ ^ S j ' S l S ' i l l T )
i s compare vith aa unpubll.hed correlation derived vith a charring ablator computer p r o g r a m \ _ 2 K _ i
C 1 M . « S ' I n - S l v l T J - T t * 1 * i , U t l O D ***•• T b e ** - h o V n i 0 F l g u " 3 0 « '.preeenTSlve of different
aa"rl^e b f Jntilll^ " £ £ S f a _ * « r-prtttnt. t h . refractory c t e l . . . graphite, r . p r c . n t . C I M . of
materials by tbameelv... boron nitride le a representative refractory ceramic, carbon phenolic le a hiah-
P ^ e ' o w ' S S D - s ' I . ' r ^ C ° T P ° B l t ! ' ^ P h e o o l i c *** - • r a p r e . o n t . t i v . of the pimatic composite
Purple blend MOD-5 Is one of a class of materlale apeciflcelly tailored t o provide lov-thermal conductivity
Hydrogen gaa and air thermal conductivities are ehovn for comparison purposes. conductivity.

B__.1V i m ! _ . a p p l l c - c l o n » requiring «°°<1 l c u l e t i v e properties COupled to long heating exposure time,


namely l i f t i n g reentry v e h i c l e s , ablative plastic Or elMtomerlc composites have been developed vith the
( b ? _ e * ^ m « _ 2 ! <!? S *T T r , 1 ' y < l " " 1 -1 t i v «B «l e *c 1- Wr -Vt i# vl gt h tperformance: (a) .urface oxidation r e . l . t a n c e ,
for cnar . ^ . n i h L J ^ ^ K ? J i? °r ° - - *-*•*»»*• Products, ( . ) fiber reinforcement
for char strength, and (f) spherical void.. Example, of the.e - e t e r i a l s are purple blend MOD-5 and
phenolic cork.

. P y r > J y , 1 ' . d e C ° ^ > 0 " l t l 0 D Predicted -»* n « the Arrhenius rate equation h e limited e f f e c t , oo
eecul• 8 0 0 " Jo S o £ J " P r ° V l d e < 1 " • d e c o ^ , l t - l o D temperature i . adequately duplicated, i . e . . f r o .

For material, vhich form thick char, evidence of "cracking" of gseeous hydrocarbons hat been
llT.til T J f b M r 3 e d ) D « « - - e . in densities of chars near the ablating .urface. The effect on the
ablative material char is to l n c r e c e i t s atreogth and at the same tine to lncreeae the char thermal
conductivity. Cbar layer apellation can reault from depoeitlon cau.lng d e c r e e . . . In char permeability
and increase. In Internal procure. -— *a*y

••- Environmental Effects

Ae indicated above, ablation performance le aenaltive to environmental effecte. An l n c r e c e


in the convectlve heetlng rate u.ually increa.e. ablation r a t . . . Hovev.r, If there i . , e . g . , . proportion-
ate l n c r . e e In reradlative e f f e c t a , the IncreMe v i l l not materialite. An example of t h l . effect i . an
Increa.e In heating caueed by higher enthalpy. Buch change. In beating i n c r e c e the ablation efficiency
of the materials (118). and therefore do not IncreMe ablation rat*, observed.

One effect of boundary layer enthalpy potential on eolation efficiency Is In combustion


rsactlons, vhich can be accounted for (119) by

K h
oe c
II -h ) (>3)
r env.v
In tbe folloving relationship

V < X * V -4.
(ov)
v' nd • fja -h rr_x (5U
c
r env.v
_ _ _

ua

AIR 10 1 ATMl

T£M*€BATUR€ I103 °RI

Figure 3C. Comparison, of Thsrmal Conductivitlea

vhere
C C
. . «.
_E

h
e " -*-t i o combustion per unit mass of oxygen

K
0# * • * • • fraction of oxygen at the outer edge of the boundary layer

The tern 5^ gives an upper bound on the effect of combustion by assuming the all oxygen
diffusing tovard the surface reacts vith the material vapor. For s i l i c a base materials this Is not true
and in a rocket n e t t l e environmental oxygen may be fixed as carbon monoxide.

In Eq (53) the ca.bu.tion contribution ( * _ / _ ) to heating end to the naea tranefer blocking la
lnd.p.nnent of the boundary layer enthelpy potential. Consequently, combustion heating reactiona arc
proportionately lees important for high enthalpy potertlal heating environments that reentry vehicles
experience over major portion, of their flight. The variation In material efflclei.cy that results vith
an lncreeeed enthalpy Is sbovn in (lift).

Environmental pressure and .hear force, strongly influence ablation perfomanre for reentry
vehicle, and to a L a t e r extent for t h r o . t . of rocket n o t t l e . . The charring ablatore are recognised to
have char etrengtb. con.ld.rably lover than the atrength of the undecompoMd materlala. Con.eouently, those
materials vhich form veak chars are restricted to application in lov pressure and shear environments.
5
-Mme-ma-s Jaas-ks
i
a.. Testing

Ablation t . e t l o g Is the aether by which the analytical models are verified, many material
propertlee are determined, and CMdidate beet ehield materials are s e r e n e d and selected. Because of the
importance of testing in providing preflight design verification and confidence, l t le obviously desirable
to perform these teets iu an accurately .imuJated If not duplicated flight environment. For many reasons
(primarily f a c i l i t y ©over requirements end model s l s e limitation.) t h i . 1. usually impossible and t . . t .
must be run under serersl types of partial flight simulation. These reeulte can then be evaluated by
meana of previously proven mathematical ablation models, or by overlapping the tests in such a vay that a
coherent composite picture of the important phenomena can be constructed (12).

Ballietic and l i f t i n g entry vehicles, designed for various mleelons, experience a vide ranee
of entry environment.. Tvo convenient parameter, for illustrating these environments. vhich depend on
flight performance rather then on geometry, are t o t a l enthalpy and stagnation point preaaure. Figure 31
ie a plot of pressure-enthalpy vith overlays of typical entry-vehicle trajectories and mapa of approximate
emulation f a c i l i t y performance. Tvo important concluaiona may be immediately reached:

1. ho one f a c i l i t y can duplicate . complete flight environment, although large portions of


some lifting-body trajectorlee can be closely approximated.

2. High pressure and high-enthalpy effecte cannot be duplicated simultaneously.

NASA I A H 6 S I I INCH PLANETARY SMW

GENERAL ELECTRIC
SMWAflC
TUNfcF'

ROCKFTMDTOP

WAVE S U P E R H E A T E R

AEDC
SMUV

ORBITAL RETURN H I F T l N G R/VI

10 10
I
STAGNATION PRESSURE IATMQSPHERESI

Figure 31- Comparison of Flight and Ablation Test Facility Performance Parameter.

For simulation, steady etate ablation i s usually de.lred since t h i s condition provides tbe
necessary material parameters, evaluation for the analytical models. For this reeson the f a c i l i t i e s most
applicable to entry ebletion studies are the pla.oa-arc tunnel and the rocket-motor exhaust, both of vhieb
have operating times renglng from .everal aecooU. to several mleutea. F a c i l i t i e s such as the b a l l i s t i c
range and shock tube are of only slight interest because of their very short test times — approximately
10 mllilaeconds and 100 microseconds, respectively.

Because of simulation d i f f i c u l t i e s , test conditions must be carefully selected to obtain \


meaningful resulta. Plaema-erc f a c i l i t i e a can frequently provide adequate aimulation up to entry velocities
of 30,000 ft/sec. The Important simulation p_raaetera for moat ablation performance and .creenlu. te«»a
are the heat flux MO tbe enthalpy (121).

Efficient performance of the glaeay ablator, depends on the retention of the l l i u l d melt layer
so ths Mrodynamic .hear l e v e l , of flight should also be duplicated, If p o . . l b l e . The eblation performance 1 1
of charring abletors i s knovn to be reduced under very high pressure, or preeaure-gradlente vhlcb tend to
mechanically remove the char layer. For flight vehicles vhich v i l l experience unusually high local i
pressures, such as lov-drsg b a l l i s t i c entry vehicles, l t may be necessary to simulate the pressure and
sheer levels M veil M the beat flu* and enthalpy. He.ever, .Inc. thle amount, to full scale flight
duplication, theae conditiona must be simulated In separate t e s t s and arpliea vith ouch caution tc the
1
flight environments. #

I
J
be

At the very high entry velocltloo which v i l l be experienced in Interplanetary return missions,
IJ t'

tbe radiant bontlng from tbe shock-heated air can be equal to or significantly greater than the eoovectlve
heating r a t e , r i t e s the efficiency of meet eblatlve materlale depend, on the beet blockage effect of the
transpiring | u u eblcb trill have l i t t l e or no effect on the radiant heating, ablation performance v i l l be
reduced. Some p l a t e - a r c f a c i l i t i e s are available (122) vhicb can superimpose radiant heating on tbe
eonveetlve b e t i n g , and t h e e must be employed for perfomv.cs evaluation of s a t . r i a l s t o be used l e t h i s
type of environment

Because of the d i f f l e u l t i e a experienced In simulation of flight conditions in plasm, arc


f w l l l t l e e and varlatione in supposedly similar t e e t conditions from f a c i l i t y to f a c i l i t y , several "round
robin" test program. (123, 12a, .?«,, 126) vere conducted to compere tbe f a c i l i t i e s end ailov for a more
meaningful comperieoD of t e s t r e s u l t . . Also, several comparative material performance t e s t s (126, 127)
for son. material, vere conducted In a "round robin" f c o l o n . As a result, better comparisons are
available. Characteristics of various f a c i l i t i e s are a l . o given in tbe above reference., as v e i l as in
(12o, 189), and v i l l not be tabulated again In t h i s review. Due to the periodic changes In existing
f a c i l i t i e s range of performance, emergence of nev f a c i l i t i e s , and difficulty ie obtaining up-to-date
performance data, such tabulations do not retain permanent value.
.7

1. Hurvica. i . , a t . a l . , •*_•«__! Proteotion System.," ML.T_R-6Ua8, Air Force Materials laboratory,


Jan* 19o5.

2. Kmeoa, t. S. mad R. J. Bplndler, "Tren.lent Thermal Behavior of Decempoclng M e t . r i a l . , Part l i


Owerel T_eory and Applieatloa t o Conveotive Boating," IA8 Paper go. 62-30, prettnted »t t h . 30th IAS
»aeu_l Meting, lav . o r * , Jan. 1962.

3. C r a t c h , E. M., L. F. tearae, and R. R. McCbeeaey, "Thermal Ferfor_ence of Hoot Shield Composite.


During Planetary Entry," presented at t b . AIAA-RASA Rational Meting, Palo A l t o , C a l i f . , Sept. 30 .
Oct. a, 1963.

e. Arne, C. L . , "Ablative Material. Subject to Combustion and Thermal Radiation Phano-ona," touglag
Paper l o . 1851, Jan. 196b.

5. Emndall, R. N . , R. A. Rindal, and E. P. B a r t l e t t , "A Multicomponent Boundary Layer Chemically Coupled


t o an Ablating Surface," AIM Journal, Vol. 5, So. 10, J I B . 1967, pp. 1063-1071.
6. Adsmm, M. C , "Recent Advance. In Ablation," J . Am. Hoenet 80c. Vol. 29, i o . 9 , 1959, pp. 625-632,

7. Steg, L., "Material, for Re-entry Heat Protection of S a t e l l i t e . , " J, Am. Pock.. Soc. Vol. 30,
Sept. I960, p. 815.

8. Hurries, H., "Aerothermoehemietry 8tudlee in Abletian," printed from Combustion and Propulsion,
(5th AQARDogreph Colloquium) Pergemon Press, I963, pp. b03-*55.

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16. Sherman, M. M., "Entry GMdymaaic Hooting," RASA SP 8XX, t o be pubUsbed.

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__-_•
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56. Feldmann, 8 . , "OB tbe Inetnbility Theory of tbe Soft Melted Surface on an Ablating Body vhen
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71.
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79. Denme, C. L. and M. L. Mlngee, "High Pressure Ablation of Pla.tlc Compoelte. and Craphltee In the
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81. MoCeuley, W. D., A. R. Seydah, e d J. F. Buetae, " E f f e t of Spherical Roughness on Hyperselc


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89.
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90. C a r r e . R. J . . "Effect of Mach Humber up tu 7-» on Boundary-Uyer T r a r e l t i e in t e Presence of


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91- B e r t r e . M. H., L. M. W.lnstein, e d A. M. Csry. J r . , "Effect of Tvo-Dlmcnelonel Multlple-Vaye


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95. Akin, C. M. e d J. 0. Marvin, "Anomeloue Convective Stagnation Point Heat T r e s f e r at High Pressure.'
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129 Rlndal, B. A., "An Bv.lu.tlon of Deign An.ly.l. T.shnloue E t ^ a ! ; 2 _ r 8 ^ S 5 1 l t J l > U l i

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