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Ablation
MAR 1972
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AGARD-AG-161
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
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:
- 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.
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
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.
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
f
I
r '1
Activation energy used in Arrhenlu,' rate expression for ths
representative solid phase resin component o
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
ss riS-_.ii
r
J Variable la the "glowing" expression
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
flu
f \ **•• * of ablation gas products, includee both sV , and _ . ,
M
\ l e»r; molecular veight of boundary lays- species
M M
jnj «»r. nole<.«_,_r .eight of Injected species
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
Local pressure
Local partial pressure of coking char material
Generalized presaure
Time
t Binder bridge thickness
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
t Foroaity
V viscosity
i Parameter defined by Eq 39
J
li Instantaneous condensed phase density of the representative solid
phase reein component of the model ablator
.J
_s> usmss
0 Stefen-Bclttmann constant
T Aerodynamic shear . t r e . . m
V
Subscripts
b Binder •
k
tg " Denotes ablator p y r o l y s i s can s p e c i e . 9
rp Pyrolyala product fl
th Thensochemical
V Pore volume H
L I
i J
1
1.0 LITRODUCTIOB
:_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
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
F t t rt.er vork in - — - J - ^ U S r S - S l ^ ^d
sira .uxncrntiorT^^^ — - - -"*—
2.0 ABUT!OB ANALYSES
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\
a • a • m •m ii)
vith
• - *s
13)
p u C
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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 .
%/Alcv - t v 1 *x M m * Shorn! t . l H
v*. *b looking (3)
vhere
tfld
(6:
Wing' V \ •%"(Vr'ur,J
vb.rs
(7
with
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,.„,
. _ _ « _ ~ £ - _ _ 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 .
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
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 . .
"' 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
Lnthelpy of decomposition, _H , and enthalpy of u.posttlon, &H , are f(P .T). Typically, an
exampl. decomposition reaction might be i 3 , ii) •
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
3 2 J - e 2(J -V (16)
h2
3J
(17)
3y"" a
J • .yV (18)
and
l-R
(20)
V^'-.I-R o
Vr-ed
and
2.5 Mechanical R
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)
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 ) .
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 .
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.
(MO X
si e. rt 21 ii oi s » z s 9 » c 2 i o
\^
^v
- 4 J O f Si
1 IUO.H.
i-esTM
juoocosr
V
/;
l^ ^
a
3
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.
I i
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.
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.
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
MICROPORES
MACROPORE
2^.2..?,
listM
SWJ A A I-
fiiijl!
— • mS .•it lf««5«E
*-* fa.' *->
»- 5. & _ 5 £.
'Ssiss
•t •tr
£_-.
1 • B o g «—»-
ff
.* 2 ** • i «-
B ~» < - o o r»
•- »• •- * .• •» vi . - „ < £
6
• - o 3 o • t-
n • _ i »~ t-> - * •»
I | 5 € So.
** P V 0
3°s2 5 r |
- . - 5 § <• 6
»- ft r r e>
8 m cr si r* £*5 D _f s
8 CB-e3
• » . - e • ••
•e •>
. • jx
»> »- •P 5.
5 tr•
3 *• 2 *» *t . M r . - ,
o aa
r r t* •- . i»
• tr o M o . ~
• •> er B • _
•» • O «- M fsfMl — » £»
x _ c • _• 1
3 • *- D »-
l_^-3 ir«_
! e.
_ fi * _
O «• * < 7 \ M <f »-
_Z51
g n
^ •
1 5 or ^ i • "p
°-g
?g.
_ • -* 1 a »-
JE IE •l n n
o<? S & : U
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.
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
1.6
137 Ln
193
< _ 132
1.4
• 87
47
1.2
o •
53
69 6 &T«
1 80 36 <>20
• 40 7115
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
t th
into t h . _ e c _ ^ _ s ^ J ^ u c ! ^ ' r ^ - n n i . * £ _ - £ * "S ~M,h H d
°*' not
»*«« "> *****
P r
^tAcUrtBUi0B ef
coupl-d S
o
f S J l s l S ; S S S i i n n _ / £ _ J-!- T » • • " • » * • - constituent.,
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.
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
4 0 B 10 12
•ARTICLI D I A M I T I - (MICRONS)
'/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
(.-«)
tad
!»v)
4 /
P„
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.
(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)
8
X
h
UJ
cc
0)
z
<
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 (%)
BINOER
i L-
6 8 10 12 14 16
VOLUME FRACTION OF PORES - V l%)
3.3.5 S m . r _ l . t l c gffeet.
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,
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
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
(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 *
it V-V (-3)
(ft Hof^)^\
«• , »« ths wall by conduction and diffusion
(..)
w-ll-S) "'•u-c« (\ • "•)
Ser "* w
(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)
(51)
H 14B } H Vad - err
l
cond
I*'y »; . - < * *J in
.
*. u. - -*- - : SMrMlM^f-^H^^«"H,.1,,
£=tt?5i_i-i?f-£«_--!S_s-
0.001
7.000 7,200 7.400 7,600 7.800
SURFACE TEMPERATURE (°R)
_*•»_
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
Figurm 20. Partition of Elemental MMS Fraction of Carbon vith Surface Temperature
!
_SSni__S__-?S _-SS^' II
! 1
• 1
_-__*. 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
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)
--A1 _____!
I 59
1
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.
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
2. PlMtice
3. ElMtomere
*». Composites.
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.
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
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
. 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
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
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:
GENERAL ELECTRIC
SMWAflC
TUNfcF'
ROCKFTMDTOP
WAVE S U P E R H E A T E R
AEDC
SMUV
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.
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
e. Arne, C. L . , "Ablative Material. Subject to Combustion and Thermal Radiation Phano-ona," touglag
Paper l o . 1851, Jan. 196b.
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.
10. Schmidt, D. Le, "Ablation," Chapter 1 3 , Engineering De.lgr for P l M t l e e , edited by Eric B u r ,
Rstanold Publishing Corp., 196*.
11. Hinges, M. La, "Ablation Phenomenology • A Reriev," High Temperatures-High Pressures Journal.
Vol. 1 , i o . 6 , 1969.
12. Cordero, J . , F. V. Diode r i c h , and H. a u r e i c i , "Aerothermodynamic Te.t Techniques for Re-fintry
Structure, end Materials," Aerospace Bngineering, Vol ?2, No. 1, Jan. 1963, pp. 166-I9I.
13. Hunrics, H. end J. E. Rogco, "Ablation," Section l o , .0 be publiehod in the Handbook of heat Trenefer,
edited by W. M. Rooenhov end J . P. H a r t c t t , McGrav Hill Book Company (in p r e s s ) .
la. Hurvics, H. sad J . B. Rogan, "High Temperature Thermal Protection Systems," Section 19, to be publlehed
io the Handbook of Heat Transfer, edited by W. M. Rcenhov end J. P. Karta.tt, McOrav H i l l Book
Company (In press).
15. Dorranee, V. H., "viscous Hypersonic Flov," McOrev Hill Book Ccmpeny, 1962.
17. Schmidt, D. L . , "Ablative Polymere for Hypareonlc Atmoepberic Flight," AFML-TP S6-78, Air Force Materials
Laboratory, May 1966.
10. Acbard, H. T . , -Fundamental Reletlonshlps for Abletion end Hyperthermal Heet Trenefer, AFFDL-TR-66-25.
April 1966.
19. Muaaon, T. R., R. g. KM c o l e , J. D. Br<*m, R. J . Spindler, end J. Mugermen, "An Advanced Analytical
Program for ttarring Ablators - Final '.Import Vol_» I , " AVCO Space Systems Dirieloo Report AVBSD-
01T2-67-RR.
20. E a U i - c , C. J . , G. E. C M t l s , and J. S. Hlgglne, "Ablation rlandhook-tntry Material. Data and Deelgm."
AFML 66-262, Air F o r e Kateriele Lnberetcry, Rov. 19C6.
23. Broen, J . D., and F. A. Shukie, "An Approximate Method Tor Desist of Thermal Protection Systems,"
presented at the IA£ 30th Annual Meeting, l e v York, S.Y., Jen. 1962.
2*. Hid__go, H. f "Abletian of C l e s y Meterial Aro\md Blxut Bodies of Revolution," ARS Journal, Vol. 30,
Sept. i960, p. 806.
25. L e e , L., "Convective Heat Transfer with K M . Addition and Chemical Reactlurs," printed from
Combustion rod Propulsion (3rd AC^RDogreph Colloquium), Perganon Press, H e l o r * , 1958.
26. Hillberg, La H., "The Convectiv- Heet ng and Abletlon Program (CHAP)," Boeing Report Bo. D2-3S-02-1.
Kay 31, 1966.
-8
27. Mathlau, R. D . , "Mschanioal Spallation of Charring Ablatcrt la _rp.rth.rmel Earl ta," AIAA
Journal, Sept. 196-.
26. rieddermann, R. Q. and H. Hurvlea, "Aaalyalt of Trans l e t An l e t Ion end Heat Conduct ion Fhenomene
at a Vaporising Surface," Chemical a _ g l n e r l _ t Symposium Series, Vol. 57, Ro. 38, P. 21 aloe AVCO
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