1.

INTRODUCTION

Ablative materials are used to protect vehicles from atmospheric reentry, to

protect rocket nozzles and ship hulls from propellant gas erosion, as protection from
laser beams, and to protect land-based structures from high heat environments.
Ablative heatshield materials protect a vehicle from excessive heating, and can also act
as a structural component. Thermophysically, ablation involves the elimination of
thermal energy by sacrifice of surface material. Some principles of this heat and mass
transfer process are melting, conduction and storage of heat in the material substrate,
absorption of heat by gases, and exothermic and endothermic chemical reactions. The
three groups of ablative materials are subliming or melting ablators, charring ablators,
and intumescent ablators. Subliming ablators, eg, Teflon, carbon and composites, act
as heat sinks until the surface reaches the sublimation or melting temperature, then
removing heat from the insulation material. In the charring ablator, the surface
material acts as a heat sink, up to the reaction temperature, where endothermic forms.
Intumescent ablators form a foam like region on exposure to heat, resulting in
improved insulation performance.

2. HISTORY OF ABLATOR

The first known ablative materials were meteorites. These thermally degraded bodies
coming to us from space were indeed a subject of great curiosity, since they had a
demonstrated in principle the utility of aerodynamic ablation for a thermal protection
of atmospheric entry object. Perhaps in these bodies were hidden the secretes to
successful re-entry of man-made vehicles. The search was thus initiated to discover
their composition and construction. The information obtained was interesting, but it
provided few usable clues. Furthermore, it was an apparent that the stony and iron
meteoritic materials were not suitable for application to man-made thermal protection
systems. Hence the search for workable ablative material was continued.
Man-made ablative materials were discovered only a decade ago. Various technique
were being explored to protect and insulate structural metals while exposed to a hot
rocket exhaust. Certain reinforced plastics and ceramics were seen to exhibit
remarkable durability during short time hyper thermal exposure. In addition, the high
temperature of the environment was restricted to the surface region of the ablative
material. These thermal barrier materials apparently and great potential for solving the
high temperature problems associated with re-entry heating and rocket propulsion
system. In the next several years, thousands of different material compositions and
construction were characterised and evaluated on a trial and error basis. The high
temperature facilities used were various combustion torches, small rocket motors, arc
plasma jets, pebble bed heaters, arc imaging furnaces and others. Environmental
simulation was often impossible to obtain these facilities, but there use permitted the
generation of the test condition in which much useful materials information was
obtained. Composite construction was most versatile, since unique properties of
individual components were incorporated into a single material system.

3. ABLATIVE MATERIALS
AEROFAST is a typical research and development project funded by
European Union, which aims at preparing a demonstration mission for aerocapture at
Mars, as well as increasing the TRL of Aerocapture technology, in order to prepare for
future missions such as Mars Sample Return (first potential mission to use the
aerocapture technology).
The aerocapture is a new technology for Solar System exploration that uses a single
pass through a planetary atmosphere to decelerate the spacecraft and achieve a targeted
orbit. Such manoeuvre saves a significant amount of mass with regard to a more
conventional technique of insertion using propelled braking.
Because of the high heat flux, aerocapture requires a thermal protection system to
shield the spacecraft from aerodynamic heating, as well as the use of a guidance
system to assure that the spacecraft leaves the planetary atmosphere on the correct
trajectory. This has inferred the key objectives for the whole project, among which the
development and modelling of an innovative TPS material.
Relying on demonstrated performance of Astrium Norcoat-Liege for atmospheric entry
probes, it has been chosen to develop advanced cork-based composites within this
study. This is undertaken by Amorim, leader in the cork industry, and supplier among
others of the P45 and P50 aerospace thermal protections.
After reminding the main considered requirements, the general rationale and the
selection process of the different formulations, the proposed paper will present the
achievements of this development.
The material must be able to withstand the severe front shield aerothermal
environment. Numerous formulations have been investigated using a parametric
combination of cork granule size, resin type/ratio, reinforcement fraction, fillers and
the mixing and agglomeration processes. A basic (thermo-mechanical) characterization
and qualitative analysis allowed for a first selection of the 4 most promising
candidates. Thesecandidates have been tested in the inductive plasma facility

(COMETE) of Astrium, for an aerothermal environment similar to the AEROFAST

mission.
In parallel, a 3D ablation and charring material model has been implemented
in the finite element program SAMCEF, and successfully validated during the
AEROFAST project. The numerical model consists of three sets of equations, namely
the transient heat balance equation, the steady state mass balance equation and the
charring equations. For the charring of the material we use a multi-species Arrhenius
model with the species densities as degrees of freedom. The ablation is modelled by a
surface imposed and temperature dependent ablation speed, followed by an in volume
mesh deformation. On the basis of these preliminary experiments, additional efforts
were also devoted to the modelling of the thermal, swelling and ablative behaviour of
the selected cork based material (developed within this project).
It was stated a few years ago that no existing European ablator was suitable for
sustaining the very high heat fluxes while coping with the stringent mass
requirements. As this component is clearly an enabling technology for the considered
mission, Astrium then initiated the development of the low density ablator named
ASTERM.
ASTERM concept is based on a low density carbon phenolic composite,
which was shown to be a quite effective solution by the US PICA. Beyond its
primary use for Sample Return missions, such a solution can indeed be used for
various applications: ISS return (ARV), Mars (cf MSL) and eventually Venus
exploration.
The Astrium ST R&T effort enabled elaborating and validating the
development process, as well as anticipating the exploration of various versions.
Quite mature solutions were thereforeproposed for evaluation within the ESA TRP
DEAM study (Development of European Ablative Materials) conducted in parallel.
Relying on the promising test results obtained from the above-mentioned
activities, ASTERM was then selected by ESA for the delta development starting
within the DEAM2 activity.

In order to be ready for subsequent mission development phases, a TRL

(Technology Readiness Level) of 6 is the current target for 2014. The associated tasks
are obviously not limited to material elaboration, and they include the following
aspects:
Manufacturing trials to consolidate fabrication approach and process

Elementary characterisation

Validation of the behaviour under aerothermodynamics conditions representative

of the atmospheric entry of the envisioned future vehicles.

Elaboration of a thermal and ablation model

The success of an asteroid sample return mission such as MarcoPolo-R or

Mars Sample Return (MSR) mission heavily relies on availability of a light European
heat shield technology able to withstand the very high energy Earth re-entry
conditions of the Earth Return Capsule (ERC), resulting typically in peak heat fluxes
in the order of 8-20 MW/m2.
World wide experience for space exploration and high heat flux entry is very
limited, and all missions to date have selected tape-wrapped carbon-phenolic
composite Thermal Protection System (TPS) with density in the range of (1.3 - 1.4)
supported by a cold structure. These missions are Pioneer-Venus (PV) and Galileo
entry probes from NASA, and Hayabusa entry probe from JAXA.

Its selection is due in particular to the fact that:

All of sample return mission with high energy ERC entry vehicles require a
robust heat shield TPS, in particular for "category 5 restricted return" such as for
MSR, with very challenging reliability requirement for the re-entry capsule.

Carbon phenolic composites of density in the 1.3-1.4 exhibit highest heat resistance
and lowest conductivity, guarantee of the lowest ablation (authorizing less TPS
thickness - i.e. minimum weight - and minimum aero-shape changing - i.e. better
aerodynamic control). Denser material are furthermore more robust with regard to
the MMOD impact.

Although carbon-phenolic is definitely the best robust TPS candidate, the

high density of the material could end up to a weight penalty in the overall mass
budget of the probe. This has been highlighted in both MarcoPolo and MSR Earth
Return design studies. Nevertheless the concept Sepcore proposed for many years by
Herakles (HKS), and based on carbon phenolic joined to a CMC hot structure, allows
to manufacture a light heat shield, but at the same time robust and reliable.

3.1 ABLATIVE MATERIALS THERMAL PROPERTIES

ESIMATING
In many practical situations it is impossible to measure directly thermal and
thermokinetic properties of analyzed composite materials. The only way that can often
be used to overcome these difficulties is indirect measurements. This type of
measurements is usually formulated as the solution of inverse heat transfer problems.
Such problems are ill-posed in mathematical sense and their main feature shows itself
in the solution instabilities. That is why special regularizing methods are needed to
solve them. The general method of iterative regularization is concerned with
application to the estimation of materials properties. The objective of this paper is to
estimate thermal and thermokinetic properties of advanced materials using the
approach based on inverse methods. An experimental-computational system is
presented for investigating the thermal and kinetics properties of composite materials
by methods of inverse heat transfer problems and which is developed at the Thermal
Laboratory of Department Space Systems Engineering, of Moscow Aviation Institute
(MAI). The system is aimed at investigating the materials in conditions of unsteady

contact heating over a wide range of temperature changes and heating rates in a
vacuum, air and inert gas medium. In estimating temperature-dependent properties of
modern composite destructive materials the most effective are methods based on
solution of the coefficient inverse heat transfer problems. The most promising
direction in further development of research methods for destructive composite
materials using the procedure of inverse problems is the simultaneous determination of
a combination of material's thermal and kinetic properties (thermal conductivity, heat
capacity, heat capacity of charring gas, thermokinetics and some other parameters).
Such problems are of great practical importance in the study of properties of
composite materials used as destructive surface coating of spacecrafts.
The experimental equipment and the presented method could be applied for
estimating of material's seven characteristics; the availability of a few specimens of
the material allows us toprovide uniqueness of the solution. The application of the
considered technique for real thermoprotective materials is presented. The results of
temperature measurements inside the specimen are assigned as necessary additional
information to solve an inverse problem. To construct an iterative algorithm of the
inverse problem solving a conjugate gradient method was used. In the approach being
developed the methods of calculus of variations are used for calculation of the
minimized functional gradient.
For partially decomposed materials the model of heat conduction with
temperature-dependent thermal characteristics is approximate, and characteristics are
effective, since the heat transfer in such material is provided not only by heat
conduction but also by different transformation processes depended on conditions of
heating. A deviation of calculated and experimental temperature values in the
experiments did not exceed 8 K, that confirms the possibility of using, for the given
material, a model of heat conduction with the effective thermal characteristics. But the
presented method can be used only for determining the effective thermal
characteristics of composite materials for particular heating conditions.

3.2 WORKING OF ABLATIVE MATERIALS

The most commonly used ablative materials are the composites, i.e., materials
consisting of a high-melting point matrix and an organic binder. The matrix can be
glass, asbestos, carbon or polymer fibers braided in different ways. In some cases, a
honeycomb construction can be used, filled with a mixture of organic and nonorganic
substances and possessing high heat-insulating characteristics (as used, for instance,
on the space vehicle Apollo).

Figure 1. Schematic model for the destruction of an ablating composite material.

Shown in Figure 1 is a schematic model of the destruction of a composite

material from a high-melting point matrix and an organic binder. The characteristic
property of such heat-shielding coverings is the presence of two fronts or zones, to be
more exact, in which physicochemical transformations take place. In convective
heating, a viscous melt film can be formed on the surface of such composite materials.
Despite its thinness, the film strongly affects the destruction process. In particular, the

coalescence of particles of the surface layer prevents their erosion blow-off by the
flow. The melt film also reduces the rate of oxidation of chemically-active components
of the material by the incoming flow of gas.
Further into the surface lies a comparatively thick layer of charred organic
binder reinforced by high-melting fibers. Still deeper is the thermal decomposition
zone, where a mixture of volatile and solid (coke) components is formed. The volatile
components filtered through the porous matrix are injected into the boundary layer of
the incoming gas flow. An intensive sublimation of glass or other oxides which form
high-melting fibers occurs on the surface of the melt film. The fraction of gaseous
ablation products in the total ablation mass can, therefore, be high. The particles of
coke are practically pure carbon; thus, at the melting temperature of glass they remain
solid. The spreading film of glass breaks out the porous structure of the charred
layer and carries away the particles of coke. The later, in turn, affects the flow of the
melt, increasing its effective viscosity.
At high temperatures, the coke particles in the melt film are not inert
components they interact actively both with glass and with any oxidant present in the
gas flow. Tens of various strongly interacting components can exist in the boundary
layer over the surface of the composite heat-shielding covering. The choice of a
theoretical model for the destruction process of such materials, presents considerable
difficulties. However, on the basis of extensive experimental and theoretical studies of
thermophysical, thermodynamic and strength phenomena which attend the process of
the incident flow effect, we have succeeded in creating a schematic model or a
mechanism for the destruction of a heat-facing layer. Such a mechanism has been
designed only for some classical representatives of the range of composites (see
Sublimation, Melting). At the same time, advances in chemistry and materials
technology extend the possibilities of selecting improved ablation materials. In this
context, a demand arose for some unique parameter to compare various types of
ablative materials convenient for both theoretical and experimental studies. One such
parameter is the effective enthalpy of destruction, symbolized as heff.
The effective enthalpy defines the total thermal energy expenditure necessary
to break down a unit mass of ablative material. The problem of comparing numerous

ablative materials is most easily demonstrated for a quasi-stationary destruction (see

Heat Conduction) when the velocity of all isotherms or destruction fronts inside the
material coincides with the velocity of the outer surface displacement. In this case, the
temperature profile inside the heat-shielding covering is described by a set of
exponents, and the heat flux spent on heating inner layers does not depend on the
material thermal conductivity .
Let us first consider a destruction process under conditions of exposure to
convective heating. The thermal balance on a destructing surface (Figure 2) can be
written as follows:

Figure 2. Destruction process with convective heating.

Here, (/cp)0 is the heat transfer coefficient, and h e and hw are the enthalpies of
the gases in the incoming flow and the wall, respectively. In contrast to a
nondestructing ablative facing, the convective heat flux supplied from without is
expended not only for heating the material ( ) and by radiant re-emission of the four
heated surfaces ( T4W ) but also for the surface (with mass loss rate and bulk (with
mass loss rate physicochemical transformations, whose thermal effects are evaluated

10

as Qw and Q. If a melt film is formed on the surface of a heat-shielding covering,

then , where is the mass loss rate of a substance in a molten form. The total thermal
effect of the bulk failure Q contains not only the heat of matrix melting, but also the
thermal effect of the thermal decomposition of an organic binder, the heat of
heterogeneous interaction between the glass and coke inside the charred layer, etc. In a
similar manner, the thermal effect of surface destruction Q w must account for the
thermal effect of evaporation of a melted film and the burning of the coke particles in
the incoming flow of gas.
Gaseous ablation products which penetrate into the boundary layer cause a
reduction of a convective heat flow due to the so-called injection effect. We can
evaluate the blocking action of the injection effect by a linear approximation.
Here, is the dimensionless coefficient of injection ( < 1), which in the
general case depends on flow conditions in the boundary layer (laminar or turbulent)
and the ratio of molecular masses of the gas injected and the incoming flow. Unlike
other effects influencing the absorption of the heat energy supplied, the injection effect
rises steeply with the increasing velocity or temperature of the incoming flow and
finally becomes predominant.
If we denote the share of gaseous ablation products in the total mass loss of the
substance by ( = / ), then we can obtain a generalized characteristic of destruction
power, namely, the effective enthalpy of destruction, heff:
The effective enthalpy determines the amount of heat which can be blocked
when breaking down a unit mass of covering material (whose surface temperature is
Tw) through physicochemical processes. The higher the effective enthalpy, the better
the heat-shielding material. We place emphasis on the independence of the effective
enthalpy from the geometrical dimensions or the shape of the body. Actually, as
distinct from a heat flux whose value, with the given parameters of the incoming flow
(pe, he), is inversely proportional to (where RN is the typical dimension of the body; for
instance, the radius of curvature in the vicinity of the critical point), the effective
enthalpy is unaffected either by the shape or the dimension of the body. This qualifies
it as a parameter for relating laboratory and real heat-loading situations.

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We can see from the definition of effective enthalpy that in all cases when
0, it must increase substantially with the rise in the enthalpy of the stagnated flow h e.
The parameters of the incoming gas flow (pressure P e and enthalpy he) can effect heff
through changes in the temperature of the destructing surface T w, the fraction of the
ablation which is in gaseous form and the thermal effect of surface processes Q w.
The effect of surface temperature Tw on heff can be considered to be rather limited. A
typical dependence of Tw, and heff on enthalpy he and pressure Pe in breaking down
glass reinforced plastics in an air flow is shown in Figures 3, 4 and 5. The flow
condition (laminar or turbulent) in the boundary layer determines the injection
coefficient (see Heat Protection), which affects radically the dependence of h eff on he
(Figure 6 ). If the ablative material does not contain oxides, then, as a rule, the share of
gasification is close to unity. For graphite-like heat-shield covering, in particular, =
1. In this case, however, the thermal effect of surface processes Qw varies from a
negative value on carbon burning C + O2 = CO2 to a positive value upon its
sublimation. An extra liberation of heat upon burning brings about surface overheating
relative to the equilibrium value of the temperature for a heat-insulated wall. In this
case, the effective enthalpy becomes negative and the notion of heff loses practical
sense. The dimensional rate of destruction is often used as an alternative parameter for
generalizing the experimental and the design data.
Its advantage is that the function (h e ) is always positive and besides, the
temperature of the destructing surface Tw and the emissivity are not warranted.
Typical dependences of on the stagnation enthalpy h e for Teflon, glass-reinforced
plastic and graphite breaking down in air flow are shown in Figure 7.

12

Figure 3. The share of gasification as a function of stagnation enthalpy of

incoming gas he.

Figure 4.

13

Figure 5.

Figure 6.

14

Figure 7. Dimensionless destruction rate ( ) as a function of stagnation enthalpy

(he) for various materials breaking down in an air flow.
Combined radiation-convection heating of the surface of an ablative material
can considerably change the mechanism of its destruction. The injection of gaseous
disintegration products in cases where they do not possess high absorption
coefficients, slightly reduces the intensity of the radiation component of the heat flow.
As the ratio grows, the mechanism of destruction of the majority of ablative materials
more closely resembles sublimation and thermal decomposition. This is due to a rapid
decrease in the contribution of convective and diffusion transfer in the boundary layer
while injecting gaseous products, to the ceasing of melt film flow and to the absence
of burning on the destructing surface.
The heat balance on the surface of an ablative material in case of high levels of
radiation of heat flows is simplified as follows.

15

Here, K,

is the absorption coefficient, which depends on the spectrum of

incident radiation heat flow () and on the spectral distribution of the destructing
surface emissivity ():
When no mechanical cracking or melting of a heat-shielding material occurs,
the total rate of ablation coincides with and the notion of effective enthalpy of the
material under intensive radiation heat influence can be introduced as:
Table 1 shows the results of the evaluation of parameters h, K, w (in the 0.2 < < 1 m
spectral range) and hR for various substances.
Table 1.
Material

h, kJ/kg

K, w

hR, kJ/kg

Graphite

30.000

0.85

35.000

Quartz

15.000

0.2

75.000

Magnesium oxide

15.000

0.13

115.000

Teflon

3.000

0.1

30.000

An analysis of the data presented in Table 1 allows us to reach a paradoxical

conclusion: under the influence of intensive radiation, the effective enthalpies of
destruction of graphite and Teflon become about equal. We should note that the
ablation rate of graphite, as compared to magnesium oxide, does not differ so strongly
as the other values of the effective enthalpies given in the table. This is associated with
the fact that the temperature of graphite destruction is almost half as great, and,
therefore, the levels of the reemitted energy differ by an order of magnitude.
Nonetheless, the main conclusion that can be drawn in analyzing Table 1 is that by
decreasing the absorption coefficient of the destructing surface (K , w), we can obtain a
greater efficiency of ablation than by increasing the heat of sublimation.

4. ADVANTAGES OF ABLATIVE MATERIALS

16

High Heat Absorption and Dissipation

Exceptional Thermal insulation

No maximum Service Temperature

Weight saving

Resistance to thermal and mechanical

Shock

availability

Design Simplicity and Flexibility

Low cost

Passive in Operation

5. LIMITATIONS OF ABLATIVE MATERIALS

Susceptible To High Mechanical Forces

Service Life is Time Dependent

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6. APPLICATION OF ABLATIVE MATERIALS

Effective and efficient design with ablative materials has seldom been
achieved, due to the newness of the materials, lack of preceding similar designs,
complexity of the design factors involved, and our incomplete knowledge concerning
realistic design criteria. In designing with ablative materials, consideration must be
given to the environmental variables and their time dependency, availability and
uniformity of candidate materials compositions and constructions, material properties
and characteristics, materials formulation and fabrication, design requirements for
thermal, mechanical and chemical properties, safety factors and other aspects peculiar
to the design. Some degree of uncertainty exists for each of these factors, and
designers have had a tendency to use an overall safety factor rather than one based on
the uncertainty of each design criterion. Further research on optimum design
techniques for ablative materials is required.
HYPERSONIC ATMOSPHERIC RE-ENTRY
One of the most difficult and challenging problems of aerospace flight is the thermal
protection of a vehicle as it enters hypersonically planetary atmosphere
ROCKET PROPULSION EXHAUSTS
The containment and control of hot combustive gases in rocket propulsion systems is
necessary for thrust purposes. These propellant gases constitute a severe engineering
environment, since they are generally characterized by high temperature, high
mechanical forces, chemical corrosion, and occasionally particle erosion.

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7. CONCLUSION
The significance of ablative materials to aerospace technology os now
apparent. Our successes in solving the Re-entry heating problem and in providing light
weight, high performance propulsion materials are history. The current stateof the art
representsonly the generatin developments,and only asmall portion of the hyperenvironmental spectrum has been investigated. Current materials deficiencies mustbe
overcome, and new ablaive materials with unique properties and characteristics are
necessary. Each new success in this work will permit a wider range of aerospace
systems and new capabilities in aerospace technology.

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8. REFERENCE

1. Duerig, T., Melton, K., Stockel, D., and Wayman, C. (Eds) Engineering aspects of
shape memory alloys, 1990 (Butterworth-Heinemann, London).

2. Lagoudas, D. C., Entchev, P B., Popov, P Patoor, E.Brinson, L. C., and Gao,
X.composite materials and alloys , part II: modeling of polycrystals. Mech. Mater.
2006, 38(56), 430462.
3. Otsuka, K. and Wayman, C. M. (Eds) Shape memory alloy and ablative materials,
1999 (Cambridge University Press, Cambridge).

4. Patoor, E., Lagoudas, D. C., Entchev, P B., Brinson, L. C and Gao, X. Composite
materials and alloys, part I: general properties and modeling of single crystals.
Mech. Mater., 2006, 38(56), 391429.

5. Srinivasan, A. V. and McFarland, M. D. Smart structures: analysis and design of

ablative materials 2000 (Cambridge University Press, Cambridge).

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