Composites: Part A 41 (2010) 1483–1490

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Carbon–phenolic ablative materials for re-entry space vehicles: Manufacturing

and properties
G. Pulci a, J. Tirillò a, F. Marra a, F. Fossati b, C. Bartuli a,*, T. Valente a
a
Dept. of Chemical Engineering, Materials, Environment, Sapienza University of Rome, via Eudossiana 18, 00184 Rome, Italy
b
Thales Alenia Space, Strada Antica di Collegno 253, 10146 Torino, Italy

a r t i c l e i n f o a b s t r a c t

Article history: Thermal protection systems (TPS) are designed to protect re-entry space vehicles from the severe heating
Received 26 April 2010 encountered during hypersonic flight through a planet’s or the earth’s atmosphere. A carbon–phenolic
Received in revised form 27 May 2010 ablative TPS was developed, manufactured and tested with the aim of fulfilling the thermal and
Accepted 18 June 2010
mechanical requirements corresponding to the actual loads experienced by a vehicle during a moon-
earth re-entry. Experimental activities were carried out on two different composite systems (a resole
resin coupled with a graphitic felt and a graphitic foam), and were aimed to the optimization of the
Keywords:
manufacturing procedure and to the characterization of the mechanical behaviour and of the insulation
A. Foams
B. High temperature properties
performance of the fabricated composites.
D. Thermal analysis Ó 2010 Elsevier Ltd. All rights reserved.
E. Cure, heat treatment

1. Introduction Reactions can be endothermic (vaporization, sublimation) or

Ablative materials represent the traditional approach to ther-
mal protection, used for over 40 years in a broad range of applica-
tions. All NASA planetary entry probes were shielded from the
severe heating encountered during hypersonic flight by ablative
thermal protection systems (TPS) [1].
Most ablative TPS materials are reinforced composites where
organic resins are used as matrices. When heated, the resin pyro-
lyzes generating gaseous products (mostly hydrocarbons) that per-
meate the solid diffusing toward the external heated surface and
proceed into the boundary layer, where the heat transfer processes
take place. The resin pyrolysis also produces a carbonaceous resi-
due, indicated as ‘‘char”. The process is typically endothermic
and pyrolysis gases are heated as they percolate toward the sur-
face, thus transferring energy from the solid to the gas. The trans-
formations and energy accommodation mechanisms of an ablative
TPS material are schematically illustrated in Fig. 1 [1].
The entering of the pyrolysis gases into the boundary layer
modifies its properties, generally producing a reduction of convec-
tive heating. However, the gases may undergo chemical reactions
with the boundary layer gases, thus influencing the net heat trans-
fer to the surface. Furthermore, chemical reactions can result in
consumption of the surface material leading to surface recession.
* Corresponding author. Tel.: +39 0644585633.
E-mail address: bartuli@uniroma1.it (C. Bartuli).
exothermic (oxidation) and will have an important impact on net
energy to the surface. Clearly, in comparison to reusable TPS, the
interaction of ablative TPS materials with the surrounding environ-
mental gases is much more complex as more numerous mecha-
nisms are active to accommodate the intense heating.
Two categories of ablative materials are available: melting and
non-melting types. In melting type (thermoplastics based), the li-
quid is removed immediately after formation and new surface is
exposed, thus the thermal protection is not efficient [2].
In non-melting and unreinforced materials, mechanical ablation
precedes chemical ablation, and a significant strength reduction is
produced as a consequence of a temperature increase. The thermal
ablation (sublimation) becomes appreciable only at very high tem-
peratures (above 3000 K) [3].
Non-melting ablative materials are made of char-forming ther-
mosetting resins, providing multiple levels of protection, and they
are suitable for thermal protection of re-entry vehicles, probes and
ballistic missiles (high heating rates, shorter duration). However
because of their low strength and stiffness, thermosetting resins
are usually reinforced with fibres and/or ceramic fillers, so that car-
bon/epoxy and carbon/phenolic composites are most widely used.
Materials such as phenolic resins, polyimides and polybenzim-
idazole are considered suitable for their char-forming ability and
high values of heat of pyrolysis (heat absorbed due to decomposi-
tion into char and gases). Due to the very high temperature at-
tained on the surface of the TPS, several phenomena can occur
[4–7]:

1359-835X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2010.06.010
1484 G. Pulci et al. / Composites: Part A 41 (2010) 1483–1490

Fig. 1. Energy accommodation mechanisms of ablative TPS materials [1].

1. re-radiation of thermal energy from outer surface to atmo- dures were optimized on the basis of the microstructure of
sphere. At equilibrium temperature the entire incoming energy manufactured components and of their thermo-mechanical
is thrown back; properties.
2. pyrolysis in the outer (hotter) layer;
3. charred outer layers and advancing of pyrolysis zone toward
inner layers; and 2. Materials and methods
4. removal of soft char on the surface by the aerodynamic shear
(mechanical ablation). 2.1. Matrix material

The extent of char removal by mechanical ablation depends on A resole phenolic resin was selected as matrix material because
the in-plane shear strength (function of temperature) and on the of the high oxidation resistance and heat of ablation of this ther-
severity of the aerodynamic surface shear. mosetting resin class, having a high char yield (55–60%) at temper-
In all cases, relevant parameters to the selection of a suitable atures above 650 °C in inert atmosphere [16] and a low viscosity
ablator system are the ablation temperature, that is, the tempera- (about 250 cP at T = 25 °C).
ture at which the material degradation begins, and the material Resoles are formed in an alkaline medium by the reaction of
overall density [8,9]. phenol with formaldehyde. Due to the presence of their reactive
Phenolic partially impregnated carbon or ceramic ablators be- methylol groups, resoles are crosslinked by exposure to heat or
long to Lightweight Ceramic Ablators family (LCA) and they repre- addition of acids.
sent the state of the art in the field of ablative thermal protection A favourable aspect in resole resin chemistry is that in the
systems for a wide range of re-entry heat fluxes [10–13]. presence of an excess of formaldehyde in the mixture a sufficient
LCA are composite materials having a density lower than 0.5 g/ number of methylol and dibenzyl ether groups remain reactive
cm3 and they are produced starting from low-density rigid carbon to complete the polymerization and cure of the resin without
tiles (<0.2 g/cm3) providing the necessary mechanical reinforce- incorporation of a curing agent, such as hexamethylene-
ment and a certain degree of thermal insulation, due to their tetramine.
comparably low thermal conductivity, <0.2 W/m K at room temper- A commercially available resole resin was employed for the
ature, caused by the insulating effect of air entrapped in the pores. present investigation. A very fast curing cycle at constant temper-
Carbon tiles are partially impregnated with an organic resin to pro- ature (T = 135 °C) was suggested for the resin. Table 1 summarizes
vide additional energy dissipation mechanisms via endothermic the main properties of the resole resin when cured at 135 °C.
decomposition, pyrolysis gas heat transport and boundary layer
blowing.
The aim of the present investigation was to develop and pro-
Table 1
duce an ablative TPS comparable with the state-of-the-art solu-
Properties of the resole resin cured at 135 °C (specifica-
tions [14,15] offering potential improvements in terms of both tions from supplier).
mechanical resistance and insulating performance. Design limita-
Solids (T = 135 °C) 60–64%
tions mainly apply to an upper density limit of 0.5 g/cm3, and to
Solvent Isopropanol
the ability of withstanding heat fluxes ranging from 2 to 9 MW/ Free formaldehyde 0.6–0.2%
m2, consistent with the moon–earth re-entry. Free phenol 11–18%
Experimental activities were oriented to the selection of both pH (T = 25 °C) 7.0–8.5
reinforcement and matrix materials. Two different ablative com- Get time (T = 135 °C) 11–18 min
Colour Golden yellow
posites were identified as possible TPS, and manufacturing proce-
 G. Pulci et al. / Composites: Part A 41 (2010) 1483–1490
However, the selection of more suitable polymerization parame-
ters (mainly temperature and time steps) can result in tailored
molecular weight distribution and suitable residual monomer
content.
2.2. Reinforcement materials
Two carbon-based reinforcements, readily available on the mar-
ket, were selected for impregnation with the phenolic resin:
– a graphitic foam (GrafoamÒ, Graftech International, Clarksburg,
WV, USA); and
– a rigid graphite felt (SigrathermÒ, SGL Carbon SE, Wiesbaden,
Germany).
The Sigratherm rigid felt is a shape retentive insulating mate-
rial, made of graphite fibres and a carbon binder, residual from
the pyrolysis of a phenolic resin. Its properties are affected by
the precursor, the type and quantity of the binder, its compression
ratio and thermal treatment. It is nominally suitable for tempera-
tures up to 3000 °C and is used to manufacture self-supporting
boards, cylinders and other components in high-temperature fur-
nace applications.
Sigratherm felts have high thermal stability in vacuum up to
2500 °C and under inert atmospheres up to 3000 °C. Above
2200 °C physical properties can change: for example the material
is expected to shrink and increase its thermal conductivity.
Moreover the felt exhibits good shape retention properties, and
it does not compress or shrink under normal operating conditions.
The bulk density thus remains unchanged throughout the entire
insulating layer. The insulating properties are constant, and no
voids, channels or hot spots occur. A micrograph of the rigid felt
is reported in Fig. 2a.
Grafoam carbon foam is an open-cell, rigid, carbon-based mate-
rial that can be produced in densities ranging from 0.03 to 0.56 g/
cm3 and in a variety of sizes. The properties of carbon foam make it
a good candidate for various applications including core material in
multi-layered sandwich panels, composite tooling and high tem-
perature components.
A micrograph of the carbon foam is reported in Fig. 2b: the
open-cell microstructure is evidenced, with macro and micro com-
munication channels among the cells, allowing for efficient resin
infiltration.
The main properties (density, thermal conductivity and
mechanical properties) of the rigid felt and carbon foam are sum-
marized in Table 2 (from suppliers specifications).
2.3. Development of impregnation process and optimization of cure
cycle
Experimental activities were first focused on the development
and optimization of the manufacturing process steps (mainly
Fig. 2. Microstructure of carbon-based reinforcements: Sigratherm felt (a) and Grafoam foam (b).
1485
Table 2
Properties of Sigratherm and Grafoam carbon reinforcement preforms (specifications
from suppliers).
Density Thermal Young’s Bending Compression
(g/cm3) conductivity modulus strength strength
(W/mK) (GPa) (MPa) (MPa)
Sigratherm 0.15 0.22 0.25 1.2 0.9
Grafoam 0.16 0.12 0.50 1.2 5.2
impregnation and curing), with the aim of improving both the
mechanical properties of the final product and the ease of impreg-
nation of the porous supports.
To this purpose the following variables were considered:
– resin/solvent ratio;
– time and temperature of cure steps (single or multi-step cure
cycles);
– samples shape;
– infiltration pressure (vacuum or atmospheric infiltration); and
– pre-heating temperature of resin before infiltration.
The selected phenolic resole resin contains phenol, formalde-
hyde and isopropyl alcohol: for this reason isopropanol was also
selected as a solvent for curing and impregnation tests. Resin/iso-
propanol ratio is a very important parameter of impregnation pro-
cess because the final density of composite samples depends on
the amount of solvent present in the infiltrated resin and removed
by thermal treatment; this parameter, on the other hand, does not
affect the cure behaviour of resin. Since the boiling point of the re-
sin is 98 °C and that of isopropanol is 82 °C, an increase of the
amount of alcohol reduces the solution boiling temperature of only
few degrees. Based on these considerations, the first step of the
curing process was always performed at a temperature slightly
lower than 82 °C, until complete removal of the solvent.
Samples were cured in a forced air circulation oven. Time and
temperature of the curing steps are the key parameters in order
to avoid undesired phenomena during polymerization, such as
bubbles formation (bulk evaporation of the solvent) or cracks orig-
ination (caused by non homogeneous stiffening of the material).
Preform size and shape can affect the efficiency of impregna-
tion. Prismatic samples of increasing size were impregnated,
checking for complete impregnation throughout the specimen. Fi-
nal characterization tests were performed on 10  10  3 cm
samples.
Infiltration process was performed by total immersion proce-
dure: the samples (both Sigratherm and Grafoam) were totally
soaked for 30 min in a phenolic solution with a isopropanol/resin
ratio tailored in order to obtain the specified density (0.5 g/cm3)
after the cure process. After resin polymerization, a resin/composite
volume ratio (ml liquid resin per cm3 of impregnated reinforcement)
1486 G. Pulci et al. / Composites: Part A 41 (2010) 1483–1490

of 0.61 and 0.59 was calculated for Sigratherm and Grafoam
composites, respectively.
Preliminary tests proved that resin pre-heating (50 °C) and vac-
uum infiltration (3 min at 10 3 bar) after soaking were mandatory
for removing excess solvent and efficient impregnation, All tests
were carried out in these conditions.
2.4. Thermo-mechanical characterization
With the aim of identifying the optimal curing conditions,
hardness of cured pure resin or resin/solvent samples was mea-
sured according to the ASTM E384-10 standard [17] using a Leika
VMHT microindenter: 40 hardness tests were performed on each
disk-shaped specimen (diameter 5 cm, height 3 cm), both on sur-
face and in cross section. More specifically, 10 measurements
were performed on sample top surface and 30 in cross section
(10 in proximity of the upper surface, 10 in the mid section
and 10 at the lower surface). Calibration tests were performed
to define the load to be applied on specimen without inducing
relevant damage. Applied load on indenter for final tests was
25 gf for 15 s.
Flexural strength of impregnated specimens was evaluated by
four-point bending tests, measuring elastic modulus (E) and Mod-
ulus of Rupture (MoR).

Fig. 3. Set up of the oxy-acetylene flame exposure test: (a) before the test: the sample is exposed at a controllable distance from the oxy-acetylene torch (endless screw) and
(b) during the test: in this configuration the calorimeter is positioned at the centre of the sample for heat flux evaluation.

Table 3
Tests for cure cycle optimization.
 G. Pulci et al. / Composites: Part A 41 (2010) 1483–1490 1487

Tests were carried out according to ASTM D7264 standard [18],
using a Z010 Zwick-Roell electromechanical testing machine
equipped with a 10 kN load cell, using a cross-head velocity of
2 mm/min. Twelve prismatic samples (125  10  12 mm) were
tested for each type of material. Strain was measured during the
test using strain gauges applied to the extrados of the samples
and connected with another resistance extensimeter in half-bridge
configuration, in order to eliminate the thermal component of
specimen strain.
Thermo-physical characterization of composite materials con-
sisted in the experimental measurement of thermal diffusivity, car-
ried out using the Flash Method (according to ASTM E1461-07
standard), followed by calculation of the thermal conductivity.
Thermal diffusivity was measured using a NETZSCH-427 laser flash
diffusivity apparatus and measurements were conducted between
room temperature and 1900 °C in a dynamic argon atmosphere at a
flow rate of 100 ml/min; specific heat values were taken from liter-
ature data [19] and were subsequently confirmed by experimental
measurements conducted using a NETZSCH model DSC 404 C Peg-
asus differential scanning calorimeter, capable of operation from
25 to 1500 °C; the value of specific heat at 1900 °C was extrapo-
lated and confirmed the mentioned literature data.

Fig. 4. Hardness of the resin during curing test no. 13: surface and cross section at three partial steps of the curing process (as indicated in Table 3).

Fig. 5. Cross sections of resin/felt (a and b) and resin/foam (c) composites: distribution throughout the 3 cm thickness (a); microstructure evidencing partial impregnation (b
and c).
1488 G. Pulci et al. / Composites: Part A 41 (2010) 1483–1490

Table 4
Results of four-point bending tests on impregnated Grafoam and Sigratherm
reinforcements.

Elastic modulus (GPa) MoR (MPa)

Resin/Sigratherm felt 1.9 ± 0.2 10.0 ± 3.7
Resin/Grafoam foam 2.2 ± 0.1 4.1 ± 0.2

2.5. Oxyacetylene exposure tests

Preliminary ablation tests were performed on the two fabri-

cated systems according to ASTM E285-08 standard. The standard
describes the testing of flat ablative panels in an environment of a
steady flow of hot gas provided by an oxyacetylene burner. This
test is intended to provide a preliminary evaluation of ablative Fig. 6. Stress–strain curves registered during four-point bending tests of infiltrated
materials, with the aim of assessing the relative thermal insulation Sigratherm and Grafoam.

Fig. 7. Thermal conductivity and thermal diffusivity as a function of temperature for composite samples: (a) Sigratherm and (b) Grafoam (down arrows: cooling; up arrows:
heating). Specific heat calculated from [19].
 G. Pulci et al. / Composites: Part A 41 (2010) 1483–1490
effectiveness and determining the relative performance merit of
different ablative systems.
The size of samples tested with oxy-acetylene torch was
100  100  20 mm or 50  50  20 mm; the distance between
nozzle and samples was 20 mm and the temperature of the front
and of the back surface of the tiles was monitored by a two-colour
digital fibre-optics non contact pyrometer (Impac Infrared, Frank-
furt, Germany) and by a type-K thermocouple, respectively. Heat
flux, as measured by a calorimeter ((HFM 1000 – Vatell Corporation,
Christiansburg, Virginia – USA) during experimental tests, was
1.5 MW/m2. The experimental set-up is shown in Fig. 3: the dis-
tance between the sample and the flame was carefully controlled
by an endless screw system. Details on the development of a Com-
putational Fluid-Dynamics (CFD) model of the flame exposure test,
simulating the combustion of an oxygen–acetylene mixture occur-
ring in a conventional welding torch, and calculating the heat flux
incident on the sample and the related temperature fields are re-
ported in [20].
Four exposure times were investigated, namely 1, 5, 10 and
20 min. Exposure tests were performed on 5 impregnated and on
2 un-impregnated samples. Maximum temperatures of about
4000 K were registered on the front face of exposed samples.
3. Results and discussion
Table 3 summarizes the experimental activities leading to the
optimization of the cure cycle. Hardness measurements were car-
ried out on all cured resin samples both on the surface and on
the cross section. Fig. 4 reports the hardness of surfaces and cross
sections of samples produced in ‘‘test 13” conditions, extracted
from the oven after the steps 1–3, as indicated in Table 3. As evi-
denced, the hardness of all samples is higher on the surface than
in the cross section. In fact specimen surface, because of heat trans-
fer occurring in the forced air circulation oven, attains thermal
equilibrium more rapidly than the bulk. Heat transfer is due to
both convective (between the hot air of the oven and the speci-
men’s surface) and conductive fluxes (occurring throughout the re-
sin sample); the conductive heat flux allows the inner parts of the
specimen to attain thermal equilibrium. The volatile components,
which are prone to delay the curing of the resin, experience several
difficulties in leaving the specimen, being trapped in the inner
zones. Therefore the curing process is slower inside the specimens
than on the surface, thus explaining the hardness values.
The optimal curing cycle was identified from the combined re-
sults of homogeneous hardness, absence of bubbles and cracks and
absence of residual formaldehyde vapors; in the three specimens
Fig. 8. Front face (from pyrometer) and back face (from thermo-couple) temperatures of Sigratherm and Grafoam composites during oxyacetylene exposure test.
1489
cured in the conditions indicated as ‘‘test 13” in Table 3, a complete
and homogeneous cure cycle of the resin could be inferred.
Sigratherm and Grafoam porous reinforcements were impreg-
nated with phenolic resin and a curing cycle in the optimized con-
ditions was applied for final polymerization and hardening of the
resin distributed inside the pores: this consisted of a total cure
time of 276 h in the temperature range of 37–138 °C, divided in
eight different steps of 12 h multiples.
Impregnated samples showed a homogeneous resin distribu-
tion throughout the thickness, as observed in Fig. 5a where the
cross section of a 3 cm thick Sigratherm composite is observed.
Fig. 5b and c shows magnified views of impregnated samples cross
sections, attesting the suitable degree of resin impregnation
achieved for both reinforcements.
In order to verify the suitable mechanical behaviour of the car-
bon–phenolic composites, four-point bending tests were per-
formed on impregnated samples: results of the extensive
experimental characterization are summarized in Table 4 in terms
of elastic modulus and modulus of rupture, and in Fig. 6, illustrat-
ing typical stress–strain curves for both types of reinforcement.
All specimens exhibited a linear elastic behaviour. Grafoam and
Sigratherm composites showed similar values of elastic modulus
(about 2 GPa) but the felt composite showed a much higher
(+144%) flexural strength than the foam composite.
Pure resin has an elastic modulus of 4 GPa, whereas un-impreg-
nated supports have a modulus of 0.25 GPa and 0.5 GPa for the felt
and the foam, respectively. It is evident that the resin is almost
completely responsible for the composite stiffness.
Results of four-point bending tests evidenced a higher flexural
strength of impregnated Sigratherm with respect to Grafoam. This
result is compatible with the different behaviour of the graphitic
reinforcements, exhibiting very different initial values of fracture
toughness (more resistant to deformation the felt, more brittle
the open-cell graphitic foam).
Thermo-physical properties (thermal diffusivity, thermal con-
ductivity and specific heat) of composite samples are shown in
Fig. 7. The same thermal parameters were measured on heating,
from room temperature to 1900 °C, and on cooling after the first
high temperature exposure. During the test, temperatures as high
as resin decomposition and pyrolysis reaction temperatures were
experienced, thus inducing the expected irreversible microstruc-
tural changes (decomposition of organics and formation of a ther-
mal conductive char at T > 700 °C). As a consequence, during the
cooling phase significant higher values for thermal diffusivity and
thermal conductivity were detected.
Similar behaviours were evidenced for the two types of materi-
als. Foam composites exhibited a slightly lower thermal conductiv-
ity at higher temperature (1500–1900 °C), while impregnated felts
1490 G. Pulci et al. / Composites: Part A 41 (2010) 1483–1490
Fig. 9. Cross sections of composite felt (a, Sigratherm, undamaged) and foam (b, Grafoam, visibly cracked) after 20 min of oxy-acetylene test.
exhibit lower thermal conductivity at temperatures lower than
800 °C.
Un-impregnated Grafoam and Sigratherm reinforcements
showed a room temperature thermal conductivity of 0.12 and
0.22 W/(m K), respectively. It is worth noting that resin impregna-
tion affects the thermal behaviour of the systems up to the point of
reversing the room temperature relative performance of the two
materials.
The results of a typical oxyacetylene exposure test on Sigra-
therm and Grafoam composite samples, in terms of front and back
surface temperature are shown in Fig 8: the two materials showed
the same temperature evolution with time, evidencing comparable
insulating properties. However, the analysis of samples after tests
showed that macroporous tiles were cracked during flame expo-
sure (Fig. 9a) whereas all felt-based samples passed undamaged
the longest oxyacetylene exposure tests (Fig. 9b).
In spite of comparable thermal insulation performance, the re-
sults of the flame exposition test are strongly affected by the
mechanical behaviour of the reinforcement materials: a lower
thermal shock resistance characterizes the brittle Grafoam com-
posites as compared to resin impregnated Sigratherm, whose frac-
ture toughness is intrinsically higher due to the active mechanisms
of elongation and sliding of graphite long fibres.
4. Conclusions
The preliminary diversified experimental activities carried out
to design a composite system and to test its final performance as
a potential candidate for space vehicles thermal protection lead
to very encouraging results.
There is a clear indication that a carbon/phenolic composite
material made of a rigid non-woven graphitic felt impregnated
with a resole phenolic resin can act as a very effective insulator
in a very wide range of temperatures (at least from room temper-
ature to about 2000 °C), while being characterized by more than
acceptable room temperature properties, making it suitable for
forming/machining operations.
However, a very accurate optimization of the main steps of the
manufacturing procedure (impregnation and curing) is required.
The research demonstrated for example that a multi-step curing
cycle of 12 days at different temperatures is required to obtain a
complete cure of the phenolic resin, and to allow for an efficient
impregnation of the porous graphitic reinforcement, thus achiev-
ing optimal microstructure and highest mechanical properties of
the composite.
It is worth highlighting the outstanding performance of the
manufactured composite system exposed to the direct and intense
heat flux of an oxy-acetylene flame: a retained structural integrity
after 20 min of testing and a difference of temperature of more
than 1000 °C between front and back surface of a 3 cm thick sam-
ple after 20 min were in fact experimentally achieved.
On the basis of these encouraging preliminary results, Sigra-
therm based ablators were selected for arc jet testing in a Plasma
Wind Tunnel (Scirocco, CIRA ScpA, Italy) in order to assess the
properties of the composite system in actual re-entry conditions,
where all the potential ablation mechanism can be more reliably
reproduced.
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