Carbon–phenolic ablative materials for re-

entry space vehicles: Manufacturing

and properties

G. Pulci , J. Tirillò , F. Marra , F. Fossati , C. Bartuli , T. Valente

a a a b a,* a

Dept. of Chemical Engineering, Materials, Environment, Sapienza University of

Rome
Need for TPS
Objects entering an atmosphere from space at high velocities relative to the
atmosphere will cause very high levels of heating.
The Space Shuttle thermal protection system (TPS) is the barrier that protected the
Space Shuttle Orbiter during the searing 1,650 °C (3,000 °F) heat of atmospheric re
entry. A secondary goal was to protect from the heat and cold of space while in
orbit.
Introduction
Ablative materials represent the traditional approach to thermal
protection, used for over 40 years in a broad range of applications.
Most ablative TPS materials are reinforced composites where organic
resins are used as matrices. When heated, the resin pyrolyzes
generating gaseous products that permeate 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 residue, indicated as
‘‘char”. The process is typically endothermic and pyrolysis gases are
heated as they percolate toward the surface, thus transferring energy
from the solid to the gas.
Schematic illustration of the transformations
and energy accommodation mechanisms of an ablative
TPS material.
Non-melting ablative materials are made of char-forming thermosetting
resins, providing multiple levels of protection, and they
are suitable for thermal protection of re-entry vehicles. However
because of their low strength and stiffness, thermosetting resins
are usually reinforced with fibres and ceramic fillers.

Materials such as phenolic resins, polyimides and polybenzimidazole

are considered suitable for their char-forming ability and
high values of heat of pyrolysis (heat absorbed due to decomposition
into char and gases).
Aim
The aim of the present investigation was to develop and produce an
ablative TPS comparable with the state-of-the-art solutions offering
potential improvements in terms of both mechanical resistance and
insulating performance. Design limitations mainly apply to an upper
density limit of 0.5 g/cm3, and to the ability of withstanding heat fluxes
ranging from 2 to 9 MW/m^2 , consistent with the moon–earth re
entry.
Experimental activities were oriented to the selection of both
reinforcement and matrix materials.
Matrix material
A resole phenolic resin was selected as matrix material because of the
high oxidation resistance and heat of ablation of this thermosetting
resin class, having a high char yield (55–60%) at temperatures above
650 C in inert atmosphere and a low viscosity.
A commercially available resole resin was employed for the present
investigation. A very fast curing cycle at constant temperature(T = 135
C) was suggested for the resin.
Reinforcement materials
Two carbon-based reinforcements, were selected for impregnation
with the phenolic resin:
a graphitic foam –Grafoam
a rigid graphite felt -Sigratherm
The Sigratherm rigid felt is a shape retentive insulating material, made
of graphite fibres and a carbon binder and is suitable for temperatures
up to 3000 C.
Grafoam carbon foam is an open-cell, rigid, carbon-based material that
can be produced in densities ranging from 0.03 to 0.56 g/cm3. it is also
suitable for high temeperatures.
Microstructure of carbon-based reinforcements:
Sigratherm felt (a) and Grafoam foam (b)
Development of impregnation process and
optimization of cure cycle
It is very important to improve the mechanical properties of the final product
and the ease of impregnation 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)
The selected phenolic resole resin contains phenol, formaldehyde and isopropyl
alcohol: for this reason isopropanol was also selected as a solvent for curing and
impregnation tests. Resin/isopropanol ratio is a very important parameter of
impregnation process because the final density of composite samples depends
on the amount of solvent present in the infiltrated resin and removed by
thermal treatment.
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 or cracks origination.

Infiltration process was performed by total immersion procedure

and 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.
Oxyacetylene exposure tests
Preliminary ablation tests were performed on the two fabricated
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 materials, with the aim of
assessing the relative thermal insulation. Maximum temperatures of
about 4000 K were registered on the front face of exposed samples
Set up of the oxy-acetylene flame exposure
test
Stress–strain curves registered during four-point
bending tests of infiltrated Sigratherm and Grafoam.
Cross sections of composite felt (a, Sigratherm,
undamaged) and foam (b, Grafoam, visibly cracked)
after 20 min of oxy-acetylene test.
RESULT
On the basis of these encouraging preliminary results,
Sigratherm based ablators were selected for arc jet
testing in a Plasma Wind Tunnel 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.
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
temperature to about 2000 C), while being characterized by more than
acceptable room temperature properties, making it suitable for
forming/machining operation.
THAT’S ALL