Ablative Cooling Materials and Systems

Progress in Materials Science 84 (2016) 192–275
Contents lists available at ScienceDirect
Progress in Materials Science

journal homepage: www.elsevier.com/locate/pmatsci
Science and technology of polymeric ablative materials for

thermal protection systems and propulsion devices: A review
Maurizio Natali ⇑, Jose Maria Kenny, Luigi Torre
University of Perugia, Civil and Environmental Engineering Department, Strada di Pentima, 4, 05100 Terni, Italy
a r t i c l e i n f o a b s t r a c t
Article history: Ablative materials are at the base of entire aerospace industry; these sacrificial materials
Received 21 August 2015 are used to manage the heat shielding of propulsion devices (such as liquid and Solid
Accepted 24 August 2016 Rocket Motors (SRMs)) or to protect vehicles and probes during the hypersonic flight
Available online 6 September 2016
through a planetary atmosphere. Accordingly they are also known as Thermal Protection
The authors wish to dedicate this work to System (TPS) materials. Some non-polymeric materials have been successfully used as
Luigi Broglio (11.11.1911–01.14.2001) who ablatives; however, due to their versatility, Polymeric Ablatives (PAs) represent the widest
was known as ‘‘the Italian von Braun’’. He family of sacrificial TPS materials. In fact, when compared to non-polymeric ablatives such
was the father of the San Marco program as high melting point metals, inorganic polymers (or metal oxides or carbides), PAs have
which led Italy to be the third country in the
some intrinsic advantages such as: tunable density, lower cost, and higher heat shock resis-
world to build, launch, and operate its own
satellite, in 1964. In 1967 Broglio was the tance. This review covers all main topics related to the science and technology of ablative
first in the world to realize, operate a launch materials with current and potential applications in the aerospace industry. After a short,
from a sea launch pad and the first to launch yet comprehensive, introduction on non-ablative materials, this review paper summarizes
from the equator. He also endorsed the use fifty years of research efforts on polymeric ablatives, starting from the state of the art solu-
of small satellites and launchers pioneering
tions currently used as TPS, up to covering the most recent efforts for nanostructuring their
the use of these technologies which are now
considered a relevant part of the future of formulations.
the space economy. He was a well known Ó 2016 Elsevier Ltd. All rights reserved.
materials scientist and engineer, fully
appreciated in the USA and a close friend of
NASA deputy administrator Hugh Dryden. In
fact, Broglio and his team was also the first
in the world to launch a satellite for NASA,
Uhuru, in 1970. Broglio was a remarkable
figure also for his humanity, the recognized
moral integrity and religious faith.
Keywords:
Thermal protection system
Propulsion devices
Ablative materials
Composites
Nanotechnology
Advanced thermal testing
⇑ Corresponding author.
E-mail addresses: maunat@hotmail.com, maurizio.natali@unipg.it (M. Natali).
http://dx.doi.org/10.1016/j.pmatsci.2016.08.003
0079-6425/Ó 2016 Elsevier Ltd. All rights reserved.
M. Natali et al. / Progress in Materials Science 84 (2016) 192–275 193
Nomenclature
Acronyms
ACE Aerotherm Chemical Equilibrium
AETB Alumina Enhanced Thermal Barrier
AHF Aerodynamic Heating Facility
APCP Ammonium Perchlorate Composite Propellant
ARAD Analog Resistance Ablator Detectors
ARD Atmospheric Re-entry Demonstrator
ARR Average Recession Rate
ASNBR asbestos-silica-filled NBR
ASRM Advanced Solid Rocket Motor
A-TPS ablative TPS materials
BLIMP Boundary Layer IMPlicit
BMC Bulk Molding Compound
BRI Boeing Rigid Insulation
C/Ph carbon/phenolic
CB carbon black
CCC Carbon/Carbon Composite
CCD Charge Coupled Device
CFEPDM carbon fiber/EPDM
CHAR CHarring Ablator Response
CMA Charring Material Ablation
CNF carbon nanofiber
CNT carbon nanotube
CVD Chemical Vapor Deposition
CTE Coefficient of Thermal Expansion
DSC Differential Scanning Calorimetry
DTA Differential Thermal Analysis
EDM Electrical Discharge Machining
EGA Effluent Gas Analysis
EHSM Elastomeric Heat Shielding Material
EPDM Ethylene Propylene Diene Monomer rubber
ERSA Effective Reactive Surface Area
ESA European Space Agency
FIAT Fully Implicit Ablation and Thermal
FRA Flame Retardant Additive
FRCI Fibrous Refractory Composite Insulation
FRPA Fiber Reinforced Polymeric Ablator
FRSI Felt Reusable Surface Insulation
GMRES Generalized Minimal RESidual method
HEAT Hollow aErothermal Ablation and Temperature
HERO Heat Transfer and Erosion Analysis Program
HRR Heat Release Rate
HRSI High-temperature Reusable Surface Insulation
HSM Heat Shielding Material
HTPB Hydroxy Terminated Poly-Butadiene
ILSS Inter Laminar Shear Strength
ICBM Inter-Continental Ballistic Missile
ICP Inductively Coupled Plasma
IHF Interactive Heating Facility
IPA isopropyl alcohol
ITAR International Traffic in Arms Regulations
ITRAC Insulation Thermal Response and Ablation Code
JAXA Japan Aerospace eXploration Agency
KFEPDM KevlarÒ-Filled EPDM
LCA Lightweight Ceramic Ablator
LEO Low Earth Orbit
LOX Liquid OXygen
LRSI Light-temperature Reusable Surface Insulation
LS Layered Silicates
194 M. Natali et al. / Progress in Materials Science 84 (2016) 192–275
MAT Multi-component Ablation Thermochemistry

MEDLI Mars Science Laboratory Entry Descent and Landing Instrumentation
MMT montmorillonite
MOS metal oxide semiconductor
MWNT multi walled carbon nanotube
NA-TPS non ablative TPS
NBR nitrile butadiene rubber
NPA Nanostructured Polymeric Ablatives
NRAM Nanocomposite Rocket Ablative Material
NS nanosilica
OAT Oxy-Acetylene Torch
OLS Organically modified Layered Silicate
PAs Polymeric Ablatives
PBI polybenzimidizole
PBINBR fiber-filled NBR
PBO poly(p-phenylene-2,6-benzobisoxazole)
PDMS polydimethylsiloxane
PG pyrolytic graphite
PHHR Peak Heat Release Rate
phr parts per hundred rubber
PI polyimide
PICA Phenolic Impregnated Carbon Ablator
PLSN Polymer Layered Silicate Nanocomposite
PSA polysulfonamide
PTF Panel Test Facility
PTFE polytetrafluoroethylene
RCC Reinforced Carbon Carbon
RF radio-frequency
RR recession rate
RSRM Reusable Solid Rocket Motor
SEB Surface Energy Balance
SEM Scanning Electron Microscopy
SPAR Structural Plastics Ablative Rocket
SRM Solid Rocket Motor
SSO Space Shuttle Orbiter
SSRM Simulated Solid Rocket Motor
STA Simultaneous Thermal Analysis
TC thermocouple
TEM Transmission Electron Microscopy
TFD Turbulent Flow Duct
TGA Thermo-Gravimetric Analysis
TITAN Two-dimensional Implicit Thermal response and AblatioN
TMA Thermomechanical Analysis
TPS Thermal Protection System
TPU Thermoplastic Polyurethane
TPUN Thermoplastic Polyurethane elastomer Nanocomposite
XRD X-ray Diffraction
Contents
1. Thermal Protection System (TPS) materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195

1.1. TPS materials: the hyperthermal environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
2. Non-ablative TPS materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
2.1. A remarkable example of NA-TPS: the Space Shuttle heat shield . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
2.2. Reusable surface insulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
2.3. Concluding remarks on the state of the art NA-TPS materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3. Ablative TPS materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.1. Metals and ceramics as A-TPS materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.2. Graphite and carbon/carbon composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3.3. Polymeric ablatives: generalities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
3.4. Fiber reinforced composites as TPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
3.4.1. Polymeric matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
3.4.2. Fiber reinforced polymeric ablatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204

3.4.3. Role of the fiber in the ablation of FRPAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
3.4.4. Powdered fillers for FRPAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
3.4.5. Basic characterization of FRPAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
4. Advanced testing techniques for TPS materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
4.1. Thermal conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
4.2. Chemical conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
4.3. Mechanical parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
4.4. An advanced test bed for SRM internal insulation materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
4.4.1. Real time X-ray radiography of tested materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
4.4.2. In-depth temperature measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
4.4.3. Total heat flux gauges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
4.4.4. Radiometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
4.5. Plasma facilities. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
4.5.1. Arc-jet torches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
4.5.2. Electrodeless torches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
5. Erosion rate sensing techniques for A-TPS materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
6. Polymeric ablatives as insulator materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
6.1. Rigid insulators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
6.2. Elastomeric based insulators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
6.2.1. Silicone based HSMs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
6.3. Elastomeric HSMs for solid rocket motor liners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
6.4. Toward a new industrial standard for SRM-EHSMs? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
6.4.1. Ablative decomposition of CFEPDM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
6.4.2. Ablative decomposition of PBINBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
6.4.3. Mechanism of char spallation of CFEPDM and PBINBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
6.4.4. Final results on the insulation capability of PBINBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
7. A new class of TPS ablatives: Lightweight Ceramic Ablators. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
7.1. Phenolic Impregnated Carbon Ablators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
8. An introduction to modeling of ablation phenomena . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
8.1. Basic principles behind analytical models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
8.2. Mechanical erosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
8.3. Differences between ablation models for full dense FRPA/HSMs and LCAs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
8.4. State of the art of ablation simulation codes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
9. Nanostructured ablative materials: introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
9.1. Nanostructured ablative materials in a low intensity hyperthermal environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
9.2. Nanostructured PAs in a severe hyperthermal environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
9.2.1. PLSNs as NRAMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
9.3. Nanosilica as filler for traditional and nanostructured PAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
9.4. Carbon nanofilaments based NRAMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
9.5. A new way to exploit boron containing fillers: nanosized boron carbide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
9.6. Nanostructured elastomeric heat shielding materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
10. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
1. Thermal Protection System (TPS) materials
Thermal Protection System (TPS) materials play a fundamental role for the entire aerospace industry. Depending on the
hyperthermal environment in which these materials must work, many types of formulations have been developed. TPS
materials are used to manufacture the heat shield which protects the structure, the aerodynamic surfaces, and the payload
of missiles, war heads, probes, and space vehicles from the severe heating encountered during the entry flight through a
planetary atmosphere [1]. In fact, due to the interaction of the vehicle with the atmosphere, its kinetic energy can be dissi-
pated via two basic mechanisms: re-radiation, and ablation. Fig. 1 summarizes the different classes of TPS materials based on
these two principles: non ablative TPS (NA-TPS), and ablative TPS (A-TPS) materials respectively.
The protective heat shield of the vehicle must work as an aerodynamic body, as a structural component, and as a thermal
insulator [1,2]. When non ablative TPS materials are used to manufacture the heat shield, re-radiation is the main phe-
nomenon exploited to insulate the body re-entering in the atmosphere; in this case, NA-TPS are produced using ceramics
or particular metals (such as tungsten or rhenium [3,4]). Ablation is the second process at the base of TPS materials. The con-
cept of ablation can be attributed to a geological term meaning ‘‘to carry away” [5,6]. Even though some non polymeric mate-
rials (such as inorganic polymers/ceramics or metals) have been successfully used as ablative TPS [7,8], polymeric based
Fig. 1. Classification by classes of Thermal Protection System (TPS) materials: ablative, and non-ablative. Not published. Credit: UNIPG.
ablators represent the widest and most versatile class of ablatives. In fact, compared to inorganic polymers i.e. polymers with
a skeletal structure that does not include carbon atoms, and metals, Polymer Ablatives (PAs) have some intrinsic advantages,
such as high heat shock resistance, low density, good mechanical strength, and good thermal insulation capabilities.
1.1. TPS materials: the hyperthermal environment
Over last fifty years, due to the very large spectrum of hyperthermal environments in which TPS materials operated, and
depending on the application, many types of heat shielding solutions have been identified and developed. During the re-
entry flight, the heating of the vehicle is approximately proportional to the square of the speed of the body to be protected;
Fig. 2. Comparison of NASA, AEDC, and Boeing arc jet facility performance with several nominal Earth return trajectories. The testing capabilities – based on
current arc-jet facilities – for TPS materials are also evidenced. The Ames Research Center (ARC), the Johnson Space Center (JSC), and the Boeing Large Core
Arc Tunnel (LCAT) simulation envelopes are at the higher altitudes, which capture the major portion of the Space Shuttle and other manned vehicle
trajectories. The Arnold Engineering Development Center (AEDC) facilities are primarily in the lower altitude regime, suitable for weapon trajectory
simulation, and capture the maximum heating point of an ICBM entry. From [9]. Credit: Image courtesy of NASA.
additionally, the heating depends on the density, and composition of the gases, as well as on the shape, position, and re-entry
trajectory of the vehicle. In general, the mechanical properties of the TPS typically increase with the density of the material
but in general, the thermal conductivity also tends to follow the same trend; thus, the necessity to produce a TPS with the
minimum sacrifice of payload is one of the primary goals of the engineers. Several system entry trajectories are shown in
Fig. 2, particularly: the Space Shuttle, the Apollo, a Mars return, a far solar system probe return, and an Inter-Continental
Ballistic Missile (ICBM). The peak heating point for each mission trajectory is also shown [9].
The testing capabilities (based on plasma jet torches) for TPS materials are also evidenced in Fig. 2. It appears that current
facility envelopes do an adequate job of covering a Low Earth Orbit (LEO) entry (such as a Shuttle return) and almost capture
the Apollo Lunar return peak heating point; however, they are inadequate for simulating the peak heating regions for Mars
and far solar system returns. The present facilities are also inadequate for simulating peak heating points for entry to other
planets such as Saturn, and Jupiter.
2. Non-ablative TPS materials
Non ablative heat shields are basically based on the use of materials which after exposure to a given hyperthermal envi-
ronment experience no changes in the mass or main properties of the material. For this family of TPS materials, re-radiation
is the main process used to insulate the body re-entering in the atmosphere (Fig. 3). Generally, NA-TPS materials are limited
to relatively moderate or mild hyperthermal environments; compared to ablative TPS materials, NA-TPS counterparts should
be able to ensure re-usability for a defined number of missions. Some metals such as rhenium are used as NA-TPS materials;
in fact, rhenium can be used to manufacture the combustion chamber of liquid fueled rocket engines employed to power the
upper stage of launchers [4]. Ceramic-based NA-TPS materials were successfully used to produce the heat shield of those
space vehicles operating the re-entry flight like the Space Shuttle Orbiter (SSO).
2.1. A remarkable example of NA-TPS: the Space Shuttle heat shield
A comprehensive introduction on the SSO NA-TPS was produced by Davis and Marshall [10]. At the end of a SSO mission,
when the vehicle re-entered the Earth’s atmosphere, the SSO had a speed of approximately 7.6 km/s; as a result, surface tem-
peratures in excess of 1650 °C were related to this re-entry profile [10]. The main role of the NA-TPS was to protect the
vehicle airframe primarily made of aluminum which was able to withstand a maximum temperature of 180 °C. Compared
to the SSO, other manned spacecrafts such as Mercury, Gemini, and Apollo, used ablative TPS materials; these vehicles were
not maneuverable and followed ballistic re-entry trajectories. In the case of the Apollo capsule, the vehicle re-entered in the
atmosphere at a speed of 11.2 km/s. For the SSO, and similarly operating space ships, a different type of heat shield was
envisioned; this TPS solution also had to satisfy a theoretical lifetime of 100 missions. A lightweight, reusable TPS com-
posed of entirely new materials was required. The SSO heat shield had to resist high acoustic loads associated with the
launch phase, and structural deflection due to aerodynamic loads; the SSO NA-TPS was made of tiles which had to be dimen-
sionally stable, low density, easy and inexpensive to produce, install, and maintain.
Fig. 3. Energy accommodation for a non-ablative TPS material. This class of materials operate in a moderate or mild hyperthermal environment. Not
published. Credit: UNIPG.
The primary TPS candidate materials for the Shuttle program included replaceable ablatives, re-radiative materials based
on Carbon/Carbon Composites (CCCs), metals, and oxide insulators [11]. Oxide based insulators were selected for all areas
except for the control surfaces that experienced the highest heat loads. Most of the surface of the SSO was originally pro-
tected with rigid insulation tiles [12]; these tiles were primarily made of silica fibers and a silicon oxide based binder.
The composition of the SSO NA-TPS tiles and the related processes used to manufacture them were deeply modified since
the first system was envisioned [10]; these modifications were introduced with the goal to improve the thermal, and
mechanical resistance of the tiles. Many efforts to decrease the cost of this concept of NA-TPS were undertaken; solutions
including flexible insulation systems and/or thermal protection blankets were also evaluated [13]. Nonetheless, even after
decades of researches, the SSO NA-TPS paradigm intrinsically remained too expensive to implement and maintain; as a
result, the primary target to introduce a low cost TPS was not achieved; as an example, a single tile could cost as much
as $1000 [14]. The fully re-usability of this system was compromised by the requirement to spend many highly time-
and cost-consuming procedures between each mission to check, and ensure the integrity of the heat shield. However, many
breakthroughs in the field of high temperature ceramics were enabled by these tremendous R&D efforts. The manufacturing
processes of high performance oxide based fibers, of advanced low density ceramic felts, and insulators was also dramati-
cally improved by these researches on the SSO NA-TPS.
At the beginning of the SSO program, NASA introduced four different NA-TPS solutions. They were referred as: Low-, and
High-temperature Reusable Surface Insulation tiles (LRSI and HRSI, respectively), the Felt Reusable Surface Insulation (FRSI)
blankets, and the Reinforced Carbon Carbon (RCC) [15]. Some basic details on the LRSI/HRSIs will be introduced in light of
their importance on the development of a state of the art class of A-TPS materials – namely the Lightweight Ceramic Ablators
(LCAs) – which started from the use of materials developed for the Space Shuttle program [16,17]; the description of the RCC
will be not addressed since the materials at the base of this solution will be reviewed in the section dedicated to graphite and
CCCs.
2.2. Reusable surface insulation
The RSI was basically composed by two types of tiles distinguishable by their outer color which were used to protect the
SSO against temperatures between 600 °C and 1200 °C [12,13]. The white tiles (LRSI) where placed on the upper surfaces
of the SSO airframe and were optimized in terms of thermal reflectivity. Due to their high emissivity of their coating, the
black tiles (referred as HRSI) could lose heat faster than LRSI counterparts thus maximize the heat rejection during the
hot phase of the entry.
All the RSI tiles were produced using a slurry binder to impregnate the ceramic fiber based felt. The first versions of the
HRSI tiles applied on the lower surface of the SSO were made from a material referred as LI-900 (density 0.15 g/cm3); a
highly pure amorphous silica fiber was at the base of this material. Prior to being impregnated, the fibers were heat treated
to stabilize their micro structure against shrinkage [10]; in fact, highly crystalline silica fibers would have exhibited phase
transformations during thermal cycling experienced during repeated re-entries compromising the performance or even the
effectiveness of the NA-TPS [10]. Moreover, the heat treatment also eliminated the porosity due to the acid leaching purifi-
cation process used to build the filaments. The silica fibers based felt was consolidated using highly pure suspensions of
amorphous, non porous, and typically spherical silica particles dispersed in a liquid phase. As a result of the pressing process,
an anisotropy in the thermal, and mechanical properties of the casted blocks was induced [18]. The consolidated and dried
Fig. 4. Aerojet ablative chamber design (a). Cross section of Aerojet ablative chamber after the firing test showing the cracked nozzle throat insert and the
char penetration (see Section 3.4) (b). From [27]. Credit: Image courtesy of NASA.
blocks were sintered at 1300 °C. Starting from these blocks, the tiles were machined into the final shape, re-heat-treated to
remove any organic contaminant, and coated. The nominal dimension of tiles was of 152.4 mm by 152.4 mm. The specific
local heat load in given point of the SSO airframe primarily determined the thickness of each tile. Since each tile had to
be machined to copy the local curvature of the vehicle airframe, considerable costs were added to the production of the
SSO NA-TPS. A thermal barrier based on an aramid felt was placed between the RSI tiles and the airframe [10]. The liner
was bonded to the tiles using a high temperature silicone binder [18].
Two different top surface coatings were used on the LI-900 RSI tiles. The HRSI tiles were externally coated with a blend
based on silicon and boron based powders (such as silicon tetraboride) [19]. The process was tailored to produce a coating
with a final thickness of about 300 lm [18]. The white coating of LRSI tiles did not contain silicon tetraboride. The LI-900 tiles
were optimized in terms of thermal conductivity, density, and thermal shock resistance. As a drawback, the optimization of
these properties tended to compromise the strength of the material; the LI-900 tiles could not be used in high stress areas of
the SSO NA-TPS such as the zone surrounding the landing gear doors, and windows. To overcome the limitations of LI-900, a
higher strength version of the material, known as LI-2200 (density 0.35 g/cm3), was designed for these areas; a different
processing was developed for this material [10].
After the development of the all silica based RSI tiles, new efforts were spent to identify other material formulations [15];
two or more types of fibrous reinforcements were introduced in the formulation with the aim to increase their specific
strength. NASA researchers identified an hybrid fiber based system referred as Fibrous Refractory Composite Insulation
(FRCI) in which alumino-borosilicate fibers were introduced [10]. A successful formulation of this new family of NA-TPS tiles
was the FRCI-12 (density 0.19 g/cm3) which comprised 21% alumino-borosilicate fibers. The FRCI-12 was considerably
lighter than LI-2200, but it exhibited a slightly higher thermal conductivity than L1-900. FRCI-12 was introduced in 1981
and this new formulation replaced the LI-900/LI-2200 tiles in many areas of the SSOs.
In 1996, NASA introduced a new tile material known as Alumina Enhanced Thermal Barrier (AETB) [10]. AETB was also
based on the use of hybrid fibers; particularly, alumina fibers were introduced to increase the service temperature. AETB
exhibited a higher dimensional stability than FRCI tiles. AETB-8 had a composition of 20% alumina fibers, 10%
alumino-borosilicate fiber, and 70% silica fiber [20]. In addition with the development of AETB-8, a new coating became
available, which, when used in conjunction with the new substrate, produced tiles known as toughened unipiece fibrous
insulation. These formulations exhibited much higher strength than earlier versions with minimal density impact. In
2005, NASA introduced a fifth tile material called Boeing Rigid Insulation-18 (BRI-18) (density of 0.29 g/cm3) [10]. BRI-
18 was the strongest formulation developed for the SSO NA-TPS with extremely high-impact resistance. BRI-18 was exten-
sively tested in the wake of the Columbia accident in 2003 and it was used to replace LI-2200 and FRCI-12 tiles in those areas
of the vehicle where impact risk resulted high such as the landing gear doors, the wing leading edge, and the external tank
doors.
2.3. Concluding remarks on the state of the art NA-TPS materials
Even after decades of researches on this class of thermal protection materials, the identified solutions to implement a NA-
TPS still remain very expensive and susceptible to a series of practical limitations. Nonetheless, the tremendous R&D efforts
spent to develop the state of the art non-ablative TPS certainly promoted many relevant breakthroughs in the field of
advanced ceramics, especially in terms of new materials, and processing techniques, also influencing the development of
state of the art ablative TPS materials. Currently, the know-how related on the Shuttle NA-TPS was resuscitated and
exploited in the Orion spacecraft program [21]; in fact, Boeing decided to cover the backshell of the capsule with several
hundred tiles (based on the legacy of the AETB-8), bonded to panels of composite laminates on a titanium honeycomb core
(Fig. 4(b)). Originally, the baseline for the TPS backshell was SLA-561V (see Section 6.2.1); however, the AETB-8 tiles showed
to provide more mass-efficient Micro-Meteoroid Orbital Debris (MMOD) protection. Moreover, as it will be pointed out in
Section 7, a new class of ablative materials (namely the Lightweight Ceramic Ablators) was based on the heritage of the
NA-TPS paradigm [16,17], and enabled the identification of an outstanding, yet low density family of ablative TPS materials.
3. Ablative TPS materials
3.1. Metals and ceramics as A-TPS materials
In the earliest phases of the cold war space race, some metals such as rhenium, molybdenum, and tungsten were tested as
heat shield materials for nose tip of re-entry articles [3,22] such as warheads; the erosion rates of metals such as rhenium
and tungsten were studied in laboratory and correlated with the flight data [23]. Rhenium and tungsten can also be used as
A-TPS material to produce the throat region of rocket engines [4]; they offer high performance in aggressive thermal and
chemical environment typically produced in solid rocket motor (SRM) chambers and throats. In most of the cases, these
A-TPS metals can provide almost zero erosion with highly aluminized solid rocket propellants. When the temperature of
the solid rocket propellant exceeds the melting point of rhenium, tungsten was one of be the best A-TPS material for
SRM throat inserts [3,24]. Nonetheless, the main drawbacks of these A-TPS metals are related to their cost, and density;
moreover, also the inability to tune the properties of the bulk material represents an intrinsic limitation. To overcome this
limitation, tungsten has been used to produce coatings on lower density materials such as graphite or CCCs [25]. In such a
way, the cost and weight related to a monolithic tungsten throat can be avoided. Chemical Vapor Deposition (CVD) is typ-
ically used to produce these coatings. The use of these coatings has to face and limit the problems related to the Coefficient of
Thermal Expansions (CTEs) of the different materials (the substrate and the coating), especially at the higher temperatures
[24]. Next-generation solid rocket propellants will have flame temperatures above the melting point of tungsten (3422 °C)
[26], so ultra high temperature ceramics will be required. Some companies such as Ultramet (US) developed fiber reinforced
ceramic throats and ceramic coated CCC based throats. Ceramic composites and coatings can also be used to prevent erosion
in the exhaust nozzle. Refractory oxides based on Hafnium (HfO2), Zirconium (ZrO2), Tantalum (Ta2O5), Yttrium (Y2O3), Alu-
minum (Al2O3), and carbides such as Zirconium carbide (ZrC), Hafnium carbide (HfC), Boron carbide (B4C), Hafnium carbide
(HfC), and Silicon carbide (SiC) were used as matrices or coatings and tested as A-TPS materials because of their high melting
point and high specific heat [25]. As an example, AVCO and Aerojet tested SiC inserts in low trust ablative combustion cham-
bers [27]. Fig. 4 reports the layout and the post burning appearance of an ablative chamber with a SiC insert. In some appli-
cations, these high temperature ceramics have been used as a porous medium; a fluid is forced through the pores of these
materials to provide transpiration cooling [22].
3.2. Graphite and carbon/carbon composites
Among A-TPS materials, carbon can be considered as a very high performance ablative; carbon possesses high heat capac-
ity and high energy of vaporization [8]. Carbon is capable of forming many allotropes i.e. two or more crystalline or molec-
ular structural forms with different chemical or physical attributes. As an example, the allotropes of carbon include diamond
(where the carbon atoms are bonded together in a tetrahedral lattice arrangement), graphite (where the carbon atoms are
bonded together in sheets of a hexagonal lattice). For graphite, the solid-liquid-vapor triple point is characterized by a pres-
sure of 10.8 ± 0.2 MPa and a temperature of 4330 ± 300 °C [28]. At atmospheric pressure, graphite has no melting point
and it sublimates at about 3620 °C [29]. For this reason, graphite was one the first TPS material used to confine or deflect
rocket combustion gases: as an example, the German V-2 rocket was one of the first engine to use graphite jet vanes to
change the direction of the thrust. Graphite is also used to produce the throat region for liquid or solid rockets [8,30].
The ablation process of graphite has been deeply investigated [8]. The vaporization rates were generally evaluated with
arcs or laser beams. Some researches on industrial graphite heated to vaporization temperature indicated that emission of
particulates may results from the expansion of the gas trapped in the closed pores created during manufacturing process of
graphite or due to the in depth sublimation of the material [8,31,32]. The surface roughening of graphite also affects the sur-
face heating. Preferential vaporization in the subsurface porosity is a mechanism for roughening [33]. If compared to indus-
trial grade counterpart (made via extruded or isostatically molded), pyrolytic graphite (PG) has shown a superior resistance
compared to other types of graphite when exposed to laser penetration tests [34,35]. PG is manufactured by decomposition
of a hydrocarbon gas at very high temperature in a chemical vapor deposition furnace. The result is an ultra-pure product
Fig. 5. Polymeric ablative materials divided into the main subclasses. Not published. Credit: UNIPG.
which is near theoretical density and extremely anisotropic [8]. This anisotropy results from the layered structure. Mechan-
ical, thermal, and electrical properties are generally far superior to conventional graphite but also the cost tends to substan-
tially increase as compared to industrial graphite. The ablation of graphite in hyperthermal environments like in rocket
nozzle throats can be estimated (as well as for graphite used to produce TPS) by the analysis of the concentration of reacting
species available by diffusion through the boundary layer of the reaction products [36].
However, graphite materials have relatively poor mechanical properties and have many problems in terms of resistance
to the thermal stresses. To overcome these limitations, 40–50 vol.% of high strength carbon fibers [37–42] are typically intro-
duced in a carbon matrix to produce a Carbon/Carbon Composite (CCC). Two-, three-, or four-dimensional reinforcements
made from laminating cloth or unidirectional tape oriented in different directions or by filament winding are used to pro-
duce the CCC. The aim is to combine the mechanical properties of carbon fibers with the high ablation resistance of a carbon
matrix [8]. In light of their remarkable ablation resistance, CCCs are used to produce both nozzle throats for SRMs [43] as
well as TPS. Typically, the fiber pre-forms are impregnated with resin (or pitch) and carbonized with several cycles to reduce
the porosity to levels where an acceptable ablation performance is obtained. High graphitizing temperatures (2500–
2800 °C) are required [41,42]. Hydrocarbon gases, such as methane or propane can also be used to prepare CCCs: they infil-
trate into the porous fibrous structure, heated to a temperature of 1000–1400 °C, and then they are made crack therein thus
to convert the gaseous precursors in a carbonaceous medium with a process similar to the manufacturing of PGs [42].
3.3. Polymeric ablatives: generalities
In light of their capability to be tuned to a wide variety of different hyperthermal environments, polymer based ablatives
represent the largest and most versatile class of TPS materials. Fig. 5 reports all main sub-classes of PAs; the description of
each type of polymeric ablative will be addressed in dedicated sections.
The history of NASA vehicles and probes showed that ablatives were able to survive in a wide range of hyperthermal envi-
ronments; ablative materials experienced heat fluxes ranging from approximately 30 W/cm2 up to 30 ⁄ 103 W/cm2
[44,45]. Fig. 6 provides a quantitative correlation between the peak heat flux and the stagnation pressure for NASA re-
entry vehicles employing PAs.
Once the mission and the working conditions of the TPS are defined, the selection of the material is related to the neces-
sity to balance the ablation resistance and insulation properties of the heat shield [44]. It means that each ablative can be
efficiently employed in a well specific condition; no single ablative can effectively work in a wide range of hyperthermal
environments. When an ablative is used outside its optimal zone in terms of heat flux and environment (Fig. 3), its perfor-
mance is inefficient, and the mass of the TPS reduces the available payload; accordingly, for each planetary probe or space
vehicle, the proper PA must be carefully selected prior to design of the heat shield [44]. From a general point of view, in the
presence of a turbulent hyperthermal environment, the ablation rate of a PA based TPS is typically higher than in the case of a
laminar stream: in fact, an ablating polymeric surface tends to remain relatively smooth during laminar ablation. On the con-
trary, turbulent heating may produce a highly irregular surface [20]. Moreover, the rate of heat transfer for a turbulent gas
boundary generally results in higher heating conditions than a laminar gas stream [30,46].
Fig. 6. Mission environments for ablative TPS applications. TPS mass fraction is that fraction of the entry probe mass devoted to TPS. The square shaped
borders of the graphs indicate the spallation (or sloughing) threshold. Above this limit, a macroscopic loss of ablating material due to mechanically induced
failure, the combined action of mechanical and thermal stresses, or particle impact is promoted. From [44]. Credit: Image courtesy of NASA, Dr. E.
Venkatapathy and Dr. B. Laub.
To correctly evaluate the performance of PAs intended for TPSs and to enable the possibility to maximize the mission pay-
load, an accurate modeling of the material ablation mechanisms is very important. To this purpose, in order to get the essen-
tial parameters used for the modeling of the ablation phenomena, a series of dedicated laboratory tests are performed on the
selected ablative [30,45]; the total heat load and heating time will also dictate the amount of material necessary for the insu-
lation. The TPS can be instrumented with a series of surface or in depth sensors; thermocouples or breaking wires can be
embedded in the heat shield. During the re-entry flight these sensors provide an evaluation of the recession rate of the
PA based heat shield [47–49] thus enabling the possibility to gather data that cannot be obtained in any man made facility.
These observations provide a validation of the models and can be used to introduce correction factors to the analytical tools
describing the ablation.
Another field in which polymeric ablatives are very important is rocketry. Basically, a rocket thrust chamber has two
major parts: a combustion chamber, and a nozzle [50]. This chamber (or case) temporarily confines the combustion gases
thus to produce a thrust in accordance with Newton’s third law; in a De Laval configuration, the combustion gases are forced
to pass through a convergent/divergent section (the throat) which is integrated with the expanding nozzle [51,52]. The
hyperthermal environment in which a rocket chamber must operate is extremely severe since the products of the combus-
tion gases are chemically corrosive [53,54], thermally reactive, an mechanically erosive [8,30,45]. The reaction gases can
reach temperatures in excess of 3000 °C and pressures as high as 100 bar [30,52,55]; the heat fluxes can exceed 103 W/
cm2. Ablative materials are extensively used in the production of chemical propulsion systems such as liquid and especially
solid propellant based rocket engines also known as solid rocket motors (SRMs) [52]. The use of ablatives enables the pro-
duction of low cost, passively cooled rocket combustion chambers both for civilian (the US Space Shuttle and Titan IV boost-
ers, the US Minotaur family, the European Ariane 5 boosters, the Italian Vega, the Japanese Epsilon, etc.) and military
launchers (the US LGM-118 Peacekeeper, LGM-30 Minuteman, the UGM-73 Poseidon, the UGM-96 Trident I and the
UGM-133 Trident II, etc.). Ablatives are also employed to shield the vehicle external surfaces from the high temperature
exhaust developed by the propulsion devices [55].
In order to study ablative materials, the laboratory reproduction of the different hyperthermal environments has been
subjected to remarkable efforts of the scientific community [22,30,56–62]. To properly simulate the working conditions
in which the ablative must operate, the laboratory facilities need to recreate at best the hyperthermal environment; the
speed, shear stresses, mass flow, pressure, temperature, and the chemical composition of the gas play a vital role in the test-
ing of the selected ablative. Sub-scale liquid or solid rocket engines, arc-jets, and other types of torches have been success-
fully used to recreate high enthalpy gas streams [45,56,58]. Nonetheless, in practically all cases, some characteristics of the
real environment are not well reproduced; thus, the data gathered in a full scale test instrumented with sensors are of
extreme importance. However, one of the most practical and cost effective way to characterize ablatives is based on the
use of an oxy-acetylene torch [30,56–59]. This simple, reliable, and affordable approach is very useful in determining the
relative merit of different materials thus weeding out the worst materials from more advanced and expensive data gener-
ation programs [56,58].
3.4. Fiber reinforced composites as TPS
3.4.1. Polymeric matrices

The organic matrices used to produce polymeric ablative materials can be divided into two main groups; non-charring
and charring matrices. In general, once exposed to a given hyperthermal environment, the gas evolution from a PA can effec-
tively interfere with the convective heat transfer from the hyperthermal environment to the material surface (Fig. 7(a)). This
process is at the base of the behavior of non-charring thermoplastic ablative matrices such as polytetrafluoroethylene
Fig. 7. Ablation processes for non-charring (a) and charring (b) polymeric ablatives. Not published. Credit: UNIPG.
(PTFE); in fact, above approximately 500 °C PTFE decomposes to form a volatile monomer and leaves no solid residue [46].
Fig. 10 shows the Thermo-Gravimetric Analysis (TGA) carried out at 20 °C/min both in nitrogen and air for different poly-
meric matrices; the single step degradation process of PTFE is clearly visible: at the end of the TGA process no residue is left.
Non-charring polymers are used when a uniform and clean removal of the ablative material is required. A low weight, PTFE
based heat shield was successfully tested on a Venus entry probe [63,64]; additionally, to further increase the insulation
capability of the shield, the back face of the TPS was combined with a reflective coating. In light of the relative simplicity
of the ablation process of PTFE compared to other PAs, the studies on this material has been used to validate or improve
the modeling tools [65].
However, in most cases, the formation of a solid carbonaceous residue (char) on the surface of the ablated material is
required (Fig. 7(b)); in this case the ablative is based on the use of charring polymers. Many matrices have been tested as
a basic component of PAs but, among common polymers, phenolic resin still remains the preferred and most widely used
charring binder. In addition to phenolics, other high char yield binders have been tested as a matrices of ablatives such as
polyimides [66], bismaleimide resins, cyanate esters [67], etc. [68–76]; however, when compared to phenolics, they gener-
ally tend to exhibit limitations in terms of cost and processability [67,68].
Other thermosetting matrices such as epoxies have a very limited char yield [77,78]. Fig. 10 shows the TGA patterns of a
diglycidyl ether of bisphenol F (DGEBF). The effect of different hardeners is also showed: aliphatic amines such as tri-
ethylenetetramine (TETA) tend to produce a smaller char yield as compared to aromatic counterparts such as diethyltoluene-
diamine (DETDA). The poor post fire properties of epoxy based carbon fiber reinforced composites were evidenced by several
researches. Sorathia and co-workers [79] exposed thin thermoset laminates reinforced with different types of fibers and
matrices to a low heat flux (2.5 W/cm2 for 20 min); carbon/epoxy composites did not retain flexural strength after burning.
Pering et al. [80] evidenced that the post fire mechanical properties of carbon/epoxy composites rapidly diminished with
increasing temperature or heating time of due to the high flammability and low char yield of the epoxy matrix.
On the other hand, if compared to other charring matrices, once exposed to an hyperthermal environment, phenolics (in
form of resols or novolacs) yield one of the higher amount of char among polymers [68–70,81]. A remarkable example of
commercial phenolic used to produce PAs is Hexion SC-1008 [82]; for over forty years this resol has been used in most of
Fig. 8. TGA patterns of different polymeric matrices carried out in a neutral (a) and oxidizing environment (c). A phenolic matrix (a resol), a
polydimethylsiloxane (PDMS), polytetrafluoroethylene (PTFE), and an epoxy system namely diglycidyl ether of bisphenol F (DGEBF) were considered. The
effect of an aliphatic hardener (triethylenetetramine, TETA) and of an aromatic counterpart (diethyltoluenediamine, DETDA) was reported. The first
derivative of the TGA curve (DTG) provides the decomposition rate as a function of the temperature (b and d). Test were carried out at 20 °C/min. Not
published. Credit: UNIPG.
Fig. 9. TGA patterns of different types of organic and inorganic fibers typically used to reinforce ablative materials carried out in a neutral (a) and oxidizing
environment (c). The first derivative of the TGA curve (DTG) provides the decomposition rate as a function of temperature (b and d). Test were carried out at
20 °C/min. Not published. Credit: UNIPG.
the phenolic based ablators. SC-1008 resin is a resol dissolved in isopropyl alcohol (IPA), which possesses a solid content
close to (60–64)%, and a viscosity of (180–300) cps. The solid content of the matrix can be increased but the viscosity also
follows the same trend. As an example, SC-1008 VHS is a variant of the same resol having a solid content of (80–85)% and a
viscosity equal to (8500–18,000) cps. When the matrix is exposed to a non-oxidizing hyperthermal environment and it is not
subject to mechanical erosion, it degrades to produce a charred layer or residue due to carbon present in the molecules of the
organic precursor [22,30,68–70]; the carbon based-residue can still partly operate as a binder of the fillers used in the for-
mulation of the ablative. Additionally, carbon is a high performance ablative material. In fact, as reported in Section 3.2, car-
bon possesses a high heat capacity and high energy of vaporization combined with high heat of ablation. In addition with
their superb thermal stability and char yield, phenolics have a remarkable dimensional stability due to the presence of highly
aromatic structures [22,30,68,69]. The matrix converted into char provides thermal insulation to the underlying virgin mate-
rial. These properties can be related to the high cross-linking density and chemical structure of the pristine matrix [81,83–
85]; besides their high carbon content which provides a high carbon yield, phenolics also have a low content of oxygen
resulting in a limited amount of volatiles like carbon monoxide and dioxide [84–88]. Moreover, phenolics possess a substan-
tial amount of carbon-hydrogen bonds, which supply the evolution gases (such as H2 and CH4) for the transpiration cooling
[22,68,69,84–88]; in fact, the pyrolysis gases produced by the charring matrix percolates through the char thus absorbing
heat and providing cooling (Fig. 7(b)). At the same time, once reached the surface, the gas film also works as a reaction bar-
rier [22,30,68]; however, when this gaseous layer is removed, due to the interaction of the hyper-thermal environment
gases, chemical erosion tends to increase. The charred region also reduces the oxygen diffusion from the boundary layer
to the virgin bulk thus playing an hindering action against the exothermic degradation reactions of the neat polymeric
matrix [88,89]. Nonetheless, in presence of an oxidizing hyper-thermal environment above a temperature of about
500 °C, the oxidation phenomena of the charred residue are dominant (Fig. 8(c) and (d)) [89–92].
3.4.2. Fiber reinforced polymeric ablatives

Even considering high carbon yield matrices such as phenolics, the residual char of the polymeric matrix is a relatively
weak medium; the carbonaceous residue can be mechanically eroded and removed by the friction action exercised by the
high pressure and temperature combustion products of the rocket propellants, or by the interaction with the atmosphere
gases during the re-entry flight. For this reason, since the polymeric matrix alone cannot effectively work as an ablative
material, some reinforcements must be added at the virgin polymer. As a result, once the matrix is converted in a carbona-
ceous residue, the retention of the charred material is promoted and the ablation process can be carried out in an effective
way since the material can continue to endothermically absorb heat (see Section 3.2). To this purpose, fibrous reinforce-
ments made of carbon, refractory oxides (such as alumina and silica), mineral asbestos, and glass, have been successfully
combined with the polymeric matrix thus producing a Fiber Reinforced Polymeric Ablator (FRPA) [8,22,30]. Some other exo-
tic fibers based on carbides or nitrides have also been tested in ablatives [93]; however, the cost tended to limit their use. The
TGA patterns of different types of fibers used in PAs is showed in Fig. 9.
The typical content of fibers in FRPAs is in the range of 60/75 wt% on the total weight [22,30,68]. The introduction of fibers
also helps to anchor the charred region on the virgin material which is undergoing pyrolysis; accordingly, the possibility to
obtain a delamination between these two phases of the FRPA characterized by different CTEs is reduced. Entrapped pyrolysis
gases in the charring matrix can cause pore pressure build-up, and also produce phenomena ranging from ply lift, sub-char
ply separations, pocketing, and loss of ablative material [22]. These processes, if severe enough, can significantly affect the
performance of the TPS. The presence of fibrous reinforcements, minimizes this series of phenomena [30]. As a result of the
conversion of the polymer in a charred medium, a substantial amount of heat is absorbed by the degradation processes and
the char which works as a heat sink [68–76]; moreover, the reinforcements embedded in the FRPA also undergo many
endothermic processes, such as melting and evaporation, thus working as an additional heat sink. The higher the retention
of ablative material, the higher the effectiveness of the material as a heat sink and shield. In some cases the fibers also
endothermically react with the matrix. As an example, glass fibers can react with the charring matrix in a highly endother-
mic manner [94]. For glass or silica/phenolic ablatives and, more in general, for silica rich FRPAs exposed to a not oxidizing
hyperthermal environment, at temperature in excess of 1200 °C, the char and the silicon dioxide chemically react to form
silicon carbide (SiC) [95]. In fact, SiC is known to form via carbothermal reduction (a high-temperature exposure in a not
oxidizing atmosphere) of solid state carbon and gaseous silica [96].
Reinforcements in the form of tapes, random continuous, and chopped fiber mat, chopped fibers, two- and three-
dimensional fabric are typically used. FRPAs are usually produced by placing the fibers or the cloth in accordance with a
determined layout, impregnating them with the resin, then molding, and curing [22,30]. A similar process is used when
chopped reinforcements are used. Pre-impregnated reinforcements are also used. In terms of performance, due to their good
Fig. 10. Film cooling technique for liquid fuel rocket engines; a series of injectors located in the periphery of the inner wall of the combustion chamber
provides a supply of fuel which work as a coolant thus to decrease the local temperature and extend the lifetime of the material. Image modified and
enhanced from [103]. Credit: Image courtesy of NASA.
Fig. 11. Appearance of a ScorpiusÒ 22 kN liquid fuel rocket engine (a). Testing of a 90 kN combustion chamber (b). From [104]. Credit: Microcosm, Inc.
mechanical properties, FRPAs are used in those hyperthermal environments in which the erosive action of the high temper-
ature gases is very severe. For this reason, FRPAs are used to manufacture the TPS of space vehicles but they are also used to
produce the thrust chambers of rocket engines [98]. In this case, as for the heat shields of a space probe or vehicle, the rocket
engines are passively cooled by virtue of the endothermic processes of the PA. For a rocket engine, the most critical part is the
throat since in this region the heat flux and the pressure of the combustion products are maximized. The erosion of the
Fig. 12. Cross section of glass/phenolic ablative exposed to a not oxidizing hyperthermal environment at an heat flux of 800 W/cm2. Not published, courtesy
UNIPG.
ablative is also higher in presence of condensed solids; as an example, during the combustion of modern solid rocket pro-
pellants such as Ammonium Perchlorate Composite Propellant (APCP), alumina is produced [97–99]. The impact of alumina
byproduct particles on the ablative material can severely increase the erosion of the FRPAs; in fact, the action of the ablated
gas which works as a reaction barrier is completely useless against the mechanical erosion of solid impinging particles [30].
This phenomenon is particularly critical in SRM throats. In fact, the performance deterioration of SRMs caused by nozzle
throat erosion becomes more severe with increased operating pressure which promotes higher rates of heat and mass trans-
fer from the core flow to the nozzle surface. Understanding of the rocket nozzle throat erosion processes and developing
methods for mitigation of erosion rate can allow higher motor operation pressures and thus better performance [100,101].
If compared to regenerative cooled engines – in which the fuel flows through channels or in a jacket around the combus-
tion chamber or nozzle to cool the engine – a passively cooled rocket engine can be very cost effective. In fact, the use of
ablative materials enables a significant simplification of the design and operational cost of the engine since the requirement
for pumping liquids in the regenerative cooling jacket can also be removed [30,102]. Moreover, the use of film cooling can
significantly extend the lifetime of the ablative walls of a rocket engine [103]; in this case, a thin layer of fuel is sprayed
above the inner wall of the engine improving the gas barrier produced by the pyrolysis of ablator, decreasing the tempera-
ture experienced by the wall of the chamber, and providing additional protection against the oxidizing agents (Fig. 10). Addi-
tionally, as for the gases produced by the pyrolysis of the ablator, in presence of a carbon rich gaseous phase derived from the
cracking of the fuel, the transmission of the heat by radiation is also reduced.
A remarkable example of passively cooled liquid fueled rocket engine based on the use of silica/phenolic FRPAs is repre-
sented by the family of chambers produced by Microcosm, Inc; Microcosm developed simple, low-cost, pressure fed Liquid
OXygen (LOX)/kerosene engines to power the ScorpiusÒ family of launch vehicles [104–106]. Fig. 11(a) shows a 22 kN cham-
ber whilst a test of a 90 kN engine is reported in Fig. 11(b). These ablative combustion chambers were made of silica/phenolic
and a carbon/epoxy filament overwrap. The tests carried out on the 90 kN chamber highlighted the high performance, reli-
ability, and cost-effectiveness of these engines especially when compared to comparable regeneratively cooled chambers
[102].
Now let’s introduce more details on the ablation process of a FRPA which is schematically summarized in Fig. 7(b) and it
can be described as follows. Fig. 12 also reports a typical cross section appearance of a glass/phenolic FRPA exposed to a non-
oxidizing hyperthermal environment at an heat flux of 800 W/cm2 [57,58].
Once exposed to an hyperthermal environment, the heat is transferred to the ablative material by conduction, convection,
and radiation [30,93]. At first, the temperature of the ablative increases at a rate which depends on the heat flux imposed by
the hyperthermal environment and on the energy absorbed into the ablator. At the surface, the temperature rises and when
the material reaches a sufficiently high temperature (typically above approximately 200 °C), thermally induced reactions
such as chemical reactions or phase changes take place and the organic matrix degrades to form gaseous products and a
charred residue [84–91]. As a result, a substantial amount of energy is absorbed by the ablative. The produced gases are
trapped in the material due to the low porosity and permeability of the medium; thus, the internal pressure can become very
high, leading to a large thermo-mechanical expansion of the solid matrix. When the pressure becomes sufficiently high, the
gases diffuse through the charring layer; by virtue of their pressure, the pyrolysis products form a boundary layer, which acts
Fig. 13. TMA patterns of a carbon/phenolic Fiber Reinforced Polymeric Ablative (FRPA) as compared to an elastomeric heat shielding material (aramid/
EPDM) for Solid Rocket Motor (SRM) liners. Not published. Credit: UNIPG.
as a barrier against heat flow from the incoming hot stream into the ablator wall [68]. This gas film also works as a diffusion
barrier and controls the chemical reaction rate between the combustion species and the charring material. Also, as the gas
phase percolates through the porous char, it absorbs a high amount of heat. Once the charred region transfers heat into the
virgin resin, new char is produced; as the pyrolysis proceeds, the porosity and permeability of the char increases and the rate
at which gas is lost by diffusion equals and then exceeds the rate at which gas is produced. These phenomena can be mea-
sured as a peak in the observed dimensional expansion of the material followed by a sharp contraction due to the escape of
the gases and the coupled reduction of the internal pressure [92]. The expansion is then followed by a slow contraction of the
solid matrix due to the continuous decrease in the rate of pyrolysis gases production. As the virgin matrix completes its con-
version into a carbonaceous medium, the endothermic degradation of organic binder vanishes and the cooling effect due the
pyrolysis gases becomes negligible. Fig. 13 reports the Thermomechanical Analysis (TMA) pattern of a carbon/phenolic (C/
Ph) FRPA carried out in nitrogen at 20 °C/min. The shrinkage of the material above 200 °C is clearly visible; the difference
between the in-plane (XY) and out-plane (Z) CTE of the carbon/phenolic laminate is also noticeable.
To further understand the behavior of a FRPA subjected to a severe hyperthermal environment, a carbon/phenolic ablator
used as a thermal protection in a solid rocket motor assembly and exposed to the combustion gases of an APCP will be con-
sidered [107]. In this case the nozzle and the elastomeric internal thermal protection liner can be exposed to fluxes in excess
of 1000 W/cm2 and temperatures as high as 3000 °C [30,68]. Depending on the depth in the FRPA laminate and thus, on the
internal temperature, the following processes are possible. Starting from the cold side of the ablative composite to the
exposed hot face, the degradation of the matrix is the first process to be considered; the endothermic cracking of the poly-
meric matrix produces gaseous hydrogen and various fragmented CAH molecules. Up to a temperature of about 350 °C, H2O
is the principal product [108,109]. Increasing the temperature, phenol and other species are released and, above approxi-
mately 550 °C, the molecular weight of the gases decreases [110–112]; in a reducing environment, H2 is produced [113].
Increasing the temperature (1000–1500 °C), the thermal cracking of the gaseous phase further continues; depending on
the local conditions, the gas can be in a state of chemical equilibrium or not-equilibrium [114,115]. In addition to these
gas-gas reactions, some other reactions and transformations may occur; a very important phenomenon is the coking process
[116]. The available carbon-rich gaseous products promote the formation of a solid carbonaceous deposition in the charred
region [107]; this mechanism can reduce the porosity and the permeability of the char, and increase the local density of the
charred PA related to the primary pyrolysis. The coking effect increases the resistance of the material to the thermo-chemical
erosion. Very close to the exposed hot surface, where the temperature exceeds 2500 °C, the thermodynamic conditions and
the chemical species of the internal gas flow change the direction of the heterogeneous gas-solid reactions; the carbon rich
char is turned into gaseous species and elemental carbon is liberated. At the surface itself, the combustion gas contains gas-
eous chemical species such as HCl, H2O, CO, CO2; as a result, the heterogeneous chemical reactions among these species exert
an erosive action against the solid surface. This process is known as thermo-chemical erosion [117–120].
Fig. 14. Post burning appearance of silica/phenolic throat sections of liquid fuel rocket engines manufactured using continuous fiber and chopped
reinforcements. It is possible to see how, in terms of erosion resistance and char depth, both types of reinforcements produced similar results. From a
practical point of view, these results confirmed that, under the test conditions considered in the research [121], both material can be considered equivalent
and, at the same time, the material based on the chopped fabric is cheaper than the long fibers based counterpart. From [121]. Credit: Image courtesy of
NASA.
3.4.3. Role of the fiber in the ablation of FRPAs

Up to now, the role of the fibrous reinforcement during the ablation process of FRPAs has not been analyzed in detail. As
long as the matrix does not suffer ablation and cover the fibers, they are protected from high temperatures; as the matrix
degrades and then erodes, the reinforcements are directly exposed to the hot stream and thus their temperature rise. As
a result, the fibers endothermically react with the hot gas stream, acting as an heat sink [93]. When the temperature of
the fiber increases, a phase change can occur. For some materials, melting occurs; sublimation or chemical dissociation
can also take place. This range of phenomena is very similar to the charring or the cracking of the organic polymeric matrix.
For those fibers experiencing melting, in order to minimize the removal of the melt, it is preferable to have a very high vis-
cosity liquid [93]. In fact, provided that the residual melt remains on the charred surface, the molten phase undergoes vapor-
izations and thus it continues to absorb additional heat and to further protect the underlying material. For this reason,
although silica fibers have a lower melting/softening temperature than alumina fibers, SiO2 based fibers are generally pre-
ferred to A12O3 counterparts since the molten SiO2 has a higher viscosity than A12O3 [93]. The molten phase on the charred
materials (Fig. 12) continues to work as an heat sink and to protect the ablative material from oxidation [30].
A fiber with a high thermal conductivity tends to increase the in-depth penetration of the charring phenomena and con-
sequently, if the pyrolysis gases cannot escape, the fibers can suffer severe in depth debonding or pull-out from the matrix
(see Section 3.4.2). Accordingly, when compared to powdered fillers, fibrous reinforcements, with their high aspect ratio, also
ensure a superior char retention (Fig. 12); additionally, since the CTE of the fibers and of the charred medium can be very
different [108] and moreover, the char tends to undergo shrinking as a result of the degradation of the polymeric matrix,
powder-like fillers tend to suffer debonding or pull-out from the matrix. However, if the filaments lie parallel to the surface
impinged by the hot stream, they can be peeled off [121]. To better explain this point, researchers have carried out on silica/
phenolic FRPAs samples evaluated as throat sections of liquid fuel rocket engines [121] also showed that fabric orientation
angles near zero (respect to the gas flow) produced the lowest amount of char-through. At the same time, for the regions of
the engine exposed to high shear stresses, a tendency to delamination was also evidenced. On the other hand, a 60° orien-
tation produced the best erosion resistance but also promoted an increased in-depth charring (Fig. 14).
In terms of reinforcements, especially for small ablatively cooled rocket engines (below 100 kN of thrust), research also
evidenced that randomly oriented short reinforcements in form of chopped fabric exhibited good performance both in terms
of erosion resistance and of mechanical properties (Fig. 15). In this case, the chopped reinforcements cut from an uncured
pre-impregnated fabric (as an example, in the shape of small squares with a dimension of one-half by one-half inch) are
compacted by means of compression molding techniques and then cured [122]; the same approach is used when the ablative
is based on chopped fibers. The effectiveness of chopped reinforcements was also confirmed by other studies [56]. For this
reason, ablative Bulk Molding Compounds (BMCs) constitute a cheap and effective approach for the production of ablative
heat shields; accordingly, small parts as well as significant portions of a rocket combustion chamber or of a TPS can be effec-
tively produced using ablative BMCs [123,124]; a wide range of commercial ablators are sold as molding compounds.
Fig. 15. Effect of different types of reinforcements on the erosion rate of different types of FRPAs evaluated as a throat region materials for liquid fueled
rocket engines. From [121]. Credit: Image courtesy of NASA.
3.4.4. Powdered fillers for FRPAs

However, among reinforcements for FRPAs, powdered fillers also play a very important role [30]; in fact, they can strongly
improve the performance of an ablative. This is particularly true for silicone dioxide in powder; as for SiO2 based fibers, once
heated up above the melting temperature, the micron sized silica particles embedded in the material form a viscous melt
layer on the charred surface. This film not only continues to absorb heat but it also protects the char from oxidation, reducing
the ablation rate of the carbonaceous substrate; this solution is used to effectively reduce the oxidations of many FRPAs [30].
Moreover, in the case of glass or silica/phenolic ablatives, the presence of micron sized silicon dioxide particles increases the
retention of the melt fibers. Moreover, in the absence of powdered silica dispersed in the matrix, since the composite is a
discrete medium, once the resin pockets become char, the droplets of the molten fibers can easily adhere one each other,
but they have a limited compatibility with the carbonaceous substrate. Fig. 12 shows a post burning appearance of a
glass/phenolic ablative exposed to an oxy-acetylene torch [8,30,57,58]: in absence of silica powder, the contact angle of
the molten droplets on the charred surface show a limited compatibility with the substrate [95]. The use of micron sized
fillers dispersed in the matrix contributes to reduce this intrinsic limitation of the composite; in fact, the droplets of the silica
particles can work as adhesion points for the molten silica fibers. For instance, these benefits related on the use of micron
silica particles were highlighted by the studies on silica/phenolic composites used to produce liquid fueled rocket engines.
Typical silica/phenolic composites have a fiber on matrix ratio equal to 70/30 wt%; Peterson et al. [121] showed that by
replacing about 10% of silica fibers with a similar amount of silica powder, the ablation resistance of the ablator was not sig-
nificantly compromised, while the cost of the material could be sensibly reduced (Fig. 15). A commercial standard for silica/
phenolic ablatives is Cytec MX-2600 (density 1.7 g/cm3); its composition is 60% silica fibers, 30% phenolic resin, 10%
silica powder. MX-2600 was employed over forty years as a material for a wide range of rocket engines; as an example, it was
used for the Lunar Module Descent Engine [125] and it is still able to provide good performances in modern civil and military
rocketry [126,127].
Another remarkable example of polymeric TPS based on silica reinforcements is the Apollo heat shield material, the
Avcoat-5026 [128]. It was a mid density ablative material (density 0.5 g/cm3) composed of an epoxy-phenolic matrix filled
with silica fibers and phenolic micro-spheres [129,130]. The compound was placed in the cavities of a fiberglass reinforced
phenolic honeycomb. During the descent into the Earth atmosphere, upon heating to 1350 °C, agglomerates of molten silica
fibers first appeared on the surface; these silica droplets then partially covered the surface [8]. Above 1850 °C, silica melt
was no longer found on the charred surface, and the material suffered mechanical erosion at pressures in excess of 1 atm.
Since the Avcoat-5026 has been used for the Apollo program, it is a man rated heat shielding material and thus, it is currently
considered by Boeing for the Orion capsule [131] which represents one of the vehicles currently proposed to replace the
Space Shuttle. Low content silica fibers such as glass filaments are also employed to produce ablatives such as Cytec
MXB-360; it is a glass/phenolic ablative in which the reinforcement is used as a mat. Koo et al. [132] reviewed the most rel-
evant researches on this important FRPA reporting the results of the testing of this material under different hyperthermal
conditions.
Powdered filler are also widely used on carbon/phenolic PAs. In this case carbon black (CB) is used as a filler of the com-
posite. As an example, among commercial carbon/phenolics, Cytec MX-4926 (density 1.45 g/cm3), a baseline material for
rocket engine assembly [76,97,98,100,133] consists of 50 wt% carbon reinforcements, 35 wt% phenolic resin, and 15 wt% car-
bon black. CB helps to reduce the shrinkage of the resin pocket due to the carbonization of the matrix in carbon fibers based
FRPAs; moreover, the use of CB also allows to reduce the cost of the material.
3.4.5. Basic characterization of FRPAs

From a general point of view, in terms of structural requirements, the FRPA must provide good mechanical properties
[30]; the strength of composite materials strongly depends on temperature, with compressive strength and modulus rapidly
decreasing once the temperature exceeds the glass transition temperature of the polymer [79,80,83]. After degradation of
the matrix, the char exercises the binding action once produced by the organic matrix precursor. Among FRPAs, glass and
silica/phenolic ablatives tend to undergo a broader series of ablation phenomena than carbon/phenolic PAs [115,134–
136]. Moreover, the stresses resulting from the thermal gradients through the thickness of these materials can limit the
use of FRPAs; for this reason, the study of the thermo-mechanical behavior of the material is very important. The decompo-
sition, the thermo-mechanical stresses, and other material properties of polymeric ablatives are strongly dependent on the
type of the hyperthermal environment and intimately on the heating rate. For polymeric ablatives used in rocketry, these
heating rates ranges from 5000 °C/min up to 100,000 °C/min [68,137,138]. Typically, the thermal expansion tends to
increase with the heating rate; this behavior is related to the increase in the rate of the gas production of the charring matrix
as compared to the diffusion rate [22].
From 1980 onwards, Henderson et al. [139–146], Ramamurthy [147], Doherty [148], and Florio et al. [149–155] published
a series of pioneering papers introducing the thermo-physical properties measurement techniques and the related numerical
modeling tools for FRPAs; in these papers, the methods to evaluate the heat capacity, the thermal expansion and other
important material properties were reported. In most cases, the attention was focused on glass/phenolic ablatives. The anal-
ysis was carried out using techniques such as: Differential Scanning Calorimetry (DSC), TGA, and TMA. Differential Thermal
Analysis (DTA) provides information on the character of the pyrolysis reactions whereas gas chromatography can be used to
determine the composition and quantities of the products evolved through these reactions. Effluent Gas Analysis (EGA) can
also be used to provide data on the total gas evolvement enabling a full integration among DTA [113], gas chromatograph,
and mass loss data [113]. These researches established the bases for a proper and comprehensive evaluation of the thermal
response of composite materials exposed to elevated temperatures; the methods and tools introduced in these researches
still represent a valuable and effective approach to measure the decomposition kinetic parameters and the thermal proper-
ties required as an input for any ablation modeling [153]. Analogous techniques were used on other FRPAs such as carbon/
phenolics; Wertheimer et al. [107] reviewed the research on the testing and modeling of the ablation processes of carbon/
phenolic composites exposed to the exhausts of solid rocket engines.
Due to the health problems related to the use of asbestos fibers, many countries developed materials to replace FRPAs
based on this reinforcement. Nonetheless, because of the high performance of asbestos based FRPAs, a wide literature on this
class of ablatives has been produced [121,154–157]. Henderson et al. [140] undertaken the testing and the ablation modeling
of asbestos/phenolic FRPAs, determining the kinetic parameters for the thermal decomposition of this class of PAs; a multiple
heating rate method was used. Bahramian and collaborators deeply investigated and modeled asbestos/phenolic ablatives
exposed both to low (10 W/cm2) and severe (800 W/cm2) [57,58] hyperthermal environments [158–161]; the ablative
performance, thermal decomposition and temperature distribution through the thickness of asbestos/phenolic were exam-
ined. The authors also estimated the effective thermal diffusivity of these materials using thermal analysis technique and
oxyacetylene flame test.
4. Advanced testing techniques for TPS materials
The primary aim of testing facilities is to identify, once specified the hyperthermal environment, the best material formu-
lations which exhibit the proper ablation resistance and insulation capability for that given environment. Combustion gas
torches and arc-plasma sources have been widely used for screening, since they are readily available, easy to operate, rela-
tively inexpensive, and provide quantitative and reproducible results [45,56–60]. The first necessity of a researcher is to
characterize all candidate materials in the proper environment and thus to identify the corresponding facility able to sim-
Fig. 16. Typical layout of an Oxy-Acetylene Torch based test bed (OAT) (a). All components of the setup are highlighted. Prior to be used, the torch must be
calibrated with a slug calorimeter (b). It basically consists of a copper mass held by a series of low thermal conductive screws designed thus to minimize the
loss of heat. Not published. Credit: UNIPG.
ulate it; the environmental variables and their intensity strongly influence the behavior and the performance of an ablative
material [30,45,56,58,163]. The experience on the material/hyper thermal environment interconnection evidenced that the
nature of the most relevant parameters is thermal, chemical, and mechanical [45,56,163].
4.1. Thermal conditions
Environmental variables and their magnitudes strongly influence the performance of an ablating TPS materials [163]. As
an example, an A-TPS designed for use in convective heating based hyperthermal environments should be tested using the
same type of incident heating; accordingly, ablatives subjected to radiant sources should be characterized in a radiant heat-
ing environment. Ablatives which pyrolyze in response to the interaction with a given hyperthermal environment effectively
exert a blocking action on a large fraction of the incident convective heat by virtue of the mass transfer of the produced gases.
These gaseous species will have little effect on radiant energy since the gases are essentially radiation transparent; thus,
radiant energy may also penetrate deeply into a transparent, ablating material and promote high in-depth and back face
temperatures. Only in the presence of a pyrolyzed gases having a strong presence of carbon-rich volatiles, the transmission
of the heat by radiation can be influenced and reduced. The temperature and enthalpy of the hyperthermal environment also
play an important role; the thermal efficiency of an ablative tends to increase with higher gas enthalpies. As a consequence,
the characterization of an A-TPS material destined to high enthalpy re-entry environments in a low enthalpy gas environ-
ment cannot be used to properly predict the real response of the ablative [163].
In all cases, the appropriate testing of ablatives would require the necessity to recreate the hyperthermal environments in
which the materials work and thus, the testing under the most representative thermal conditions should be implemented. In
Fig. 17. Appearance of a slug calorimeter (a). Sample holder and fully assembled experiment with in-depth thermocouples (b). OAT setup installed at
University of Perugia – STM group, Terni, Italy (c). Test execution of an ablative material via OAT (d). Not published. Credit: UNIPG.
terms of temperatures, even considering high performance TGA, a maximum temperatures of about 1800 °C can be reached,
a value lower than the actual operating temperature produced inside a rocket combustion chamber which can exceed
3000 °C [22,30,52,68]. Moreover, TGA can reproduce heating rates up to about 500 °C/min at best. Accordingly, parameters
such as the heating rate experienced by a rocket engine or a TPS cannot be reproduced by any TGA; as an example, depending
on the rocket engine working conditions, these heating rates can reach values up to 100,000 °C/min [138]. This consider-
ation is particularly true for TPS materials intended of rocket nozzle assemblies such as the throat region of SRMs which is
directly exposed to the hot combustion stream and experiences higher heating rates than the liner placed between the case
and the propellant grain. Additionally, TGA cannot reproduce any shear stress caused by the combustion gases or by the re-
entry flight and thus, the mechanical erosion cannot be evaluated.
The most common, affordable, and reliable way to perform a test which can partially simulate the severe hyperthermal
environment of a rocket engine is based on the use of an oxy-acetylene torch [30,45,56–59,163,164]. This test method is gen-
erally intended to screen the most obvious poor materials from further consideration [57–59]. Since the combustion prod-
ucts of an oxy-acetylene torch more closely resemble the environment generated in rocket motors, this test method is more
applicable to screening materials for rocket nozzles and liners than for aerodynamic heating; however, this test was also
used to evaluate ablatives intended for TPSs [164,165]. The conditions generated by the oxy-acetylene heat source represent
only one set of real conditions; they do not simulate any specific application [163]. Thus, the test results cannot be used to
directly and precisely predict the behavior of materials for a specific environment. Nonetheless, the test is very useful in
determining the relative merit of different materials thus weeding out worst materials from more advanced and expensive
data-generation programs [57–59]. The method has also been considered for use as a production quality control test for
rocket insulation materials.
The oxy-acetylene torch is generally able to produce a high temperature flame (up to approximately 3000 °C) and a heat
flux up to 900 W/cm2. ASTM-E-285-80 [57] provides the general guidelines to arrange a test bed based on an oxy-acetylene
torch. Fig. 16(a) reports a typical layout of an Oxy-Acetylene Torch based test bed (OAT). It essentially consists of the follow-
ing devices: the acetylene and oxygen tanks, the pressure gauges, the flow meters and the torch compose the heat source
[57–59]. The possibility to finely control the pressure and the gas flow is essential to perform any repeatable, quantitative
test: thus, gauges capable to provide precise pressure measurements and to maintain an accurate flow of gases must be
employed. In order to align the torch tip at the sample holder, these parts composing the OAT can be mounted on a proper
sliding system; other equivalent solutions can also be considered [58,59]. The temperature of the torch plume also depends
on the distance between the torch and the sample; accordingly, in order to carry out measurements at a well defined hyper-
thermal condition, a tunable distance-regulator is typically placed between the sample holder and the torch tip. The power
output of the plume is measured using a slug calorimeter in which a copper slug of known mass (Figs. 16(b) and 17(a)) is
Fig. 18. Structural Plastics Ablative Rocket (SPAR). From [167]. Credit: Paul V. Galvin Library at Illinois Institute of Technology. The sub-scale nozzle
specimens before and after exposure are also visible. From [163].
exposed to the oxy-acetylene torch; the copper mass is held by a series of low thermal conductive screws designed to min-
imize the loss of heat. A thermocouple is embedded within the copper slug (cold side) providing a temperature versus time
curve for the slug. The slope of this curve, along with the properties of the slug and the area of the plume are used to calculate
the heat flux produced by the oxyacetylene torch: ASTM-E457-08 [166] describes the measurement of heat transfer rate
using a thermal capacitance-type calorimeter which assumes one-dimensional heat conduction into a cylindrical piece of
material (slug) with known physical properties. The cross section area of the slug is used to evaluate the heat flux. The sam-
ples to be tested can possess different geometries and dimensions. Five specimens of each materials are typically tested. A
series of thermocouples embedded in the sample at well defined depths from the exposed surface (hot face) combined with a
real time data acquisition system allow to record the in depth temperature profiles (Fig. 17(b)); in such a way, the insulation
capability of the tested material can be evaluated. In some cases, X-rays are used to determine the real depth of the thermo-
couple head [98]. The erosion rate, the loss of mass, the post burning morphology of the material can also be studied; thus,
the results obtained with this method can also be exploited to model the ablation processes of different materials. Fig. 17
(c) and (d) reports a picture of an OAT built according to ASTM-E-285-80; it is possible to identify all basic components
at the base of this testing facility. The operating costs of a test performed via OAT are of the order of some ten or hundred
of dollars depending on the required quantities to study.
4.2. Chemical conditions
It is well established how hyperthermal environments may contain reactive chemical species which tend to increase the
material degradation [30,45,52,56,163]. The thermo-chemical attack of the ablating surfaces by oxidizing species has been
Fig. 19. Simulated Solid Rocket Motor (SSRM) installed at Texas State University (a). Post testing appearance of a sample exposed to the SSRM alumina rich
exhaust plumes; it is possible to see the alumina coating on the charred surface of the ablative material (b). Credit: Dr. J. Koo.
evidenced in many different environments; more in general, charring polymers are particularly susceptible to the oxygen
content. As an example, it has been reported how arc heated oxygen produced ablation rates of phenolic/nylon PAs up to
twenty times higher than the erosion rate obtained in an inert gas [163]; high temperature water vapor present in the com-
bustion products of solid propellants may also promote appreciable oxidation of ablating carbonaceous surfaces [167].
Accordingly, the possibility to simulate different hyperthermal environments is quite important. For an OAT, depending
on the oxygen to acetylene volume ratio, different conditions can be recreated; a volume ratio equal to 1.2 [57,58] essentially
corresponds to a neutral hyperthermal atmosphere (the oxygen/acetylene molar ratio for complete combustion in the pri-
mary flame is 1:1). Increasing the oxygen content, oxidizing plumes can be produced thus to partially simulate the effect of
oxidizing species on the tested material.
4.3. Mechanical parameters
The mechanical forces acting on an ablative material alter its performance in an unpredictable manner [76]; with the
increase of stagnation pressures, the thermally degraded surface of an A-TPS tends to be crushed and removed before it
effectively completes its endothermic action. A high speed combustion gas produces very high interface shear stresses.
These induced stresses can be sufficiently severe to mechanically scrub the ablating surface or increase the melt run
off. As an example, phenolic/nylon ablatives has been observed to entirely lose their charred surface when exposed to
high mass flow rocket exhaust whereas, in subsonic arc heated air, they can form and retain a thick, protective char layer
[163,168–170]. Ablating surfaces may also be mechanically abraded by energetic particles contained in the gas stream
[171–173]. With this respect, the main drawback and limitation of the OAT is related to its limited capability to repro-
duce high shear stresses [58,59]; in fact, the pressure of the gases supplied to the torch generally does not exceed 1 bar.
As a consequence a replacement of the OAT able to simulate higher pressures or even mechanical erosion has been
sought.
A remarkable attempt to use a small scale rocket to screen ablatives was constituted by the Structural Plastics Ablative
Rocket (SPAR) [56,167]; it used gaseous oxygen and gaseous hydrogen as oxidizer and fuel respectively [30]. The SPAR motor
(Fig. 18) was designed to be fired with a stagnation temperature controllable from 1100 to 3300 °C, and a chamber pressure
controllable from 5 to 50 bar. Samples were fabricated into small test nozzles directly fitted into the aft end of the motor;
the throat diameters of test nozzles could be varied from 6.3 to 19.1 mm (Fig. 18). The firing duration of the SPAR motor
was automatically or manually controlled, depending on the type of data desired. Initial SPAR motor researches were
designed to establish testing variables and procedures, thus to provide information on the general characteristics of specific
classes of materials. Tests revealed that the ablation rate of a given throat-nozzle material and the post burning inner shape
of the samples depended on firing time, chamber pressure, and temperature [56].
Another way to overcome the limitation of the oxy-acetylene torch based systems in terms of combustion gas-pressure is
constituted by the use of sub scale liquid or hybrid liquid/gaseous fueled rocket engine; in fact, to limit the operating cost of
liquid fueled facility and improve the reliability and safety of the test, the oxidizers which are generally constituted by cryo-
genic liquids such oxygen or very toxic acids such HNO3 are replaced by gaseous oxygen. A remarkable example of a device
designed around this principle is the Simulated Solid Rocket Motor (SSRM) installed at Texas State University [174]; in fact,
the SSRM is a small scale rocket engine which burns a mixture of liquid kerosene and gaseous oxygen. The layout of the SSRM
is showed in Fig. 19(a).
The key feature of SSRM is that aluminum oxide particles can be injected into the plume to simulate the particle laden
flow of solid rocket exhaust plumes. In fact, as pointed out in Section 3.4.2, during the combustion of modern solid rocket
propellants, alumina is produced; these high speed particles exert an additional mechanical erosion on the internal walls
of the solid rocket [173]. Under given conditions, the deposit of a substantial amount of alumina is also possible (see
Fig. 19(b)). Thus, if compared to the OAT, the SSRM and other similarly designed facilities are also able to simulate the
mechanical erosion of the tested material in presence of condensed solids. The SSRM is capable of producing a particle laden
exhaust environment with an heat flux up to 1400 W/cm2. The flame temperature is approximately 2200 °C and the velocity
of the particle-laden exhaust is approximately 2000 m/s. The standard sample size is 10.2 by 10.2 by 0.64 or 1.28 cm thick.
The samples are bonded to a steel substrate. A thermocouple is placed at the center point of the cold side of the sample. The
test samples can be placed in a fixture downstream from the SSRM nozzle exit: the fixture can be adjusted in axial distance
and the impingement angle with reference to the plume centerline. A normal 90 deg impingement is typically used (Fig. 19
(b)). The following data can be acquired during the experiment; peak erosion, residual mass, maximum backside heat soaked
temperature, time to reach maximum heat soaked temperature, surface temperature (using a pyrometer). Concerning the
detection of the hot surface temperature, one of the biggest issue is the emission from the gas phase, mostly because it can-
not be taken into account in the calibration phase; in fact, the nature of the produced gases cannot be known precisely. It
would be necessary to check that the hot gas mixture around the tested sample would not emit radiation at the wavelength
in which pyrometer is measuring. Thus, it is fundamental to account for the operating waveband of the pyrometer. One way
to partially minimize this limitation and get a measurement less dependent on the emissivity of the material is based on the
use of pyrometers able to operate in a 2-color mode. The operating costs of a test performed via SSRM are of the order of
some hundred of dollars.
Fig. 20. Cut away view of the subscale SRM designed and used to characterize ablative internal insulator materials for solid rocket motors. From [175].
Credit: NASA and H.T. Martin.
4.4. An advanced test bed for SRM internal insulation materials
With the aim to properly study A-TPS materials intended for the case insulation of solid rocket motors, H.T. Martin and
co-workers [175] with support from NASA and Alliant Techsystems Inc. (ATK) recently developed a unique test bed at Penn
State University (PSU) which represents the most valuable and comprehensive design ever conceived, and implemented to
this purpose. For these reasons, this setup deserves to be reviewed in detail. The description of this setup will follow the very
clear and effective approach of the author. This research also allows to evidence the unique R&D efforts spent by PSU on the
study of ablative materials intended for SRMs [176–179].
In order to correctly study these insulation materials in an environment nearly identical to that one present in a full-scale
SRM in terms of – temperature, pressure, convective, and radiative heat transfer, chemical species of the combustion prod-
ucts, viscous shear, and alumina particle impact – the subscale SRM displayed in Fig. 20(a) and (b) was developed. Two sam-
ples of the ablative insulation to test are located downstream of an end-burning, aluminized solid rocket propellant grain;
this solution ensured similarity of temperature, gaseous species, alumina particle content, and radiative heat transfer rates of
the combustion product flow associated to a full-scale SRM. The nozzle and flow channel cross-sectional areas are sized to
produce full scale similar chamber pressures and flow velocities and thus, viscous shear and convective heat transfer rates,
respectively.
The formation, development, and erosion of the char layer on the ablative material samples as a result of their exposure to
the SRM environment can be observed and recorded with real-time X-ray radiography (X-ray RTR), which produced time-
resolved image sequences of the SRM interior. The in-depth thermal response of the ablative material samples can be mon-
itored by embedding multiple micro-thermocouples at different depths within the samples to produce temperature histories
Fig. 21. X-ray radiograph of charred ablative material (a). X-ray radiograph frame from a test showing the edges detected by the image analysis software
including the definition and zero location of y for each material sample (b). From [175]. Credit: NASA and H.T. Martin.
related to the given subsurface locations. The precise quantification of the conditions to which the samples are exposed
within the SRM is critical for the interpretation of the X-ray RTR data; the knowledge of the subsurface temperature is essen-
tial for the validation of the ablation modeling, since the model inputs as well as their corresponding outputs must be
known. To this purpose, the SRM chamber pressure, the total wall heat flux, and the radiative wall heat flux are measured
in the SRM firings. While pressure is measured using commercially available transducers, the total heat and thermal-
radiation-only fluxes to the SRM chamber wall in the section of the flow channel are measured using ad hoc designed gauges.
Like the degradation behavior and the subsurface temperatures, all SRM environment measurements are time-resolved, so
that the behavior of the ablative material samples at any particular moment can be directly correlated to values of pressures
and heat fluxes.
4.4.1. Real time X-ray radiography of tested materials

In order to examine the ablative degradation of the ablative material samples in a time-resolved manner, real-time X-ray
radiography was introduced as a tool to peering into the subscale SRM chamber during firing [98]. As the X-rays pass through
the constituent materials of the subscale SRM, some are absorbed or scattered due to their interaction with the atoms com-
prising these materials, reducing the intensity of the X-ray beam collected by the image intensifier. The attenuation of the X-
rays traveling through a particular medium is dependent on the density of the material and the path of the X-rays through
the material. Therefore, due to the two-dimensional geometry of the SRM test section, contrast in the X-ray images is pro-
vided by means of density gradients between and within the ablative material samples in the SRM test section. This contrast
mechanism makes X-ray RTR an ideal means for the study of the ablation mechanism of A-TPS materials, as it is capable of
Fig. 22. Detail cut-away view of an ablative temperature sensor embedded in the material to be tested (a). High-resolution X-ray radiograph of an ablative
temperature sensor (b). From [175]. Credit: NASA and H.T. Martin.
distinguishing not only the material interface between the surface of the char layer and the combustion products, but also
the interface between the porous, low-density char layer and the virgin material (Fig. 21(a)).
The location histories of the ablative sample surface and char-virgin interface are determined from the X-ray RTR images
using the edge detection tool in National Instrument’s Vision Assistant software. As shown in Fig. 21(b), at three discrete
streamwise (x) locations on each sample, two different edges, one corresponding to the char surface and the other corre-
sponding to the interface between the char and the virgin material (char-virgin interface), can be found by searching in
the vertical (y) direction for the first instance where the gray level crosses a specified value: to detect edges between the
virgin and charred material, a simple threshold-based method was employed [175]. Fig. 21(b) displays the edges found
by the detection tool denoted by bright green boxes. The y = 0 location for each sample corresponds to the sample surface
location at the time of the SRM ignition. The reported char layer thicknesses are merely the differences between the (y) loca-
tions of the char surface and the char-virgin interface at a given (x) locations.
4.4.2. In-depth temperature measurements

Since the controlling parameter of ablative degradation is the temperature, a record of the transient internal temperature
profile is essential to understand and characterizing the ablator thermal response [61]. This data can be obtained by embed-
ding thermocouples within the ablative material at specified distances from the surface. However, inserting a thermocouple
into a material whose thermal diffusivity is much lower than its own, may distort the temperature field in its immediate
vicinity. In general, in order to reduce the intrusiveness of the thermocouple based approach, two main solutions can be con-
sidered; the size of the thermocouple itself can be reduced to the smallest size that ensured a robust and repeatable setup;
the thermocouple wires are installed perpendicular to the direction of the heat flow. A representative installed configuration
is shown schematically in Fig. 22(a), in which multiple thermocouples were installed at different distances from the exposed
surface. To maximize the accuracy of the measurements, the holes into which the thermocouples were installed were filled
with shavings of material recovered from the drilling process: in such a way the thermal contact between the thermocouple
and the sample was maximized, and the disturbance of the temperature field caused by the thermocouple installation was
minimized. The thermocouple wires were coated with a thin layer of zirconia, in order to prevent them from making elec-
trical contact with one to another. High-resolution X-ray radiographs (Fig. 22(b)) of the thermocouple-instrumented cylin-
drical samples were taken prior to their use in SRM firings, so that the precise location of the thermocouple heads relative to
Fig. 23. Schematic of heat flux gauge installed in subscale SRM (a). Schematic of radiometer with alumina accumulation relief (b). From [175]. Credit: NASA
and H.T. Martin.
the initial surface of the sample can be determined. The uncertainty in this measurement is directly related to the X-ray
image resolution in terms of pixels.
4.4.3. Total heat flux gauges

In the initial phase of the design of the subscale SRM, the measurement of the total heat flux to the interior wall of the
motor was based on a slug calorimeter. However, to further increase the accuracy of the test bed, the slug calorimeter was
eliminated due to its vulnerability to thermal perturbation and cross-conduction errors. The only way to totally eliminate
thermal perturbations would be to use a gauge made of the same material into which the gauge is installed. However, this
solution could not be adopted since the gauge should have been made of the ablative material. In such a case, the heat flux
gauge would be identical to the ablative temperature sensors, with thermocouples embedded in a plug of the ablative mate-
rial that is installed in the ablative material sample itself. While the fabrication of such a gauge is practicable, the method of
deducing the surface heat flux from the subsurface temperature measurements is extremely complex, as it requires the use
of an inverse analysis coupled with a thermo-ablative code.
The ad hoc made heat flux gauge designed for this test bed (Fig. 23(a)) spanned the entire width of the flow channel and
was made of the same material to ensure that the effect of the inevitable thermal boundary-layer perturbation was one-
dimensional. The sensors of the total heat flux gauge was practically identical to the ablative temperature sensors, with mul-
tiple micro-thermocouples embedded at different depths, but in a cylinder of graphite, rather than ablative material. Gra-
Fig. 24. Arc-jet torch layout (a). Electrodeless plasma jet (b). Credit: Courtesy of Plasma Test & Diagnostics Laboratory (University of Vermont).
phite was chosen for this application for its thermal stability and erosion resistance; accordingly, phase-change and oxida-
tion phenomena occurring at the surface of the graphite could be neglected in heat transfer analyses of the gauge. This con-
clusion was supported by comparison of pre- and post-firing measurements and observations of the graphite slabs from both
the short- and long-duration subscale SRM firings, which indicated that no significant degradation or erosion of the graphite
occurred during the firings. The micro-thermocouples provide the time-resolved thermal profile within the graphite plug,
which was used to deduce the total heat flux to its surface. The concerns mentioned in previous section and regarding
the response-time and intrusiveness of the thermocouples embedded in the temperature sensors could be extended with
equal consequences to the heat flux gauges. The thermocouples were installed in the graphite plugs in the same manner
as in the ablative temperature sensors, with the primary exception being that the thermocouple heads, as well as the wires,
were purposely coated with an approximately 150 lm thick layer of zirconia in order to electrically insulate them from the
graphite.
4.4.4. Radiometer
A radiometer was designed and integrated in the SRM used in this test bed [180]; the design basically consists of a ther-
mal radiation sensor isolated from convective heat transfer from the combustion products flow by a window. It was recess-
mounted in the combustion chamber wall to prevent thermal damage to the window from convection. This recess intro-
duced a backward-facing step into the flow channel wall, which induced a particle-trapping recirculation zone directly in
front of the radiometer. A jet of inert gas injected into the SRM at an oblique angle to the combustion product flow was incor-
porated into the initial design to divide this zone into two regions; an upper one consisting of hot gaseous combustion prod-
ucts and Al2O3 particles, and a lower one consisting almost entirely of cold inert gas. Sapphire was chosen as the window
material for the radiometer because it has an essentially constant spectral transmittance (approximately 0.84) over a rela-
tively wide range of wavelengths in the infrared spectrum (about 0.4–4 lm), as well as excellent mechanical strength for
withstanding the pressure loads to which it was subjected in the SRM. An alumina accumulation relief was also cut into
the chamber liner downstream of the radiometer port to allow the molten particles to flow downstream and prevent them
from disrupting the radiometer port flow field or obstructing the radiometer view of the combustion products. After a series
of tests, a secondary shield-gas jet flowing directly through the radiometer aperture was added to improve the blocking
action on the alumina smoke particles (Fig. 23(b)).
4.5. Plasma facilities
Currently two basic types of plasma jet facilities exist: arc-jets (or arc heaters) [9,22,56] and Inductively Coupled Plasma
(ICP) (or electrodeless plasma jet) torch facilities [181–184]. Both type of torches are capable of replicating the local
trajectory-heating rates for the stagnation point of a wide range of trajectories for different gas mixtures. Induction coupled
plasma facilities rely on radio-frequency (RF) magnetic field coupling with the test gas to produce high enthalpy flow. This
inductive coupling means that no contamination is introduced in the gas environment. The clean test gas presents a more
favorable environment for testing techniques attempting to isolate pertinent physical phenomenon. As a drawback, com-
pared to arc-jet torches, ICP torches can typically reproduce smaller heat fluxes.
4.5.1. Arc-jet torches

To simulate the intense heat fluxes experienced by the TPS of spacecrafts and probes, a high temperature gas jet gener-
ated with an electric arc heater can be used to determine both the transient and steady state response of ablatives [9,22,55].
This test facility can be operated with practically any gas, thus providing wide versatility in terms of possibility to imple-
ments different chemical conditions. The basic layout of a traditional arc-jet torch is shown in Fig. 24(a). It consists of
two electrodes embedded in a water cooled chamber. The arc heater can be operated by injecting a gas into the arc chamber
and then establishing an arc between the electrodes. The injected gas is heated as it passes through the region occupied by
the electrical arc discharge; once heated up, the gas is exhausted through a nozzle thus to obtain a uniform, high temper-
ature stream. Typical test specimens can be prepared in the form of rods or flat panels. Prior to test a given material, a slug
calorimeter mounted on a movable arm is placed in the plasma jet thus to measure its heat flux. Once calibrated the plasma
source, the instrumented sample is moved in the region of the plasma jet in which the slug calorimeter carried out the mea-
Fig. 25. VKI Plasmatron facility overview (a). Test chamber with the characterization tools for plasma free-stream and ablation (b). Credit: von Karman
Institute.
surement. After an established exposure time, the tested specimen is removed from the gas stream. The arc heater can also
operate in a vacuum chamber, simulating a reduced pressure hyperthermal environment and thus, altitude dependent test
conditions. It is also possible to obtain supersonic and hypersonic gas speeds. The duration of such testing can range from a
few seconds to more than an hour, and from one exposure to multiple exposures of the same sample. The main drawback of
arc jet plasma torches is related to the flow contamination from eroded material inside the chamber; this limitation makes
isolating specific free-stream and surface chemistry analysis difficult.
In general, to achieve the level of accuracy required in these tests, special equipments and instrumentations are required.
If compared to other testing facilities such as the OAT [57–59], which can be built with commercial raw materials and parts,
the initial capital cost and operating expenses, combined with the spaces required to implement plasma jet are generally
quite high. In some cases, the upfront costs for these devices can run into the millions of dollars; thus, only a few laboratories
in the world can afford this type of characterization. The time investment for each test with this level of accuracy is very
large. In addition to the time required to prepare and complete the test, due to the limited number of facilities there may
be a significant time delay before the material may even be tested. Thus, these limitations make this technique prohibitive
for initial evaluation purposes.
A remarkable example of plasma based facilities is the NASA Ames Arc Jet Complex [9]. The Ames Arc Jet Complex has a
rich heritage of over 40 years in TPS development for every NASA space transportation and planetary program including
Apollo, Space Shuttle, Viking, Pioneer-Venus, Galileo, Mars Pathfinder, Stardust, NASP, X-33, X-34, SHARP-B1 and B2, and
most recently X-37 and Mars Exploration Rovers. The Ames Arc Jets began in the 1950s with the founding of a permanent
facility in 1961. A breakthrough patented design in 1964 enabled TPS development for Mercury and Apollo missions. The
Ames Arc Jet Complex is a key facility for end users involved in the three major areas of TPS development; selection, vali-
dation and qualification. The arc jet data are critical for validating TPS thermal models, heat shield designs and repairs,
and ultimately for flight qualification [9].
NASA Ames Arc Jet Complex currently hosts four bays containing arc jet units of different configurations and serviced by
common facility support equipment. These are the Aerodynamic Heating Facility (AHF), the Turbulent Flow Duct (TFD), the
Panel Test Facility (PTF), and the Interactive Heating Facility (IHF). The support equipments include [9]: two power supplies,
a steam ejector driven vacuum system, a water cooling system, high pressure gas systems, data acquisition system, and other
auxiliary systems. The magnitude and capacity of these systems makes the Ames Arc Jet Complex unique in the world. The
largest power supply can deliver 75 MW for a 30 min duration or 150 MW for a 15 s duration [9]. This power capacity, in
combination with a high volume steam ejector vacuum pumping system, enable the facility operations to match high alti-
tude atmospheric flight conditions with samples of large size. The IHF with an available power of over 60 MW, is one of the
highest-power arc jets available. It is capable of long run times of up to 1 h, and able to test large samples in both a stagna-
tion and flat plate configuration. The PTF uses a unique semi-elliptic nozzle for testing panel sections. Powered by a 20 MW
heater, the PTF can perform tests up to 20 min. The TFD provides supersonic, turbulent high-temperature air flows over flat
surfaces: the TFD is powered by a 20 MW arc heater. The AHF has similar characteristics to the IHF arc heater, offering a wide
range of operating conditions, samples sizes and extended test times. A cold air mixing plenum allows for simulations of
ascent or high-speed flight conditions. Catalycity studies using air or nitrogen can be performed in this flexible rig. A 5-
arm model support system allows the user to maximize testing efficiency. The AHF can be configured with different arc hea-
ters up to 20 MW.
4.5.2. Electrodeless torches

An example of ICP facility (Fig. 25(a)) is the Plasmatron installed at von Karman Institute (Belgium), a high enthalpy facil-
ity in which a jet of plasma is generated in a test chamber kept at sub-atmospheric pressure (between 5 and 250 mbar) [181–
184]. The plasma is generated by heating the test gas (usually argon, N2, CO2, air) to temperatures up to about 10,000 °C,
using electrical current loops induced inside a plasma torch (Fig. 25(b)). Electrodeless inductively coupled plasma generators
can offer much better plasma purity compared to classical arc-jets, as there is no pollution from any vaporized electrode
material.
Plasmatron is the most powerful induction-coupled plasma wind tunnel in the world: due to its unique features, it
deserves to be described in detail. The Plasmatron uses a high frequency, high power, high voltage (400 kHz, 1.2 MW,
2 kV) solid state metal oxide semiconductor (MOS) technology generator, feeding the single-turn inductor of an 80 mm or
160 mm diameter plasma torch. The torch (Fig. 25(b)) is mounted on a 1400 mm diameter, 2500 mm long, water-cooled test
chamber, fitted with nine 500 mm diameter portholes that allow unrestricted optical access to the horizontally oriented
plasma jet. The facility is used for space re-entry materials testing at heat fluxes up to 500 W/cm2; in the typical setup used
for ablation tests the available instrumentation allows for intrusive measurements (stagnation-point probes for cold-wall
heat flux and stagnation point pressure) as well as for optical ones (broad-band radiometer, two-color pyrometer and infra-
red camera for surface temperature and material emissivity estimation, high-speed camera for ablation visualization, and an
emission spectrometer combined with a charged coupled device (CCD) camera for boundary layer species probing. In addi-
tion, a dedicated laser-spectroscopy laboratory is currently being developed for plasma diagnostics. The use of Plasmatron
for ablation tests mainly focused on the study of the gas-surface interaction at the stagnation-point. The usual shape of the
tested ablative samples is a hemisphere with 2.5 cm radius [181–184]. In dedicated test campaigns, samples with cross-
section radii up to 10 cm were tested. Advanced numerical modeling capability is also available to assist in designing exper-
iments, to extract more information from test results, and for relating test conditions to flight [185].
Fig. 26. Scheme of a breaking wire recession sensor (a). Alternative to the traditional breaking wire recession sensor based on the use of ultra small, fully
sheathed thermocouples (b). Reprinted from [196] with permission from Elsevier.
5. Erosion rate sensing techniques for A-TPS materials
The selection of the proper ablative material is strictly related to the properties of the hyperthermal environment in
which the ablative must work. The material selection for a given environment requires a balance between ablative and insu-
lation efficiency while recognizing the optimal performance regime for each class of material [44,45]. In order to optimize
the material selection, the shape and the sizing of an heat shield, the TPSs of various probes were instrumented with a wide
range of sensors, such as recession and heat flux sensors, and thermocouples [47]. The study of the Galileo TPS, which was
based on carbon/phenolic composites, is a very instructive example of the reason why recession sensors are used during the
re-entry flight of probes. In fact, the Galileo TPS was instrumented with numerous sensors embedded in the heat shield [48]
to measure the temperature and the erosion of the probe heat shield. Particularly, ten Analog Resistance Ablator Detectors
(ARADs) were inserted in the TPS. The erosion models of the Galileo entry predicted that the nose of the shield would have
receded more than the shoulder region of the TPS. However, the data gathered during the re-entry flight by the ablation sen-
sors showed a very different result; the Galileo heat shield recessed 44 mm in the shoulder region [186], compared to an
estimated ablation value equal to 33 mm [49], leaving a margin of only 11 mm. At the stagnation point, the ablation
model predicted that the nose would have eroded of 88 mm, whilst the measured recession was equal to only 41 mm.
The thickness of the Galileo TPS was designed with a safety factor of two on the data on the base of the available ablation
models; however, in the shoulder region, the recession could have compromised the mission while the nose was sized with
an excessive safety factor margin, leading to an unnecessarily large TPS mass fraction [44]. The Galileo mission clearly
showed how it is important to acquire the erosion rate data during the re-entry flight of a probe and how models based only
on laboratory tests can produce results with a limited value. Accordingly, the use of erosion sensors enables the possibility to
improve the understanding of the ablation processes, allows the optimization of the mass fraction of a TPS but also provides
precious data enabling the re-entry flight; in addition, even considering the use of Lightweight Ceramics Ablators (LCAs) such
as Phenolic Impregnated Carbon Ablators (PICAs) [16,17] (see Section 7), deep space mission probably would preclude con-
servative TPS design. As a result, the use of precise models could be essential.
Many technologies for detection of the erosion rate have been tested on entry vehicles; in most cases these technologies
have been flight tested on mid and high-density PAs. Erosion sensors can be classified as intrusive and non intrusive: most of
them are of the first type. The intrusive concepts involve installing hardware in the ablator [187] whilst non-intrusive meth-
ods rely on sensors and hardware in the substructure below (outside) the ablator. Intrusive recession measurement tech-
niques include the breaking wires ablation gauge [188], radiation transducer sensor, and light pipe.
Among them, the most popular approach is based on the use of breaking wires also referred as break-wire arrangement.
In a breaking-wire approach a series of wires are embedded in a TPS plug and they are positioned at different depths as
showed in Fig. 26(a). As the heat shield erodes, the temperature inside the material tends to increase and at a certain point
each wire will melt; an electronic device will detect the event and mark it as a recession. However, the charred material is
electrically conductive and thus, it can lead false signals, hindering a good detection of the real thickness of the heat shield.
Most important, the manufacturing of this type of erosion sensor is generally relatively easy but at the same time it is also
time consuming and cannot be easily scaled up or industrialized. In some cases and for some materials, the implementation
Fig. 27. MEDLI Instrumented Sensor Plug (MISP) with multiple temperature and recession sensors (a). MEDLI Plug (b). The Mars Science Laboratory heat
shield contained embedded sensors to measure actual atmospheric conditions on Mars and TPS performance during atmospheric entry. The MSL-MEDLI
MISPs were strategically installed on the heat shield to measure its performance during entry into Mars atmosphere. Each instrumented plug, containing
temperature and ablation sensors, was designed to make measurements of the heating environment as the vehicle enters the atmosphere of Mars at a speed
in excess of 5.4 km/s. Credit: NASA.
of this type of sensor is not allowed. As an example, for carbon/carbon composites, due to the high temperature treatments
necessary to char the organic precursor, the use of traditional break-wire sensor arrangement is not possible.
As another intrusive method, the radiation transducer sensor relies on radioactive sources placed at known depths within
the TPS. As the ablator recedes, radiation sources are removed and the reduction in radiation is measured by a Geiger counter
[187]. In the light pipe sensor, quartz fibers are implanted in an ablator and terminated at known depths [188]. When the TPS
recedes where a fiber terminates, light transmits down to a photodiode.
An example of a non-intrusive sensor, ultrasonic transducer technology has been tested to measure recession rates of
ablative materials by determining the time of flight of sound waves in a typical pulse-echo setup scenario where the sound
waves reflect back from the interface [189–191]. McGunigle and Jennings [189] described an ultrasonic TPS recession sensor;
this sensor was successfully tested on the ground and in flight. However, in general, transit time of sound waves is strongly
affected by the structural characteristics of the material, which in turn are affected by temperature. As a result, inaccurate
determination of the distance to the interface results from not knowing the temperature distribution correctly. Certain
assumptions and empirical trends need to be deployed to post-process the transit time measurements and correct for the
temperature effect on the acoustic velocity. Clearly, such an approach that utilizes a priori knowledge of the temperature
distribution from assumed trends has severe limitations when applied to non-isotropic materials and atypical heating sce-
Fig. 28. Drilling layout for the 4- (a) and 8-levels (b) plug. The blind holes were machined into the carbon/carbon composite (CCC) plugs via Electrical
Discharge Machining (EDM). Scanning Electron Microscopy (SEM) analysis of the surface of the 4- and 8-levels CCC plugs are reported in (c and d). Reprinted
from [196] with permission from Elsevier.
narios [191]. Furthermore, determining changes in transit time to resolve small changes or for application to thin materials
requires highly fast and resolved data acquisition equipment that makes sensor miniaturization challenging [191]. Another
example of non-intrusive sensor is the backscatter radiation ablation gauge: a gamma ray source and detector unit are used.
The radiation amount that is reflected from the ablator is directly proportional to its thickness. According to Legendre [192]
this sensor provided an effective method of measuring recession on graphite TPSs without disturbing the material.
Current non-intrusive sensors tend to display a series of weaknesses and limitation as compared to intrusive counterpart
devices [187–191]. One of the more successful efforts in the development of a flight recession sensor is the ARAD sensor
[186]. The fundamental principle at the base of the ARAD (developed by GE) and of the following versions developed at NASA
Ames is the same; an electrically insulating barrier becomes conductive at high temperatures and closes an electrical circuit.
Many different types of the ARAD were developed to work on different TPS materials. The Galileo ARAD used carbon/phe-
nolic as a core material combined with a polyimide tape wrapped around the core for electrical insulation. At high temper-
atures, the polyimide sheath chars and becomes electrically conductive. A hole is drilled into a TPS plug and the sensor is
glued in place with a bonding agent. A variation in the measured resistance is correlated to a change in the thickness of
the TPS in which the ARAD is installed. The data acquired on flight showed that during the reentry flight of the Galileo probe
the ARAD sensors experienced multiple failures [186]: a high level of noise to signal ratio also contributed to the failures
[193]. For the ARAD used in the Galileo the recession uncertainty was equal to ±2.5 mm. Arc jet test results indicated that
the ARAD occasionally lost its internal electrical connections or had a large measurement uncertainty: most likely, this type
of sensor had intrinsic problem related to its fragile design. The study of the Galileo ARAD continued at NASA Ames Research
Center for the purpose of evolving its design and implementing the sensor in low-density TPS materials, such as SLA-561V
and PICA [194]. An evolved version of the ARAD sensor – the Hollow aErothermal Ablation and Temperature (HEAT) – was
recently tested on the Mars Science Laboratory Entry Descent and Landing Instrumentation (MEDLI) Project [195]. The col-
lected data by the Mars lander will be analyzed and studied: in this case, the HEAT sensor should have ensured a measure-
ment range from 0 to 13 mm with a measurement accuracy of ±0.5 mm. The MEDLI suite also contained seven pressure
sensors enabling a complete reconstruction of the guided flight trajectory of the entry vehicle toward the surface of Mars
(Fig. 27(a) and (b)).
Natali and Koo [196] (KAI, LLC) designed a low intrusiveness sensor based on the break-wire like concept with the aim to
be cost effective and easy to manufacture; to this purpose, the metal wires typically used in this arrangement were replaced
with ultra-miniature commercial thermocouples (TCs). Although thermocouples were successfully used to instrument TPS
materials [195], the approach introduced in this research deserves to be described more in details due its effectiveness, ver-
satility, reliability. In fact, only commercially available processing techniques and raw materials were considered; this is a
unique and cheaper approach compared to other equivalent solutions in which each single block of the measurement chain
was produced ad hoc. K-type TCs with a stainless steel outer sheath and a diameter of 250 lm were chosen. The TCs were
embedded in the TPS, perpendicularly to the TPS surface. Each sensing head of the TC was positioned at a well-defined depth
from the surface (Fig. 26(b)). This technology was preliminary tested on carbon/carbon materials. Using blind holes and
knowing the depth at which the TC was placed, a given arrangement of the holes could be produced: the accuracy of the
holes. The drilled samples were produced using Electrical Discharge Machining (EDM) (Fig. 28(a) and (b)). The actual depth
of the produced holes was checked by means of a caliper coupled with gauge pins: the quality of the holes was very high and
all the holes matched the theoretical depths within 10 lm [196]. During the heating of the TPS, each TCs first works as a local
temperature sensor providing valuable data on the ablation process of the TPS. Once the temperature rises above the melting
point of the stainless sheath and of the Seebeck junction, the TC experiences a break. Due to this twofold nature of these
Table 1
Erosion rate obtained for the 4- and 8-levels CCC plugs as compared to a manual estimation of the recession rate. Reprinted from [196] with permission from
Elsevier.
Fig. 29. 8-levels temperature profiles. During the heating of the TPS, each thermocouple (TC) first worked as a local temperature sensor providing data on
the thermal response of the material; above a certain temperature, the TCs experienced a break marked with a discontinuity in the electrical signal,
followed by noise (a). Detail of the profiles in which all TCs broke; it is possible to confirm the dependence of the breakage events on the actual depth of the
TCs in the material (b). Reprinted from [196] with permission from Elsevier.
sensing heads – as a traditional Seebeck junction and as a position marker – it is possible to obtain a wide range of data on
the recession state of the TPS. In the earliest phases of this research, the proposed technology was tested on carbon/carbon
composites. Two types of carbon/carbon materials were considered: a 2D low density material (LDCC, 1.34 g/cm3) and a 2D
high density material (HDCC, 1.70 g/cm3).
Plugs with 4 levels of depths (Fig. 28(a)) were firstly considered using both the LDCC and HDCC; then the possibility to
scale-up the technology from 4 to 8 levels was considered. A series of 8 levels CCC plugs produced using the HDCC material
were prepared (Fig. 28(b)). The surface of the drilled sample was studied via Scanning Electron Microscopy (SEM). Fig. 28(c)
reports the surface of the 4-levels plug whilst Fig. 28(d) shows the appearance of the holes for the 8-levels plug. Once the
holes were drilled in the cubic sample, the TCs were inserted and then glued into the CCC plug using a high temperature
adhesive suitable for carbon/carbon composites (Aremco Graphi-BondTM 551-RN) [196]. The CCC plugs were tested with
an OAT at an heat flux of (930 ± 30) W/cm2 [57,58]. To minimize the length of the test and increase the erosion rate, a
strong oxidizing flame was used (oxygen to acetylene volume ratio equal to 5/1 [57]). For each material and for each drilling
layout (4 or 8 levels), a series of pristine CCCs were tested to produce a crater deep enough to ensure the burning of the TC
placed at the higher depth. At the end of the tests, once the depth of the craters was obtained and considering the corre-
sponding exposure times, an estimation of the erosion rates was also obtained (indicated as ARR in Table 1). Once the depth
of the crater was established for all materials and drilling configurations, the erosion rate was shown to depend both on the
density of the CC, as well as on the drilling layout [196]. As an example, the 4-level plugs produced with the HDCC exhibited
a recession rate equal to 0.023 ± 0.005 mm/s whilst the 8-level plugs produced with the same material showed an erosion
rate equal to 0.043 ± 0.003 mm/s. Accordingly, the recession rate was determined to also depend on the depth of the pro-
Fig. 30. Position of the markers vs. time of the first break of each marker (TC) (a). Position of the markers (considering a virtual TC placed on the surface of
the sample and experiencing a breakage at the time zero) vs. time of the first break of each marker (b). Reprinted from [196] with permission from Elsevier.
duced crater. Such a situation can be explained considering that the piercing capability of the torch changed as a function of
the shape of crater, and increased with the exposure time (Table 1). This phenomenon is also related to the fact that with the
increase of the time, the torch produced a blind hole which trapped the combustion gas and confined them producing a
higher erosion rate.
A representative temperature profile acquired during the experiment on the 8-level plug (namely sample identified as
HDCC8L1) is shown in Fig. 29. All temperature patterns displayed a behavior characterized by the three steps. In the first
part (Fig. 29(a)), all TCs properly worked as a temperature sensor; the smaller the distance of the TC from the surface, the
higher the temperature displayed. After about 100 s, the first TC reached the melting point of the Seebeck junction and then
it experienced a break. Consequently, this point marked the exact time at which the TC1 was broken.
This event is clearly marked by a strong discontinuity in the temperature profile. Fig. 29(b) shows the details of the tem-
perature profiles in the range of time in which all TCs experienced the first break. After the first failure of TC1, the junction
provided an intermittent signal; due to the presence of the direct flame, after the TC experienced the first loss of electrical
contact, the terminals of the TC continued to melt and the resulting droplets of melt metal were able to intermittently close
the electrical contacts between terminals, producing a detectable signal forming a new junction. The steel sheath of the TC
provided an additional source of liquid metal able to close the electrical loop. This process was regulated by several uncon-
trollable factors producing random and continuous opening or closing of the circuit. The above described mechanism
involved all the eight TCs but, due to the different depths in which each junction was embedded in the CCC, the first break
of each TC happened at different times. In general, the TCs broke according to their distance from the surface marking the
recession layer of the material; the working principle of this recession sensor is exactly based on this behavior. In the second
step it is possible to see that once the TCs experienced the first break, all of them continued to display the previously men-
tioned intermittent signal. Finally, in the third step of Fig. 29(a), the TCs recorded the cooling down of the system. However,
after exposed to the torch plume, the original material composition of each Seebeck junction was contaminated, and the
voltage versus temperature calibration of the pristine K-TC resulted altered.
In order to get a quantitative evaluation of the real erosion rate provided by the sensor, the actual positions of the eight
spatial markers (the TC heads) was plotted as a function of time in which they experienced the first break. This calculation
was carried out in two ways and the numerical results are summarized in Table 1. In the first method, the eight positions of
each TC were considered and correlated with the time of their first break (Fig. 30(a)). In the second approach (Fig. 30(b)) the
RR was calculated considering the (0;0) point as if there was a virtual TC placed on the surface of the plug experiencing a
breaking at the time 0 s. In the first case, the resulting was equal to 0.0510 ± 0.0008 mm/s whilst in second case it was
0.0336 ± 0.0004 mm/s. According to the experimental results, both approaches provided a significant agreement with the
manually evaluated (0.043 ± 0.003 mm/s) [187–197]. Other 8-level plugs were tested confirming the effectiveness of the
approach. In fact, as summarized in Table 1, all the RR values provided by the three different plugs were in very good agree-
ment with the erosion rate calculated as a function of the final depth of the crater and of the exposure time.
The extrapolated erosion rate provided by the approach introduced by Natali and Koo for carbon/carbon composites
resulted to be in very good agreement with the recession rate of the tested material (Table 1) [196]. These results are quite
important both from scientific as well as on industrial point of view; the authors also suggested to extend the use of the pro-
posed system to monitor the erosion rate of insulating liners [197] and nozzle throats of SRMs which are typically produced
with carbon/carbon materials. The technology was also successfully tested in the erosion rate detection technology on sev-
eral – state of the art – ablative materials ranging from densities of 0.30–1.83 g/cm3 which are listed below [198–200]:
Phenolic Impregnated Carbon Ablator (PICA) – Fiber Materials, Incorporated (FMI). PICA is based on a low-density carbon
fiber preform impregnated with a phenolic polymer with a density of 0.3 g/cm3 [16,17] (see Section 7).
AVCOAT 5026-39 (Textron Specialty Materials) based on an epoxy/novolac resin impregnated with fiberglass in an alu-
minum honeycomb (density of 0.5 g/cm3). Used on the Apollo Command Module, is now used on the Orion Command
Module [128–130].
MX-4926 – (Cytec Engineered Materials) is an industry standard carbon/phenolic (C/Ph) ablative for solid rocket nozzle
with a density of 1.45 g/cm3.
PyroSic 4686 and PyroSic 2704 – (Pyromeal Systems) are silicon carbide fiber reinforced glass ceramic composites with a
density of 1.83 g/cm3.
These tests showed the effectiveness and scalability of the proposed technology as well as the possibility to apply the
approach on different ablative materials.
6. Polymeric ablatives as insulator materials
6.1. Rigid insulators
As it was pointed out in Section 3.4, fiber reinforced polymeric ablators [22,30,68,69], are used when the shape preser-
vation of the TPS and in general, of the material surface, is one of the primary requirement. However, in many other situa-
tions, the ablator must work as a thermal insulation material and the erosion rate is less critical. Ablatives used as insulation
materials or as Heat Shielding Materials (HSMs) have two main fields of application: in one case, the heat shield simply
needs to insulate a certain surface from the high temperatures operating as a rigid body [22]. As an alternative, the insulator
must work as a flexible shield, also ensuring a high elongation at break [30,52]. In the first case, the organic binder can be a
rigid, high char yield thermosetting such as a phenolic matrix. Among the fillers used in insulation ablatives, when a low
density is the primary requirement, a very effective and low specific weight filler is cork [201]. It is intrinsically a thermal
insulating ablative material, which can be used in mild hyperthermal environments and it was successfully combined with
organic matrices like phenolics. Basically, cork possesses a peculiar closed cellular morphology structure consisting of a
membrane, filled with an organic matter; the most relevant characteristic of its chemical composition is the presence of sub-
erin, a kind of polymer made of polyols, which is the main cell wall component. The studies on cork based HSMs revealed
that in absence of external shear stress, even up a temperature of 2500 °C, a stable, closed cell morphology is still present in
the amorphous residual char [201]. As a comparison, open cell carbonaceous residues (or foams) with a similar apparent
density allows fluid or gas to percolate through the interconnected meso- or macro-pores [69,202]; accordingly, these
two classes of foams offer different insulation response especially regarding the effect of convection phenomena. Many
important commercial HSMs are based on the use of cork. In Europe, Norcoat-Liege [203] was used for two re-entry pro-
grams, namely the Atmospheric Re-entry Demonstrator (ARD) which performed a guided and controlled re-entry on Earth
in 1998 [204], and the Beagle 2 probe [205] that entered the Mars atmosphere in 2003. The Norcoat-Liege is made of hot
pressed cork particles and a polymeric binder. This material is a very good insulator with a density of 0.47 g/cm3. It contains
50% of pure cork particles, 30% of a phenolic resin, and 20% of both a fungicide and a mineral fire proof filler.
Due to the morphology of cork, once exposed to the hyperthermal environment, a closed porous system is produced
[201]; the reduced gas circulation through the carbonized layer limits the convective heating and thus the pyrolysis of cork
and of the phenolic resin; a reduced charring rate and heat transfer is then obtained. Norcoat-Liege was arc-jet tested up to
200 W/cm2 [201]; these tests proved the good performance of the material both in air as well as a in CO2 atmospheres.
Currently, Norcoat-Liege is also used to shield some components in the Ariane 5 launcher. Also in the US, cork based mate-
rials are quite used in the production of ablatives. Amorim Cork Composites produces two phenolic based formulations espe-
cially designed for the space sector, the P45 and P50, having different densities and properties [206]. The P45 and P50 are
mainly used for the thermal protection of various portions of solid rocket boosters such as the frustum bolt catcher and
the external skirt insulation; Amorim has also been responsible for integrating cork solutions in thermal and anti-
vibration shields within the framework of the Italian Vega launcher or the European Ariane 5 [207].
6.2. Elastomeric based insulators
6.2.1. Silicone based HSMs

As it was pointed out in Section 6.1, there also exists a second area in which the ablative must work as a flexible insulation
material [30,55,208,209]. Accordingly, the rigid, high char yield thermosettings used for FRPAs must be replaced by some
elastomeric matrices exhibiting a comparable thermal resistance. These ablatives are also referred as elastomeric HSMs
(EHSMs) [208]. Among them, polysiloxanes (or silicones) showed to be very effective matrices for polymeric TPS; silicone
is a relatively medium density matrix (typically 1/1.2 g/cm3 depending on the type of silicone) with good thermal resis-
tance. In fact, among the organic polymer materials, the organosilicon polymers with SiAOASi bond in the main chain have
excellent heat resistance; the SiAO bond of organosilicon polymer has very high binding energy (443.7 kJ/mol) [210]. The
most common siloxane used as a matrix of EHSMs is linear polydimethylsiloxane (PDMS). In presence of a hyperthermal
environment, the organic polymer decomposes with the evolution of volatile compounds (water, methanol, and carbon diox-
ide). Silicone is then converted in a hybrid siliceous/carbonaceous char; after being pyrolyzed and charred at high temper-
ature, the residues of the silicone resin and silicone rubber are mainly silica compounds (such as SiO2 and SiCO) [8,209]. Due
to their structure, silicones also tend to exhibit a higher oxidation resistance then other high char yield polymers. One of the
main advantages of silicones over other elastomers is that it can be directly processed in a liquid state at room temperature.
Among polysiloxanes, silicones containing the phenyl group tends to exhibit a higher thermal stability. As for FRPAs, elas-
tomeric based TPS are produced combining the polymer with several kinds of fillers as powders and fibers. Silicone based
EHSMs are prepared by blending the silicone polymers, the fillers/chopped fibers and the vulcanizing agent; the modified
silicone can also be used to impregnate the reinforcing woven fabrics of glass, silica, KevlarÒ, and carbon. Among fillers com-
bined with silicone, Flame Retardant Additives (FRAs) such as antimony trioxide and polychlorinated compounds [208] can
also be used. A comprehensive review of all the most important silicone based ablatives was produced by Donskoy [208].
Silicone based EHSMs were also used on rockets to protect the surfaces of the vehicles from the flame exhausts [30,55];
as an example, they were used to protect some components of Saturn V [211] and Polaris [212,213] rockets.
MG Chemicals RTV 560 and Dow Corning 93-104 are two remarkable examples of silicone based insulators. RTV 560 is a
foamed silicone elastomer loaded with silicon dioxide and iron oxide (Fe2O3) particles [209]. During the exposure to a hot
stream this EHSM decomposes producing a foam mainly composed of silica, silicon carbide, and FeSiO3 [209]. DC 93-104
[214] is a two components, highly loaded silicone rubber filled with SiO2, SiC and carbon fibers [174,215]. It is an high vis-
cosity, troweable paste, used as a protective coating for rocket cases [216] and ramjet combustion chambers [217–219]. DC
93-104 has shown to provide superior performance such as a high char retention, low ablation rate even under the influence
of high shear stress hyper-thermal environments [220]. Some versions of DC 93-104 were modified with asbestos or poly-
imide fibers [221]; the use of aramid pulp in silicone based HMSs was also reported [222].
Fig. 31. Exploded view of the Low Cost Pintle Engine (LCPE) developed by TRW (now Northrop Grumman Aerospace Systems) (a). It is possible to verify the
intrinsic simplicity of this engine which exploited the synergy between an outer structural metal case and an inner sacrificial Elastomeric Heat Shielding
Material (EHSM) based liner. Such a configuration ensured a remarkable affordability and an unprecedented high reliability. Fully integrated LCPE with the
turbopumps (b). Credit: Northrop Grumman Aerospace Systems.
DC 93-104 was successfully used by TRW (now Northrop Grumman Aerospace Systems) in the manufacturing of the Low
Cost Pintle Engine (LCPE) [223–226]; this rocket chamber was able to produce 2.9 MN of thrust and constituted the most
valuable example of reusable yet passively cooled engine (Fig. 31). The thrust chamber and nozzle of the LCPE were fabri-
cated in separated sections to be easily assembled thus to allow a film cooling injector ring (evidenced in green in Fig. 31
(a)) to reduce throat ablation rates. The chamber sections were made of HY80 steel, then lined with a modified DC 93-
104 EHSM [223]. By molding the ablative into the chamber wall, the structural metal shell could be reused. At the end of
the ablative material’s life, it could be stripped from the chamber and a new layer could be reapplied. If required, the ablative
liner could also be patched before or after testing (Fig. 31(a)). Northrop Grumman Aerospace Systems acquired a wide expe-
rience with this type of ablative material and found it to be extremely more versatile and less expensive then FRPA coun-
Fig. 32. Post-burnt images of the silicone rubber composites. (a) No oxides or carbides added, (b) ZrO based formulation, and (c) ZrC based formulation.
Reprinted from [228] with permission from Elsevier.
terparts. This company developed a reliable method for mixing and pouring the ablative in the chamber, and identified a
primer able to promote high adhesion between the ablative and the chamber wall. A conical mixer and a pump were used
to prepare and distribute the ablative through a closed system mold under vacuum. After the ablative was cast, the mold
remained in place until the ablative completed its curing into the chamber wall. A low cost silica/phenolic throat section
was used to reduce the erosion of this region of the engine [224,225]. This section was tape wrapped over a male mandrel
in three sections to obtain optimum ply orientations and the wraps were bonded and cured in place in the steel nozzle shell.
The design demonstrated a unique paradigm shift for large liquid fueled rocket engines and enabled impressive cost reduc-
tions. In fact, it was showed that the this engine could enable a cost reduction as high as 90% compared to a traditional regen-
eratively cooled counterpart; the exploitation of the metal structural case combined with an elastomeric ablative also
constituted a cheaper alternative to traditional chamber entirely based on FRPAs. The intrinsic simplicity and the reliability
of this engine (Fig. 31(b)) which were directly related to the unique technologies and solutions identified by the company
clearly evidenced the versatility of elastomeric ablatives and their huge potential to reduce the cost of rocket combustion
chambers also enabling the possibility to recover the hardware and implement its reusability.
In general, toluene is typically used to dilute the given paste thus to introduce a higher amount of fillers and tune the
viscosity of the final formulation. To increase the carbonaceous residue of the ablatives, a high char retention polymer like
a phenolic resin can also be combined with the main elastomeric matrix. To minimize the char removal due to the spallation
phenomena, fiber-reinforced phenolic honeycombs can be used to contain the ablative compound [227]. Yang and coworkers
[228] evaluated the thermal stability and ablative properties of the silicone rubber ablative composites modified with zir-
conium carbide (ZrC) or zirconium oxide (ZrO2); according to authors, the addition of ZrC or ZrO2 into silicone rubber com-
posites improved the thermal and ablation properties (Fig. 32). Ceramic layers containing ZrO2, SiO2, and SiC were formed on
the ablated surface of the composites with ZrO2 or ZrC, and acted as effective oxygen and heat barriers. The ablated surface of
the composite with ZrO2 was more uniform than that of the composite with ZrC in the OAT experiment. The linear ablation
rates of the composites were reduced by 40% and 72% by the incorporation of 40 phr ZrC and ZrO2, respectively.
In order to control the void fraction and thus the final density of the EHSM material, elastomers may contain hollow
spheres of glass, silicon dioxide or phenolic [229–231]. Torre et al. produced a series of papers in which a silicone based abla-
tor (ALS-051) was deeply investigated [229–231]; the authors reported a comprehensive theoretical and experimental
Fig. 33. SEM analysis of ALS-051 at increasing magnifications. The void volume introduced in the formulation by the hollow spheres is clearly visible (a).
The chopped fibers dispersed in the matrix are also identifiable (b). Not published. Credit: UNIPG.
approach of the studied ablative. In the first part of this research, thermal analysis techniques were used to obtain the
parameters of interest for the ablative system which consisted of a silicone resin filled with fibers, phenolic and quartz
spheres. Fig. 33 reports the appearance of the vulcanized material analyzed via SEM.
The heat of ablation was calculated in a non-oxidative atmosphere while the effect of the presence of oxygen on the
thermo-degradation reaction was investigated by Simultaneous Thermal Analysis (STA) tests conducted in air. A general
kinetic model for the degradation process was derived and their parameters were computed applying non-linear regression
techniques. Once acquired these parameters the behavior of the TPS was modeled and the energy and mass balance equa-
tions were applied to a flat (1D) geometry. In order to confirm the validity of the results, the mathematical model was tested
with plasma arc techniques; the developed modeling tools resulted to be able to simplify the design of the thermal shield.
Fig. 34 reports the correlation between the predicted and experimental in-depth temperature profiles confirming the high
fidelity of the developed model.
Fig. 34. Experimental and simulated in-depth temperature profiles for a silicone based ablator (ALS-051). The model produced by Torre et al. [229–231]
(UNIPG) was able to properly predict the insulation capability of the studied heat shielding material. Not published. Credit: UNIPG.
Fig. 35. SLA-561V sample tested at the Arc-Jet Facility at NASA Ames Research Center; post-burned surface appearance of SLA-561V tested under a heat flux
of (b) 30 W/cm2, (c) 90 W/cm2, and (d) 150 W/cm2. From [233]. Credit: NASA.
A very important class of silicone based, low density ablative is the Super Light Ablator (SLA); cork is an essential part of
this ablative. A remarkable example of SLA is the Lockheed Martin’s SLA-561V [208]. It is a low-density (density 0.25 g/
cm3) cork-filled silicone contained in a Flexcore honeycomb. The silicone matrix represents about the 25% in weight of
the material, while the silica microspheres and chopped fibers approximately constitute 40% of the formulation [208].
SLA-561V was originally developed for the Viking lander missions in 1976 by the Martin Marietta Corporation. The SLA-
561V was originally successfully used in re-entry flight of Mars Viking (peak heat flux approximately 24 W/cm2). However,
this lightweight ablator continued to provide excellent mass and cost efficient performance; in 1990s, the ablator was re-
certified for the higher entry heating of the Mars Pathfinder lander [232]. As a result, it was used for the Mars Pathfinder
mission (approximate heat flux equal to 54 W/cm2), and Mars Exploration Rover (115 W/cm2). At those conditions
SLA-561V worked as a charring insulator and experienced moderate surface recession. According to arc-jet tests performed
on the material (Fig. 35(a)), only above 120 W/cm2 there was a clear indication of glass melt and surface erosion. At higher
heat fluxes the experiments showed that material exhibited a higher recession than the honeycomb walls [233]. Recently, as
a part of MESUR-Pathfinder program, the SLA-561V was ground tested at heat fluxes in the range of 100–200 W/cm2 at pres-
sures from 0.2 to 0.3 atm; tests showed that above pressures of 0.26 atm there was clear evidence of char spallation [234].
Fig. 35(b)–(d) shows the appearance of SLA-561V tested at increasing heat fluxes. Other tests were carried out for the Mars
Science Laboratory program [235]; in 2012, SLA-561V successfully protected the MLS capsule during the re-entry flight on
Mars [236,237].
6.3. Elastomeric HSMs for solid rocket motor liners
Elastomeric heat shielding materials are also used when the ablative must work as an insulation material having a high
strain capability (high elongation at break); as an example, the structural case of a solid rocket motor, which serves as a pres-
sure vessel, must be protected against the high temperature combustion gases [30,52,238,239]. Fig. 36(a) reports the appear-
ance of a typical SRM and its components. The SRM case is conventionally manufactured from metals such as steel or carbon/
epoxy filament-wound composite [30,52]; an ablative liner is placed between the case and the solid propellant grain. The
primary function of internal insulation is to prevent the rocket motor case from reaching temperatures that may compromise
its structural integrity [240]. If the insulating liner is pierced during rocket motor operation, the casing is susceptible to melt-
ing or degradation, and consequent catastrophic failure of the rocket motor. Accordingly, with the exception of the nozzle,
EHSMs are used to protect the internal surfaces of rocket engines. This class of ablatives must withstand extreme hyperther-
mal environments; in fact, the temperatures inside the rocket motor case typically reach 2800 °C and interior pressures may
exceed 100 bar [52]. The insulator should have high elongation at break thus to absorb the mechanical stresses induced to
the rocket motor during propellant casting, storage, transportation and flight. Elastomeric HSMs also enable the possibility to
Fig. 36. The Vega third stage, Zefiro 9, is derived from a 16 tons solid rocket motor (Zefiro 16) development initiated by Avio SpA under contract to the
Italian Space Agency (ASI). The Zefiro 9 SRM is composed of a 1.9 m diameter carbon/epoxy filament wound case and a low density insulation. The solid
propellant is referred as HTPB 1912. It is also visible the nozzle based on a flexible joint technology (flex seal) and the electromechanical thrust vector
control system (a). Integrated nozzle for P80 SRM used in the Italian Vega launcher (b). Credit: European Space Agency.
integrate a movable nozzle to the engine; in fact, in order to vector the trust, the nozzle of SRMs is oriented by hydraulic or
electric actuators, with the constrain to preserve the confinement of the combustion gas within the case. Fig. 36(b) shows a
nozzle assembly of a SRM. Typically, the insulation liner is bonded to the inner surface of the case with special adhesives;
recently, some companies (such as AVIO, Italy) also introduced alternative procedures in which an elastomeric HSM tape is
wrapped around a mandrel as in a traditional filament winding process [241]; then the filament-wound carbon/epoxy outer
case is produced and the whole structure is cured in autoclave.
Nitrile butadiene rubber (NBR) is a synthetic rubber used for elastomeric SRM liners [30,239]; NBR is a copolymer of acry-
lonitrile and butadiene and its density typically ranges between 1 and 1.2 g/cm3. Physical properties of NBR particularly
depend on the content of acrylonitrile; as the acrylonitrile increases, the intermolecular interaction between the polymer
chains tends to increase as well as the density, and glass transition temperature of the elastomer. The processing of NBR
is relatively difficult due to the high intrinsic rigidity of the elastomer which is strictly related to the strong intermolecular
interaction; preliminary plastification is generally required before the NBR can be processed in open or closed mixers. NBR
can be cross-linked by sulfur or peroxides; vulcanization is performed at temperatures of 140–190 °C. NBR based EHSMs
usually contain silicon dioxide as a powder and asbestos fibers [242–244]. Typical composition of NBR based EHSMs may
include 40 phr of asbestos fibers and 20 phr (parts per hundred rubber) of silica oxide [245]. One of the reasons because
NBR is used in elastomeric HSMs is related to its compatibility with high char yield resins such as phenolic thus to increase
the erosion stability and char yield; as an example, Rock Island Arsenal Company worked on a NBR based EHSM, combining
this elastomeric phase with a phenolic resin and asbestos fibers [246]. The density of material was 1.34 g/cm3 and the elon-
gation at break equal to 40%. In some cases the amount of phenolic resin could be equal to the content of the elastomeric
phase (100 phr) [239]. However, the main drawback due to the introduction of phenolic resins in a NBR matrix is the loss
of elasticity of the modified elastomer. Boric acid or boron containing phenolic resins were also successfully introduced
to improve the ablation and oxidation resistance of these EHSMs. The higher resistance is related to the presence of B-O link-
ages [239]. A remarkable example of NBR based EHSM was Hitca 6520: it was developed by HITCO and it was used to protect
the steel case of Titan III-C solid rocket boosters [239]. The liner in form of calendered elastomeric sheets was applied by
means of adhesives on the metal case and then the vulcanization was carried out via autoclave. Similar solutions were used
by Thiokol Chemical Corporation [247]. As an alternative, the thermal protection is produced starting from pre-vulcanized
sections of the liner; this solution can be adopted to increase the accuracy of the insulation layer in terms of shape.
However, even if the technology of NBR based EHSMs has been well established, it also tended to reach its limit. In fact,
nitrile rubber based insulation suffers from the disadvantages such as a limited shelf life, high density, and poor low tem-
perature properties. Among elastomers used for SRM liners, Ethylene Propylene Diene Monomer rubber (EPDM) currently
represents one the best matrices for SRM liners [239,248]. EPDM which is manufactured by solution/suspension polymer-
ization, is a terpolymer made of ethylene, propylene, and a diene (such as ethylidene norbornene (ENB) or dicyclopentadiene
(DCPD)) in varying ratios. The thermal stability of EPDM which is comparable or higher than nitrile rubber, can be attributed
to its saturated main chain structure [249]. EPDM typically starts to decompose at around 400 °C similarly to NBR [250]; in
nitrogen, the residual mass is dependent on the terpolymer composition but typically the char yield is as low as (10%).
EPDM exhibits outstanding resistance to oxidation, ozonisation, and weathering effects; this outstanding ageing resistance
is essential to ensure the required lifespan of SRMs especially for military purposes. Peroxide curing imparts better ageing
characteristics as compared to sulfur curing [248]. EPDM also possesses excellent low temperature properties such as a glass
transition temperature close to about 50 °C [248] enabling the use of this elastomer also in the presence of severe environ-
mental conditions. All these features combined with an extraordinary long shelf life makes the EPDM the best candidate
matrix for EHSMs used in SRMs and especially for military rockets. Additionally, EPDM possesses the lowest density among
elastomer (0.85 g/cm3); this is a very important property since the lower the weight of the EHSM liner, the higher the pay-
load of the SRM. For all these reasons EPDM is the ideal candidate matrix for elastomeric ablatives; as a matter of fact, EPDM
based EHSMs are replacing all other elastomers like nitrile and silicones as insulators in advanced SRM boosters
[52,239,248].
Commonly used EPDM based EHSMs usually consist of more than one polymeric phase; in fact, with EPDM as a primary
polymer base, matrices such as liquid EPDM [251–253] and adhesion promoting polymers such as Hydroxy Terminated Poly-
Butadiene (HTPB) [248] have been successful used as secondary polymers. Since HTPB is generally used as a binder of mod-
ern ammonium perchlorate propellant [54], the introduction of HTPB in the formulation of the EPDM based EHSM also helps
in anchoring the propellant grain to the insulating liner. According to literature, when employed as a secondary polymeric
phase, phenolic resins can increase the char formation and enhance erosion resistance [252,254,255]. The EPDM matrix can
also be compounded with flame retardant additives; as an example, chlorinated organic compounds [254,256] were used in
combination with antimony oxide or hydrated alumina. Ammonium poly-phosphate was also used as a fire retardant addi-
tive for this class of EHSMs [257–259]. As for NBR based EHSMs for SRMs [239], boron containing fillers have been combined
with EPDM matrices to improve the ablation and oxidation resistance of these materials [260]. To properly tune the mechan-
ical properties of the elastomeric liner, high levels of fibrous reinforcing (up to 50 wt% on the matrix) have been added to the
neat matrix [248,261]. Once the EPDM is degraded and charred, the presence of fibers promote the formation of a skeleton-
like structure with high dimensional and thermal stability; fibers also decrease the erosion rate and increase the char reten-
tion between the virgin substrate and the carbonaceous residue. Nanosilica synergically works with the other components of
the ablative; in fact, as for FRPAs, silica as a powder is widely used to increase the heat of ablation, improve the char reten-
tion and decrease the oxidation rate of the EHSM [22,30].
However, not all fibers are satisfying reinforcements for the elastomeric thermal insulation of a SRM. Asbestos fiber, tra-
ditionally combined with NBR, has been banned because of its carcinogenicity, and it was replaced by other man-made fibers
in the form of chopped filaments or pulps [262,263]. Glass fibers have been reported to improve the ablative efficiency of
EPDM based EHSMs [264]. Carbon fibers typically reduce the loss of mass, but due to their thermal conductivity, they also
tend to increase the backside temperature of the liner [261]. Moreover, during the processing of the insulation materials,
under the effect of the high shear forces produced by the mixer, and due to their fragility, carbon and glass fibers are sus-
ceptible to deterioration into smaller particles or portions. Synthetic organic fibers showed to better withstand the shear
stress during of the mixing process of EPDM based EHSMs. Aramid (KevlarÒ or TwaronÒ) fibers or pulp were successfully
used as a low density reinforcement; as a matter of fact, so far, aramid is still the most used fiber in EPDM based SRM liners
[261–264]. Aramid fibers have been incorporated in the EPDM based EHSMs because of their high thermal capacity, high
chemical stability, high fire resistance, low thermal conductivity, and high ablation resistance [261–265]. Due to an
enhanced degree of fibrillation, the use of aramid pulp also promotes an high physical adhesion with the matrix. Accordingly,
the use of aramid pulp not only enhances the mechanical properties of the insulator but also helps to form a relatively strong
char thus reducing the degradation of the virgin material. Table 2 reports the name and chemical structure of most important
organic fibers [265] used in EHSMs.
The processing of EPDM based insulators can be improved by the addition of processing aids such as aromatic or hydro-
carbon oil [222,266–268]. The use of oils reduces the viscosity, the mixing energy, and time, also improving the preservation
Table 2
List of main organic fibers currently used as a reinforcements of elastomeric heat shielding materials for solid rocket motor liners. Image modified from [265].
Chemical designation of the Chemical structure Trade name Continuous operating References
fiber temperature (°C)
Poly(p-phenylene-2,6- ZylonÒ 310 [265,273,274]
benzobiso-xazole) – (PBO) (Toyobo)
Poly(2,20 -(m-phenylene)-5,50 - PBI (Celanese) 250 [175,265,292]
bisbenzimi-dazole) – (PBI)
Polyimide – (PI) P84TM (Inspec 260 [265,277]

Fibres)
Phenolic (or novoloid) KynolÒ (Nippon 200 [265,282]

Kynol Inc.)
Melamine BasofilÒ (BASF) 200 [265,275]
Poly(p-phenylene terephtal- KevlarÒ 190 [248,261–

amide) – (PPTA) (DuPont) 265,278–281]
Twaron (Teijin)
Polysulfonamide – (PSA) PSA (Shanghai 250 [270,271]
Tanlon Fiber)
of the fibrous reinforcements. As for NBR based EHSMs, the processing of EPDM can be carried out via two-roll calenders and
internal mixers such as Banbury. It is worth to remark that if compared to FRPAs, EPDM based ablatives and, more in general,
HSMs based on elastomers, have been produced with a wider range of formulations. As an example, according to literature,
the amount of aramid pulp can range from a few percentage points up to about 30 wt% [261,269]; increasing the content of
the fibrous reinforcement, the erosion rate is reduced but also the elongation to break typically tends to decrease. Moreover,
at high fiber percentages, it can be difficult to obtain an homogeneous distribution of the filaments, and the material could
tend to suffer a non uniform ablation rate.
Recently, new high performance fibers [265] having higher heat and flame resistance than aramid fibers have been eval-
uated as a reinforcement of EPDM based heat shield. Some interesting results on the addition of new fibers were obtained by
Jia et al. [270,271]; they proposed to replace aramid with polysulfonamide (PSA) fibers. According to the authors, compared
to aramid fiber based EHSMs, the ablative properties of the PSA-pulp/EPDM blends were enhanced; such a result was related
to thermal stability of the PSA fibers. The role of aramid and PSA pulp on EPDM based EHSMs was evidenced studying the
properties of the charred layer. According to Foldi and co-workers, the actual ablation efficiency of an EHSM mainly depends
on the carbonaceous region of the insulator [272]; the material with the best char tends to exhibit the highest performance.
In fact, the contribution of the fibers on the char yield of the ablated EHSM resulted to be quite higher than the char released
by the EPDM matrix [270,271]. To this purpose, Jia et al. studied the pyrolysis products of the constituents of aramid/EPDM
EHSMs; benzene and methyl benzene were found, products which are the basic precursors of the char. However, benzene,
and methyl benzene generated from EPDM represented a small portion (7%) of the total percentage. Thus, the contribution
of the EPDM on the char formation was limited; after the introduction of the fibers, the pyrolysis products of aramid and PSA
were mainly composed of aromatic compounds which could be converted to form much more char than the matrix. In terms
of produced aromatic compounds, the contribution of these precursors on the total percentage was equal to about 62% for
PSA and 66% for aramid fibers. Thus, both fibers strongly contributed to the char formation and their role on the char for-
mation was comparable. The char produced by these compounds could retain a certain degree of the original shape of
the fibers; then, once turned into carbonaceous worm-like residues [271], the resulting structure could promote the reten-
tion of the burnt material. Moreover, even if the char of both fibers was comparable, TGA results evidenced that PSA exhib-
ited a higher thermal stability than aramid; the degradation peak temperature of the PSA fiber was 100 °C, higher than
aramid fiber. According to authors, the enhanced properties of PSA/EPDM over aramid/EPDM was attributed to the sulfone
group (ASO2A) present in the molecular structure of PSA fibers. The improved ablation properties were also related to stron-
ger interfacial bonding between the fiber and the matrix in the PSA/EPDM EHSMs.
Among new generation organic fibers, poly(p-phenylene-2,6-benzobisoxazole) – PBO (ZylonÒ) filaments showed to be
very promising candidates when used as a replacement of aramid counterpart. It has been reported that the thermal stabil-
ity, the decomposition temperature, and the carbon residue of PBO fibers under nitrogen at 1000 °C (64%) are much higher
than aramid fiber (40.0%) [273].
According to Gao et al. [274] if compared to traditional aramid/EPDM EHSMs, the erosion rate as well as the loss of mass
of the PBO/EPDM was lower than 50%; however, to date, the main drawback related to the use of PBO fiber is due to its cost,
which is an order of magnitude higher than aramid. Rajeev et al. [275] reported the study of EPDM reinforced with melamine
fibers, one of the new generation, high performance fibers [265,276]. The authors evidenced that the presence of melamine
reinforcement produced a significant improvement in the ablation resistance of the EPDM based EHSM; however, the
researchers did not report any direct comparison with other fibers. Han et al. [277] also reported the use of polyimide
(PI) short fiber filled EPDM insulators. Compared with aramid fibers, polyimide fibers exhibited better thermal stability
and higher char residue because of their stiff aromatic backbones and aromatic imide groups of the molecular main chains
[278–281]. In order to improve the low adhesion between PI fibers and the EPDM matrix the authors introduced a surface
modification of the reinforcements which mainly relied on immersion of the fibers into a potassium hydroxide aqueous solu-
tion to form carboxylic acid groups via an imide-ring cleavage reaction. The authors reported that after the ablation test, a
rigid char layer remained on the surface of the remaining virgin insulation with 10 phr PI fibers. Natali and co-workers [282]
reported the use of KynolÒ fiber – a phenolic based reinforcement made by acid-catalyzed crosslinking of melt spun novolac
as a reinforcement of EPDM based EHSMs. It was found that compared to EDPM/aramid pulp, KynolÒ/EPDM composition
produced the char with the smaller dimensional change and the higher adhesion on the virgin material. SEM analysis
revealed that on a micron scale, aramid pulp produced a more compact char than KynolÒ based formulation; however, macro
fractures were identified on the surface of the charred region. On the other hand, KynolÒ/EPDM burnt samples showed a ser-
ies of many smaller micro cracks. This result can be explained considering that due to their dimensions, KynolÒ filaments
were able to reinforce the material on a larger scale than aramid pulp; for TwaronÒ based formulation, once turned into a
carbonaceous residues, aramid microfibers with their high degree of fibrillation, better worked as a local reinforcement.
In terms of insulation capability, aramid fibers, exhibited the best performance. This result can be directly related to two fac-
tors. First, the greater the length of the fibers, the higher the possibility for the filaments to conduct heat into the inner layers
of the material. The second is reason because KynolÒ produced higher in-depth temperatures than aramid which is related to
the intrinsic thermal conductivity of charred KynolÒ fiber; in fact, once turned in carbon based residues, KynolÒ filaments
had higher thermal conductivity than aramid pulp. Thus, the length of the KynolÒ fibers combined with the thermal conduc-
tivity of their carbonaceous residue minimized the insulation capability of KynolÒ. To confirm this conclusion, it is known
that carbon fibers reduce the loss of mass of EHSMs but, due to their thermal conductivity, they also tend to increase the
backside temperature of the liner [261]. As a result, a formulation with both KynolÒ fibers and aramid pulp could maximize
the properties of the char in terms of adhesion with the virgin substrate and, at the same time, could increase the insulation
capability of the EHSM.
6.4. Toward a new industrial standard for SRM-EHSMs?
A remarkable example of SRM application was the Space Shuttle’s Reusable Solid Rocket Motor (RSRM) [283], which pro-
vided the majority of the liftoff thrust for the launcher; the same SRM booster concept is also used by the European Space
Agency (ESA) Ariane V launch vehicle [284], the Japan Aerospace eXploration Agency (JAXA) H-II [285], the Epsilon launch
vehicle [286,287], and others launchers [288]. Moreover, SRMs are heavily utilized for ICBMs due to their storability, relia-
bility and responsiveness directly related to the ignition characteristics of solid propellants. The contract to develop the
Space Shuttle SRM was awarded to Thiokol Corporation in 1974. The baseline motor, was flown on the first seven Space Shut-
tle missions between 1981 and 1983. Following the Challenger accident, a redesigned SRM (the RSRM) was developed and
qualified between the spring of 1986 and the summer of 1988. The majority of changes made to the RSRM were due to mate-
rial obsolescence. For example, during a 10-year period beginning in the mid-1990s, more than 100 RSRM materials became
obsolete [283]. The Space Shuttle’s RSRM and many ICBMs employed asbestos-silica-filled NBR (ASNBR) [262] as a primary
internal case insulation; however, as highlighted in previous sections, due to cancerogenicity effects attributed to asbestos,
NASA sought a replacement for many years, but this goal has been very challenging to achieve since the comprehensive per-
formance of ASNBR was and is still difficult to match. Moreover, for any SRM, the qualification testing, the proper dimension-
ing and reshaping of the liner are typically very expensive and challenging tasks [263,289]. After a series of studies, the aft
dome of the RSRM was insulated with carbon fiber/EPDM (CFEPDM), since it showed to exhibit higher ablation resistance in
this region of the motor [262,290]. However, the use of different types of insulators in the same SRM design is neither con-
venient nor affordable. Due to the excellent performance in sub-scale SRM firings of KevlarÒ-Filled EPDM (KFEPDM), Fitch
and Eddy [290] and Tam and Bell [291] selected this material as the most promising candidate to replace both ASNBR
and CFEPDM in the design of the Advanced Solid Rocket Motor (ASRM) developed to replace the RSRM [283].
Nevertheless, KFEPDM was ultimately rejected as a suitable replacement because of its poor performance as compared to
CFEPDM in the full scale RSRM aft dome, and due its lack of wide ranging applicability; in fact, different KFEPDM formula-
tions were required to meet the different requirements of the regions of the booster. With the Space Shuttle retired, a mod-
ified version of the RSRM is currently proposed to be used as a booster for NASA’s next-generation heavy-lift Space Launch
System (SLS); thus, there still exists the necessity to replace the current ASNBR/CFEPDM insulation binary system with a
safer and more cost effective formulation.
Within the past decade, another candidate material has been proposed; polybenzimidizole (PBI) fiber-filled NBR
(PBINBR). The use of PBI fibers in combination with NBR was envisioned in a patent by H.M. Gajiwala [292]. However, to date
a very limited number of tests has been reported in open literature on this material. Thus, a lot of work has to be done also
considering the fact that this material has to be used on a man-rated launch system. PBI fibers are very similar to aramid
[265], and offer comparable mechanical and high temperature stability; however, even if the thermal stability of PBI eval-
Fig. 37. Average (y) location histories of the char surface (top) and of the char-virgin interface (bottom) for CFEPDM samples for all SRM firings. From [175].
uated via TGA can be considered better than aramid, it had to be determined if PBI presented the same weakness of aramid
fibers once tested on full scale tests. In a recent and comprehensive research carried out at Penn State University by H.T.
Martin and coworkers with the support of Alliant Techsystems Inc. (ATK) [175], the producer of the SLS SRM boosters, this
question has been partially addressed. This work can be considered of an exceptional importance for the adopted approach,
the testing protocol and for the ad-hoc solutions introduced to face the proper characterization of EHSMs for SRMs (see Sec-
tion 4.4). In fact, despite the characterization and modeling research carried out on KFEPDM, it is still unknown why KFEPDM
tended to perform differently during full scale motor firings than during sub scale motor tests [290]; the processing of the
material, the hyperthermal environment, especially when turbulent, the local thermo-mechanical properties of the obtained
charred KFEPDM influence the response of the material. In general, for an ablative material, the removal of the char in a given
region of the liner promotes a local, non-uniform flow which consequently modifies the boundary conditions in which the
material has to work. Though this situation is true for all types of ablatives, when compared to FRPAs such as silica/ or car-
bon/phenolics, ESHMs tend to exhibit a lower erosion resistance and thus, a more non-uniform and unpredictable response.
This limitation on current capabilities to predict the behavior of EHSMs highlights the necessity to further research their
exact decomposition phenomena, particularly under realistic SRM conditions. In fact, beyond any scientific consideration
and interest, this uncertainty puts practical problems and increases the risks associated with the insulating liner design, pro-
ducing excessive conservatism in the sizing of insulation thicknesses, thus reducing the SRM performance and increasing the
launching cost due to a reduction of the payload.
The research of Martin et al. [175] was undertaken with the precise aim to characterize the decomposition behavior of
two ablative EHSMs used in SRMs under realistic and precisely quantified operating conditions; CFEPDM, a current standard
Fig. 38. Two post burning X-ray radiographs depicting the observed behavior of the char layers for each ablative PBINBR (top) and CFEPDM (bottom). From
[175]. Credit: NASA and H.T. Martin.
Fig. 39. Average (y) location histories of the char surface (top) and of the char-virgin interface (bottom) for PBINBR samples for all SRM firings. From [175].
for SRM liners, and PBINBR, the candidate for the SLS launcher. In order to test the PBINBR and CFEPDM samples in an envi-
ronment nearly identical to that present in a full scale SRM in terms of temperature, pressure, convective and radiative heat
transfer rates, chemical species of combustion products, viscous shear, and alumina particle impact, a subscale SRM based
test bed was developed. The precise description of this unique and exceptionally well designed facility has been done in Sec-
tion 4.4; this test bed can be considered as a new paradigm in the advanced testing of EHSMs. Unfortunately, due to export
control restrictions placed on this work, certain results concerning the length, mass, temperature, and flux units were nor-
malized by an arbitrary, yet consistent factor. However, even considering these limitations, some valuable and uncommon
results deserve to be commented.
6.4.1. Ablative decomposition of CFEPDM

The images acquired via X-ray RTR from six different subscale SRM firings revealed that once exposed to SRM conditions,
the decomposition of the CFEPDM generated a porous char layer which, throughout the duration of test, continuously
swelled into the engine channel; the thickness of the charring sample was continuously increasing and, at the same time,
it was continually losing mass. The exposed surface of the char layer advanced into the SRM flow channel, whilst the
char-virgin interface receded; these phenomena are summarized in Fig. 37 (top) and (bottom) where the average location
histories of the char surface and of the char-virgin interface are respectively reported.
Fig. 40. Char layer thickness histories for each (x) location on the PBINBR sample measured in Test ABLMAT-33. From [175]. Credit: NASA and H.T. Martin.
The uncertainty in the X-ray radiography detection of (y) location of the char surface and char-virgin interfaces presented
in each figure is ±0.04 normalized units. It appeared that, due to increasing thermal insulation derived from the thickening
char layer, while the char-virgin interface histories exhibited a non-constant, decreasing slope with time, the rate of expan-
sion of the char surface did not exhibit a decreasing, time dependent slope. This result confirmed the conclusion of Foldi and
co-workers that the actual ablation efficiency of an EHSM mainly depends on the carbonaceous region of the insulator [264].
As evidenced by the X-ray images shown in Fig. 38 (bottom), as the char layer of the CFEPDM sample developed, the portion
of the sample nearest the heated surface became darker, not only relative to the region closer the virgin material, but also in
absolute terms; this fact indicated that the near surface region of the char layer was becoming denser with the increase of
the time. This observation is consistent with charring phenomenon; the pyrolysis gases percolating through the porous char
region increased its density, reduced its permeability and increased the pore pressure within the char layer [293,294]. As the
duration of SRM firings increases, the internal pressure can induce mechanical stress which, once exceeded the binding force
between the char and the virgin material, could eventually promote the spallation (or sloughing) of the char layer from the
CFEPDM sample. Due to the continuous swelling of the char surface into the flow channel, it was impossible to determine the
erosion rate of the char from the X-ray images. Other tests were carried out with the aim to evaluate the recession rate and it
resulted that in certain conditions, where adequate viscous shear forces and heat transfer were applied, the CFEPDM expe-
rienced a surface erosion sufficiently fast to overcome its char surface expansion mechanism, and the insulation thickness
continually decreased, rather than increase [175].
6.4.2. Ablative decomposition of PBINBR

As shown in Fig. 39, at the beginning of an SRM firing, the charring behavior of the PBINBR samples appeared very similar
to that of CFEPDM; as the material decomposed a char layer is formed and its surface advanced into the SRM flow channel
while the char-virgin interface receded into the sample. Comparing the CFEPDM and PBINBR charring mechanism (Figs. 37
and 39 respectively), the char layer thicknesses increased with the same trend for the first 2–3 s of the test.
Once the char layer reached a particular thickness, it suddenly sloughed from the sample, exposing the beneath virgin
material. This sloughing phenomenon is illustrated by the two X-ray images in Fig. 38 (top) one of which shows the PBINBR
sample exhibiting a thick char layer on its surface (test time equal to 8.84 s) and the other (0.89 s later in the same SRM
firing) showing the charred material detached from the surface. This process repeatedly occurred throughout the duration of
an SRM firing, as demonstrated by the char thickness histories extracted from the X-ray image sequences. Experimental data
also evidenced an increasing trend in the amount of charred material remaining on the surface of the PBINBR sample after
each sloughing event. To some extent, this trend was present in each SRM firings used to test the PBINBR; however, the
increasing amount of post-slough char could also be apparent since the sloughing events did not necessarily occur at the
same time or uniformly across the sample. As an example, Fig. 40 reports the first sloughing event occurring in test reported
ABLMAT-33; in this firing three discrete streamwise (x) locations were considered. The char layer sloughed completely from
the x1 location about 3 s after the beginning of the test, whilst the char layer continued to increase in the x3 location; the
boundary between the region where the char was retained and the region where the char was removed was not constant in
the in depth direction, resulting in decreased contrast in the X-ray image. Post-test observations of the fired samples
revealed non-uniform sloughing as highlighted by the X-ray images. As time in an SRM firing progresses, the non-
uniformity of the char surface increased, resulting in an increasingly vague surface location appearing in the X-ray images.
6.4.3. Mechanism of char spallation of CFEPDM and PBINBR

The occurrence of char sloughing from the PBINBR samples was due to the structure of the material and ultimately was
strictly related to PBI fibers and only secondarily to the matrix. As explained in Section 6.3, EHSMs for SRMs such as CFEPDM
and PBINBR are fabricated by mixing chopped fibers into unvulcanized matrices (EPDM or NBR respectively) and then, they
are processed into thin sheets. The production of these sheets causes the fibers to become preferentially oriented in the
direction of the extrusion, that is, in the plane of the sheet. To produce the required thicknesses of the SRM liner, these sheets
are overlapped one on each other and, during the cure in autoclave they adhere by virtue of the contact between the non-
vulcanized polymer; in some cases, an adhesive or an additional polymeric phase is used to promote the adhesion. Thus,
basically no mechanical linkage exists between adjacent sheets, or plies, of the insulating liner since the fibers embedded
in each layer have practically no chance to work as a reinforcement at the interface between two layers; only a very limited
portion of the actual length of the exposed filaments can penetrate in an adjacent layer of the non-vulcanized material. In
any case, in presence of fibers preferentially oriented perpendicular to the direction of char formation, these filaments have
limited capability to support the char layer beyond the thickness of the single ply. This limitation with the impossibility to
remove the discontinuities within the liner layers certainly play a fundamental role in the sloughing mechanism; however,
since comparable processes are used to produce CFEPDM and PBINBR based liners, most of the differences between the two
materials can be attributed to the material composition and mainly on the type of fiber embedded in these EHSMs. The
experimental results would suggest that carbon fibers are able to produce a char with improved mechanical properties com-
pared to PBI based counterpart; it is reasonable to suppose that the charred PBI filaments lost part of their mechanical prop-
erties whilst carbon filaments retained a higher structural integrity. The experience on Shuttle RSRMs showed that CFEPDM
exhibited higher ablation resistance than aramid filled EPDM [290]; thus, it could be inferred that PBI and KevlarÒ, with their
comparable chemical structure suffer similar limitations.
Fig. 41. Subsurface temperature histories of PBINBR samples. From [175]. Credit: NASA and H.T. Martin.
6.4.4. Final results on the insulation capability of PBINBR

The repeated removal of the PBINBR charred layer had an obvious impact on its insulation capability and on the in depth
temperatures, thus directly influencing the actual effectiveness of the material [272]. These temperatures are also related to
the char penetration rate; Figs. 37 and 39 show the char-virgin interface (y) location histories for both CFEPDM and PBINBR
averaged over all six SRM firings.
After 20 s of SRM operation, the average char-virgin interface (y) location of the PBINBR samples is about 40% deeper than
the CFEPDM sample. Additionally, due to the inhomogeneous sloughing phenomenon among the individual SRM firings, the
spread of char-virgin interface data was quite wider for PBINBR than for CFEPDM; thus, the thermal response of PBINBR
seems to be less predictable than CFEPDM increasing the concerning on the design conservatism. Due to the superior char
retention of CFEPDM and in light of PBINBR tendency to suffer spallation, CFEPDM samples exhibited a loss of mass equal to
approximately 60% of the PBINBR counterpart.
The normalized in depth temperature profiles of PBINBR are reported in Fig. 41; they are labeled according to their depth
into the ablative material sample and followed by the number of the test from which they were obtained; the data are nor-
malized. The profiles of PBINBR samples exhibited similar slopes and, once reached a normalized temperature equal to 1
(which should correspond to 1400/1500 °C since the temperatures were acquired with K-type thermocouples), the TCs
experienced a break [196] (see Section 5). The normalized subsurface temperature histories acquired from the CFEPDM sam-
ples are plotted in Fig. 42.
Fig. 42. Subsurface temperature histories of CFEPDM samples. From [175]. Credit: NASA and H.T. Martin.
For both materials, the temperatures were ordered according to depth in which the thermocouples was embedded, with
the deeper thermocouples experiencing later temperature rises. Moreover, combining the subsurface temperature histories
of CFEPDM with their respective (y)-location histories it could be found that the break in the temperature history for the
0.215-units-deep TC in test ABLMAT-35 corresponded to the time of arrival of the char-virgin interface at that (y)-
location (8.6 s). Thus, comparing this data with the break-time of the TC placed at a similar depth in the PBINBR counterpart
sample (0.224-units-deep), it can also be inferred that the in depth temperature profiles tended to highlight a higher insu-
lation capability of CFEPDM over PBINBR.
7. A new class of TPS ablatives: Lightweight Ceramic Ablators
In the early nineties, with the aim to improve the performance of traditional polymeric ablators for TPS, a unique and
brand new family of PAs, namely the Lightweight Ceramic Ablators (LCAs) was developed at NASA Ames Research Center.
Unlike traditional polymeric composite ablators, LCAs use a porous ceramic or carbon fiber felt as substrate and for structural
support; an organic matrix works as a binder. If compared to traditional FRPAs, these new materials offer a weight savings as
high as 50%. Phenolic Impregnated Carbon Ablators (PICAs), a carbon fiber based subclass of LCAs, were successfully used as
primary TPS material for the Stardust probe [295]. Different polymers and fiber felts were selected for the screening phases.
Among tested substrates there were: the flight certified reusable surface insulations (see Sections 2.1 and 2.2) such as Lock-
heed LI-900 (an high purity microquartz fibrous substrate), the NASA Ames Insulation AI-8 (which basically consists of 98.5%
microquartz fibers and 1.5% by weight of SiC powder), the NASA Ames developed alumina enhanced thermal barriers (AETB-
20 and AETB-50), and the Fiber Materials Inc. (FMI) carbon FiberformÒ insulation (Fiber Materials, Inc.). Methylmethacrylate,
epoxy, phenolic were studied as infiltrants: depending on the type of organic binder the char yield ranged from 0 to 60 wt%.
To control the resin fraction, and meet the target requirements in terms of high porosity and low thermal conductivity, spe-
cial impregnation and curing techniques were developed. Tran et al. [16] tested two versions of LCAs: a partially dense ver-
sion (0.24 g/cm3), where the amount of resin infiltrated in the matrix was controlled, and fully dense (1.36 g/cm3), in
which the resin filled the entire volume. The ablation performances of the produced LCAs were studied within an arc-jet test
facility; conventional ablators such as the Avcoat-5026 and the SLA-561 were tested for direct comparison. The studies were
carried out at different heat fluxes ranging from 110 to 1650 W/cm2 and stagnation pressures from 0.02 to 0.330 atm.
At the higher fluxes the main heat dissipation process was based on the re-radiation and the blockage action due to the poly-
mer decomposition became a secondary mechanism. At heat fluxes in excess of 950 W/cm2, the alumina based LCAs expe-
rienced recession rates comparable to, or higher than, silica based LCAs. It also appeared that the use of SiC particles
improved the performance of silica based felts due the increased emittance of the substrate. For carbon based LCAs (c-
LCAs), at heat fluxes higher than 450 W/cm2, the carbon based materials impregnated with phenolic showed to be the most
mass efficient ablatives; no spallation, mechanical failure, and shape changes were observed during the testing of the c-LCAs
up to heat flux of 1250 W/cm2. Due to the physical properties of the carbon fiber felts at the base of c-LCAs, this class of
LCAs could withstand higher temperatures than silica based counterparts. Accordingly, c-LCAs were able to remain stable
even at the higher temperatures, and most of the absorbed energy was re-radiated both by the carbon substrate (emittance
equal to 0.9) and by the char layer [17].
7.1. Phenolic Impregnated Carbon Ablators
Due to its superior performance, PICA became the most known and used version of LCAs; in light of its importance and
due to the wide range of ablation mechanisms which also depend on the heat flux, the study of PICA deserves particular
attention. In fact, the research of Tran and collaborators showed that due to their low densities, low thermal conductivity,
and high effective heat of ablation, both the standard PICA and densified PICA offer great weight savings over conventional
TPS ablators such as Avcoat 5026, SLA-561, and FRPAs (silica/ or carbon/phenolic composites). PICA is generally based on the
use of a carbon felt, FiberformÒ insulation and a phenolic resin as a binder. FiberformÒ is a low density carbon felt that can be
used in a vacuum or inert environment at temperatures up to 2800 °C. Due to its low density (from 0.14 up to 0.18 g/
cm3) and high porosity, the FiberformÒ felt has a very low thermal conductivity compared to high density solid graphite and
the carbon foam. The felt is produced by chopping carbon fibers having a diameter of 14–16 lm and a length of 1.6 mm in a
water slurry. Tran et al. [296] used the following processing technique to produce PICA samples; a water soluble phenolic
resin (Borden Chemical SC-1008) was used as infiltrant. The resin was added to the slurry, mixed and then vacuum cast.
The obtained green billet was dried and cured; this innovative impregnation techniques ensured final standard densities
ranging from 0.22 to 0.27 g/cm3. The thermal performance and ablation characteristics of PICA were evaluated in an oxi-
dizing environment in the Ames Research Center IHF. The materials were studied in a heat flux range from 350 to
3350 W/cm2 and surface pressures from 0.1 to 0.43 atm. Standard density PICA showed that from 350 to 450 W/cm2,
the ablation mechanism was oxidation rate controlled; accordingly, the higher the stagnation pressure, the higher the con-
centration of oxygen diffusing into the boundary layer thus increasing the oxidation rate and consequently the surface reces-
sion. Above 450 W/cm2 and up to about 1600 W/cm2 the main mechanism of heat rejection was re-radiation. The effective
heat of ablation curves showed that at a higher stagnation pressure, PICA exhibited the maximum effectiveness in the range
of 1350 to 2050 W/cm2; however, due to limitations of the used arc-jet facility, it was not possible to test PICA at higher
stagnation pressures. At a heat flux in excess of 2050 W/cm2, PICA exhibited a surface recession primarily due to sublimation
of carbon based constituents. However, at the highest heat fluxes, the effectiveness of PICA was significantly higher than in
the oxidation controlled regime. Densified version of PICAs – in which the amount of the resin was increased – were also
tested; the process used increased the final densities of the PICAs from 0.29 to 0.37 g/cm3. According to the experimental
results, the densification of PICA showed very promising improvements coupled with a moderate increase of the density. If
compared to standard PICA, the densified PICA exhibited lower recession rates and higher effective heats of ablation. The
effective heat of ablation of densified PICA resulted to be about a factor two higher than standard PICA and an order of mag-
nitude higher than the Avcoat 5026. Moreover, the in-depth temperature profiles of the densified PICA showed marginal dif-
ferences with the standard PICA. The authors concluded that these improvements of densified PICA over standard version
could result very promising for future re-entry missions in presence of extremely severe hyperthermal environment char-
acterized by pressure in excess of 10 atm and heating fluxes above 1800 W/cm2 [296].
8. An introduction to modeling of ablation phenomena
8.1. Basic principles behind analytical models
Analytical models have been developed to predict the response of polymeric composites and ablatives such as FRPAs
exposed to different hyperthermal environments. The necessity for reliable thermal, thermal-physical and thermal-
mechanical models was originally recognized in the 70s when these materials began to be essential in high temperature
aerospace applications. Mouritz and Gibson [297] reviewed in detail the researches on the basic approaches used to model
this wide range of phenomena. These mathematical models are largely based on the theoretical studies carried out since 40s
on the fire behavior of wood and related materials [298–303]; in fact, many of the processes occurring in burning wood can
constitute a valuable starting base for the modeling of those phenomena involved in the degradation of polymeric ablatives.
Burning wood was essentially modeled as a two component material consisting of a residual char and a virgin material; this
scheme was extended to ablatives. Some of these thermal-chemical models were developed considering the processes of
transient heat conduction, endothermic decomposition reactions, convection flow of volatile gases, and combustion of vola-
tiles near the solid surface [301–303]. The current state of the art models for the response of composites exposed to hyper-
thermal environments are based on the works published between the 80s and 90s by research groups led by Henderson
[142,144,150,304–307], Sullivan [308–310], Springer [311–314], Dimitrienko [315–317], and Gibson [318,319].
The simplest models only consider the effect of the heat conduction whilst, the more sophisticated approachers consider
many thermal, chemical and physical processes involved in ablation. The starting model is generally a one dimensional (1D)
analysis that considers heat conduction in the through-thickness direction of a composite material that is heated from one
side (hot or exposed surface). This model assumes that the composite is a thermally thick slab with a uniform in-plane tem-
perature distribution. Heat conduction modeling is very accurate to determine the temperature distribution through PAs
when exposed to low heat flux such that material decomposition does not occur. The cold (or unexposed) surface of the slab
is assumed to be adiabatic. Given the proper boundary conditions, the temperature distribution in a flat composite slab sub-
jected to one sided heating can be determined. In this basic approach both the heat capacity (Cp), and the thermal conduc-
tivity (k) are assumed to be independent from the temperature. This approach does not consider any thermally activated
processes such as the degradation of the polymeric matrix or the convective flow of pyrolysis gases; thus, for most types
of FRPAs, this model can only be properly applied at very small heat fluxes (up to approximately 1–2 W/cm2). This 1D heat
transfer analysis is used in most of the approaches used to model the response of composites subjected to a given hyperther-
mal environment; in some cases 2D or 3D heat transfer models are used to model the temperature distribution in composites
exposed to a localized surface heating [320–322].
Starting from the simplest 1D heat conduction based model, a first approach able to predict the thermal response of FRPAs
in presence of thermal degradation of the polymeric matrix was developed [311]. The heat conduction is calculated using the
1D heat transfer description while the heat of pyrolysis (Qp) must be experimentally determined. In this approach, the
energy transfer by convection is assumed to be negligible and the volatile gases produced by the pyrolysis reaction are
assumed to instantaneously escape from the FRPAs with no effect on the temperature. Henderson et al. [142] developed a
model for the decomposition of glass reinforced FRPAs. The decomposition reaction of the polymer matrix and the
carbon-silica reaction occurring between the char and glass fibers at high temperatures were analyzed in the model. Since
the thermal conductivity (k) is generally a function of both temperature and the stage of the decomposition reaction, k must
be experimentally evaluated over the temperature range of interest for the modeling. The authors also take into consider-
ation the transpiration cooling effect due to the flow of hot decomposition reaction gases through the char structure. The
rate of heat consumed or produced due to the matrix decomposition (or to the carbon/silica reaction) was then considered;
the decomposition reaction rate was determined from the mass loss rate using an Arrhenius kinetic rate equation. In the
same research Henderson and co-workers also considered the radiant and convective heat exchange on the hot surface.
For composite materials the emissivity is typically of the order of 0.8/0.9. Dimitrienko et al. [308] also proposed a modified
form of the Arrhenius equation able to account the dependence of the reaction rate both on the temperature as well as on the
gas pressure in the pores of the decomposing ablative. Henderson et al. [142] evaluated the accuracy of their model by com-
paring the theoretical temperature against measured temperature profiles for a glass/phenolic FRPA exposed to a moderate
heat flux of 30 W/cm2. The in depth temperature profiles were well described by the model. The combined effects of the
thermal expansion of the composite and of the storage of degradation gases within the composite were also considered
[144]. Florio et al. [307] developed a model able to account the internal pressure rise caused by the accumulation of volatile
gases. This approach is important in order to evaluate the diffusion properties of hot gases through a composite and the for-
mation of delamination cracks which occur when the pressure exceeds the inter-plies failure stress. Pressure rise measure-
ments within a burning glass/phenolic FRPA were assessed to test the model [323]; however, the agreement between the
calculated and measured pressures resulted to be low. The authors attributed this discrepancy to the inability to properly
measure the pressure inside the material. Some attempts were also undertaken to develop a thermal-physical model able
to predict the expansion of FRPAs when exposed to an hyperthermal environment [144,150,313]. Thermal-mechanical mod-
els capable of predicting the reduction to the stiffness, strength and creep resistance of composites exposed to moderate heat
fluxes were also introduced [324].
8.2. Mechanical erosion
The possibility to model the mechanical erosion of an A-TPS materials subjected to shear stresses is important to optimize
the heat shield size and shape (see Section 5). Ommati et al. modeled the erosion FRPAs exposed to severe hyperthermal
environment produced via oxy-acetylene torch [325]; the introduced model was based on the approach introduced by
the leading studies of Dimitrienko [326,327]. This author proposed a number of analytical models to predict the mechanical
erosion of carbon/phenolic FRPAs; Ommati et al.’s model was introduced to describe the erosion rate of randomly dispersed
chopped carbon fibers impregnated with a phenolic resin and exposed to high speed hot gas flow. The fiber orientation dis-
tribution density function was employed to determine the mechanical and chemical erosion of the composite, and to eval-
uate the fibers angles with respect to their flow direction. The model described the composite erosion rate as a function of
the thermo-physical properties of the fibers and the matrix, also keeping into account the composite surface temperature
and the pressure of the gases supplied to the oxy-acetylene torch used to test the material; in fact, to test the validity of
the results obtained by the model, a series of experiments were carried out testing the carbon/phenolic BMC composite sam-
ples using an oxy-acetylene torch. The results obtained from the model exhibited impressive agreement with the experimen-
tal data collected from the oxyacetylene flame tests. The effectiveness of the model was also tested studying the erosion rate
as a function of the pressure of the combustion gas; to this purpose, three series of tests were conducted for different values
of pressure of the gases (mass flow) supplied to the oxy-acetylene torch. It resulted that the theoretical values well corre-
Fig. 43. Surface ablation phenomena description of a traditional PAs (a). Volume ablation process for porous ablatives such as PICA (b). Credit: Dr. J.
Lachaud.
lated with the experimental data [325]. Accordingly, the introduced model could be effectively used in the design of thermal
protection shields both for the material selection and for the calculation of the carbon/phenolic FRPA thickness.
When the surface of an ablative is attacked thermally and mechanically by a high-temperature particle-laden flow, both
thermo-chemical ablation and mechanical erosion can take place simultaneously and interact with one each another; Koo
and co-workers investigated this complex interaction of the ablation problem [171,172]. Starting from these experimental
results, Yang et al. [173] developed a one-dimensional material erosion model to describe the simultaneous processes of
thermo-chemical ablation and mechanical erosion of ablatives exposed to high-temperature particle-laden flows produced
by solid propellants in SRMs. These model accounts for the effect of mechanical erosion due to thermo-chemical weakening
of the material and the influence of particle impact on the thermo-chemical ablation. Numerical calculations of the erosion
depth (i.e., surface recession) were made for various thermal and particle loading conditions. The predicted results were
found to agree reasonably well with available experimental data. More recently, Xu et al. [328] extended this research
and produced a comprehensive and very instructive paper combining the testing and modeling of EPDM based EHSMs
[294] and producing a numerical code with remarkable prediction capability.
8.3. Differences between ablation models for full dense FRPA/HSMs and LCAs
The ablation process of PICA and full dense ablators such as FRPAs/HSMs presents some differences which deserves to be
highlighted: moreover, the response of these materials also strongly depends on the heat flux. Accordingly, the state of art
results on the modeling of these two classes of PAs needs to be reviewed. As pointed out in the previous sections, during the
interaction with an hyperthermal environment, such as in a re-entry flight, part of the heat flux is transferred inside the TPS
producing a gradual temperature increase of the material. In its virgin state, PICA consists of a fibrous carbon preform con-
solidated by a pore filling high surface area phenolic resin [329]. With the increase of temperature, the virgin material is
transformed by two mechanisms. The first is pyrolysis: the phenolic resin is progressively charred and, depending on the
type of surrounding atmosphere, it loses a substantial amount of its mass, producing pyrolysis gases: the role of the gas evo-
lution from an ablative material was deeply investigated in the previous sections. After pyrolysis, the charred material is
composed by the fibrous carbon preform (unaffected by pyrolysis) and by the carbonized phenolic resin [330]. The second
transformation phenomenon is ablation. Depending on the re-entry conditions, ablation is driven by chemical reactions such
as oxidation, phase change (sublimation), and mechanical erosion (spallation) of the char. These processes lead to mass
losses of the char and to a wall recession: material response models should estimate these mechanisms.
Most of the standard models introduced in previous section describe ablation as a surface phenomenon [331,332] (see
Fig. 43(a)): it is supposed that all the mass is lost at the surface and the material density is considered constant in the char
layer. These models are based on two major assumptions: (a) ablation does not occur in volume, (b) the equilibrium chem-
istry is considered in a volume close to the wall. Using this description [333], the Stardust post-flight data shown that the
recessions on the flank and near the stagnation point was overestimated by 20% and 60% respectively. Some models (known
as finite rate chemistry models) have been proposed and implemented to improve the accuracy of standard models [334]. To
improve the reliability of these models, an estimation of the Effective Reactive Surface Area (ERSA) of the exposed material
was required. This is a complicated problem because the ERSA evolves with the time: in the case of dense materials the ERSA
seems to be proportional to the surface roughness [335–337]: in the case of porous materials, the ERSA is a complex function
of the porosity of the material and of the mass transport inside the pores [338]. As a result, a model predicting the ERSA for
PICA like materials is very important: the estimation of the ERSA is also required for the implementation of finite rate chem-
istry models including a proper evaluation of the surface ablation. It is also important that a given model correctly predicts
the evolution of the density profile of the TPS material.
In general, the ablation models developed for traditional, full dense FRPAs or HSMs applied to PICA overestimated the
char layer density near the wall: the reason for this discrepancy could be that ablation of porous materials like PICA, cannot
be properly described by a surface recession, i.e. considering a sharp ablation front propagation. This evidence suggested to
add an ablation zone to account for subsurface phenomena. In fact, chemical reactions, phase changes, and even spallation
may occur in volume (Fig. 43(b)). Accordingly, the ERSA prediction model needs to take into consideration this evidence:
multiscale approaches, reflecting the material response on a microscopic scale, are required to provide a phenomenological
macroscopic description. From a microscopic scale point of view (on the fiber scale), when the conditions allow oxygen
molecules to penetrate into the porous material, inhomogeneous in depth oxidation and recession of the matrix and fibers
can occur: as evidence to support the fact that the carbonized matrix can be removed for the carbon preform is that the
recession due to oxidation is typically faster for the matrix than for the fibers. If this hypothesis was correct, for PICA-like
materials the ablation by oxidation would not be a surface process, but instead a volumetric phenomenon.
Lachaud et al. [329] developed a new model answering to many of the above mentioned questions. They considered the
oxidation of carbon based LCAs such as PICA under the effect of the earth atmosphere (air) with the idea that oxygen diffuses
through the pores of the char and ablate the material in depth (see Fig. 43(b)). The local surface recessions of the carbon
fibers and of the carbonized matrix were individually modeled and coupled with the oxygen transport in the porous char.
The model was then applied to the analysis of the behavior of a carbon preform and of two PICA materials: one version
of the PICA material had a low density pore filling phenolic resin, whilst the matrix for the second PICA had a dense phenolic
resin coating the fibers. The standard ablation models would have predicted the same ablative behavior for these two mate-
Table 3
List of main available simulation tools for the ablation response of A-TPS materials. Table re-adapted from [339] with permission of the author.
Name Contact Owner/Country Users Application

Amaryllis T. van Eekelen Samtech, Belguim EADS Astrium, ESA Design
CAMAC W.S. Lin CSIST, Taiwan Taiwan Ins. of Sci. Tech. Unknown
CAT N.N. Mansour NASA ARC, USA NASA ARC Analysis
CHALEU B. Blackwell SNL, USA SNL Design
CHAP P. Keller Boeing, USA Boeing Design
CMA R. Beck Aerotherm, USA NASA, SNL Design
CMA/SCMA C. Park Tokyo Univ., Japan JAXA Design
CMA/KCMA P. Reygnier ISA, France ISA/ESA Analysis
COYOTTE2 W. Kuntz SNL, USA SNL Design
FABL J. Merrifield Fluid Gray. Eng. Ltd., UK ISA/ESA/FG E Analysis
FIAT Y.K. Chen NASA ARC, USA NASA, SpaceX Design
FIAT3D Y.K. Chen NASA ARC, USA NASA ARC Analysis
HERO M.E. Ewing ATK, USA ATK Analysis
ITARC M.E. Ewing ATK, USA ATK Design
libAblation R.R. Upadhyay Univ. Of Tex. Aust., USA UTA Analysis
MIG S. Roy Univ. Of. Flo., USA Univ. of Florida Analysis
MOPAR Martin Univ. Of Mich., USA Univ. Of Michigan Analysis
NEQAP J.B. Scoggins N. Carol. St. Univ., USA NCSU Analysis
NIDA G.C. Cheng Univ. Alab. Birm., USA UAB Analysis
PATO J. Lachaud NASA ARC, USA Univ. Calif. Santa Cruz Analysis
PRESENT J. Dec NASA LaRC, USA NASA LaRC Analysis
STAB Remark NASA JSC, USA Fluid Gr. Eng. Design
TITAN F.S. Milos NASA ARC, USA NASA Analysis
CHAR n.a. NASA JSC, USA NASA n.a.
TMU A.R. Bahramian T. Modares Univ., Iran TMU Analysis
US3D G. Candler Univ. Of Minn., USA UM Analysis
SCMA n.a. JAXA/Nagoya University, Japan JAXA n.a.
SCMA2 n.a. JAXA/Nagoya University, Japan JAXA n.a.
n.a. – not available.
rials because they have the same chemical composition. The numerical simulations showed that the ablation was controlled
by the competition between reaction and diffusion and that it could be both a volume or a surface process.
The macroscopic model showed that two main processes can occur: when the reaction rate is fast compared to mass
transfer rate, the oxidant is mostly consumed at the surface and cannot diffuse through the porous char. In this case, the
ablation is a surface process and the thickness of the ablation zone is small compared to fiber diameter. On the contrary,
when the oxidizer concentration becomes relevant inside the porous char, the ablation occurs in volume, i.e. the ablation
zone involves many fiber layers. Lachaud and collaborators also analyzed PICA under the Stardust re-entry conditions
[329]. It was found that oxidation occurred in volume at the stagnation point during the whole trajectory: this can be a pos-
sible explanation to the lower than expected density measured for the top layer char (0.5 mm) of the Stardust TPS. Micro-
scopic scale simulations showed that volume ablation weakens the structure of the material because the carbonized matrix
was deeply ablated thus leaving the fibers without protection. It was also concluded that the upper layer of the ablation zone
was likely to undergo spallation under the effect of the shear stress exerted at the surface by the surrounding flow. This phe-
nomenon can represent a concern in the case of PICA like materials: Lachaud also pointed out the necessity to develop a spal-
lation model coupled with a physico-chemical model, thus to properly estimate mass loss in volume.
8.4. State of the art of ablation simulation codes
During last forty years, with the aim to produce simulation tools enabling the use or the optimization of ablative mate-
rials in practical applications, a series of proprietary software packages was developed by government sponsored agencies
and private companies involved in the field of the TPS materials. Each simulation tool was optimized for a given class of
TPS materials and application. Lachaud et al. [339] provided a review of ablation solvers identifying practically all codes
developed during last fifty years or currently in use (Table 3); in this paper, the main differences among these codes were
summarized.
Among the earliest attempts to introduce a tool able to simulate the pyrolysis and the ablation of A-TPS based heat
shields, the Charring Material Ablation (CMA) code [340,341] developed by Aerotherm Corporation in the 1960s, was the
first 1D code to couple the internal energy balance and decomposition equations with a general Surface Energy Balance
(SEB) boundary condition, and a thermo-chemical ablation model. One of the most successful and known ablation code is
the Fully Implicit Ablation and Thermal (FIAT) code developed starting from the end of nineties by Milos and Chen at NASA
Ames Research Center [342,343]; basically, FIAT is based on the same analytical equations used by the CMA. Ahn and Suzuki
[344,345] developed the SCMA and SCMA2 codes that solve the one and two dimensional charring ablation problems includ-
ing pyrolysis gas flow within the char layer. Mahzari provided a very detailed description of the assumptions behind FIAT
code [346]; accordingly, this section strongly follows the approach introduced by this author. Compared to CMA, FIAT uses a
fully implicit finite difference approach able to enhance the numerical stability and convergence [343]. Since its introduction
at the end of nineties, FIAT became the most popular simulation tool in industry and for many recent NASA missions and
programs such as Mars Science Laboratory, and Orion. The FIAT code can be obtained by qualified individuals/organizations
under a Non-Disclosure and Software Usage Agreement with NASA Ames Research Center. Both ITAR (International Traffic in
Arms Regulations) and non-ITAR versions of FIAT code and materials database are available; the ITAR version is subject to
export-control and distribution restrictions and is available to NASA and its US contractors. FIAT can simulate 1D transient
thermal energy transport in a multilayer stack of isotropic materials undergoing ablation from the front surface, and in-
depth decomposition; the modeling involves solving the internal energy balance, decomposition, and mass balance equa-
tions [342]. Internal energy balance is characterized using the transient thermal conduction approach coupled with internal
radiation and pyrolysis [346].
The individual terms in the analytical model are mainly: the rate of storage of energy, the net rate of thermal conductive
and radiative heat fluxes, the pyrolysis energy consumption rate, the net rate of energy convected by the pyrolysis gas. The
pyrolysis gas enthalpy is assumed as a function of temperature and pressure and is calculated using multi species equilib-
rium solvers such as the Multi-component Ablation Thermochemistry (MAT) [347] or the Aerotherm Chemical Equilibrium
(ACE) code [348]. The specific heat and thermal conductivity are included in the material database and are defined as a func-
tion of temperature for the virgin and the char. These properties at any given location in the pyrolysis zone are calculated
using a linear density interpolation of the virgin and char properties. The internal decomposition of the material is charac-
terized using a three component model; the resin is assumed to contain two components while the third component is the
reinforcing material. The volume fraction of resin and the porosity of the material is also considered; each component
decomposes independently according to an Arrhenius type reaction model. The Arrhenius parameters for each component
are determined with the curve fitting of the data collected via TGA test. Internal mass balance allows to take into account the
convection of pyrolysis gas through the material generated from internal decomposition; to this purpose, assuming a quasi-
steady 1D flow, the conservation of mass can be imposed. The surface conditions are defined through distinct back- and
front-face boundary conditions. The back-face boundary can be specified in terms of known temperature history or using
a fluid convection boundary condition; an insulated boundary condition for the back-face can also be used. The front-face
boundary condition can be set to a known temperature history or defined as a non-ablating surface with incoming convec-
tive and radiative heat flux balanced by re-radiation. The SEB can also account for chemical reactions occurring at the surface
during ablation; from an analytical point of view, the SEB employed in FIAT are summarized and described in [346]. FIAT
operates using three input files that provide the run settings, initial conditions, back-face boundary conditions, the front-
face heating environment, and the material database.
Some of the assumptions used in FIAT can promote a certain degree of uncertainty to its prediction of recession and ther-
mal response; accordingly, there is extensive research to implement higher fidelity approaches. Some models employ the
same theories as CMA, and FIAT adding new equations to the assumptions [346]. However, other approaches were also intro-
duced [339,349]. Milos and Chen have also developed the 2D (TITAN – Two-dimensional Implicit Thermal response and
AblatioN) [350–352], and a 3D version of the FIAT code [353] (3D-FIAT) that more accurately model cross flow or multidi-
mensional material property. These multi-dimensional codes allow the analysis of the entire heat shield unlike the point-
analysis approach used by the 1D analysis tool like FIAT; in fact, highly curved regions of a TPS cannot be properly modeled
as 1D areas, and their analysis requires multi-dimensional capability. These enhanced features, and the higher accuracy
requires higher computational resources; they can also promote lower stability. Other studies were undertaken to develop
3D ablation and thermal response code using the finite element method [354,355]. Mahzari evidenced that unlike FIAT
which makes an equilibrium assumption for the in-depth pressure, these efforts include the use of Darcy’s Law to model
the flow of the pyrolysis gases through the ablative material. The aim is to obtain a better prediction of the in-depth pore
pressure due to these new approaches use Darcy’s Law to model the flow of the pyrolysis gas through the ablative material
and to predict of the in-depth pressure; efforts were also spent to model pyrolysis gas in more detail by adding gas-species
conservation equations [65,356,357]. Moreover, the thermal stresses in addition to thermal response can be studied. Other
efforts were undertaken to model the surface thermo-chemical ablation [65]. Multi-scale approaches (introduced in the
precedent section) were recently introduced [329,336] to model the diffusion of boundary layer species within the char layer
and allow ablation to occur in volume. This approach was able to explain the unexpected drop in char-layer density observed
in the post-flight analysis of Stardust sample return capsule PICA heat shield [333]. However, while these higher-fidelity
approaches show great promise and provide a more accurate characterization of the physics of the problem, more sophis-
ticated experimental techniques are required to acquire the data needed for their validation.
Another popular code is the CHarring Ablator Response (CHAR) code [358] developed at NASA Johnson Space Center to
solve problems involving 1D, 2D, and 3D charring ablators, general porous flow, and parallel or serial heat transfer. Notable
contributions to this code come from the CMA, ACE and Boundary Layer IMPlicit (BLIMP). The code uses the first and second
order implicit time integrators and the Galerkin spatial discretization on unstructured hybrid meshes. Supported element
types include: quadrilaterals and triangles in two dimensions; tetrahedrons, hexahedrons, prisms, and pyramids in three
dimensions. The code is capable of solving problems using adaptive mesh refinement on all element types in both 2D and
3D. The equations are fully implicitly solved with Newton’s method (with exact Jacobian terms), and the Generalized Min-
imal RESidual method (GMRES) is used to solve the linear system [357]. The exact Jacobian terms are calculated through the
use of the complex perturbation method rather than being analytically derived. This method ensures optimal convergence of
the nonlinear solver as opposed to degraded convergence rates from approximate Jacobians. The method dramatically
reduces development effort and the potential for bugs resulting from derivation and coding errors.
Some simulation tools were also developed to model the ablation of PAs used to manufacture rocket engines such as
SRMs. A remarkable example of code used to model the response of SRM liners is the Insulation Thermal Response and Abla-
tion Code (ITRAC) developed by ATK Launch Systems [359]. The ITRAC program provides a modern alternative lacking the
numerical issues commonly encountered with the CMA code; these include unexpected solution instabilities and failure
to converge with discretization refinement under certain conditions. Other advantages include various options for:
temperature-based boundary conditions; multicomponent pyrolysis analysis with no limitations on the number of compo-
nents; mechanical erosion; full pore pressure solutions for applications where mechanical loading cannot be neglected; mul-
tiple options for the definition of the property dependence; internal diffusion of absorbed constituents (such as moisture)
[359]. The program is extensively used within the ablation modeling community and consistently provides stable solutions
even with conditions of extreme heat flux and ablation conditions. For complete descriptions of the program, the reader is
referred to the ITRAC manuals [360,361].
Heat Transfer and Erosion Analysis Program program (HERO) [362–365] developed by ATK Launch Systems is another
code currently used to address ablation problems: it is used to study and design solid rocket motors by ATK. HERO is a mul-
tidimensional solver based on a variable-grid finite-element (hierarchical) method. The fluid-thermal-structural interaction
(FTSI) is an additional feature of this code. HERO also encompasses adaptive refinement and parallel processing.
9. Nanostructured ablative materials: introduction
Traditional PAs are structured on the micron scale, have several limitations; these limits, which are basically related to
the nature of a PA which can be considered as a discrete medium [22,30,68] have motivated the efforts to identify new gen-
eration ablative materials [366]. As an example, in some cases, the char of PAs such as FRPAs is structurally weak and sus-
ceptible to mechanical erosion, severely reducing the lifetime and the performance of the PA [366]; the resistance to thermal
and chemical ablation also tends to limit the lifetime and the performance of PAs structured on a micron scale. Composite
materials designed and produced with nanosized reinforcements, also known as nanocomposites [97,367] led to a new para-
digm for polymeric ablators. In contrast to conventional composites containing micron scale structured reinforcing con-
stituents [22,30,68], nanocomposites contain ultrafine phases, typically on the order of a few nanometers; if a traditional
composite structured on the micron scale can be considered a discrete system, a nanocomposite can be thought as a contin-
uous medium. Nanocomposites can exhibit a unique combination of properties which cannot be found in traditional com-
posites. Nanostructured Polymeric Ablatives (NPAs) are a class of nanocomposites particularly designed to work both in mild
and severe hyperthermal environments (Fig. 7); NPAs includes Nanocomposite Rocket Ablative Materials (NRAMs) [366].
Many types of nanoparticles such as layered silicates (LSs) for example nanoclay such as montmorillonite (MMT), nanosil-
ica (NS), carbon nanofibers (CNFs), and carbon nanotubes (CNTs) [97,367], have already been tested as fillers of nanostruc-
tured PAs [97,368]. If compared to traditional PAs, the technology of NPAs can be considered at its infancy; nonetheless, as
pointed out in the previous sections related to FRPAs and HSMs, the use of nanostructured fillers such as carbon black
[76,97,98,100,133] or nanosilica [264,270,271,277,282] has been widely adopted in the production of PAs. The studies car-
ried out on NPAs tested both in low intensity and severe hyperthermal environments evidenced the wide series of heat resis-
tance mechanisms of materials structured on the nanoscale; as a result, these phenomena in response to the exposure to
NPAs to an hyperthermal environment need to be reviewed more in detail. Moreover, since the behavior of nanocomposites
exposed to an hyperthermal environment are strongly related to the intensity of the heat flux, the review on NPAs will be
summarized in two different sections as a function of the heat flux; the most relevant details on the processing of nanostruc-
tured PAs will be discussed. The study of NPAs will also allow to improve the comprehension of the ablation mechanisms of
traditional ablatives.
9.1. Nanostructured ablative materials in a low intensity hyperthermal environment
In presence of hyperthermal environment of a limited intensity (order of 10 W/cm2) [44,68] the possibility to improve
the thermal stability and reduce the flammability of polymers or FRPAs/HSMs is generally based on two approaches. One
strategy is related on the use of high char retention thermosets such as phenolics, bismaleimides, benzoxazines, or cyanate
esters [67]; as an alternative, the use of flame retardant additives is also very effective to reduce the flammability and
increase the char yield of the polymeric matrices [369–372]. Even though 10 W/cm2 can be considered the lower limit of
typical hyperthermal environments in which PAs operate [44,68], in order to understand the behavior of NPAs exposed to
severe heat fluxes it is essential to study their response under these moderate conditions. In this case, apart from the exper-
imental techniques such as TGA, DSC and TMA [76,139–155], one of the most effective and common approach to study the
thermal stability and fire response of nanostructured polymers and nanostructured FRPAs is cone calorimetry [158,160]. In a
typical cone calorimeter experiment, the sample is exposed to a source of heat under monitored concentration of oxygen;
accordingly, a cone calorimeter [373] basically simulates an oxidizing low intensity hyperthermal environment; the maxi-
mum heat flux typically reaches values in excess of 10 W/cm2. The Heat Release Rate (HRR) is recorded as a function of time:
in order to evaluate the fire behavior, the value of its peak (PHRR) is also taken into account.
Fig. 44. Polymer Layered Silicate Nanocomposites appearance. Fire retardant mechanism for PLSNs exposed to moderate hyperthermal environments (a).
Response of PLSNs exposed to severe hyperthermal environments (b). Not published. Credit: UNIPG.
Polymer Layered Silicate Nanocomposites (PLSNs) can be considered as a new class of FRAs for polymeric ablatives [374].
FRAs are used to increase the insulation capability of ablatives such as elastomeric heat shielding materials for SRM liners
(see Section 6.3) [261]; as a results, the possibility to study and identify new fire retardant additives is very important for
many classes of polymeric ablators. PLSNs are obtained combining an organic matrix with layered silicates reinforcements
such as nanoclays [367]. Basically, nanoclays are composed by stacked layers of aluminosilicate sheets [97]. The nanoscale
structure of PLSN nanocomposites is associated with the thickness of these sheets (1 nm). Organically modified Layered
Silicate (OLS) (such as modified montmorillonite) are produced introducing organic modifiers in the layer inter spaces
[367]. The presence of these molecules promotes the penetration of the polymer into the OLS framework. Depending on
the degree of polymer penetration into the stacked structures of the layered silicates, the morphologies ranging from inter-
calated to exfoliated are obtained [367]. Polymer penetration resulting in a finite expansion of the LS layers produces an
intercalated morphology, consisting of ordered multilayers of alternating polymer/silicate with a repeated distance of a
few nanometers. An extensive polymer penetration resulting in delamination of the silicate layers produces exfoliated PLSN
consisting of individual LS layers dispersed in the polymer matrix (Fig. 44(a)). The final properties of the obtained nanocom-
posites depends on these types of morphologies. A detailed discussion on the different processing techniques (solution,
in situ polymerization and melt processing) to produce various types of PLSNs can be found in literature [375].
While traditional FRAs used in PAs such as phosphorus based fillers can act in the condensed phase by enhancing charring
or yielding intumescence [376], the flame retardant mechanism of PLSNs is completely different [377–385]. The intrinsic
advantage of PLSNs over other families of nanocomposites is that LSs are affordable and relatively easy to incorporate in
many polymers. According to some recent research, a relatively low concentration (5/10 wt%) nanoclay showed to sensibly
reduce the maximum heat release rate [377,381,386,387]; on the other hand, classic FRAs such as aluminum and magnesium
hydroxides require a high filler content to properly work and achieve acceptable flame retardancy properties [261,376].
Some studies carried out on PLSNs exposed to heat fluxes up to 10 W/cm2 showed that the fire retardant mechanism is
related to the formation of a hybrid silicate/carbonaceous char layer that works as a heat shield during burning [388]. Such
a phenomenon is driven by the ablative reassembling of the inorganic nanoclay platelets once the matrix is charred. Fig. 44
(b) summarizes the formation of the charred layer of PLSNs under mild heat fluxes (order of 10 W/cm2).
For PLSNs exposed to an oxidizing hyperthermal environment, the thermal oxidation of the char is reduced by the barrier
effect due to the inorganic layers reassembled on the surface of the material [368]. Schartel et al. [388] deeply investigated
the properties of thermosetting (epoxy) based PLSNs exposed to heat fluxes of the order of 10 W/cm2. The authors revealed
that in order to obtain a homogeneous residue surface skin exhibiting the desired flame retardancy it is essential to produce
a homogeneous nanoscaled dispersion of the nanoclay layers; the better the nanocomposite formation through a wide dis-
persion of the nano-platelets, the higher the efficiency in terms of fire retardancy. The same conclusion is reported by other
Fig. 45. In depth temperature profiles plotted against time for embedded thermocouples with different distances to the surface of the matrix (a) and (b)
PLSN during exposure to an oxidizing hyperthermal environment with of 10 W/cm2. Reprinted from [388] with permission from John Wiley & Sons, Ltd.
authors for different polymeric matrices [379–391]. The morphology of the nanocomposite strongly changes by virtue of
ablative reassembly [392,393]; only few studies have investigated the evolution of the barrier formation [394]. Nonetheless,
it is commonly accepted that a closed and homogeneous silicate/carbonaceous surface layer yields an effective reduction in
PHRR. The presence of cracks on the surface or even the formation of single domains of hybrid char led to an ineffective pro-
tection (Fig. 44(b)) [371]; the fact that these cracks were not closed, even though the thickness of the layer increased, clearly
showed that the enrichment in layered silicates on the surface is a very complex phenomena. It is this unpredictable
response of PLSNs exposed to low hyperthermal environments to have motivated their exploitation in synergy with tradi-
tional flame retardants [388,395–406]. Combined with the ablative reassembly, migration, bubbling, and accumulation in
distinct morphologies are believed to play a role in the fire retardant mechanism of PLSNs [391,392,407–409].
The study of Schartel and collaborators [388] also reported that PLSNs tested in a cone calorimeter did not reach temper-
atures allowing crystallographic changes all over the tested sample; in fact, X-ray Diffraction (XRD) and SEM results did not
show sintering of the inorganic silicates; the fire residue after the exposure to cone calorimeter was a silicate/carbonaceous
hybrid material, in which silicate platelets with their typical sharp contours were stacked together by the carbonaceous char
[388]. Since the maximum temperature reached by the PLSNs was lower than 900 °C, it was possible to conclude that an
heat flux of 10 W/cm2 did not promote the sintering of the nanoclay platelets. Heating tests carried out up to 1100 °C via
thermo-gravimetric balance showed that the LS platelets underwent sintering (Fig. 44(b)). Accordingly, it is possible to con-
clude that the unpredictable response of PLSNs exposed to low hyperthermal environments (heat fluxes of 10 W/cm2) is
due to the fact that once the polymer matrix is degraded, the nanoclay platelets simply stacked as overlapping tiles dispersed
Fig. 46. Response of a FRPA impregnated with PLSNs under a moderate (a) and a severe (b) hyperthermal environment. Not published. Credit: UNIPG.
in the charred residue (no sintering of the platelets); as a result, the produced skin exhibited poor mechanical properties and
the resulting char could be affected by defects such as cracks or voids [379,388]. The in-depth temperature profiles in the
neat control matrix and in PLSN tested by cone calorimetry showed that during burning, the surface of the PLSN reached
temperatures 400 °C higher than the surface of burning neat polymer. The corresponding re-radiation from the surface
is increased by a factor 4–5, since it depends on the T4 [388]; the increased re-radiation from the hotter surface is coupled
with a reduced heat flux transferred into the material and thus the degradation rate of the material is reduced. This is a sec-
ondary, yet important, mechanism at the base of fire retardancy of PLSNs (Fig. 45).
Some researchers also tested the effectiveness of nanomodified thermosetting polymers as matrices of fiber reinforced
composites [160,161]. Koo et al. [410] carried out a series of researches in which a phenolic resin (a resol, Borden Chemical
SC-1008) was modified using an OLS MMT (Cloisite 30B). These nanocomposites were used to modify a commercial carbon/
phenolic FRPAs (Cytec MX-4926) [76,97,98,100,133]; its precise composition was introduced in Section 3.4.4. Cone calorime-
ter tests were performed on the traditional FRPA and on the nanostructured counterpart. Compared with the control mate-
rial, the nanostructured MX-4926 (5% Cloisite 30B in the resin) showed improvements in the Peak Heat Release Rate (PHHR)
(25% lower), and on the average heat release rate (28% lower) than the baseline MX-4926. Bahramian et al. [160] inves-
tigated the flame retardant properties of an asbestos cloth FRPA impregnated with a resol PLSN. The authors produced the
PLSN using a resol and a laboratory modified natural nanoclay; then, the asbestos cloth was impregnated by the neat phe-
nolic and the nanocomposite. The laminates were tested by cone calorimetry (at an heat flux of 10 W/cm2). The PLSN based
composites exhibited a 35% lower HRR and a 22% lower mass loss than the control asbestos cloth/phenolic FRPA. The
morphology of the burnt surfaces showed that the spatially uniform distribution of silicate platelets led to an uniform hybrid
char. These researches [160,161,410] showed that if compared to a nanostructured polymeric matrix in which the nanoclay
platelets are dispersed as a local reinforcements, the presence of a micron-scale structure (the woven fabric) promoted the
production of a compact and homogeneous thermal barrier (Fig. 46(a)). The heat shield mechanism of PLSNs based on the
ablative reassembly of the nanoclay platelets resulted to be enhanced in presence of a structure – the fabric – able to work
as an holder of the un-sintered nanoclay sheets (Fig. 46(b)); these tiles packed in the char pockets of the laminate tended to
fill the voids among the fiber bundles, improving the fire resistance of the laminate, and enabling a synergetic exploitation
the intrinsic properties of both types of fillers. Accordingly, the ineffective and unpredictable thermal protection provided by
traditional PLSNs was minimized once a woven fabric was introduced.
Carbon nanotubes or nanofibers were also evaluated as potential flame retardant additives. CNTs [411] or CNFs [412] are
a form of vapor grown carbon fibers constituted by discontinuous graphitic filaments produced from the pyrolysis of gaseous
hydrocarbons and a catalyst. CNTs/CNFs have transport and mechanical properties that approach the theoretical values of
single-crystal graphite, but they can be produced in high volumes at relatively low cost [97]. An example of CNFs tested
in nanostructured PAs is Pyrograf III (Applied Sciences); Pyrograf III have a diameter ranging between 100 and 300 nm
Fig. 47. Transmission Electron Microscopy (TEM) micrographs of the virgin (a) and charred (b) NCH5 nanocomposites. Reprinted from [366] with
permission from Elsevier.
with lengths varying between 10 and 100 lm. Unlike most fibers used for composite reinforcement, CNFs come as a fluffy
mass of carbon bundled filaments [97].
Recent studies evidenced that CNTs can effectively work as FRAs [413–416]. The research evidenced that the enhanced
flame resistance is related to the formation of a continuous protective nanotube network structure working as a protective
barrier; this region slows down the mass loss rate and the material flammability. As a result, the fire retardancy resulted to
be improved at high filler loads and with the use of high aspect ratio CNTs [417–419]. Due to the high emissivity of carbon,
the CNTs embedded in the charred surface also re-emits part of the incident radiation from the hot surface into the gas
phase, decreasing the heat transferred into the inner layers of the material [388]. The main drawback related to the use
of CNTs is strictly connected to their processing; in fact, the addition of this filler in the matrix significantly increases its vis-
cosity [97]. Additionally, the single CNTs tend to be clustered in bundles, thus increasing the difficulty to uniformly disperse
and distribute them into the polymer matrix. To overcome this limitation, some researchers successfully proposed the use of
buckypapers made of CNTs and CNFs as an alternative at the use of these fillers directly dispersed in the matrix [420–422]. In
order to minimize the oxidation of carbon based nanofillers, the use of hybrid buckypaper systems using LSs resulted to be
very effective; the nanoclay sheets can protect the carbon nanofibers from oxidation by virtue of the ablative re-assembly of
the platelets [422]. However, to date, the industrial use of buckypapers is inhibited by their cost; however, the potentiality
related to their use in the whole aerospace sector is promoting the identification of cost effective production processes.
9.2. Nanostructured PAs in a severe hyperthermal environment
9.2.1. PLSNs as NRAMs

The studies on the improved flammability resistance of PLSNs encouraged the examination of this unique class of mate-
rials as potential ablatives for severe hyperthermal environments. The work of Vaia and collaborators [366] can be consid-
ered as one of the most pioneering research on nanostructured ablatives. They studied the ablative properties of a poly
(caprolactam) (nylon 6) comparing the response of this material with a 2 wt% (NCH2) and 5 wt% (NCH5) layered silicate/
poly(caprolactam) nanocomposite. These materials were synthesized by in situ polymerization of e-caprolactam in presence
of a laboratory organically modified montmorillonite. Additionally, the ablation resistance of a 5 wt% layered silicate/poly(-
caprolactam) nanocomposite NLS5 formed via melt process of poly(caprolactam) (Capron B135WP, Allied Signal) and a com-
mercial organically modified montmorillonite (Cloisite 30A) was examined. The ablation rate of the materials was
determined from exposure to a subscale SRM. The nanocomposites were tested without any micron-sized reinforcements
but, to enhance the retention of material during the test, a series of samples were produced consolidating the resins into
a polyimide mat. The nanocomposites were compared with an EPDM based EHSM loaded with 30% of silica powder and with
another composition based on EPDM loaded with 15% of KevlarÒ fibers. Transmission Electron Microscopy (TEM) microscopy
indicated that layer distribution was generally more uniform in NCH5 than in NLS5; Fig. 47(a) reports the TEM micrographs
of NCH5 nanocomposites.
Fig. 48. SEM micrographs of NCH2 ablative sample. (a) Surface region (sample tilted to observe cross-section and surface features) and (b) char layer. SEM
images of NCH5 ablative sample. (c) Surface region and (d) char layer. (VM: virgin material, RZ: reaction zone, CL: char layer). Reprinted from [366] with
This mesoscopic mixing of the inorganic and organic phases drastically altered the ablative properties of the neat matrix.
The pure poly(caprolactam) did not survive the experimental conditions; the erosion rate of the neat polymer was estimated
to be at least 1.5 mm/s. The presence of the polyimide mat improved the retention of charred surface, slightly decreasing
the erosion rate. A marked reduction in erosion rate was observed with a very limited concentration of filler – 2 wt% (0.8 vol.
%) – of exfoliated LS. In general, an increased mass flux of the impinging SSRM plume, increased the mechanical erosion rate
of all nanocomposites. Moreover, an higher erosion rate of NLS5 relative to NCH5 and NCH2 indicated that polymer-silicate
interactions could impact the toughness of the char. However, the major factor leading to the improved ablation perfor-
mance and char toughness relative to the neat resin or to the traditional micron-structured ablatives was the nanoscopic
distribution of the silicate layers present in all the examined nanocomposites. The TGA studies on the produced nanocom-
posites showed that the presence of the LSs did not alter the primary polymer decomposition in the reaction zone (where the
polymer matrix underwent decomposition) [366]. As a result, the enhanced ablation performance of the nanocomposites
must be related to the microstructure and composition of the char layer (Fig. 47(b)). SEM micrographs of the tested NPAs
were collected; the SEM post testing appearance of NCH2 is showed as a reference in Fig. 48(a) and (b) whilst the morphol-
ogy of NCH5 is reported in Fig. 48(c) and (d). The ablated materials comprised a dense char layer, the reaction zone, and the
virgin material; the residual char was porous with solid regions exhibiting a lamellar morphology.
The microstructural features of the char showed that increasing LS content resulted in a tougher char; in fact, a relatively
weak, sub-micron lamellar structure is most prevalent in NCH2 char and in smaller extent in NCH5 (and NLS5) char (Fig. 47
(b)). An higher silicate content also resulted in a thicker char. Additionally, the char layer better adhered to the underlying
virgin material with increased silicate content. Moreover, the rougher surface in NLS5 reflected a non-uniform mass loss and
agreed with the higher erosion rate relative to NCH5 [366]. As a result, the spatially uniform arrangement of the silicate lay-
ers on an ultra-fine nanometer level facilitated the formation of a spatially uniform inorganic char. At 5 wt%, the layers are on
average only 20–25 nm apart; thus, the efficient distribution of the inorganic precursors necessary to form a uniform char
Fig. 49. The experimental temperature distribution of top surface and through the thickness of the composite and nanocomposite (NMA3) samples tested
via OAT. Reprinted from [162] with permission from Elsevier.
layer was the key structural characteristic of the nanocomposites leading to the enhanced ablative performance at very low
additions of a reinforcing phase [358]. This nanoscopic morphology is comparable to the length scale of char forming reac-
tions determined by the temperature profile and the diffusivities of the reactants. At temperatures in excess of 1500 °C –
within the char layer it exceeded 1000 °C, and approached 2000–2500 °C at the surface – the inorganic transformed into a
high viscosity melt on the surface improving the ablation resistance by flowing to self-heal surface flaws. As pointed out for
FRPAs/HSMs, this is a well known mechanism which occurs in silica filled ablatives [22,30,68]. However, the localization of
inorganic on the micron scale associated with the traditional filled systems required a higher inorganic loading for the for-
mation of a uniform inorganic char at the surface. At loading fractions comparable to the nanocomposites, large regions void
of inorganic precursor are present in micron-structured ablatives resulting in locally, nonuniform erosion rates, leading to
rough surfaces more susceptible to mechanical erosion.
Another important research pointing out the role of the nanoclays for NPAs was carried out by Bahramian and collabo-
rators [158–162]. They studied the ablative performance, the thermal decomposition, and temperature distribution through
the thickness of asbestos/phenolic composites impregnated with a PLSN [161]; these data were compared with the results
obtained for traditional asbestos/phenolic ablators (1.45 g/cm3) [162]. Ethyl alcohol was employed to disperse the layered
silicates (Cloisite 15A) and dissolve the phenolic resin. The asbestos cloth was impregnated with the produced PLSN. Three
composites having different nanoclay percentages were studied: 3 wt% (NMA1), 4 wt% (NMA2) and 6 wt% (NMA3) (1.52 g/
cm3) [161]. Samples were tested via OAT test (heat flux 900 W/cm2) [57]; the temperatures at 2, 4, 6 mm from the surface
were acquired. The morphology study confirmed the penetration of the resol molecules between the clay sheets. TGA ther-
mograms showed the presence of clay improved the thermal stability of the composites; the higher the LS content, the better
the thermal stability. As highlighted in Section 9.1 and by the research of Vaia and co-workers [366], the dispersed large
Fig. 50. Burnt surface of control formulation (BMC1) (a) and ablation mechanism (b). Burnt surface of BMC2 formulation (c) and ablation mechanism (d).
Burnt surface of BMC3 formulation (e) and ablation mechanism (f). Reprinted from [425] with permission from Elsevier.
aspect ratio platelets hindered the diffusion of the decomposed volatile products, as a direct result of the decreased perme-
ability. For the thermal oxidation process, the mass transfer of oxygen into the gallery was slowed down, decreasing the
degradation of the matrix. The ablative re-assembly of LS platelets combined with the sintering at elevated heat fluxes
led to the formation of a homogeneous, hybrid silicate/carbonaceous char layer that works as a heat shield [366]. The heat
capacity measurements were carried out up a temperature of 800 °C; the values of the specific heat of the asbestos/phenolic
composite and of the NMA3 were in the range of 1000–1500 and 3300–5800 J/kg K respectively. The higher value of the
NMA3 was one of the key factors to cause the better insulation performance of the NMA3 over the asbestos/phenolic com-
posite. The dynamic DSC scans also showed that the heat of ablation of the NMA3 composite was quite higher (950 J/g)
than the control material (45 J/g). Moreover, at the same experimental conditions, the steady state surface temperature
of the asbestos/phenolic composite and of the NMA3 were about 1500 °C and 2100 °C respectively (Fig. 49). The higher
value of surface temperature of the NMA3 was another key factor to cause the higher insulation performance of nanostruc-
tured composite over traditional asbestos/phenolic laminates (the re-radiated energy follows a T4 law) [388].
Koo’s research group carried out a series of studies on the possibility to nano modify state of art ablatives such as Cytec
MX-4926 (density 1.45 g/cm3) a state of the art carbon/phenolic loaded with carbon black [423,424]. Cloisite 30B was
selected as a LS to be added in the formulation. XRD and TEM results showed that CB particles in the baseline MX-4926
caused interference during dispersion of the nanoparticles in the matrix. As a result, CB (15 wt% in the original MX-4926 for-
mulation) was eliminated in subsequent blending experiments; the LS in loadings of 5, 10, and 15 wt% resulted to be well
dispersed into the SC-1008 (the densities of these materials ranged from 1.42 to 1.43 g/cm3). The ablation resistance of
the studied materials was evaluated through SSRM. It resulted that compositions with 2.5 and 5 wt% were not as erosion
resistant as the control MX-4926 whilst the 7.5% composition exhibited better erosion resistance than MX-4926 (14%).
A comparison of maximum backside temperatures indicates that all the nanoclay compositions were better than MX-
4926; at the higher filler content the reduction was equal to 28%.
Fig. 51. SEM micrographs of the burnt samples, (a and b) refer to BMC1; (c and d) refer to BMC2; (e and f) refer to BMC3. The benefits of nanosilica on the
charred layer are clearly visible. Reprinted from [425] with permission from Elsevier.
Fig. 52. Morphology of charred surface of BMC3. The adhesive effect of the sintered nanosilica particles is clearly visible. Reprinted from [425] with
9.3. Nanosilica as filler for traditional and nanostructured PAs
As pointed out in sections on FRPAs and HSMs, for over forty years, micron or nanosized silicon dioxide has been success-
fully used as a filler for almost any type of PAs [22,30,68,264,270,271]. For this reason the role of nanosilica deserves to be
described more in detail.
Natali et al. reported the effects on nanosilica on the ablation resistance and insulation capability of glass/phenolic FRPAs
pointing out the remarkable benefits due to this filler [425]. The authors studied glass/phenolic FRPAs based on the use of
nanosized silica as an alternative to micron-sized counterpart. Typically, in glass/phenolic or silica/phenolic FRPAs loaded
with micron sized silica (such as MX-2600) the amount of SiO2 particles is of 8–10 wt% (see Section 3.4) [76,77]. Nanocom-
posites based on 5 and 20 wt% nanosilica [95] were used as matrices for the impregnation of E-glass chopped fibers; the neat
resin was used to produce the control formulation (BMC1). In all the formulations, the fiber percentage was kept constant at
60 wt%. The amount of nanosilica on the composite formulation was 8 wt% (BMC3) when the 20 wt% loaded nanocomposite
was used to impregnate the chopped fibers; this formulation strongly resembles the composition of MX-2600 [76,77] with
the difference that the micron sized silica was replaced by the nanosized SiO2. To further investigate the effects of the NS
content, another formulation (produced using the 5 wt% loaded nanocomposite) containing a nanosilica percentage equal
to 2 wt% was studied (BMC2). OAT tests were carried out at an heat flux of 850 W/cm2 [57].
Fig. 50(a) highlights the burnt surface of the control formulation (BMC1) whilst Fig. 50(b) summarizes the related ablation
mechanism. In absence of nanosilica, under exposure to OAT, the glass fibers melted into a low viscosity liquid, leading to a
high erosion rate. As a result of the shear stresses produced by the combustion gases [58], the glass droplets moved to a well
defined corona on the external edge of the torch plume. In terms of contact angle with the charred surface, the marked
Fig. 53. Ablated surface of the blank carbon/phenolic (C/Ph) composite (a). 2.0 wt% nanosilica loaded C/Ph after ablation (b). Reprinted from [426] with
spheric shape of the glass droplets clearly evidenced the poor compatibility of the melt with the charred substrate. The
results of the BMC2 formulation are shown in Fig. 50(c) and (d). Under exposure to the OAT the glass fibers and nanosilica
melted together to form a blend. In comparison with BMC1, the glass droplets moved to a corona with a smaller diameter,
evidencing a lower erosion rate, and an increased stickiness of the charred surface. The contact angle of the melted droplets
with the exposed surface, indicated that the char increased its compatibility with the melt. The most interesting results were
obtained from the BMC3 formulation (Fig. 50(e) and (f)). In this case, the protection of the char resulted to be highly
increased also significantly reducing the erosion rate; the presence of a high viscosity silica based melt on the charred surface
improved the ablation resistance by self-healing the surface flaws [366]. Analyzing the contact angle of the melted droplets
with the surface, it was possible to highlight the high compatibility between the charred region and the droplets of melt.
Since the charred substrate better adhered above the virgin, the re-radiation efficiency was also increased [161,388]. The
SEM characterization on the burnt samples confirmed the indication obtained with the optical analysis (Fig. 51).
Fig. 52 also shows how nanosilica particles adhered on the glass fibers, acting as a binder [95]. The in depth temperature
profiles also evidenced that increasing the nanosilica content, the BMC formulations exhibited an improved degree of insu-
lation; the higher the amount of nanosilica, the higher the amount of heat absorbed by the filler (the higher the nanosilica
content, the thicker the char above the thermocouples) [425].
Srikanth et al. [426] studied the effect of nanosilica on the ablation resistance and on the Inter Laminar Shear Strength
(ILSS) of carbon/phenolic composites. The through thickness thermal conductivity was also measured at 300 °C under
steady-state conditions and according to ASTM E-1225-99. A rayon based carbon fabric was used as a reinforcing material
and a resol was used as a matrix. Three different formulations were prepared by adding 0.5 (density 1.41 g/cm3), 2.0 (den-
sity 1.38 g/cm3), and 4.0 wt% (density 1.27 g/cm3) of NS in the phenolic resin; the pristine resin was used to produce the
control formulation (1.42 g/cm3) and the nanocomposites were used to impregnate the carbon fabric. The produced mate-
rials were exposed to a plasma arc jet at an heat flux of 1250 W/cm2.
The authors reported as follows. Due to the presence of nanosilica, the ILSS increased with the NS content up to a filler
percentage equal to 2.0 wt%; above this threshold the ILSS decreased. This result indicated that up to 2.0 wt%, the nanosilica
particles acted as anti-slippage agent whilst, above this threshold, nanosilica compromised the adhesion among fabric layers.
An increased ILSS makes the composites more resistant to the high shear forces; this evidence should promote in an
increased ablation resistance. Plasma arc jet test results were in good agreement with the ILSS trend; the ablation resistance
increased with the nanosilica content up to 2.0 wt% and above this threshold was lower than the control formulation. In the
case of nano silica loaded C/Ph composites, when the temperature exceeded 1600 °C, nanosilica particles melted to form a
viscous and adhesive layer which acted as a high temperature binder [425,427]. This layer was able to hold the underlying
phenolic matrix and the char thus ensuring a higher radiant emission and leading to a complete charring of the resin, thereby
absorbing an increasing amount of heat. The use of nanosilica also decreased the measured thermal conductivity of the C/Ph
composites. Since the thermal conductivity depends on the lattice vibrations and on the microstructure (micro cracks, grain
boundaries, porosity, etc.), the introduction of NS increased the number of grain boundaries, resulting in lower thermal con-
ductivity. As a result of a reduced thermal conductivity, the ablation resistance resulted improved [425].
The SEM (Fig. 53) and XRD analysis showed that the damage to the carbon fibers in the control C/Ph was considerably
higher to the damage occurring in the presence of NS. The ablated surfaces of nanostructured C/Ph composites showed that
SiC formed on carbon fibers during ablation [95]; in fact, the molten silica could react with carbon thus to form a hard SiC
phase [428]. The resulting carbon/silicon carbide composite could withstand the aerodynamic shear forces under high tem-
perature erosive environments, thereby enhancing the ablation resistance [429].
9.4. Carbon nanofilaments based NRAMs
Among nanofillers recently evaluated as a reinforcement for NRAMs there are carbon nanofibers. Koo et al. [423,430]
compared the ablation resistance of MX-4926 with laboratory produced nanocomposites based on SC-1008 phenolic resin
and CNFs (PR-24-PS Pyrograf Products, Inc). A molding compound was considered to include large loadings of CNFs [423].
Three loadings of CNFs (20, 24, and 28 wt%) were dispersed into SC-1008 without the carbon fabric reinforcement (densities
equal to 1.35 g/cm3, 1.38 g/cm3, and 1.41 g/cm3 respectively). The developed materials were tested via SSRM (heat flux
1150 W/cm2. All three CNFs loadings showed lower ablation rates than MX-4926, with 28% CNF-NRAM being the lowest. In
terms of residual mass, if compared to MX-4926 which had a value close to 92%, the CNF-NRAMs had values in the range
(86/88) wt%. The backside heat-soaked temperature of all CNF-NRAMs outperformed the MX-4926. The surface tempera-
ture of the CNF NRAMs was higher than MX-4926; this result suggested that better in-plane than out-plane heat transfer was
occurring with the CNF-NRAMs. The glowing heat of the surface observed during materials testing also supported this
hypothesis.
Patton et al. [431] produced nanocomposites with CNF amounts up to 40 wt% in absence of fabric reinforcement (density
1.47 g/cm3). CNFs (Pyrograf III, Applied Sciences) and phenolic resin SC-1008 were used in this study. MX-4926 was the
control formulation. A plasma torch test bed was used for the ablation testing (heat flux of 1600 W/cm2). Under these test
conditions, as compared to the MX-4926 baseline, depending on the CNF content, the nanocomposites experienced an higher
(58–114%) erosion rate and a lower mass loss (10–26%). The higher erosion rates of the CNF-NRAM samples probably
reflected their lower carbon content as compared to the MX-4926: in fact, the CNF-NRAM samples had a significantly lower
carbon loading (in the range of 30–50 wt%) than the MX-4926 composite (65 wt%). As a result, the erosion rates per weight
Fig. 54. Post-burning surfaces of the PR-MWNT system (a and c) and PR-CB composite (b and d). Reprinted from [432] with permission from Elsevier.
Fig. 55. SEM analysis of the post-burning surfaces of the PR-CB (a and c) and of the PR-MWNT (b and d) composites. Reprinted from [432] with permission
from Elsevier.
percent of carbon reinforcement present in the composites were very similar between MX-4926 and the CNF loaded
nanocomposites. However, the CNF-NRAMs appeared to be far better insulators than the MX-4926; once applied a mechan-
ical load on the produced materials, the load changes for the burnt CNF-NRAMs were significantly lower than MX-4926. The
load change can be considered an indirect measure of heat penetration and char depth; an increase in loading change indi-
cates an increase in heat penetration and char depth. Plasma tests also showed that when MX-4926 was exposed to the
torch, a bright, glowing spot appeared exactly on the zone where the flame impinged. On the contrary, there was no bright
spot where the torch impinged the nanocomposite specimens. Instead, the heat appeared to be spread far more uniformly
across the surface of the CNF-NRAM samples. This result suggested a good in-plane thermal conductivity. Also, the very short
lengths of CNFs prevented rapid heat transfer deeply inside the sample [423,430]. Instead, the lateral spread of the heat
caused the surface region of the resin to become more graphitic over a larger surface area than in the case of the MX-
4926 sample. Moreover, the ablation proceeded with a flaking phenomenon; very small flakes of heated material peeled
off or dislodged from the specimen. According to Patton and collaborators, if a 65 wt% CNFs loading could be achieved, then
the ablative properties would be comparable to or better than the traditional carbon/phenolic composites currently in use in
SRM nozzle assemblies. However, currently the cost of CNFs is still higher than the carbon fibers used to produce MX-4926.
Another intrinsic advantage of these CNF based NRAMs would be related on the possibility to use low cost processing tech-
niques such as compression molding.
Natali et al. [432] highlighted the main differences in terms of ablation resistance among Multi-Walled Carbon Nanotubes
(MWNTs) and carbon black, a traditional carbonaceous extensively used in the production of polymeric ablators such as MX-
4926. Two different NRAMs were produced, both consisting of 50 wt% of a phenolic matrix (Bakelite PF-GA-T 6) and 50 wt%
of carbon nanofiller; one formulation was based on CB (Vulcan 7H) referred to as PR-CB, the other one was based on MWNTs
(Arkema Graphistrength C100) referred as PR-MWNT. An OAT was used to test the materials (heat flux 500 W/cm2). The
post burning images of the tested materials showed that the PR-MWNT exhibited an higher erosion than the PR-CB system.
The PR-MWNT samples suffered a marked erosion and the flame produced a crater exactly in a zone confined under the
plume of the torch (Fig. 54(a) and (c)). During the tests, small flakes of the material were peeled off the surface of the PR-
MWNT samples [423,430,431]. The PR-MWNT samples also showed a very thin charred region above the virgin material
and a very limited number of in depth cracks propagating from the mantel surface to the center of the sample. For the
PR-CB composites, the ablation mechanism was quite different; the flame produced a broad and deep charred region having
relatively good integrity. However, the flame did not produce any crater. Also, during the test, this material did not show any
macroscopic ejection of burning material. The PR-CB burnt samples exhibited a remarkable number of macro cracks starting
from the mantel of the samples up to the lower limit of the charred region. PR-CB system suffered a char penetration
extended on a wider and deeper region of the sample as compared to PR-MWNT (Fig. 54(b) and (d)).
The morphology of the burnt surfaces was also investigated by SEM (Fig. 55(a) and (b)). At low magnification the PR-CB
revealed the cracking phenomena also identified with visual inspection. The top surface of the PR-CB showed a morphology
characterized by micron and sub-micron sized open and closed bubble-like structures; the carbon black particles were not
distinguishable from the charred layer.
If compared to the PR-CB system, the surface of the PR-MWNT samples showed a homogeneous morphology free of any
macro cracks (Fig. 55(c) and (d)). The ablation appeared to be a surface phenomenon with a very thin transition zone – the
charred region – between the virgin and burnt material. The char was constituted by many irregular aggregates mainly com-
posed of entangled MWNTs; SEM also evidenced many bright spots clearly related to the metal precursors used to produce
the nanotubes.
The temperature profiles showed that the PR-MWNT system exhibited higher thermal diffusivity than the PR-CB formu-
lation. If compared to the PR-CB system, the PR-MWNT composite showed a higher thermal conductivity in the direction of
the flame plume; however, loss of mass data indicated that both materials experienced a similar removal of mass. As a con-
sequence, since the surfaces of PR-MWNT samples experienced a more severe erosion than the PR-CB specimens and con-
sidering that the amount of loss of mass was of the same order of magnitude for both materials, it was concluded that the
ablation mechanisms of the two materials was deeply different. For the PR-MWNT, the loss of mass was due to the physical
erosion of material whilst, since the PR-CB did not erode appreciably (Fig. 54), the loss of mass could be attributed to the
higher degree charring of the organic matrix.
9.5. A new way to exploit boron containing fillers: nanosized boron carbide
The researches on FRPAs and HSMs evidenced the effect of boron containing fillers in terms of possibility to increase the
thermal stability and char yield [30,239] In Section 6.3 it has also been reported the possibility to improve the thermal resis-
tance of phenolics by means of boron containing precursors [239,260]. Gao et al. [433] obtained solid boron containing phe-
nol formaldehyde resin with an increased heat oxidative resistance and thermal stability as compared to the unmodified
resin. The higher resistance was attributed to the BAO borate linkages [239,434,435]. More recently Farajpour and coworkers
[260] evidenced the effect of borax (Na2B4O75H2O) on the mechanical and ablation properties of three different EPDM based
EHSMs evidencing the remarkable effects of this filler in terms of char yield. Other authors such as Wang and co-workers
[436–439] envisioned an alternative approach to exploit boron containing additives; particularly, the authors investigated
the use of micron sized boron carbide (B4C) as a modifier of phenolic based adhesives for carbon/carbon composites. The
authors reported that after heat treatment at different temperatures (from 400 to 1500 °C), the adhesive strength of the
modified phenolic adhesive underwent a substantial change. The highest strength values were registered at 1000 °C, while
at lower and higher temperatures the adhesive showed poor bonding capability. These results were directly related to the
chemical reactions occurring to boron carbide once exposed to high temperatures [436]: above 800 °C, B4C reacted with
the oxygen present in the environment and with the degradation products of the matrix (carbon monoxide, and water).
Following Eqs. (1)–(3) summarize these processes:
B4 CðsÞ þ 4O2 ðgÞ ! 2B2 O3 ðlÞ þ CO2 ðgÞ ð1Þ
B4 CðsÞ þ 6COðgÞ ! 2B2 O3 ðlÞ þ 7CðsÞ ð2Þ
B4 CðsÞ þ 6H2 OðgÞ ! 2B2 O3 ðlÞ þ CðsÞ þ 6H2 ðgÞ ð3Þ
Fig. 56. Post testing appearance of the neat carbon/epoxy laminate (a) tested under mild heat fluxes (of 10 W/cm2) as compared to the nanostructured
counterpart containing 5 wt% of nano boron carbide (b). Images modified from [440] with permission from Elsevier. Appearance of a bulk neat carbon/
phenolic FRPA sample (c) as compared to the nanostructured counterpart containing 5 wt% of nano boron carbide (d) isothermally tested at 750 °C for 600 s.
Images modified from [441] with permission from John Wiley & Sons, Ltd.
According to these reactions, boron carbide originates boron oxide (B2O3) and solid amorphous carbon (C) [436–439]. In
this way boron carbide acts both in condensed and in gaseous phase; the gas production is reduced, and solid amorphous
carbon is continuously added in the char. As a result, the carbonaceous residue exhibits a lower volumetric shrinkage
[432] and a more dense structure; a denser and stronger char better works as a binder. Boron oxide also acts as a high tem-
perature adhesive and, as a glassy, protective layer inhibiting the oxidation processes. Above 1200 °C the strength of the
bond decreases as a consequence of the carbon-thermal reduction and the volatilization of B2O3 at higher temperatures
[436]. The mode of carbon-thermal reduction reaction is expressed as follows (4):
2B2 O3 ðlÞ þ 7CðsÞ ! B4 CðsÞ þ 6COðgÞ ð4Þ

Rallini et al. [440] extended the use of B4C exploiting the benefits of this filler in terms of nanosized particles (n-B4C): the
aim was to bypass the limitations related to the use of traditional micron sized counterpart [366]. The thermal behavior of a
carbon/epoxy composites impregnated with n-B4C based nanocomposites was investigated. The thermal stability of the
nanostructured composites was investigated by TGA in air and nitrogen evidencing the remarkable effect of this filler in
terms of improvement of the oxidation resistance. Their fire reaction and resistance was studied under mild heat fluxes
(of 10 W/cm2); the post burning analysis evidenced that the nanostructured composite with 5 wt% n-B4C allowed main-
taining a residual structural integrity of the composites because of phenomena and chemical reactions (1)–(3). Fig. 56
(a) and (b) reports the appearance of the neat composite and 5 wt% n-B4C counterpart evidencing the integrity of the nanos-
tructured system as compared to the fluffed mass of fibers related to the traditional laminate.
The authors also evidenced as the boron carbide reactions strongly depend on the dimension of the particles: n-B4C begun
to oxidize above 200 °C and the oxidation completed at 700 °C as compared to micron sized counterpart (above 800 °C)
[436–439]. Accordingly, whilst the micron sized B4C converted in B2O3 can exercise its anti-oxidizing/adhesive action from
about 800 °C to about 1200 °C, due to its lower reaction temperature, the n-B4C can exert this function in a wider temper-
ature window (from about 200 °C to about 1200 °C).
The same research group also studied nanostructured carbon/phenolic FRPAs based on the use of n-B4C [441]. Beyond
TGA characterizations which confirmed the effectiveness of boron carbide as an anti oxidizing agent, the neat and n-B4C
based carbon/phenolic FRPAs were isothermally exposed at 750 °C for 10 min in a muffle furnace to simulate a mild oxidiz-
ing hyperthermal environment. Since the heat was transferred to the samples by direct conduction, convection, and radia-
tion, this characterization was more severe than the set of testing conditions reproducible via radiant panels like in a cone
calorimeter [373]. Moreover, this test was also able to ensure higher heating rates than a dynamic scan produced via TGA,
thus to reproduce more severe thermal shocks and better highlight the effect of n-B4C on the thermal and dimensional sta-
bility of the material.
The visual analysis of the burnt samples (Fig. 56(c) and (d)) showed that only the composite containing the 5% n-B4C
maintained a structural integrity after burning whilst the control formulation appeared as a fluffed mass of unbundled fibers.
The behavior of the 5% highlighted the impressive benefits due to the use of boron carbide even in presence of a severe oxi-
dizing hyperthermal environment and when high heating rates were applied which typically tend to promote delamination
and spallation of the material [22,30].
This research on the use of n-B4C evidenced how this filler can promote an increased char yield, and exert an adhesive/
self-healing and anti oxidizing action in the charred medium; as a result, in the temperature range of (300–1000) °C, the
use of nano boron carbide can promote a better adhesion among inner layers of A-TPS materials such as FRPAs. To further
highlight the role of n-B4C on the thermal and oxidation resistance of charring A-TPS materials, some tests under severe
hyperthermal conditions recreated through OAT should also be carried out. The main drawback of n-B4C is related to its high
price as compared to nanofillers such nanoclay, nanosilica, and even MWNTs.
9.6. Nanostructured elastomeric heat shielding materials
Few attempts to use nanofillers as additives of EHSMs are documented in open literature. Gao et al. reported the use of
nanoclays as novel fillers of traditional heat shielding elastomers [442]. They investigated the possibility to nanomodify the
state of art thermal insulation material for SRMs, namely the aramid/EPDM EHSMs; an organically modified layered silicate
was added to the EPDM matrix and the synergy of the nanoclay with the traditional fillers of the formulation was studied. In
their research the content of OLS was increased from 1 phr to 15 phr. The ablative properties were evaluated using an OAT. In
terms of mechanical properties, the elongation at break of the KevlarÒ/EPDM EHSMs was analyzed as a function of the fiber
content; these results were compared with the corresponding data of the KevlarÒ/EPDM/OLS system and analyzed as a func-
tion of to the OLS percentage. For the baseline KevlarÒ/EPDM, above a fiber content equal to 6 phr, the elongation at break
strongly decreased with the increasing content of the fibers; over 8 phr of fibers, the elongation at break of the KevlarÒ/EPDM
became too small to meet the requirements of SRM liners (see Section 6.3). However, the KevlarÒ/EPDM formulation con-
Fig. 57. TEM images of montmorillonite (MMT) clay dispersion in the TPUN formulations with 2.5 (a), 5.0 (b), and 10.0 (c) wt%. TEM images of multi walled
carbon nanotubes (MWNT) dispersion in the Thermoplastic Polyurethane elastomer Nanocomposite (TPUN) formulations with 2.5 (d), 5.0 (e), and 10.0 (f)
wt%. Reprinted from [454] with permission from Elsevier.
Fig. 58. Post OAT testing appearance of the KevlarÒ/EPDM control material (a, b), MMT-TPUNs (c, d), MWNT-TPUNs (e, f). Reprinted from [454] with
taining 12 phr fibers was chosen for the next step of the research in which the OLS were introduced in the heat shielding
material; this formulation displayed an elongation at break below to 50%. It resulted that even at this high fiber content,
the nanostructured counterpart of the KevlarÒ/EPDM exhibited an impressive increase of the maximum strain: as an exam-
ple, at 13 phr OLS the elongation to break displayed by the KevlarÒ/EPDM/OLS system showed a value equal to approxi-
mately 560%. However, at an OLS content equal to 7 phr, the elongation to break displayed its maximum (630%): above
this threshold, the elongation to break tended to decrease. The authors attributed the enhanced elongation at break to
the good dispersion of OLS in EPDM matrix; SEM scanning on the KevlarÒ/EPDM/OLS fracture surfaces evidenced that the
OLS platelets reduced the interfacial adhesion of the aramid fibers with matrix and the OLSs acted as a lubricating agent.
The authors concluded that at the higher filler content the reduction of the elongation at break could be attributed to the
aggregation of the silicate layers. In terms of ablation resistance, up to 11 phr OLS, with the increase of the nanoclay content,
the loss of mass as well as the erosion rate tended to decrease; above this threshold, the erosion rate and the loss of mass
slightly increased.
Koo et al. [443–453] investigated Thermoplastic Polyurethane elastomer Nanocomposites (TPUNs) as a potential alterna-
tive to the current state of art EHSMs for SRMs (aramid/EPDM). Thermoplastic polyurethane (TPU) is a class of elastomeric
polyurethane which consists of linear segmented block copolymers composed of hard and soft segments (density 1.1 g/
cm3) [453]. TPU is formed by the reaction of diisocyanates with short-chain diols (chain extenders) and diisocyanates with
long-chain diols. Unlike thermoset rubbers (such as EPDM), in TPUs there are no chemical cross-links; these physical cross-
links melt under heat and repack when the matrix is cooled down. As a result, the TPU based EHSMs do not require the use of
any peroxide (or sulfur) to vulcanize. The authors of this research were aimed at the possibility to directly injection mold net
shaped parts of an SRM liner; in such a way, an alternative to traditional processes could be envisioned. Moreover, an addi-
tional benefit of TPU based EHSMs could be related to the possibility to reprocess and reuse the scrap material. In the earlier
stages of this research, the effects of weight loadings of different nanoparticles (MMT, CNFs, and MWNTs) on the thermal and
flammability performance of this novel class of materials were explored using a variety of test methods, such as TGA, and
cone calorimeter [443–451]. The same team introduced new screening protocols testing the materials using more severe
hyperthermal environments created via OAT test [452,454].
In these studies, DesmopanÒ DP 6065A, (BayerÒ Material Science) a soft aromatic polyether-based TPU, was the baseline
elastomeric matrix. Three different nanofillers were tested – MMT (CloisiteÒ 30B), MWNTs (GraphistrengthÒ C100), and
CNFs (PyrografÒ PR-19-XT-LHT); the TPUNs were processed using twin screw extrusion and several weight loadings of nano-
material were used to make different nanocomposite formulations. The MMT and MWNT formulations ranged from 2.5 to
10 wt%, while the CNF formulations ranged from 5 to 20 wt%. Prior to any thermal testing, dispersion analysis via XRD
Fig. 59. SEM results of the charred materials (in-depth). MMT (a, b), MWNT (b, c), and CNF (d, e)-based TPUNs. Reprinted from [454] with permission from
Elsevier.
and TEM was done to investigate the dispersion and distribution of the different fillers. Fig. 57 reports the morphology of the
MMT- and MWNT-TPUNs evaluated via TEM. It appears that the extrusion process was able to unpack MWNT bundles and,
to lesser extent, to increase the interlayer spacing of the nanoclay, promoting an intercalate structure [367].
Ablation testing was performed using an OAT (heat flux 500 W/cm2) [57]: mass loss, recession, and char thickness val-
ues were measured in addition to in situ internal temperatures. An KevlarÒ/EPDM formulation was used as a control formu-
lation. Fig. 58 reports the post OAT testing appearance of the KevlarÒ/EPDM control material (a, b), MMT-TPUNs (c, d),
MWNT-TPUNs (e, f).
The results of the mass loss measurements for the TPUN formulations showed that for all three nanomaterials a similar
trend is observed with a decrease in mass loss up to a certain weight percent – about 8% for the MMT/MWNT-TPUNs (density
1.2 g/cm3) and about 18% for the CNF-TPUNs (density 1.2 g/cm3) – and then a slight increase beyond that value. Recession
rate results roughly followed the same trends of the mass loss and the best performing weight percent values match up to
those for minimal mass loss. Overall, none of the TPUN formulations outperformed the KevlarÒ/EPDM baseline; however, it
must be pointed out that for KevlarÒ/EPDM materials the amount of the fillers – the fibers, the micron, and nanosized addi-
tives like the mineral oxides and flame retardants – is higher than in the case of the produced nanocomposites. Conse-
quently, since the filler content of the KevlarÒ/EPDM is typically higher than the TPUNs produced in this research, these
results can be considered reasonably promising. When the nanomaterials are compared to one another, both MWNT- and
CNF-TPUNs have similar minimum recession values. However, MMT clay performs better than the other materials displaying
the minimum recession: this value was comparable to KevlarÒ/EPDM material. As highlighted by Vaia and co-workers [358],
these results would confirm the effectiveness of layered silicates as a fillers of NPAs. Fig. 58 evidences the main differences
among the charred surfaces of the traditional and nanostructured materials; the KevlarÒ/EPDM did not exhibit macro frac-
tures whilst the MMT-TPUNs and especially the MWNT-TPUNs showed a tendency to crack. The MMT-TPUNs surface
showed a limited number of fractures whilst the MWNT-TPUNs responded to the exposure to the OAT with a wide series
of fractured zones. This evidence indicated that the nanoclay platelets embedded in the material tended to sinter and to cre-
ate an hybrid carbonaceous/ceramic skin with relatively good mechanical properties [366]; on the other hand, the MWNTs
embedded in the TPU tended to promote higher heating rates and more violent degradation processes which produced deep
charring, cracking of the char, and spallation. However, it must also be remarked that the TPUNs tended to produce a worse
char as compared to the KevlarÒ/EPDM baseline due to lower amount of fillers in the formulation. In terms of insulation
capability, the MMT clay formulations showed the lowest peak temperature values, while the MWNT and CNF have mixed
results. Some notable formulations resulted to be the 5 wt% and 7.5 wt% weight loadings of MMT clay, which appeared to
match or even outperform the baseline KevlarÒ/EPDM material; as an example, at 5 mm from the exposed surface both
the 5 wt% MMT-TPUN and the KevlarÒ/EPDM baseline displayed a temperature close to 165 °C. It is reasonable to infer that
the MWNT and CNF formulations performed worse than MMT clay because these fillers manifested the tendency to increase
the thermal conductivity of polymer materials as compared to MMT clay.
According to SEM analysis (Fig. 59(a) and (b)) the char of the MMT clay TPUNs resulted to be composed of a microstruc-
ture of layered aligned platelets (ablative re-assembly) [366,388]. Empty pockets or bubbles within the char produced by the
gas formed during the degradation of the matrix were also formed; this mechanism caused the intumescent behavior
[402,403] observed in this char. The MWNT-TPUN char (Fig. 59(c) and (d)) appeared to have a relatively isotropic structure.
The MWNT char was clearly composed entangled MWNTs embedded in the carbonaceous residue of the matrix [432]. This
structure of entangled conductive nanotubes resulted in a much more thermally conductive char, which could contribute to
the poorer performance of the MWNT formulations overall. The CNF-TPUNs char (Fig. 59(e) and (f)) showed a relatively iso-
tropic structure, similar to MWNT-TPUN char. There also was evidence of pockets within the char, which could account for
the highly intumescent behavior of the CNF ablatives. The char resulted to be composed of a matrix of entangled CNFs; this
structure produced a thermally conductive char, resulting in poorer overall performance of the CNF-TPUNs. The larger
dimension of CNFs as compared to MWNTs tended to promote a deeper charring (lower insulation) and a wider foaming
of the material.
These results on nanostructured TPU based EHSMs for SRMs evidenced that this class of elastomeric NPAs have good
potential and some benefits in terms of processing as compared to state of the art aramid/EPDM. Future research on this class
of materials should certainly address the study of the effect of the introduction of heat resistant fibers [265] typically used in
EHSMs such as aramid or even more advanced candidates such as PBI [175,292], PI [277], or ZylonÒ [273,274] fibers would
work in synergy with the nanosized fillers and would promote a better char retention and lower cracking of the charred sub-
strate. Moreover, because of the higher specific weight of TPU (1.1 g/cm3) as compared to EPDM, the possibility to decrease
the density of TPUNs should be investigated. To this purpose, since TPU is processed in a melt state, the introduction of a
consistent fraction of density-tuner fillers (such as glass or phenolic micro-spheres) would be enabled. On the other hand,
the high viscosity of EPDM tends to limit the survived fraction (unbroken fraction of empty fillers) of these fillers during
the processing of the material. Other research should be aimed to verify the surface compatibility of TPUNs with modern
solid rocket propellants based on the use of HTPB as a binder.
10. Conclusions
During last 50 years the access to the space changed our lives in so many ways that it is very difficult to fully understand
the nature of this change: if we consider all the technological returns, new materials, patents, and breakthroughs related to
the space activity then it is practically impossible to draft a comprehensive list. The space sector is a very profitable market:
in ‘‘The Space Report 2015” recently released by The Space Foundation it was estimated that in 2014, the global space econ-
omy grew slightly more than 9%, reaching a total of $US 330 billion worldwide, up from 2013s $US 302.5 billion. Previous
reports indicated that the space economy grew to $US 290 billion in 2011 with an increase of 12% compared to 2010 and
of 41% compared to 2006. The US government space spending went up slightly (2.9% from 2013 to 2014). The US devoted
1.2% of the government’s national budget to space in 2014. During that year, US government space spending made up more
than half of what all governments around the world spent on space. Space expenditures by governments other than the US
grew 12.9% in 2014, in spite of decreases in budgets of international cooperative efforts such as the European Space Agency.
Moreover, nano- and micro-satellites (from 1 to 100 kg) also represent a huge opportunity for civilian (scientific or commer-
cial), and military activities which have been made economically feasible by micro-electronics and new materials. The nano-
and micro-satellite market is estimated to grow from $US 0.7 billions in 2014 to $US 1.9 billions in 2019.
However, the development and growth of the space activities and economy are closely related to the space access i.e. to
Thermal Protection System (TPS) materials; in fact, rocket launchers as well as the heat shields used to protect probes, and
space vehicles are enabled by this class of materials. There is no single part of the lifetime of a space system – from the
launch, to the orbiting, to the re-entry – which could be enabled in absence of a thermal protection solution. Polymer Abla-
tives (PAs) represented and still remain the most versatile class of TPS materials. The widespread availability of some tech-
nologies related to TPS materials also constituted a breeding ground for the appearance of many small companies which are
proposing new, cheap, small, launchers able to offer a superior responsiveness as compared to traditional vehicles, thus to
address the market request for the launch nano- and micro-satellites. These private players have also been exerting an essen-
tial role in terms of contribution to the science and technology of TPS materials; as an example, Space Exploration Technolo-
gies Corporation (SpaceX, US) developed PICA-X – a proprietary version of NASA’s Phenolic Impregnated Carbon Ablator
(PICA). Based on PICA-X, SpaceX developed the heat shield of its Dragon capsule which represents one of the solutions
funded by NASA through the Commercial Orbital Transportation Services (COTS) program to replace the Space Shuttle cargo
capabilities. PICA-X material and heat shield was designed, developed, and fully qualified by a small team of engineers and
technicians in less than four years. As compared with earlier NASA PICA formulations, PICA-X exhibits improved ablation
resistance, and is one order of magnitude cheaper to manufacture.
TPS material science evidenced how the introduction of nanotechnology enabled the identification of a brand new class of
PAs. If compared to traditional ablatives, the technology of Nanostructured Polymeric Ablatives (NPAs) can be considered at
its infancy; nonetheless, the use of nanotechnology is very promising. Beyond any future and exotic and development of this
class of materials, it is reasonable to envision that nanotechnology will influence the properties of state of the art ablative
TPS materials. As an example, the use of nanostructured polymeric matrices could boost the performance of Lightweight
Ceramic Ablators (LCAs) such as PICAs in terms of oxidation and ablation resistance and thus when exposed to moderate heat
fluxes (below 500 W/cm2); an hybrid ceramic/carbonaceous residue on the fibers of the PICA skeleton could promote the
formation of this anti-oxidation coating and reduce the in-depth, volume ablation processes. The researches reported in this
review contribution support this conclusion.
The use of nanosized fillers can also enable new approaches to exploit the properties of many materials at the base of TPS
formulations. As an example, in order to increase the oxidation resistance of ablative TPS materials such as Carbon/Carbon
Composites (CCCs), a ceramic coating based on ultra high temperature ceramics can be applied on the surface of CCCs. This
solution presents two main limitations: once the coating is ablatively removed, it vanishes to exert the protective function;
the ceramic coating can also tend to crack or debond from the substrate as a result of the different coefficients of thermal
expansion between the substrate and the coating. To overcome these limitations, in analogy to NPAs, the same anti-
oxidizing fillers used to produce these coatings but exploited in terms of nanoparticles dispersed in CCC carbonaceous matrix
could introduce an anti-oxidizing protection which would work in-bulk, as compared to a surface solution. However, as a
final remark on nanostructured TPS materials, even if the price of nanomaterials is quickly decreasing, a systematic study
must be done in the identification of the best processing techniques suitable for nanomodified TPS materials to improve their
reliability and decrease the manufacturing costs.
Acknowledgements
During the preparation of this review paper, a great help in terms of theoretical and experimental data as well as in terms
of practical contributions (as an example, as images used in the manuscript) was provided by a number of organizations,
companies, and people whom we would like to thank.
First of all, a special thank is due to NASA. The contribution of NASA in the field of ablative materials is priceless as most of
the breakthroughs on TPS materials were enabled by fifty years of researches sponsored by this agency. The huge amount of
data and papers freely available through the NASA Technical Reports Server (NTRS) and other channels, helped us to not only
prepare this contribution but also to integrate all the different information on TPS materials and introduce a deep and critical
reasoning: these NASA online free resources represented and still are a unique and extraordinary tool for young students and
for the entire scientific community involved in the study of TPS materials. Moreover, many pictures used in this chapter
directly come from NASA servers.
We wish to thank Northrop Grumman Aerospace Systems and Dr. Gordon Dressler for helping us to assemble all data
related to the Low Cost Pintle Engine (LCPE). We wish to express our gratitude to Heather A. Brennan of the American Insti-
tute of Aeronautics and Astronautics (AIAA) which helped us to establish a contact with Dr. Dressler. We want to thank Mr.
M. Rufer, Dr. N. Sarzi-Amade, Dr. J. Wertz and in general, Microcosm, Inc for their availability to share data and pictures with
us related to their family of ScorpiusÒ rocket engines. We thank the European Space Agency (ESA) for the images related to
the Vega launcher Solid Rocket Motor (SRM) assembly. A special thanks go to Dr. Heath Martin (NASA, MSFC) who helped us
to collect all essential info/images related to a unique test bed for SRM insulation materials recently developed by Penn State
University, NASA and Alliant Techsystems Inc. (ATK). Since, this facility represents the most valuable and comprehensive
screening protocol ever conceived for the testing of this class of ablative materials, we absolutely wanted to add its descrip-
tion in this review paper: Dr. Martin’s help was essential to accomplish this goal.
We want to thank Dr. J. Lachaud for his advices and sharing with us some figures related to Phenolic Impregnated Carbon
Ablators (PICAs). We are grateful to Dr. O. Chazot, Dr. D. Masutti, Dr. A. Turchi, and D. Helber at Von Karman Institute for
providing comments and images related to their PLASMATRON plasma jet facility. We also thank Dr. J. Koo (University of
Texas at Austin), Dr. E. Venkatapathy (NASA), Prof. Dryver Huston and Prof. Doug Fletcher (University of Vermont), Mr. J. Fon-
gheiser (Historic Space Systems), and Paul V. Galvin Library at Illinois Institute of Technology for sharing with us some
images thus enabling the preparation of this contribution. We are grateful to Prof. Ever Barbero (West Virginia University)
which helped us to prepare the first draft of this contribution using his LaTeX template and skills. We extend our sincere
gratitude to Dr. M. Rallini and Dr. D. Puglia (University of Perugia) who helped us to revise the final version of the manu-
script. We also thank Miss S. Natali (GL Tipografia) which helped us to enhance the quality of some images included in
the manuscript. Finally the authors wish to thank Dr. Giorgio Di Bernardo for his help to prepare the dedication of this work
to Luigi Broglio; by virtue of his special friendship with Broglio, he was the author of the most comprehensive biography on
this pioneer of the space age.
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Ablative Cooling Materials and Systems

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Progress in Materials Science 84 (2016) 192–275

Contents lists available at ScienceDirect

Progress in Materials Science

Science and technology of polymeric ablative materials for

MAT Multi-component Ablation Thermochemistry

1. Thermal Protection System (TPS) materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195

3.4.2. Fiber reinforced polymeric ablatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204

1. Thermal Protection System (TPS) materials

1.1. TPS materials: the hyperthermal environment

2. Non-ablative TPS materials

2.1. A remarkable example of NA-TPS: the Space Shuttle heat shield

2.2. Reusable surface insulation

2.3. Concluding remarks on the state of the art NA-TPS materials

3. Ablative TPS materials

3.1. Metals and ceramics as A-TPS materials

3.2. Graphite and carbon/carbon composites

3.3. Polymeric ablatives: generalities

3.4. Fiber reinforced composites as TPS

3.4.1. Polymeric matrices

3.4.2. Fiber reinforced polymeric ablatives

3.4.3. Role of the fiber in the ablation of FRPAs

3.4.4. Powdered fillers for FRPAs

3.4.5. Basic characterization of FRPAs

4. Advanced testing techniques for TPS materials

4.1. Thermal conditions

4.2. Chemical conditions

4.3. Mechanical parameters

4.4. An advanced test bed for SRM internal insulation materials

4.4.1. Real time X-ray radiography of tested materials

4.4.2. In-depth temperature measurements

4.4.3. Total heat flux gauges

4.5. Plasma facilities

4.5.1. Arc-jet torches

4.5.2. Electrodeless torches

5. Erosion rate sensing techniques for A-TPS materials

6. Polymeric ablatives as insulator materials

6.1. Rigid insulators

6.2. Elastomeric based insulators

6.2.1. Silicone based HSMs

6.3. Elastomeric HSMs for solid rocket motor liners

Polyimide – (PI) P84TM (Inspec 260 [265,277]

Phenolic (or novoloid) KynolÒ (Nippon 200 [265,282]

Melamine BasofilÒ (BASF) 200 [265,275]

Poly(p-phenylene terephtal- KevlarÒ 190 [248,261–

6.4. Toward a new industrial standard for SRM-EHSMs?

6.4.1. Ablative decomposition of CFEPDM

6.4.2. Ablative decomposition of PBINBR

6.4.3. Mechanism of char spallation of CFEPDM and PBINBR

6.4.4. Final results on the insulation capability of PBINBR

7. A new class of TPS ablatives: Lightweight Ceramic Ablators

7.1. Phenolic Impregnated Carbon Ablators

8. An introduction to modeling of ablation phenomena

8.1. Basic principles behind analytical models

8.2. Mechanical erosion

Name Contact Owner/Country Users Application

n.a. – not available.

8.4. State of the art of ablation simulation codes

9. Nanostructured ablative materials: introduction

9.1. Nanostructured ablative materials in a low intensity hyperthermal environment

9.2. Nanostructured PAs in a severe hyperthermal environment

9.2.1. PLSNs as NRAMs

9.3. Nanosilica as filler for traditional and nanostructured PAs