CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9

Available at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/carbon

Surface temperature jump beyond active oxidation

of carbon/silicon carbide composites in extreme
aerothermal conditions
a,* a,b
Francesco Panerai , Bernd Helber , Olivier Chazot a, Marianne Balat-Pichelin c

a
Aeronautics and Aerospace Department, von Karman Institute for Fluid Dynamics, Chaussée de Waterloo 72, 1640 Rhode-Saint-Genèse,
Belgium
b
Research Group Electrochemical and Surface Engineering, Vrjie Universiteit Brussel, Pleinlaan 2, B-1050 Elsene/Brussel, Belgium
c
PROMES-CNRS Laboratory, 7 Rue du four solaire, 66120 Font-Romeu Odeillo, France

A R T I C L E I N F O A B S T R A C T

Article history:
Received 11 November 2013
Accepted 13 January 2014
Available online 21 January 2014
The behavior of carbon/silicon carbide composites at very high temperatures is investi-
gated in an inductively-coupled plasma generator that simulates atmospheric re-entry
aerothermal conditions for space vehicles. Samples exposed to heat fluxes exceeding
1.2 MW/m2 and low pressures of 2000–6000 Pa show a spontaneous jump in surface tem-
perature near 2100 K, rapidly leading to temperatures above 2400 K. Under these conditions
the silicon carbide coating at the samples’ surface is entirely eroded and the bare carbon
fibers of the substrate are left exposed to the incoming flow. The material loses nearly half
of its mass and is no longer reusable. The temperature jump phenomenon is described by
means of infrared temperature measurements and real time visible recordings of the sur-
face. Space- and time-resolved optical emission spectroscopy and scanning electron
microscopy analysis of the samples are used to discuss and explain the chemical processes
occurring at the surface. Jump conditions are compared to the passive and active oxidation
regimes for carbon/silicon carbides, showing that such a sudden temperature increase
occurs at conditions beyond active oxidation and cannot be attributed to the passive/active
transition itself.
 2014 Elsevier Ltd. All rights reserved.

1. Introduction
The success of any spacecraft entering a planetary atmo-
sphere relies to a great extent on the Thermal Protection Sys-
tem (TPS), which is designed to shield crew and payload from
the severe aerothermal conditions during the hypersonic
flight. Heatshield materials developed for such purpose are
classified in two main categories: reusable and ablative [1].
The former are able to handle multiple entries at moderate
speeds (<7.5 km/s) and mild heat fluxes (<1.2 MW/m2). The
second can survive one single entry maneuver and are typi-
cally used for planetary entry and sample return missions
at speeds exceeding 8.5 km/s [2,3]. In this paper we focus on
carbon/silicon carbide composites or C/SiC that belong to
the first class. Their typical composition is based on a weaved
carbon preform, filled and coated with SiC, according to dif-
ferent manufacturing processes. The thermophysical proper-
ties of these materials and their interactions with the
surrounding plasma are of high scientific and technical inter-
ests, for both a correct sizing of the heatshield and an

* Corresponding author. Current address: Department of Mechanical Engineering, University of Kentucky, 151 Ralph G. Anderson
Building, Lexington, KY 40506, USA. Fax: +32 2 359 96 00.
E-mail address: panerai@vki.ac.be (F. Panerai).
0008-6223/$ - see front matter  2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2014.01.018
 CARBON 7 1 (2 0 1 4) 1 0 2–11 9
improvement of the materials performances. One of the main
contributions to the heat transferred to the wall comes from
the catalytic nature of the surface, which is the probability
of promoting recombination of dissociated species from the
incoming flow [4]. A non catalytic surface can halve the con-
vective heat flux with respect to a fully catalytic one. The
main mechanism of heat release, for passively-cooled Ther-
mal Protection Materials (TPM), is surface re-radiation, which
is proportional to the fourth power of the temperature, and
can be computed if the emissivity of the material is known
[5]. Oxidation phenomena are also of primary importance
for SiC-based surfaces exposed to high enthalpy, oxygen-rich
environments. It is well known that low surface temperatures
and high oxygen partial pressures promote the formation of a
glassy SiO2 layer over the surface [6]. This situation is often
referred to as passive oxidation and often corresponds to a
net mass increase. Higher temperatures and lower pressures
can lead, instead, to the volatilization of silicon oxide prod-
ucts into the gas phase, hence a net mass loss. This scenario,
referred to as active oxidation, can become a harmful condi-
tion for the integrity of the TPS. Ideally one desires a low cat-
alytic, high emissive and high oxidation resistant material to
be used as heatshield.
Several studies, both theoretical and experimental, have
been conducted on the identification of the transition bound-
ary between the passive and the active regimes for silicon car-
bide-based composites. Authors have studied different
atmospheres and different materials [7–24]. The dispersion
of proposed transitions is significant and a universal law is
difficult to provide. Differences are attributed to both experi-
mental factors and materials properties. Ruled by oxygen par-
tial pressure and temperature, the transition is affected by the
gas mixture (pure oxygen, O2/Ar, O2/He, O2/N2, dry air, atmo-
spheric air), that determines the oxygen potential, by the de-
gree of dissociation, the reactants transport, and the Knudsen
regime (equivalent to the effect of the total pressure). Related
to the material, key factors are microscopic characteristics
like the crystalline structure (a-SiC or b-SiC) and macroscopic
properties like surface roughness or emissivity. Therefore, a
dedicated characterization in a relevant environment is
needed for a specific TPM and a specific flight trajectory.
The demand of higher velocities and higher heat fluxes is
pushing reusable TPS materials to the edge of their opera-
tional limits. Speed entries to Earth above 7.5 km/s develop
enthalpies above 28 MJ/kg and peak heating conditions that
could bring SiC based surfaces far into the active oxidation re-
gime and prevent their reusability. The Intermediate eXperi-
mental Vehicle (IXV), a lifting re-entry spacecraft developed
by the European Space Agency [25], is designed to fly a C/
SiC TPS covered by a b-SiC coating in such demanding condi-
tions. The testing of its heatshield materials is an ideal frame
to investigate the behavior of this class of materials under a
strong oxidizing environment. The catalytic and radiative
behavior of the IXV materials were studied in [26], during
induction plasma experiments in a representative atmo-
sphere for the vehicle trajectory. A study on the passive/active
transition of C/SiC materials similar to those of the IXV was
proposed in [13].
The present work focuses on the active oxidation regime
and studies the behavior of C/SiC composites close to their
103
reusability limit. Studies on the oxidation transition of sili-
con carbide-based materials, conducted in high enthalpy
plasma facilities, led many authors to observe spontaneous
jumps in surface temperature, of the order of hundreds of
Kelvin, during exposure of the samples to high heat flux,
low pressure, dissociated flows. The phenomenon was firstly
observed during arc-jet experiments of C/SiC samples at
temperatures up to 2120 K [27]. Hald discussed temperature
jumps on similar Ceramic Matrix Composited (CMC) materi-
als and suggested an explanation based on exothermic cata-
lytic reactions of gaseous silicon with atomic nitrogen,
which would raise the temperature of the boundary layer
and hence the convective component of heating to the sur-
face [28]. The phenomenon was observed by Herdrich et al.
[19] and Laux et al. [18] both in inductively heated and arc-
jet facilities, during testing of sintered and CVD b-SiC coated
C/C. Herdrich used increased N-atom recombination on SiC
versus SiO2 to explain part of the increased heat flux to
the surface under temperature jumps, observed during plas-
ma testing of passive/active oxidation transition. Silicon
emissions, detected by optical emission spectroscopy, were
used to distinguish between passively and actively oxidized
samples. Investigations were performed in the VKI Plasma-
tron facility [29] on CVD b-SiC specimens at surface temper-
atures of 2000–2800 K and various pressures. Sudden
temperature jumps for constant freestream conditions were
observed, corresponding to high mass loss and strong in-
crease in silicon volatilization, detected by optical emission
spectroscopy near the surface. The phenomenon was also
observed during testing of Ultra-High Temperature Ceramics
(UHTC), containing SiC. Gasch et al. documented arc-jet tests
of HfB2–20%SiC samples at high surface temperatures,
observing a slow and constant surface temperature increase,
of 300–400 K, starting near 2100 K, about 400 s after the
beginning of the plasma exposure [30]. This behavior was
attributed to the presence of a thick porous hafnium oxide
layer, changing surface catalycity, emissivity and conductiv-
ity of the material. Recent Plasmatron experiments were per-
formed by Marschall et al. [31] on zirconium diboride-based
UHTC materials. Above a certain heat flux, samples reached
temperatures near 2200 K (at 10,000 Pa) at which their sur-
face oxide scale was no longer protective or stable and
underwent temperature jump. Based on computational anal-
ysis, the authors attributed the temperature jump to a tran-
sition in surface chemistry involving the silica-rich oxide
scale and the silica former SiC.
This paper focuses on the temperature jump phenomenon
observed on the IXV C/SiC materials. High heat flux experi-
ments are conducted in the Plasmatron facility at von Kar-
man Institute for Fluid Dynamic. Samples are tested at
pressures between 2000 and 6000 Pa and temperature above
1900 K. The practical challenges arising when performing
temperature jump experiments are discussed. The jump phe-
nomenon is illustrated by means of infrared pyrometry mea-
surements and real-time visible emission recording of the
samples’ surface. A discussion on the phenomenon is pro-
vided, based on Scanning Electron Microscopy (SEM) analysis,
spatially- and temporally-resolved optical emission spectros-
copy and comparison with passive and active oxidation
regimes.
104 CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9
2. Experimental
2.1. Test setup
The present research is carried out at the 1.2 MW Plasmatron
facility at VKI. It is a high enthalpy, subsonic wind tunnel that
generates plasma by electromagnetic induction, at sub-atmo-
spheric pressure [32–35]. The Plasmatron allows the simula-
tion in ground of the chemically reacting boundary layer
around a reentry body [36,37]. Its long test time (up to hours
uninterruptedly) and high purity flow make it an ideal setup
for material thermochemistry testing and studies of gas/sur-
face interactions. A schematic of the system and instrumen-
tation is shown in Fig. 1. Displacement mechanisms,
mounted on a 1.4 m diameter, water-cooled test chamber, al-
low moving the test models into or out of the flow. Optical
accesses equip the system for non-invasive measurements.
A 50 mm diameter copper water-cooled probe, mounting a
copper calorimeter in the center of the front face, is used for
the calibration of plasma flow conditions. The cold wall
(350 K) stagnation point heat flux is determined by the cool-
ing water mass flow rate, controlled by a calibrated rotameter,
and the inlet/outlet temperature difference, measured by two
calibrated type E thermocouples. The calorimeter is inserted
in the probe, wrapped by a Teflon insulator that prevents
heat conduction exchanges with inner walls of its lodging.
Both the probe and calorimeter have copper surfaces, which
are highly catalytic to nitrogen and oxygen atoms recombina-
tion. The heat flux can be measured with ±10% accuracy.
A water-cooled Pitot probe is used to perform stagnation
pressure measurements. The pressure line is connected to a
Validyne variable reluctance pressure transducer and the out-
put is amplified by a voltage demodulator. Validyne and
amplifier are calibrated prior to the test by means of a Betz
Fig. 1 – Schematic of the Plasmatron setup. (A color version of this figure can be viewed online.)
water manometer, leading to an uncertainty of ±7%. The Plas-
matron chamber is also equipped with an absolute pressure
transducer that measures the static pressure. This is con-
trolled with ±1% accuracy.
A MR1SC Marathon Series pyrometer, operating at 1300–
3200 K, records the front surface temperature of the sample.
It measures over two overlapping, narrow wavebands around
1 lm, at 1 Hz frequency. The two-color scheme provides an
output value independent on emissivity, if the observed sur-
face satisfies the graybody assumption over the operating
range. This condition is typically valid for ceramic materials,
as those investigated in the present research. The pyrometer
points to the stagnation area of the sample through a 1 cm
thick quartz window. The calibration is performed by means
of a blackbody reference source, with the window in place,
allowing a maximum calibration value of 1800 K. The linear
behavior within the calibration range is extrapolated to high-
er temperatures. The overall uncertainty of those measure-
ments is estimated to be ±1%.
Real-time visual recordings of the samples’ surface are ac-
quired with a high-definition (HD) digital dual camera
(VPCGH1, Sanyo Europe, Ltd.). The camera has a 1920 · 1080
C-MOS sensor and a double-range focal lens. The frame rate
for the recording is set to 30 fps.
Measurements of erosion products from the material’s
surface are performed by means of temporally- and spa-
tially-resolved optical emission spectroscopy in front of the
test model. Volatilization of SiO during active oxidation tests
of SiC-containing samples is expected to occur according to
the reaction mechanism SiC(s) + 2O ! SiO + CO. We take into
account only the formation of CO instead of CO2 as the reac-
tion occurs at high temperature where the CO formation is fa-
vored. Excited Si atoms, likely to be formed as SiO is
transported to the high temperature boundary layer, radiate
 CARBON 7 1 (2 0 1 4) 1 0 2–11 9
strongly in the UV-range and can be detected using available
Ocean Optics HR4000 spectrometers. The optical diagnostic
bench consists of a light collection system, optical fibers
and the three spectrometers covering a spectral range of
200–1100 nm. The light emitted by the plasma is collected
through a variable aperture and focused by a plano-convex,
uncoated, fused silica lens (LA4745, 750 mm focal length) via
two mirrors, to the entry of three optical fibers (Ocean Optics
QP600–2-SR/BX, 600 ± 10 lm core diameter). A numerical
aperture of 0.22 ± 0.02 is optimized to match the 5 lm wide
entrance slit of the spectrometers. The slit and a
300 grooves/mm grating lead to a typical resolution of approx-
imately 0.65 nm (Full Width Half Maximum (FWHM)), as
determined by a low pressure Oriel 6060 Hg lamp. The spec-
trometers are set to an acquisition frequency of 0.75 Hz,
allowing the acquisition of multiple time-resolved spectra
during one test run. The integration time was set to 100 ms
for all tests (comparable to the shutter of a camera). The ac-
quired spectra are averaged during this acquisition period.
The optical path is aligned perpendicular to the flow and tan-
gential to the test sample surface. The bench is mounted on a
movable holding system, enabling horizontal movements to
place the line of sight at the desired position. The positioning
is adjusted before each experiment using a laser beam sent
through the optics and located ahead of the stagnation point
of the sample. The spectrometers’ lines of sight are fixed at
the desired distance from the sample front face respectively,
and not moved during the whole experiment. A magnification
of 1.5 is used, resulting in a distance between each probing
volume of Dd = 3.5 mm, the respective distances from the sur-
face (y = 0) being y1 = 2 mm, y2 = 5.5 mm, y3 = 9 mm. Calibra-
tion of the whole system in relative intensity is performed
using a deuterium lamp in the UV range (<400 nm) and a
tungsten ribbon lamp (OSRAM WI 17G) in the visible range
(>400 nm), to obtain comparable intensities to those during
the tests.
Two sample holders, equipped with adequate water-cool-
ing, are used to install the TPS samples in the setup. The
Fig. 2 – Stagnation point test models with sample holder and sustaining water-cooled arm. (a) Standard model and (b)
mushroom model. (A color version of this figure can be viewed online.)
105
probes are mounted inside the Plasmatron test chamber
at 0.445 m from the ICP torch exit. The placement ensures
that the axis of the probe and the axis of the torch itself
coincide. The test configurations are shown in Fig. 2. The
first is a standard 50 mm diameter model, mounting a
30 mm diameter, 60 bevel disk sample. The samples are
kept in place by a sintered SiC or graphite cover. The sec-
ond is a 30 mm diameter probe holding mushroom shaped
models. These are mounted by interference-fitting their
stem into the graphite holder. The geometry of the samples
from Herakles, France (HER) and MT Aerospace, Germany
(MTA) is detailed in Fig. 3.
Microscale morphology analysis of post-test samples is
performed using SEM (Hitachi S-4500). High resolution pic-
tures are acquired using a commercial SLR camera. The mass
of the samples is measured with a high precision scale
(±0.01 mg accuracy), prior to and after plasma exposure.
2.2. Materials
The ceramic matrix composites analyzed in this research are
those mounted on the IXV thermal protection systems, pro-
vided by Herakles (Safran Group, Le Haillan, France) and MT
Aerospace (Augsburg, Germany). Herakles material (SEPCAR-
BINOX L6) manufacturing [38] starts from a carbon fiber pre-
form, based on a multi-layer woven architecture. The
preform is constructed from a lay-up of pre-preg that is cured
in a mold, and densified with consecutive depositions of sili-
con carbide by Chemical Vapor Infiltration (CVI) [39]. The last
CVI cycle allows at the same time to achieve the requested
density, and to ensure a full coating of the composite surface
by a b-SiC layer of 80 lm thickness.
The MT Aerospace samples are produced using a near net
shaped layup technique via Polymer Vapor Infiltration (PVI). A
pre-impregnated carbon fiber structure (7 lm filament diame-
ter) is cured before undergoing pyrolysis, which turns the
polymer into an amorphous carbon phase. The pyrolized car-
bon-fiber-reinforced polymer is then coated with b-SiC by a
106 CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9
Fig. 3 – Geometry of the test articles. (a) Standard model and
(b) mushroom model. Dimensions in mm. Drawings are not
in scale. The thickness of model (a) samples is 2 mm for HER
material and 3 mm for MTA material.
Chemical Vapor Deposition (CVD) process. The SiC coating
has an average thickness between 60 and 80 lm [5].
Herakles and MTA materials are denoted as HER and MTA
in the following sections.
2.3. Test protocol
The Plasmatron tests are performed under standard air plas-
ma (79% N2 and 21% O2) at a mass flow of 16 g/s. Flow condi-
tions are initially calibrated according to the real-time reading
provided by the calorimetric and pressure probes. Those are
alternatively swung into the plasma stream and the torch
power is progressively adjusted to obtain the desired values.
The chamber static pressure is adjusted by air by-pass and
vacuum pumps regulation. After the establishment of a stea-
dy-state flow, the calibration probes are maintained into the
plasma stream for a total exposure time of 100–200 s to en-
sure the stability of the test conditions. Following the calibra-
tion phase the sample is injected into the flow and, after
steady-state temperature is achieved, constant conditions
are maintained for a total steady-state time of 600 s. For some
tests, this is shortened in order to avoid damages to the setup
or to prevent the complete destruction of the test article.
3. Results
Experiments are performed at static pressures of 2000, 5000
and 6000 Pa. The test conditions are summarized in Tables 1
and 2, respectively for the standard and mushroom test mod-
els. The cases highlighted in bold show the jump phenome-
non (J). For the experiments with the standard model, two
tests are reported as comparison, respectively under passive
(P) oxidation and active (A) oxidation regimes. For the set of
experiments on the HER material at 6000 Pa, the jump regime
could not be achieved due to the challenges of the facility
operating conditions. Only tests under active (A) oxidation
are available for comparison with the mushroom model.
The distinction between the passively and actively oxidized
samples is preliminary based on the measured mass loss
due to plasma exposure and later confirmed by SEM imaging,
being the presence of a passive and continuous SiO2 layer at
the surface used as discriminant. This technique is well con-
solidated from existing literature [13,17]. A steady state expo-
sure time of 600 s is imposed to actively and passively
oxidized samples. Test MTA 9 is run for 400 s and earlier inter-
rupted due to an excessive heating of the test model, causing
a sudden shut-down of the plasma flow. For the temperature
jump experiments, the duration is determined according to
the performance of the sample holder during the test, the test
being interrupted according to the experimenter’s best judg-
ment to prevent the model failure.
3.1. Description of the temperature jump phenomenon
Fig. 4 shows the temperature measured during the cases that
present the temperature jump phenomenon. For both materi-
als, the temperature history measured during a jump test is
compared with that in passive and active regime, at the same
static pressure (Fig. 5, tests of HER samples at 2000 Pa and test
of MTA samples at 5000 Pa).
Test HER 17 represents a well-suited case to illustrate the
evolution of the surface. A sintered SiC cover is used to hold
the sample. The insertion of the test model into the flow at
1.3 MW/m2 heat flux leads to a natural rise of the surface tem-
perature, stabilizing to a plateau of 2095 K after approxi-
mately 40 s. Differently from tests in passive and active
oxidation, where a steady state is reached and maintained
constant throughout the test, a temperature plateau is mea-
sured only until 120 s, when a sudden jump of 400 K leads
to a surface temperature near 2500 K. Power, pressure, and
mass flow (i.e. total enthalpy and total pressure) are main-
tained constant throughout the test, hence the phenomenon
results as spontaneous process at constant freestream
conditions.
A visual observation of the sample’s surface during the
tests shows a large increase in the light emitted from the test
article. Frame images extracted from HD video recording at
3 s time intervals are shown in Fig. 6 and compared with a de-
tail of the temperature history near the jump. The camera
operating mode automatically adjusts the exposure to the
variation of light intensity, therefore the changes of bright-
ness between different frames cannot be directly correlated
to the temperature. Nevertheless, the images clearly show
the progression of the phenomenon over the sample surface,
and the brightness pattern within one single image gives a
good representation of the temperature gradient over the sur-
face. A bright spot appears at the bottom left edge of the sam-
ple at 106 s. It progresses as a high emission front expanding
at the edges of the sample and reaches the center of the sur-
face. After about 30 s the surface is entirely covered and no
brightness gradients can be observed. The rate of progression
of the bright front is calculated to be 0.9 mm/s. One should
note that the phenomenon can be observed along the temper-
ature history only 12 s after it actually starts (s = 118 s), that is
 CARBON 7 1 (2 0 1 4) 1 0 2–11 9 107

Table 1 – Test conditions for the standard model experiments: electric power Pel, sample wall temperature, Tw , cold-wall heat
flux qcw , static pressure ps , dynamic pressure pd , and time of exposure to plasma sexposure . ‘‘P’’, ‘‘A’’, and ‘‘J’’ indicate tests in
passive, active, and temperature jump regime respectively.
Sample/Test Pel [kW] Tw [K] Tw;postjump [K] qcw [kW/m2] ps [Pa] pd [Pa] sexposure a [s] Holder Regime

HER 26 264 1917 – 1021 2000 154 600 SiC P

HER 14 310 2065 – 1215 2000 178 600 SiC A
HER 17 322 2115b 2512 1304 2000 189 206 (tot) SiC A!J
HER 15 270 1942 – 1194 5000 74 600 SiC P
HER 20 331 2090 – 1417 5000 86 600 SiC A
HER 23 384 2141c 2734 1587 5000 95 131 (tot) Graphite J
HER 16 299 1967 – 1345 6000 69 600 SiC P
HER 29 328 2063 – 1499 6000 76 600 SiC A
MTA 1 260 1870 – 963 2000 146 600 SiC P
MTA 2 304 2014 – 1196 2000 176 600 SiC A
MTA 11 340 2066c 2589 1237 2000 181 121 (tot) Graphite J
MTA 5 291 1956 – 1398 5000 85 600 SiC P
MTA 6 348 2119 – 1575 5000 94 600 SiC A
MTA 12 283 2064c 2542 1403 5000 85 130 (tot) Graphite J
MTA 7 326 1981 – 1399 6000 71 600 SiC P
MTA 9 362 2105 – 1497 6000 76 400 SiC A
MTA 13 320 2122c 2593 1394 6000 71 121 (tot) Graphite J
a
Exposure time is the total time at steady state for tests in active and passive regimes, while the total time into the flow for the jump samples.
b
Jump temperature, Tw;jump . Tw = 2095 K steady state before jump.
c
Jump temperature, Tw;jump .

Table 2 – Test conditions for the mushroom model experiments: electric power Pel, sample wall temperature, Tw , cold-wall
heat flux qcw , static pressure ps , dynamic pressure pd , and time of exposure to plasma sexposure . ‘‘P’’, ‘‘A’’, and ‘‘J’’ indicate tests in
passive, active, and temperature jump (in bold) regime respectively. A graphite holder is used for all the experiments.
Sample/Test Pel [kW] Tw [K] Tw;postjump [K] qcw a [kW/m2] ps [Pa] pd [Pa] sexposure b [s] Regime

HER M37 234 1920 – 900 2000 257 124 A

HER M32 200 2083c 2470 1200 2000 343 132 J
HER M36 254 2101c 2465 1100 2000 314 181 A!J
HER M35 246 2093c – 100 2000 290 184 A ! J (interrupted)
MTA M21 225 1905 – 900 2000 219 120 A
MTA M22 229 2073 2475 1000–1200 2000 304 153 A!J
a
Rounded reference values with the standard heat flux probe.
b
Total time into the flow.
c
Jump temperature, Tw;jump .

Fig. 4 – Temperature jump time-histories during standard model testing. (a) HER material and (b) MTA material. (A color
version of this figure can be viewed online.)
108 CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9

Fig. 5 – Comparison of temperature time-histories measurements during temperature jump tests (J), with those recorded
during passive (P) and active (A) regime experiments at the same pressure. (a) HER samples at 2000 Pa static pressure and (b)
MTA samples at 5000 Pa. (A color version of this figure can be viewed online.)

Fig. 6 – Details of the temperature jump phenomenon observed during test HER 17. The temperature plot is an enlargement of
Fig. 4(a) around the jump region. The images are frames extracted from the HD video recording, each 3 s starting at the onset
of the jump phenomenon. The total duration of the process is 27 s. (A color version of this figure can be viewed online.)

when the bright front reaches the edge of the two-color
pyrometer field of view. This is a nearly circular 12 mm diam-
eter spot, centered over the samples surface.
During other attempts performed to obtain a similar
phenomenology to that observed in the test HER17, the
SiC holder experiences a sudden failure when running at
very high heat fluxes, as temperature jump conditions for
C/SiC are beyond the heating load that sintered SiC can
support. Therefore, graphite sample holders are adopted
in place of SiC holders for experiments at different pressure
conditions. Graphite offers better performances when ex-
posed to sharp heating rates, nonetheless it has the incon-
venience of rapidly recessing due to ablation when exposed
to plasma. Erosion is likely to occur at the graphite edges
surrounding the C/SiC samples, resulting in highly reactive
hot zone transferring side-heating to the test samples,
which sums to the incoming heat flux from the dissociated
flow. Consequently, as it can be observed in Fig. 4, for sam-
ple HER 23 and samples MTA 11–13, the initial temperature
rise is significantly accelerated, for similar heating levels to
that used with sample HER 17. As a result, steady state
temperature prior to the jump cannot be achieved and the
phenomenon is observed during the transient heating of
the samples.
Details of visual recording for sample MTA 12 are shown in
Fig. 7. Differently from test HER 17, the graphite is a brighter
emitter than both SiC and C/SiC, such that the exposure
auto-adjustment shows the inner sample as a darker surface
prior to the onset of the temperature jump phenomenon. The
progress of the bright front over the surface is then analogous
to what is observed before, but faster (18 s). A front propaga-
tion rate of 1.5 mm/s can be estimated in this case.
 CARBON 7 1 (2 0 1 4) 1 0 2–11 9 109

Fig. 7 – Details of the temperature jump phenomenon observed during test MTA 12. The temperature plot is an enlargement
of Fig. 4(b) around the jump region. The images are frames extracted from the HD video recording, each 2 s starting at the
onset of the jump phenomenon. The total duration of the process is 18 s. (A color version of this figure can be viewed online.)

For experiments with the standard model using a graphite

holder, like those described (HER 23, MTA 11–13), the identifi-
cation of the jump temperature is particularly involved be-
cause the temperature increases very quickly compared to
the acquisition frequency of the pyrometer. The used crite-
rion to place the jump temperature is based on synchronizing
camera and pyrometer recordings, observe the progression of
the surface erosion front from the video and assume as Tw;jump
the closest temperature value when the front reaches the
pyrometer field of view. For some experiments (for example
sample MTA 11 at 11 s in Fig. 4(b)), changes in Tw are ob-
served, not to be confused with the temperature jump phe-
Fig. 8 – Comparison between temperature jumps during
nomenon. Those are just temperature fluctuations that
testing of HER and MTA mushroom models. (A color version
could be reasonably related to fluctuations of the plasma
of this figure can be viewed online.)
jet. The jump phenomenon in this paper is reported and iden-
tified in correspondence of a transition on the characteristics
of the surface of the materials.
Experiments conducted with the mushroom model pre-
vent problems arising with the ablation of graphite. The HER and MTA materials which show identical performance
backing holder is protected by the sample itself, allowing at similar freestream conditions. The green curves show
for longer life-times. Therefore, this appears to be a conve- experiments at 0.9 MW/m2, providing active oxidation condi-
nient solution for temperature jump testing. A minor draw- tions for the material. During the test of MTA M22 the flux
back is represented by the holding mushroom stem. The was increased from 1.1 to 1.2 MW/m2 at around 50 s after
heat exchanged by conduction with the holder graphite the injection. As a result, the MTA M22 sample initially fol-
produces a heat sink effect leading to longer heating times lows the behavior of the HER M36 sample (tested at
toward steady state conditions. This can be clearly noticed 1.1 MW/m2), the temperature jump is anticipated after the
in the temperature histories of mushroom experiments, increase and the final temperature is similar to that of the
shown in Fig. 8. Steady state conditions are reached at test sample HER M32 (tested at 1.2 MW/m2).
times greater than 100 s, compared to 40 s in the case of
back insulated samples. Current state-of-the-art simulation 3.2. Temperature jump and passive/active oxidation
tools are not able to predict the response of C/SiC samples,
coupled with the incoming plasma flow, therefore the To further analyze the temperature jump, it is interesting to
conductive heating dispersed thorough the stem is difficult compare the phenomenon to passive and active oxidation re-
to quantify. Its determination shall be subject of future gimes. Oxygen partial pressures are reported in Tables 3 and
investigation. Fig. 8 allows a direct comparison between 4, together with temperature data and mass loss. The mass
110 CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9

Table 3 – Oxidation and mass loss data for the standard model tests. ‘‘P’’, ‘‘A’’, and ‘‘J’’ indicate tests in passive, active, and
temperature jump (in bold) regimes respectively.

Sample Tw [K] poxygen [Pa] mpreplasma [g] mpostplasma [g] Dm=m [%] Regime

HER 26 1917 452 2.0281 2.0116 0.8136 P

HER 14 2065 457 2.0847 1.8430 11.5940 A
HER 17 2512a 460 2.0386 1.1751 42.3575 A!J
HER 15 1942 1066 2.0701 2.0644 0.2753 P
HER 20 2090 1068 2.0242 1.9139 5.4491 A
HER 23 2734a 1070 2.0466 0.9123 55.4236 J
HER 16 1967 1274 2.0375 2.0287 0.4319 P
HER 29 2063 1276 1.9560 1.9016 2.7812 A
MTA 1 1870 451 3.6229 3.6028 0.5548 P
MTA 2 2014 457 3.7108 3.5471 4.4114 A
MTA 11 2589a 458 3.5128 2.4481 30.3092 J
MTA 5 1956 1068 3.7010 3.6897 0.3053 P
MTA 6 2119 1070 3.7102 3.5547 4.1911 A
MTA 12 2542a 1068 3.5008 2.4330 30.5016 J
MTA 7 1981 1275 3.6450 3.6476 0.0713 P
MTA 9 2105 1276 3.7660 3.7446 0.5682 A
MTA 13 2593a 1275 3.7005 2.6605 28.1043 J
a
Post-jump temperature.

Table 4 – Oxidation and mass loss data for the mushroom model tests. ‘‘P’’, ‘‘A’’, and ‘‘J’’ indicate tests in passive, active, and
temperature jump (in bold) regimes respectively.
Sample Tw [K] poxygen [Pa] mpreplasma [g] mpostplasma [g] Dm=m [%] Regime

HER M37 1920 474 2.6610 2.6479 0.4923 A

HER M32 2470a 492 2.6853 2.2217 17.2644 J
HER M36 2465a 486 2.6802 2.0490 23.5505 A!J
HER M35 2105a 481 2.6830 2.4470 8.7961 A ! J (interrupted)
MTA M21 1905 466 3.4127 3.3949 0.5216 A
MTA M22 2475a 484 3.4885 2.6145 25.0537 A!J
a
Post-jump temperature.

Fig. 9 – Comparison between the passive/active oxidation transition and the temperature jump regime during tests of
standard model samples. The solid line is the passive/active transition law from Balat [13], determined for the same HER
material tested in the present campaign. Labels on the data points correspond to the sample number (see Table 1). (a) HER
material and (b) MTA material. (A color version of this figure can be viewed online.)

loss is measured by weighing the sample before and after the Fig. 9 compares the three regimes for both HER and MTA
tests and is expressed as percent variation with respect to the standard samples, in a classical oxygen partial pressure versus
initial mass. reciprocal temperature plot for the passive/active oxidation
 CARBON 7 1 (2 0 1 4) 1 0 2–11 9 111

transition. The boundary between active and passive regimes,

represented by a solid black line, is taken from [13], where oxi-
dation experiments were performed on a similar HER material
analyzed in the present work. The microscopic analysis of the
surface is used as criterion to determine the transition. Sam-
Fig. 11 – Post-tests photograph of a HER virgin sample (left)
ples showing a thin and uniform SiO2 scale are classified as un-
and sample subjected to temperature jump (right),
der passive oxidation. Sample where the silica is significantly
highlighting the thickness reduction due to erosion of the
deteriorated, and holes and damages appear on the SiC coating
coating under extreme heat flux. (A color version of this
are instead considered in active regime. Plasmatron data show
figure can be viewed online.)
a good agreement with the published law. For the temperature
jump experiments, both jump and post-jump temperatures are
shown. Since the phenomenon is relatively fast compared to
Fig. 12. Micro-cracks are present on the pristine b-SiC layer.
the acquisition frequency of the pyrometer, it is difficult to
Microscopic analyses of the materials’ cross section show
accurately place the jump temperature, therefore large error
that the cracks can extend through the whole coating thick-
bars are computed. It is clear from the figure that jump condi-
ness, nevertheless their width never exceeds 5 lm
tions reside in the active regime. Overall, jump temperatures
(Figs. 12(a) and 13(a)). The morphology of the cracks and the
are higher than active oxidation temperatures, therefore the
coating itself are not seen to be affected by exposure to pas-
jump cannot be considered discriminant between passive
sive oxidation conditions (Figs. 12(b) and 13(b)). Within the
and active regime, i.e. jump temperatures are not transition
investigated pressure range, passive oxidation occurs at sur-
temperatures. Similarly, mass loss values are 30–55% for the
face temperatures below 2000 K. Under passive oxidation
jump cases, while below 10% for active oxidation conditions.
condition, a uniform silica scale is formed constituting a pro-
Values below 1% are measured for passively oxidized samples.
tective barrier for the surface from the incoming reactants.
Visual inspection of the samples in Fig. 10 reveals a signif-
After the passive/active oxidation transition, increasing
icant erosion of the surface exposed to plasma, subjected to a
temperatures promote the decomposition and volatilization
temperature jump. Compared to the virgin material, passively
of SiO2 into SiO and Si. High evaporation rates would eventu-
oxidized samples present a brownish yellowish surface, typi-
ally lead to its depletion, hence to the onset of active oxida-
cal of silica scales of different thicknesses. Samples in active
tion conditions, where the b-SiC coating is progressively
oxidation have a light grey color typical of SiC, where numer-
consumed by oxygen reactants. This condition is revealed
ous defects, pores or degradation regions start to appear.
by Figs. 12(c) and 13(c) where, despite some traces of SiO2
Sample subjected to the temperature jump present a dark/
are still present, several damages and holes in the SiC layer
grey surface with shining net structure, revealing a complete
are observed.
removal of the superficial SiC layer and nude carbon fibers at
During the temperature jump experiments, the samples
the surface. The thickness of the sample is significantly re-
are injected into the flow at very high enthalpies and a very
duced (HER 23 and MTA 12) (see Fig. 11).
steep temperature rise is experienced upon insertion. The
3.3. Microscale morphology and surface chemistry surface temperature reaches values above 2000 K in less than
30–40 s. The progression of silica formation/evaporation inter-
The information obtained by visual imaging of the surface is ests only the first 20 s and represents therefore a minor con-
confirmed at microscopic scale by SEM analysis, shown in tribution to the chemical history of the surface, while active

Fig. 10 – Virgin and post-test pictures of samples tested at 5000 Pa under different regimes. Top row: HER material and bottom
row: MTA material. (A color version of this figure can be viewed online.)
112 CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9

Fig. 12 – Micrographs of HER samples at 5000 Pa under different regimes.

Fig. 13 – Micrographs of MTA samples at 5000 Pa under different regimes.

oxidation starts soon after the injection into the flow. Under
this condition, the silicon carbide reacts with oxygen atoms,
producing mainly SiO and CO. The higher the incoming flux
the higher the rate of consumption of the b-SiC layer. Ther-
modynamic calculations (Fig. 14) show that, if temperatures
exceed 2100 K (jump temperature), sublimation of SiC into
Si and in lesser extent into Si2C largely contributes to the
chemistry of the surface. Further exothermicity might be pro-
moted by N radicals that are present in large quantities in the
mixture, and by cracks enlarged by active oxidation, that
 CARBON 7 1 (2 0 1 4) 1 0 2–11 9
Fig. 14 – Equilibrium thermodynamic calculations at 2000 Pa
for a mixture of 10 mol SiC, 8 mol of N2, and 2 mol of O2,
obtained using the GEMINI software. Similar behavior can
be calculated at 5000 Pa. (A color version of this figure can be
viewed online.)
allow O atoms to diffuse and react with the substrate (carbon
fibers and SiC matrix). As a result the volatilization rate of SiC
turns into a self-augmenting process, leading to a rapid tem-
perature rise and to the fast erosion of the material.
Following the complete depletion of SiC (post-jump condi-
tions), the bare carbon fibers of the substrate are left exposed
to incoming reactants, as revealed by micrographs in
Figs. 12(d) and 13(d). The fibers present the characteristic
pointed morphology observed in several studies on oxidized
carbon [40,41]. Dominant reactions, under this condition,
are exothermic carbon oxidation C(s) + O ! CO and nitridation
C(s) + N ! CN. Active oxidation processes continue at the
interstices between the fibers, occupied by the SiC matrix fil-
ler used to densify the carbon preform.
It is also remarked that the jump process starts at the
edges of the probe, where indeed the heat flux is higher due
to the turning of the streamlines and the thinning of the
boundary layer [42], and where the SiC coating is thinner,
hence more quickly consumed.
Similar features observed for the disk samples, can be also
found for the mushroom specimens. Sample HER M35 repre-
sents a very interesting case, since the test was interrupted
during the progression of the temperature jump phenomenon
(right after its onset is seen in the HD recording). It allows
tracking different features described above over the same sur-
face, as described in Fig. 15.
3.4. Species volatilization by space- and time-resolved
optical emission spectroscopy
An emission spectrum of freestream air plasma measured
during temperature jump testing with a mushroom model
(HER M32) is presented in Fig. 16(a). N and O emission lines
can be observed in the infrared range (>700 nm).
The main contributing species in the UV range are the Nþ2
first negative system, overlapped by the CN violet (B2R+–X2R+)
band system. CN originates from few ppm concentrations of
carbon dioxide in the test gas, as normal atmospheric air is
used for the tests. Once the C/SiC sample is swung into the
flow, volatilization products from the material surface are
detected in the emission spectra Fig. 16(b). Intensity lines
113
are identified using the NIST atomic spectrum database [43].
Within the UV range the Si I emission multiplet at 252 nm
(consisting of several, not resolved single lines) and at
288 nm are the main contributors to radiation. They were ob-
served by several authors [19,26,44–46], during plasma testing
of C/C–SiC composites or as ablation products of silicon-
based materials in oxygen atmosphere [47].
The CN violet (B–X) system is also found during material
testing, at much higher intensity compared to the freestream.
A Si emission line overlapped with the CN violet system is ob-
served at 390 nm. In addition to the freestream contribution,
the source of CN observed during material testing is twofold:
(1) reactions of SiC oxidation products (CO or CO2) with nitro-
gen in the flow, and (2) under temperature jump conditions
when the coating is depleted, direct nitridation of the sub-
strate carbon fibers and reactions between of the incoming
nitrogen with the gases produced from the oxidation of car-
bon. For the first contribution, the leading reaction mecha-
nism is CO + N ! CN + O [48]. For the second, possible
reaction mechanisms are C(s) + N ! CN and CO + N ! CN + O,
where CO is provided by the oxidation reaction C(s) + O ! CO.
According to Park et al. [48] and consistently with Boudou-
ard’s equilibrium theory CO2 is less likely to form at these
temperatures and was not observed during oxidation experi-
ments of graphite. It is acknowledged that, for experiments
performed using the standard model, contributions might
come from the test article holder (especially when graphite
is used), which are difficult to isolate. Nevertheless, analogous
species volatilization is detected during experiments per-
formed using the mushroom model, where the sample holder
is behind the sample and is expected to have a limited partic-
ipation to the boundary layer chemistry. This strongly sup-
ports that the main contribution to volatilization comes
from the sample.
No CN emission other than the contribution from the free-
stream flow was detected for tests in passive oxidation, and
only a small increase was observed during active tests. As
shown later in Fig. 18, the CN violet emission constantly rise
in time during the temperature jump, followed by a constant,
high emission. Hence, it seems to be an indicator for the pro-
gression of the temperature front during jump conditions.
Temporally resolved spectral profiles within the 240–
290 nm band are compared in Fig. 17 for tests, MTA 5, MTA
6 and MTA 12, respectively under passive oxidation (1956 K),
active oxidation (2119 K) and jump regime (2064 ! 2542 K),
at similar oxygen partial pressure (1000 Pa). No Si emission
is recorded for sample MTA 5, consistent with a stable silica
scale that protects the SiC, formed under passive oxidation.
For MTA 6, as temperature increases to steady state, we have
a rise in Si emission, which then stabilizes to constant values
throughout the whole length of the test. This case is represen-
tative of active oxidation of SiC at low rate producing Si gas-
eous products in the boundary layer. For the temperature
jump case (MTA 12) an initial sharp increase in Si emission
is observed, leading quickly to values well above active oxida-
tion. An intensity peak is observed around 40 s after sample
injection, followed by a successive attenuation and final stea-
dy emission from 55 s till the end of the run. This behavior is
consistent to what is described in the previous section about
the jump. Strong active oxidation starts soon after the sample
114 CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9

Fig. 15 – Micrographs of HER M35 sample (left figures) and correspondent location over the sample surface (right top). Pressure
is 2000 Pa for this test. The right bottom figure shows a still image from HD recording of the instant at which plasma
conditions are extinguished and the test is interrupted. (A color version of this figure can be viewed online.)

injection into higher heat flux flow, with a lot of SiO produced
into the gas phase. After 2100 K (see also temperature his-
tory in Fig. 19(a)) the onset of SiC sublimation, producing Si
and Si2C, would lead to a peak intensity in Si emission, which
would then decrease as the b-SiC layer is completely eroded.
The final constant phase in Si intensity represents constant
rate active oxidation reaction at the SiC filler matrix that
starts after the substrate is left exposed and continues to oc-
cur until the end of the run.
A similar behavior on the Si time history can be observed
from temporally- and spatially-resolved emission spectra,
shown in Fig. 18, for test MTA 12. Left-panel plots show the
range 240–290 nm where most of Si emission can be identified
and plots on the right-panel show CN violet emission in the
range of 340–440 nm. Spectra shown in the upper plots are
collected close to the sample surface (2 mm) with increasing
distance to bottom plots (lowest plot taken at 9 mm distance
from the sample). High intensity Si emission at 243 nm,
252 nm, 263 nm and 288 nm is clearly evident, sharply
increasing after the first 20 s of sample exposure to plasma.
It leads to an intensity peak and a following steady emission
recorded by all three spectrometers. It can further be ob-
served that Si emission collected by the spectrometer point-
ing 5.5 mm ahead of the sample is stronger than that close
to the wall (2 mm ahead), with the weakest emission collected
at the farthest probing volume (9 mm). Opposed to that of Si,
CN violet emission sharply decreased through the boundary
layer, almost vanishing at 9 mm distance.
 CARBON 7 1 (2 0 1 4) 1 0 2–11 9 115

Fig. 16 – Radiative signature of characteristic emission lines for (a) freestream and (b) material testing, for HER M32
experiment.

Fig. 17 – Temporal emission spectra of Si erosion products for experiments on MTA samples at 5000 Pa, under different
regimes, measured with the spectrometer at 2 mm ahead of the surface (closest). (a) MTA 5, passive oxidation, (b) MTA 6,
active oxidation and (c) MTA 12, temperature jump.

For a clearer visualization, Fig. 19(a) plots Si 228 and CN
violet (B–X) emissions, along with the temperature measured
from the pyrometer. Measurements for a mushroom model
test (HER M32) are also shown for completeness in Fig. 19(b).
Si emission at 5.5 mm (dashed line) is higher than at 2 mm
(full line). Instead, the response of the two spectrometers is
nearly identical during the part before the jump (first 30 s
for MTA 12 and first 80 s for HER M32). The most plausible
explanation for this behavior is related to the dissociation of
SiO produced by active oxidation. Assuming a Boltzmann dis-
tribution of excited states, Si emission increases along with Si
species concentration. It is plausible that SiO molecules are
not fully dissociated 2 mm ahead of the surface, while they
break up as they travel away from the wall encountering
increasing temperatures. This effect might be enhanced dur-
ing the temperature jump due to the increasing rate of SiO
production and due to an injection of sublimation products
into the boundary layer. Feigel [49] found during arc-jet tests
performed on SiC samples with the same geometry as used
for this work that the zone of detectable SiO by laser induced
fluorescence (LIF) extends to 9 mm at 30 Pa ambient pressure.
This is likely due to the higher mean free path in arc-jet
experiments at 30 Pa than in our test conditions (from 2000
to 6000 Pa).
The temporal evolution of CN shows a small amount of
radiation captured from the beginning of the test. This is
likely coming from ablation of the graphitic sample holder
used for test MTA 12. Indeed, no CN violet emission prior to
the temperature jump was found during tests where a SiC
cover was used, except the weak signal coming from the free-
stream. The strong emission increase during the temperature
jump is consistent with the removal of the SiC coating and
the onset of carbon fibers oxidation and nitridation. The CN
bandhead emission decays moving away from the surface
and is not detected by the spectrometer at 9 mm from the
sample. Excited CN molecules are very strong radiators and
small mole fractions would already lead to a radiative signa-
ture of CN violet at the surface. The emission would decrease
as the CN dissociates towards the edge of the boundary layer,
responsible for a gradient of 60% between the locations at
2 mm and 5.5 mm. For the standard sample configuration
CN did not show an emission peak as it was observed for Si
and reached a steady state following the temperature jump.
A spatially stronger decrease of CN emission
(2 mm ! 5.5 mm) was observed when testing with the mush-
room model, likely due to a thinner boundary layer surround-
ing the mushroom shape probe.
4. Discussion of the temperature jump
Based on the described experimental observations, the
temperature jump can be associated to an augmented
116 CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9

Fig. 18 – Time- and space-resolved radiative signature of characteristic emission lines of (a, b, c) atomic silicon in the UV
range and (a 0 , b 0 , c 0 ) CN violet (B2R+–X2R+) band system in the visible range for test MTA 12. From top to bottom measurements
are at increasing distance from the sample’s surface along the stagnation line.

exothermicity in the surface chemistry of the b-SiC coating of
C/SiC composites. The primary contribution to this transition
appears to be the onset of SiC sublimation that accelerates
the erosion of the coating. This is consistent with a steep rise
in the volatilization of Si-containing species observed in the
temporal emission spectra, as well as with predicted temper-
atures for SiC sublimation, which starts at low rate around
1800 K and accelerates at temperatures near 2100 K (jump
temperature), where production of Si and Si2C sharply in-
creases. The other important contribution to the chemistry
of the surface is provided by carbon reactions with O and N
atoms from the freestream flow. Temperature jump condi-
tions are far in the active oxidation regime for C/SiC. At these
conditions any SiO2 phase produced during transient or stea-
dy passivation is fully decomposed and the b-SiC layer is sig-
nificantly attacked by the reactants in the boundary layer. As
a result of the SiC volatilization several holes enlarge over the
coating, allowing passages for the transport of O and N atoms
to the substrate carbon, where oxidation and nitridation
reactions occur. These further increase the temperature
accelerating the rate of volatilization of SiC. Once the coating
is completely eroded, that is once the observed temperature
front has covered the whole surface, the substrate preform
is directly exposed to the incoming plasma and carbon oxida-
tion and nitridation become the leading reaction mecha-
nisms. Beside those primary effects, further contributions to
the convective heating might come for exothermic processes
in gas phase in the vicinity of the surface, like reactions of the
sublimated silicon with nitrogen radicals, or O- and N-atom
recombination.
5. Conclusions
Air experiments were performed in low pressure plasma
flows on carbon/silicon carbide heat shield materials at tem-
peratures above 1900 K. The tests aimed to simulate enthalpy
levels experienced by the IXV TPM during hypersonic reentry,
and to exceed nominal heat flux conditions. A sudden and
 CARBON 7 1 (2 0 1 4) 1 0 2–11 9 117

Fig. 19 – From top to bottom: time history of surface temperature, emission intensity of Si 288 in the UV range and emission
intensity of CN violet (Dm = +1 peak) in the visible range as a function of time, at the three spectrometer positions probing
ahead of the sample. (a) MTA 12 sample in standard configuration and (b) HER M32 sample in mushroom configuration.

spontaneous surface temperature increase of several hun-
dred Kelvin, at constant freestream condition, was observed
under different operating conditions. The phenomenon oc-
curred at wall temperatures near 2100 K. Infrared pyrometry
temperature measurements and real time HD recording of
the surface were used to characterize the phenomenon, to-
gether with an arrangement of optical emission spectroscopy
to follow the evolution of the chemical species along the
boundary layer of the tested sample. A mass loss exceeding
30% of the initial values was found, one order of magnitude
higher than that experienced by the material under active
oxidation regime. A strong reduction in thickness and a deep
erosion of the surface were also observed, consistent with a
strong increase in Si radiation detected by emission spectros-
copy close to the surface. The jump is explained with aug-
mented surface chemistry characterized by sublimation of
SiC around 2100 K and onset of O and N reactions with the
carbon substrate, leading to a quick and complete erosion of
the superficial b-SiC coating and to the exposure of the carbon
fibers to the incoming plasma.
Acknowledgements
This work was funded by the European Space Agency through
the Technology Research Program on Passive/Active Oxida-
tion of CMC Structural Materials, led by PROMES-CNRS. The
research of H.B. is supported by a fellowship of the Agency
for Innovation by Science and Technology in Flanders (IWT,
dossier #111529). Herakles and MT Aerospace are acknowl-
edged for the procurement of material samples used for the
experiments. The authors are grateful to Prof. K. Nickel for
the fruitful advises and discussions and to Mr. P. Collin for
his unwavering dedication in operating the Plasmatron
facility.
R E F E R E N C E S
[1] Dec JA, Braun RD, Laub B. Ablative thermal response analysis
using the finite element method. J Thermophys Heat Transfer
2012;26(2):201–12.
[2] Venkatapathy E, Laub B, Hartman GJ, Arnold JO, Wright MJ,
Allen Jr GA. Thermal protection system development, testing,
and qualification for atmospheric probes and sample return
missions: examples for Saturn, Titan and Stardust-type
sample return. Adv Space Res 2009;44(1):138–50.
[3] Parmenter KE, Shuman K, Milstein F, Szalai CE, Tran HK,
Rasky DJ. Compressive response of lightweight ceramic
ablators: phenolic impregnated carbon ablator. J Spacecraft
Rock 2001;38(2):231–6.
[4] Herdrich G, Fertig M, Petkow D, Steinbeck A, Fasoulas S.
Experimental and numerical techniques to assess catalysis.
Prog Aerosp Sci 2012;48–49:27–41.
[5] Alfano D, Scatteia L, Cantoni S, Balat-Pichelin M. Emissivity
and catalycity measurements on SiC-coated carbon fibre
118 CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9
reinforced silicon carbide composite. J Eur Ceram Soc
2009;29(10):2045–51.
[6] Presser V, Nickel KG. Silica on silicon carbide. Crit Rev Solid
State Mater Sci 2008;33(1):1–99.
[7] Rosner DE, Allendorf HD. High-temperature kinetics of the
oxidation and nitridation of pyrolytic silicon carbide in
dissociated gases. J Phys Chem 1970;74(9):1829–39.
[8] Hinze JW, Graham HC. The active oxidation of Si and SiC in
the viscous gas-flow regime. J Electrochem Soc
1976;123(7):1066–73.
[9] Vaughn WL, Maahs HG. Active-to-passive transition in the
oxidation of silicon carbide and silicon nitride in air. J Am
Ceram Soc 1990;73(6):1540–3.
[10] Narushima T, Goto T, Iguchi Y, Hirai T. High-temperature
active oxidation of chemically vapor-deposited silicon
carbide in an Ar/O2 atmosphere. J Am Ceram Soc
1991;74(10):2583–6.
[11] Balat M, Flamant G, Male G, Pichelin G. Active to passive
transition in the oxidation of silicon carbide at high
temperature and low pressure in molecular and atomic
oxygen. J Mater Sci 1992;27(3):697–703.
[12] Narushima T, Goto T, Yokoyama Y, Hagiwara J, Iguchi Y, Hirai
T. High-temperature active oxidation and active-to-passive
transition of chemically vapor-deposited silicon nitride in
N2–O2 and Ar–O2 Atmospheres. J Am Ceram Soc
1994;77(9):2369–75.
[13] Balat MJH. Determination of the active-to-passive transition
in the oxidation of silicon carbide in standard and
microwave-excited air. J Eur Ceram Soc 1996;16(1):55–62.
[14] Schneider B, Guette A, Naslain R, Cataldi M, Costecalde A. A
theoretical and experimental approach to the active-to-
passive transition in the oxidation of silicon carbide:
experiments at high temperatures and low total pressures. J
Mater Sci 1998;33(2):535–47.
[15] Hilfer G. Ceramic thermal protection materials – how far can
we go? (Part II), A detailed look into the oxidation behavior of
Si-containing ceramics. In: 53rd International Astronautical
Congress, Houston, Texas, 2001.
[16] Hilfer G. Ceramic thermal protection materials – how far
can we go? New aspects on the oxidation behavior
during re-entry flight. In: 2nd International Symposium
on Reentry Vehicles and Systems, Arcachon, France;
2001.
[17] Goto T, Homma H. High-temperature active/passive
oxidation and bubble formation of CVD SiC in O2 and CO2
atmospheres. J Eur Ceram Soc 2002;22(14–15):
2749–56.
[18] Laux T, Herdrich G, Auweter-Kurtz M. Oxidation behavior of
sintered silicon carbide in various plasma wind tunnels. In:
4th European Workshop for Hot Structures and Thermal
Protection Systems for Space Vehicles, Palermo, Italy, 2002;
[ESA SP-521].
[19] Herdrich G, Fertig M, Löhle S, Pidan S, Auweter-Kurtz M, Laux
T. Oxidation behavior of siliconcarbide-based materials by
using new probe techniques. J Spacecraft Rock
2005;42(5):817–24.
[20] Wang J, Zhang L, Zeng Q, Vignoles GL, Guette A. Theoretical
investigation for the active-to-passive transition in the
oxidation of silicon carbide. J Am Ceram Soc
2008;91(5):1665–73.
[21] Jacobson NS, Myers DL. Active oxidation of SiC. Oxid Met
2011;75(1–2):1–25.
[22] Harder B, Jacobson N, Myers D. Oxidation transitions for SiC
part II: Passive-to-active transitions. J Am Ceram Soc
2013;96(2):606–12.
[23] Jacobson N, Harder B, Myers D. Oxidation transitions for SiC
part I: Active-to-passive transitions. J Am Ceram Soc
2013;96(3):838–44.
[24] Nickel KG. The role of condensed silicon monoxide in the
active-to-passive oxidation transition of silicon carbide. J Eur
Ceram Soc 1992;9(1):3–8.
[25] Tumino G. IXV: the Intermediate eXperimental Vehicle. ESA
Bulletin 128; 2006.
[26] Panerai F, Chazot O. Characterization of gas/surface
interactions for ceramic matrix composites in high enthalpy,
low pressure air flow. Mater Chem Phys 2012;134(2–
3):597–607.
[27] Lacombe A, Lacoste M. Investigation of C/SiC ‘‘breaking
point’’ under arc-jet environment at NASA JSC. High Temp
Chem Proc 1994;3:285–96.
[28] Hald H. Operational limits for reusable space transportation
systems due to physical boundaries of C/SiC materials.
Aerosp Sci Technol 2003;7(7):551–9.
[29] Sakraker I, Asma CO. Experimental investigation of passive/
active oxidation behavior of SiC based ceramic thermal
protection materials exposed to high enthalpy plasma. J Eur
Ceram Soc 2013;33(2):351–9.
[30] Gasch M, Ellerby D, Irby E, Beckman S, Gusman M, Johnson S.
Processing, properties and arc jet oxidation of hafnium
diboride/silicon carbide ultra high temperature ceramics. J
Mater Sci 2004;39(19):5925–37.
[31] Marschall J, Pejakovic D, Fahrenholtz WG, Hilmas GE, Panerai
F, Chazot O. Temperature jump phenomenon during
plasmatron testing of ZrB2–SiC ultrahigh-temperature
ceramics. J Thermophys Heat Transfer 2012;26(4):559–72.
[32] Bottin B. Aerothermodynamic model of an inductively-
coupled plasma wind tunnel [Ph.D. thesis]. Université de
Liège, von Karman Institute for Fluid Dynamics; 1999.
[33] Bottin B, Carbonaro M, Zemsch S, Degrez G.
Aerothermodynamic design of an inductively coupled
plasma wind tunnel. In: 32nd Thermophysics Conference,
Atlanta, GA, USA 1997; [AIAA 1997-2498].
[34] Bottin B, Paris S, Van Der Haegen V, Carbonaro M.
Experimental and computational determination of the VKI
Plasmatron operating envelope. In: 30th Plasmadynamic and
Lasers Conference, Norfolk, VA, USA, 1999; [AIAA 1999-3607].
[35] Bottin B, Paris S, Van Der Haegen V, Carbonaro M, Novelli A,
Vennemann D. The VKI 1.2 MW Plasmatron facility for the
thermal testing of TPS materials. In: 3rd European Workshop
on Thermal Protection Systems, Noordwijk, The
Nerderlands; 1998.
[36] Barbante P, Chazot O. Flight extrapolation of plasma wind
tunnel stagnation region flowfield. J Thermophys Heat
Transfer 2006;20(3):493–9.
[37] Kolesnikov AF. Conditions of simulation of stagnation point
heat transfer from a high-enthalpy flow. Fluid Dyn
1993;28(1):131–7.
[38] Pichon T, Barreteau R, Soyris P, Foucault A, Parenteau JM, Prel
Y, et al. CMC thermal protection system for future reusable
launch vehicles: generic shingle technological maturation
and tests. Acta Astronaut 2009;65(1–2):165–76.
[39] Naslain RR, Pailler R, Bourrat X, Bertrand S, Heurtevent F,
Dupel P, et al. Synthesis of highly tailored ceramic matrix
composites by pressure-pulsed CVI. Solid State Ionics
2001;141–142:541–8.
[40] Jacobson NS, Curry DM. Oxidation microstructure studies of
reinforced carbon/carbon. Carbon 2006;44(7):1142–50.
[41] Glime WH, Cawley JD. Oxidation of carbon fibers and films in
ceramic matrix composites: a weak link process. Carbon
1995;33(8):1053–60.
[42] Gorshkov AB. Numerical investigation of heat transfer on the
surface of experimental models in the test chamber of an
induction plasmatron. High Temp 2010;48(3):427–35.
[43] Kramida A, Ralchenko Y, Reader J, Team. NA. NIST atomic
spectra database (ver. 5.0), [online]. Gaithersburg, MD, USA:
National Institute of Standards and Technology 2012.
 CARBON 7 1 (2 0 1 4) 1 0 2–11 9
[44] Hirsch K, Roth B, Altmann I, Barth K-L, Jentschke H, Lunk A,
et al. Plasma-induced silica-like protection layer formation
on C/C–SiC heat-shield materials for re-entry vehicles. High
Temp High Press 1999;31(4):455–65.
[45] Jentschke H, Hirsch K, Klenge S, Schumacher U. High
resolution emission and absorption spectroscopy for erosion
product analysis in boundary plasmas. Rev Sci Instrum
1999;70(1):336–9.
[46] Altmann I, Bauer G, Hirsch K, Jentschke H, Stefan K, Roth B,
et al. In-situ diagnostics of the interaction region between a
nitrogen–oxygen plasma jet and hot C/C–SiC ceramic
materials. High Temp High Press 2000;32:573–9.
119
[47] Marine W, Tokarev V, Gerri M, Sentis M, Fogarassy E. Ablation
dynamics of silicon based targets in oxygen and nitrogen
atmospheres. Thin Solid Films 1994;241(1–2):103–8.
[48] Park C, Jaffe RL, Partridge H. Chemical-kinetic parameters of
hyperbolic earth entry. J Thermophys Heat Transfer
2001;15(1):76–90.
[49] Feigl M. Experimentelle Untersuchung des Erosionsprozesses
von SiC-haltigen Hitzeschutzmaterialien rückkehrfähiger
Raumtrasnportsysteme mit Hilfe der Methode der
laserinduzierten Fluoreszenz [Ph.D. Thesis]. Universität
Stuttgart; 2005.