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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: The behavior of carbon/silicon carbide composites at very high temperatures is investi-
Received 11 November 2013 gated in an inductively-coupled plasma generator that simulates atmospheric re-entry
Accepted 13 January 2014 aerothermal conditions for space vehicles. Samples exposed to heat fluxes exceeding
Available online 21 January 2014 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 second can survive one single entry maneuver and are typi-
cally used for planetary entry and sample return missions
The success of any spacecraft entering a planetary atmo- at speeds exceeding 8.5 km/s [2,3]. In this paper we focus on
sphere relies to a great extent on the Thermal Protection Sys- carbon/silicon carbide composites or C/SiC that belong to
tem (TPS), which is designed to shield crew and payload from the first class. Their typical composition is based on a weaved
the severe aerothermal conditions during the hypersonic carbon preform, filled and coated with SiC, according to dif-
flight. Heatshield materials developed for such purpose are ferent manufacturing processes. The thermophysical proper-
classified in two main categories: reusable and ablative [1]. ties of these materials and their interactions with the
The former are able to handle multiple entries at moderate surrounding plasma are of high scientific and technical inter-
speeds (<7.5 km/s) and mild heat fluxes (<1.2 MW/m2). The 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 9 103
improvement of the materials performances. One of the main reusability limit. Studies on the oxidation transition of sili-
contributions to the heat transferred to the wall comes from con carbide-based materials, conducted in high enthalpy
the catalytic nature of the surface, which is the probability plasma facilities, led many authors to observe spontaneous
of promoting recombination of dissociated species from the jumps in surface temperature, of the order of hundreds of
incoming flow [4]. A non catalytic surface can halve the con- Kelvin, during exposure of the samples to high heat flux,
vective heat flux with respect to a fully catalytic one. The low pressure, dissociated flows. The phenomenon was firstly
main mechanism of heat release, for passively-cooled Ther- observed during arc-jet experiments of C/SiC samples at
mal Protection Materials (TPM), is surface re-radiation, which temperatures up to 2120 K [27]. Hald discussed temperature
is proportional to the fourth power of the temperature, and jumps on similar Ceramic Matrix Composited (CMC) materi-
can be computed if the emissivity of the material is known als and suggested an explanation based on exothermic cata-
[5]. Oxidation phenomena are also of primary importance lytic reactions of gaseous silicon with atomic nitrogen,
for SiC-based surfaces exposed to high enthalpy, oxygen-rich which would raise the temperature of the boundary layer
environments. It is well known that low surface temperatures and hence the convective component of heating to the sur-
and high oxygen partial pressures promote the formation of a face [28]. The phenomenon was observed by Herdrich et al.
glassy SiO2 layer over the surface [6]. This situation is often [19] and Laux et al. [18] both in inductively heated and arc-
referred to as passive oxidation and often corresponds to a jet facilities, during testing of sintered and CVD b-SiC coated
net mass increase. Higher temperatures and lower pressures C/C. Herdrich used increased N-atom recombination on SiC
can lead, instead, to the volatilization of silicon oxide prod- versus SiO2 to explain part of the increased heat flux to
ucts into the gas phase, hence a net mass loss. This scenario, the surface under temperature jumps, observed during plas-
referred to as active oxidation, can become a harmful condi- ma testing of passive/active oxidation transition. Silicon
tion for the integrity of the TPS. Ideally one desires a low cat- emissions, detected by optical emission spectroscopy, were
alytic, high emissive and high oxidation resistant material to used to distinguish between passively and actively oxidized
be used as heatshield. samples. Investigations were performed in the VKI Plasma-
Several studies, both theoretical and experimental, have tron facility [29] on CVD b-SiC specimens at surface temper-
been conducted on the identification of the transition bound- atures of 2000–2800 K and various pressures. Sudden
ary between the passive and the active regimes for silicon car- temperature jumps for constant freestream conditions were
bide-based composites. Authors have studied different observed, corresponding to high mass loss and strong in-
atmospheres and different materials [7–24]. The dispersion crease in silicon volatilization, detected by optical emission
of proposed transitions is significant and a universal law is spectroscopy near the surface. The phenomenon was also
difficult to provide. Differences are attributed to both experi- observed during testing of Ultra-High Temperature Ceramics
mental factors and materials properties. Ruled by oxygen par- (UHTC), containing SiC. Gasch et al. documented arc-jet tests
tial pressure and temperature, the transition is affected by the of HfB2–20%SiC samples at high surface temperatures,
gas mixture (pure oxygen, O2/Ar, O2/He, O2/N2, dry air, atmo- observing a slow and constant surface temperature increase,
spheric air), that determines the oxygen potential, by the de- of 300–400 K, starting near 2100 K, about 400 s after the
gree of dissociation, the reactants transport, and the Knudsen beginning of the plasma exposure [30]. This behavior was
regime (equivalent to the effect of the total pressure). Related attributed to the presence of a thick porous hafnium oxide
to the material, key factors are microscopic characteristics layer, changing surface catalycity, emissivity and conductiv-
like the crystalline structure (a-SiC or b-SiC) and macroscopic ity of the material. Recent Plasmatron experiments were per-
properties like surface roughness or emissivity. Therefore, a formed by Marschall et al. [31] on zirconium diboride-based
dedicated characterization in a relevant environment is UHTC materials. Above a certain heat flux, samples reached
needed for a specific TPM and a specific flight trajectory. temperatures near 2200 K (at 10,000 Pa) at which their sur-
The demand of higher velocities and higher heat fluxes is face oxide scale was no longer protective or stable and
pushing reusable TPS materials to the edge of their opera- underwent temperature jump. Based on computational anal-
tional limits. Speed entries to Earth above 7.5 km/s develop ysis, the authors attributed the temperature jump to a tran-
enthalpies above 28 MJ/kg and peak heating conditions that sition in surface chemistry involving the silica-rich oxide
could bring SiC based surfaces far into the active oxidation re- scale and the silica former SiC.
gime and prevent their reusability. The Intermediate eXperi- This paper focuses on the temperature jump phenomenon
mental Vehicle (IXV), a lifting re-entry spacecraft developed observed on the IXV C/SiC materials. High heat flux experi-
by the European Space Agency [25], is designed to fly a C/ ments are conducted in the Plasmatron facility at von Kar-
SiC TPS covered by a b-SiC coating in such demanding condi- man Institute for Fluid Dynamic. Samples are tested at
tions. The testing of its heatshield materials is an ideal frame pressures between 2000 and 6000 Pa and temperature above
to investigate the behavior of this class of materials under a 1900 K. The practical challenges arising when performing
strong oxidizing environment. The catalytic and radiative temperature jump experiments are discussed. The jump phe-
behavior of the IXV materials were studied in [26], during nomenon is illustrated by means of infrared pyrometry mea-
induction plasma experiments in a representative atmo- surements and real-time visible emission recording of the
sphere for the vehicle trajectory. A study on the passive/active samples’ surface. A discussion on the phenomenon is pro-
transition of C/SiC materials similar to those of the IXV was vided, based on Scanning Electron Microscopy (SEM) analysis,
proposed in [13]. spatially- and temporally-resolved optical emission spectros-
The present work focuses on the active oxidation regime copy and comparison with passive and active oxidation
and studies the behavior of C/SiC composites close to their regimes.
104 CARBON 7 1 ( 2 0 1 4 ) 1 0 2 –1 1 9
Fig. 1 – Schematic of the Plasmatron setup. (A color version of this figure can be viewed online.)
CARBON 7 1 (2 0 1 4) 1 0 2–11 9 105
strongly in the UV-range and can be detected using available probes are mounted inside the Plasmatron test chamber
Ocean Optics HR4000 spectrometers. The optical diagnostic at 0.445 m from the ICP torch exit. The placement ensures
bench consists of a light collection system, optical fibers that the axis of the probe and the axis of the torch itself
and the three spectrometers covering a spectral range of coincide. The test configurations are shown in Fig. 2. The
200–1100 nm. The light emitted by the plasma is collected first is a standard 50 mm diameter model, mounting a
through a variable aperture and focused by a plano-convex, 30 mm diameter, 60 bevel disk sample. The samples are
uncoated, fused silica lens (LA4745, 750 mm focal length) via kept in place by a sintered SiC or graphite cover. The sec-
two mirrors, to the entry of three optical fibers (Ocean Optics ond is a 30 mm diameter probe holding mushroom shaped
QP600–2-SR/BX, 600 ± 10 lm core diameter). A numerical models. These are mounted by interference-fitting their
aperture of 0.22 ± 0.02 is optimized to match the 5 lm wide stem into the graphite holder. The geometry of the samples
entrance slit of the spectrometers. The slit and a from Herakles, France (HER) and MT Aerospace, Germany
300 grooves/mm grating lead to a typical resolution of approx- (MTA) is detailed in Fig. 3.
imately 0.65 nm (Full Width Half Maximum (FWHM)), as Microscale morphology analysis of post-test samples is
determined by a low pressure Oriel 6060 Hg lamp. The spec- performed using SEM (Hitachi S-4500). High resolution pic-
trometers are set to an acquisition frequency of 0.75 Hz, tures are acquired using a commercial SLR camera. The mass
allowing the acquisition of multiple time-resolved spectra of the samples is measured with a high precision scale
during one test run. The integration time was set to 100 ms (±0.01 mg accuracy), prior to and after plasma exposure.
for all tests (comparable to the shutter of a camera). The ac-
quired spectra are averaged during this acquisition period. 2.2. Materials
The optical path is aligned perpendicular to the flow and tan-
gential to the test sample surface. The bench is mounted on a The ceramic matrix composites analyzed in this research are
movable holding system, enabling horizontal movements to those mounted on the IXV thermal protection systems, pro-
place the line of sight at the desired position. The positioning vided by Herakles (Safran Group, Le Haillan, France) and MT
is adjusted before each experiment using a laser beam sent Aerospace (Augsburg, Germany). Herakles material (SEPCAR-
through the optics and located ahead of the stagnation point BINOX L6) manufacturing [38] starts from a carbon fiber pre-
of the sample. The spectrometers’ lines of sight are fixed at form, based on a multi-layer woven architecture. The
the desired distance from the sample front face respectively, preform is constructed from a lay-up of pre-preg that is cured
and not moved during the whole experiment. A magnification in a mold, and densified with consecutive depositions of sili-
of 1.5 is used, resulting in a distance between each probing con carbide by Chemical Vapor Infiltration (CVI) [39]. The last
volume of Dd = 3.5 mm, the respective distances from the sur- CVI cycle allows at the same time to achieve the requested
face (y = 0) being y1 = 2 mm, y2 = 5.5 mm, y3 = 9 mm. Calibra- density, and to ensure a full coating of the composite surface
tion of the whole system in relative intensity is performed by a b-SiC layer of 80 lm thickness.
using a deuterium lamp in the UV range (<400 nm) and a The MT Aerospace samples are produced using a near net
tungsten ribbon lamp (OSRAM WI 17G) in the visible range shaped layup technique via Polymer Vapor Infiltration (PVI). A
(>400 nm), to obtain comparable intensities to those during pre-impregnated carbon fiber structure (7 lm filament diame-
the tests. ter) is cured before undergoing pyrolysis, which turns the
Two sample holders, equipped with adequate water-cool- polymer into an amorphous carbon phase. The pyrolized car-
ing, are used to install the TPS samples in the setup. The bon-fiber-reinforced polymer is then coated with b-SiC by a
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.)
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 Fig. 4 shows the temperature measured during the cases that
(b) mushroom model. Dimensions in mm. Drawings are not present the temperature jump phenomenon. For both materi-
in scale. The thickness of model (a) samples is 2 mm for HER als, the temperature history measured during a jump test is
material and 3 mm for MTA material. 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).
Chemical Vapor Deposition (CVD) process. The SiC coating Test HER 17 represents a well-suited case to illustrate the
has an average thickness between 60 and 80 lm [5]. evolution of the surface. A sintered SiC cover is used to hold
Herakles and MTA materials are denoted as HER and MTA the sample. The insertion of the test model into the flow at
in the following sections. 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-
2.3. Test protocol mately 40 s. Differently from tests in passive and active
oxidation, where a steady state is reached and maintained
The Plasmatron tests are performed under standard air plas- constant throughout the test, a temperature plateau is mea-
ma (79% N2 and 21% O2) at a mass flow of 16 g/s. Flow condi- sured only until 120 s, when a sudden jump of 400 K leads
tions are initially calibrated according to the real-time reading to a surface temperature near 2500 K. Power, pressure, and
provided by the calorimetric and pressure probes. Those are mass flow (i.e. total enthalpy and total pressure) are main-
alternatively swung into the plasma stream and the torch tained constant throughout the test, hence the phenomenon
power is progressively adjusted to obtain the desired values. results as spontaneous process at constant freestream
The chamber static pressure is adjusted by air by-pass and conditions.
vacuum pumps regulation. After the establishment of a stea- A visual observation of the sample’s surface during the
dy-state flow, the calibration probes are maintained into the tests shows a large increase in the light emitted from the test
plasma stream for a total exposure time of 100–200 s to en- article. Frame images extracted from HD video recording at
sure the stability of the test conditions. Following the calibra- 3 s time intervals are shown in Fig. 6 and compared with a de-
tion phase the sample is injected into the flow and, after tail of the temperature history near the jump. The camera
steady-state temperature is achieved, constant conditions operating mode automatically adjusts the exposure to the
are maintained for a total steady-state time of 600 s. For some variation of light intensity, therefore the changes of bright-
tests, this is shortened in order to avoid damages to the setup ness between different frames cannot be directly correlated
or to prevent the complete destruction of the test article. to the temperature. Nevertheless, the images clearly show
the progression of the phenomenon over the sample surface,
3. Results and the brightness pattern within one single image gives a
good representation of the temperature gradient over the sur-
Experiments are performed at static pressures of 2000, 5000 face. A bright spot appears at the bottom left edge of the sam-
and 6000 Pa. The test conditions are summarized in Tables 1 ple at 106 s. It progresses as a high emission front expanding
and 2, respectively for the standard and mushroom test mod- at the edges of the sample and reaches the center of the sur-
els. The cases highlighted in bold show the jump phenome- face. After about 30 s the surface is entirely covered and no
non (J). For the experiments with the standard model, two brightness gradients can be observed. The rate of progression
tests are reported as comparison, respectively under passive of the bright front is calculated to be 0.9 mm/s. One should
(P) oxidation and active (A) oxidation regimes. For the set of note that the phenomenon can be observed along the temper-
experiments on the HER material at 6000 Pa, the jump regime 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
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
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 which sums to the incoming heat flux from the dissociated
pyrometer field of view. This is a nearly circular 12 mm diam- flow. Consequently, as it can be observed in Fig. 4, for sam-
eter spot, centered over the samples surface. ple HER 23 and samples MTA 11–13, the initial temperature
During other attempts performed to obtain a similar rise is significantly accelerated, for similar heating levels to
phenomenology to that observed in the test HER17, the that used with sample HER 17. As a result, steady state
SiC holder experiences a sudden failure when running at temperature prior to the jump cannot be achieved and the
very high heat fluxes, as temperature jump conditions for phenomenon is observed during the transient heating of
C/SiC are beyond the heating load that sintered SiC can the samples.
support. Therefore, graphite sample holders are adopted Details of visual recording for sample MTA 12 are shown in
in place of SiC holders for experiments at different pressure Fig. 7. Differently from test HER 17, the graphite is a brighter
conditions. Graphite offers better performances when ex- emitter than both SiC and C/SiC, such that the exposure
posed to sharp heating rates, nonetheless it has the incon- auto-adjustment shows the inner sample as a darker surface
venience of rapidly recessing due to ablation when exposed prior to the onset of the temperature jump phenomenon. The
to plasma. Erosion is likely to occur at the graphite edges progress of the bright front over the surface is then analogous
surrounding the C/SiC samples, resulting in highly reactive to what is observed before, but faster (18 s). A front propaga-
hot zone transferring side-heating to the test samples, 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.)
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
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
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
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
oxidation starts soon after the injection into the flow. Under exceed 2100 K (jump temperature), sublimation of SiC into
this condition, the silicon carbide reacts with oxygen atoms, Si and in lesser extent into Si2C largely contributes to the
producing mainly SiO and CO. The higher the incoming flux chemistry of the surface. Further exothermicity might be pro-
the higher the rate of consumption of the b-SiC layer. Ther- moted by N radicals that are present in large quantities in the
modynamic calculations (Fig. 14) show that, if temperatures mixture, and by cracks enlarged by active oxidation, that
CARBON 7 1 (2 0 1 4) 1 0 2–11 9 113
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 range of 340–440 nm. Spectra shown in the upper plots are
into the gas phase. After 2100 K (see also temperature his- collected close to the sample surface (2 mm) with increasing
tory in Fig. 19(a)) the onset of SiC sublimation, producing Si distance to bottom plots (lowest plot taken at 9 mm distance
and Si2C, would lead to a peak intensity in Si emission, which from the sample). High intensity Si emission at 243 nm,
would then decrease as the b-SiC layer is completely eroded. 252 nm, 263 nm and 288 nm is clearly evident, sharply
The final constant phase in Si intensity represents constant increasing after the first 20 s of sample exposure to plasma.
rate active oxidation reaction at the SiC filler matrix that It leads to an intensity peak and a following steady emission
starts after the substrate is left exposed and continues to oc- recorded by all three spectrometers. It can further be ob-
cur until the end of the run. served that Si emission collected by the spectrometer point-
A similar behavior on the Si time history can be observed ing 5.5 mm ahead of the sample is stronger than that close
from temporally- and spatially-resolved emission spectra, to the wall (2 mm ahead), with the weakest emission collected
shown in Fig. 18, for test MTA 12. Left-panel plots show the at the farthest probing volume (9 mm). Opposed to that of Si,
range 240–290 nm where most of Si emission can be identified CN violet emission sharply decreased through the boundary
and plots on the right-panel show CN violet emission in the 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 likely coming from ablation of the graphitic sample holder
violet (B–X) emissions, along with the temperature measured used for test MTA 12. Indeed, no CN violet emission prior to
from the pyrometer. Measurements for a mushroom model the temperature jump was found during tests where a SiC
test (HER M32) are also shown for completeness in Fig. 19(b). cover was used, except the weak signal coming from the free-
Si emission at 5.5 mm (dashed line) is higher than at 2 mm stream. The strong emission increase during the temperature
(full line). Instead, the response of the two spectrometers is jump is consistent with the removal of the SiC coating and
nearly identical during the part before the jump (first 30 s the onset of carbon fibers oxidation and nitridation. The CN
for MTA 12 and first 80 s for HER M32). The most plausible bandhead emission decays moving away from the surface
explanation for this behavior is related to the dissociation of and is not detected by the spectrometer at 9 mm from the
SiO produced by active oxidation. Assuming a Boltzmann dis- sample. Excited CN molecules are very strong radiators and
tribution of excited states, Si emission increases along with Si small mole fractions would already lead to a radiative signa-
species concentration. It is plausible that SiO molecules are ture of CN violet at the surface. The emission would decrease
not fully dissociated 2 mm ahead of the surface, while they as the CN dissociates towards the edge of the boundary layer,
break up as they travel away from the wall encountering responsible for a gradient of 60% between the locations at
increasing temperatures. This effect might be enhanced dur- 2 mm and 5.5 mm. For the standard sample configuration
ing the temperature jump due to the increasing rate of SiO CN did not show an emission peak as it was observed for Si
production and due to an injection of sublimation products and reached a steady state following the temperature jump.
into the boundary layer. Feigel [49] found during arc-jet tests A spatially stronger decrease of CN emission
performed on SiC samples with the same geometry as used (2 mm ! 5.5 mm) was observed when testing with the mush-
for this work that the zone of detectable SiO by laser induced room model, likely due to a thinner boundary layer surround-
fluorescence (LIF) extends to 9 mm at 30 Pa ambient pressure. ing the mushroom shape probe.
This is likely due to the higher mean free path in arc-jet
experiments at 30 Pa than in our test conditions (from 2000 4. Discussion of the temperature jump
to 6000 Pa).
The temporal evolution of CN shows a small amount of Based on the described experimental observations, the
radiation captured from the beginning of the test. This is 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 reactions occur. These further increase the temperature
C/SiC composites. The primary contribution to this transition accelerating the rate of volatilization of SiC. Once the coating
appears to be the onset of SiC sublimation that accelerates is completely eroded, that is once the observed temperature
the erosion of the coating. This is consistent with a steep rise front has covered the whole surface, the substrate preform
in the volatilization of Si-containing species observed in the is directly exposed to the incoming plasma and carbon oxida-
temporal emission spectra, as well as with predicted temper- tion and nitridation become the leading reaction mecha-
atures for SiC sublimation, which starts at low rate around nisms. Beside those primary effects, further contributions to
1800 K and accelerates at temperatures near 2100 K (jump the convective heating might come for exothermic processes
temperature), where production of Si and Si2C sharply in- in gas phase in the vicinity of the surface, like reactions of the
creases. The other important contribution to the chemistry sublimated silicon with nitrogen radicals, or O- and N-atom
of the surface is provided by carbon reactions with O and N recombination.
atoms from the freestream flow. Temperature jump condi-
tions are far in the active oxidation regime for C/SiC. At these 5. Conclusions
conditions any SiO2 phase produced during transient or stea-
dy passivation is fully decomposed and the b-SiC layer is sig- Air experiments were performed in low pressure plasma
nificantly attacked by the reactants in the boundary layer. As flows on carbon/silicon carbide heat shield materials at tem-
a result of the SiC volatilization several holes enlarge over the peratures above 1900 K. The tests aimed to simulate enthalpy
coating, allowing passages for the transport of O and N atoms levels experienced by the IXV TPM during hypersonic reentry,
to the substrate carbon, where oxidation and nitridation 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- for Innovation by Science and Technology in Flanders (IWT,
dred Kelvin, at constant freestream condition, was observed dossier #111529). Herakles and MT Aerospace are acknowl-
under different operating conditions. The phenomenon oc- edged for the procurement of material samples used for the
curred at wall temperatures near 2100 K. Infrared pyrometry experiments. The authors are grateful to Prof. K. Nickel for
temperature measurements and real time HD recording of the fruitful advises and discussions and to Mr. P. Collin for
the surface were used to characterize the phenomenon, to- his unwavering dedication in operating the Plasmatron
gether with an arrangement of optical emission spectroscopy facility.
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 R E F E R E N C E S
higher than that experienced by the material under active
oxidation regime. A strong reduction in thickness and a deep
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