Journal of the European Ceramic Society 36 (2016) 3717–3723

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Journal of the European Ceramic Society

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

Ablation resistance of precursor derived Si-Hf-C-N(O) ceramics

Eranezhuth Wasan Awin, Soumya Sridar, Adhimoolam Bakthavachalam Kousaalya 1 ,
Ravi Kumar ∗
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras (IIT Madras), Chennai 600036, India

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

Article history: Polymer derived Si-Hf-C-N(O) foams were produced by the pyrolysis of polysilazane containing varying
Received 15 January 2016 amounts of hafnium tetra n-butoxide. X-ray tomography was used to determine the cell size distribu-
Received in revised form 30 March 2016 tion. The ablation resistance of the foams was studied by subjecting it to different oxyacetylene flame
Accepted 31 March 2016
temperatures. After ablation, fragmentation was not observed and the mass ablation rate was found to
Available online 18 June 2016
be minimal for the foams produced from highest vol% of hafnium tetra n-butoxide. The foams remained
X-ray amorphous after ablation and the presence of Hf O and Si O bonds were confirmed using ATR
Keywords:
spectroscopy. For comparison, a reasonably dense spark plasma sintered pellet was also ablated and
Ablation
Oxyacetylene flame the evolution of monoclinic hafnia was confirmed using X-ray diffraction. The microstructural charac-
Ceramic foam terization exhibited three different zones on the ablated surface for sintered sample and the ablation
Spark plasma sintering mechanisms were understood using thermodynamic calculations.
Microstructure © 2016 Elsevier Ltd. All rights reserved.

1. Introduction be coated/immersed in a polyurethane sponge, which upon pyrol-

The ablation resistance of materials is a major concern in
the aerospace industry since several components of a hypersonic
spacecraft are subjected to temperatures as high as 1650◦ C [1] due
to aerodynamic heating during re-entry. Concomitantly, the design
demands the material to possess high strength in addition to low
density. Recent studies [2,3] focus on the usage of sandwich struc-
tured composites ie., ceramic foam positioned between ceramic
matrix composite panels. The ceramic foam which forms the core
of the composite must withstand high temperature, mechanical
load and thermal shock resistance [4]. A detailed review on the
optimal design of foams suggests that micro-architected cellular
materials possess superior mechanical properties [5]. Recently, in
SiC foams, it was shown that the pore and strut diameter affects
the heat transfer (thermal radiation) [6]. The usage of these foams
leads to reduction in weight of the structural components, thus
increasing the fuel efficiency. Currently, some of the established
methodologies for producing foams are by using a replica [7], use
of sacrificial templates [8,9], direct foaming and reaction tech-
niques [10–12]. In the replica method, the polymeric solution will
∗ Corresponding author.
E-mail address: nvrk@iitm.ac.in (R. Kumar).
1
Present address: Department of Automotive Engineering, Caroll A. Campbell Jr.
Graduate Engineering Center, Clemson University International Center for Automo-
tive Research (CU-ICAR), Greenville, SC 29607, USA.
ysis leads to a porous ceramic. The sacrificial template method
envisages the use of a sacrificial template into which the polymeric
precursors will be impregnated followed by pyrolysis to remove the
template. The direct foaming method involves the creation of bub-
bles in the polymeric solution so as to produce a foamy structure
where as in the reaction technique the foamy structure is produced
as a result of the reaction that takes place between the polymers
and fillers. In this study, the initial precursor mixture when sub-
jected to pyrolysis leads to the formation of bubbles. It is believed
that the since the viscosity of the mixture is high, the bubbles do
not break and moves upwards, eventually leading to the foam for-
mation. The release of butanol and gases such as CH4 , NOx, CO2 and
CO during pyrolysis is expected to be the reason for pore formation.
Several studies were carried out to develop material systems
that possess high oxidation resistance, thermal shock resistance
and chemical stability at higher temperatures. The material system
being studied involves C/C composites [13–15], ultra high tempera-
ture ceramics (UHTC’s) coated C/C composites [16–21] and Cf /Si3 N4
[22]. However, the debonding of these coatings at high tempera-
tures was a major concern. Recently, ablation resistance studies
were performed on SiBCN based ceramic composites with fiber
reinforcements such as SiC, C [23] and their combinations [24].
The fabrication of the above mentioned material systems were
carried out using several methods comprising of chemical vapor
infiltration [25,26], reactive melt infiltration [27], slurry infiltra-
tion by hot pressing [28], and precursor infiltration and pyrolysis
(PIP) [29]. In this study, we have adopted polymer derived ceramic

http://dx.doi.org/10.1016/j.jeurceramsoc.2016.03.038
0955-2219/© 2016 Elsevier Ltd. All rights reserved.
3718 W.A. Eranezhuth et al. / Journal of the European Ceramic Society 36 (2016) 3717–3723

Fig. 1. 2D slice of front view of the foams produced from (a) 5 vol% HfTb (b) 15 vol% HfTb (c) 25 vol% HfTb and (d) 3D CT-X ray tomographic image foam derived from 25 vol%
HfTb.

Fig. 2. Average cell size distribution of the foams produced from (a) 5 vol% HfTb (b) 15 vol% HfTb and (c) 25 vol% HfTb.
 W.A. Eranezhuth et al. / Journal of the European Ceramic Society 36 (2016) 3717–3723 3719

Table 1
Parameters used for spark plasma sintering.

Temperature 1400◦ C

Pressure 30 MPa
Atmosphere vacuum
Heating rate 100 ◦ C/ min
Holding time 30 min

route (PDC) for the processing of our material system. This pro-
cess allows enough flexibility in producing large sized and complex
shape components. To the best of our knowledge, the ablation stud-
ies on either foams or densely sintered ceramics produced through
a PDC route are limited.
This work focuses on the ablation resistance of polymer derived
Si-Hf-C-N(O) based foams produced by varying the hafnium pre-
cursor content in polysilazane, using an oxyacetylene flame.
Concomitantly, spark plasma sintered pellet was also ablated for
comparison with the ablation resistance of the foams. The mass
ablation rate was calculated and detailed structural characteriza-
Fig. 3. Mass ablation rate of Si-Hf-C-N(O) foams and pellet.
tion was carried out in order to ascertain the ablation products and
to understand the ablation mechanism of the foams as well as the
sintered pellet.

2. Experimental details

Polysilazane (Clariant) and hafnium tetra n-butoxide (HfTb)

(Sigma Aldrich) were chosen as the starting precursors to synthe-
size Si-Hf-C-N(O) ceramics. Three different foams were produced
by varying the vol% of HfTb (ie; 5, 15 and 25%) and the foam pro-
duced from 5 vol% HfTb was chosen for spark plasma sintering.
The foam produced from 5 vol% HfTb was crushed to powder and
subjected to sintering to obtain a pellet in order to compare its
properties with the foam. The spark plasma sintering conditions
are illustrated in Table 1.
X-ray computed tomography (General Electric Measurement
and Control Solutions, USA), a non-invasive technique was used to
study the foam morphology. The data acquisition and reconstruc-
tion of the image was carried out using Pheonix Datos-X software
and Volume Graphics-Studio max which was eventually used to
create two dimensional slices of the 3D image. Image J software
was used to process the image which led to distinguishing the cells
and quantification. Fig. 4. FTIR spectrum of foam (25 vol% of HfTb) before ablation.
The cylindrical foams were ablated using an oxyacetylene torch.
The foams obtained from 5, 15 and 25 vol% of HfTb were exposed
to the flame at three different temperatures ie., 1400, 1500 and
trometer (EDS) of AMETEK Process and Analytical Instruments) in
1600◦ C and the samples hereafter will be referred as AXXXXXX
order to determine the compositional changes, if any has occurred
where first two digit refers to vol% of HfTb and the last four digits
after ablation. A small portion of the exposed foam was crushed
denote the ablation temperature. The sintered pellet was ablated at
into fine powders and was analyzed using X-ray diffraction (XRD)
a constant temperature of 1600◦ C. All the results discussed further
(Bruker Discover D8, USA) and attenuated total reflectance (ATR)
will be based on a representative ablation temperature of 1600◦ C.
(Bruker Alpha Platinum, USA).
In order to maintain a uniform flame temperature the ratio of
oxygen to acetylene was varied, maintaining the distance between
nozzle tip and sample as 10 cm. All the samples were ablated for
3. Results
90 s and the surface temperature was observed using an optical
pyrometer which can measure in the range of 600–3000◦ C (Raytek-
3.1. X-ray tomography
Marathon series, USA) with an accuracy of 20◦ C.
The mass loss after ablation was measured from which the mass
The foams were subjected to X-ray tomography to inspect the
ablation rate was calculated using the following expression
cell morphology as well as to quantify the porosity. Fig. 1a, b and
mo − mt c represent a 2D front view of the foam produced from 5, 15 and
Rm = (1)
t 25 vol% HfTb and suggests that the cell walls are interconnected.
where Rm is the mass ablation rate, m0 and mt are mean mass mea- A representative three dimensional view of the foam derived from
sured before and after ablation respectively and t is the ablation 25 vol% HfTb is shown in Fig. 1d. The cell size distribution of the
time. The samples were observed using scanning electron micro- foams were determined and represented in the form of histogram
scope (SEM) (FEI Quanta 200, USA) and elemental analysis was in Fig. 2. The average cell size assuming it to be spherical in shape
performed (lithium doped silicon energy dispersive X-ray spec- was found to be in the range of 0.7–1.15 mm.
3720 W.A. Eranezhuth et al. / Journal of the European Ceramic Society 36 (2016) 3717–3723
Fig. 5. ATR spectra of A051600, A151600 and A251600 foams.
Fig. 6. XRD of the sintered pellet before and after ablation.
3.2. Mass loss
Fig. 3 illustrates the ablation resistance of the samples after 90 s.
The mass ablation rate of A251600 was 1.22 × 10−3 g/s which is
significantly lower when compared to A051600 (11.44 × 10−3 g/s).
The mass ablation rate of the sintered pellet was found to be
1.33 × 10−3 g/s.
3.3. Phase evolution and spectroscopic analysis
The X-ray diffractograms of the foams were found to be amor-
phous in nature before and after ablation. A representative FTIR
spectrum of the foam produced from 25 vol% HfTb before ablation is
shown in Fig. 4. The broad peak in the range of 800–1100 cm−1 cor-
respond to the overlapping peaks from the vibrations of Si C, Si N
and Hf C N bonds [30] and the peak at 1639 cm−1 corresponds to
C C bond. Since the ablated foams were X−ray amorphous, ATR
was used to study the bonding characteristics of the ablated foams.
Fig. 5 exemplifies the ATR spectra of the ablated foams and the
peaks observed at 770 and 665 cm−1 in the spectra were attributed
to the presence of Hf-O peaks [31].
However, the X-ray diffractogram (Fig. 6) of the sintered pellet
before exposure indicated the presence of hafnium nitride (HfN),
silicon carbide (SiC) and silica (SiO2 ) in contrast to the amor-
phous character of the foams. The high intense peaks at 2␪=34.3◦ ,
35.6◦ and 26.6◦ for HfN, SiC and SiO2 respectively confirmed the
presence of the aforementioned phases. After ablation, the appear-
ance of peaks at 2␪ = 28.3◦ , 31.6◦ and 34.3◦ indicated the formation
of monoclinic hafnia.
3.4. Microstructural analysis
The SEM of A051400 foam (Fig. 7a) showed SiO2 layer with
bubbles formed over it where as in all the other ablated foams,
the presence of hafnium enriched layers (possibly hafnia) along
with silica layer and bubbles were visible. Fig. 7b and c shows the
A251600 foam in secondary electron (SE) and backscattered image
(BSE) mode respectively.
The scanning electron micrographs in Fig. 8 exemplify mor-
phological differences in different regions of the ablated sintered
sample. These regions can be distinguished by an inner zone, a tran-
sition zone and an outer zone based on the morphological features.
The inner zone (inner dotted circle) exhibits discontinuously dis-
tributed hafnia layers along with SiO2 layer. In addition to this, a
central crack was also observed in the inner zone which extends till
the outer zone. The transition zone located within the two dotted
circles exhibits a highly porous silica layer along with discontin-
uous patches of hafnia. The outer zone, however, is completely
characterized by the bubbles of silica formed over the silica layer.
4. Discussion
4.1. Ablation mechanism
As evident from the X-ray diffractograms and FTIR spectrum,
the amorphous foam before ablation comprises of Hf C N, Si C,
Si N and C C bonds. These bonds on exposure to oxyacetylene
flame (>1300◦ C) are expected to dissociate and form their respec-
tive oxides. As observed from the SEM, the hafnium enriched layer
might have formed as a result of splitting of Hf C N bonds while
the dissociation of Si C and Si N bonds might have led to the for-
mation of SiO2 layers. All these processes are accompanied by the
evolution of COx and NOx gases. The splitting of C C also results in
the release of COx gases. The escape of these gases contributes to
the mass loss as noticed in these foams after ablation. The residual
oxide layers formed on the surface are X-ray amorphous since the
high specific surface area of the foam could have resulted in high
heat dissipation rate, thus inhibiting the crystallization of these
oxides. Since fragmentation was not observed in any of the ablated
foams, it can be confirmed that these foams possess extremely high
thermal shock resistance and mechanical stability.
The foams remained amorphous after ablation whereas in the
case of the sintered pellet, the crystallization of monoclinic haf-
nia was observed. The possible reactions which can occur when
a sintered pellet is ablated are listed below. The Gibbs energy of
these reactions as a function of temperature was plotted using HSC
Chemistry 8 software as shown in Fig. 9.
C + O2 → CO2 (R1)
1
C+ O2 → CO (R2)
2
C + CO2 → 2CO (R3)
SiC + O2 → SiO (g) + CO (R4)
3
SiC + O2 → SiO2 (l) + CO (R5)
2
 W.A. Eranezhuth et al. / Journal of the European Ceramic Society 36 (2016) 3717–3723 3721

Fig. 7. SEM of (a) A051400, (b) A251600 (SE mode) and (c) A251600 (BSE mode).

Fig. 8. Scanning electron micrographs of sintered pellet after ablation exhibiting three different zones which are distinctly characterized by the morphological features.
3722 W.A. Eranezhuth et al. / Journal of the European Ceramic Society 36 (2016) 3717–3723
Fig. 9. Gibbs energy of the possible reactions during ablation of sintered pellet.
SiC + 3CO2 → SiO2 (l) + 4CO
3 Si-Hf-C-N(O) foams with varying hafnium precursor content
HfN + O2 → HfO2 + NO
2
HfN + 2O2 → HfO2 + NO2
It can be observed that at 1600◦ C all the reactions are possible
since their Gibbs energy of reaction is negative as seen in Fig. 9. The
most spontaneous reaction will be R5 followed by R7, R4, R6 and R8.
Hence, this confirms that during ablation, hafnia and liquid silica
forms on the surface along with the evolution of gases such as CO,
CO2 , SiO and NOx . The release of these gases along with mechanical
denudation and chemical erosion could be the possible reason for
the mass loss in the pellet. These observations from thermodynam-
ics will be useful in correlating the results obtained from structural
characterization.
X-ray diffractogram of the sintered pellet after ablation confirms
the oxidation of HfN to monoclinic HfO2 . Careful observation of the
diffractogram, reveals the presence of an amorphous hump at lower
angles (<25◦ ). This feature along with the presence of a grey layer
containing Si and O (from EDS but not shown) as revealed from SEM,
confirms the formation of amorphous SiO2 layer. This amorphous
layer can be expected to form since the sample rapidly dissipates
heat at a high cooling rate and thus not allowing sufficient time
for the formation of crystalline SiO2 from its melt. The small pores
in amorphous SiO2 and the patchy HfO2 layer might be due to the
release of gases during ablation.
In the inner zone, the formation of crack could be attributed
to the thermal shock experienced by the sample. In the outer
zone, where the temperature is much lower compared to the other
regions, stable bubbles were observed over the silica layer due to
the entrapment of gases. Since the temperature was lower in this
region, the viscosity of silica (liquid flowing from the transition
zone) will increase, leading to the formation of spherical bubbles
owing to its minimal Gibbs energy [23]. The hafnon (HfSiO4 ) forma-
tion as reported by Shinoda et al. [32] during the oxidation studies
of Si-Hf-C-N(O) composites was not observed in this study. Since
hafnon formation requires high temperature annealing of hafnia-
silica mixture for a longer duration [33], the possibility of hafnon
formation can be ruled out due to the high heating and cooling rates
experienced by the sample during ablation.
(R6) 5. Conclusions
(R7) and compacted pellet produced through PDC route were ablated
using oxyacetylene flame and the following can be concluded.
(R8)
i X-ray tomographic studies revealed well interconnected foams
of cell size in the range of 0.7–1.15 mm. It seems that 25 vol% HfTb
turns out to be an optimal amount to be added to the polysilazane
for obtaining a uniform cell size distribution.
ii The mass ablation rate was found to decrease with increase in
hafnium precursor content and the foams were X-ray amor-
phous before and after ablation.
iii From spectroscopic and SEM analysis of the ablated foams, it
could be inferred that the hafnia and silica layers are formed on
the surface with no fragmentation.
iv Monoclinic hafnia and amorphous silica were formed on the
surface of ablated pellet and the ablation mechanism was pos-
tulated with the aid of thermodynamic calculations.
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