Ceramic International
Ceramic International
Ceramic International
Ceramics International
journal homepage: www.elsevier.com/locate/ceramint
High Temperature Ceramic Laboratory, Department of Materials Science and Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India
Keywords: The demand of a new generation spacecraft component has led to the development of a novel structure, which
Carbon nanotubes (CNT) combines the traits of both functionally graded material (FGM) as well as an ultra-high temperature ceramics
ZrB2-20SiC ceramic (UHTC). Herein, FGM based on the well-established ZrB2-20SiC (vol%) UHTC with the reinforcement of carbon
Functionally graded material (FGM) nanotubes (CNT) is processed via powder metallurgy and spark plasma sintering (SPS). A densely graded mi-
Ultra-high temperature ceramics (UHTC)
crostructure with a crack-free seamless interface is witnessed along the cross-section of the FGM. The CNT in the
Spark plasma sintering (SPS)
Finite element method (FEM)
optimized FGM is found to be efficaciously embedded in the matrix retaining its structure during sintering (at
1850 °C), shown microstructurally and supplemented by Raman spectroscopy. Enhanced mechanical and wear
resistance of the FGM when compared to that of the conventional ZrB2 UHTC is attributed to the dense, crack-
free microstructure and CNT pull-out mechanism. Oxidation test revealed an enhancement in the thermal sta-
bility as the onset of oxide formation starts above 886 °C (i.e. > 30% when compared to that of monolithic
ZrB2). The thermo-structural performance of the processed FGM simulated using finite element method (FEM)
indicated a reduction in the thermal residual tensile stresses (~ 8.1 times) which mitigates the crack propaga-
tion. The FEM analysis complements the high indentation fracture toughness values of the FGM even at the
interfaces (similar to that found in each layer), establishing FGM approach superior to that of the conventional
UHTC composites. Thus, addition of CNT in ZrB2-20SiC based FGM are conducive enough to be engineered as a
potential material, poised to shape the future of re-entry vehicles.
1. Introduction ZrB2 ceramic has been circumvented via adopting spark plasma sin-
tering (SPS, at ~0.5 Tm) technique, which further reduces the sintering
Hypersonic re-entry vehicles undergo aerodynamic drag and are temperature with reinforcements of silicon carbide (SiC) and carbon
subjected to extreme heat fluxes where the temperature of the surface nanotube (CNT) [13,15], etc. The extensive research on these materials
can exceed 2400 °C [1–3]. Improved technologies and materials, cap- ascertain that ZrB2-20SiC (vol%) is an optimal material for ultra-high
able of operating at ultra-high temperatures under the conditions of temperature applications [13,16] with improved thermo-mechanical
aerodynamic heating, need to be developed. In this regard, the mod- performance compared to that of monolithic ZrB2. However, the in-
ifications of the classical ceramics composites: such as C/C, SiC, and satiable demand to further improve its damage tolerance has led the
SiC/C etc. have been incorporated with ultra-high temperature cera- researchers to add graphene platelets [17,18], CNT [13,15,19], ZrO2
mics (UHTC) to significantly increase the oxidation resistance without [20], carbon fibres [21], boron nitride (BN) [22] etc. Among them, CNT
sacrificing their thermo-mechanical performance [1,4,5]. has been regarded as a promising reinforcement due to its high me-
Among UHTCs, ZrB2 ceramic, owing to low density (6.09 g/cc), high chanical properties and thermal conductivity. Recently [13,15], the
melting point (3245 °C), high electrical and thermal conductivities addition of CNT (10 vol%) in ZrB2-20SiC has not only suppressed the
(2.17 × 107 S/m [6] and 60–120 W mK [7], respectively) and chemical crack formation via crack deflection and pull-out mechanisms (in-
inertness, has gathered attention for ultra-high temperature applica- dentation fracture toughness increases up to 1.5 times), but also im-
tions where damage tolerance [8–10], resistance to oxidation [11–13] proved the thermal stability (temperature of oxide formation shifts
and wear [9,14] are issues of concern. The problem of sinterability in from 679 °C to 706 °C) which is attributed to the enhanced thermal
⁎
Corresponding authors.
E-mail addresses: ambreen.nisar@ubc.ca (A. Nisar), kbalani@iitk.ac.in (K. Balani).
1
Current address: School of Engineering, The University of British Columbia, Kelowna V1V 1V7, Canada.
2
Current address: National Institute of Technology Srinagar 190006, India.
https://doi.org/10.1016/j.ceramint.2018.12.097
Received 18 September 2018; Received in revised form 8 November 2018; Accepted 13 December 2018
Available online 20 December 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
A. Nisar et al. Ceramics International 45 (2019) 6198–6208
conductivity (from 42.3 W/mK to 52.3 W/mK at 1200 °C) and oxidation contains 0, 5 and 10 vol% of CNT, respectively, in a systematic con-
resistance via grain sealing mechanism. figuration (each layer ~ 1 mm thick), as presented in Table 1. Each
During applications under extreme temperatures, the region of the powder mixture was dry ball milled for 8 min at 500 rpm using tungsten
UHTC (or their reinforced composites) in direct contact with the severe carbide jar and tungsten carbide balls, with the ball to powder weight
environment needs to possess high thermal conductivity, thermal ratio of 5:2. The mixture was, then, weighed and poured in the graphite
shock, oxidation and wear resistance, whilst the other end should ex- die (~ 15 mm) lined with a graphite sheet (as per the stacking sequence
hibit lower thermal conductivity to protect the underlying material. In displayed in Table A1) and manually pressed. The FGMs were, then,
this regard, designing a gradient material may substantially decrease sintered using spark plasma sintering (SPS, Dr. Sinter, SPS-515S, Japan)
the interfacial thermal stress and effectively extend the working tem- at 1850 °C by holding 10 min with a heating rate of 100 °C/min. The
perature range up to 2400 °C [23,24]. The aspiration of the functionally samples were then cooled at the rate of 50 °C/min to obtain a final
graded material (FGM) is to utilize the individual attributes of the pellet of 15 mm diameter and 3 mm thickness. The schematic of the
constituting materials to form a potentially new and improved combi- FGM processing is shown in Fig. 1.
nation in a wide array for structural applications. The graded compo-
sition in the multi-layered structure for the wide range of the applicable 2.2. Characterization
materials (and its compositions) can be controlled by the powder me-
tallurgy techniques. A different composition for each of the layer in the The bulk density of the intact FGM is measured via Archimedes
FGM is difficult to be sintered at the same temperature because of their method (using ethanol as an immersion medium) on a hydrostatic
different optimal sintering temperatures. However, SPS has proved to balance. Phase analysis of the FGM was carried out using PanAnalytical
be a remarkable technique for fabricating materials with graded com- X-ray diffractometer operated at 25 kV and 15 mA (Cu Kα, λ = 1.54 Å
position [23,25]. In this perspective, engineering a layered FGM of at a scan speed of 0.5 s/step and a step size of 0.02°) in the 2θ range
ZrB2-based ceramic composites become a need for satisfying such de- from 20° to 90°. In order to obtain the microstructural evolution of each
manding requirements. The idea behind calling these multi-layered layer, the cross-section of the FGM was polished and analyzed by field
structures as functionally graded is due to an expected heterogeneity in emission scanning electron microscope (FESEM, JSM-7100F, JEOL,
the microstructure created by reinforcements of different shape, con- Netherlands), coupled with an energy dispersive X-ray micro-analyzer
tent, and sizes with different properties (i.e. SiC and CNT) in a con- (EDS, Oxford Instruments, UK).
tinuous fashion. Such a distribution leads to a gradient change in the The mechanical properties (hardness and elastic modulus) of the
mechanical properties and, thus, eliminates the stress concentration polished cross-sectional surface was measured using an instrumented
generally encountered in the conventionally processed laminated micro indenter (MHT, CSM Instruments, Germany). The load function
composites. comprises loading to 2 N (at a rate of 4 N/min and holding at maximum
The detailed study of individual compositions, reported in the re- load for 10 s) followed by unloading at the same rate (of 4 N/min) using
cent literature [13,15], has impelled the authors for designing ZrB2- Vickers’ indenter of type V-I51. Further, the indentation fracture
20SiC based FGM in the present work. Herein, the aim is to fabricate a toughness was calculated at a loading of 19.6 N load using the universal
multi-layered functionally graded structure of ZrB2-20SiC UHTC with hardness testing machine (FH-10, Tinius-Olsen Ltd.) with a dwell time
CNT reinforcement (in 0, 5 and 10 vol% for different layers) to tailor its of 10 s. The crack lengths were measured using SEM from the center of
microstructure and thermo-mechanical performance. The design of the indents and fracture toughness was computed employing Anstis equa-
FGM has further been asserted by analyzing its thermo-structural be- tion [26]:
havior using the finite element method (FEM) to simulate the genera-
tion of thermal residual stresses at the interfaces. Based on the concept, E P
KIC = 0.016
the thermo-mechanical performance of the FGM has been compared H c 3/2 (1)
with the conventional UHTC component. The exceptional performance where c is the crack length, E is the elastic modulus and H is the
of the FGM, as discussed later, strongly endorse its application as hardness (measured experimentally) of the FGM. An average of five
leading edge in a reusable space vehicle. values is reported for each layer in FGM. The measurement of the cri-
tical energy release rate, GIC is calculated using the following equation
[27]:
2. Experimental procedure
1 2
2
2.1. Materials and method G IC = KIC
E (2)
Commercially available raw powders of ZrB2 (H. C. Starck, where is the Poisson’s ratio calculated using the rule of the mixture for
Germany, purity > 99.9%, particle size < 2 µm), SiC (H. C. Starck, all composites [8].
Germany, purity > 99.9%, particle size < 1 µm) and multi-walled Micro-scratch tester (MHT, CSM Instruments, Germany) with a
carbon nanotubes (CNT, Nanostructured and Amorphous Materials Inc., Rockwell indenter (tip radius = 0.1 mm) under constant loading con-
TX, USA, purity > 94%, outer diameter of 50 nm, inner diameter of dition of 20 N and scratch length of 2 mm was utilized to measure the
30 nm, and 1–2 µm long) were procured to prepare the FGM. The de- wear resistance of the FGM. Based on the test, the wear volume (WVS) in
tails of the initial powder compositions can be found in the recent re- scratch can be obtained as:
port [13,15]. The optimization and successful formulation of the FGM WVS = AL (3)
with their compositions have been summarized in Table A1. Con-
d
sidering ZrB2-20SiC as a base material, the stepwise graded structure where, A = R2 cos 1 1 R
(R d ) 2Rd d2 is the cross-sectional
Table 1
Composition and theoretical density of the stacking sequence in the SPS processed FGM.
FGM Compositions ρtheo. (g/cc) ρtheo. (g/cc) ρexp. (g/cc)
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area and L is the scratch distance. Three scratches were made on each of
sample and the scratch path was analyzed using scanning electron
microscope (W-SEM, JSM-6010LA, JEOL, Germany) and an optical
profilometer (Bruker GT-KO, UK). The scratch hardness HS was esti-
mated using the equation:
8Fn
HS =
w2 (4)
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Fig. 3. (a): XRD pattern and (b) Raman spectra showing TO and LO peaks of
SiC as well as D and G peaks of CNT in the SPS processed FGM.
Fig. 4. (a): SEM image showing microstructural evolution of FGM, arrows mark
CNT retains its structure even after SPS processing (shown micro- compositional change, micrograph of each layer in the FGM (b) layer 1-Z20S,
structurally in Fig. 4). (c) layer 2-Z20S5C, (d) layer 3-Z20S10C, (e) micrograph showing the presence
The layered architecture of the SPS processed FGM, as shown in of CNT at intragranular regions of ZrB2 and SiC.
Fig. 4a elicits that the microstructure is fully dense, with a homo-
geneous distribution of SiC (darker phase) and CNT (black patches) in (SiC and CNT) and presence of CNT at the interface may govern the
each scale. No cracks in each of layer or even at the interface due to the mechanical properties of the processed FGM, discussed in the following
CTE mismatch were observed, which also prove a high interfacial section.
compatibility and a high relative densification of the processed FGM,
Fig. 4. The thickness of each layer varied from 0.95 mm to 0.99 mm (see
Table 2). The microstructure evolution of each layer is shown in 3.3. Mechanical properties
Fig. 4b-d and is analogous to that reported in the previous report
[13,15]. The structural integrity of the FGM was assessed in terms of the
The presence of CNT at the grain interface of ZrB2 and SiC is evident hardness and elastic modulus, tabulated in Table 3, are calculated from
from the micrograph shown in Fig. 4e. No significant change in the the load vs displacement graph (as shown in Fig. 5a) using Oliver-Pharr
average grain size (~ 1.8–2 µm) of each layer in the FGM has been indentation method. The hardness and modulus vary with the position
observed with CNT addition, calculated from the fractographs using along the gradient direction, see Fig. 5b. The hardness was found to
linear intercept method. The uniform distribution of the reinforcements gradually increase along the gradient direction from ~20 to 23 GPa and
~ 27 GPa with the addition of CNT (0, 5 and 10 vol%, respectively). The
Table 2
Raman peak corresponding to SiC and CNT as well as the thickness of each layer in the SPS processed FGM.
FGM layer SiC peaks (cm−1) CNT peaks (cm−1) ID/IG Thickness of layer (mm)
TO LO D G
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Table 3 Based on the maximum depth (hm) and final depth (hf) of indenta-
Mechanical properties of the consecutive layers in the SPS processed FGM. tion, the plasticity index (re) i.e. the elastic recovery of the FGM is given
FGM layer HV (GPa) E (GPa) H/E re KIC (MPam0.5) GIC ratio by the relation:
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Fig. 6. (a): Optical micrograph of the overall scratch at a constant load of 20 N; (b) Optical profilometry of the scratch; (c) depth profile of the scratch; SEM
micrograph of the scratch in the regions of (d) layer 1, (e) layer 2 and (f) layer 3; (g-h) high magnification images showing scratch traces at the interface of ZrB2, SiC
and CNT (i) high magnification image of the marked region in (h).
each layer as well as at the interfaces was observed in the micro- hardness (Table 3), the pull-out mechanism (microstructurally shown in
structure, see Fig. 6g-i. The presence of only trivial scratch traces was Fig. 4e, Fig. 6h and i) and the lubricating nature of CNT [9,32] which
observed in the first layer (Fig. 6g), which fades away as we move to- restricts the wear of the material during scratch testing.
wards the CNT rich region (Fig. 6h). The result reveals that dry particle In order to correlate the dependence of bulk mechanical properties
abrasion is the dominant wear mechanism during the scratch test of with the macro-wear properties, a theoretical model is utilized to cal-
processed FGM. This behavior has been attributed to an enhanced culate the hardness from the scratch test (see Eq. 4). The scratch
Table 4
Scratch parameters of the constituent layers in the SPS processed FGM at a constant load of 20 N.
FGM layer Scratch width, Scratch Roughness, Ra (μm) Wear Wear Wear volume Fracture Wear rate Critical
w (μm) hardness, depth constant, k × 10−2 (mm3) toughness (mm3 N−1 m−1) pressure, PC
HS (GPa) As processed After (μm) exponent, a (GPa)
scratch
test
Layer 1 51.4 ± 1.6 20.9 ± 1.2 ~ 0.27 ~ 0.43 1.06 0.029–0.035 2.76 ± 0.09 1.36–1.38 0.68 ± 0.04 5.6–6.9
Layer 2 46.3 ± 1.0 23.8 ± 0.9
Layer 3 45.6 ± 1.3 25.1 ± 1.0
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plies improved abrasion resistance of the processed FGM. ZrB2 24 679.3 ± 6.4 [13]
The modified Evans Marshall equation (see Eq. 7) [34] illustrates Z20S 5 718.5 ± 3.8
the dependence of mechanical properties (hardness and fracture Z20S10C 2 706.3 ± 2.1
toughness) with the wear volume of the material. FGM 1 886.1 ± 3.2 Present study
ln(Wv HSb)
a=
lnKIC (7) formation of oxide layers of the SPS processed FGM up to 1500 °C is
shown in Fig. 7. It is worthy to note that the mass gain is < 1% up to
where a is the fracture toughness exponent (ranges between 1.36 and 1500 °C and the onset of rapid weight change starts above 886 °C
1.38), which determines the wear volume loss and b is known as (Table 5). The oxidation of each layer in the FGM component, reported
hardness exponent and chosen as 1.5 for ceramics [34]. CNT content in the literature [8] is compared to that of the processed FGM, see
and dispersion (it is noteworthy that the aspect of agglomeration may Table 5. The shift to the higher onset temperature of oxide formation in
be neglected, as discussed in the recent literature [13,15]) not only FGM, when compared to each layer of the FGM (Table 5) shows that the
reinforce the ZrB2-20SiC (as a matrix) but, also resist abrading inter- resistance to oxidation increases in case of the processed FGM when
faces by CNT pull-out and lubrication (Fig. 6h and i). In the present compared to that of conventional UHTCs.
case, since the average initial roughness of the sample is very low The preliminary oxidation studies establish the superiority of the
(~ 0.27 µm) therefore, its effect on the fracture toughness exponent can processed FGM over conventional ZrB2-ceramics. But, further study,
be neglected [34]. which closely approximates an intense aero-thermal condition where
Further, the critical pressure (Pc) at which cracking initiate in the the temperature exceeds 2400 °C, is required on this multi-layered
FGM (locally) is coupled with the fracture toughness and friction to- material to reveal the thermo-mechanical performance of the processed
gether with the previously calculated material properties k and a, is FGM. The residual stress due to the relative mismatch in the CTE may
given by the following relation [35]: incur cracking in the material and debonding of the interfaces. The
b +1
b
a
residual stress distribution can affect the mechanical property of the
kFn W v b material, against which the distribution of thermal residual stresses,
Pc =
4.5 arising from the difference in composition of each layer in the processed
1 + 10f ao (8) FGM at high temperature, has been simulated using FEM in the fol-
lowing section.
where ao (taken as 1 µm) is the particle size. Putting the known values
in the above equation, the critical pressure that initiates cracking in the
material lies in the range of 5.6–6.9 GPa (see Table 4). Regardless of the 3.6. Stress distribution in FGM
fact that the initial contact of the indenter tip induces pressure of a few
GPa (high enough to initiate crack) [34,35], it is noteworthy that no The thermo-structural stability of the FGM component depends on
micro-cracking was observed in the FGM (microstructurally shown in the internal stresses that develop when the sample temperature is raised
Fig. 4). An enhanced mechanical property of the FGM together with the up to 2400 °C. Herein, the contributions of thermal residual stresses in
observed CNT pull-out mechanism (which imparts crack-resistance) are FGM, which arise due to the coupling of different phases within and
in good agreement with the numerical calculation of the critical pres- among the layers (incorporating their thermo-elastic properties), have
sure obtained from the wear model. Similar conduct for the Al2O3 re- been isolated. As per the boundary conditions mentioned in Section 2.3,
inforced CNT coatings has been comprehended in the literature [34]. the steady state solution from a homogeneous temperature of 2400 °C to
cooling it down to 25 °C was determined. The stress contours obtained
3.5. Oxidation resistance of the SPS processed FGM from FEM analysis is shown in Fig. 8. Under restricted conditions in
which layer 3 is not allowed to deform, the distribution of stresses was
The oxidation behavior in terms of the weight change due to the tensile in Z20S10C layer (with max. stresses ~ 5.4 MPa, Fig. 8a) and
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Fig. 8. The principal stress contour (right) and stresses distribution along the thickness direction (left) under restricted deformation in (a) layer 3 (b) layer 1 and (c)
along the circumference.
compressive in Z20S layer (in the range of 0.6–0.9 MPa, Fig. 8a). The Fig. 8a and b) and thus, lowers the tensile stresses in the material.
observations were reversed by inverting the condition i.e. when layer 1 However, under restricted condition along the circumference, the
is not allowed to deform. In such a case, the stresses were tensile at the compressive stresses are accumulated at the periphery of the disk (with
periphery of the Z20S layer (~ 4.91 MPa, Fig. 8b) which linearly varied max. stress of ~ 10 MPa in layer 2 Fig. 8c) whereas layer 1 and layer 3
along the thickness direction and then showed compression in Z20S10C experience an equal magnitude of stress ranging from 2 MPa to 6 MPa,
layer (~ 0.7 MPa, Fig. 8b). When restriction (at 2400 °C) is reduced, the Fig. 8c). As far as the distribution of stresses along the thickness in the
sample relaxes stress by bending (as seen from the stress contours, central region is concerned, all the three layers exhibit same magnitude
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(~ 2 MPa) of stresses with their nature being compressive, which re- 4. Conclusions
sisted the FGM from delamination at interfaces (see Fig. 4a). It is im-
portant to note that the tensile stresses at both the extreme layer are not A functionally graded composite design consisting of ZrB2-SiC-CNT
high enough to create deformation (< 4.5 MPa) in the material. This composites were successfully fabricated using SPS, which is achieved
can be further supported by the observations that the change in stress is through careful tailoring of the stacking sequence and processing con-
so high that the compression at the periphery changes to tension ditions. The individual layer in the FGM was observed to be well de-
~ 4 MPa from the periphery to the center line, leading to crack free fined with straight interfaces and no significant residual porosity. The
surfaces and interfaces (after processing, see Fig. 4). It can also be ob- hardness, modulus, and gradual increase in indentation fracture
served that the restricted surface is usually tensile which gradually toughness mapped well with increased CNT content in the graded
change to compressive stresses with an increase in distance from the structure (i.e. from 20.2 GPa to 27.3 GPa; 448–498 GPa and 6.4
restricted surface to the interface. Also, the stresses abruptly change MPam0.5 to 10.0 MPam0.5, respectively). This augmentation in the
their nature from tensile to compressive near the edge of the specimen. mechanical properties with CNT reinforcement has been attributed to
Since cracks are suppressed in the regions of compressive stress, the CNT pull-out mechanism. The processed FGM exhibited higher wear
which then restricts crack propagation, and results in crack-free sur- resistance with a wear rate of ~ 0.68 mm3 N−1 m−1, which is attrib-
faces and interfaces, as observed from the microstructure shown in uted to an enhancement in the mechanical properties with CNT re-
Fig. 4. Hence, it can be anticipated from the study that FGM would be inforcement. Thermal studies up to 1500 °C showed minimal weight
able to withstand the thermal shock (at least up to 2400 °C). Future gain (> 1%) and the temperature of oxide formation shifted towards
work could involve experimental verifications of these results by testing higher temperature (~ 886 °C) when compared to that of conventional
the multi-layered architecture in the ultra-high temperature regime ZrB2 ceramics (~ 679 °C). The computational results suggested that
under intense plasma conditions or wind tunnel with fuel injection and microstructure has a great effect on thermal stress alleviations as FGM
combustion, as the diffusion processes are strongly dependent on the is proved to be better than conventional UHTCs. Indicative calculations
temperature and it is of primary importance to establish operating of the residual stresses confirm that the presence of low tensile stresses
limits for these kind of UHTC composites. (< 0.7 MPa) at the interfaces were not enough to create delamination
As a closure, it is worthwhile to emphasize the benefits of FGM of the interface, which supplements the inference that interfaces possess
approach over conventional UHTC composites. In summary, the sche- similar fracture toughness values when compared to that of their vici-
matic illustrating the overall findings has been presented in Fig. 9. The nity. In light of this, the preliminary characterization of the processed
systematic addition of CNT (0, 5 and 10 vol%) in conventional Z20S FGM demonstrates to be an efficient method to obtain tough ultra-high
UHTC has led to the gradual enhancement in the mechanical properties temperature ceramic composite with improved oxidation resistance.
of the graded material via well-established crack deflection, pull-out
and branching mechanisms of CNT. An enhancement in the wear re-
sistance has been attributed to the reinforcement rendered by CNTs Acknowledgments
against the indenter. Further, the generation of compressive stresses in
the FGM when it is brought from 2400 °C to room temperature can Authors at Indian Institute of Technology Kanpur (IITK) acknowl-
abate cracks growing through interfaces and thus, establish the sus- edge the financial support received from IITK-Space Technology Cell
tainability of these materials under ultra-high temperatures. The im- and Indian Space Research Organisation (ISRO), Trivandrum, India.
proved oxidation resistance during the primary oxidation test (up to Authors also acknowledge the support from the Advanced Center for
1500 °C) with negligible weight gain has also been established. Thus, Materials Science (ACMS) at IITK for extending characterization facil-
the enhanced thermo-mechanical performance of FGM gives them an ities (SEM and instrumented indentation testing). KB acknowledges
edge over conventional UHTCs to be used as a potential high-damage Swarnajayanti Fellowship (DST/STF/ETA-02/2016-17).
tolerant structural material
Appendix
Fig. A1. The figure elicits the structural boundary conditions used in the FEM calculations. Under the restricted condition, the bottom of the sample was fixed in (a)
layer 3 and (b) layer 1 (c) along the circumference.
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Table A1
Stacking sequence composition and processing conditions of spark plasma sintered FGM.
Based on the recent work by authors [13,15] on ZrB2-based UHTC composites, herein, ZrB2 was reinforced with different compositions depending
on the specific function (which serves as a sintering aid, enhancement in the thermo-mechanical properties): the outermost layer contained 20 vol%
of SiC and 10 vol% of CNT (labelled as Z20S10C); followed by 20 vol% of SiC and 5 vol% CNT (Z20S5C) was added in the intermediate layer, whilst,
to avoid spallation in the pellet due to CTE mismatch; and an inner layer with 20 vol% of SiC (labelled as Z20S) on ZrB2. Herein, the authors have
played with the composition which suggested that Z10C layer (probably due to CTE mismatch) has led to the spallation in the FGM even if the
samples were prepared with a controlled cooling rate of 50 °C/min (to avoid thermal shock due to default rapid cooling of ~ 600 °C/min during SPS).
Hence, the characterization of the intact sample has only been studied in the present finding.
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References thermal shock resistance of ZrB2–SiC ceramic toughened with graphite flake and
SiC whiskers, Scr. Mater. 61 (2009) 809–812.
[19] W.-B. Tian, Y.-M. Kan, G.-J. Zhang, P.-L. Wang, Effect of carbon nanotubes on the
[1] N.P. Padture, Advanced structural ceramics in aerospace propulsion, Nat. Mater. 15 properties of ZrB2–SiC ceramics, Mater. Sci. Eng.: A 487 (2008) 568–573.
(2016) 804. [20] D. Chen, W. Li, X. Zhang, P. Hu, J. Han, C. Hong, W. Han, Microstructural feature
[2] D. Lahiri, V. Singh, G.R. Rodrigues, T.M.H. Costa, M.R. Gallas, S.R. Bakshi, S. Seal, and thermal shock behavior of hot-pressed ZrB2–SiC–ZrO2 composite, Mater.
A. Agarwal, Ultrahigh-pressure consolidation and deformation of tantalum carbide Chem. Phys. 116 (2009) 348–352.
at ambient and high temperatures, Acta Mater. 61 (2013) 4001–4009. [21] F. Yang, X. Zhang, J. Han, S. Du, Characterization of hot-pressed short carbon fiber
[3] W.G. Fahrenholtz, G.E. Hilmas, Ultra-high temperature ceramics: materials for ex- reinforced ZrB2–SiC ultra-high temperature ceramic composites, J. Alloy. Compd.
treme environments, Scr. Mater. 129 (2017) 94–99. 472 (2009) 395–399.
[4] W.G. Fahrenholtz, E.J. Wuchina, W.E. Lee, Y. Zhou, Ultra-High Temperature [22] Y. Chen, D. Zhao, F. Qi, W.W. Liu, Scratch behavior of boron nitride nanotube/
Ceramics: Materials For Extreme Environment Applications, John Wiley & Sons, boron nitride nanoplatelet hybrid reinforced ZrB2-SiC composites, Ceram. Int. 44
2014. (2018) 3277–3281.
[5] M. Pavese, P. Fino, C. Badini, A. Ortona, G. Marino, HfB2/SiC as a protective [23] X. Zhang, W. Li, C. Hong, W. Han, J. Han, A novel development of ZrB2/ZrO2
coating for 2D Cf/SiC composites: effect of high temperature oxidation on me- functionally graded ceramics for ultrahigh-temperature application, Scr. Mater. 59
chanical properties, Surf. Coat. Technol. 202 (2008) 2059–2067. (2008) 1214–1217.
[6] M. Mallik, A.J. Kailath, K.K. Ray, R. Mitra, Electrical and thermophysical properties [24] L. Silvestroni, C. Capiani, D. Dalle Fabbriche, C. Melandri, Novel light and tough
of ZrB2 and HfB2 based composites, J. Eur. Ceram. Soc. 32 (2012) 2545–2555. ZrB2-based functionally graded ceramics, Compos. Part B: Eng. 99 (2016) 321–329.
[7] J.W. Zimmermann, G.E. Hilmas, W.G. Fahrenholtz, R.B. Dinwiddie, W.D. Porter, [25] Da Jayaseelan, Y. Xin, L. Vandeperre, P. Brown, W. Lee, Development of multi-
H. Wang, Thermophysical properties of ZrB2 and ZrB2–SiC ceramics, J. Am. Ceram. layered thermal protection system (TPS) for aerospace applications, Compos. Part
Soc. 91 (2008) 1405–1411. B: Eng. 79 (2015) 392–405.
[8] A. Nisar, K. Balani, Phase and microstructural correlation of spark plasma sintered [26] G.R. Anstis, P. Chantiklul, B.R. Lawn, D.B. Marshall, A critical evaluation of in-
HfB2-ZrB2 based ultra-high temperature ceramic composites, Coatings 7 (2017) dentation techniques for measuring fracture toughness: I, dircet crack measure-
110. ments, J. Am. Ceram. Soc. 64 (1981) 533–538.
[9] A. Nisar, K. Balani, Role of interfaces on multi-length scale wear mechanics of TaC- [27] C. Yue, W. Liu, L. Zhang, T. Zhang, Y. Chen, Fracture toughness and toughening
based composites, Adv. Eng. Mater. 19 (2017) (1600713-n/a). mechanisms in a (ZrB2–SiC) composite reinforced with boron nitride nanotubes and
[10] A. Nisar, A. S, K. Balani, Synergistic reinforcement of carbon nanotubes and silicon boron nitride nanoplatelets, Scr. Mater. 68 (2013) 579–582.
carbide for toughening tantalum carbide based ultrahigh temperature ceramic, J. [28] J. Watts, G. Hilmas, W.G. Fahrenholtz, D. Brown, B. Clausen, Stress measurements
Mater. Res. 31 (2016) 682–692. in ZrB2–SiC composites using Raman spectroscopy and neutron diffraction, J. Eur.
[11] T.A. Parthasarathy, R.A. Rapp, M. Opeka, R.J. Kerans, A model for the oxidation of Ceram. Soc. 30 (2010) 2165–2171.
ZrB2, HfB2 and TiB2, Acta Mater. 55 (2007) 5999–6010. [29] X. Wang, N.P. Padture, H. Tanaka, Contact-damage-resistant ceramic/single-wall
[12] A. Nisar, S. Ariharan, T. Venkateswaran, N. Sreenivas, K. Balani, Oxidation studies carbon nanotubes and ceramic/graphite composites, Nat. Mater. 3 (2004) 539.
on TaC based ultra-high temperature ceramic composites under plasma arc jet ex- [30] R.J. Butcher, C.E. Rousseau, H.V. Tippur, A functionally graded particulate com-
posure, Corros. Sci. 109 (2016) 50–61. posite: preparation, measurements and failure analysis, Acta Mater. 47 (1998)
[13] A. Nisar, S. Ariharan, T. Venkateswaran, N. Sreenivas, K. Balani, Effect of carbon 259–268.
nanotube on processing, microstructural, mechanical and ablation behavior of ZrB2- [31] J. Das, B.C. Kesava, J.J. Reddy, V. Srinivas, S. Kumari, V.V.B. Prasad,
20SiC based ultra-high temperature ceramic composites, Carbon 111 (2017) Microstructure, mechanical properties and oxidation behavior of short carbon fiber
269–282. reinforced ZrB2-20v/oSiC-2v/oB4C composite, Mater. Sci. Eng.: A 719 (2018)
[14] D. Ghosh, G. Subhash, N. Orlovskaya, Measurement of scratch-induced residual 206–226.
stress within SiC grains in ZrB2–SiC composite using micro-Raman spectroscopy, [32] B. Yazdani, F. Xu, I. Ahmad, X. Hou, Y. Xia, Y. Zhu, Tribological performance of
Acta Mater. 56 (2008) 5345–5354. graphene/carbon nanotube hybrid reinforced Al2O3 composites, Sci. Rep. 5 (2015)
[15] A. Nisar, S. Ariharan, K. Balani, Establishing microstructure-mechanical property 11579.
correlation in ZrB2-based ultra-high temperature ceramic composites, Ceram. Int. [33] J.F. Archard, Contact and rubbing of flat surfaces, J. Appl. Phys. 24 (1953)
43 (2017) 13483–13492. 981–988.
[16] L. Zhang, N.P. Padture, Inhomogeneous oxidation of ZrB2-SiC ultra-high-tempera- [34] K. Balani, S.P. Harimkar, A. Keshri, Y. Chen, N.B. Dahotre, A. Agarwal, Multiscale
ture ceramic particulate composites and its mitigation, Acta Mater. 129 (2017) wear of plasma-sprayed carbon-nanotube-reinforced aluminum oxide nanocompo-
138–148. site coating, Acta Mater. 56 (2008) 5984–5994.
[17] X. Zhang, Y. An, J. Han, W. Han, G. Zhao, X. Jin, Graphene nanosheet reinforced [35] D. Casellas, J. Caro, S. Molas, J.M. Prado, I. Valls, Fracture toughness of carbides in
ZrB 2–SiC ceramic composite by thermal reduction of graphene oxide, RSC Adv. 5 tool steels evaluated by nanoindentation, Acta Mater. 55 (2007) 4277–4286.
(2015) 47060–47065.
[18] X.H. Zhang, Z. Wang, P. Hu, W.B. Han, C.Q. Hong, Mechanical properties and
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