Ceramics International 45 (2019) 6198–6208

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Enhanced thermo-mechanical damage tolerance of functionally graded T

ZrB2-20SiC ceramic reinforced with carbon nanotubes
⁎,1
Ambreen Nisar , Mohammad Mohsin Khan2, Kantesh Balani
⁎

High Temperature Ceramic Laboratory, Department of Materials Science and Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India

ARTICLE INFO ABSTRACT

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
Hypersonic re-entry vehicles undergo aerodynamic drag and are
subjected to extreme heat fluxes where the temperature of the surface
can exceed 2400 °C [1–3]. Improved technologies and materials, cap-
able of operating at ultra-high temperatures under the conditions of
aerodynamic heating, need to be developed. In this regard, the mod-
ifications of the classical ceramics composites: such as C/C, SiC, and
SiC/C etc. have been incorporated with ultra-high temperature cera-
mics (UHTC) to significantly increase the oxidation resistance without
sacrificing their thermo-mechanical performance [1,4,5].
Among UHTCs, ZrB2 ceramic, owing to low density (6.09 g/cc), high
melting point (3245 °C), high electrical and thermal conductivities
(2.17 × 107 S/m [6] and 60–120 W mK [7], respectively) and chemical
inertness, has gathered attention for ultra-high temperature applica-
tions where damage tolerance [8–10], resistance to oxidation [11–13]
and wear [9,14] are issues of concern. The problem of sinterability in
ZrB2 ceramic has been circumvented via adopting spark plasma sin-
tering (SPS, at ~0.5 Tm) technique, which further reduces the sintering
temperature with reinforcements of silicon carbide (SiC) and carbon
nanotube (CNT) [13,15], etc. The extensive research on these materials
ascertain that ZrB2-20SiC (vol%) is an optimal material for ultra-high
temperature applications [13,16] with improved thermo-mechanical
performance compared to that of monolithic ZrB2. However, the in-
satiable demand to further improve its damage tolerance has led the
researchers to add graphene platelets [17,18], CNT [13,15,19], ZrO2
[20], carbon fibres [21], boron nitride (BN) [22] etc. Among them, CNT
has been regarded as a promising reinforcement due to its high me-
chanical properties and thermal conductivity. Recently [13,15], the
addition of CNT (10 vol%) in ZrB2-20SiC has not only suppressed the
crack formation via crack deflection and pull-out mechanisms (in-
dentation fracture toughness increases up to 1.5 times), but also im-
proved the thermal stability (temperature of oxide formation shifts
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.
conductivity (from 42.3 W/mK to 52.3 W/mK at 1200 °C) and oxidation
resistance via grain sealing mechanism.
During applications under extreme temperatures, the region of the
UHTC (or their reinforced composites) in direct contact with the severe
environment needs to possess high thermal conductivity, thermal
shock, oxidation and wear resistance, whilst the other end should ex-
hibit lower thermal conductivity to protect the underlying material. In
this regard, designing a gradient material may substantially decrease
the interfacial thermal stress and effectively extend the working tem-
perature range up to 2400 °C [23,24]. The aspiration of the functionally
graded material (FGM) is to utilize the individual attributes of the
constituting materials to form a potentially new and improved combi-
nation in a wide array for structural applications. The graded compo-
sition in the multi-layered structure for the wide range of the applicable
materials (and its compositions) can be controlled by the powder me-
tallurgy techniques. A different composition for each of the layer in the
FGM is difficult to be sintered at the same temperature because of their
different optimal sintering temperatures. However, SPS has proved to
be a remarkable technique for fabricating materials with graded com-
position [23,25]. In this perspective, engineering a layered FGM of
ZrB2-based ceramic composites become a need for satisfying such de-
manding requirements. The idea behind calling these multi-layered
structures as functionally graded is due to an expected heterogeneity in
the microstructure created by reinforcements of different shape, con-
tent, and sizes with different properties (i.e. SiC and CNT) in a con-
tinuous fashion. Such a distribution leads to a gradient change in the
mechanical properties and, thus, eliminates the stress concentration
generally encountered in the conventionally processed laminated
composites.
The detailed study of individual compositions, reported in the re-
cent literature [13,15], has impelled the authors for designing ZrB2-
20SiC based FGM in the present work. Herein, the aim is to fabricate a
multi-layered functionally graded structure of ZrB2-20SiC UHTC with
CNT reinforcement (in 0, 5 and 10 vol% for different layers) to tailor its
microstructure and thermo-mechanical performance. The design of the
FGM has further been asserted by analyzing its thermo-structural be-
havior using the finite element method (FEM) to simulate the genera-
tion of thermal residual stresses at the interfaces. Based on the concept,
the thermo-mechanical performance of the FGM has been compared
with the conventional UHTC component. The exceptional performance
of the FGM, as discussed later, strongly endorse its application as
leading edge in a reusable space vehicle.
2. Experimental procedure
2.1. Materials and method
Commercially available raw powders of ZrB2 (H. C. Starck,
Germany, purity > 99.9%, particle size < 2 µm), SiC (H. C. Starck,
Germany, purity > 99.9%, particle size < 1 µm) and multi-walled
carbon nanotubes (CNT, Nanostructured and Amorphous Materials Inc.,
TX, USA, purity > 94%, outer diameter of 50 nm, inner diameter of
30 nm, and 1–2 µm long) were procured to prepare the FGM. The de-
tails of the initial powder compositions can be found in the recent re-
port [13,15]. The optimization and successful formulation of the FGM
with their compositions have been summarized in Table A1. Con-
sidering ZrB2-20SiC as a base material, the stepwise graded structure
Table 1
Composition and theoretical density of the stacking sequence in the SPS processed FGM.
FGM Compositions
Layer 1 ZrB2 + 20 vol% SiC (Z20S)
Layer 2 ZrB2 + 20 vol% SiC + 5 vol% CNT (Z20S5C)
Layer 3 ZrB2 + 20 vol% SiC + 10 vol% CNT (Z20S10C)
6199
Ceramics International 45 (2019) 6198–6208
contains 0, 5 and 10 vol% of CNT, respectively, in a systematic con-
figuration (each layer ~ 1 mm thick), as presented in Table 1. Each
powder mixture was dry ball milled for 8 min at 500 rpm using tungsten
carbide jar and tungsten carbide balls, with the ball to powder weight
ratio of 5:2. The mixture was, then, weighed and poured in the graphite
die (~ 15 mm) lined with a graphite sheet (as per the stacking sequence
displayed in Table A1) and manually pressed. The FGMs were, then,
sintered using spark plasma sintering (SPS, Dr. Sinter, SPS-515S, Japan)
at 1850 °C by holding 10 min with a heating rate of 100 °C/min. The
samples were then cooled at the rate of 50 °C/min to obtain a final
pellet of 15 mm diameter and 3 mm thickness. The schematic of the
FGM processing is shown in Fig. 1.
2.2. Characterization
The bulk density of the intact FGM is measured via Archimedes
method (using ethanol as an immersion medium) on a hydrostatic
balance. Phase analysis of the FGM was carried out using PanAnalytical
X-ray diffractometer operated at 25 kV and 15 mA (Cu Kα, λ = 1.54 Å
at a scan speed of 0.5 s/step and a step size of 0.02°) in the 2θ range
from 20° to 90°. In order to obtain the microstructural evolution of each
layer, the cross-section of the FGM was polished and analyzed by field
emission scanning electron microscope (FESEM, JSM-7100F, JEOL,
Netherlands), coupled with an energy dispersive X-ray micro-analyzer
(EDS, Oxford Instruments, UK).
The mechanical properties (hardness and elastic modulus) of the
polished cross-sectional surface was measured using an instrumented
micro indenter (MHT, CSM Instruments, Germany). The load function
comprises loading to 2 N (at a rate of 4 N/min and holding at maximum
load for 10 s) followed by unloading at the same rate (of 4 N/min) using
Vickers’ indenter of type V-I51. Further, the indentation fracture
toughness was calculated at a loading of 19.6 N load using the universal
hardness testing machine (FH-10, Tinius-Olsen Ltd.) with a dwell time
of 10 s. The crack lengths were measured using SEM from the center of
indents and fracture toughness was computed employing Anstis equa-
tion [26]:
E P
KIC = 0.016
H c 3/2 (1)
where c is the crack length, E is the elastic modulus and H is the
hardness (measured experimentally) of the FGM. An average of five
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]:
1 2
2
G IC = KIC
E (2)
where is the Poisson’s ratio calculated using the rule of the mixture for
all composites [8].
Micro-scratch tester (MHT, CSM Instruments, Germany) with a
Rockwell indenter (tip radius = 0.1 mm) under constant loading con-
dition of 20 N and scratch length of 2 mm was utilized to measure the
wear resistance of the FGM. Based on the test, the wear volume (WVS) in
scratch can be obtained as:
WVS = AL (3)
d
where, A = R2 cos 1 1 R
(R d ) 2Rd d2 is the cross-sectional
ρtheo. (g/cc) ρtheo. (g/cc) ρexp. (g/cc)
5.5 5.2 5.19
5.3
5.1
A. Nisar et al. Ceramics International 45 (2019) 6198–6208

Fig. 1. Schematic illustrating fabrication of

FGM.

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)

where Fn is the applied load, w is the scratch width. The scratch

hardness is the measure of the wear resistance of the material.
In order to understand the thermal stability of the processed FGM,
an isothermal thermogravimetric analysis was carried out using si-
multaneous thermal analyzer (STA 8000, Perkin Elmer, USA) with an
accuracy of 0.2% and furnace stability of ± 0.5 °C. The sample with an
initial mass of ~ 35 mg was heated from room temperature to 1500 °C
at a rate of 20 °C/min in an oxygen atmosphere for 30 min holding at
Fig. 2. Plot showing the variation of instantaneous densification with time
maximum temperature. The reported value is an average of at least
during SPS processing of the intact FGM.
three experiments.

(increasing trend, step I) due to the rearrangement of powder particles,

2.3. Computational modelling of thermo-structural behavior
The thermo-mechanical performance of the material is governed by
the residual stresses existing in the multi-component system. The re-
sidual stress exits due to difference in coefficient of thermal expansion
(CTE) of matrix and reinforced particles which creates a local com-
pressive stress field in the matrix thus, decreasing the stress intensity
factor. The introduction of compressive stresses at interface provides an
enhanced structural integrity as well as toughness to the material [13].
With reference to the individual behavior of each layer against plasma
arc jet test [12], reported in the recent literature [13], FE modelling has
been carried out to simulate the residual stresses of the SPS processed
FGM using ANSYS Mechanical 15 software (ANSYS, Canonsburg, PA,
USA). The geometry of the samples (disks of 15 mm with ~ 1 mm
thickness of each layer) and the physical properties for each layers such
as Poisson’s ratio, υ (= 0.164); specific heat, Cp (= 446.0, 495.4 and
485.2 J kg−1 K−1, respectively); coefficient of thermal expansion, CTE
(6.14 × 10−6, 5.93 × 10−6 and 5.71 × 10−6 K−1, respectively);
thermal conductivity, κ (67.6, 48.2 and 61.8 Wm−1 K−1, respectively)
[13]; density, ρ, and elastic modulus, E, (as per the present study) were
used for the analysis. The boundary conditions (as shown Fig. A1) were
such that the component is exposed to a homogenous temperature of
2400 °C (which approximately equals the re-entry temperature) and,
consequently, the steady-state stress solution down to room tempera-
ture was determined. The effect of composition on the distribution of
the residual stresses was also elucidated, by first keeping layer 1 on the
top (see Fig. A1a) and then layer 3 in the latter case (see Fig. A1b). In
the first two cases, the bottom layer is restricted to move upwards (see
Fig. A1a) whereas in the third case, the disk was fixed along the cir-
cumference to obtain a comparison with the second case (see Fig. A1c).
3. Results and discussion
3.1. Densification of FGM
The instantaneous densification curve of the SPS processed FGM at
1850 °C is shown in Fig. 2. The recorded punch displacement profile
during sintering reveals three distinct regions, i.e. (i) initial compaction
(ii) intermediate step (decreasing trend, step II) corresponding to the
thermal expansion, and finally, (iii) shrinkage (increasing trend, step
III) corresponding to the final densification as shown in Fig. 2. The
measurable shrinkage starts after 1350 °C, however, no shrinkage was
observed during holding for 10 min at 1850 °C. The experimental data
indicating higher relative densification 99.8% is in agreement with the
general observations made from punch displacements.
3.2. Phase and microstructural evolution of the FGM
XRD pattern of the SPS processed FGM, presented in Fig. 3a elicits
that no new phases, other than the reinforced materials, are observed.
The characteristic peaks of ZrB2 and 6H-SiC were clearly observed,
indicating that SiC is not dissolved in ZrB2 up to the processing tem-
perature of 1850 °C. No peaks corresponding to CNT was detected in
XRD, hence Raman analysis was carried out to elucidate the presence as
well as retention of CNT even after SPS processing at such high tem-
perature (1850 °C) and pressure (30 MPa). Raman spectra (shown in
Fig. 3b) corresponding to each layer in FGM is obtained and compared
with the pristine CNT powder. The peak positions corresponding to SiC
and CNT in each layer of the FGM are compared and presented in
Table 2. In each of the layer, the transverse optic (TO) and linear optic
(LO) peaks corresponding to SiC are respectively observed at
~789.68 cm−1 and ~970.57 cm−1. The observed spectra match well
with that of unstressed SiC particles in which TO and LO peaks are
respectively observed at 789.2 cm−1 and 970.1 cm−1 [28]. It is elicited
from the spectra (see Fig. 3b) that ZrB2, being Raman in-active, showed
no peaks. Further, two distinct peaks of carbon corresponding to D- and
G-peaks were, respectively, observed at 1352.87 cm−1 and
1590.36 cm−1 for the Z20S5C layer and 1352.87 cm−1 and
1590.04 cm−1 for the Z20S10C layer. The shift in the D- and G-peaks in
FGM, when compared to that of pristine CNT powder (1350.58 cm−1
and 1589.13 cm−1, see Table 2), supports the generation of compres-
sive stresses in the material during high temperature (1850 °C) SPS
processing. This observation is similar to that reported in the previous
literature [8,10,12,13]. No significant change in the ID/IG ratio in FGM
(~ 0.98) when compared to that of pristine CNT (~ 0.99) elicits that

6200
A. Nisar et al. Ceramics International 45 (2019) 6198–6208

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.
CNT retains its structure even after SPS processing (shown micro-
structurally in Fig. 4).
The layered architecture of the SPS processed FGM, as shown in
Fig. 4a elicits that the microstructure is fully dense, with a homo-
geneous distribution of SiC (darker phase) and CNT (black patches) in
each scale. No cracks in each of layer or even at the interface due to the
CTE mismatch were observed, which also prove a high interfacial
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
Fig. 4b-d and is analogous to that reported in the previous report
[13,15].
The presence of CNT at the grain interface of ZrB2 and SiC is evident
from the micrograph shown in Fig. 4e. No significant change in the
average grain size (~ 1.8–2 µm) of each layer in the FGM has been
observed with CNT addition, calculated from the fractographs using
linear intercept method. The uniform distribution of the reinforcements
Fig. 4. (a): SEM image showing microstructural evolution of FGM, arrows mark
compositional change, micrograph of each layer in the FGM (b) layer 1-Z20S,
(c) layer 2-Z20S5C, (d) layer 3-Z20S10C, (e) micrograph showing the presence
of CNT at intragranular regions of ZrB2 and SiC.
(SiC and CNT) and presence of CNT at the interface may govern the
mechanical properties of the processed FGM, discussed in the following
section.
3.3. Mechanical properties
The structural integrity of the FGM was assessed in terms of the
hardness and elastic modulus, tabulated in Table 3, are calculated from
the load vs displacement graph (as shown in Fig. 5a) using Oliver-Pharr
indentation method. The hardness and modulus vary with the position
along the gradient direction, see Fig. 5b. The hardness was found to
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

Layer 1 789.68 970.57 N.A. N.A. 0.99 ± 0.01

Layer 2 788.43 971.82 1352.87 1590.36 0.98 0.95 ± 0.02
Layer 3 788.68 971.82 1352.87 1590.04 0.98 0.98 ± 0.01
Pristine CNT N.A. 1350.58 1589.13 0.99 N.A.

N.A. = not applicable.

6201
A. Nisar et al. Ceramics International 45 (2019) 6198–6208

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:

Layer 1 20.2 ± 0.5 448 ± 3.6 0.45 0.35 6.4 ± 1.2 1 hm hf

Layer 2 23.4 ± 1.5 487 ± 4.8 0.48 0.40 9.2 ± 0.7
Layer 3 27.3 ± 0.9 498 ± 5.5 0.54 0.43 10.0 ± 1.1
Fig. 5. (a): A representative load-displacement curve of consecutive layers in
the FGM and (b) Hardness and elastic modulus of the FGM related to distance
from the inner layer to the gradient direction.
average hardness at every corresponding position in each layer of the
processed FGM is very high, which is ascribed to the dense micro-
structure achieved under the high sintering temperature during SPS
processing. The weaker interface in the FGM has always been a chal-
lenge as it restricts their wider applications, generally characterized in
terms of lower hardness near interface [23]. It is to be noted that the
hardness values at each interface were similar to that obtained in the
vicinity of each layer, which affirms that the FGM exhibits a strong
interface. An enhanced hardness of the layers reinforced with CNT has
been attributed to an improved indentation resistance of the composite
provided via grain embedment of CNTs (see Fig. 4e). Similar to hard-
ness, graded variations in the elastic modulus is also exhibited (see
Fig. 5b). The modulus was observed to gradually increase from 448 GPa
to 498 GPa with increasing CNT content in ZrB2-20SiC ceramics. Along
with the graded variation in the microstructure, a consecutive and
graded variation in the properties (hardness and modulus) was also
achieved in the SPS processed FGM. The increase in the H/E ratio from
0.45 to 0.54 with increase in the CNT content (from 0, 5 and 10 vol%,
respectively) in each layer elicits that the resistance to plastic de-
formation increases with CNT addition.
re =
1.9 hm (5)
2.2
An increase in the elastic recovery (0.35–0.43, see Table 3) has
resulted in the higher hardness and modulus of the FGM.
Similar to the hardness and modulus, the indentation fracture
toughness of the FGM is expected to show the graded variation. But,
due to the small thickness of the consecutive layers (~ 1 mm), the
toughness evaluation was restricted within each layer (away from the
interface). For ceramics, the fracture toughness is often tested using a
single-edge notched beam (SENB) [29] on a three-point bend test rig. In
the case of FGM, it becomes difficult to estimate the toughness by SENB
method due to the restriction of sample size. As reported in the litera-
ture [23,30], the indentation method was utilized for the evaluation of
fracture toughness (KIC, using Eq. (1)) as presented in Table 3. The
toughness gradually increased with an increase in the CNT content (see
Table 3). In the first layer, the toughness is ~ 6.4 MPam0.5, which is in
good agreement with the toughness values reported for dense ZrB2-
20SiC ceramics [31]. With the increased content of CNT in the other
layers, the toughness increases via well-established mechanisms such as
CNT pull-out (Fig. 4e), crack-branching, crack-bridging, crack-deflec-
tion and strong interfacial bonding (evidenced microstructurally in the
recent work by authors [15]). The study [15] also revealed that the CNT
addition has contributed up to 1.5 times enhancement in the indenta-
tion fracture toughness of ZrB2-20SiC ceramic, analogous to that ob-
served in the present study. The measurement of modulus and in-
dentation fracture toughness enable us to compute the critical energy
release rate (GIC, using Eq. (2)), see Table 3. In accordance with the
other mechanical properties, the critical energy release rate, GIC, which
is a measure of the energy required to propagate a crack in the material
increases up to ~ 2.2 times with an increase in the CNT reinforcement
(up to 10 vol%) in the graded structure. It is to be noted that the ratio of
GIC is presented (Table 3) to show the gradient in the energy with re-
spect to the change in microstructure in each layer (considering the GIC
value for base layer i.e. Z20S to be unity). This means that when the
crack propagates in the vicinity of CNT reinforced composites, bending
deformation might occur, therefore dissipating more energy. Subse-
quently, the stress concentration within the frontal zone of the crack tip
reduces, which inhibit crack propagation. Since, the properties of the
interfaces are similar to that obtained in the each layer, therefore si-
milar inference can be drawn for the interfaces, leading to a crack free
interface (microstructurally shown in Fig. 4). Based on the mechanical
properties (E, H, KIC etc.) assessment, FGM undertaken in the present
study is proved to be a better performer over conventional ZrB2-based
UHTC ceramics.
3.4. Scratch resistance of the SPS processed FGM
Micro-scratch deformation of the processed FGM was evaluated at a
constant load of 20 N, as shown in Fig. 6. The optical image of the
overall scratch (of 2 mm length) during the test is shown in Fig. 6a. The
wear damage has been assessed quantitatively using optical profil-
ometer in terms of wear volume (calculated from the 3D image, Fig. 6b,
Table 4) and the corresponding wear track profile (for the depth,
Fig. 6c, Table 4) of the scratch. The starting surface roughness of the as-
processed FGM was ~ 0.27 µm, which is increased to ~ 0.43 µm after
the scratch test (see Table 4). The SEM micrographs of the scratched
surface in each layer of the FGM is shown in Fig. 6d-f. The typical
scratch width (Table 4) was observed to decrease from ~ 51.4 µm for
the first layer (Fig. 6d) to ~ 46.3 µm for the second layer (Fig. 6e) and
~ 45.6 µm for the third layer (Fig. 6f) with the increasing content of
CNT. The absence of micro-cracking, spallation or delamination within

6202
A. Nisar et al. Ceramics International 45 (2019) 6198–6208

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-
structure, see Fig. 6g-i. The presence of only trivial scratch traces was
observed in the first layer (Fig. 6g), which fades away as we move to-
wards the CNT rich region (Fig. 6h). The result reveals that dry particle
abrasion is the dominant wear mechanism during the scratch test of
processed FGM. This behavior has been attributed to an enhanced
hardness (Table 3), the pull-out mechanism (microstructurally shown in
Fig. 4e, Fig. 6h and i) and the lubricating nature of CNT [9,32] which
restricts the wear of the material during scratch testing.
In order to correlate the dependence of bulk mechanical properties
with the macro-wear properties, a theoretical model is utilized to cal-
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

6203
A. Nisar et al. Ceramics International 45 (2019) 6198–6208

hardness, HS corresponding to each layer is calculated and presented in

Table 4. Similar to the indentation hardness, scratch hardness in each
layer increases from ~ 20.9 GPa for the first layer to 23.8 GPa for the
second layer and 26.1 GPa for the third layer with the addition of CNT
from 0, 5–10 vol%, respectively. Such behavior establishes a good
corroboration of the mechanical properties with wear properties of the
processed FGM.
To further establish the aforementioned proclamation, Archard’s
wear theory [33] was utilized, which relates the rate of change of wear
volume with the normal load and hardness as per the relation:
HS
WV = k L
Fn (6)
where k is a dimensionless wear coefficient indicating the probability of
forming wear particles.
The wear volume (using Fig. 6b) and the corresponding wear rate Fig. 7. Thermogravimetric analysis of SPS processed FGM up to 1500 °C.
(using Eq. 3) of the processed FGM are 2.76 × 10−2 mm3 and
~ 0.68 mm3 N−1 m−1, respectively (see Table 4). Putting the values in
Table 5
above equation, the wear coefficient k is found to be in the range of
Comparative analysis of the thermal studies on FGM up to 1500 °C.
0.029–0.035 (see Table 4) for each layer which represents the depen-
dence of applied load in wear loss resisted by the inherent hardness of Composition % weight Onset rapid weight change Reference
the FGM. Such low values of k (ranges between 0.029 and 0.035) im- gain temperature (°C)

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)
where a is the fracture toughness exponent (ranges between 1.36 and
1.38), which determines the wear volume loss and b is known as
hardness exponent and chosen as 1.5 for ceramics [34]. CNT content
and dispersion (it is noteworthy that the aspect of agglomeration may
be neglected, as discussed in the recent literature [13,15]) not only
reinforce the ZrB2-20SiC (as a matrix) but, also resist abrading inter-
faces by CNT pull-out and lubrication (Fig. 6h and i). In the present
case, since the average initial roughness of the sample is very low
(~ 0.27 µm) therefore, its effect on the fracture toughness exponent can
be neglected [34].
Further, the critical pressure (Pc) at which cracking initiate in the
FGM (locally) is coupled with the fracture toughness and friction to-
gether with the previously calculated material properties k and a, is
given by the following relation [35]:
b +1
b
a
kFn W v b material, against which the distribution of thermal residual stresses,
Pc =
4.5
1 + 10f ao (8)
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
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
micro-cracking was observed in the FGM (microstructurally shown in
Fig. 4). An enhanced mechanical property of the FGM together with the
observed CNT pull-out mechanism (which imparts crack-resistance) are
in good agreement with the numerical calculation of the critical pres-
sure obtained from the wear model. Similar conduct for the Al2O3 re-
inforced CNT coatings has been comprehended in the literature [34].
3.5. Oxidation resistance of the SPS processed FGM
The oxidation behavior in terms of the weight change due to the
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
1500 °C and the onset of rapid weight change starts above 886 °C
(Table 5). The oxidation of each layer in the FGM component, reported
in the literature [8] is compared to that of the processed FGM, see
Table 5. The shift to the higher onset temperature of oxide formation in
FGM, when compared to each layer of the FGM (Table 5) shows that the
resistance to oxidation increases in case of the processed FGM when
compared to that of conventional UHTCs.
The preliminary oxidation studies establish the superiority of the
processed FGM over conventional ZrB2-ceramics. But, further study,
which closely approximates an intense aero-thermal condition where
the temperature exceeds 2400 °C, is required on this multi-layered
material to reveal the thermo-mechanical performance of the processed
FGM. The residual stress due to the relative mismatch in the CTE may
incur cracking in the material and debonding of the interfaces. The
residual stress distribution can affect the mechanical property of the
arising from the difference in composition of each layer in the processed
FGM at high temperature, has been simulated using FEM in the fol-
lowing section.
3.6. Stress distribution in FGM
The thermo-structural stability of the FGM component depends on
the internal stresses that develop when the sample temperature is raised
up to 2400 °C. Herein, the contributions of thermal residual stresses in
FGM, which arise due to the coupling of different phases within and
among the layers (incorporating their thermo-elastic properties), have
been isolated. As per the boundary conditions mentioned in Section 2.3,
the steady state solution from a homogeneous temperature of 2400 °C to
cooling it down to 25 °C was determined. The stress contours obtained
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
tensile in Z20S10C layer (with max. stresses ~ 5.4 MPa, Fig. 8a) and

6204
A. Nisar et al. Ceramics International 45 (2019) 6198–6208

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.

Fig. 9. Schematic illustrating the overall summary of the work.

compressive in Z20S layer (in the range of 0.6–0.9 MPa, Fig. 8a). The
observations were reversed by inverting the condition i.e. when layer 1
is not allowed to deform. In such a case, the stresses were tensile at the
periphery of the Z20S layer (~ 4.91 MPa, Fig. 8b) which linearly varied
along the thickness direction and then showed compression in Z20S10C
layer (~ 0.7 MPa, Fig. 8b). When restriction (at 2400 °C) is reduced, the
sample relaxes stress by bending (as seen from the stress contours,
Fig. 8a and b) and thus, lowers the tensile stresses in the material.
However, under restricted condition along the circumference, the
compressive stresses are accumulated at the periphery of the disk (with
max. stress of ~ 10 MPa in layer 2 Fig. 8c) whereas layer 1 and layer 3
experience an equal magnitude of stress ranging from 2 MPa to 6 MPa,
Fig. 8c). As far as the distribution of stresses along the thickness in the
central region is concerned, all the three layers exhibit same magnitude

6205
A. Nisar et al.
(~ 2 MPa) of stresses with their nature being compressive, which re-
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
high enough to create deformation (< 4.5 MPa) in the material. This
can be further supported by the observations that the change in stress is
so high that the compression at the periphery changes to tension
~ 4 MPa from the periphery to the center line, leading to crack free
surfaces and interfaces (after processing, see Fig. 4). It can also be ob-
served that the restricted surface is usually tensile which gradually
change to compressive stresses with an increase in distance from the
restricted surface to the interface. Also, the stresses abruptly change
their nature from tensile to compressive near the edge of the specimen.
Since cracks are suppressed in the regions of compressive stress,
which then restricts crack propagation, and results in crack-free sur-
faces and interfaces, as observed from the microstructure shown in
Fig. 4. Hence, it can be anticipated from the study that FGM would be
able to withstand the thermal shock (at least up to 2400 °C). Future
work could involve experimental verifications of these results by testing
the multi-layered architecture in the ultra-high temperature regime
under intense plasma conditions or wind tunnel with fuel injection and
combustion, as the diffusion processes are strongly dependent on the
temperature and it is of primary importance to establish operating
limits for these kind of UHTC composites.
As a closure, it is worthwhile to emphasize the benefits of FGM
approach over conventional UHTC composites. In summary, the sche-
matic illustrating the overall findings has been presented in Fig. 9. The
systematic addition of CNT (0, 5 and 10 vol%) in conventional Z20S
UHTC has led to the gradual enhancement in the mechanical properties
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
against the indenter. Further, the generation of compressive stresses in
the FGM when it is brought from 2400 °C to room temperature can
abate cracks growing through interfaces and thus, establish the sus-
tainability of these materials under ultra-high temperatures. The im-
proved oxidation resistance during the primary oxidation test (up to
1500 °C) with negligible weight gain has also been established. Thus,
the enhanced thermo-mechanical performance of FGM gives them an
edge over conventional UHTCs to be used as a potential high-damage
tolerant structural material
Appendix
See Fig. A1 and Table A1
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.
6206
Ceramics International 45 (2019) 6198–6208
4. Conclusions
A functionally graded composite design consisting of ZrB2-SiC-CNT
composites were successfully fabricated using SPS, which is achieved
through careful tailoring of the stacking sequence and processing con-
ditions. The individual layer in the FGM was observed to be well de-
fined with straight interfaces and no significant residual porosity. The
hardness, modulus, and gradual increase in indentation fracture
toughness mapped well with increased CNT content in the graded
structure (i.e. from 20.2 GPa to 27.3 GPa; 448–498 GPa and 6.4
MPam0.5 to 10.0 MPam0.5, respectively). This augmentation in the
mechanical properties with CNT reinforcement has been attributed to
the CNT pull-out mechanism. The processed FGM exhibited higher wear
resistance with a wear rate of ~ 0.68 mm3 N−1 m−1, which is attrib-
uted to an enhancement in the mechanical properties with CNT re-
inforcement. Thermal studies up to 1500 °C showed minimal weight
gain (> 1%) and the temperature of oxide formation shifted towards
higher temperature (~ 886 °C) when compared to that of conventional
ZrB2 ceramics (~ 679 °C). The computational results suggested that
microstructure has a great effect on thermal stress alleviations as FGM
is proved to be better than conventional UHTCs. Indicative calculations
of the residual stresses confirm that the presence of low tensile stresses
(< 0.7 MPa) at the interfaces were not enough to create delamination
of the interface, which supplements the inference that interfaces possess
similar fracture toughness values when compared to that of their vici-
nity. In light of this, the preliminary characterization of the processed
FGM demonstrates to be an efficient method to obtain tough ultra-high
temperature ceramic composite with improved oxidation resistance.
Acknowledgments
Authors at Indian Institute of Technology Kanpur (IITK) acknowl-
edge the financial support received from IITK-Space Technology Cell
and Indian Space Research Organisation (ISRO), Trivandrum, India.
Authors also acknowledge the support from the Advanced Center for
Materials Science (ACMS) at IITK for extending characterization facil-
ities (SEM and instrumented indentation testing). KB acknowledges
Swarnajayanti Fellowship (DST/STF/ETA-02/2016-17).
A. Nisar et al. Ceramics International 45 (2019) 6198–6208

Table A1
Stacking sequence composition and processing conditions of spark plasma sintered FGM.

Processing and optimization condition of 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.

6207
A. Nisar et al.
References
[1] N.P. Padture, Advanced structural ceramics in aerospace propulsion, Nat. Mater. 15
(2016) 804.
[2] D. Lahiri, V. Singh, G.R. Rodrigues, T.M.H. Costa, M.R. Gallas, S.R. Bakshi, S. Seal,
A. Agarwal, Ultrahigh-pressure consolidation and deformation of tantalum carbide
at ambient and high temperatures, Acta Mater. 61 (2013) 4001–4009.
[3] W.G. Fahrenholtz, G.E. Hilmas, Ultra-high temperature ceramics: materials for ex-
treme environments, Scr. Mater. 129 (2017) 94–99.
[4] W.G. Fahrenholtz, E.J. Wuchina, W.E. Lee, Y. Zhou, Ultra-High Temperature
Ceramics: Materials For Extreme Environment Applications, John Wiley & Sons,
2014.
[5] M. Pavese, P. Fino, C. Badini, A. Ortona, G. Marino, HfB2/SiC as a protective
coating for 2D Cf/SiC composites: effect of high temperature oxidation on me-
chanical properties, Surf. Coat. Technol. 202 (2008) 2059–2067.
[6] M. Mallik, A.J. Kailath, K.K. Ray, R. Mitra, Electrical and thermophysical properties
of ZrB2 and HfB2 based composites, J. Eur. Ceram. Soc. 32 (2012) 2545–2555.
[7] J.W. Zimmermann, G.E. Hilmas, W.G. Fahrenholtz, R.B. Dinwiddie, W.D. Porter,
H. Wang, Thermophysical properties of ZrB2 and ZrB2–SiC ceramics, J. Am. Ceram.
Soc. 91 (2008) 1405–1411.
[8] A. Nisar, K. Balani, Phase and microstructural correlation of spark plasma sintered
HfB2-ZrB2 based ultra-high temperature ceramic composites, Coatings 7 (2017)
110.
[9] A. Nisar, K. Balani, Role of interfaces on multi-length scale wear mechanics of TaC-
based composites, Adv. Eng. Mater. 19 (2017) (1600713-n/a).
[10] A. Nisar, A. S, K. Balani, Synergistic reinforcement of carbon nanotubes and silicon
carbide for toughening tantalum carbide based ultrahigh temperature ceramic, J.
Mater. Res. 31 (2016) 682–692.
[11] T.A. Parthasarathy, R.A. Rapp, M. Opeka, R.J. Kerans, A model for the oxidation of
ZrB2, HfB2 and TiB2, Acta Mater. 55 (2007) 5999–6010.
[12] A. Nisar, S. Ariharan, T. Venkateswaran, N. Sreenivas, K. Balani, Oxidation studies
on TaC based ultra-high temperature ceramic composites under plasma arc jet ex-
posure, Corros. Sci. 109 (2016) 50–61.
[13] A. Nisar, S. Ariharan, T. Venkateswaran, N. Sreenivas, K. Balani, Effect of carbon
nanotube on processing, microstructural, mechanical and ablation behavior of ZrB2-
20SiC based ultra-high temperature ceramic composites, Carbon 111 (2017)
269–282.
[14] D. Ghosh, G. Subhash, N. Orlovskaya, Measurement of scratch-induced residual
stress within SiC grains in ZrB2–SiC composite using micro-Raman spectroscopy,
Acta Mater. 56 (2008) 5345–5354.
[15] A. Nisar, S. Ariharan, K. Balani, Establishing microstructure-mechanical property
correlation in ZrB2-based ultra-high temperature ceramic composites, Ceram. Int.
43 (2017) 13483–13492.
[16] L. Zhang, N.P. Padture, Inhomogeneous oxidation of ZrB2-SiC ultra-high-tempera-
ture ceramic particulate composites and its mitigation, Acta Mater. 129 (2017)
138–148.
[17] X. Zhang, Y. An, J. Han, W. Han, G. Zhao, X. Jin, Graphene nanosheet reinforced
ZrB 2–SiC ceramic composite by thermal reduction of graphene oxide, RSC Adv. 5
(2015) 47060–47065.
[18] X.H. Zhang, Z. Wang, P. Hu, W.B. Han, C.Q. Hong, Mechanical properties and
6208
Ceramics International 45 (2019) 6198–6208
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
properties of ZrB2–SiC ceramics, Mater. Sci. Eng.: A 487 (2008) 568–573.
[20] D. Chen, W. Li, X. Zhang, P. Hu, J. Han, C. Hong, W. Han, Microstructural feature
and thermal shock behavior of hot-pressed ZrB2–SiC–ZrO2 composite, Mater.
Chem. Phys. 116 (2009) 348–352.
[21] F. Yang, X. Zhang, J. Han, S. Du, Characterization of hot-pressed short carbon fiber
reinforced ZrB2–SiC ultra-high temperature ceramic composites, J. Alloy. Compd.
472 (2009) 395–399.
[22] Y. Chen, D. Zhao, F. Qi, W.W. Liu, Scratch behavior of boron nitride nanotube/
boron nitride nanoplatelet hybrid reinforced ZrB2-SiC composites, Ceram. Int. 44
(2018) 3277–3281.
[23] X. Zhang, W. Li, C. Hong, W. Han, J. Han, A novel development of ZrB2/ZrO2
functionally graded ceramics for ultrahigh-temperature application, Scr. Mater. 59
(2008) 1214–1217.
[24] L. Silvestroni, C. Capiani, D. Dalle Fabbriche, C. Melandri, Novel light and tough
ZrB2-based functionally graded ceramics, Compos. Part B: Eng. 99 (2016) 321–329.
[25] Da Jayaseelan, Y. Xin, L. Vandeperre, P. Brown, W. Lee, Development of multi-
layered thermal protection system (TPS) for aerospace applications, Compos. Part
B: Eng. 79 (2015) 392–405.
[26] G.R. Anstis, P. Chantiklul, B.R. Lawn, D.B. Marshall, A critical evaluation of in-
dentation techniques for measuring fracture toughness: I, dircet crack measure-
ments, J. Am. Ceram. Soc. 64 (1981) 533–538.
[27] C. Yue, W. Liu, L. Zhang, T. Zhang, Y. Chen, Fracture toughness and toughening
mechanisms in a (ZrB2–SiC) composite reinforced with boron nitride nanotubes and
boron nitride nanoplatelets, Scr. Mater. 68 (2013) 579–582.
[28] J. Watts, G. Hilmas, W.G. Fahrenholtz, D. Brown, B. Clausen, Stress measurements
in ZrB2–SiC composites using Raman spectroscopy and neutron diffraction, J. Eur.
Ceram. Soc. 30 (2010) 2165–2171.
[29] X. Wang, N.P. Padture, H. Tanaka, Contact-damage-resistant ceramic/single-wall
carbon nanotubes and ceramic/graphite composites, Nat. Mater. 3 (2004) 539.
[30] R.J. Butcher, C.E. Rousseau, H.V. Tippur, A functionally graded particulate com-
posite: preparation, measurements and failure analysis, Acta Mater. 47 (1998)
259–268.
[31] J. Das, B.C. Kesava, J.J. Reddy, V. Srinivas, S. Kumari, V.V.B. Prasad,
Microstructure, mechanical properties and oxidation behavior of short carbon fiber
reinforced ZrB2-20v/oSiC-2v/oB4C composite, Mater. Sci. Eng.: A 719 (2018)
206–226.
[32] B. Yazdani, F. Xu, I. Ahmad, X. Hou, Y. Xia, Y. Zhu, Tribological performance of
graphene/carbon nanotube hybrid reinforced Al2O3 composites, Sci. Rep. 5 (2015)
11579.
[33] J.F. Archard, Contact and rubbing of flat surfaces, J. Appl. Phys. 24 (1953)
981–988.
[34] K. Balani, S.P. Harimkar, A. Keshri, Y. Chen, N.B. Dahotre, A. Agarwal, Multiscale
wear of plasma-sprayed carbon-nanotube-reinforced aluminum oxide nanocompo-
site coating, Acta Mater. 56 (2008) 5984–5994.
[35] D. Casellas, J. Caro, S. Molas, J.M. Prado, I. Valls, Fracture toughness of carbides in
tool steels evaluated by nanoindentation, Acta Mater. 55 (2007) 4277–4286.