Composites Part B 79 (2015) 392e405

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Development of multi-layered thermal protection system (TPS)

for aerospace applications
D.D. Jayaseelan a, *, Y. Xin a, L. Vandeperre a, P. Brown b, W.E. Lee a
a
Centre for Advanced Structural Ceramics, Department of Materials, Imperial College, London SW7 2AZ, UK
b
Dstl, Porton Down, Salisbury, Wiltshire SP4 0JQ, UK

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

Article history: Multi-layered UHTC composites for use in an extreme oxidation environment were fabricated by co-
Received 17 October 2014 sintering. The multi-layered composite system consists of three layers and was designed with (i) an
Received in revised form outer surface with the capacity to withstand heat uxes in excess of 25 MW m
2, (ii) an intermediate
23 February 2015
layer with the ability to curtail diffusion of O2 and (iii) a bottom layer with better performance at high
Accepted 11 April 2015
Available online 27 April 2015
temperatures. One design has MeB2 (where Me Zr or Hf) as the outer or top layer, MeCxOy as the
intermediate layer and MeB2/SiC as the bottom layer. Since little is known about MeCxOy ceramics, a
detailed study has been carried out to synthesise and characterise them focussed on controlling MeCxOy
Keywords:
A. Ceramic-matrix composites (CMCs)
stoichiometry. During co-sintering, the outer MeB2 layer thickness played a crucial role in providing a
Layers crack-free component. Indicative calculations of the residual stresses conrm that a compressive stress
B. Interphase/interface due to bending of the disks can stop crack growth through the MeB2 layer when its thickness is increased
D. Electron microscopy to 3 mm, and that the tensile stress in the bottom layer is also reduced. The cross-section microstructure
E. Joining of the optimised multi-layered UHTC composite shows a crack-free seamless interface.
E. Sintering 2015 Elsevier Ltd. All rights reserved.

1. Introduction properties of the base materials. However, at very high tempera-

Improved technologies and materials capable of operating at
ultra-high temperatures under the conditions of aerodynamic
heating is important in development of hypersonic ight vehicles
and in rocket engineering. To reduce aerodynamic drag and in-
crease lifting force and maneuverability, hypersonic ight vehicles
must have proles with sharp leading edges [1e5]. As a result, the
leading edges are subjected to extreme heat ux at the stagnation
point (>20 MW m
2); correspondingly, the temperature of the
surface can be greater than 2800  C [6], which exceeds the
exploitation temperature of current materials [1,2,4,5,7e9].
The current state-of-art in developing materials for leading edge
components ranges over several areas. The rst is connected with
the modication of classical ceramic composites such as Cf/C and Cf/
SiC by Ultra High Temperature Ceramic (UHTC) materials [10e13],
by using ceramic matrices and/or protective antioxidant coatings,
with the purpose to signicantly increase their oxidation resistance
without signicant loss of the excellent thermo mechanical
* Corresponding author.
E-mail address: d.j.daniel@imperial.ac.uk (D.D. Jayaseelan).
tures, the protective layer of SiC on C/SiC composites becomes
chemically active causing rapid ablation of the material and the
levelling off of the protective properties of SiC with respect to the
reinforcing carbon bres. The use of materials with a high thermal
conductivity ensures a more rapid redistribution of the excessive
heat and favours its removal from the line of total stagnation of the
air stream in the case of components with sharp leading edges. C/C
composites are attractive materials for hypersonic ight vehicles
but they oxidise in air at relatively low temperatures >500  C and
hence need a thermal protection system (TPS) to survive aero-
thermal heating. In both C/C and SiC based composites, develop-
ment of the TPS represent a key issue for the successful re-entry of
space vehicles and substantial improvements in the operational
efciency and reliability are needed, as well as cost reduction
[7,14,15].
Another method of reducing the oxidation of C/C composites is
to coat them with a durable multilayer Zr/Pt coating that forms
ZrPt3 as it anneals. The coating was adherent and provided oxida-
tion resistance to the substrate. Preliminary results showed that the
coating provided protection to graphite and a phenolic resin/
graphite bre composite from a 2800  C ame. This protection is
due to the oxidation resistance of the ZrPt3, and to the reectivity of

http://dx.doi.org/10.1016/j.compositesb.2015.04.017
1359-8368/ 2015 Elsevier Ltd. All rights reserved.
 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405
Fig. 1. Conceptual diagram of a possible multi-layered UHTC component consisting of
a range of potential outer protective and intermediate layers.
the Zr/Pt coating, which reduces the heat load on the substrate for
short time and high-temperature applications. Biamino et al., [16]
developed SiC-based TPS for C/C composites to decrease the ther-
mal conductivity through the thickness of SiC multilayers. The rst
system included the presence of SiC layers containing pores after
sintering. The second system involved depositing an external
insulation coating made of yttria-partially stabilized zirconia
(YPSZ) by means of spray combustion synthesis. The presence of
porous layers in the architecture of the specimen can be effective in
decreasing the thermal diffusivity. By inserting highly porous layers
in the multilayer it has been possible to halve the thermal diffu-
sivity through the thickness, that goes from 0.53 to 0.27 cm2/s at
room temperature and from 0.15 to 0.08 cm2/s at 900  C [16]. The
presence of highly porous layers however degrades the mechanical
properties, with the exural strength being lowered from 342 to
250 MPa for a sample with halved thermal conductivity, even
allowing for triggering of crack deection mechanisms. On the
other hand, the deposition of an external insulating coating of
mainly dense or slightly porous layers allows reduction of the
through thickness thermal diffusivity. Corral and Loehman [17]
fabricated TPS using multilayers of high temperature ceramics
such as ZrB2 and SiC to protect CeC against oxidation. Their
Fig. 2. Optical images of monolithic HfB2 samples (10 mm long  5 mm diameter) following exposures to a heat ux of 44 MW m
2 for 1e7s as labelled. Some exposed to 15s not
shown as it could not be detached from the graphite holder.
393
approach combined pre-treatment and processing steps to create
continuous and adherent high temperature ceramic coatings from
inltrated preceramic polymers.
An alternative approach is to make highly dense UHTC com-
posites with high thermal conductivity, oxidation resistance and
other high temperature mechanical properties such as exural
strength, hardness and fracture toughness [18e30]. This will allow
efcient heat removal from the regions adjacent to the points or
lines of the total ow stagnation, which will work as separate
segments of a complex composite system [31,32], whose different
parts will bear different types of load-thermal, oxidation, shock,
shear, etc. An additional argument in favour of the selection of the
design of the thermo loaded parts of the ight vehicles in the form
of an assembly of several segments is that the UHTCs are brittle
ceramic materials; therefore, from the viewpoint of repairability,
structures are preferable that have a limited size or volume of
components and, therefore, have a reduced probability of the
appearance of defects, which can decrease the strength. Interfaces
between the segments and the locations of junctions with other
components are important from the viewpoint of construction [33].
Such segmental structures have been developed within the NASA
program of the Next generation launch technology (NGLT) [32].
The UK research programme on the development of UHTC com-
ponents for aerospace applications is expected to include C/UHTC
composites on which layered structures of protective UHTC mono-
liths will be attached to enhance protection against oxidation and
heat ux. Fig. 1 shows a multi-layered UHTC concept consisting of
different layers combining various refractory ceramics with various
functions, which full different roles but provide better performance
as a whole system. In the proposed design, the outer MeB2 accom-
modates high heat ux, the intermediate layer MeOxCy acts as an
anti-oxygen diffusion layer as it is expected to have lower oxygen
mobility than MeO2 or MeC, and the bottom substrate layer helps to
increase the high temperature strength of the component. Special
attention should be given to the thickness of the coating layers in
order to limit cracking and the quantity of the oxidation products.
(1) Candidate materials for an oxidation protective top layer to
withstand high heat ux
The outer layer should have a high melting point exceeding
3000  C, should serve as an oxidation protective layer and also
should withstand high heat ux. Many studies have examined the
oxidation behaviour of UHTCs from intermediate temperature to
ultra high temperature using techniques such as furnace oxidation
394 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405

[34], oxyacetylene torch testing [2], arc jet testing [9] and laser
heating [35]. Previously, we demonstrated the effect of additives on
the oxidation behaviour of UHTCs [30,36e38]. In the intermediate
temperature regime, <1600  C, rare earth additions such as La2O3,
LaB6 or Gd2O3 improved the oxidation resistance of MeB2/SiC by
forming a protective refractory oxide phases such as La2Me2O7 and
MeO2 phases in the top layer [30,37,39]. These refractory phases
delay the oxidation resistance of UHTCs. When laser tested at high
heat ux, HfB2 samples with SiC or SiC/La2O3 were more severely
damaged than monolithic HfB2 [39]. Extreme environment testing
of UHTC monoliths by laser exposure conrmed that a 10 mm long
cylinder of monolithic HfB2 can survive about 15s exposure to
44 MW m
2 (see Fig. 2) and that airow reduces the presence of
un-oxidised material at the surface [40]. It can be seen that while

Fig. 3. Cross-section microstructure of HfB2/SiC/La2O3 following exposures to a heat ux of 32 MW m
2.

 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405 395

Table 1 or 2000  C [34] or by laser testing [41] revealed the intermediate

Weight of carbon and zirconia in different composition of mixtures. layers of the oxidised portion contain different crystalline and non-
No. X Composition m(C) (g) m(ZrO2) (g) crystalline phases including oxycarbides. For example, the cross-
1 1 ZrC 6.7878 23.2122
section microstructure of HfB2/SiC/La2O3 samples following expo-
2 0.95 ZrC0.95O0.05 6.6114 23.3886 sure to a heat ux of 32 MW m
2 is shown in Fig. 3 [40]. The top
3 0.9 ZrC0.9O0.1 6.4320 23.5680 surface layer exposed to laser consisted mainly of columnar grains
4 0.8 ZrC0.8O0.2 6.0660 23.9340 and the corresponding EDS reveals this phase as HfO2. The inter-
5 0.7 ZrC0.7O0.3 5.6874 24.3126
mediate layer is porous and EDS shows the presence of Hf, O and C.
6 0.6 ZrC0.6O0.4 5.2974 24.7026
Zapta-Solvas et al. also conrmed the presence of zirconium oxy-
carbides and hafnium oxycarbides in La containing ZrB2 and HfB2-
based UTHCs. Bargeron et al. [42] have shown that HfCxOy has a
the lower parts were intact the upper part of the pellets deterio- remarkably low diffusion coefcient (CoeffDi 1.1 10
7 cm2/s at
rated with increasing test duration. Monolithic HfB2 can withstand 2060  C) and is an oxygen diffusion barrier. Hence, oxycarbide was
extreme heat ux without addition of any secondary phases such as selected as the intermediate layer in the multilayered composite
SiC and La2O3 because they form oxide melts and eventually form design.
high vapour products which are detrimental in producing pores,
voids and bubbles at high heat ux. First order theoretical simu- (3) Candidate materials for bottom layer to be stacked on C/C
lations of the test [40] then suggested that sample length could composites
have a major inuence with longer samples showing enhance
endurance under the heat ux. Most research to date has focused on developing more
oxidation-resistant UHTCs composites. Better densication
(2) Candidate materials for intermediate layers [43e48], improved mechanical properties [38,44,49e51] and
oxidation resistance [2,30,37,52,53] have been found for UHTCs
The selection of intermediate layers is restricted by the fact that containing SiC, typically additions between 10 and 30 vol.%. For
they should have low oxygen diffusivity and low thermal conduc- example, ZrB2 with 20 vol.% SiC had room temperature strength of
tivity. ZrO2 or HfO2 could have been easily picked as candidates 700 90 MPa, fracture toughness of 6.4 0.6 MPa, Vickers
owing to their low thermal conductivity, however the oxygen hardness at 9.8 N load of 21.1 0.6 GPa, 1400  C strength of
diffusion in both oxides is high and also they undergo high phase 400 30 MPa and room temperature strength after 1 h oxidation
transformations during heating and cooling. Previous analyses of at 1400  C of 678 15 MPa with an oxide layer thickness of
cross-section microstructures of samples oxidised at 1600  C [37] 45 5 mm [38]. HfB2 with 20 vol.% SiC showed room temperature

Fig. 4. Temperature prole of the synthesis of ZrCxOy powders.

396 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405

20

11

Fig. 5. Temperature prole of the pressureless sintering of ZrCxOy samples.

Fig. 6. Temperature and pressure proles of the SPS of ZrCxOy samples.

 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405 397

Table 2 be seen as a surface nish to protect the composites. As the UHTC

The composition and layer thickness of the designed multilayered composites. phase is now the outer layer on the composite samples, this
Layers Materials Thickness (mm) Materials Thickness (mm) makes the joining process easier in the event of joining the pro-
MLC3 MLC4
posed multi-layered composites with C/C composite structures
1st layer ZrB2 1 ZrB2 1 since it will replicate joining between identical ceramics.
2nd layer ZrC0.6O0.4 0.5 ZrC0.6O0.4 0.5 Hence, the main purpose of this study is to fabricate crack-free
3rd layer ZS20 3 ZSLO 3 seamless multilayered composites using the synthesized oxy-
MLC5 MLC6
carbide powder as the intermediate layer. Although, HfB2 out-
1st layer ZrB2 1 ZrB2 3
2nd layer ZrC0.6O0.4 0.25 ZrC0.6O0.4 0.5 performs ZrB2 in terms of oxidation behaviour, as both HfB2 and
ZrC0.9O0.1 0.25 ZrB2 are considered as twin borides, ZrB2 based multi-layered
3rd layer ZSLO 3 ZSLO 3 composites are presented in this paper considering the cost
involved in many trials.

strength of 620 50 MPa, fracture toughness of 5.0 0.4 MPa,

Vickers hardness at 9.8N load of 27.0 0.6 GPa, 1400  C strength
of 590 150 MPa and room temperature strength after 1 h
oxidation at 1400  C of 660 25 MPa with an oxide layer thick-
ness of 12 1 mm [38]. Because of these excellent high temper-
ature properties, C/C or C/SiC composites are now being backlled
with UHTC particles [2,54,55]. Eventually, the UHTC particles will
2. Experimental details
2.1. Synthesis of zirconium oxycarbide powders
The most common way to synthesize ZrC is via carbothermal
reduction of zirconia by the following equation:

Fig. 7. Temperature and pressure proles of the SPS of multilayered composites.

Table 3
Densities and lattice parameters of the ZrCxOy samples.

Compositions Lattice parameter () (0.001) Theoretical density (g/cm3) (0.01) Measured density (g/cm3) Relative density

PLS (0.01) SPS (0.01) PLS SPS

ZrC 4.693 6.65 5.48 4.66 83% 70%

ZrC0.95O0.05 4.695 6.62 6.28 5.18 85% 78%
ZrC0.9O0.1 4.688 6.66 5.91 5.65 89% 85%
ZrC0.8O0.2 4.677 6.73 5.51 5.87 82% 87%
ZrC0.7O0.3 4.656 6.85 6.26 6.55 91% 91%
ZrC0.6O0.4 4.656 6.88 6.32 6.29 92% 94%

PLS: Pressureless sintering and SPS: Spark plasma sintering.

398 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405

Fig. 8. XRD of as-synthesised ZrCxOy powders.

Fig. 9. XRD of sintered ZrCxOy samples.

 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405 399

Fig. 10. SEI SEM microstructures of sintered ZrCxOy ceramics; 1 e ZrC, 2 e ZrC0.95C0.05, 3 e ZrC0.9C0.1, 4 e ZrC0.8C0.2, 5 e ZrC0.7C0.3 and 6 e ZrC0.6C0.4.

ZrO2s 3Cs /ZrCs 2COg (1) oxycarbide powders with controlled stoichiometry, Equation (1)
has been modied into:
The mechanism of this reaction has been the subject of recent
studies [56], it is known that a zirconium oxycarbide phase will ZrO2s 2 x
yCs /ZrCx O1
xs 2
yCOg (2)
appear during this reaction. As a result to synthesize zirconium

Fig. 11. Photographs of sintered multi-layered composites. Row 1 corresponds to bottom surface, row 2 corresponds to top surface and row 3 corresponds to the cross-section.
400 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405
Fig. 12. BSE images of cross-section microstructures of four different multi-layered composites.
In these studies [56], x C/Zr and y O/Zr has been xed to be
equal to 1, which means no carbon vacancies are present in the
zirconium oxycarbide lattice. Then, the carbothermal reduction can
be expressed as:
ZrO2s 1 2xCs /ZrCx O1
xs 1 xCOg (3)
By using different values of x, these studies [56] have success-
fully proved the possibility of synthesising zirconium oxycarbide
with controlled stoichiometry.
Equation (3) was followed to full the carbothermal reduction of
zirconia. Similar to the previous studies [57,58], six values for x
(respectively 1
x) have been selected: 1(0), 0.95(0.05), 0.9(0.1),
0.8(0.2), 0.7(0.3) and 0.6(0.4) to control the stoichiometry of zir-
conium oxycarbide. The starting materials for the reaction are
carbon (carbon black, 99%, ABCR, Germany), ZrO2 (monoclinic,
>99%, Acros Organics, Belgium) and ZrO2 (monoclinic, >99%, ABCR,
Germany). The amount of each reactant for synthesising zirconium
oxycarbide was calculated according to Equation (3), and the
weights of carbon and zirconia in each blend of mixture are given
in Table 1. The compositions were dry mixed in plastic containers
(VWR, Radnor, USA), together with same amount of zirconia balls as
grinding media. The bottles were then sealed with container seal
tape (VWR, Radnor, USA) to avoid leak during milling. The powder
mix was ball milled at a rate of 200 rpm. The wet balled slurry was
dried at 80  C using a rotary evaporator. The powder mixtures were
placed in six graphite crucibles of and heat treated at 1800  C for 3 h
in a hot press (HP) furnace (Type HP W 25, FCT Systeme GmbH,
Germany) under owing argon. The actual temperature prole was
plotted in Fig. 4.
2.2. Sintering of ZrCxOy ceramic samples
2.2.1. Pressureless sintering of ZrCxOy samples
As-synthesised oxycarbide powders were pressed into 11 mm
diameter and 5 mm average thickness of 5 mm pellets using a hy-
draulic press (Atlas Manual 25T, Specac, Slough, UK). For each pellet,
25 MPa and 3 min hold was found to be the optimum combination.
Very slow unloading was also applied to even out the high surface
stress of the pellets in the die. PEG 400 (Alfa Aesar, Ward Hill, USA)
was added as a binder. The pellets were dried to remove any
adsorbed moisture and placed in graphite crucibles. The pellets
were then pressureless sintered (PLS) in a hot press furnace (Type
HP W 25, FCT Systeme GmbH, Germany) at 2000  C for 1 h in vac-
uum. The temperature prole shown in Fig. 5 was used for sintering.
2.2.2. Spark plasma sintering of ZrCxOy samples
SPS experiments (Type HP D, FCT Systeme GmbH, Germany)
were performed at NanoForce (Queen Mary, University of London,
UK). The as-synthesised oxycarbide powders were inserted in a
graphite foil lined 30 mm diameter graphite die. The upper and
lower punches of the die are also graphite. The powder was then
treated in the SPS furnace for 10 min at 2100  C in vacuum at a
heating rate of 100  C/min, with an applied pressure of 50 MPa. The
temperature and pressure proles are plotted in Fig. 6.
2.3. Fabrication of multilayered composites
2.3.1. The arrangements of the multilayered composites
Multilayered UHTC composites were fabricated using ZrCxOy as
an intermediate layer. Table 2 gives the arrangements of
 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405
multilayered composites in terms of the composition and thickness
of each individual layer. ZrC0.6O0.4 composition mix was mainly
used as the intermediate layer in all multilayered UHTC composites.
Table 2 reveals, in sample MLC3, 3 mm thick ZrB2/20 vol.% SiC (ZS),
has been used as the base material, 0.5 mm thick ZrC0.6O0.4, as in-
termediate layer and 1 mm thick ZrB2 as the outer layer. In sample
MLC4, instead of ZS20, ZrB2/20 vol.% SiC/2 wt% La2O3 (ZSLO) was
used as the substrate. In sample MLC5, instead of one intermediate
layer, two intermediate layers with two different compositions of
ZrCxOy were used in an attempt to ease the thermal expansion
mismatch. MLC6 and MLC3 are identical except in ZrB2 thickness,
which was 3 mm instead of 1 mm for MLC6.
2.3.2. Sintering of the multi-layered composites
Co-sintering of the multi-layered composites was performed
using SPS and HP techniques. Fig. 7 shows the temperature and
pressure proles of spark plasma sintering of the multilayered
composites samples. HP was done using the temperature prole
used for synthesising oxycarbides (Fig. 4) except for an increase in
the temperature to 2000  C. SPS of the multilayered composites
was conducted in 20 mm diameter dies at 1950  C, with a pressure
of 50 MPa (16 kN for 20 mm pellets). The sintering can be seen as a
sintering joining process.
2.4. Characterisation
Phase analysis of the synthesised oxycarbide powders and sin-
tered pellets was carried out using an X-ray diffractometer (D2
PHASER, Bruker, Madison, USA). The powders were analysed be-
tween 20 and 120 with spinning mode (step size: 0.03 , step
Fig. 13. BSE images of cross-section microstructures of MLC3.
401
time: 0.5 s) to identify the crystallized phases. Rietveld renement
was carried out with X'Pert HighScore Plus (PANalytical,
Netherlands) software to obtain accurate lattice parameters. The
density measurements were carried out using Archimedes method
using water as the medium. Table 3 shows the chemical composi-
tion of 6 different zirconium and hafnium oxycarbides prepared by
the carbothermic route. Bulk densities for both pressureless and
spark plasma sintered samples were calculated using the dimen-
sional method and the relative densities were determined using the
theoretical densities given in Table 3.
Secondary electron images (SEI) and the back-scattered electron
images (BSE) of the sintered samples were taken with a JEOL 6400
(JEOL, Tokyo, Japan) scanning electron microscope (SEM) tted
with an INCA (Oxford Instruments, Oxfordshire, UK) energy-
dispersive X-ray spectroscopy (EDS) analysis system. The acceler-
ating voltage used was 20 kV and the working distance was 15 mm.
Cross-section microstructures of the multilayer composites were
observed in a LEO 1525 Gemini (Carl Zeiss Microscopy, New York,
USA) eld emission gun scanning electron microscope (FEGSEM).
The accelerate voltage was 20 kV and the working distance ranged
from 7 mm to 9 mm.
2.5. Numerical simulations
Numerical simulations of the residual stresses were made using
nite element software (ABAQUS). Axisymmetric disks of 15 mm
radius and layer thicknesses as given in Table 2 were created and
given elastic properties of pure ZrB2 at room temperature
(E 560 GPa, n 0.14) and for the coefcients of thermal expansion
the measured data was used [36]. As no data is available for Zr-
402 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405
oxycarbides, data for the Hf-oxycarbides was used. Since this is
always a relatively thin layer, this is not expected to have a strong
enough effect to limit the overall understanding.
3. Results and discussion
3.1. Fabrication of ZrCxOy ceramics
XRD phase analysis of the as-synthesised ZrCxOy powders
(Fig. 8) revealed residual zirconia peaks labelled as Z in all pow-
ders. This could be a result of insufcient reaction time (3 h
compared to 8 h reported previously [59]). All other higher in-
tensity peaks are attributed to ZrCxOy the peak positions being
similar those in the ZrC data le (Fm-3m, JCPDS 00-035-0784) but
the composition is different. A gradual peak shift is observed with
change in composition. The increase in shift with larger oxygen
content gives further credence to the formation of oxycarbide
phase [56]. XRD was carried out also for the sintered samples
(Fig. 9) revealing that the peaks move towards high angles signif-
icantly, which was not observed in the patterns from synthesized
powder. This indicates that zirconia and carbon in these powders
further reacted with each other during sintering. However, there is
no available JCPDS card le to index the zirconium carbide phase, so
a lattice parameter renement is necessary. Previous study [56]
claimed that zirconium oxycarbide adopts the same structure as
ZrC (e.g. Fm-3m, JCPDS 00-035-0784). As the radius of oxygen
(0.66 ) is smaller than that of carbon (0.76 ), the shifted
diffraction peaks was then explained as the result of carbon atoms
replaced by oxygen atoms in the ZrC crystal lattice.
The most common way to characterize the x O/Zr and y C/Zr
ratios of ZrCxOy composition consists in determining the lattice
parameter of the oxycarbide phase by X-ray diffraction (XRD). Zir-
conium (ZrCx) exhibits rock salt structure (Fm-3m space group) in
which the oxygen could either be incorporated in the remaining
vacant octahedral sites or be partly substituted to carbon. Hence,
the oxycarbide phase (ZrCxOy/HfCxOy) adopts the same structure as
respective carbides: but, the lattice parameter of the oxycarbide
phase (ZrCxOy) is signicantly modied by the incorporation of
oxygen in ZrCx lattice and it is decreased with increase in the ox-
ygen content.
Fig. 10 shows the secondary electron SEM microstructures of SPS
ZrCxOy ceramics. Densication has been enhanced by addition of
more oxygen in the carbide matrix resulting in samples 5 and 6
having denser microstructures although with excessive grain
growth. No surface cracks were observed. The dark phases in
samples 1e4 are likely unreacted carbon.
3.2. Fabrication of multi-layered composites
Zirconium based multilayer UHTC composites were fabricated
with four different arrangements. The arrangement of multi-layered
composites is shown in Table 2. All samples were co-sintered in an
SPS furnace. Fig. 11 shows the photographs of sintered samples. In all
arrangements, thickness of the bottom and the intermediate layers
are kept constant as 3 mm and 1 mm, respectively. Only in sample
MLC3, has ZS20 been used as the bottom layer whereas in all other
samples ZSLO was the bottom layer. In Fig. 11, row 1 corresponds to
the bottom surfaces, row 2 to the top surfaces and row 3 corresponds
to their cross-sections. MLC3 sample has 1 mm thick top ZrB2 layer,
0.5 mm thick intermediate ZrC0.6O0.4 layer and 3 mm ZS20 layer.
Cracks were visible on both sides of sintered MLC3 after surface
grinding. In sample MLC4, instead of ZS20, ZSLO was used as the
substrate. However again, surface cracks occurred on the top ZrB2
layer. In sample MLC5, instead of one intermediate layer, two inter-
mediate layers with two different compositions of ZrOxCy (ZrC0.6O0.4
and ZrC0.9O0.1) were used to ease the thermal expansion mismatch.
Still, surface cracks were observed on the outer surface ZrB2 layer.
MLC6 has a similar arrangement as to that of MLC4 but different ZrB2
thickness, 3 mm instead of 1 mm. Fig. 11 clearly shows that no surface
cracks were observed in both top and bottom sides of MLC6. The
impression left by graphite foil is seen on the top surface. The cross-
section image shows that different layers are well adhered with each
other and no visible spallation or cracks are observed at the interfaces.
BSE images of cross-section microstructures of four different
samples are shown in Fig. 12. Except for MLC6 (with 3 mm thick top
and bottom layers) all samples have surface cracks in the ZrB2 layer.
In MLC3, MLC4 and MLC5 samples, the ZrB2 layer is thin enough for
the cracks to propagate to top surface. Fig. 13 shows the SEI of cross-
section microstructure of MLC3. It can be seen clearly in Fig. 13(a)
that crack originates at the interface between the intermediate and
top ZrB2 layers, and propagates to the surface eventually forming
the surface cracks observed in Fig. 11. Fig. 13(b) shows the inter-
mediate layer at higher magnication comprising two contrasting
phases. Both dark and light grey phases contain Zr, O and C.
However, the bright phase is oxygen rich ZrCxOy and light grey
phase is carbon rich ZrCxOy. Fig. 13(c) shows the interface between
bottom and intermediate layer. As observed previously, a thin
(<50 mm) interlayer is observed and EDS shows predominantly Zr
and C and a weak O peak.
3.3. Cracks in the multilayer structures
The observations show that cracks are found in the ZrB2 layer in
all multi-layered structures. However, in the last version, MLC6,
15 mm
A
Top (a)
A
A
A
A Bottom
15 mm
A
Top (b)
A
A
A
A Bottom
Fig. 14. Boundary conditions for the FEM calculation. In all cases axisymmetric
boundary conditions were applied to the centre line. To model the pressurised situa-
tion, the bottom of the disk was prevented from moving upwards (a), whereas for the
free disk, the latter boundary condition was removed (b).
 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405
with a thicker ZrB2 layer, these cracks originating at the ZrB2eZr-
oxycarbide layer do not grow through the entire ZrB2 layer and
hence do not reach the free surface.
The boundary conditions (Fig. 14) were that the calculation
started from a homogeneous temperature of 1425  C and then the
steady state stress solution for cooling to 25  C was determined.
This temperature range was used based on evidence from neutron
diffraction that stresses freeze in around this temperature. In all
cases axis symmetric boundary conditions were applied to the
centre line. In order to model the situation with and without
pressure, the bottom of the disk was prevented moving upwards
(Fig. 14a), whereas for the free disk with no constraints, the latter
boundary condition was removed (Fig. 14b). Key results are illus-
trated in Fig. 15. The rst point to note is that when bending of the
disks is prevented e e.g. by the containment in the SPS or hot press
e then the stresses are quite homogeneous in the layers only
tapering off towards the edges of the sample, see Fig. 15(a) and (c).
However, it is also clear that one side of the sample experiences
compressive stress (the ZSLO or ZS20 layers with their lower
Fig. 15. (a) MLC-3 with no bending allowed, (b) MLC-3 with bending allowed, (c) MLC-6 with no bending allowed, (d) MLC-6 with bending allowed.
403
thermal expansion) while the other side of the sample experiences
tension (the ZrB2) layer. This is encouraging as cracking was mostly
seen in the ZrB2 layers.
The fact that tension and compression occur on opposite sides of
the samples means that if the vertical pressure is reduced, the
sample will release these stresses by bending so that it becomes
shorter where the material is in tension (ZrB2 side) and longer at
the other side (ZSLO or ZS20). The results for this case are shown in
Fig. 15(b) and (d). To clarify the bending it has been widely exag-
gerated. The linear stress distribution associated with this bending
changes the stress from homogeneous through thickness in each of
the layers, to a linearly varying stress in the layers. In fact it can be
seen that the change in stress in the case of MLC-3 is not sufcient
to induce compression near the top of the ZrB2 layer whereas in the
case of MLC-6, the change in stress is stronger and stress goes from
tension at the interface with the zirconium oxycarbide layer to
compression at the free surface. Since cracks are very reluctant to
enter into regions of compressive stress, this explains why the
cracks did not grow to the free surface in the case of MLC-6. Note
404 D.D. Jayaseelan et al. / Composites Part B 79 (2015) 392e405
that as a result, the bottom ZSLO layer is in tension as well. Hence,
although a crack free structure has not been produced, the patterns
of cracking seem to be in line with what can be predicted with the
thermo-physical data points. Better predictions will require elastic
properties of each of the layers and the coefcients of thermal
expansion of the zirconium oxycarbide layers. It should be noted
that for the hafnium oxycarbide layers the CTE data is available.
4. Conclusions
Multilayered composite designs consisting of ZrB2 top layers,
intermediate ZrOxCy layers and bottom ZrB2/SiC/La2O3 layers were
fabricated. ZrCxOy with different controlled stoichiometry was
synthesized using a carbothermic reduction method. The lattice
parameter of the oxycarbide phase (ZrCxOy) is signicantly modi-
ed by the incorporation of oxygen in the ZrCx lattice and it is
decreased with increase in the oxygen content. Densication of
ZrCxOy has been enhanced by the incorporation of more oxygen in
carbide matrix. A co-sintering method has been successfully
employed to fabricate multi-layered composites using an SPS
furnace with varying the thickness of the top layer. Samples with
large thickness (3 mm) survived from stress induced cracks
whereas vertical and surface lateral cracks were observed in ZrB2
top layer when its thickness is <3 mm. Indicative calculations of the
residual stresses conrm that a compressive stress due to bending
of the disks can stop cracks growing through the ZrB2 layer.
Acknowledgement
The Authors' acknowledge Prof. Mike Reece, Nanoforce Tech-
nology Ltd., Queen Mary, University of London, UK for providing
access to the Spark Plasma Sintering facility. DDJ acknowledges the
support of DSTL, UK for providing the nancial support for this
work under contract number DSTLX-1000015413.
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