Journal of Alloys and Compounds 811 (2019) 151939

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Journal of Alloys and Compounds

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Correspondence

Coarsening kinetics of nanostructured ZrO2 in Zr-doped SiCN ceramic

hybrids
a b s t r a c t

Keywords: A commercial polyvinylsilazane was doped with an alkoxide of Zr, followed by crosslinking and pyrolysis
Polymer derived ceramics in N2 atmosphere over a temperature range of 1000e1400
C, to yield homogeneously distributed
Polysilazanes nanostructured ZrO2 crystallites with size in the range of 2.5e8.8 nm in the amorphous SiCN matrix.
SiCN
Coarsening kinetics of ZrO2 in the SiZrCNO system was studied at 1400
C using the Lifshitz-Slyozov-
ZrO2
Ostwald ripening
Wagner model, which exhibited cubic kinetics indicating diffusion controlled growth. The coarsening
rate constant at 1400
C was found to be 1.568  1029 m3 s1. The diffusivity of Zr in the SiCNO matrix
was calculated to be 7.124  1020 m2 s1, which is similar to that of Hf in SiOC and SiCNO matrix.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction 2. Experimental

Ceramics synthesized from the pyrolysis of silicon containing
polymers, generally termed as polymer derived ceramics (PDC),
possess unique nanostructures, excellent thermo-mechanical prop-
erties, oxidation and corrosion resistance up to 1500
C and higher
[1,2] In addition, several investigations have suggested that by incor-
porating different types of metal ion in the precursors at molecular
level, including Al [3,4], Ti [5], Zr [6,7], or Hf [8,9], the nanostructure,
phase, and high temperature properties of the synthesized ceramics
can be altered. Saha et al. [7]. incorporated Zr into SiCNO matrix at
molecular level and showed the reduction of its parabolic oxidation
rate as compared to the same in undoped SiCNO system, and
concluded that lower content and the lower activity of the free car-
bon in the Si-Zr-C-N-O system decreases its oxidation rate. Ionescu
et al. [10] observed that the incorporation of ZrO2 into the polymer
derived SiOC matrix remarkably increases the crystallization and
decomposition temperatures exceeding 1300
C. Zirconia
embedded SiCN ceramic is being studied as materials for enhanced
corrosion resistant coatings for different components of gas turbine
engine blades [11]. Low thermal conductivity of the protective coat-
ings is considered as one of the vital parameters for the efficiency
improvement as well as protection of substrates [12]. A phase sepa-
rated nanocrystalline ZrO2 can drastically decrease the thermal con-
ductivity by limiting the mean free path of phonons, and make it as
superior candidate for high temperature protective coat application
in gas turbine engine coating systems [13]. Understanding the rate
kinetics of the evolved phases is important to be able to improve
the thermal properties of SiZrCNO in terms of conductivity and sta-
bility (e.g. crystallization and phase separation). In this work, a
commercially available polyvinylsilazane precursor was doped
with an alkoxide of Zr to get SiZrCNO hybrid ceramic with nano-
structured precipitates of ZrO2. Subsequently, the coarsening ki-
netics of ZrO2 in the amorphous SiCN ceramic was studied.
To synthesize zirconium modified SiCN, a polyvinylsilazane
(Durazane® 1800) was blended with 25 wt % of zirconium (IV) n-
propoxide solution (Sigma-Aldrich®, density ¼ 1.044 g cc1 at
25
C). Dicumyl peroxide was used (1 wt%) as the crosslinking
agent. The mixed solution was crosslinked in nitrogen atmosphere
with a heating rate of 2
C min1 to 300
C and holding at the peak
temperature for 2 h in a furnace designed in-house. A glassy mass
was obtained after crosslinking and was crushed into fine powders
by a high energy ball mill (SPEX 8000 M, SPEX SamplePrep, Metu-
chen, NJ, USA). Subsequently the crosslinked powders were pyro-
lyzed in a tube furnace at various temperatures ranging between
1000
C and 1400
C. Thermal treatments of all the samples were
carried out in a flowing nitrogen atmosphere condition with a heat-
ing rate of 2
C min1. To understand the coarsening mechanism,
samples were heat treated at 1400
C for various times. The ob-
tained powder was milled with agate mortar and the phases of ob-
tained pyrolyzed SiZrCNO samples were identified by X-ray
diffraction (XRD) technique using Rigaku Ultima IV X-ray diffrac-
tometer with Cu Ka radiation (l ¼ 1.5408 Å) in the 10
e80
2q
range with 20
min1 scan rate. The peaks were identified with
reference to inorganic crystal structure database (ICSD). Polynomial
fitting of the XRD curves as per Gaussian function were performed
to calculate the full width at half-maximum (FWHM) of the
maximum intensity ZrO2 peaks and the crystallite sizes of the
phase separated ZrO2 were calculated using the Scherrer formula.
The high resolution images were recorded using transmission elec-
tron microscopy (TEM, Technai G2, FEI, Eindhoven, NL) at an accel-
erating voltage of 300 kV.
3. Results and discussion
The crystallization behavior of SiZrCNO ceramics derived from

https://doi.org/10.1016/j.jallcom.2019.151939
0925-8388/© 2019 Elsevier B.V. All rights reserved.
2 Correspondence / Journal of Alloys and Compounds 811 (2019) 151939
polyvinylsilazane and metal precursor systems was studied by X-
ray diffraction (Fig. 1). The ceramics pyrolyzed at 1000
C (for 4
hours) exhibited pseudo-amorphous structure of the material.
The broad hump at 22
can be ascribed to SiO2 nanodomains in
the ceramic matrix, due largely to the oxygen pick up by the system
during wet processing. The small hump at ~30
, albeit unclear, is
indicative of formation of ZrO2 nuclei from the saturation of molec-
ular Zr in the SiCN matrix. The SiZrCNO ceramic pyrolyzed at
1400
C was found to be pseudo-amorphous with only discernible
peaks of t-ZrO2 (ICSD-98-065-5671) indicating that the ceramic is
composed of fine crystallites of t-ZrO2 embedded in the amorphous
SiCN matrix (Fig. 1). Gradual increase in the t-ZrO2 signal was
evident for samples pyrolyzed for 1 and 1.5 h at 1400
C. For sam-
ples pyrolyzed at 1400
C for 2 h, the presence of a low fraction of
residual carbon (ICSD -98-061-7290) and fine crystallites of a-Si3N4
(ICSD-98-003-5563) was detected along with the presence of t-
ZrO2. Size of the ZrO2 crystallites was calculated for all of the sam-
ples following Scherrer's formula (Eq. (1)) using the maximum in-
tensity peak positioning at 2q ¼ 30
.
0:89 l
d¼
b Cos q
In Eq. (1), d is the crystallite size, l is the wavelength of the X-
ray, b is the full width at half maximum of the most intense peak
(in rad), and Q is half of the diffraction angle. The average crystallite
size varied between 2.5 and 8.8 nm.
TEM imaging was used to directly observe the composite nano-
structure. The SiZrCNO ceramic pyrolyzed at 1000
C constituted of
extremely fine precipitates (Fig. 2a) dispersed quite homogeneously
in the matrix. The selected area diffraction (SAD) pattern (inset of
Fig. 2a) exhibited a diffused ring pattern indicating the ceramic to
be largely amorphous. With high resolution transmission electron
microscopy (HRTEM), the crystallites were imaged (Fig. 2b), which
Fig. 1. X-ray diffractograms of the pyrolyzed SiZrCNO ceramics.
indicated crystalline domains of size in the range of 3 nm, corrobo-
rating well with the crystallite size calculation from Scherrer formula.
From the above results it can be safely inferred that the SiZrCNO
ceramic is a pseudo-amorphous system with fine crystallites of
ZrO2 homogeneously distributed in an amorphous matrix of SiCN.
The TEM image of SiZrCNO sample pyrolyzed at 1400
C for 2
hours exhibited a microstructure which is self-similar to the one at
1000
C (Fig. 3a), with similar precipitation of nanostructured ZrO2.
HRTEM imaging of the sample (Fig. 3b, arrows pointing upwards)
indicated lattice fringes, which could be indexed for t-ZrO2 phase
(cf. the inset image with Fourier filtered lattice fringes). Nano precip-
itates of a-Si3N4 phase have also been observed and indexed (marked
with arrows pointing downwards, Fig. 3b). The high angle annular
dark field (HAADF) images in scanning transmission electron micro-
scopy (STEM) mode of SiZrCNO samples pyrolyzed at 1400
C is
exhibited in Fig. 4. Through energy dispersive X-ray spectroscopy
(EDS), the elemental mappings of the zirconium, silicon, carbon, ni-
trogen, and oxygen further indicate the uniform distribution of the
elements present in the nanocomposite. In particular, the elemental
mapping of Zr ion indicates its homogeneous distribution
(1) throughout the SiCN matrix (Fig. 4c). With regards to the size of
the ZrO2 crystallites, the average crystallite size calculated using
ImageJ software from the TEM images matched well with the XRD
based crystallite size calculations (cf. Eq. (1)). From Figs. 2 and 3,
one can opine that the nanostructure of the SiZrCNO system has
remained consistent over the temperature conditions studied, the
only difference being the coarsening of the ZrO2 nanoprecipitates.
This is a classic case of Ostwald ripening where the growth ki-
netics of the nanocrystalline t-ZrO2 particles can be understood.
Ostwald ripening occurs with the overall reduction in particle sur-
face area providing the driving force for particle growth at the
expense of crystallites that are smaller than a critical size. This
can be modeled with the Lifshitz-Slyozov-Wagner (LSW) model
[14,15] with a generic expression of:
r n  r n0 ¼ KT t (2)
where r is the size of the crystal at time t and temperature T, r0 is
size of the crystallite at t ¼ 0 at T, n is the growth exponent, KT is the
rate constant at temperature T. Experimental determination of the
crystallite size for multiple dwell times enables calculation of the
rate constant. Additionally, when n ¼ 2, the growth process is
considered to be interface controlled, and when n ¼ 3, the growth
process is controlled by diffusion.
Crystallite size for the powders pyrolyzed for different times at
1400
C were calculated from the X-ray diffractograms. Interest-
ingly, the cubic growth process was found as best fit to the kinetics
data (cf. Fig. 5). This indicates that the growth of the crystallites is
not limited at the attachment of Zr or O at the growing crystal inter-
face. Rather, it must be controlled by the diffusion of either the ox-
ygen ions or the Zr ions through the bulk (which essentially is the
SiCN matrix).
The value of the rate constant KT was found to be 1.568  1029
3 1
m s . The coarsening rate of other nanocrystalline phases such as
HfO2 and SiC dispersed into SiHfCN and SiBCN composite matrix
has been reported by Sujith et al. [8] and Schmidt et al. [16], respec-
tively, who also have reported that the growth of the nanoprecipi-
tates follows cubic kinetics. The diffusivity of the Zr (DZr) in the
SiCNO matrix can be calculated from the coarsening rate constant
as per Eq. (3):
9RTKT
DZr ¼ (3)
8CZr gU2
where g is the matrix-ZrO2 interface energy, CZr is the dissolved Zr
 Correspondence / Journal of Alloys and Compounds 811 (2019) 151939 3

Fig. 2. TEM images of 1000
C heat-treated SiZrCNO, inset image is of corresponding SAD pattern showing an amorphous state, (b) High-resolution TEM (HRTEM) image of SiZrCNO
pyrolyzed at 1000
C.

Fig. 3. Transmission electron micrographs of SiZrCNO annealed at 1400
C for 2 h; (a) bright field image (inset: SAD), (b) high resolution image of t-ZrO2 (upward arrows) and a-
Si3N4 (downward arrows) nanocrystals (inset images: corresponding Fourier filtered lattice fringes).

in the host matrix at equilibrium concentration, U is the molar
volume of t-ZrO2, T is pyrolysis temperature (1673 K), and R is the
universal gas constant. The molar volume U (20.07 cm3 mol1) of t-
ZrO2 is calculated as ratios of the molar mass and the theoretical
density. Interfacial energy for SiZrCNO interfaces was estimated
using related systems. We have used interface energy as 0.25 J m2
for the ZrO2-SiCNO interface. CZr was taken as 20.43 mol m3,
which is calculated by taking differences of the theoretical molar
volume of t-ZrO2 computed by initial composition of chemically
added Zr (O-CH3)4 and the molar volume obtained of t-ZrO2
computed using TEM-EDS analysis. The density of SiCNO ceramic is
assumed as 2.00 g cm3 for all calculations in this study, though the
density may vary slightly based on the local arrangement of Si, C, N,
O in the structure. Using these data, we obtained diffusivity of Zr in
the SiCNO system as 7.124  1020 m2 s1. Subtle change in the
above parameters can only affect the diffusivity by a factor; the
order of the value will not be changed.
The obtained diffusivity of Zr in SiCNO may be seen in the context
of previous literature data (see Table 1). Saha et al. studied the diffu-
sion of oxygen into SiCN and SiZrCN system and reported the diffu-
sion coefficient of O2 of order of 1018 m2 s1 from oxidation
studies (albeit at 1300
C) [7], which is considerably higher as
compared to the current results. O2 diffusion generally being fast
in silica based glass systems, it can be safely assumed that in the
diffusion limited growth process of ZrO2 crystallites in this work,
diffusion of Zr through the SiCNO matrix is the slower process than
that of O2. Additionally, it can also be seen that the obtained diffu-
sivity of Zr in SiCNO is almost 3 orders of magnitude lower than
that in SiO2 [17], underscoring the fact that the presence of C and
N in the polymer derived amorphous ceramic network impedes
cation diffusion. It is also remarkable that the calculated diffusivity
of Zr (at 1400
C) is within the range of the Hf diffusivity in amor-
phous SiOC and SiCN investigated by Kleebe et al. and Nonnen-
macher et al., at 1300
C, respectively [18,19]. However, in the
diffusion work of Hf in SiOC and SiCN, different diffusivities have
been calculated for bulk and the internal surface of the compacts
with values spread over two orders of magnitude (see Table 1).
This was justified due largely to the clearly different growth rate of
HfO2 crystals in the bulk and near the internal pore surfaces. On
the contrary, the current experiments and annealing have been car-
ried out on loose powders of SiZrCNO. TEM imaging of the nanocom-
posite powder fragments with size in the range of a micron, indicated
4 Correspondence / Journal of Alloys and Compounds 811 (2019) 151939

Fig. 4. (a) HAADF-STEM image of SiZrCNO pyrolyzed at 1400
C for 2 hours in STEM mode and the corresponding element mappings: (b) Si (c) Zr (d) C (e) N and (F) O.

nanostructured ZrO2 precipitates in an amorphous SiZrCNO

ceramic matrix derived from zirconium alkoxide-modified polyvi-
nylsilazane via polymer precursor route. The obtained ceramic re-
mains primarily amorphous up to 1000
C pyrolysis temperature
without any phase separation of the dopant. Heat treatment in
the temperature range 1000
Ce1400
C exhibited separation of
the ZrO2 crystallites from the amorphous matrix. Coarsening of
the crystallites could be modeled with cubic kinetics following
LSW theory indicating that growth was controlled by diffusion
through the amorphous SiCNO ceramic. The cubic rate constant
was 1.568  1029 m3 s1, from which the diffusivity of Zr was
calculated to be 7.124  1020 m2 s1. These results are comparable
to that of Hf in similar polymer derived Si ceramics systems.

Acknowledgement

The support of Mr Nitin Gala and Mr Amit Sharma of Merck

Fig. 5. Kinetics of ZrO2 coarsening at 1400 C. Chemicals is gratefully acknowledged.

Table 1
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