Nuclear Engineering and Design 251 (2012) 191202

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Nuclear Engineering and Design

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Effects of phosphorous-doping and high temperature annealing on CVD grown

3C-SiC
I.J. van Rooyen a,b,c, , J.H. Neethling b , A. Henry d , E. Janzn d , S.M. Mokoduwe c , A. Janse van Vuuren b ,
E. Olivier b
a

CSIR, National Laser Centre, PO Box 395, Pretoria 0001, South Africa
Department of Physics, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth 6031, South Africa
c
Fuel Design, PBMR, 1279 Mike Crawford Avenue, Centurion 0046, South Africa
d
Department of Physics, Chemistry and Biology, Semiconductor Materials, Linkping University, Linkping 58183, Sweden
b

a r t i c l e

i n f o

Article history:
Received 17 January 2011
Received in revised form
22 September 2011
Accepted 22 September 2011

a b s t r a c t
The integrity and property behavior of the SiC layer of the Tri-isotropic (TRISO) coated particle (CP) for
high temperature reactors (HTR) are very important as the SiC layer is the main barrier for gaseous and
metallic ssion product release. This study describes the work done on un-irradiated SiC samples prepared with varying phosphorus levels to simulate the presence of phosphorus due to transmutation. 30 Si
transmutes to phosphorous (31 P) and other transmutation products during irradiation, which may affect
the integrity of the SiC layer. The P-doping levels of the SiC samples used in this study cover the range
from 1.1 1015 to 1.2 1019 atom/cm3 and are therefore relevant to the PBMR operating conditions.
Annealing from 1000 C to 2100 C was performed to study the possible changes in nanostructures and
various properties due to temperature. Characterization results by X-ray diffraction (XRD), secondary
ion mass spectrometry (SIMS), scanning electron microscopy (SEM), transmission electron microscopy
(TEM) and high resolution transmission electron microscopy (HRTEM), are reported in this article. As
grain boundary diffusion is identied as a possible mechanism by which 110m Ag, one of the ssion activation products, might be released through intact SiC layer, grain size measurements is also included in
this study. Temperature is evidently one of the factors/parameters amongst others known to inuence
the grain size of SiC and therefore it is important to investigate the effect of high temperature annealing
on the SiC grain size. The ASTM E112 method as well as electron back scatter diffraction (EBSD) was used
to determine the grain size of various commercial SiC samples and the SiC layer in experimental PBMR
Coated Particles (CPs) after annealing at temperatures ranging from 1600 C to 2100 C. The HRTEM micrograph of the decomposition of SiC at 2100 C are shown and discussed. Nanotubes were not identied
during the TEM and HRTEM analysis although graphitic structures were identied. The preliminary conclusion reached is that the P-content at these experimental levels (1.1 1015 to 1.2 1019 atom/cm3 )
does not have a signicant inuence on the nanostructure of SiC at high temperatures without
irradiation.
Published by Elsevier B.V.

1. Introduction
Abbreviations: ACF, advance coater facility; AFM, atomic force microscopy;
BF, bright eld; CP, coated particle; CVD, chemical vapor deposition; EAG, Evans
Analytical Group; EBSD, electron back scatter diffraction; FTIR, Fourier transformed infrared; HRTEM, high resolution transmission electron microscopy; HTR,
high temperature reactors; LiU, Linkping University; NMMU, Nelson Mandela
Metropolitan University; ORNL, Oakridge National Laboratory; SAD, selected area
diffraction; SEM, scanning electron microscopy; SIMS, secondary ion mass spectrometry; TBP, tertiary butyl phosphine; TEM, transmission electron microscopy;
TRISO, tri-isotropic; XRD, X-ray diffraction.
Corresponding author. Present address: Fuel Performance and Design Department, Idaho National Laboratory, PO Box 1625, Idaho Falls, ID 83415, USA.
Tel.: +1 2085337199.
E-mail address: Isabella.vanrooyen@inl.gov (I.J. van Rooyen).
0029-5493/$ see front matter. Published by Elsevier B.V.
doi:10.1016/j.nucengdes.2011.09.066

The integrity and property behavior of the SiC layer of the triisotropic (TRISO) coated particle for high temperature reactors
(HTR) are very important. The SiC is the main barrier for gaseous
and metallic ssion product release. Although most ssion products are retained by the combination of SiC and pyrolytic carbon
layers, previous observations of silver release during fuel testing
and operations identied the release of silver by so-called intact
SiC layers (Nabielek et al., 1977; Yurko et al., 2008). Nabielek and
Brown (1975) proposed grain boundary diffusion as a mechanism
for 110m Ag release through intact SiC layers. Petti et al. (2003)
also microscopically compared US manufactured- with German

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manufactured TRISO CPs and found that the grain size and structure inuence the 110m Ag release. It was found that 90% of the
110m Ag was released from the large columnar grained SiC, whereas
only 30% was released from the small grained SiC particles. Therefore this study was undertaken to determine the grain size of
chemical vapor deposition (CVD) grown SiC. The reason for this
investigation is to determine the change in grain size after high
temperature annealing as grain size may inuence the strength of
the CP and further may inuence the silver release from the CP during operation. It was decided to initially do grain size evaluation
after annealing from 16002100 C on at commercial 3C-SiC samples, due to the relatively ease of sample handling and preparation.
This work was followed by the annealing of two selected experimental PBMR CP batches at temperatures from 1600 to 2000 C.
These very high annealing temperatures were chosen because
Snead et al. (2007) found that no signicant strength degradation
of CVD SiC occurs for temperatures up to 1500 C. Long duration
annealing (>100 h) studies, although important for the effect on
SiC strength (Van Rooyen et al., 2010) as it is an indication of
how the grain size will be modied during the reactor operation
under specic conditions, is not included in this phases of work.
Work by Byun et al. (2009) also makes reference to the inuence
of grain size on the SiC strength. This temperature range is also
of interest as the fuel sphere manufacturing process make use
of a 1 h sintering process at 1950 C and this study will indicate
if any grain size changes could be expected due to the sintering
operation. This work forms part of a larger experimental programme of the PBMR Fuel Design department to test the design
parameters of the CPs for application in very high temperature
reactors.
Additionally an investigation was also proposed to determine
the effect that different Si isotopes may have on the SiC crystal structure during the CVD manufacturing process and after
transmutation due to irradiation. 30 Si transmutes to phosphorous
(31 P) and other transmutation products during irradiation, which
may affect the integrity of the SiC layer. This study describes
the work done on unirradiated SiC, but the SiC samples were
prepared with varying phosphorous levels to simulate the presence of P due to transmutation. Heinisch et al. (2004) reported
that 36 appm P are produced by neutron irradiation-induced
transmutation in a modular pebble bed reactor (265 MWth,
total neutron ux 1.25 1014 n/cm2 s for 10 full power years
(4.4 displacements per atom (dpa)). This amounts to 8.2 appm/dpa
phosphorous.
Calculations of material activation due to neutrons were done by
the PBMRs Nuclear Engineering Analysis (NEA) group using European Activation System-2007 (EASY) comprising of the EAF-2007
nuclear data and the FISPACT-2007 inventory code. These calculations were done for the different isotopic compositions of SiC as
part of the Fuel Design study, but only the results for the natural Si-isotopic composition (92.2% 28 Si, 4.6% 29 Si, and 3.1% 30 Si) for
SiC are described in this paper. Density of SiC used is 3.20 g/cm3
and the total volume of SiC layer irradiated is 7.13 1005 cm3 .
The fuel residence time in the reactor core was determined by
VSOP and is 925 days, meaning that one cycle through the PBMR
will take in average 152.16 days (925/6). Thus the irradiation time
used for this calculation is for the fuel residence time of 925 days
and is applicable to the 6 passes for the 400 MWth PBMR design.
The cooling period applied for this activation is 30 days (Maage,
2009). These calculations revealed that 10 appm P are produced
by neutron irradiation-induced transmutation under PBMR conditions.
The main purpose of this work is therefore to investigate
the effects of high temperature annealing and P-doping on
the micro- and nanostructure of the SiC layer of PBMR TRISO
CPs.

2. Materials and characterization methods

2.1. Materials
Three sample sets are used in this study namely bulk CVD 3CSiC, two PBMR CP batches and P-doped CVD 3C-SiC. The rst two
sample sets are used for the grain size determination and the third
sample set is used to study the effect of P-doping on the SiC microand nanostructure after high temperature annealing. The rst two
sample sets for the grain size characterization are shown in the
Experimental Research Plan ow diagram in Fig. 1.
The bulk CVD-grown polycrystalline 3C-SiC (at samples) used
for the rst phase of this study was prepared by Rohm and Haas,
Advanced Materials Co., USA. This commercial available SiC was
chosen since it provided similar grain sizes to that used in the PBMR
fuel SiC layer. Five small square samples were cut from the original sample received from Oakridge National Laboratory (ORNL)
and prepared for grain size determination. Four at CVD-grown
SiC samples were annealed at temperatures 1600 C, 1700 C,
2000 C, 2100 C in a Webb 89 Vacuum furnace at Nelson Mandela
Metropolitan University (NMMU), South Africa, and one sample
kept as reference.
Two experimental CP batches used for the second phase of this
study were produced by PBMR Fuel Development Laboratories at
NECSA during 2007. These two batches were chosen as it gave a
range of different manufacturing conditions manufactured in the
Advance Coater Facility (ACF). It is noted that the SiC deposition
temperatures (1450 C, 1510 C) and the SiC thickness are different
for these two batches. The SiC thicknesses of the two batches (39
and 32 m, respectively) represent also the highest and the lowest
of the SiC thickness specication values. The SiC deposition rate is
0.23 m/min for both batches.
The third sample set consist of phosphorous-doped 3C-SiC layers deposited, at the Linkping Universitys (LiU) facility, on Si (100)
substrates using the concept of the hot wall chemical vapor deposition with silane (SiH4 ) and propane (C3 H8 ) as precursors diluted
in hydrogen (H2 ). Propane was introduced in the reactor chamber
prior to the silane addition during the heating-up cycle to prepare
a thin layer of SiC on the silicon substrate. This was to ensure epitaxial growth of mono-crystalline layers once silane is added at
the growth temperature. However by changing growth procedures
polycrystalline layers were also obtained. Phosphorus doping of
the layers was done during epitaxy using tertiary butyl phosphine
(TBP) (C4 H9 PH2 ) as a donor source (Henry and Janzn, 2005). The
SiC deposition temperature varies between 1210 C and 1320 C for
the 13 samples manufactured.
2.2. Grain size determination
Grain size determination was carried out using two methods
namely the Heyn Lineal Intercept procedure in accordance with
ASTM E112-96 (2004) and electron back scatter diffraction (EBSD)
analysis (Tan et al., 2008; Helary et al., 2004).
2.2.1. Grain size determination using Heyn Lineal Intercept
method
The at SiC samples were polished with 30, 9, 6, 3 and 1 m
polishing cloths to obtain a mirror nish side to be analyzed.
The TRISO CPs under investigation was prepared by grinding the
particles to half-way through in order to expose the different
layers. The particles were polished with the nal polishing done
with colloidal silica, containing particles with an average size of
0.05 m. All prepared samples were then etched using a modied
Murakamis etchant. The modied Murakamis etchant was prepared by adding 25 g of both KOH and NaOH to 100 ml of distilled
water. After the fore mentioned dissolved and the liquid cleared,

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193

Fig. 1. Experimental research plan for grain size measurements.

25 g of K3 [Fe(CN)]6 (potassium-hexa-ferricyanide) was added to

the mixture and stirred while heated until it dissolved. The reagent
was kept at approximately 200 C throughout the etching process.
The CPs were then added and left in the etchant for approximately 1 h and separately, the CVD-grown samples were etched
for 30 min. The samples were then removed from the etchant and
rinsed repeatedly in distilled water containing KOH and then in distilled water only. Finally the samples were placed in an ultrasonic
bath for a few minutes and then mounted and placed in the SEM
for investigation of the grains and grain boundaries.
The average grain size of the at CVD SiC samples and the
two batches CPs were determined using the Heyn Lineal Intercept method on 10 SEM micrographs for each sample and it was
calculated as follows.
Every micrograph has a demonstration line at the bottom with
the size of the line, SD , given in microns. The length of the demonstration line, LD can be measured in cm. Draw 15 test lines on the
micrograph, see example in Fig. 2, measure the length of one test
line, LT in cm (the measurement will apply to all the test lines). Now,
the size of the test lines, ST can be calculated using the following
expression:
ST =

SD LT
LD

(2004) is in all cases calculated to be lower than 10% and is considered to be acceptable precision. However, the grain size of the SiC
layer of the TRISO CPs are not equiaxed in shape and therefore the
grain sizes determined in this study, should be clearly indicate the
measurement direction for comparison purposes with results from
other researchers.

2.2.2. Grain size determination using EBSD

The coated particles containing the SiC layers were embedded
in an epoxy resin and mechanically thinned and polished using a
Buehler-Beta grinder polisher down to a 0.05 m colloidal silica
nish.

(1)

Grain size, G, is therefore the size of the line, ST , divided by the

number of grains cut by the test line, N, and mathematically it is
expressed as:
G=

ST
N

(2)

Follow the same procedure for all 10 micrographs and for every
test line drawn on each micrograph and take the average grain size.
The % relative accuracy (RA) as determined according to ASTM E112

Fig. 2. Example of a SEM micrograph used for grain size determination.

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Fig. 3. Typical example of the schematic presentation of LiU P-doped polycrystalline X377 sample and characterization identication.

The analysis of the prepared samples was done using a HKL

electron backscattered detector coupled to a JEOL 7001F scanning
electron microscope. The sample was tilted to 70 within the chamber with ne calibration of the detector geometry done using the
crystal structure for 3C-SiC, the expected SiC polytype to be present.
The area for the EBSD analysis was selected with a step size of
0.1 m for the mapping chosen. The scan duration was typically
between 9 and 11 h for each scan. In addition the crystal structure
for the 6H-SiC phase was also included during the analysis to check
if any grains of this structure were present.
2.3. Characterization of P-doped SiC samples (sample set 3)
The P-doped SiC layers were characterized after high temperature annealing from 1600 C to 2100 C using various techniques.
The LiU samples were further divided in smaller samples and
the specic characterization work executed on the sub-samples is
determined and a typical example is schematically shown in Fig. 3.
Annealing was performed in a resistively heated Webb 89 vacuum furnace supplied by R.D. Webb Company USA. The samples
were loaded in graphite or ceramic holders at room temperature and heated to the required temperature at a rate of 25 C
per minute. After completion of annealing at the required holding time and temperature, the samples were furnace-cooled to
room temperature. As the Linkoping samples were SiC grown on
Si-wafers, argon annealing atmosphere were chosen to ensure that
the vaporized silicon be removed from the sample surfaces to prevent contamination of the SiC samples itself. However, due to the
furnace maximum temperature limitations, the annealing of sample X377CB at 2100 C were conducted under vacuum for 10 min
only. The rest of the samples were annealed under argon for 1 h and
0.5 h for the 1600 C and 2000 C cycles, respectively.
The results of only ve techniques namely X-ray diffraction
(XRD), secondary ion mass spectrometry (SIMS), scanning electron

microscopy (SEM), transmission electron microscopy (TEM) and

high resolution transmission electron microscopy (HRTEM), are
briey described in this paper. The results obtained from the other
techniques like the atomic force microscopy (AFM) and Fourier
transformed infrared (FTIR) will be described in separate articles
at a later stage. The basic principles of the specic ve techniques
are not described in this paper.
It needs to be noted that although different structure morphologies were found and briey discussed in this paper, the relevant
subsamples used for the TEM observations, exhibited similar morphologies. The annealing studies on X364 subsamples which show
globular structures were therefore not considered in reaching conclusions in this study. A large number of TEM micrographs (>250)
were analyzed for this study to facilitate the conclusions reached.
3. Results and discussion
3.1. Grain size determination using Heyn Lineal Intercept method
The grain size measurement of the annealed bulk CVD 3CSiC results indicates that the grain size increases with increasing
annealing temperature. This can be seen in Fig. 4, which shows the
micrographs of etched grains and in Fig. 5. The average grain size
increases from 7.6 m for the unannealed sample to 10.1 m for
the sample annealed at 2100 C. The observation made from these
results is that the average grain size seems to reach an upper limit
after annealing at 2000 C. This however needs to be conrmed with
more samples to increase the statistical condence. Further examination reveals that the shape of the grains also change signicantly
from elongated in the unannealed sample, to more spherical grains
after annealing as shown in Fig. 4. The high concentration of twins
and stacking faults present in the SiC grains contributes to the difculty to differentiate between grain boundaries and this is partly
responsible for the relatively large standard deviations obtained

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Fig. 4. (ae) SEM micrographs showing the average grain size increase and shape changes occurred with increased annealing temperature.

Fig. 5. Inuence of high temperature annealing on the CVD ORNL polycrystalline 3 C-SiC.

195

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Fig. 6. Inuence of high temperature annealing on the polycrystalline 3 C-SiC layer of PBMR TRISO CP batches D and E.

for the measured grain sizes. Another possible reason for the large
deviation in measured grain sizes is most probably due to the fact
that the samples were only prepared in one direction (perpendicular to the plane of deposition), therefore the shape factor is not
taken into account.
The results of grain size determination of the SiC layer of the
two experimental PBMR TRISO CP batches are presented in Fig. 6
and although the results suggest also a slight increase in grain size
within experimental error, after high temperature annealing, the
increase in grain size is smaller than that reported in Fig. 4 for the
at SiC samples. It should be noted however, that the grain size
in the at SiC samples exhibited a denite distribution of large
and small grains which is most likely the reason for the larger
increase in average grain size upon annealing measured in these
samples. From the data shown in Fig. 6 it is clear that the average
grain size of batch D is larger than that of batch E for temperatures
up to 1600 C. For annealing temperatures above 1600 C the average grain sizes seems to remain the same. This phenomenon is in
agreement with the ndings by Van Rooyen et al. (2010) where the
strength measurements of CPs showed also that no signicant difference in strength values of these two batches exists at 2000 C.

Fig. 7. Micrograph showing a typical etched image of the SiC layer of the CP batch
D after annealing at 2000 C with an average grain diameter of 3.7 m (Heyn Lineal
Intercept method). The etching process also accentuated the high density of stacking
faults.

Fig. 7 shows a typical etched structure used for the grain size determination of the SiC layer of the TRISO CP. This gure also illustrates
the difculty to identify the grain boundaries due to the presence
of high density stacking faults which also are accentuated during
the etching process.
3.2. Grain size determination using EBSD
Fig. 8 shows an example of an IPF coloured crystal orientation
map of the 3C-SiC structure across the layer of the reference sample of CP batch D. No 6H-SiC areas could be detected during the
mapping of any of the layers investigated. In all the cases studied the grain sizes across the layer progressively varied from being
sub-micron at the inner-PyC and SiC interface to being several
micrometers in size at the outer PyC and SiC interface. Fig. 9 shows

Fig. 8. An example of an IPF coloured orientation map of the 3C-SiC structure across
the layer of the reference sample of CP batch D. The grain sizes across the layer
progressively varied from being sub-micron at the inner-PyC and SiC interface to
being several micrometers in size at the outer PyC and SiC interface.

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Fig. 9. A histogram of grain size distribution and grain size statistics of the analyzed
region of the reference sample of CP batch D.

a histogram of grain size distribution and Table 1 the grain size

statistics of the analyzed region.
The grain size statistics for D-REF show an average grain diameter of 0.368 m, however if the histogram of grain size distribution
is considered, a large contribution towards the grain size statistics
originate from grains smaller in size or close to 0.1 m in diameter
which is comparable to the step size used. Thus these grains
cannot be considered for the analysis. Setting a threshold grain
diameter value of at least 0.4 m to be included for the analysis

197

Fig. 10. This histogram showed the recalculated grain size statistics of the reference
sample of CP batch D after removing the grains with a minimum grain size of 0.4 m
(two adjacent indexed spots in the x and y directions) which would minimize the
incorrect statistical evaluation.

and removing all the grains less than this would remove any
uncertainty. Thus choosing a minimum grain size of 0.4 m (two
adjacent indexed spots in the x and y directions) would minimize
the incorrect statistical evaluation. Removing these grains form
the data set for the case under discussion, the size is being reduced
from 1533 grains to 355. The recalculated grain size statistics is
shown in Table 1 with the re-plotted histogram in Fig. 10.

Table 1
EBSD grain size statistics of the analyzed region of the SiC layer of the CP batches D and E.
Measurement
Average, expectation (EX), m
Variance, dispersion (D2 X)
Standard deviation (s)
Coefcient of variation (s/EX)
Minimum value (Xmin), m
Maximum value (Xmax), m
Size of the data set (N)
a
b

D-REF
a

0.368 (3.0)
0.340
0.583
1.587
0.113
6.502
1533

D-2000 C

E-REF

0.307 (3.6)a
0.276
0.525
1.710
0.113
10.466
2786

0.343 (2.7)a
0.279
0.528
1.539
0.113
6.651
1564

D-REF re-calculated
1.158
b

0.928
b

0.407
6.502
355

Determined ASTM E 112.

Not available.

Fig. 11. Batch 361 XRD diffractogram of the 3C-SiC grown on Si(1 0 0). The epilayer is grown heteroepitaxially and only the (h 0 0) peaks are visible since there is a preferred
orientation.

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Fig. 12. Average grain size distribution in the LiU P-doped polycrystalline 3C-SiC sample X364.

3.3. Characterization of the P-doped SiC samples

3.3.1. Chemical analysis
The P-content in selected LiU P-doped prior to annealing was
measured by the Evans Analytical Group (EAG), USA, using SIMS
with a detection limit of 1 1013 atom/cm3 and these measurements are shown in Table 2. The doping level varied between
1.1 1015 and 1.2 1019 atom/cm3 . Sample X377 has the highest
doping level at 1.2 1019 atom/cm3 and was therefore chosen to
discuss further in this paper.

The PBMR calculated value for the typical PBMR reactor yields
a P concentration of 9.8 1017 atom/cm3 . The P-doping levels of
the selected samples indicated in Table 2, showed that these
LiU prepared samples are relevant to the PBMR conditions as
it gives a representative P concentration spread around typical PBMR conditions. This phosphorous concentration is also in
the same order found by neutron-transmutation studies done by
Baranov et al. (2007) for a neutron dose of 1 1020 cm2 for
30 Si enriched SiC. Wellmann (2005) found that P-doping concentrations of up to 1.3 1018 atom/cm3 were achieved and further

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199

Fig. 13. Average grain size distribution in the LiU P-doped polycrystalline 3C-SiC sample X377.

suggested that much higher doping levels are achievable. The work
presented in this paper showed achieved concentrations up to
1.19 1019 atom/cm3 .
Hendriks et al. (1982) found that for low doping concentrations, the P atoms will be trapped at the grain boundaries, but that
for higher doping concentrations only a small fraction of P atoms
will be trapped at the grain boundaries and therefore only a small
depleted zone next to the grain boundaries are expected. The SIMS
analysis of the LiU samples was done on bulk areas and therefore
no detail prole is available to conrm or reject this statement.

3.3.2. X-ray diffraction

X-ray diffraction measurements were conducted using the
Philips PW1729 diffractometer at the LiU Physics department and
the Philips PW1840 diffractometer at NMMU. The diffractograms
for all samples showed the 3C-SiC phase grown on Si(1 0 0). A typical diffractogram of the single crystal sample X361 measurement
is shown in the diffractogram (2-scan) in Fig. 11 and were used
to identify the SiC phase and the orientation of the epilayer. The
epilayer is grown heteroepitaxially and only the (h 0 0) peaks are
visible since there is a preferred orientation.

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Table 2
Bulk SIMS analysis of P in SiC.
Sample no.

X380-C
X377-E
X383-BA
X387-BA
X382-G
X391-B
X392-B
X393-B

EAG SIMS P concentration (atom/cm3 )

Analysis 1

Analysis 2

Average

6.46 1018
1.20 1019
5.23 1017
5.36 1015
1.65 1018
1.08 1015
1.75 1015
6.68 1015

6.72 1018
1.18 1019
5.45 1017
5.35 1015
1.57 1018
1.13 1015
1.71 1015
6.74 1015

6.59 1018
1.19 1019
5.34 1017
5.36 1015
1.61 1018
1.11 1015
1.73 1015
6.71 1015

3.3.3. Scanning electron microscopic evaluation

A XL30 Philips SEM at NMMU was used to investigate the top
surface morphology of the samples prepared at LiU and to determine the grain sizes.
The grain sizes of selected samples from X364, X377, X380 and
X383 were determined using the Heyn Lineal Intercept method in
accordance with ASTM E112 (2004). The SEM micrographs in Fig. 12
show globular top surface structure for sample X364 and the grain
size measurement shows a large variation in grain size, which probably indicated a large variance in the SiC deposition temperature.
The grain sizes of sample X377 showed approximately even average
sizes and fairly homogeneous morphologies (Fig. 13).
From the grain size determination schematically presented in
Fig. 14, it is shown that grain sizes of the P-doped polycrystalline
samples are fairly evenly sized whereas large grain size variances
are visible for the un-doped sample X364. This fairly homogeneous
grain size distribution of the P-doped samples, showed that the
deposition temperature were in a narrow range as in contrast with
those of sample X364. During the preparation of sample X364 it
was also further observed that the substrate sample was located
near the input end of the chamber and that the temperature in that
region was most probably higher as reported for this growth. The
presence of molten Si substrate was observed during the removal
of the sample which is also an indication of much higher temperature. The yellow optical colour of the top edge of sample X364 also
indicate that the substrate temperature for sub-samples X364AB
and X364AC may have been higher as the recorded 1210 C. Deductions from work by Chin et al. (1977) showed that the yellow optical
colour may indicate a higher substrate temperature.
Lpez-Honorato et al. (2008) indicated that the top surface
changed from a globular to a faceted structure as stoichiometry
improves. Fig. 15 is included to show the difference between typical

Fig. 14. Schematic presentation of the grain size distribution measured on different
positions on the sample. The grain size distribution curve of un-doped polycrystalline sample X364 is shown for comparison.

Fig. 15. SEM micrographs showing the difference between typical globular and
faceted top surface structures.

globular and faceted top surface structures. The stoichiometry of

these samples is however not conrmed at time of this study. The
effect of deposit temperature on these three examples are not
as clear as described by Lee et al. (2001) and Chin et al. (1977),
but it is important to notice that the doping levels are varying
and therefore the manufacturing conditions are different for
each sample as well. It is recommended that these morphologies
together with the rest of the 13 LiU samples be investigated in
conjunction with the respective manufacturing parameters.
3.3.4. Transmission electron microscopic evaluation
A 200 kV Philips CM20 transmission electron microscope was
used for the TEM analysis. A large amount of TEM micrographs were
taken and evaluated to determine the effect of temperature and Pdoping level on the nanostructures of 3C-SiC. Only selected images

Fig. 16. Bright eld TEM micrograph and SAD pattern of sample X364CA after
annealing at a temperature of 1600 C. The SAD is consistent with the cubic 3CSiC phase with the beam along the 1 1 0 direction. The streaks in the SAD are due
to the thin twin platelets visible in the bright-eld TEM image.

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201

Fig. 17. Bright eld TEM micrograph and SAD of sample X377I after annealing at
a temperature of 2000 C. The SAD indicates that a phase transformation to 6H-SiC
hexagonal phase occurred. The beam is along the 1 0 0.

are shown in this paper as it represents the typical results obtained

from the full TEM evaluation.
High resolution TEM images were acquired using a JEOL
2200MCO aberration corrected (S)TEM operated at 200 kV with an
in-column omega lter (Oxford University).
The single crystal LiU 3C-SiC samples (P concentration from 0 to
6.71 1015 atom/cm3 ) were annealed at 1600 C and 2000 C. The
TEM evaluation of these samples showed that no phase transformation, no nanotubes and no decomposition were observed for these
P-doping levels up to an annealing temperature of 2000 C.
The annealing of the polycrystalline LiU 3C-SiC samples were
done at 1600 C, 2000 C and 2100 C respectively where phase
transformation from 3C- to 6H-SiC were observed for samples X364
(un-doped) and X377 (highest P-doped sample) at 2000 C. As both
these samples showed a phase transformation, it indicates that the
P-doping level is not a contributing fact towards this phase transformation, but it is temperature dependant. Figs. 16 and 17 show
the bright eld (BF) TEM image and corresponding selected area

Fig. 18. Bright Field TEM micrograph and SAD of sample X377CB after annealing at
a temperature of 2100 C. The SAD shows the four rings of the graphite namely 002,
101, 004 and 112.

Fig. 19. HRTEM image (250,000) of the SiCgraphite interface region of sample
X377CB after annealing at 2100 C.

diffraction (SAD) of the samples X364 and X377 after annealing at

1600 C and 2000 C, respectively. Fig. 18 shows the BF TEM image
and SAD of the sample X377CB after annealing at 2100 C. Evidence
of decomposition of SiC is clearly visible. The diffraction ring pattern in Fig. 18 shows that the SiC transformed to polycrystalline
graphite. The rst four rings of graphite 0 0 2, 1 0 1, 0 0 4 and 1 1 2,
are visible. No nanotubes were observed in any of the polycrystalline LiU samples.
The HRTEM image in Fig. 19 shows the SiCgraphite interface
region of sample X377CB after annealing at 2100 C. Randomly
orientated graphite lamella which has the (0 0 2) parallel to the
electron beam, display the typical HRTEM fringe image of the basal
planes. The SiCgraphite interface region and the graphite lamella
are shown in Fig. 20 at a higher magnication.

Fig. 20. HRTEM image of sample X377CB after annealing at a temperature of 2100 C
showing the basal planes in the graphite lamella at higher magnication (800,000).

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4. Conclusions
The average grain size determined on the at CVD SiC samples,
suggests an increase from 7.6 m for the unannealed sample to
10.1 m for the sample annealed at 2100 C. An interesting observation made from these results is that the average grain size seems
to level off after annealing at 2000 C. Further examination reveals
that the shape of the grains also change signicantly from elongated
in the unannealed sample, to more spherical grains after annealing.
The increase of average grain size of the SiC layer of the two
experimental PBMR TRISO CP batches with increasing annealing
temperature is smaller than that determined for the at CVD 3CSiC. Although there is a difference in grain size noted between the
two batches after annealing at 1600 C (3.9 and 3.0, respectively),
the average grain size of the two batches levels off at temperatures above 1600 C. This result is in agreement with the ndings
by Van Rooyen et al. (2010) where the compression strength measurements of CPs showed this same trend.
The average grain size values from EBSD are approximately 10
lower than those measured by the Heyn Lineal Intercept method
and this is most likely a consequence of the different approximations used for the quantication schemes.
The preliminary conclusion reached is that the P-content at
these experimental levels (1.1 1015 to 1.2 1019 atom/cm3 ) does
not have a signicant inuence on the nanostructure of SiC after
annealing at high temperatures without irradiation.
Although phase transformations from 3C- to 6H-SiC were
observed after annealing at 2000 C, it is not attributed to the Pdoping concentrations.
Decomposition of the SiC is only observed at 2100 C annealing
temperature and no nanotubes were identied during the TEM and
HRTEM analysis although graphitic structures were identied.
5. Recommendations
The observed grain size increase with increasing annealing temperature for both the at SiC and SiC layer of the CPs needs to be
veried with a larger statistical sample. Furthermore, it is important to include the shape factor in these determinations by doing a
qualication measurement test on different oriented sections with
regards to the growth direction.
As no grain size specication for SiC layers for TRISO CPs is documented, it is recommended that a statistical sample of CPs per
batch needs to be investigated with the following in mind:
The grain size of actual CPs are investigated with specic reference to long duration (>100 h) annealing as a function of
temperature to relate the grain size modication with specic
reactor operational requirements.
The grain size and strength correlation be determined.
The inuence of grain size on the Ag transport rate be determined.
It is also recommended that the EBSD results be further interpreted with regards to the grain boundary orientation. The EBSD
map could also give valuable information with regards to the orientation with respect to the growth direction and needs to be
evaluated further to do comparisons between the two batches and
the inuence of this orientation on the strength of the CP.

It is also recommended that the morphologies and stoichiometry of the three samples mentioned in this paper together with the
rest of the 13 LiU samples be investigated in conjunction with the
respective manufacturing conditions and inuence of the P-doping
on the resistivity of SiC. It is also recommended that the inuence of
P-doping level on the heat conductivity and mechanical properties
of SiC be determined.
Acknowledgements
This research was sponsored by PBMRs Fuel Optimization
Technology Programme. The use of the NMMU and PBMR Fuel
Development Laboratory facilities are gratefully acknowledged.
Johannes Mahlangu (PBMR), Ellen Nquma (PBMR), Jaco Olivier
(NMMU) and Jacques O Connell (NMMU) are thanked for the
annealing operations. The HRTEM images were produced by Dr.
Sarah Haigh at Oxford University.
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