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Bahan Bacaan
Bahan Bacaan
Nuclear Magnetic
Resonance
ELSEVIER
Structural characterisation
of Na,ZrO,
Abstract
A combination of X-ray and electron diffraction, electron microscopy and solid-state nuclear magnetic resonance
(NMR) has been used to elucidate the structure and the ordering of Na,ZrO,. The diffraction data confirm a
monoclinic crystal structure. A sample prepared by a conventional solid-state reaction of the components is shown
by both X-ray diffraction and electron microscope imaging to have an extremely high concentration of planar defects
associated with stacking disorder of the planes along the c-axis. The incidence of these defects is significantly
reduced in a sample recrystallised from a bismuth oxide flux. NMR indicates that the local coordinations are well
defined in both samples but with some sharpening of the spectra from the recrystallised sample indicative of the
increase of long-range order. The 23Na magic angle spinning (MAS) NMR spectra clearly show three distinct sites
with widely differing quadrupolar interaction parameters that can be related to the known site symmetries. Two
distinct oxygen resonances are observed in the MAS NMR spectrum from an O-enriched sample while the static
9Zr NMR spectrum can be simulated with one set of interaction parameters.
Key words: Magic-angle spinning nuclear magnetic resonance; Structure; Na,ZrO,;
1. Introduction
Structural
characterisation
of solid materials
has developed rapidly over the last decade as new
methods have become available to augment the
established
techniques
of diffraction
and microscopy. A methodology
that employs a suite of
complementary
techniques
that are sensitive to
50
T.J. Basfow et al. /Solid State Nucl. Magn. Reson. 3 (1994) 49-57
2. Experimental
Zirconium dioxide and anhydrous sodium carbonate in stoichiometric proportions were intimately mixed and pressed into a pellet. The pellet was heated in a stream of nitrogen to 950C
for 16 h. 0 isotopically enriched Na,ZrO, was
prepared by starting with ZrO, that had been
enriched in 0 by reaction of 10 mol% O-enriched H,O with zirconium isopropoxide, as previously described [12]. Then further annealing for
24-h periods at various temperatures in the range
500-1050C
was performed.
A sample of
Na,ZrO,
powder was then mixed with 10%
(w/w) of Bi,O, powder, pressed into a pellet and
annealed at 950C in either a nitrogen atmosphere or under vacuum until all the Bi,O, had
evaporated from the specimen.
X-Ray powder diffraction
patterns
were
recorded on a Rigaku Miniflex X-ray spectrometer using CuKa radiation. Electron micrographs
and selected area diffraction patterns were obtained with a JEOL 2010 electron microscope,
from crushed powders suspended on holey carbon grids.
The NMR was carried out on a Bruker MSL
T.J. Bastow et al. /Solid State Nucl. Magn. Reson. 3 (1994) 49-57
(a)
51
0
Na
Zr
(b)
000
OO
00
Q
O
000
00
so0
00s
00
Table 1
Atomic coordinates for monoclinic (group C2/c) Li,TiO, [2]
which is isostructural to Na,ZrO,
Atom
Equipoint
Li(l)
Li(2)
Li(3)
Ti(1)
Ti(2)
OfI)
O(2)
O(3)
8f
4d
4e
4e
4e
8f
8f
8f
Coordinates
x
0.238
0.250
0.000
0.000
0.000
0.141
0.102
0.138
0.077
0.250
0.045
0.415
0.747
0.265
0.586
0.906
0.000
0.500
0.250
0.250
0.250
0.138
0.138
0.135
52
T.J. Bastow et al. /Solid State Nucl. Magn. Reson. 3 (1994) 49-57
algorithm for calculating the intensities of powder diffraction patterns in the presence of planar
faulting and shown that the diffraction peak
widths become index-dependent.
The proposed
stacking pattern is shown in Fig. 1. Fig. la shows
the structure of unfaulted Na,ZrO,
using the
fractional coordinates found from the refinement
of the Li,TiO, structure and listed in Table 1.
For this structure the sequence of sodium and
mixed sodium-zirconium
layers up the c-axis is
. . . ABAB . . . Fig. lb shows the cation layers only
of a faulted stacking sequence ABC. Such stacking faults account for the marked variation in the
relative peak heights of the 002 and 020 X-ray
of a crystal of Na,ZrO,
showing
stacking
direction
to
T.J. Bastow et al. /Solid State Nucl. Magn. Reson. 3 (1994) 49-57
53
co
0
0
0
00
00
0
0
00
80
0
0
0
0
0
0
0
0
260
160
-lb0
-2bo
54
T.J. Bastow et al. /Solid State Nucl. Magn. Reson. 3 (1994) 49-57
(b)
1000
750
500
250
-250
-500
320
310
300
290
280
T.J. Bastow et al. /Solid State Nucl. Magn. Reson. 3 (1994) 49-57
Cc)
50
25
-25
-50
-75
-100
50
25
-25
-50
-75
T.J. Bastow et al. /Solid State Nucl. Magn. Reson. 3 (1994) 49-57
56
Table 2
23Na NMR interaction parameters that gave the best simulations for all magnetic fields and the measured intensities, fractions of
magnetisation of the (l/2, - l/2) transition in the centre band at 9.4 T and the corrected intensities
Site designation as for the crystal structure; A = Gaussian smoothing used for simulations; Int. intensity = intensity derived from
the simulations at 9.4 T; CB fraction = the fraction of the (l/2, - l/2) transition intensity in the centre band at 9.4 T calculated
using functions of intensity against v~/Y,Y, in ref. 22, corrected intensity = intensity corresponding to the sodium distribution in
the actual structure.
Site
Na(l)
Na(2)
Nat31
77
siw
(ppm)
$Hz)
15.0 + 0.2
27.0 f 0.2
19.5 rf:0.2
2.52 + 0.02
2.08 + 0.02
4.20 f 0.04
0.67 f 0.02
0.05 + 0.05
0.27 f 0.02
A
(Hz)
Int.
intensity (%)
CB
fraction
Corrected
intensity (%)
150
150
150
53 f 3
31+2
16f4
0.79
0.91
0.30
44+5
22 f 4
34 f 8
T.J. Bastow et al. /Solid State Nucl. Magn. Reson. 3 (1994) 49-57
4. Conclusion
l0, 23Na and 91Zr NMR spectra have been
reported for Na,ZrO,. A single zirconium site
can be resolved within the static NMR spectrum.
For 0, despite there being three sites in the
crystal structure, two of these are locally identical
as only two separate oxygen resonances are seen
in the ratio 2: 1. For 23Na three sites can be
resolved that are consistent with the structural
distribution 2: 1: 1, with widely differing C, values. On the basis of the intensity distribution and
C, values the resonances can be assigned to
specific sites within the structure. NMR spectra
of the sample prepared by direct solid-state reaction and that flux-annealed in Bi,O, show only
minor differences so that the local coordinations
are very similar in both samples. Diffraction and
electron microscopy data show that flux-annealing removes disorder due to stacking faults. A
methodology combining diffraction, microscopy
and NMR holds much promise for characterising
solid materials.
57
6. References
1 G. Lang, Z. Anorg. Allg. Chem., 276 (1954) 71.
2 G. Lang, Z. Anorg. Allg. Chem., 348 (1966) 246.
3 Powder Diffraction File (JCPDS), File No. 35-770, Pub.
International
PA, 1992.
4 J. DAns and
1.
5 S.O. Ampian,
6 J.F. Dorrian
Data, Swarthmore,
191 (1930)
(1969) 179.
7 M. Troemel
8
9
10
11
12
268.
16 A.J.C. Wilson, Proc. Roy. Sot. A, 180 (1942) 277.
17 M.M.J. Treaty, J.M. Newsam and M.W. Deem, Proc. Roy.
SK A, 433 (1991) 499.
18 J.G.P. Binner, R. Stevens and S.R. Tan, Trans. J. Br.
Ceram. Sot., 82 (1983) 98.
5. Acknowledgements
M.E.S. thanks the SERC
T service at the University
Parkinson for his help there
(University of Warwick) for
(1984) 2502.