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ELSEWIER Solid State Ionics 83 (1996) 225-228
STATE
IONICS

The chemical transformation of single-crystal a-Al,O, platelets

to pI-Al,o,
Chu Km Kuo, Patrick S. Nicholson *
Ceramic Engineering Research Group, Department of Materials Science and Engineering, McMaster University, Hamilton, Ontario,
Canada LSS 4L7

Received 29 September 1995;accepted 15 November 1995

Abstract

Single-crystal Na-$‘-Al,O, micro-platelets have been prepared by heating a-Al,O, platelets in an alkali-containing
atmosphere. The cu-Al,O,-to-Na-P”-A1,03 transformation rate and the development of microstructure have been studied.
Preliminary results on the preparation of K-P”-Al,O, are also given.

Keywords: @‘-alumina - potassium; v-alumina - sodium; Synthesis - ceramic

1. Introduction of pure P”-Al,O, powder requires the appropriate

Na,O-to-Al,O, ratio, stabilising catalyst and calci-
Single-crystal ‘Y-AI,O, platelets transform epitax- nation conditions. Excess Na,O produces sodium
ially to Na+“-Al,O, when heated in a sodium-con- meta-aluminate, a hygroscopic product. An Na,O-
taining atmosphere. Full transformation occurs at deficiency composition, or, high calcination tempera-
1280°C after 24 h [ 1,2]. This procedure was devel- ture, on the other hand, result in mixtures of P-Al,O,
oped to prepare p”-Al,O, platelets as potential hosts and/or ~Al,0,.
for luminescence and a weak-interface component In comparison with conventional preparative
for ceramic composites. The present investigation routes for Na-P”-Al,O,, the characteristics of the
measures the transformation rate from a-Al,O, to present one are:
p”-Al,O, and examines the morphology of the trans- (1) The p”-Al,O, is epitaxially grown from the
formed platelets. The work was extended to K-P”- a-A1,03 parent-crystal-lattice and retains the shape
Al,O, and results are reported. and single crystallinity thereof.
Na+“-Al,O, ceramic powders are usually syn- (2) Since the transformation takes place isother-
thesised by solid state reaction.‘The starting material mally at equilibrium or near-equilibrium vapour
is mixed or co-precipitated powder, a sprayed aque- pressures over a @‘-Al,O, powder bed, no by-prod-
ous solution or suspension or a sol-gel [31. Synthesis ucts are produced and high purity is expected.
temperatures are = 1150-1250°C. The preparation (3) No sodium meta-aluminate or transient unsta-
ble phases are produced thus avoiding transient or
partial melting, grain agglomeration and exaggerated
* Corresponding author. grain growth.

0167-2738/96/$15.00 0 1996Elsevier Science B.V. All rights reserved

SSDI 0167-2738(95)00244-S
226 C.K. Kuo, P.S. Nicholson/
2. CC-Al,O, platelets and their transformation
Na-P”-AI,O,
o-Al,O, platelets (grades 1 and 3, Atochem.,
Paris, la Defense Cedex 42, France) were employed
as raw material. These platelets were single-crystal,
basal Al,O, of hexagonal form with equivalent di-
ameter, 5 and 15 pm and thickness, 0.5-l pm.
a-Al,O, platelets were loosely packed to 2-3
mm depth in a Na+“-Al,O,-coated alumina boat.
This was then placed in a platinum crucible inside an
alumina one and the intervening space filled with
(Na,,, Li o,Os>-or (Ko.9Lio,l)-P”-Al,0, powder. The
latter acts as the source Na- or K- and Li-vapour.
The Li+ ions are required to stablise the @‘-Al,O,
structure.
Transformation was undertaken between 1280 and
1310°C for 0 to 24 h at a heating and cooling rate of
S”C/min. lO”C/min was used following short soak-
ing times at top temperature. The increased cooling
rate was employed to suppress any chemical reaction
during cooling. The transformed fraction with rising
temperature was estimated from the zero-soaking-
time, experimental runs.
Transformation fraction was determined
X-ray quantitative analysis (Cu Ko radiation) using
the relative diffraction intensities of the Z(O2,
lO)Na-a”-Al,O, and Z(113),_A,203 peaks at 20=
46.14” and 43.36” 111. The Z(206),,_,_,,20, at 28 =
44.47” was used to detect Na+-Al,O,. The pow-
ders analysed were ground and mixed to avoid X-ray
absorption errors arising from the j3”-Al,O, surface
layers.
The microstructural morphology of the platelets
before and after transformation was observed by
SEM. Powders were dispersed in acetone in an
ultrasonic bath and deposited on a well-polished
aluminum sample holder. A gold coating was sput-
tered onto the powders to avoid surface charge accu-
mulation.
3. Results and discussion
3.1. The transformation of a-Al, 0, to Na-P”-Al,
X-ray diffraction patterns of platelets with various
transformation fractions are shown in Fig. 1. Intensi-
Solid State Ionics 83 (1996) 225-228
to ties were normalised to the reflection with the high-
est intensity. The high diffraction intensity of the
(113)&&o, ensures the high detectability of non-
transformed a-A120s. The range 20 = 3-60” was
scanned.
P-Also, was found in some samples following
prolonged heating, or, after too high temperatures. It
was always low relative to P”-Al,O, and thus ne-
glected in the quantitative X-ray analysis. p”-Al,O,
and P-Al,O, are polytypic structures with different
stackings of close- and loose-packed oxygen layers
along the c-axis. Syntaxial intergrowth is well known
[4,5]. The polytypes observed are likely intergrown
rather than on separate platelets.
The transformed fraction of ol-Al,O, was calcu-
lated via:
Transformed volume
dP,,
= Transformation-volume._,,, X d,
a
where the Transformation-volumex_~~Y is the p”-
Al,O, volume determined by X-ray analysis and d,
and dPn are the densities of the rw- and Na+“-Al,O,,
respectively. Na+“-Al,O, is assumed to form at the
by
expense of the o-Al,O, platelet and any influence of
a diffuse reaction layer is discounted. The trans-
formed thickness-fraction versus time at 1280°C is
plotted in Fig. 2. A 15 pm size OL-Al,O, platelet
exhibits a larger transformation thickness than a 5
pm one, for the same heating period. This difference
is enhanced at 1310°C (Fig. 2). This result is ex-
plained by the higher gas-permeability in the packing
of large particles. The transformation is also acceler-
ated on sequential heating with intermediate mixing
to refresh the contact of the platelets with the reac-
tion atmosphere. This sequential heating protocol
was employed to prepare Na-@‘-Al,O, platelet
powders in beds of packed thickness > 3 mm.
3.2. Microstructural observations of the Na-p”-
Al, 0, platelets
Figs. 3 and 4 are SEM micrographs of unreacted
0, o-AlzO, and completely transformed Na-+“-Al,O,
platelets respectively. l3”-Al,O, platelets essentially
retain the original hexagonal shape of the cx-Al,O,
precursor. Growth steps and layers trace on the
 C.K. Kuo, P.S. Nicholson/Solid State Ionics 83 (1996) 225-228 227

Fig. 3. SEM of starting CY-Al,O, platelets (grade l), bar = 5.7

km.

surface and at the edges. The surface shows a less

41 .3wa-A1203 pseudomorphic growth pattern than the partially
transformed p”-Al,O, platelets prepared at lower

J kwmd”L 62.&a-Ai203
temperatures. This indicates a higher reaction rate.

I I I I I I 3.3. K-P”-Al,O, platelet preparation and mi-

42 43 44 45 46 47
crostructure
20(“)
Fig. 1. Typical X-ray diffraction patterns of various transforma- K-v’-Al,O, platelets were grown from cx-Al,O,
tion fractions at 128O’C in the Na-P”-Al,O, /a-Al,O, system. using a (K, Li)+“-Al,O, vapour source. Complete
transformation was achieved after 6 h at 1310°C.
Fig. 5 is an SEM micrograph of K-P”-Al,O,
platelets showing a layered structure the develop-
ment of which is attributed to the increased reaction
; 0.9 A 0
rate at the higher vapour pressure and reactivity of
A

30.8 A
l
r 0
_ 0.7 l
s 0
g 0.6 A
Y A*

A 15pm. 1310°C
0 5pm.1310°c
A 15pm, 1280°C
a 5pm.1280°C

0.0 I I r I I I I I I
0 100 200 300 400 500 600 700 800
Time (minute)
Fig. 2. Transformation-thickness fraction versus time plots for 5 Fig. 4. SEM of Na-P-Al,O, platelets prepared at 1310°C for 7 h,
and 15 pm platelets at 1280°C and 1310°C. bar = 3.4 pm.
228 C.K. Kuo, P.S. Nicholson/Solid State Ionics 83 (1996) 225-228

4. Conclusions

(1) Micro, single-crystal Na-+“-Al,O, platelets

have been prepared from ~Al~0, platelets by
chemical reaction with Na-vapour.
(2) Th e cx-Al,O,-to-Na-P”-AI,O, transformation
rate at 1280°C and 1310°C was determined.
(3) SEM observations show that the transformed
Na-/3”-Al,O, essentially retained the original form
and single-crystallinity of precursor a-Al,O,
platelets.
(4) K-P”-Al,O, platelets were prepared by an
identical procedure using K-P”-Al,O, vapour
source. The high transformation rate in the K-v-
Al,O, case produced multiple-layered structures and
more control was necessary to avoid polycrystallisa-
tion.

References

[l] X.-N. Huang, C.K. Kuo and P.S. Nicholson, J. Am. Ceram.
sot. 78 (1995) 892.
[2] C.K. Kuo, X.-N. Huang and P.S. Nicholson, J. Am. Ceram.
Fig. 5. K-P”-AI,O, platelets, prepared at 1310°C for 16 h, Sot. 78 (1995) 824.
showing (a) a layered structure (bar = 3.3 pm) and (b> split layers [3] J.H. Duncan, R.S. Gordon, R.W. Powers and R.J. Bones, in:
leading to polycrystallisation (bar = 1.3 Frn). The Sodium Sulfur Battery, eds. J.L. Sudworth and A.R.
Tilley (Chapman and Hall, London, 1985) pp. 79- 127.
[4] D.J.M. Bevan, B. Hudson and P.T. Moseley, Mater. Res. Bull.
the K-species. Fig. 5b shows a particle on which 9 (1974) 1073.
multiple and radiating, split layers have grown, lead- [5] D. Gratias, J.P. Boilot, Y. Le Cars and J. Th&y, Phys. Status
ing to polycrystallisation. Solidi (a) 38 (1976) 595.