Materials Chemistry and Physics, 24 299-3 14

(1990)

STRUCTURAL CHARACTERIZATION OF ALUMINA METASTABLE PHASES

IN PLASMA SPRAYED DEPOSITS

D.FARGEOT, D.MERCURIO and A.DAUGER

Laboratoire de C&ramigues Nouvelles - U.A. CNRS n'320,
73 Avenue Albert Thomas, 87036, Limoges (France)

Received May 28,1989;accepted July 12,1989

ABSTRACT
Plasma sprayed coatings were used as rapidly solidified pure
alumina samples. The crystallographic structure of as-sprayed
deposits has been previously shown to be a metastable one, the
so-called r modification. During heat treatments between 850°C and
105O"C, the r to a transformation was studied through X-ray powder
or single-crystal experiments, and transmission electron microscopy
observations.
This transformation occurs through a single intermediate phase,
called 6*, with an orthorhombic unit cell (a=0.793 nm, b=0.795
nm,c=1.171 nm). 6* has a domain structure deriving from a
quasi-periodic antiphase boundaries mechanism in the (100) planes
of a defective spine1 lattice.

INTRODUCTION
Alumina is a very important material used in large quantities for
high strength and temperature applications in its stable alpha form,
and for chemical and catalytic use in the metastable gamma
modifications [l].
The only well known structure is that of the a corundon stable
phase. Since most of production or forming processes lead to
metastable forms, 7 phases are only known through powder
characterizations. Moreover there seems to be little agreement about
the structural mechanism of the r-z-a phase transformation [2].

0254-0584/90/$3.50 OElsevier
Sequoia/printed
inTheNetherlands
 In previous studies [3,4], we have shown that the plasma sprayed
material is mainly made of r-alumina, with a crystallographic
structure deriving from a defective spine1 lattice through
quasi-periodic antiphase boundaries.
The purpose of this paper is to describe the only intermediate
phase, called 6*, appearing during the r to a phase transformation
of plasma sprayed samples, between 85O'C and 1050°C.

EXPERIMENTAL PROCEDURE
The two starting powders used to obtain plasma sprayed [5] solid
specimens are 99.9% pure a-alumina with narrow particle size
distributions, about 18 and 60 jbrnin diameter, respectively.
The structural state of as-sprayed samples is the r phase, with
a low residual a-Also3 content, estimated at less than 5% [6]. No
difference is observed between samples obtained with N2-HZ or with
Ar-H2 mixtures as a plasma forming gas. The volume fraction of
porosity is about 15% and grain size is often very small.
Single crystalline small samples are obtained from 60 wrn powder
directly sprayed into water.
Cu Ku radiation is used for X-ray powder diffraction experiments
carried out with a Guinier focusing goniometer, and MO Ka for single
crystal diagrams obtained with Bragg, Weissenberg or Buerger
cameras.
Samples of 3 mm in diameter for transmission electron microscopy
are taken out by diamond sawing, grinding, polishing and ion beam
thinning.

RESULTS
X-Ra
v
Two kinds of specimens, respectively 150 Mm and 5 mm thick, were
used. No structural difference has been evidenced between them in
the initial state and the observed phase sequence induced by
annealing was the same.
Figure 1 shows X-ray powder diagrams in the three main steps of
the transformation: the as-sprayed (Fig.la), the intermediate
(Fig.lb) and the final a state (Fig.lc) obtained at 1050°C for 3
hours.
As-sprayed samples are in the r-A1203 form,a crystallographic
state deriving from the spine1 structure with ordered vacancies in
the cationic sublattice. Quasi-periodic antiphase boundaries [7]
 301

explain the abnormally high background of scattered intensity

observed on the powder diagrams in the vicinity of (220),(113) and
(511) spine1 lines.

b)

Fig. 1. X-ray powder diffraction patterns: a) as sprayed alumina, b)

intermediate state, 6*, 16 h at lOOO"C, c) final a state, 3 h at
1050°C.

Before a complete development of the Q phase (Fig.le), only one

intermediate diffraction diagram is observe?, a well developed state
which is illustrated on Fig.lb (after 16 hours at 1OOO'C). Whatever
the heat treatment used, the angular position of the diffracted
lines remains unchanged, only their intensity and width are
modified.
This powder diagram cannot be simply indexed on the basis of
known Al.203 intermediate phases. Only some very weak lines
302

reveal the presence of a small amount of the 8 phase. The comparison

between transmission patterns carried out on ground samples, and
reflexion experiments on the massive state of the same samples,
shows that this small amount of 8 phase exists only near the
surface. Therefore the corresponding weak diffraction peaks will not
be taken into account.
The X-ray powder pattern clearly derives from that of ~-A1203
with the splitting of the (400) and (440) spine1 lines. Furthermore,
the odd fundamental (113) and (115) lines disappear, and new
diffracted peaks are observed in the high background domains, near
the (220), (113) and (115) positions.
The corresponding structure cannot be determined from its powder
diffraction diagram only.

Transmission electron microscowy

In earlier studies [3,4], we have shown that the electron
diffraction patterns of the as-sprayed material exhibit additional
diffuse reflections. Symmetrical diffuse satellite spots always
appear around the (ill), (220), (311), (115) . . . nodes of the spine1
lattice which are all the reciprocal points of the cationic
sublattice. These satellite spots are oriented and elongated in the
(hO0) directions and are produced by quasi periodic arrays of (hO0)
l/4 <llO> or (hO0) l/2 ~100~ antiphase boundaries.
The complex selected area diffraction pattern of Fig. 2a
corresponding to the first step of transformation from the r phase,
results from the superposition of a new modulation and from a
twinning effect. The new modulation appears with a periodicity of
2/3 a,, as being the lattice parameter of the spine1 structure.
The dark field micrograph of Fig. 2b reveals the microstructure
of the sample. The shape, orientation and size of the ordered
domains, resulting from an antiphase boundary mechanism, explain
the complexity of the observed diffraction pattern.
Further heat treatment leads to more and more ordering. Figure 3
shows the basal plane of the new phase, corresponding to a
structural state which is the same as that of Fig. lb. Pattern 3a
is obtained from 3b by a twinning effect, and is more frequently
observed due to the small size of the domains.
Because of the twinned microstructure and of the lack of accurate
intensity measurements, X-rays powder diagrams and electron
diffraction patterns do not allow the determination of the
crystallographic structure.
 303

b)
Fig. 2. Transmission electron microscopy. Plasma sprayed alumina
annealed at 950°C. a) Selected area diffraction pattern jn [lOOI
orientation of the spine1 lattice. bf (220) dark field image.

X-Ray sinqle crystal. diffraction

cr-A1203 particles of about 60 pm in diameter are direGUy
sprayed into water. Their X-ray powder diffraction patterns show the
presence af a great amount of the a-phase. All other diffraction lines
are characteristic of the intermediate 6* phase. The surprising lack
of r-phase indicates that water quenching is less efficient than
quenching on a metallic substrate.
a)

b)
Fig. 3. Selected area diffraction pattern in the [OlO] direction of
the 6* structure. a) untwinned area, b) twinned area.

The selected grains of the intermediate 6* phase are studied by

single crystals diffraction methods (Bragg, Weissenberg and Buerger)
and the main observations are :the persistence of even fundamental
spots (400)s, (44O)S, (220)s.. .,the disappearence of the odd
fundamental spots (113),, (115)s... which are replaced by
satellite reflexions oriented in the <lOO> directions of the spine1
lattice,and the appearence of diffuse satellite pairs oriented in the
<lOO> spine1 directions near the weak even fundamental spots, (220)s
for example, whose structure factor is only due to cations sites.
Their distance from the corresponding fundamental position is two
times greater than the distance between fundamental odd spots and
their satellites.
 305

The Buerger diffraction patterns of Fig. 4 and 5 show these

characteristic features. A new pseudo quadratic symmetry and a
complex twinning effect appear. Now, these single crystal results
allow us to give a complete indexation of X-ray powder patterns.

a)

a*, b” or c* a*

006 406
400 - -I

,i 203
. i l
l .*
II
.
II

tI
l
00 400 006 -*
a*, b*or c* c 006 c
b) cl

Fig. 4. Buerger diffraction experiment. a) &rate 0 pattern, b)

twinned, and c) untwinned effect.
306

+
a* , b* or c*
01 d45678
” I I I , I
c*
b) C)
Fig. 5 .Buerger diffraction experiment. a) strate L pattern,
b) twinned, and c) untwinned effect.

Lattice constants and space qroux)

A X-ray diffraction powder pattern of the 5* state, performed
with improved resolution conditions, shows a slight orthor~o~ic
distortion of the structure, as appearing on the (400) line profile
of Fig. 6.
 006

23"5 23' 22-5 (4

Fig. 6. X-ray powder Guinier pattern . The splitting of the (400)

line shows the orthorhombic distorsion of the 6* phase.

After complete indexation (see Table I), the unit cell parameters
were refined by a least-squares program on the basis of measured d
spacings :
a = 0.7936 + 0.0001 nm
b = 0.7956 + 0.0001 nm
c = 1.1711 + 0.0002 nm

No general extinction rule appears and thus, 4 space groups have

to be considered : P222, P2221, Pmm2 and Pmmm.
TEM studies of both as-sprayed [1,2] and intermediate state have
clearly shown the existence of quasi-periodic antiphase boundaries,
with R = (100) I/4 <llO> or R = (100) l/2 <lOO> as defect vectors.
As a first assumption, we may assume that the S* structure derives
from an ordering in one <OOl> direction of such defects, every 3/2
as. Then, only the R = (100) l/2 <loo> defect is possible. As a
matter of fact, the R = l/4 1110> vector could not cancel all the
odd fundamental spine1 reflexions, and should give rise to satel-
lites at distances half that observed. The satellite spots flanking
the (22O)S reflexions must be attributed to an interreticular
distance modulation associated with some ordering of cationic
vacancies along the planar defects. This interpretation is supported
by the observed asymmetry in the satellite intensities [8].
308

Table I. A1203 a* : a=0.7934 nm; b=0.7956 nm; c=1.0711 nm

Int. d(obs.) d(ca1.) h,k,l Int. d(obs.) d(ca1.) h,k,l

W 7.97 7.956 010 m 2.308 2.311 132

7.932 100 2.306 312

W 6.55 6.581 011 m 2.280 2.280 223

6.567 101

m 5.06 5.065 111 vw 2.256 2.260 124

2.259 214
VW 4.716 4.716 012
4.711 102 W 2.162 2.162 115

W 4.054 4.054 112 VW 2.019 2.018 025

2.017 205
VW 3.754 3.767 021
3.756 201 S 1.990 1.989 040

VW 3.550 3.556 120 S 1.983 1.983 400

3.549 210
m 1.951 1.952 006
W 3.394 3.403 121
3.397 211 VW 1.907 1.908 134
1.905 314
W 3.282 3.291 022
3.284 202 W 1.799 1.799 225

W 3.210 3.206 113 VW 1.701 1.701 242

1.698 422
W 3.006 3.039 122
3.035 212 W 1.615 1.611 144
1.608 414
VW 2.923 2.928 004
W 1.602 1.603 117
W 2.808 2.809 220 1.603 226

m 2.787 2.786 023 W 1.542 1.547 151

2.782 203 1.542 511

m 2.731 2.731 221 W 1.508 1.508 152

W 2.627 2.629 123 W 1.503 1.504 512

2.626 213
W 1.463 1.463 335
s 2.596 2.596 114
VW 1.417 1.417 118
S 2.457 2.459 131
2.453 311 S 1.405 1.404 440

VW 2.353 2.358 024 vs 1.392 1.393 046

2.355 204 vs 1.391 1.391 406

VS : very strong S : strong m : mean

w : weak VW : very weak
 309

Then, considering an undisturbed anionic compact cubic lattice

and a periodic array of planar defects giving rise to a
reorganisation of the cationic sites and vacancies in their
vicinity, only the P222 space group is possible. The symmetry
operations of the three other space groups are not compatible with
such spine1 blocks separated by (001) l/2 <lOO> planar defects.

Structure determination
Because of the lack of suitable single crystals, the structure
has been resolved on the basis of X-ray powder diffraction patterns.
The intensities of 40 reflexions, 25 being independant, were
measured. The program POWDER, derived by Rossel [9] for
polycrystalline structures from the program of Busing and Levy [lo],
was used, allowing a number of parameters equal to a third of the
number of independent reflexions. Thus, only two isotropic thermal
parameters were considered, B(A13+) and B(02-), initially fixed
respectively to 0.5 10s2 and 2 10e2 nm2.

Table II. A1203 6* : calculated and observed intensity.

h,k,l M" I(ca1.) I(obs.) h,k,l M" I(ca1.) I(obs.)

112 8 109 120 132 8 198.8

021 4 7.9 312 8 201.9 400.7 395
201 4 24.6 32.5 25 223 8 198.6 190
120 4 0.2 115 8 164 160
210 4 27.4 27.7 30 224 8 45 36
121 8 27.3 040 2 401.1
211 8 13.8 41.2 46 400 2 395.9 797 800
022 4 114.6 006 2 385.6 400
202 4 15 129.7 124 243 8 60.2
113 8 43.9 54 423 8 40.9 101.1 111
122 8 19.8 151 8 73.2
212 8 69.4 89.3 82 511 8 56.3 129.5 120
023 4 127.8 045 4 19.2
203 4 91.5 219.4 240 405 4 13.6
221 8 198.7 211 152 8 141.3
114 8 569.6 550 512 8 123.4 297.5 300
131 8 276.3 335 8 62.5 30
311 8 481.6 757.8 780 046 4 609.7
024 4 4.4 406 4 609.5 1219.2 1240
204 4 19.2 23.6 25 440 4 668.1 680

M" : multiplicity
310

The calculation has been performed in three steps:

all possible octahedral and tetrahedral positions are first tested
in order to determine the cationic order near the planar defects.
Only the scale factor is allowed to change. The reliability factor
R is equal to 0.1.
After refinement of cationic and anionic coordinates, eight parameter
only being simultaneously modified, the R factor decreases to 0.04.
In the third step, the refinement of other atomic positions and
isotropic thermal parameters decreases R to 0.02.
Table II gives a comparison between observed and calculated
intensities. The reduced coordinates and isotropic thermal parameters
are listed in Table III, though in accord with the used refinement
method, they present a rather large standard deviation. Nevertheless,
the derived interatomic distances are in good agreement with the mean
commonly used anion-cation distances, as shown in Table IV.

Table III. A1203 6* :reduced coordinates and isotropic thermal

parameters.

Atoms X Y Z B(nm2)

All 0 0 0.5 0.13*10-2

Al2 0.5 0.5 0.5
Al3 0 0.333 0.133 (5)
Al4 0.247 (9) 0.262 (9) 0.671 (4)
A15 0.121 (11) 0.136 (9) 0.242 (5)
Al6 0.118 (14) 0.387 (17) 0.414 (11)
Al7 0.356 (15) 0.130 (15) 0.410 (10)
Al8 0.378 (18) 0.364 (15) 0.255 (7)
A19 0 0.266 (28) 0
All0 0.345 (11) 0.360 (11) 0.929 (4)
All1 0.235 (30) 0 0
01 0.132 (16) 0.116 (15) 0.088 (15) 3.48*10-2
02 0.117 (14) 0.124 (14) 0.417 (6)
03 0.125 (20) 0.127 (15) 0.756 (9)
04 0.127 (22) 0.364 (15) 0.257 (11)
05 0.116 (12) 0.389 (13) 0.579 (6)
06 0.144 (16) 0.376 (17) 0.899 (9)
07 0.388 (19) 0.123 (16) 0.241 (11)
08 0.390 (12) 0.120 (16) 0.584 (8)
09 0.360 (15) 0.123 (15) 0.892 (7)
010 0.352 (12) 0.428 (9) 0.099 (10)
011 0.377 (14) 0.379 (17) 0.414 (8)
012 0.382 (19) 0.369 (15) 0.744 (10)

*The atomic number are those of Fig. 7a.

**The standard deviation are noted () and concern the two
least numbers.
 311

Table IV. A1203 (J* :principal interatomic distances in mm

All-02 0.166 (98) (*4) A17-02 0.189 (15)

-07 0.200 ii7j
A12-011 0.170 (11) (*4) -08 0.203 (16)
-08 0.210 (16)
A13-04 0.207 (14) (*2) -08 0.200 (16)
-06 0.155 (12) (*2) 0.181 -011 0.199 (16) 0.200

A14-03 0.175 14) A18-04 0.199 (18)

-05 0.179 11) -07 0.193 (17)
-08 0.185 12) -010 0.190 (15)
-012 0.161 14) 0.175 -011 0.186 (16)
-012 0.190 (17)
A15-01 0.180 16) -012 0.212 (17) 0.195
-02 0.205 '12)
-03 0.194 '14) A19-01 0.175 (16) (*2)
-03 0.208 114) -06 0.198 (14) (*2) 0.187
-04 0.182 15)
-07 0.212 '15) 0.197 A110-06 0.164 (14)
-09 0.193 (13)
A16-02 0.210 (16) -010 0.207 (12)
-04 0.184 (18) -010 0.171 (12)
-05 0.194 (15) -010 0.248 (12)
-05 0.186 (15) -012 0.218 (15) 0.200
-05 0.177 (15)
-011 0.205 (17) 0.193 Alll-01 0.160 (16)
-09 0.188 (13) 0.174

DESCRIPTION OF THE STRUCTURE AND COMPARISON WITH THE 7 PHASE

A projection of the idealized cationic lattice of the 6*
structure on the YOZ plane is represented in Fig. 7a. Figure 7b
shows an equivalent projection of the 7 spine1 structure with (001)
l/2 <loo> planar defects every 3/2 as along [OOl] direction. By
comparison of these two projections, it can be seen that in 6* phase
the reorganisation of cationic lattice near the antiphase boundaries
involves the following modifications : the disappearance of
tetrahedral sites (circled sites in Fig. 7b) near the shear
planes, and the migration of half of the cations initially
localized In the octahedral sites towards tetrahedral sites
unoccupied in the spine1 lattice as arrowed in Figs. 7b and 8a.
The replacement of a block of 4 edges linked octahedra by a block
of 4 corners linked tetrahedra is evidenced in Fig. 8b.
Some distortion of the compact cubic anionic lattice follows, but
in the slightly distorted polyhedra, the mean <Al-O> distances
remain very close to those observed in r-A1203: 0.198 nm for
octahedral sites and 0.171 nm for tetrahedral sites.
312

v . v I A v * - I A V *
s .
I v 1
* v I
A v
- - -a-- -ytT - -n - *-_a- _ -
*9-
V . , v . I V *

n n

A v 1 I A v
% v -*- a- __
_ - _o__o-_o- - -a
V * V . I V A
t
n m

A V A 1 . . V A t . . V

Fig. 7a. 6* phase. Projection of the idealized cationic lattice on

YOZ plane.
tetrahedral sites: n 4 m 0
height in as/8 : 0 2 4 6
octahedral sites : 7 A V A

height in a,/8 : 1 3 5 7

a.“.mA+Va’o.mA+V8
.

modified
structure

unmodified
VAIAV..
spine1
structure

l 0 l 0

Fig. 7b. Projection of the idealized cationic lattice containing

(100) l/2 [olo] antiphase boundaries every 3/2 a,.The tetrahedral
vacant sites appear inlO'.
 313

a) b)
Fig. 8. a) octahedral sublattice in the vicinity of the XOY shear
plane, b) tetrahedral and octahedral sites after reorganisation near
the XOY shear plane.

CONCLUSION
We have shown that only one intermediate phase appears during the
A1203 ?-+a transformation.This intermediate 6* phase appears
from the spinel-like lattice of r-A1203, through a progressive
ordering, every 3/2 as in one <OOl> direction, of antiphase planes
with a characteristic vector R = l/2 [loo].
The consecutive ordering of cationic vacancies results in an
increase of the ratio between the numbers of octahedral and
tetrahedral occupied sites. This ratio grows from 2 for the ideal
spine1 structure to 2.22. The 6* structure may then be written as :
(A10.833)[A11.833]04*

ACKNOWLEDGEMENTS
We would like to thank MM. M.Vardelle and P.Fauchais for their
aid in preparing the plasma sprayed samples without which this work
could not have been carried out. We also thank the Centre de
Microscopic Electronigue de 1'Universite de Limoges, and especially
M. P.Lortholary for the facilities to use their equipment.
314

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cible Thesis, Limoges, 1980.
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6 M.Vardelle and J.L.Besson, Ceramics international, 7, 2 (1981)
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