Powder Technology 107 Ž2000.

48–53
www.elsevier.comrlocaterpowtec

Transition of g-Al 2 O 3 into a-Al 2 O 3 during vibro milling

´ S.J. Kiss, S. Zec, S. Boskovic
E. Kostic, ˇ ´ )

ˇ P.O.B. 522, 11001 Belgrade, YugoslaÕia

Institute of Nuclear Sciences ‘ Vinca’,
Received 27 March 1997; received in revised form 31 March 1999; accepted 23 April 1999

Abstract

™
The results obtained in studying the phase transition of g- into a-Al 2 O 3 during intense mechanical activation by vibro milling are
presented in this paper. It was found that depending on experimental conditions, the g a-Al 2 O 3 transition through d- and u-phases, can
be initiated. X-ray and SEM analyses of activation products show that the phase transition is preceded by intense reduction of g-phase
particles. The produced a-Al 2 O 3 crystallites have a distorted lattice and are larger than the initial crystallites in the starting powder. The
change of specific surface area Ž Sp . with activation time shows the presence of high internal porosity of g-Al 2 O 3 which disappears
during the complex process of the phase transition. An attempt was made to present the specific surface area change via its g- and
a-phase contributions. In this respect, detailed analyses of g-Al 2 O 3 particle size reduction along with reduction of their internal porosity
and agglomeration of ground powder were performed, which explain the change of the specific surface area with activation time. q 2000
Elsevier Science S.A. All rights reserved.

Keywords: Mechanical activation; Phase transformation; Grinding; Gamma Al 2 O 3

1. Introduction
The possibility of development of various solid state
reactions during the intense grinding of powders has been
the subject of numerous studies lately w1–3x. Different
grinding methods are applied concerning the grinding
forces. It was shown that the course of the solid state
reactions as well as the reaction product increment de-
pended not only on the activation time but also on the
other experimental conditions including the type of grind-
ing facility w4x.
The phase transition g-Al 2 O 3 to a-Al 2 O 3 was studied
as a function of the activation time whereby the decrease
of temperature at which individual interphases Ž d-; u-
Al 2 O 3 . appeared, was found w5x. The temperature at which
a-Al 2 O 3 appeared was lower too, if g-Al 2 O 3 powder was
activated for a longer time. The transition temperature into
the thermodynamically stable phase, is affected by impuri-
™
ties, both cations w6x and anions w7x. It was also observed
that g-Al 2 O 3 a-Al 2 O 3 transformation can be induced
)
Corresponding author. Tel.: q381-11-45-82-22; fax: q381-11-43-
94-54
by high energy ball milling w8x. The aim of this work is to
investigate the possibility of a thermal transition of g-
Al 2 O 3 into a-Al 2 O 3 during vibro milling. Special atten-
tion was paid to the effect of the amount of powder being
ground as well as to the effect of activation time on phase
transition rate. In addition, the mechanism of transition of
g-Al 2 O 3 into a-Al 2 O 3 during grinding was suggested.
2. Experimental procedure
The starting g-Al 2 O 3 powder properties are shown in
Table 1. During the experimental work, the laboratory
vibro mill Pulverisett 9 ŽFritsch. was used, with bowl and
grinding media made of hard metal. The useful volume
was 100 ml. Vibration speed was 1000 miny1 . The amount
of the powder was 10 g, 20 g and 50 g per batch.
Activation time ranged from 2 to 600 min.
The untreated and activated powders were characterized
by BET specific surface area Ž Sp . measurement and by
observation of agglomerate morphology on the SEM. The
mean particle size of untreated powder was determined by
SEM analysis as an arithmetic average value of linear
dimensions of 50 particles. X-ray analysis was used to

0032-5910r00r$ - see front matter q 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 3 2 - 5 9 1 0 Ž 9 9 . 0 0 0 8 7 - X
 E. Kostic´ et al.r Powder Technology 107 (2000) 48–53 49

Table 1 Table 2
Properties of the starting powder Existing Al 2 O 3 phases during grinding of different batches
Crystall. Purity Particle Crystal Specific Weight Producer Grinding time Žmin. 10 g 20 g 50 g
phase size size ŽA. surface loss
0 g g g
Žmm. area Ž%.
2 gqdq a gqdq a gqd
Žm2 rg.
5 dq a gqdq a gqd
g-Al 2 O 3 Extra 5 58 60.5 5 E. Merck, 7 dquq a dq a gqd
pure Darmstadt 15 uq a dquq a gqd
Ž278795. 30 uq a uq a gqd
50 a uq a gqd
90 uq a gqd
120 a gqd
600 gqdqu
determine the amount of a-Al 2 O 3 by comparing the inte-
gral intensities of diffraction peaks at 2 u s 43.288 and the
rest of the phases at 2 u s 67.148, for each experiment.
Crystallite size and lattice strain were determined from the
half-width of diffraction lines w9x. The change of interpla- case brings about only a smaller increase of lattice strain
nar spacing Ž d . for some crystal planes was followed Ž0.326% after 120 min grinding., whereby the crystallite
during grinding of g-Al 2 O 3 powder. size remains practically unchanged.
With ground 50 g batches for 2 and 120 min, the
thermodynamically stable phase appeared only during
3. Results heating, at 11308 and 10308C, respectively. With all heated
powder mixtures, transformation took place via d- and
The crystalline phases present in the activated powder u-Al 2 O 3 w5x.
are given in Fig. 1 and Table 2, as a function of activation Change of interplanar spacing for the characteristic
time and the amount of the powder being ground. crystallographic planes of g-Al 2 O 3 having structure simi-
The increase of a-Al 2 O 3 fraction with prolonged acti- lar to a-Al 2 O 3 planes was followed during grinding ŽTa-
vation time is given in Fig. 2. The specific surface area as ble 3..
a function of the activation time is given in Fig. 3. In Fig.
4, some characteristic SEM microphotographs of powders
are given. 4. Discussion
The crystallite size of g-Al 2 O 3 was 58 A, ˚ without
lattice strain. g-Al 2 O 3 can be transformed into a-Al 2 O 3 during in-
The newly formed a-Al 2 O 3 crystallites size was 226 A ˚ tense grinding as shown in this paper, at a rate depending
in powder ground 2 to 30 min in 10 g batches. With on the experimental conditions which enable introduction
prolonged grinding the crystallites of a-Al 2 O 3 get smaller of more or less mechanical energy into the mixture being
with increasing activation time Ž170 A ˚ after 60 min.. The ground. Non-ground powder g-Al 2 O 3 undergoes transfor-
lattice strain in the formed a-Al 2 O 3 crystallite Ž10 g mation under thermal conditions which allow nucleation
batch. was 0.196% up to 60 min grinding.
The crystallite size of a-Al 2 O 3 formed up to 60 min of
grinding was 313 A ˚ and the lattice strain was 0.228% in
experiments with 20 g g-Al 2 O 3 . Prolonged grinding in this

Fig. 1. Characteristic XRD patterns of g-Al 2 O 3 : ŽA. unground, ŽB. 10 g

ground for 60 min and ŽC. 20 g ground for 60 min. Fig. 2. Fraction of a-Al 2 O 3 as a function of activation time.
50 E. Kostic´ et al.r Powder Technology 107 (2000) 48–53

and the growth of newly formed crystal phase w10x at

12408C.
The obtained X-ray data of the ground powders prove
the considerable effect of introduced mechanical energy on
the course of the process under study. The quantity of
energy, observed by the system being ground, is indirectly
controlled by the amount of the material in the grinding set
and the activation time. The influence of the material
amount on the phase transition is shown in Fig. 1. This
parameter affects the kinetics of g- into a-Al 2 O 3 phase
transition, including both the rate of interphase formation
ŽTable 2. and the rate of the end-product formation ŽFig.
2..
The course of g- to a-Al 2 O 3 through d- and u-Al 2 O 3
was obvious. However, the intermediate phases appeared
and disappeared after shorter times if the amount of grind-
ing powder kept decreasing. While with 10 and 20 g
batches almost complete transition into a-phase took place
in 60 and 120 min, the 50 g batch needed additional
heating to complete the phase transition. However, in spite
of the necessity to add thermal energy into the system, the
beneficial effect of previous grinding Žup to 120 min. on
the g- to a-Al 2 O 3 transition rate with 50 g batches was Fig. 4. Characteristic scanning electron micrographs of g-Al 2 O 3 : ŽA.
proved w5x. unground, ŽB. 20 g ground for 50 min, ŽC. 20 g ground for 300 min and
ŽD. 10 g ground for 2 min.
Mechanical activation brings about the change of spe-
cific surface area of the starting g-Al 2 O 3 as seen from Fig.
3. The dependence of specific surface area on the activa- surface area can be a consequence of the crystallite ag-
tion time for different batches of Al 2 O 3 needs additional glomeration of the phases present, decrease of internal
analysis. The calculated specific surface area of untreated porosity of g-Al 2 O 3 particles and phase transformation
Žbecause the density of a-Al 2 O 3 is 6.2% higher than that
g-Al 2 O 3 of about 0.3 m2rg was obtained on the basis of
the average diameters of spherical powder particles Ž5 for g-Al 2 O 3 .. The remarkable decrease observed in the
mm., assuming smooth surfaces, which is noticeable from specific surface area along with a-Al 2 O 3 formation, points
Fig. 4A. The measured value of 60.5 m2rg indicates very to the absence of internal porosity in newly formed a-
high internal porosity of the starting g-Al 2 O 3 particles. Al 2 O 3 particles ŽFigs. 2 and 3.. According to these results
The difference in measured and calculated specific surface one can outline that in the complex process of phase
area points to internal porosity of 60.2 m2rg. Therefore, transformation during mechanical activation, the internal
by considering the specific surface area change during porosity of starting Al 2 O 3 particles disappears. Under the
activation, the fraction of internal porosity of the g-phase assumptions that Ž1. crystallites of formed a-Al 2 O 3 are
should be taken into account. The increase of the specific individual particles Žthe mean size of particles in this case
surface area during activation can be expected to be due to can be obtained by X-ray analysis, and Ž2. the non-trans-
g-Al 2 O 3 particle size reduction, while the drop of specific formed g-Al 2 O 3 particles retained unchanged internal
porosity, the quantitative analysis of the specific surface
area change with the change of activation time can be
performed on the basis of X-ray Ždefinite fractions of
individual phases in the mixture. and SEM analyses. It is
to be expected that in the case of agglomeration andror
gradual decrease of internal porosity of g-Al 2 O 3 particles,
some discrepancy will arise between experimental results
and the calculated values under the assumptions made
above.
On the basis of previously introduced limitations the
specific surface, Sp , obtained by BET method, of activated
powders can be described as
S p s Sg q Sa Ž 1.
Fig. 3. BET specific surface area of ground powders as a function of where Sg and Sa are specific surface areas of g- and
activation time. a-phases per mass unit of activated mixture. Due to con-
 E. Kostic´ et al.r Powder Technology 107 (2000) 48–53 51

Table 3
˚ during grinding of g-Al 2 O 3
The change of some interplanar spacings, d, in A,
Crystall. planes of 10 g batch Crystall. planes of
g-Al 2 O 3 and activation time Žmin. a-Al 2 O 3 and
corresponding d w12x 0 5 15 30 60 corresponding d w12x

3114g , d s 2.39 2.398 2.385 2.382 2.382 2.383 1104a , d s 2.379

4004g , d s 1.977 1.983 1.985 broad peakU broad peakU –
2.085 2.085 2.087 2.089 1134a , d s 2.085
4404g , d s 1.395 1.394 1.395 1.393 1.393 –
1.401 1.402 1.402 1.405 1244a , d s 1.404
1.376 1.375 1.375 1.376 0304a , d s 1.374
U
d value cannot be calculated.

siderable internal porosity of the g-phase, Sg can be split
into two parts
Sg s Sg1 q Sg 2
where Sg1 represents the outer surface of the g-phase
particles and Sg 2 represents the contribution of internal
porosity.
On the basis of phase composition of activated powders
and a-phase crystallite size, Sa can be estimated according
to
Sa s Sp ,a Ž a phase fraction.
where Sp,a is calculated under given assumption 1.
Since experimental data on g-phase particle size in the
ground mixtures are lacking, Sg1 can be obtained via
Sg 2 s Sgo Žfraction of g-phase. and Sp , according to
Sg1 s Sp y Sa y Sg 2
where Sgo is the contribution of internal porosity per gram
of g particles Ž60.2 m2rg..
With all of the samples, the initial specific surface Ž60.5
2
m rg. increases already up to 2 min of activation indepen-
dent of the amount of material in the batch. This increase
of the specific surface area for short activation times points
to intense size reduction of g-phase particles, which is in
agreement with SEM analysis ŽFig. 4.. In this stage of
grinding the internal porosity of the g-phase does not
change.
The specific surface area change with 50 g batches
Ž 2. indicates that up to 120 min of activation, starting particles
get only finer up to 1100 A, ˚ under the condition that
internal porosity is unchanged ŽFig. 3.. The mechanical
energy introduced is not high enough to provoke, under the
given experimental conditions, the structural changes
within the particles. Only after longer grinding does weld-
ing together of the particles takes place, which could be
realized via OHy ions at the surface, causing the drop of
the specific surface area thus preventing phase transition.
Ž 3. The appearance of some a-phase in the mixtures could be
due to the presence of Al-hydrate in starting powder,
which transforms directly to a-phase w6x.
The change of the specific surface area with time of
activation in 20 g batches is different as compared to 50 g
batches ŽFig. 3.. By applying the previous consideration of
specific surface area change the obtained results are given
Ž 4. in Table 4. The applied correlation of relevant powder
properties and the measured specific surface area, point to
justification of assumptions made for the period up to 60
min of activation. With longer grinding Ž120 min., how-
ever, the discrepancy is obvious. SEM analysis of acti-
vated powders shows a weak agglomeration up to 60 min
of grinding, but after this time, the agglomeration gets
stronger ŽFig. 4C.. We introduce a quantitative measure
for agglomeration. It is defined as the decrease of the
specific surface due to agglomeration compared to the

Table 4
Calculated contributions to measured specific surface area Žm2 rg. coming from grinding process as well as from powder properties, for 20 g batches
tg Žmin. 0 2 5 7 15 30 60 120
Sa 6.3 12.6 13.5 20.3 30.0 35.8 47.4
Sg 60.5 65.5 58.4 56.9 40.8 29.5 16.0
Sg1 0.3 13.2 13.9 15.6 5.8 6.6 0.3
Sg 2 60.2 52.3 44.5 43.4 34.9 22.8 15.6
Sp 60.5 71.8 71.0 70.5 61.1 61.0 51.6 43.2
52 E. Kostic´ et al.r Powder Technology 107 (2000) 48–53

Table 5
Calculated contributions to measured specific surface area Žm2 rg. coming from grinding process as well as from powder properties, for 10 g batches
tg Žmin. 0 2 5 7 15 30 60
Sa 18.1 20.8 26.1 38.8 49.6 84.0
Sg 60.5 51.1 41.2 34.9 9.3
Sg1 0.3 7.2
Sg 2 60.2 43.9 41.5 36.7 25.3 15.6
Sp 60.5 69.2 62.0 61.1 48.2 34.5 30.0

value calculated on the basis of crystallite size, given as
percent of agglomeration. For the surface of a-phase
particles a corrected value is obtained according to
100 y Ž percent of agglomeration.
Sa ,corr .s Sa
100
In the mixture activated for 120 min, the measured Sp is
43.2 m2rg, but the value calculated on the basis of
a-Al 2 O 3 crystallite Žparticle. size is 47.4 m2rg. In this
case, the g-Al 2 O 3 content is zero and the agglomeration
degree is about 9%.
The analysis of specific surface area change during
grinding for 10 g batches gives the results which are
summarized in Table 5. It can be seen that calculated
values do not coincide with the experimental data after 5
min of activation. For the internal porosity of a nontrans-
formed g particle Ž Sg 2 ., a value is obtained which is
higher than the total surface of g-phase Ž Sg . ŽTable 5..
Taking into account the considerable agglomeration of
powder already after 2 min of activation ŽFig. 4., accept-
able agreement for the period of up to 15 min grinding
ŽTable 6. can be reached by increasing agglomeration
percentage from 5 to 43%. With longer grinding, however,
the results could be explained only if gradual decrease of
internal porosity of nontransformed g particles is accepted.
Kinetics of phase transition g- into a-Al 2 O 3 during
mechanical activation, as shown in various cases w1,2,4x,
depends on experimental conditions and cannot be ana-
lyzed by comparing the course of this phase transition with
the equations derived for thermally induced solid state
reactions w11x.
The existing data suggest the following mechanisms are
operative during phase transition caused by mechanical
activation. In the initial stage, the particle size reduction of
starting g-particles takes place up to 200–300 A. ˚ This
process turned out to be more intense with 10 g and 20 g
batches. Although the g-Al 2 O 3 crystallize size of the 50 g
batch series was about 200 A ˚ after 60 min, further intro-
duction of mechanical energy into the system does not
bring about structural changes. However, the g-Al 2 O 3
particle size reduction up to 200–300 A ˚ in 10 and 20 g
batches is expected already after about 2 min of grinding.
As shown by X-ray data in 20 g batches, after 2 min of
grinding, structural changes of larger particles occurred,
which resulted in larger newly formed a-phase crystallites
having a more deformed lattice than the particles ground in
10 g batches. In the latter case, the crystallites are not only
smaller, but also less deformed. The structural changes
mentioned take place in the bulk of the particles built up of
g-phase crystallites of 58 A ˚ in size Žwhich remained
unchanged during grinding . The particles lose internal
.
porosity and thereafter a gradual loss of hydroxyl ions
takes place enabling the amplification of the number of
Al–O–Al bondings w10x. With increasing activation time
the change of the interplanar distance ŽTable 3. was ob-
served for  3114 ,  4004 and  4404 crystallographic planes
of g-Al 2 O 3 towards values corresponding to crystallo-
graphic planes  1104 ,  1134 ,  2144 , and  3004 for a-Al 2 O 3
ŽTable 3.. Close values of interplanar spacings of the
mentioned planes for g- and a-Al 2 O 3 come from the
similarities of their atomic structures w12x. Within these
planes first indications of phase transition were observed

Table 6
Calculated contributions to measured specific surface area Žm2rg. coming from grinding process as well as from powder properties including
agglomeration, for 10 g batches
tg Žmin. 0 2 5 7 15 30 60
Estimated 4.9 8.5 19.6 43.4 45.5 64.3
agglom. Ž%.
Sa 17.2 19.0 21.0 22.0 27.0 30.0
Sg 60.5 52.0 43.0 40.0 26.2 7.5
Sg1 0.3 8.1 1.5 3.3 0.9
Sg 2 60.2 43.9 41.5 36.7 25.3 15.6
Sp 60.5 69.2 62.0 61.1 48.2 34.5 30.0
 E. Kostic´ et al.r Powder Technology 107 (2000) 48–53
by X-ray, because the corresponding diffraction lines be-
long to stronger X-ray peaks of both phases. Data obtained
indicate that the crystallite sizes of a-phase are consider-
ably higher as compared to the starting one Žfor g-Al 2 O 3 .
and do not change until the amount of a-Al 2 O 3 reaches
74%. This means that the newly formed phase is being
formed in the frame of starting powder fragments consist-
ing of 3–5 g-phase crystallites. Due to distortion of the
original ordering in the bulk of starting particles, crystal
boundaries gradually disappear because of the higher con-
centration of structural defects. Total energy of the parti-
cles increases by prolonged grinding, making the initial
structure more unstable. After a definite number of impacts
in the grinding set, the particle transforms throughout the
bulk into thermodynamically more stable a-phase. The
energy introduced to the particles is high enough to enable
the transition into the a-phase after 60 min of grinding for
10 g batch series, i.e., after 120 min of grinding for the 20
g batch series. However, the crystallites of the newly
formed phase, according to X-ray analysis have internal
strains, as has already been shown for the case of chemical
compound formation by mechanical activation w2x.
5. Conclusion
The results of the investigation of the influence of
mechanical activation in the grinding set Pulverisett 9
™
ŽFritsch. with the action of impact and friction forces on
the phase g a-Al 2 O 3 transition show the following.
™
Ž1. During mechanical activation it is possible to pro-
voke g a-Al 2 O 3 transition via interphases d- and u-
Al 2 O 3 .
Ž2. The degree of transformation strongly depends on
the experimental conditions: phase transition is intensified
by decreasing the weight of g-Al 2 O 3 powder being ground
in the grinding set. With the batch of 10 g, complete g- to
a-Al 2 O 3 transition is achieved after only 60 min.
53
Ž3. Prior to phase transition, remarkable g-particles size
reduction takes place without the change of g-crystallite
size.
Ž4. During phase transition, the internal porosity of the
g-phase disappears and a deformed structure of a-Al 2 O 3
crystallites is formed. With decreasing crystallite size of
a-phase, agglomeration in the powder being ground is
intensified.
Ž5. Phase transformation takes place in small g parti-
cles whereby a-phase crystallites are formed, the size of
which is higher than the size of g-phase crystallites.
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