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ELSEVIER Powder Technology 91 t 199"/) 49-54

Mechanical activation of the gamma to alpha transition in AI203

E. Kosti6, ~. Kiss, S. Bogkovi6, S. Zec
Materials Science laboratory, Institute of Nuclear Sciences "VIN~A', PO Box 522. l IO01 Belgrade, Yugoslavia
Received27 July 1995; revised I I October 1996

Abstract

The phase transformation of mechanically treated y-AI203 for grinding times up to 600 rain was studied. The grinding was performed under
a centrifugal force, through impact and friction, at a speed of 1000 rain- J. After mechanical activation up to 120 rain, the powder was heated
in the temperature range 800-1100°C, from I to 4 hours. The phase composition of samples that were only milled and of those that were
milled and heated was followed using an X-ray method, The change in the specific surface area of the starting powder subjected to grinding
was measured. In the case of powders mechanically treated up to ! 20 rain and not heated afterwards, the y--* 8-AI203 transition was observed
with the appearance of small amounts of the or phase. After 600 rain of grinding the previously formed 6 phase was transformed into 0-A120~.
In the case of both mechanically treated and unground powders which were heated afterwards, the phase transition to the ot phase could b¢
described by the scheme y.-* 6 ~ O~ a-AI20~, it developed at lower temperatures in the case of powders ground for a longer time. The
kinetics of a-phase formation was also dependent on the time of previous mechanical treatment.

Kcywords: Mechanical activation; Phasetmnsitlon; Aluminium oxide phasetransformation; Grinding

I. Introduction mill (Fritsch Pulverisen 9) at a speed of 1000 rain: ~. 50 g

The beneficial influence of mechanical energy on solid
slate reaction development, including phase transformations,
was reported earlier, by the application of different milling
devices [I.2]. Using vibratory milling, the phase Iransforo
marion of Nb~Os was activated through amorphization [3 ],
which was also proved during th~ mieronization of diff~re.!
minerals 141.The degree of amorphizationdependedon the
kind of material treated and the experimental conditions. In
this paper a device which contributed to mechanical activa-
tion by friction and impact was used. The aim of the study
was to investigate the possibilities of the device to facilitate
the phase transformation of y-AltO3 into a-AIzO~ which is
of importance in catalyst fabrication, as well as in the solid
state synthesis of compounds containing AI20,~,such as spi-
nel. cordiorite and mullito. It was also important to establish
the activating mechanism of the phase transformation,as well
as to prove the effect of mechanical activation on the rate of
this process.
2. Experimental
2. I. Material preparation
An extra-pure commercial y-Ai203 (Merck, Darmstadt)
was used. Grinding was performed in a laboratory vibratory
0032.5910197/$17.00 © 1997 ElsevierScience S.A. All rights reserved
PIISe032.5910(96)03244-5
of starting powder were dry milled using a tungsten carbide
grinding set, without cooling during the treatment.The useful
volume was 100 ml. The grinding times were 2, 5, 7, 30, 60,
90, 120 and 600 rain, The ground powders were thermally
treated in the form of pellets obtained under a pressure of 25
MPa. Heating was performed in the temperature range 800-
1100oC lbr 1--4 hours in an electric furnace, under heating
and cooling rates of 5 and 15+C/rain, respectively,
2.2. Sample characterization
The specific surface area of'y-AI20++as well as that of the
ground powd¢rs was measured by the BET method (AREA
meter, Strohlein). All the analyzed powders were subjected
to differential thermal analysis (DTA) and thermogravime-
tric analysis (TGA) using a Netzsch STA-409 EP apparatus
Cheating rate 10°C/rain). Scanning electron microscopy
(SEM) was performed with a JEOL-35 instrument. The
phase composition of the treated powders was determined by
X-ray analysis (Siemens D-500), The phase composition
change of the activated powder with prolonged grinding lime
is given on the basis of the intensities of the diffraction lines
of the existing phases ( (311 ), (400), (112) and (113) for
the 'y-, 5-, 0- and or-AltOs phases, respectively), For samples
50 E. Kosttd ¢~al, I Pmtvkr Technology 91 ( i 997~ 49-54

TaMe I
Specific surface mea of the powders used

Grinding dme (mia) 0 2 5 7 30 60 90 120 600

Specific surface area (m~/g) 61.0 68.8 69. I 72.0 75,5 78.3 76.8 75.5 55.8

cA)minedafter thermal treatment, the same presentation of

results is used for the'y-, ~- and 0-A1203phases. The fraction
of the a phase in the heated samples was calculated on the
"tt C
*A
wee-- o -

basis ofsemiquantilative analysis by comparison of the inten-

,

sity of the ( ! 13) diffraction line for the a phase with the sum
of the in~nsities of the su'ongest diffraction peaks of all the
phases present. The cryslallite size in the starting powder was
calculated from the broadening of the (400) reflection under
the assumption that the crystallites were not deformed [ 5].
-- 100~

~1~ A vv v
3. Results

By applying this method of activation, changes in powder

structure were noticed during grinding, even without addi- 2e
tional heating. The starting ~/-Al~Os was composed of large Ng. 2, Chara~erisli¢ XRD panems of*t-Al~O~mechanically lrealed for ( A )
plate-like particles, The erystallite size, however, was very 0 rain. (B) 60 rain and (C) 600 rain.
small (ca. 60 ,~). The high specific surface area (Table ! ),
therefore, indicates considerable internal porosity of the pow-
der particles.
Grinding up to 120 rain causes micronization of the powder
particles. It does not bring about a decrease in the starting
powder erystallite size, but causes a change of the specific
sttrfm~earea and appearance of the ~ phase, The intensity of
the (400) reflection is shown to be increasing (Pig. 1)0 The
I~e~nce of the a phase was al~o detecl~J (Pig. 1). The
~h~ra¢leristi~ XRD patterns are 8ivan in Pig, 2, A~¢ordin8 Io
SI~M analysis, prolonged grinding of the microni~ed pemieles
¢au~.s their ~81omeratlon (Fig~ 3), Ptg~ 3, $¢mt#iq electro, mi~rogmp~ of*t~AlaO~: (a) u~jout~d ~ d (b)
On increasing the grilMin8 time to 600 rain, the amount of ground for 120 mln~
c, phase continues to increase (up to 8%), the micronization
proce~ keepa developing, followed by the appearanceofthe
0 phase. At~er long grinding times, strong tungsten carbide
reflections were detected by the X-ray method; these were

I]-J --,-- eHO0)

1000

6OO eo
J:i, 'l
m

8,
~t

Ng, 4, ~ t e d ~ XRD patterns ef "~-AI~O~ground for 120 ndn and

I"~.,.~m~a*9~0~ for 4 heu~
N ~ee ~
not observed up to 120 min of grinding. A typical XRD
Pig, I, ( ~ q t e s ~ the duncu~r~¢ X-my diffmctloa peak intensities of pattern of mechanically activated ( 120 rain) and thermally
pMttcul~rA|~O~~ in mlatt~mIo the iptndialg time of'~AlaO~, treated (950eC, 4 h) powder is given in Fig. 4.
 K Kostk~el el,/Peatier Technology 91 f 1997) 49-54 51

Table 2
Amount of o-AI20.~ (%) in the mechanically and thermally treated samples
- v - ~ l t) ./*
Heating Grinding time (rain) -e-~,mo) /
conditions --A-e(112) ,~/
0 2 5 ? 30 90 120 '~00. --'~113)

800°C, i h 0 ? 7 8 8 g 9
800°C, 4 h 6 8 8 9 9 II g-
9000C, 2 h traces 9 16 19 21 23 '
900~:~,4 h 6 II 21 25 30 39 44
950eC, 4 h 8 31 42 49 55 69 74 t ~

I000~C, I h 8 43 60 80 80 80 81
I O00~C,4 h 8 60 85 87 91 96 96
• - • - • . . - •

Table 2 gives the increase in the a-phase content during Temperature(~1

heat treatment. The dependence of the intensities of the 3,-, Fig, 7, Changesof the characteristic X-ray diffraction peak intensities of
~- and 0-AI~O3 phase diffraction lines on the thermal treat- paxttcular AI~O~ phases in relation to the heating temperature (4 hours
mcnt conditions is shown in Figs. 5-7. isothermally) or .y-AI20~ ground for 120 rain,
In the case of samples heated at 800°C for ! hour (with
the exception of the unground powder in which only the '~ time up to 120 min. Prolonged heating for 4 hours (800°C)
and ~ phases were found), the a phase was detected, the further increased the amount of ct phase in the mechanically
amount of which slowly increased with increasing grinding treated samples. With prolonged mechanical activation and
thermal treatment, the 3, ~ 8-AI203 transition is intensified.
During heating at 900°C for 2 hours, traces of a phase were
~e-a(4oo)
-&-e(112)
/ found in the unground powder, along with a considerable
amount of 8 phase and a small amount of 3, phase. After only
:l~O, --0~zt113) 2 rain of mechanical treatment, formation of the a phase is
obvious, as well as transition of 3,- into 8-Al:Oa. With pro-
longed mechanical treatment, the amount of a phase increases
to 23% (after 120 rain). An increase in the beating time to 4
, . / / hours brings about the formation of about 6% of the ~ phase
in the unground powder along with traces of the 8 ;rod 3'
phases, while mechanical treatment produces a filrther
increase in the amount e r a phase up to 44%, in the premnco
of only the 5 and 0 phases. At 950°C, 8% of the ~ pha~¢,
~0tm t~o t0~ t0~ ~100 along with the 8 phase and the newly appearing 0 phase were
Y,ml~mu¢~pc) found itt the unground powder, Prolonged mechanical treat°
Fig, $, Changes of the charactertstk: X - r ~ diffraction peak Intensities of meat caused a decrease in 8. and 0°phase contents in favour
p~icular AI~O~ phttses in relation to the heating temperature (4 hours of the a phase, the amount of which attained 74%. Further
Isothermally) of ungreund 'y-Al:O~, increase in the ~-phase content, in the presence of the ~, and
0 phases, was observed at 1000°C after ! hour. With pro°
longed heating, the amount of c~ phase was higher than 40%
4000,
in a powder vibrated for only 2 rain (compared with the
-e=~(400)
starting powder which contained 8% of tx-Al:O~ along with
~.alumina). The amount of 0 phase which was usually tbund
-4'-~(113) at shorter grinding times decreased in s~m~plesground for ! 20
e rain. Alter 4 hours of heating the amount of¢~ phase seemed
to be unchanged in the unground powder, while with mechan-
ical treatment up to 120 rain the amount increased to 96%, in
the presence of traces of the 0 phase.
A pressing pressure of 25 MPa did not affect the degree of
the 3'-~, ct-Al20~ transformation compared with that of the
loose powder. However, when green pellets were obtained
100 mOO ~ 1t00
I~0 'lO00 10S0
under a pressure of 300 MPa, the phase transition was con-
Temperature(~)
Fig. 6, Changes of the characteristic X.ray diffraction peak intensities of
siderably enhanced.
particular AI20:, phases in relation to the heating temperature (4 hours DTA of the activated powders shows that the temperature
isothermally ) of'v-AI20~ ground for 2 min, of the characteristic exothermic peak of the 3' -" c~-AI20~tran-
52 E, Ko~li~et aLI Po.~ler Tectmology 91 ~1997)49-54

Ta~3 while the specific surface area is increasing, crystallites

I)TA and TGA data of the investigated .y-Al,O~ absorb additional energy which, beside micronization, is
spent on the r~~ 8-AI2Os transformation, as well as on a-
~,-AIzO~powder Exothennicpeaktemp. (°C) Weightloss (%)
phase formation. The amount of the a phase formed slowly
Ungroond 1240 4.68 increases with increasing grinding time (Fig. ! ). This effect
Gmtmd2 min ! 130 5.71 is the consequence of the loss of OH- ions, located on the
120rain 1030 7.56 surface of the powder particles. During this treatment the
surface is exposed to enormous changes, not excluding amor-
phizafion during the micronizafion process (Figs. 2 and 3),
followed by an increased hygroscopic capability, as can be
seen from the weight loss data in Table 3. The additional
~J0 400 U0 ~ 'HMO tiM0 14D~1
energy causes the formation of a deformed spinel structure
with new AI-O bonds on the surface, and also the redistri-
bution of cations between octahedral and tetrahedral sites
( forming the 8 phase) in the structure of the starting-/-Al~O~.
The appearance of the a phase in the mechanically treated
powder, without additional heating, indicates that in the stud-
ied •y-A|2Oj other hydrated aluminas (such as diaspore ) were
present, which directly transformed to the ct phase [6].
In the latter stage of the treatment, the specific surface area
decreases, which means that, after 60 min of grinding,
micronization of the particles does not occur in spite of the
energy introduc~,,d. ~,,~ applied energy is mostly spent on
t0 breaking down OH bonds (both by the removal of absorbed
Pi~, 8, Weight Io~ during heating of "¢AI~O~.ungrou~ aml ground for
moisture and the loss of chemically bound water), affecting
120ram,
the welding of micronized particles and rearrangement of the
anion sublattice. This causes the 8 ~ 0~AI~Q~ transformation
in the stmling'y-Al=Os, while the amount of(x phase increases
sition shii'~edtoward lower values with increasing activation very slowly. Additional grinding of the powder for 2 rain,
time (Table 3), The ~sult~ of T e A show increased weight already ground for 600 rain, did not cause changes in the
Ios~ with increasing a~tivation time (Table 3), A change in amounts of the a and 0 phases, but influenced the formation
the course of the Am ~f(T) curve i~ al~o ob~rved (Fig, 8), of 8oAI~O~,These data show that a higher energy is needed
for the 0 ~, aoAl~O~ transfo~ation Ihan for the ~ ~ B~AI~O~
during this procedure.
4, D i j o n The temperature at which, for a constant isothermal heating
time, the fraction of one of the intermediate phases decreases
According to the ligature data [6,'/], the 'y~*aoAl:O~ below the diffractometer sensitivity was chosen to indicate
transformation proceeds via the 8 and O phases, and is com- the positive effect of mechanical activation on the phase tran-
pleted within the temperature range 1170--1350~C. sition. [n this analysis the'y -*a-Al20~ transition is observed
The mcchaflical activation used in this study enables the as a con,vocative reaction with ~. and 0-AI.~O3 intermediate
phase transition to start without additional heating, The phases.
r~ults iudicate that the transition is strongly The h~ted unground ~-AI~O~ powder undergoes transfer-
affected by the grinding tit~, marion to the ~xphase predominantly via the 6 (800°C, 4 h)
it is generally known that the 'y ~a-Al~O~ transition is and 0 (9(X)~, 4 h) phases. At shorter heating times at 800
followed by loss of water during the thermal tr~tment [6]. and 900~, the ct phase was not detected, indicating the slow
TGA of ~tivated powder~ shows increased weight loss with development of the dehydration process. The amount of c~-
prolonged activation time, As the activation proceeds in a Ai~O~ formed in the starting ungroand powder up to 1000°C
hcrn~t¢ bowl, we assume that the increased weight loss is a is about 8%, which is in agreement with data obtained during
con~qucnc~ of the rehydration of the'y pha~ and/or higber mechanical treatment up to 120 rain, showing the direct tran-
water~ i o n on the newly form~ d~ f~ct ~urface after the sition of a limited amount of the powder into a-Al~O~. The
has ~ exposed to the environment, The shape of transformation of the unground'y-Al20~ into the ct phase via
the TG curve of the activated powder compared with that of the detected intermediate phases (the 8 and 0) may be
~be unactivatud powdm' (Fig, 8) indicates the stronger chem. described schematically as
i~gption of water,
IOL~°C I IOi~C 1240~C
oocurdng during ~ctivation can them forebe dis- ~t -'* ~ "* 6 "-* c*-AI20~
e u ~ l as two-stage processes, in the initial s t ~ oftreatment,
 E, gosli¢"el al, / Powder Technology 91 ~1997J 49-54
on the basis of the data given in Fig. 5, while the temperature
of the 0--* ¢t-Al..,O3 transition for unground, 2 rain ground
and 120 rain ground powders is based on the results of DTA
(Table 3 ).
The effect of grinding on the phase transition becomes
more evident after heating of the ground powders. It is obvi-
ous that the energy introduced during the grinding causes the
OH bonds to break in the starting powder in which, after
adding thermal energy, the a phase was already identified at
800~'C. With increased heating time (4 hours) the influence
of grinding time is much more pronounced than after 1 or 2
hours of heating. Analysis of the results given in Table 2
reveals that the highest increments of the ,~ phase were
noticed for all thermal conditions used for shorter grinding
times (up to 7 rain). It follows that the influence of previous
activation on the thermally caused 'y ~ ¢t-Ah.O3 transition is
most intensive at the very beginning of the activation. In this
activation stage, strong micronization of the "y-AltO3 takes
place, followed by an increase in the specific surface area.
Therefore, the results suggest that the transition is influenced
by the specific surface area, probably due to the loss of OH
ions from the surface. The growth rate of the amount of a
phase in the above.mentioned grinding time interval
increases with the temperature and time of isothermal heating.
Prolonged grinding, from 7 to 120 min, causes further
increase in the amount of~ phase, but at a considerably lower
rale.
The mechanical energy introduced is more effective during
the aboveqnentioned phase transition than may be deduced
from the increase in the ~-Al:Os reflection intensities during
grinding (Fig. I ), This phase is most probably being amor-
phized during the applied activation, The data obtained
('l~tble 2) prove that the greatest changes in structure take
place during micronization of the starting powder, which is
also observed during thermal treatment. Throughout the pro+
longed grinding time, slowing down ofthe ~, ~ 8-Al:Os phase
transformation is caused by a slower increase in the micron°
ization rate.
A difli~rence in the formation kinetics of all the above-
mentioned phases during heating was also observed as a func-
tion of the time of mechanical treatment. With a mechanical
activation of 2 rain, the mnount of the a phase at 1000°C is
60%, 8-AI203 slowly disappears from the system, while the
amount of 0-AI20.~ passes through a maximum at 950°C
(Fig. 6, "Fable 3). This phase transition develops according
to the scheme
'i,lSOoC I004)°C I 131)°(?
y "-+ 5 + 0 -~ ¢t-Al+Os
Alter 120 min of mechanical activation and subsequent
heating, the phase transformati~ms are faster (Fig. 7,
Table 3), giving 96% of the ¢~ phase at 1000°C, while the 8
and 0 phases disappear above 900~C and 1000°C, respec-
tively. The course of the transforrqation can be described
schematically as
53
~OoC 950oC IO3OoC
~' -~ ~i -+ 0 "+ ¢t-A1203
The heating time also affects the amount of the detected
¢t phase, as can be seen from the data given in Table 2. This
indicates that the temperature range ofthe-y + ~x-Al203trans-
formation given in the literature [6,7] is valid for these par-
titular working conditions, because the rearrangement in the
cation and anion sublattices is a slow process during this
phase transition, which is typical for reconstructive
transformations.
On the basis of the data obtained, it is obvious that pro-
longed grinding exhibits a beneficial influence on both the
beginning and completion of {x-phase formation. The tem-
perature of the appearance and disappearance of the observed
intermediate phases during the y-+ {x-Al203 phase transfor-
mation is affected by the time of activation. This indicates
that both of the introduced energies, mechanical and thermal,
contribute to overcome the activation energy gap for the
observed phase transformation.
5. Conclusions
Under the applied experimental conditions, the possibility
of activating the y ~ {x-Al2Os transition by introducing addi-
tional mechanical energy through friction and impact was
proved. Daring grinding up to 120 min, the appearance of 8+
AI~O~ and a small amount of ¢~+AI~O~,besides the original
'y.AI:O~, was noticed, With prolonged grinding up to 600
min, the 8-AI2Os formed transforms into 0-Al~Os. The sped
cific surface area of the micronized powders increases up to
60 rain and thin1 decreases with increasing grinding time.
Additional thermal energy conwibules to the completion of
the investigated phase transformation, The more mechanical
energy is introduced, the less thermal energy is needed to
form the most stable oL°AI2Oj,With mechanically untreated
powder the formation of {x.AI2Os, through 8° and 0-Al:Os,
starts above 1000°C. With powders mechanically activated
up to 120 rain, the 'y-~ 8-Al2Os transition is lowered by
100°C, the 8-~0-AI2Os by 150°C and the 0 ~¢~°AI20~ by
about 200°C, as compared to the unground powder. The con-
tent of the ot phase in samples ~round for ! 20 rain and heated
at IO00°C is 96%.
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