2nd International Conference on Ultrafine Grained &

Nanostructured Materials (UFGNSM)

International Journal of Modern Physics: Conference Series
Vol. 5 (2012) 638645
World Scientific Publishing Company
DOI: 10.1142/S2010194512002577

ROLE OF PROCESS CONTROL AGENTS ON MILLING BEHAVIOR OF Al

AND TiO2 POWDER MIXTURE TO SYNTHESIZE TiAl/Al2O3 NANO
COMPOSITE
Int. J. Mod. Phys. Conf. Ser. 2012.05:638-645. Downloaded from www.worldscientific.com

S. ALAMOLHODA
School of Metallurgy and Materials Engineering, University of Tehran,
P.O. Box: 14395-553, Tehran, Iran.
alamhoda@ut.ac.ir
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S. HESHMATI-MANESH
School of Metallurgy and Materials Engineering, University of Tehran,
P.O. Box: 14395-553, Tehran, Iran.
sheshmat@ut.ac.ir

A. ATAIE
School of Metallurgy and Materials Engineering, University of Tehran,
P.O. Box: 14395-553, Tehran, Iran.
aataie@ut.ac.ir

A. BADIEI
School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
abadiei@khayam.ut.ac.ir

In this study effect of adding various process control agents (PCAs) to powder mixtures of Al and
TiO2 which are mechanically activated so as to form TiAl-Al2O3 nano-composite have been
investigated. Phase constitutions and morphology of the milled powders were evaluated by XRD and
SEM techniques, respectively. The mean crystallite sizes of the milled powders were calculated by
Cauchy-Gaussian method. Thermal behavior of the milled powders was also studied by DTA to
investigate formation of the final phases.
The results showed that the mean crystallite size of the milled powders in the presence of PCAs was
smaller than that of the sample milled without PCA addition. DTA traces showed that addition of
PCAs retards the reduction of TiO2 by Al. In samples milled in presence of PCA, the reductive
reaction generally took place after melting of Al particles whereas the sample milled without PCA
addition showed an opposite behavior. Also, in comparison with the sample milled with no PCA
addition, in other samples the reductive reaction took place at relatively lower temperatures.
Keywords: Mechanical alloying; Process control agent, Nano composite, Alumiothermic reduction.

1. Introduction
Mechanical alloying exerts high energy impacts to the powder particles. The severe
plastic deformation of particles caused by high energy impacts leads to cold welding of
powder particles. This phenomenon is more intense in ductile materials. Cold welding

638
 Role of Process Control Agents on Milling Behavior 639

and fracturing make a good contact between clean surfaces with minimum diffusion
paths. Lack of cold welding causes poor contact between surfaces for the purpose of
diffusion while severe cold welding causes formation of large particles and therefore,
clean surfaces could be formed in order to facilitate the diffusion. In most cases, the
balance between cold welding and fracturing does not happen naturally and even cold
welding of powder particles either to one another or to the milling media may become a
serious problem. In this case making a balance between cold welding and fracture is
possible by addition of a PCA. PCAs are added to powder mixtures during the milling to
reduce the effect of cold welding1-6.
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In this research, various PCAs including an organic acid, isobutyl alcohol (C4H10O)
and Al-tri-sec butylate Al(C4H9O)3, a polymer and a low temperature sublimating
chloride were used. Milling behavior of the powder mixtures and thermal behavior of the
milled powders were studied and the results were compared with the sample milled with
no PCA so as to evaluate the effect of these compounds on the reduction of TiO2 with Al
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to form TiAl/Al2O3 nano-composite.

2. Experimental Procedure
The starting chemical commercially pure TiO2 and Al reagents have been precisely
weighed according to reaction (1), even though 10 mole% excess Al powder was used to
ensure the existence of sufficient Al for the reaction. The mixture was milled in a Fritch
P6 type planetary ball mill for 8 hours in pure argon atmosphere. The milling speed was
300 rpm and the ball-to-powder mass ratio was 20:1

3TiO2 +7Al3TiAl+2Al2O3 (1)

Furthermore, 5 wt. % of various PCAs including stearic acid [CH3 (CH2)16COOH], PVA
([-CH2CHOH-]n ), isobutyl alcohol (C4H10O), Al-tri-sec butylate Al(C4H9O)3 and
aluminum chloride (AlCl3) were added to the initial powder mixtures. For comparison, a
sample was also milled without PCA addition. Phase composition and morphology of the
samples were evaluated by XRD (Philips PW-1730) using a Co-K radiation and SEM
(CamScan MV2300), respectively. The mean crystallite size of the milled powders was
calculated by Cauchy- Gaussian method using XRD patterns 7. Thermal behavior of the
milled powders was analyzed by DTA with a heating rate of 20 K/min up to 1200 C
under flowing argon using a Netzsch STA 409 PC/PG instrument.

3. Results and Discussion

Macroscopic observations revealed that all compounds used in this research as PCAs can
prevent severe cold welding and improve the powder yield. In case the powder yield is
low, either the PCA has not been enough or it has not been a proper compound 6.
 640 S. Alamolhoda et al.

Presence of carbon in organic compounds makes these compounds to act as lubricants

[6]. Also, they could be absorbed on the surfaces of the powder particles and reduce their
surface tensions and prevent severe cold welding. It seems that the mechanism is
different in the case of AlCl3. As this compound has covalent bonding in the solid state
and a dimmer in liquid or gas states, in any case it is non-polar. The local temperature
rise during the milling and the applied energy of collisions of balls, may cause
sublimation of this compound since the reported local temperature rise during ball
collisions (about 40-300 C) are close to sublimation point (178C) 8of this compound.
Therefore, sublimation of this compound may prevent the cold welding. Even if the
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compound does not sublime, it may form a physical barrier between powder particles and
consequently it prevents the cold welding.
XRD results of the milled powders in presence of different process control agents are
shown in figure 1. The results show that no reaction takes place between Al and TiO2.
XRD results show that in all samples containing PCA, Al peaks broadened. The
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calculated mean crystallite size of Al in all samples obtained by Cauchy-Gaussian

method is shown in table 1. The results show that the reduction in crystallite size of Al
particles in the presence of stearic acid is less than those calculated for samples milled in
presence of other PCAs. However, it is less than that calculated for the sample milled
with no PCA. Presence of PCAs prevents from cold welding of Al particles in all
samples. Therefore, in the course of milling operation smaller agglomerates will be
formed and the energy exerted by balls during their collisions, would be inserted to
smaller agglomerate. This causes an increase of impact energy per unit volume which
could reduce the size of crystallites. High mechanical tensions and high local temperature
rise in ball collisions during mechanical alloying decomposes most of the PCA. It may
also cause phase transformations such as melting or sublimation of PCAs. In fact, there is
a balance between the increase in inserted energy by reduction of agglomerate size and
damping of exerted energy of ball collisions by decomposition and phase transformation
of PCA molecules. These two factors will determine the final crystallite size. The
calculated crystallite size in table 1 show that the reduction in crystallite size of Al
particles in samples milled with PCAs is the dominant process.
Also, TiO2 peaks broadened in samples milled with different PCAs except the one
containing stearic acid. Peak broadening in these samples was so intense that the mean
crystallite sizes of TiO2 structure could not be calculated.
It seems that in sample containing stearic acid, large molecules of stearic acid
consume a high amount of energy for decomposition. Also, a part of inserted energy
would be used for melting of this compound. During the milling process, large molecules
of stearic acid surround powder particles. These large molecules create a barrier which
damps the exerted energy to powder particles. So the crystallite size of TiO2 particles in
this sample is even larger than that of the milled powder with no PCA.
SEM micrographs of the milled samples are shown in figure 2. It could be seen that
the addition of PCAs reduces the size of the agglomerates and the large agglomerates
present in the sample milled with no PCA are not detectable in these samples and the
 Role of Process Control Agents on Milling Behavior 641

distribution of agglomerate size in these samples is narrow .This means that these
compounds create a balance between cold welding and fracturing of powder particles.

PVA

AlCl3
Intensity(a.u)
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C4H9OAl

C4H10O
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C18H36O2

No- PCA

20 25 30 35 40 45 50 55 60 65 70 75 80
2(degree)
Fig. 1. XRD patterns of the samples milled with PCAs and without PCA. : TiO2 and : Al.

Table 1. Mean crystallite sizes of the Al particles in samples milled with PCAs and without PCA, calculated by
Cauchy- Gaussian method.
Used PCA Mean Crystallite Size (nm) Correlation (R2)
PVA 23 0.9846
Al(C4H9O)3 26 0.9164
C4H10O 27 0.9694
AlCl3 28 0.9379
C18H36O2 47 0.9105
No- PCA 58 0.6107

High magnification SEM images of these samples show that large agglomerates
contain very small particles in the range of 60-80 nm. These particles were compressed to
each other and form agglomerates. The high magnification microstructure of Al(C4H9O)3
is shown in Fig. 3 as an example. DTA traces of the milled samples are shown in figure
4. There is an endothermic peak at 180C in the sample containing AlCl3 which relates to
sublimation of AlCl3 (178C) (Fig. 4 (d)). EDX results of the sample annealed at 250C
in vacuum for 0.5 hour reveal that chlorine exists in it. This means that this compound
has not been completely eliminated from the milled powder. DTA traces of the sample
milled with no PCA (Fig. 4 (f)) do not exhibit any reaction between TiO2 and Al at
temperatures below 500 C. An exothermic reaction begins at about 500 C in this sample
which relates to the aluminothermic reduction of TiO2 by Al. There is a step on this peak
 642 S. Alamolhoda et al.

below 600C pertaining to the reduced reaction rate in the activated material which shifts
the reaction to higher temperatures and goes to be concurrent with the melting of residual
Al which is an endothermic transformation. Around 660 C (melting point of Al) a tiny
dip appears which is believed to be related to the melting of residual Al. Comparison of
DTA results of this sample with those milled with PCAs reveals that the aluminothermic
reduction takes place in this sample at a temperatures of at least 60 C lower than other
samples. In this sample, there is no barrier preventing the contact of metallic clean
surfaces with TiO2 particles. Therefore, short diffusion paths caused by compaction of
powders during ball collisions will result in a solid state reaction between TiO2 and Al at
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lower temperatures.

(a) (b) (c)

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(d) (e) (f)

Fig. 2. SEM micrographs of the milled samples a) PVA, b) Al(C4H9O)3, c) C4H10O, d) AlCl3, e) stearic acid, f)
no PCA.

In all samples containing PCA except the one milled with Al(C4H9O)3 (Fig. 4 (b)),
there is an endothermic peak at 660 C, before aluminothermic reaction, which relates to
the melting of Al. In samples containing PVA, isobutyl alcohol and stearic acid the
reductive reaction occurs right after melting of Al. A layer of these compounds which
surrounded the particles in the course of milling is the main reason of this hindrance. This
layer prevents the contact of TiO2 and clean surfaces of Al. After melting of Al, in these
samples liquid phase surround TiO2 particles and dissolve PCA molecules (disintegrated
 Role of Process Control Agents on Milling Behavior 643

PCA molecules), so the diffusion paths are shortened and the reaction between liquid and
solid phase occurs.
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Fig. 3. SEM micrograph of sample milled with Al(C4H9O)3 using higher magnifications.

DTA traces of the sample milled with Al(C4H9O)3 indicates that in this case the
reaction begins before melting of Al and endothermic peak of melting creates a dip on the
exothermic peak. Most of the reaction in this case happens after melting of Al. It seems
that decomposition of this sample in the course of milling due to the energy exerted by
the balls during their collisions will extricate some Al atoms which are in close contact
with TiO2 particles like other PCA atoms.
The short diffusion path between these Al atoms and TiO2 particles facilitates their
diffusion and they can react with TiO2 at a lower temperature than the Al available in the
powder mixture. Al powder particles in the powder mixture are unable to have such a
close contact with TiO2 particles because there is coverage of PCA layer on all powder
particles in the powder mixture which has created a barrier for diffusion of atoms to react
with each other.
Even if these PCAs were decomposed during milling, atoms of O and C could be
absorbed on the clean surfaces of Al particles and make a barrier for diffusion. PCAs
such as stearic acid decompose in the course of milling or during further heating. This has
been confirmed by others who have detected formation of carbide phase in the samples
milled with stearic acid9, 10.
The reductive reaction in sample containing AlCl3 has two steps. There is an
exothermic peak right after melting of Al and then exists another large exothermic peak.
The higher reduction temperature in this sample may be related to the nature of AlCl3.
Unlike other PCAs, AlCl3 sublimes during the heating and it is expected that diffusion
paths in this case be longer than that of samples decompose during the milling or further
heating. In those samples the barriers are limited to presence of C or O atoms.
 644 S. Alamolhoda et al.

(a) (b)
Endotherm Exotherm

Endotherm Exotherm
50 250 450 650 850 1050 50 250 450 650 850 1050
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Temperature(C) Temperature(C)

(c) (d)
Endotherm Exotherm

Endotherm Exotherm
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50 250 450 650 850 1050 50 250 450 650 850 1050
Temperature(C) Temperature(C)

(e) (f)
Endotherm Exotherm

Endotherm Exotherm

50 150 250 350 450 550 650 750 850 950 1050 50 250 450 650 850 1050
Temperature(C) Temperature(C)

Fig. 4. DTA results of the sample milled with a) PVA, b) Al-tri-sec butylate, c) isobutyl alcohol, d) AlCl3, e)
stearic acid and f) no PCA.

4. Conclusions
A mixture of Al-TiO2 powders was milled in presence of different compounds as PVA,
Al-tri-sec butylate, isobutyl alcohol, AlCl3 and stearic acid as PCA in preparation of an
ultra fine TiAl/ Al2O3 composite. All PCAs used in this research could prevent severe
cold welding from happening. It was observed that addition of these compounds reduces
the Al crystallite size of the milled powder. The crystallite size of TiO2 particles in all
samples except the sample milled with stearic acid was found to be smaller than that of
the sample milled with no PCA. Addition of PCAs reduces the size of agglomerates and
large agglomerates are not present in these samples. DTA results reveal that addition of
 Role of Process Control Agents on Milling Behavior 645

PCAs retards the aluminothermic reduction of Al when TiO2 is used and prevents close
contacts between TiO2 particles and clean surfaces of Al.

Acknowledgments
The financial support of this work by Iran National Science Foundation is gratefully
acknowledged.

References
Int. J. Mod. Phys. Conf. Ser. 2012.05:638-645. Downloaded from www.worldscientific.com

1. C. Suryanarayana, Prog. Mater. Sci., 46, 1 (2001).

2. Y. F. Zhang, L. Lu, S.M. Yap, J. Mater. Process. Technol. , 89-90, 260 (1999).
3. L. Lu, Y.F. Zhang, J. Alloys and Compd., 290, 279 (1999).
4. R. Juarez, J.J. Sunol, R. Berlanga, J. Bonastre, L. Escoda, J. Alloys Compd., 434435, 472
(2007).
5. M. Pilar, L. Escoda, J.J. Sunol, J.M. Greneche, J. Magn. Magn. Mater., 320, e823 (2008).
by 14.139.204.146 on 05/10/17. For personal use only.

6. S. Sheibani, A. Ataie, S. Heshmati-Manesh, J. Alloys Compd., 465, 78 (2008).

7. HP. Klug, L. Alexander, X-ray diffraction procedures for poly-crystalline and amorphous
materials, (John Wiley & Sons, New York, 1974), p. 618.
8. CRC handbook of chemistry and physics, (Taylor and Francis Group, London, 2008-2009).
9. S. Kleiner, F. Bertocco, F.A. Khalid, O. Beffort, Mater. Chem. Phys., 89, 362 (2005).
10. Mirko Schoenitz, Xiaoying Zhu, Edward L. Dreizin, Scr. Mater., 53, 1095 (2005).