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Powder Technology 192 (2009) 346–351

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Powder Technology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p ow t e c

Production of Al–20 wt.% Al2O3 composite powder using high energy milling
S.S. Razavi Tousi ⁎, R. Yazdani Rad, E. Salahi, I. Mobasherpour, M. Razavi
Ceramic Department, Materials and Energy Research Center, P.O. Box 31787/316, Karaj, Iran

a r t i c l e i n f o a b s t r a c t

Article history: High energy ball milling was used to produce a nanostructured Al matrix composite reinforced by submicron
Received 18 April 2008 α-alumina particles. Scanning electron microscopy analysis as well as tap and green density measurements
Received in revised form 30 December 2008 were used to optimize the milling time needed for the completion of the mechanical milling process. Results
Accepted 26 January 2009
show that addition of alumina particles as the reinforcement has a drastic effect on the size, morphology and
Available online 4 February 2009
pressability of the powder. Scanning electron microscopy shows that distribution of alumina particles in the
Al matrix reaches a full homogeneity after steady state. This would increase the hardness of powder due to a
Keywords:
Metal–matrix composites
nano-structured matrix and oxide dispersion strengthening.
Nano-structured materials © 2009 Elsevier B.V. All rights reserved.
Steady state

1. Introduction in the glove box in the Ar atmosphere to prevent oxidation. The


powders produced after different stages of milling were examined
An optimum combination of high strength and ductility gives Al using a Cambridge (Stereo Scan s360) scanning electron microscope
based metal matrix composites (MMCs) a wide range of possible (SEM) operating at a voltage of 30 kV.
advanced applications [1,2]. A survey of the previous studies indicates Particle size and its mean deviation were obtained by a visual basic
that a homogenous dispersion of fine particles in a fine grained matrix software using several SEM images. The mean deviation from the
is beneficial to the mechanical properties of MMCs [2–6]. average particle size was used as a criterion for the estimation of
Mechanical alloying (MA) is a simple and useful technique for particle size distribution:
attaining a homogeneous distribution of the inert fine particles within
a fine grained matrix [7]. Addition of ceramic reinforcements into a X
n
Di − DAv
d= j j ð1Þ
ductile matrix has a great effect on the structural evolution during ball i=1
DAv
milling. Many researchers focused on the addition of low percentages
of the ceramic phases to the Al matrix by mechanical alloying [8–14]. where n is the number of particles, d mean deviation from the average
This study shows that addition of 20% wt. Al2O3 markedly influences particle size, Di the diameter of the particle i and DAv is the average
the structural evolution of the Al matrix during milling process. The particle size.
time needed to reach the steady state also depends on the distribution X ray diffraction (XRD) patterns of powders were taken in air
of alumina particles in the Al matrix. In spite of the absence of alloying atmosphere using a Philips (PW3710) X ray diffractometer (30 kV and
elements, the ultimate powder has an excellent hardness and 25 mA) with Cu Kα radiation. Grain size and lattice strain changes
acceptable morphology for the powder metallurgy process. during milling stages were calculated by the Williamson–Hall method
for at least three peaks [15]:
2. Experimental procedure
B cos θ = 0:9λ = D + 2η sin θ ð2Þ
Commercial purity Al powder (Merck, Art. No: 1056) as a mono-
where B, λ, θ, D and η are full width at half maximum (FWHM), the
lithic system and a mixture of Al–20 wt.% alumina powder (Martins-
wave length, peak position, crystallite size and lattice strain, respec-
werk, MR70, d50: 0.5–0.8 μm) were separately milled in a P5 planetary
tively. A Philips CM 200 FEG transmission electron microscopy (TEM)
mill for various periods of time up to 25 h. The ball to powder ratio was
was used to investigate grain size and dispersed particles. The powders
approximately 15:1 and the mill speed was maintained at 250 RPM.
were mounted, cross sectioned and polished in preparation for the
3 wt.% of stearic acid as process control agent (PCA) was added to
microhardness test. Micro-hardness values were obtained averaging
retard excessive welding. The milling atmosphere was Ar which was
5–10 indents of 50 g force; error bars indicate the positive/negative
purged into the cups before milling. Product sampling was performed
deviation from the average hardness. To study the green density
changes, the powders were first pressed by an isostatic press in the air
⁎ Corresponding author. Tel./fax: +98 2616201888. atmosphere (500 MPa) and then the BS1902A standard was applied
E-mail address: s.razavitousi@gmail.com (S.S. Razavi Tousi). using methanol via the Archimedes method. The density values were

0032-5910/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2009.01.016
S.S. Razavi Tousi et al. / Powder Technology 192 (2009) 346–351 347

obtained by averaging the values of the three specimens for each


duration of milling.

3. Results and discussion

3.1. Particle size distribution

The effect of milling time on the particle size of ductile powders has
been studied separately by Rodiguez, El-Eskandarany and Fogagnolo in
the case of monolithic and composite powders [16–18]. In the all cases
a similar trend was observed — an increase in the particle size followed
by a decrease and then steady state. This can be attributed to the cold
welding of primary particles followed by work hardening and thus
activating the fracture mechanism. When welding and fracture
mechanisms reach equilibrium, the steady state is achieved.
The average particle size of the monolithic Al has a maximum at
10 h milling and then stabilizes between 15–25 h (Fig. 1). The addition
Fig. 2. Effect of milling time on the mean deviation from the average particle size.
of 20% wt. alumina has a drastic effect on the variation of the average
particle size of the composite powder; there is no considerable
increase–decrease trend. This can be explained by the effect of the
high volume fraction of Al2O3 particles on the welding behavior of the Bhaduri used larger reinforcement compared to that used by
Al particles. The alumina particles are imbedded between the Al Fogagnolo or in this study, and thus a considerable amount of milling
particles, thus preventing cold welding from occurring. Another energy should be consumed by fracturing the SiC particles.
reason is the local deformation of the Al particles in the vicinity of
ceramic particles during the milling process. The result of this local 3.2. Morphological changes
deformation is increase in the hardness of powders and decrease in
weldability. The Al particles in their initial state are predominantly equiaxed
Particle size distribution can be considered as another criterion for and irregular in shape (Fig. 3(a)). After 5 h milling, the particles
estimating the steady state (Fig. 2). In the case of composite powder, deform into a flake like shape (Fig. 3(b)). Due to ductile nature of the
an increase in the mean deviation is attributed to the formation of few aluminum powder, welding seems to be the dominating mechanism
large particles at presence of a lot of fine particles (Fig. 4-b). over the next stage [18], and thus the 10 h milled particles have large
It can be found that composite powder reaches steady state after size and flattened shape (Fig. 3(c)). The plate like particles are work
15 h while it takes 20 h for monolithic Al. Indeed, the presence of the hardened after 15 h milling, hence fracture mechanism is activated.
ceramic phase accelerates the rate at which the milling process (Fig. 3(d)). The flake-like morphology remains after 15 h milling but
reaches completion. The presence of alumina particles increases local particle size distribution and the average particle size is decreased.
deformation which improves the particle welding process. Beside this, Indeed, the large flaky particles are crushed by intense impacts. After
the higher local deformation imposed by reinforcement particles 20 h, a lower aspect ratio can be seen and size distribution has a
increases the deformation hardening, which helps the fracture narrow range (Fig. 3(e)). Further milling up to 25 h has no effect on
process. The small hard brittle particles in the matrix act as small the morphology (Fig. 3(f)); indeed at milling times longer than 20 h
milling agents, and thus the steady state milling time is reduced. A the steady state predominates. Nonetheless, it is important to note
similar behavior was observed by Fogagnolo studying the ball milling that after stabilizing the size of powder, microstructural refinement
of Al–AlN system [17,19,20]. can still take place and terminate at a later time [21].
On the other hand, Bhaduri et al. have found that addition of SiC to Fig. 4 shows the morphology of the mechanically milled Al–20%
Al-7010 alloy inhibits the milling progress [3]. This contradiction may wt. Al2O3 powder. Considering the changes of morphology; one can
be due to the different reinforcement size of the mentioned studies; notice the effect of reinforcement addition on the MA process [11].
Despite the ductile nature of the Al powder, the formation of large
flake like particles was canceled by the presence of alumina particles.
After 5 h milling (Fig. 4(a)), the powder had a broad distribution of
irregular particles with a slight aspect ratio. Because of the soft Al
matrix, cold welding was the predominant mechanism at this stage
and hence, large aggregates were formed. However, the presence of
alumina particles decrease the weldability of the Al powder, and
resultantly fine irregular particles were also formed. Fig. 4(b) shows a
typical large particle consisting smaller microwelded particles. Each of
these large particles would be fractured by the more intensive impacts
due to the work hardening of the Al matrix. As the milling time
increased to 10 h (Fig. 4(c)), work hardening activated the fracture
mechanism and the particle size distribution become limited. Notably
there was no flake like particle in the case of composite powder during
milling stages. The presence of the alumina particles in the Al matrix
decreases ductility; so fracture occurs before impacts cause lamina-
tion [19]. With 15 h milling time (Fig. 4(d)), particles had a stabilized
shape and size distribution; further milling up to 20–25 h makes no
significant difference. Considering Figs. 3 and 4, it is apparent that the
Fig. 1. Effect of milling time on the average particle size of monolithic and composite presence of alumina particles reduces the steady state time, in
powders. agreement with the results of particle size distribution.
348 S.S. Razavi Tousi et al. / Powder Technology 192 (2009) 346–351

Fig. 3. Morphology of monolithic Al after (a) 0 h, (b) 5 h, (c) 10 h, d (15 h), (e) 20 h and (f) 25 h milling.

3.3. Structural evolution in the Al matrix. Accordingly, the steady state could be attained only
after full homogenization of the reinforcement particles in the matrix.
The effect of milling time on the distribution of Al2O3 particles is Considering the initial size of the alumina particles (D50: 0.5–
examined by SEM. Fig. 5(a) shows the distribution of reinforcement 0.8 µm) it is clear that these particles did not fracture markedly during
particles obtained by a simple mixing method (0 h milling) which is the intensive impacts of balls. α-alumina is the most stable oxide of
known as the routine powder metallurgy process. The reinforcement aluminum. The phase diagram indicates that no compound can be
particles adhere together and a heterogeneous distribution of Al2O3 formed at the Al/Al2O3 interface [5,22]. The only probable reaction at
particles is obtained. After 5 h milling (Fig. 5(b)), these particles were the interface is dissolving of alumina in the Al and/or formation of a
spread throughout the Al matrix with a better homogeneity, though thin amorphous alumina layer at the interface [23]. In this work, since
clustering could still be seen in some areas. A milling time longer than no heat treatment was applied, alumina particles seem to have
10 h provided a homogeneous distribution of the reinforcement engaged in the Al matrix mechanically and formation of a chemical
particles (Fig. 5(c)) with further milling giving no noticeable effect interface seems unlikely.
(Fig. 5(d)).Comparing Fig. 5 with Figs. 1–4, one can find that the steady Fig. 6 shows the tap density dependence on the milling time for the
state has a strong dependence on the distribution of alumina particles monolithic and reinforced Al. It should be noted that tap density

Fig. 4. Morphology of composite powder after (a) & (b) 5 h, (c) 10 h, (d) 15 h milling.
S.S. Razavi Tousi et al. / Powder Technology 192 (2009) 346–351 349

Fig. 5. Distribution of alumina particles in the Al matrix with milling time after (a) 0 h, (b) 5 h, (c) 10 h, (d) 15 h.

depends only on the shape and size of powder particles and not on the analogous to the tap density curve, including three stages due to the
micro-structural properties of powder. For the monolithic Al, three powder morphology and particle size changes already mentioned
stages can be seen; a declining, then increasing and finally steady [18,20]. Though the particles have a quite similar morphology at the
state. With short milling times, there was a continuous decrease in the start and end of the process, high plastic deformation reduces the
tap density with a minimum between 5–10 h. This reduction can be pressability, hence generating the lower green density for final
attributed to the formation of large flake like particles (as shown in monolithic Al powder [24]. Additionally, a thin brittle layer of
Fig. 3(b)) and consequently the worst packaging properties of the aluminum oxide on the surface of the Al particles retards cold
powder [24]. With further milling, the powder particles are work welding [25]. By contrast, for the composite powder, density changed
hardened and fractured, thus quasi spherical particles are produced in a different manner during the milling time, i.e. first decreasing and
and packaging properties improve. Between 20–25 h milling, no then stabilizing. The fact that the energy needed to crush the particles
change in tap density is seen, as confirmed by SEM images, this is increases with decreasing the particle size as well as work hardening
because the steady state had being already attained. and the adherent oxide film on the aluminum particles, explain why
For the composite powder, a milling time up to 15 h increased the the curvature tends toward zero with time. After 10–15 h milling, the
tap density continuously due to fragmentation of large particles. green density becomes constant due to completion of the milling
Between 10–15 h, the slope of diagram diminishes and after 15 h tap process. Comparing the green density of the composite and mono-
density does not change vs. milling time. As shown by SEM images, lithic Al, one can clearly see that the presence of the alumina particles
15 h is an adequate time for the reinforced Al to achieve a steady state. decreases the time required to reach a steady state, something which
Any change in the powder morphology has a great effect on the is consistent with the changes of morphology witnessed [11,17].
packing characteristics of the powder. In the case of bulk density and The result of dividing the principal (111) and secondary (200)
pressability, both the morphology and hardness of the powder are reflections of aluminum in the X-ray diffraction pattern at different
effective. The green density curve of the monolithic Al (Fig. 7) is milling times is shown in Fig. 8. Observing these curves, one can

Fig. 6. Changes of tap density versus milling time for monolithic and reinforced Al. Fig. 7. Changes of green density versus milling time for monolithic and reinforced Al.
350 S.S. Razavi Tousi et al. / Powder Technology 192 (2009) 346–351

Fig. 8. Effect of milling time on the I111/I200 ratio of Al in the case of monolithic and
composite powders.

assume three periods for milling of the monolithic Al, in a manner


similar to the density curves. This can be understood considering the
anisotropy in the elastic modulus of the single-crystal Al. Therefore,
grains within the powder particles are deformed into thin layers in the
‘soft’ direction, perpendicular to the direction in which the powder
particles were flattened by milling ball. When the sample is prepared
to perform the powder XRD analysis, this flattened powders and its
(200) planes are arranged parallel to the sample-holder and as a
consequence I200 increases whereas I111 decreases. With further
milling, flattened particles are fractured and divided into equiaxial
particles. Accordingly the particles lose their texture or preferential Fig. 10. (a) Bright field and (b) dark field TEM image of Al powder milled for 25 h.
orientation and their reflection planes randomly arranged again and
I111 recovers its significance. [19,24]. The result of dividing the
principal (111) and secondary (200) reflections of the reinforced Al structure, so dislocations reach readily to the grain boundaries, causing
has no marked change during milling stages, confirming the lack of diminution of total lattice strain [28].
lamination for the Al particles in the presence of alumina particles. A TEM image of 25 h milled Al powder confirms the results
Fig. 9 shows grain size and lattice strain of monolithic Al vs. time obtained by Williamson–Hall method (Fig. 10(a)). These fine grains
obtained by Williamson–Hall method. Analytical models predict that create many spots in the selected area electron diffraction (SAED)
grain size decreases by milling time according to the equation D=Kt− 2/3, pattern which causes a ringed shape SAED (Fig. 10(b)).
where K is a constant [13]. Considering the exponent of time, one can The nanostructured Al matrix influences strength according to the
anticipate that the reduction of grain size occurs at the first milling Hall–Petch equation [29,30];
stages. In this work, grain size decreases rapidly in the early stage of
1−
=2
milling and then it is fixed at about 46 nm. The lattice strain increases H = H0 + KD ð3Þ
with time due to distortion effect caused by dislocation in the lattice. The
lattice strain curve has a maximum [19,26,27] which is ascribed to the where Ho and K are appropriate constants associated with the hard-
grain size reduction and its effect on strain reduction. With a short ness measurement and D is the size of crystallite [31,32]. The hardness
milling time, severe plastic deformation brings about a deformed lattice of both the monolithic Al and composite powder increases with milling
with high density of dislocations. Further milling gives a nano-grained time (Fig. 11). The difference between hardness of the monolithic and
composite powder arises from the presence of alumina particles and

Fig. 9. Grain size and lattice strain of monolithic Al versus milling time. Fig. 11. Powder hardness of the monolithic and reinforced Al versus milling time.
S.S. Razavi Tousi et al. / Powder Technology 192 (2009) 346–351 351

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Acknowledgements

The authors would like to thank Mrs. Nicola Forrest for her help.
Also, they acknowledge professor M. Zakeri, whose ongoing help and
advice is much appreciated.

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