Materials Science and Engineering A301 (2001) 180– 186

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Effect of hot rolling and heat treatment of Al–5Ti–1B master

alloy on the grain refining efficiency of aluminium
K. Venkateswarlu a, B.S. Murty b,1, M. Chakraborty b,*
a
National Metallurgical Laboratory, Jamshedpur 831007, India
b
Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Kharagpur 721302, India

Received 30 May 2000; received in revised form 14 August 2000

Abstract

The influence of hot rolling and annealing of Al–5Ti– 1B master alloy on its grain refining efficiency has been studied in detail.
Both hot rolling and annealing improve the grain refining efficiency of the master alloy. Rolling results in the fracture of TiAl3
particles. The amount of deformation required for achieving good grain refinement decreases with increase in rolling temperature.
Grain refining efficiency of the master alloy also increases with increase in annealing temperature. The improved grain refining
efficiency of the master alloy on annealing is attributed to the increased fraction of TiAl3 and the possible formation of (Ti,Al)B2.
© 2001 Elsevier Science B.V. All rights reserved.

Keywords: Grain refinement; Heat treatment; Hot rolling; Al– 5Ti– 1B; Aluminium

1. Introduction equiaxed grain structure. Several researchers [1,5 –9]

It is a common industrial practice to add Al –Ti and
Al –Ti –B master alloys to molten aluminium alloys
prior to casting to achieve fine equiaxed grain structure
suppressing the columnar grains. The fine and homoge-
neous structure in the as cast alloys improves mechani-
cal properties such as fabricability, yield strength and
toughness. Most aluminium industries use these master
alloys as grain refiners in various compositions. System-
atic studies on the effect of Ti:B ratio on the grain
refining response of aluminium and its alloys have
shown that the Al – 5Ti – 1B master alloy is the best
grain refiner [1–4] among all the compositions for most
aluminium alloys.
It is well known that the addition of Al – Ti – B master
alloy to the aluminium melt introduces a large number
of intermetallic particles such as TiAl3, TiB2 and
(Al,Ti)B2 into the melt [1 – 6]. These intermetallic parti-
cles are believed to act as heterogeneous nucleating sites
during solidification of aluminium resulting in fine
* Corresponding author. Fax: +91-3222-55303.
E-mail address: madhu@metal.iitkgp.ernet.in (M. Chakraborty).
1
Present address: National Research Institute for Metals, Tsukuba
3050047, Japan.
have studied the role of TiAl3 and TiB2 in the master
alloys on their grain refining efficiency. The size, size
distribution and morphology of TiAl3 particles play an
important role in the grain refining efficiency of a given
master alloy. The influence of reduction in TiAl3 parti-
cle size by thermo-mechanical treatment of as cast
master alloy on its grain refining efficiency has not yet
been studied in detail. The present paper attempts to fill
this gap by a detailed study on the effect of hot rolling
and heat treatment of as cast master alloys on their
grain refining efficiency.
2. Experimental details
The Al –Ti –B master alloys were prepared in an
induction furnace by the reaction of molten aluminium
(commercial purity) with K2TiF6 and KBF4 salts at
1000°C. The master alloys so prepared and the com-
mercial purity Al were chemically analysed using a
flame emission spectrometer (model AA-670 of Shi-
madzu, Japan), and the compositions are shown in
Table 1. The master alloys were hot rolled at 200, 300
and 400°C for reduction levels of 20, 40, 60 and 80%.
The rolling process includes a 20% reduction level at

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PII: S 0 9 2 1 - 5 0 9 3 ( 0 0 ) 0 1 4 2 2 - 2
 K. Venkateswarlu et al. / Materials Science and Engineering A301 (2001) 180–186 181

Table 1 the standard linear intercept method using a LECO

Chemical composition of Al and Ti–B–Al master alloy
(DM-400) optical microscope. Scanning electron mi-
Alloy Composition (wt.%) croscopy was carried out using scanning electron mi-
croscopy (model JSM-840A, JEOL, Japan). X-ray
Fe Si Ti B Al diffraction (XRD) patterns of the master alloys were
obtained using X-ray diffractometer (model D-500,
Al 0.16 0.11 – – Balance
Al–Ti–B 0.16 0.10 5.0 1.0 Balance
Siemen’s make).

the beginning at a predetermined temperature. For 3. Results and discussion

further reduction levels, the samples were again heated
to the same temperature and rolled. Similar processing
steps were followed for all the rolling experiments. The
details of the rolling conditions are given in Table 2.
The as cast master alloy was also subjected to heat
treatment at 300, 400, 500 and 600°C for 4 h.
In order to carry out the grain refinement, 1 kg of
commercially pure aluminium was melted in a clay
graphite crucible using a pit type resistance furnace
under a cover flux; 0.2 wt.% of master alloy (Table 1)
was added to the melt at 720°C. The melt was stirred
for 30 s immediately on addition of the grain refiner
and no further stirring was carried out. Parts of the
melt were poured at regular intervals (2, 5, 30, 60 and
120 min) into a cylindrical graphite mould (25 mm
diameter and 100 mm height) surrounded by a fire clay
brick with its top open for pouring [10]. The cast bars
were sectioned at a height of 25 mm from the bottom,
and the section surfaces so obtained were polished and
etched. Macrostructures were obtained by etching with
standard Poulton’s reagent, while etching with Keller’s
reagent revealed the microstructures. The microstruc-
tural features were studied by optical microscopy, scan-
ning electron microscopy (SEM) and EDS X-ray
microanalysis. Grain size analysis was carried out by
The X-ray diffraction studies have shown the pres-
ence of TiAl3 and TiB2 phase along with a-Al in the as
cast Al –Ti –B master alloy. The size of TiAl3 particles
was measured and the results of particle size analysis of
all hot rolled samples are given in Table 2 along with
those of the as cast alloy. The size of 100 particles has
been analysed in each case. The results indicate that the
mean particle size decreases with the increase in per-
centage reduction at any rolling temperature, and at a
given percentage reduction, it increases with increase in
rolling temperature (Fig. 1). The table also gives the
standard deviation on the mean particle size, which is
quite large, suggesting that particles vary widely in their
size.
The number of particles below 20 mm also increased
with the increase in percentage reduction at all the
rolling temperatures (Table 2). The decrease of mean
particle size of TiAl3 during hot rolling is due to
fracture of these brittle intermetallic particles, which is
clearly evident from the SEM studies. Fig. 2a and b
show the SEM photomicrographs of as cast master
alloy and after 80% reduction at 200°C, respectively.
TiAl3 particles (needle/flake shaped) in the as cast
condition (Fig. 2a) have become finer in size after

Table 2
Size distribution of TiAl3 particles in as cast and rolled master alloys

Master alloy Processing condition Statistical data (mm)

Rolling temperature (°C) Reduction (%) Mean S.D. Size range Percent less than 20 mm

Minimum Maximum

R0 (as cast) – – 29.1 14 5 70 30

R1 200 20 23.3 13.3 5 54 52
R2 200 40 20.1 13.2 5 58 59
R3 200 60 13.8 9.1 6 46 74
R4 200 80 10.5 6.3 4 41 93
R5 300 20 25.2 13.6 5 58 36
R6 300 40 21.3 13.3 4 52 58
R7 300 60 18.2 13.0 4 47 60
R8 300 80 13.8 12.7 4 43 72
R9 400 20 27.1 13.7 5 63 38
R10 400 40 24.1 13.2 4 52 49
R11 400 60 20.3 13.9 5 51 59
R12 400 80 15.4 12.5 5 49 61
182 K. Venkateswarlu et al. / Materials Science and Engineering A301 (2001) 180–186
Fig. 1. Mean particle size vs. percent reduction of 5/1 master alloys at
different temperatures.
Fig. 2. Microstructural features of 5/1 master alloys (a) as cast and
(b) with deformation.
rolling (Fig. 2b). Fig. 3 shows an intermediate stage
(40% reduction at 200°C), which clearly demonstrates
the fracture of the TiAl3 particles. As the TiB2 particles
are usually very fine ( 0.5 mm) they could not be
observed in the present SEM investigation and hence it
is difficult to comment on their features during rolling.
The fracture of TiAl3 particles is due to stress concen-
tration at the particle matrix interface during rolling.
As the particles are brittle, the stress concentration
results in their fracture. At lower rolling temperature
the stress concentration is expected to be higher and the
particles are expected to be more brittle causing exten-
sive fracture of these particles as the rolling temperature
is decreased.
Fig. 4a–e show the photomacrographs of Al grain
refined with as cast master alloy and after rolling at
200°C for different levels of reduction (20 –80% reduc-
tion) respectively, and for different holding times. A
change from columnar to fine equiaxed grain structure
is clearly evident in both the cases with the increase in
holding time. However, the grains are much finer in the
case of the sample grain refined by the rolled alloy
when compared with that refined by as cast master
alloy. It is interesting to note that the holding time at
which the conversion from columnar to equiaxed grain
structure occurs, decreases with increasing amount re-
duction. This clearly brings out the fact that thermome-
chanical treatment improves the grain refining efficiency
of the master alloys probably due to the fracture of
TiAl3 particles to finer sizes on rolling. At the same
time the formation of duplex particles due to such
treatments cannot be ruled out. This may improve the
grain refining efficiency of the hot rolled master alloys.
The possibility of formation of duplex particles,
(Al,Ti)B2, as a result of heat/thermomechanical treat-
ment exists in view of the observations of Arnberg et al.
[2]. These authors had found that TiB2 particles held in
liquid Al for a long time show a deficiency in Ti relative
to TiB2 stoichiometry and had suggested the formation
of duplex particles. Heat treatment or thermomechani-
cal treatment enhances diffusivities that may result in
Fig. 3. Fracture of TiAl3 particles in Al– 5Ti– 1B master alloys at
200°C, 40% reduction.
 K. Venkateswarlu et al. / Materials Science and Engineering A301 (2001) 180–186 183

Fig. 4. Macrostructures of Al grain refined by Al– 5Ti– 1B master alloys (a) as cast; (b) 20; (c) 40; (d) 60; (e) 80% reduction.

the formation of such duplex particles. However, further
investigations are necessary to confirm whether such
duplex particles can form at all.
On holding the Al melt at 720°C after the addition of
the master alloy, the TiAl3 particles start dissolving in
the melt, as they are not expected to be stable at the
addition level of Ti used for grain refinement. Due to the
dissolution, the size of the particles decreases while the
Ti content in the melt increases. This may alter the
surface tension characteristics of the melt such that
heterogeneous nucleation occurs on the large number of
sites provided by the remaining TiAl3 and/or TiB2
and/or the duplex particles in the melt. This perhaps
explains the delayed conversion of columnar grain to
fine equiaxed grains in the case of the as cast master alloy
(Fig. 4a).
The holding time at which the conversion from colum-
nar to equiaxed grains occurs is thus related not only to
the availability of a sufficient number of fine TiAl3/TiB2/
duplex particles, but also to the surface tension charac-
teristics of the melt in relation to such particles when all
other conditions are maintained constant. Hence, with
increase in the fraction of fine TiAl3 particles and/or the
formation of duplex particles in the hot rolled master
alloys, the holding time required for the conversion of
columnar to equiaxed grain structure decreases.
184 K. Venkateswarlu et al. / Materials Science and Engineering A301 (2001) 180–186
The grain size analysis of the aluminium grain refined
by the master alloy rolled at 200, 300 and 400°C for
different amounts of reduction is compared with the as
cast master alloy in Fig. 5a – c, respectively. A continu-
ous decrease in the average grain size with the increase
of holding time from 2 to 120 min is evident when both
as cast and rolled master alloys are used. However, the
extent of grain refinement is higher in the case of rolled
master alloy when compared with the as cast one at all
rolling temperatures. This is direct evidence of the
efficacy of fine TiAl3 particles obtained by rolling in
improving the grain refining efficiency of the master
alloy. Fig. 6a and b show the average grain size of Al
grain refined for 2- and 120-min holding with different
rolled master alloys. The amount of deformation re-
quired to achieve best grain refinement appears to
decrease with increase in deformation temperature (Fig.
5). Thus, rolling at 400°C appears to give the best
results as good grain refinement could be achieved with
a small amount of reduction (40%) of the master alloy.
The XRD patterns of the as cast master alloy and
after annealing at 300, 400, 500 and 600°C for 4 h are
shown in Fig. 7. It is clear from the XRD patterns that
the relative peak intensity of TiAl3 increases with heat
treatment temperature. Fig. 8 shows the variation of
Fig. 5. Grain size analysis curves of aluminium, grain refined by Al– 5Ti– 1B master alloys at (a) 200; (b) 300; (c) 400°C.
relative intensity of TiAl3 peak (in percent) with anneal-
ing temperature. The relative intensity is the ratio of the
intensity of the most intense peak of TiAl3 to that of
Al. The increase in the TiAl3 peak intensity with an-
nealing temperature suggests an increase in the volume
fraction of the phase. The increase in the TiAl3 fraction
on annealing indicates that the alloy does not reach
equilibrium during its manufacture, wherein liquid Al is
allowed to react with K2TiF6 and KBF4 at 800°C for 60
min. During this reaction, the liquid metal is enriched
in Ti from which TiAl3 particles are precipitated. It
appears that the precipitation of TiAl3 is not complete
during the above reaction and a-Al probably remains in
a supersaturated state. Heating the alloy during anneal-
ing provides sufficient thermal activation for the diffu-
sion of Ti causing further precipitation or growth of the
existing TiAl3 particles. Energy dispersive X-ray micro-
analysis revealed that the a-Al in as cast and in the
heat-treated condition contained 0.36 and 0.24% Ti,
respectively. This is therefore, an evidence of the de-
crease in Ti content on heat-treatment. The larger
fraction of TiAl3 observed at higher annealing tempera-
ture, may be attributed to faster diffusion.
Fig. 9 compares the grain size analysis of Al grain
refined with as cast and annealed master alloys. The
 K. Venkateswarlu et al. / Materials Science and Engineering A301 (2001) 180–186 185

their grain refining efficiency on aluminium. However,

with the present understanding it is not clear why the
grain refinement is partially lost at higher amounts of
reduction when the master alloy is rolled at higher
temperatures. It is possible that the TiAl3 particles grow
at higher rolling temperatures and higher amount of
reduction due to intermediate heating of the alloy be-
tween each rolling pass, which could be a possible
reason for the loss of grain refining efficiency of the
master alloy under these conditions.

Fig. 6. Grain size analysis curves of aluminium, grain refined by

different rolled master alloys (Al–5Ti–1B), (a) 2-min and (b) 120-min
holding timings.

figure clearly shows that the grain size of Al grain

refined with annealed master alloy is lower than that
refined with as cast master alloy at all holding times. In
addition, the grain size is also finer with increase in
annealing temperatures in the range of annealing tem-
peratures studied. The improved grain refining effi-
ciency of the master alloy on annealing could be
attributed to the increased fraction of TiAl3. In addi- Fig. 7. XRD patterns of Al-5Ti-1B master alloy (a) as cast and 4 h
tion, it is possible that duplex particles (Ti,Al)B2 may heat-treatment at (b) 300; (c) 400; (d) 500; (e) 600°C.
also form during annealing which can act as additional
nucleating sites as suggested earlier [2]. These particles
could contribute partly to the improved grain refining
efficiency of the master alloy. Unfortunately, the duplex
particles if any, could not be observed in the XRD and
SEM studies probably because they are very fine and
their volume fraction is quite low. In the light of the
results of annealing, the decrease in the amount of
deformation required to achieve good grain refinement
with increase in rolling temperature can be understood
better. It is possible that when the master alloy is rolled
at higher temperature, the preheating/intermediate
heating between the different reduction levels also influ-
ence the volume fraction of TiAl3 as has been seen in
the annealing of as cast master alloy. Thus, the heating
and rolling both have effects on the volume fraction of Fig. 8. Relative percent of TiAl3 vs. different heat-treatment tempera-
TiAl3 particles in the master alloy, which in turn affects tures of Al– 5Ti– 1B master alloys.
186 K. Venkateswarlu et al. / Materials Science and Engineering A301 (2001) 180–186
Fig. 9. Grain size analysis curves for different heat-treated Al– 5Ti–
1B master alloys.
4. Conclusions
Rolling and annealing of the Al – 5Ti – 1B master
alloy improves its grain refining efficiency. Rolling in-
duces fracture of the TiAl3 particles, thus increasing the
number of effective nucleating sites for Al. The amount
of deformation required to achieve good grain refine-
ment decreases with increase in rolling temperature.
Grain refining efficiency of the master alloy improves
with increase in annealing temperature. The improved
grain refining efficiency of the master alloy on anneal-
ing is attributed to the increase in the volume fraction
of TiAl3 and the possible formation of duplex particles
(Ti,Al)B2.
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