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Acta Materialia 84 (2015) 292304
www.elsevier.com/locate/actamat

Grain rening mechanism in the Al/AlTiB system

Z. Fan,a, Y. Wang,a Y. Zhang,a T. Qin,a X.R. Zhou,b G.E. Thompson,b T. Pennycookc,d and
T. Hashimotob
a

BCAST, Brunel University, Uxbridge, Middlesex UB8 3PH, UK

School of Materials, University of Manchester, Manchester M13 9PL, UK
c
SuperSTEM, STFC Daresbury Laboratories, Keckwick Lane, Warrington WA4 4AD, UK
d
Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, UK
b

Received 5 September 2014; revised 19 October 2014; accepted 21 October 2014

Available online 26 November 2014

AbstractAlTiB is the most widely used grain rener for many Al alloys. However, the precise mechanism of grain renement is still not clear after
60 years of intensive research. This work aims to further our understanding on the grain rening mechanism involving AlTiB-based grain reners.
Extensive high-resolution electron microscopy investigation has conrmed the existence of a Ti-rich monolayer on the (0 0 0 1) TiB2 surface, which is
most likely to be a (1 1 2) Al3Ti two-dimensional compound (2DC). Further experimental investigation was carried out to understand the potency of
TiB2 particles and the stability of the Al3Ti 2DC. Our results showed that the potency of TiB2 particles is signicantly increased by the formation of a
monolayer of Al3Ti 2DC on their surface. The Al3Ti 2DC forms at the liquidAl/TiB2 interface in concentrated AlTi solutions, but dissolves in
dilute AlTi solutions, although the kinetics of both the formation and dissolution of Al3Ti 2DC are relatively sluggish. Eective grain renement
by the Al5Ti1B grain rener is directly attributed to the enhanced potency of TiB2 particles with the Al3Ti 2DC and sucient free Ti solute in the
melt after grain rener addition to achieve the columnar-to-equiaxed transition.
2014 Published by Elsevier Ltd. on behalf of Acta Materialia Inc.
Keywords: Grain renement; Nucleation; Aluminum; TiB2; Interfacial layer

1. Introduction
Grain renement of Al alloys is desirable since it facilitates the casting process, reduces cast defects and therefore
oers improved casting quality [1]. To achieve a grainrened cast microstructure, chemical inoculation by the
addition of grain reners has become a common industrial
practice [2]. The most widely used grain rener for Al alloys
is the Al5Ti1B (all compositions are in wt.% unless
otherwise specied) master alloy, which contains both the
Al3Ti intermetallic compound and TiB2 particles in an aluminum matrix. The Al5Ti1B master alloy contains 2.8%
excess Ti over the stoichiometric ratio of TiB2 (i.e., 2.2:1 in
wt.%). The Al5Ti1B master alloy is very eective for the
grain renement of most of Al alloys with a nucleation
undercooling of usually less than 1 K [2]. Since the
introduction of AlTiB-based grain reners over 60 years
ago [3], tremendous eorts have been made to understand
the mechanism of grain renement, which has been the
subject of a number of review papers (e.g. [2,4,5]).
However, until now, there has been no consensus on the
exact mechanism for grain renement involving the
addition of AlTiB-based grain reners [5].

Corresponding author; e-mail: zhongyun.fan@brunel.ac.uk

In the 1950s, the carbideboride particle theory was rst

proposed by Cibula [3]. This theory proposed that insoluble
TiB2 particles in the melt acted as the heterogeneous nucleation sites. However, Mohanty and Gruzleski [6] observed
that the borides are pushed to grain boundaries, and no
grain renement was observed in the absence of Ti solute.
This contradicted the carbideboride particle theory.
Similarly, AlB2 particles (less stable than TiB2 particles in
the Al melt) do not act as heterogeneous nucleation sites
[7].
Parallel to the carbideboride particle theory is the
peritectic theory proposed by Crossley and Mondolfo [8]
in the early 1950s. This theory conjectured that Al3Ti, not
TiB2, nucleated a-Al via the peritectic reaction. There were
experimental observations that appeared to support the
peritectic theory. For example, Marcantonio and Mondolfo [9], and Maxwell and Hellawell [10] showed that the
nucleation of a-Al required a smaller undercooling in the
presence of Al3Ti compared with TiB2, indicating that
Al3Ti is a more potent nucleant than TiB2. Davies et al.
[11] observed Al3Ti at the centres of the grains and suggested that Al3Ti maybe the nucleant. However, during
the grain renement of Al alloys using AlTiB master
alloys, the amount of free Ti added to the melt via the master alloy is usually less than 0.01%, which is much lower
than the Ti level required for peritectic reaction (0.15%).

http://dx.doi.org/10.1016/j.actamat.2014.10.055
1359-6462/ 2014 Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

Z. Fan et al. / Acta Materialia 84 (2015) 292304

Therefore, Al3Ti is not thermodynamically stable for the

hypoperitectic case. For example, Johnsson [12] indicated
that the aluminides probably take less than 1 min, but definitely less than 5 min to dissolve at a holding temperature
of 775 C. Jones and Pearson [7] suggested that all aluminides dissolved in molten Al in less than 30 s. Although
the dissolution time depends on both the holding temperature and the size of the Al3Ti particles, the resulting consensus is that Al3Ti dissolves rapidly above the Al liquidus and
hence the peritectic reaction is not thermodynamically
feasible.
For Al3Ti to be responsible for grain renement during
solidication of hypoperitectic alloys, other factors have to
be operational. Vader et al. [13] and Backerud et al. [14]
proposed the peritectic hulk theory in the early 1990s. This
theory recognized that Al3Ti is a more potent nucleant than
the TiB2 and attempted to explain how the borides increase
the stability of aluminides. It was suggested that the borides
form a shell around the aluminides, and slow down dissolution of the aluminides. The aluminides eventually dissolve
and leave a cell of liquid with approximately the peritectic
composition. The peritectic reaction can then take place to
form the a-Al. In addition, Marcantonio and Mondolfo
[15] suggested that boron additions could change the phase
diagram considerably, so that Al3Ti could be stable even at
lower concentration. However, a number of researchers
(e.g., Refs. [7,16]) investigated the Al-rich corner of the
AlTiB phase diagram and showed that boron had virtually no eect on the AlTi phase diagram. Therefore, the
nucleation process cannot be explained purely based on
theories which attempt to modify the conditions for the
peritectic reaction to occur.
Both TiB2 and Al3Ti have been observed within individual Al grains [6]. It has been generally recognized that both
can act as nucleation sites for Al [17], although Al3Ti is
more potent than TiB2. It is also known that incorporating
a small amount of excess Ti (less than 0.15%) in the melt
can cause a drastic reduction of grain size compared with
the grain rening using solely TiB2 [3]. Subsequently, the
necessity for both TiB2 and the small amount of excess Ti
has led to other theoretical developments.
The hypernucleation theory was proposed by Jones [18],
who suggested that Ti atoms in the melt segregated to the
melt/TiB2 interface and subsequently promoted the formation of a pseudo-crystal with a structure similar to that of
a-Al. This pseudo-crystal would be stable at temperatures
above Al liquidus and could grow at temperatures below
the liquidus, thus requiring little or no nucleation undercooling. Since this theory was proposed, the stability of the
pseudo-crystal above the Al liquidus has become the main
focus of debate because it appears to violate the principles
of thermodynamics. However, the recent high-resolution
transmission electron microscopy (HRTEM) study of
liquid Xe/a-Al [19] and liquid Al/a-Al2O3 [20] interfaces
and molecular dynamics (MD) simulation [21] have shown
that there is considerable atomic ordering at the liquid/
substrate interface, providing both experimental and
theoretical support for the existence of pseudo-crystals at
the liquid/substrate interface.
The duplex nucleation theory was proposed by Mohanty
and Gruzleski [6], who suggested that Ti segregation to the
melt/TiB2 interface can reach such a level that the formation of Al3Ti would be favored, implying that the Ti content in the melt close to the interface would exceed 0.15%
to allow the peritectic reaction to take place. However, this

293

concept was dismissed by Sigworth [22] based on thermodynamic argument. In order to verify the duplex nucleation
theory, Schumacher et al. [23,24] used a melt spinning technique to produce amorphous Al85Y8Ni5Co2 alloy ribbons
containing TiB2 particles. They observed that a thin crystalline phase of 3 nm thickness with a lattice spacing close to
that of Al3Ti phase existed between TiB2 and the amorphous Al. However, it was dicult to precisely identify
the Al3Ti phase. It is possible that the observed 3 nm crystal
layer on the TiB2 surface is a-Al formed in the solid state
since the amorphous Al85Y8Ni5Co2 alloy is highly metastable and crystallization may take place in the solid state.
The solute theory [10,25] suggested that both the nucleating particles and the solute elements in the alloy melt
were important factors aecting grain renement. The eect
of solute elements on heterogeneous nucleation was taken
into account through their eect on growth restriction to
allow more nucleating substrates to be active before
recalescence [26]. Easton and StJohn [26,27] proposed a
semi-empirical model based on the constitutional undercooling theory. Their analysis showed that grain size can be
related closely to the growth restriction factor. In such an
approach, the grain renement due to the increased solute
contents was explained by the increased nucleation events
through delayed recalescence [27,28]. Further development
along this direction has seen a more analytical approach to
the solute eect [29,30] and the postulation of the interdependence theory by StJohn et al. [31]. They proposed that
grain formation was the result of repeated cycles of growth
and nucleation events moving towards the thermal centre
of the casting. However, it is likely that the solute theory
and its extension may have over-estimated the eect of solute on grain renement. Recently, Du and Li [32] extended
the KampmannWagner numerical model [33] for solid
state precipitation to predict grain size in solidied multicomponent alloys. Their simulation results showed that
the solute suppressed nucleation (SSN) eect has a negligible inuence on the nucleation behavior and the nal grain
size during isothermal melt solidication.
One of the major challenges in nucleation research is the
experimental diculties in examining the nucleation process
in situ since nucleation occurs in a non-opaque medium at
high temperature and in an extremely short time scale.
Consequently, nucleation research is usually conducted by
postmortem examination of the solidied materials combined with some speculations. Alternatively, modeling techniques have been employed for investigating heterogeneous
nucleation at the atomic level, such as the density functional
theory (DFT) and the MD simulations. DFT calculations
suggested that an Al3Ti-like thin layer could be thermodynamically stable on the TiB2 surface prior to Al solidication [34], but the ab initio MD simulations failed to show
the existence of such a layer of Al3Ti on the top of TiB2 surface [35], which may have been due to the time limitation of
ab initio MD. However, the more recent MD simulation by
Qin and Fan [36] has conrmed that an atomic monolayer
of (1 1 2) Al3Ti could be stable at the liquid Al/TiB2 interface
at temperatures above the melting point of Al.
A particularly important aspect of grain renement is
the crystallographic matching across the solid/substrate
interface at the moment of heterogeneous nucleation.
Relevant to this is epitaxial growth of a thin layer of one
material on the surface of another material (the substrate)
[37]. The scientic basis for epitaxial growth of strained
layers on a substrate originates from the theory of Frank

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Z. Fan et al. / Acta Materialia 84 (2015) 292304

and Van der Merwe [38]. Interestingly, Frank and Van der
Merwes theory was applied to study heterogeneous nucleation of a solid on a crystalline substrate during solidication of a metallic melt by Turnbull and Vonnegut [39] as
early as 1952. They based their analysis on classical heterogeneous nucleation theory [40], which we now know breaks
down for systems with a small contact angle [41], such as
systems where grain renement is relevant. Nevertheless,
their analysis suggested that nucleation undercooling
increased sharply with increasing lattice mist between
the solid and the substrate. Further realization of the
importance of lattice matching at the solid/substrate interface in more recent years has led to the development of the
edge-to-edge matching approach for the identication of
new substrates for grain renement [42,43] and the development of a more general epitaxial nucleation model [44].
In this paper we present our experimental evidence for
the existence of an atomic monolayer of (1 1 2) Al3Ti twodimensional compound (2DC) on the (0 0 0 1) TiB2 surface
of commercial AlTiB-based grain reners. We will demonstrate experimentally that the Al3Ti 2DC forms at the
liquid Al/TiB2 interface in concentrated AlTi solutions,
but dissolves in dilute AlTi solutions, although the kinetics
of both formation and dissolution of Al3Ti 2DC are relatively sluggish. The eective grain renement of Al5Ti
1B grain rener can be attributed to the enhanced potency
of TiB2 particles with the Al3Ti 2DC monolayer in place
and adequate free Ti solute in the melt after grain rener
addition to achieve the columnar-to-equiaxed transition.
2. Experimental
2.1. Materials
Commercial-purity aluminum (hereafter referred to as
CPAl) is commonly used as a standard material for
assessing the eectiveness of grain reners [2,45]. In this
work CPAl (>99.86% Al) was used as the base material
for all experiments. Commercial Al5Ti1B (equivalent
to Al2.8Ti3.2TiB2) grain rener, supplied by LSM
(Rotherham, UK), was used as the reference grain rener
for assessing the eectiveness of other grain reners.
According to Quested and Greer [46], commercial
Al5Ti1B grain rener contains TiB2 particles with a size
range of 0.56 lm, an average size of 0.72 lm and a particle number density of 7.3  1012 m3 with 0.1% addition. A stoichiometric grain rener, Al2.2Ti1B
(equivalent to Al3.2 TiB2), supplied by LSM, was also
used in this work, which provided the same TiB2 particle
number density as the commercial Al5Ti1B grain rener
but with no excess Ti. In addition, an Al10Ti master
alloy, supplied by LSM, was used to vary the Ti concentration and to prepare new grain reners based on synthetic TiB2 particles (unlike TiB2 particles formed in situ
during grain rener production). The synthetic TiB2

particles (>99% purity) used in this work had a particle

size range of 110 lm and an average particle size of
3.1 lm. The detailed chemical compositions of the
materials used are listed in Table 1.
2.2. Intensive melt shearing
Intensive melt shearing was achieved by a rotorstator
high-shear device [47], which provides both dispersive
mixing at the gap between the rotor and the stator and
distributive mixing of the dispersed particles in the melt.
The rotation speed between 5000 and 15,000 rpm provides
a local shear rate as high as 105 s1. The key functions of
the high-shear device include eective forced wetting of
solid particles by the melt, enhanced kinetic conditions
for any chemical reaction involving the liquid phase, eective dispersion of particle agglomerates and the uniform
distribution of the dispersed solid particles in the melt. In
this work, intensive melt shearing was used to wet, disperse
and distribute synthetic TiB2 particles in CPAl, and to
enhance the kinetic condition for the interaction between solute
Ti and TiB2 particles. For the intensive melt shearing in this
work, the high-shear device was immersed in the melt and
operated at 8000 rpm for a pre-determined period of time.
2.3. Preparation of AlTiB grain reners from synthetic
TiB2particles
To investigate the eect of processing conditions on the
eectiveness of AlTiB grain reners, two non-standard
AlTiB grain reners were prepared under laboratory
conditions using synthetic TiB2 particles and Al10Ti
master alloy. These were Al5.5Ti2.5B (equivalent to
stoichiometric Al8TiB2) and Al1Ti0.2B (equivalent to
Al0.56Ti0.64TiB2).
To prepare the stoichiometric Al5.5Ti2.5B grain rener, the high-shear device was used to wet, disperse and distribute the synthetic TiB2 particles in the CPAl melt.
Synthetic TiB2 particles were preheated to 300 C and
sieved to eliminate large particle agglomerates, and then
wrapped in pure Al foil before being fed into the melt
underneath the high-shear device. Intensive shearing was
conducted at 750 C and 8000 rpm for 15 min after the
addition of synthetic TiB2 particles. The prepared
Al8TiB2 melt was then cast into 10 mm diameter grain
rener rods.
The non-standard Al1Ti0.2B grain rener was prepared in two sequential steps. In the rst step, the
Al0.636TiB2 melt was prepared following the procedure
for the stoichiometric Al5.5Ti2.5B (Al8TiB2) grain
rener. The prepared Al0.636TiB2 melt was then heated
to 850 C, and the Al10Ti master alloy was added into the
melt to provide the required level of free Ti. The Al1Ti
0.2B melt was then isothermally held at 850 C for 1 h
followed by intensive melt shearing for a pre-determined

Table 1. Compositions (wt.%) of the materials used in this work.

Alloy

Ti

Fe

Si

Zn

Ni

Cu

Cr

Al

Supplier

CPAl
Al-10Ti
Al-2.2Ti-1B
Al-5Ti-1B

0.006
9.90
2.26
4.80

0.96
0.85

0.08
0.10
0.12
0.09

0.03
0.02
0.11
0.08

0.09
0.04

0.003

0.005

0.001

0.001

Bal.
Bal.
Bal.
Bal.

Norton
LSM
LSM
LSM

Z. Fan et al. / Acta Materialia 84 (2015) 292304

period of time before being cast into 10 mm diameter grain

rener rods.

295

3. Results
3.1. Reference microstructures for grain renement

2.4. TP-1 test and grain size assessment

In order to assess the eectiveness of dierent grain
reners, a standard TP-1 test [48] was used to provide consistent solidication conditions. All the TP-1 tests were
operated in conditions to provide a consistent cooling rate
of 3.5 Ks1 at the central region of a cross-section 38 mm
from the bottom of the TP-1 sample. For all TP-1 tests,
the melt with and without grain rener addition was always
poured at 720 5 C into the TP-1 mould pre-heated to
350 C, which was then placed onto the water spray with
a controlled water ow rate of 3.8 lmin1. The addition
of commercial Al5Ti1B grain rener was made at 0.2%,
and followed by isothermal holding for 20 min at 720 C
with occasional stirring with a ceramic rod to prevent
particle settling. For other grain reners, the addition level
was chosen so that the number density of TiB2 particles was
kept consistent at a level equivalent to that of 0.2% commercial Al5Ti1B addition (1013m3).
The specimens for grain structure examination were
sectioned from a cross-section 38 mm from the base of
the TP-1 sample, providing a cross-section of 43.3 mm
diameter. The specimens for grain size assessment were
taken from the centre region of the cross-section and prepared using a standard metallographic technique. Electropolishing was performed prior to anodizing with Barkers
reagent (4% HBF4 in distilled water) to show the grain
boundaries. All the samples were examined under polarized
light, using a Zeiss optical microscope tted with the Axio
Vision 4.3 image analysis system. The mean linear intercept
technique was used to quantify grain size with at least 500
grains. In addition, both the cross-section (38 mm from the
base) and the vertical section of the lower part of the TP-1
sample (38 mm in height) were polished, etched and photographed to review the grain structure of the TP-1 sample.
2.5. HRTEM and high-resolution scanning transmission
electron microscopy (HRSTEM)
A pressurized melt ltration technique [49] was used to
collect the TiB2 particles in aluminum melt for examination
by high-resolution TEM and STEM. The solidied
material immediately above the lter, which contained the
locally concentrated TiB2 particles, was sectioned and
prepared for metallographic examinations.
To prepare thin foils for conventional HRTEM, and
HRSTEM examinations, slices from the ltered residue
material above the lter were mechanically ground and
cut into 3 mm diameter discs. The discs were then hand
ground to a thickness of less than 70 lm and dimpled,
and then ion-beam-thinned using a Gatan precision ion
polishing system under conditions of 1.55.0 kV and an
incident angle of 36. Conventional TEM and HRTEM
analyses were conducted using a Tecnai FEG F30 microscope operated at an accelerating voltage of 300 kV.
HRSTEM with high-angle annular dark eld (HAADF)
imaging (Z-contrast) and atomic resolution electron energy
loss spectroscopy (EELS) mapping across the TiB2/Al
interface were carried out using an aberration corrected
Nion UltraSTEM 100 instrument (second generation)
operated at an accelerating voltage of 100 kV.

For assessing the eectiveness of dierent grain reners,

CPAl has been frequently used as a reference material
[2,45]. However, it is also well appreciated that variation
in impurity level in CPAl and in solidication conditions
during the TP-1 test will lead to changes in grain structure
in the TP-1 sample. Therefore, it is necessary to establish
reference microstructures using the same base materials
and the same solidication conditions for all the TP-1 tests
in this work. Fig. 1a and b presents the grain structure of
CPAl solidied in the TP-1 mould. It shows a completely
coarse columnar grain structure. The solidication of CPAl
began by heterogeneous nucleation in the melt near the wall
of the TP-1 mould followed by columnar growth without
any signicant further heterogeneous nucleation. This
coarse columnar grain structure will be taken as the reference for a non-grain-rened structure in this work.
Another reference in this work is the fully grain-rened
microstructure. Fig. 1c and 1d shows the grain structure of
CPAl with the addition of 0.2% commercial Al5Ti1B
grain rener. Both the cross-section and the vertical section
show a ne and equiaxed grain structure. The detailed
microstructural analysis conrmed that the average grain
size is 175 lm, suggesting that TiB2 particles in the
Al5Ti1B grain rener are very eective for grain
renement. This ne and equiaxed microstructure (Fig. 1c
and d) was taken as the reference for fully grain-rened
microstructures.
It should be pointed out that it is not adequate to assess
the grain structure only using the cross-section of the TP-1
sample as described in the standard of the TP-1 test [48].
For example, Fig. 1a shows columnar grains at the edge
and equiaxed grains at the central region of the sample,
suggesting that a columnar-to-equiaxed transition occurred
at some stage of the solidication process. This is misleading, since the vertical section of the same sample in Fig. 1b
shows a fully columnar grain structure. The equiaxed grain
morphology in Fig. 1a is a result of sectioning of the
columnar grains at the centre of the TP-1 sample. For this
reason, vertical sections were used for assessing grain structures and cross-sections were only used for assessing the
grain size of fully equiaxed microstructures, i.e., fully
grain-rened structures.
3.2. Grain rening with TiB2 particles and free Ti
A number of investigations in the literature (e.g. [6]) suggested that TiB2 particles are not eective substrates for
heterogeneous nucleation of the a-Al. However, a fully
columnar grain structure is not conclusive evidence of the
ineectiveness of TiB2 particles since, for eective grain
renement, the solid particles not only need to have a good
lattice matching [44], but also need to be completely wetted,
well dispersed and uniformly distributed in the liquid
phase, and need to have sucient particle number density
[44,50]. In this work, intensive melt shearing was used to
ensure complete wetting, eective dispersion and uniform
distribution of the synthetic TiB2 particles during the preparation of Al8TiB2 grain rener without any free Ti.
Fig. 2a shows the grain structure of the CPAl TP-1 sample
with the addition of Al8TiB2 grain rener to provide TiB2

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Z. Fan et al. / Acta Materialia 84 (2015) 292304

Fig. 1. Macrographs showing the grain structures of commercial purity aluminum (CPAl) solidied in the TP-1 mould. (a, b) are for CPAl without
grain rener addition, and (c, d) are for CPAl with addition of 0.2% commercial Al-5Ti-1B grain rener. (a, c) are cross-sections, and (b, d) are
vertical sections. Without grain rener addition, CPAl has a coarse and fully columnar grain structure (a, b), which will be taken as a reference for the
non-grain-rened structure; with 0.2% addition of commercial Al-5Ti-1B grain rener, CPAl has a ne and fully equiaxed grain structure (c, d),
which will be taken as a reference for the fully grain-rened structure.

particles with a number density equivalent to that of 0.2%

addition of commercial Al5Ti1B grain rener. This TP1 sample exhibits a fully columnar grain structure, although
the width of the columnar grains is ner (Fig. 2a) than that
of the TP-1 sample without addition of any grain rener
(Fig. 1b). A similar result was obtained by the addition of
0.2% stoichiometric Al3.2TiB2 grain rener, which contains TiB2 particles formed by in situ chemical reaction
but without any excess Ti, (Fig. 2b) and by simultaneous
addition of Al8TiB2 grain rener and Al10Ti master
alloy to provide the equivalent TiB2 particle number density (1013m3) and free Ti (56 ppm) to that of the addition
of 0.2% commercial Al5Ti1B grain rener (see Fig. 2c).
These results conrmed that TiB2 particles are not eective
for nucleating a-Al, even with the simultaneous addition of
free Ti.
3.3. Identication of Ti atoms adsorbed at the (0 0 0 1) TiB2
surface
To understand the grain rening mechanism of Al5Ti
1B grain rener, we focused our eort on the investigation
of the Al/TiB2 interfaces in the commercial Al5Ti1B
grain rener. Fig. 3a is a SEM secondary electron image
showing the morphology of the TiB2 particles in a deep
etched sample of commercial Al5Ti1B grain rener.
The boride particles present a typical hexagonal plate-like
shape with the average size being 0.21.5 lm. The TEM
bright eld image in Fig. 3b, with the incident electron
beam being perpendicular to the [0 0 0 1] direction of TiB2,

shows two such TiB2 particles. The TiB2 particles are facetted with their {0 0 0 1} basal and {1 1 0 0} prism planes displayed. Heterogeneous nucleation of Al is believed to occur
on the {0 0 0 1} surfaces of the boride particles [23].
The TEM observation of the interface between the TiB2
particle and Al was focused on the surface of the faceted
{0 0 0 1} planes of multiple boride particles. An example
of such observation using high-resolution lattice imaging
is given in Fig. 4a, where the incident electron beam is parallel to the [1 1 2 0] zone direction of TiB2 (bottom part)
and the [0 1 1] zone direction of the adjacent Al grain
(upper part). This gives the following well-dened orientation relationship (OR) between the two crystals:
000111-20TiB2 ; == 1110-11Al:
This observation of the much expected OR in a solidied
AlTiB2 sample provides for the rst time evidence to verify that the TiB2 particle does nucleate a-Al. The above OR
was also conrmed by the selected area electron diraction
(SAED) pattern, as shown in Fig. 4b that is indexed in
Fig. 4c.
TEM observation showed that the majority of the TiB2
particles were not in the above OR, indicating that the
majority of the boride particles from the commercial
AlTiB grain rener did not contribute to the nucleation
process during the solidication. This is consistent with
the conclusion derived from the free growth model that
only 0.11% of the added TiB2 particles are active for heterogeneous nucleation [50]. However, careful investigations
by HRTEM at high magnications on multiple TiB2

Z. Fan et al. / Acta Materialia 84 (2015) 292304

297

(a)

500nm
(b)

Fig. 3. (a) Scanning electron micrograph showing the hexagonal

morphology of the TiB2 particles in a deep etched sample of
commercial Al-5Ti-1B grain rener; and (b) transmission electron
microscopy image showing the morphology of the TiB2 particles with
their typically faceted (0 0 0 1) crystal planes.
Fig. 2. Macrographs showing the fully columnar grain structure of
CPAl inoculated with the TiB2 particles and solidied in the TP-1
mould. For all the cases, the number density of TiB2 particles is
equivalent to that of 0.2% addition of commercial Al-5Ti-1B grain
rener. (a) with synthetic TiB2 particles (via Al-8TiB2 grain rener); (b)
with addition of 0.2% stoichiometric Al-2.2Ti-1B master alloy (without
free Ti); and (c) with simultaneous addition of synthetic TiB2 particles
(via Al-8TiB2 grain rener) and free Ti (56 ppm). These results suggest
that synthetic TiB2 particles have no grain rening power even with the
simultaneous addition of free Ti.

particles showed that there was apparently a monolayer on

the {0 0 0 1} surface of all of the observed boride particles.
Fig. 5a gives an example of such a phenomenon, where
the incident electron beam is parallel to the [1 1 2 0] TiB2
zone direction, but is o from any low index zone axis of
the adjacent Al grain. It is seen that an atomic monolayer
is uniformly located on the TiB2 surface, with the
position of every atom column in the monolayer shifted
in the [1 1 0 0] TiB2 direction for a distance of a certain
fraction of the (1 1 0 0) d-spacing (0.26 nm).
To understand the chemical nature of this atomic
monolayer at the Al/TiB2 interface, atomic resolution
superSTEM was carried out. Fig. 5b is a STEM HAADF
Z-contrast image showing the detail of the Al/TiB2 interface, with the incident electron beam being parallel to

[1 1 2 0] TiB2 but o from any low-index zone axis of Al.

It shows clearly the atomic monolayer in which the atom
columns have a brightness comparable to that of the Ti
atom columns in TiB2, suggesting that the atomic columns
in the monolayer are likely to be Ti-rich. It is also noted
that the spacing between the atomic monolayer and the
Ti (0 0 0 1) plane of TiB2 is 0.25 nm, being shorter than
the (0 0 0 1) TiB2 spacing (0.32 nm), as indicated in
Fig. 5b. This suggests that the monolayer is dierent from
the Ti-terminated TiB2 surface.
Atomic resolution EELS mapping in superSTEM was
performed in order to characterize the chemical nature of
this atomic monolayer. EELS mapping was carried out
on a small area (4  6 d-spacing2 as marked by the green
box in Fig. 6a) across the Al/TiB2 interface. The local
HAADF Z-contrast image, Ti K-edge map (green) and
superimposition of the local HAADF image and Ti K-edge
map are shown in Fig. 6bd, respectively. The atom columns with blue circles were identied as Ti-rich columns,
whilst those with red circles were Ti columns of TiB2.
The EELS mapping conrms that the atomic monolayer
contains Ti atoms.
As suggested by our previous MD simulation [36], a
monolayer of Al3Ti 2DC can be stable at the liquid
Al/TiB2 interface. Therefore, it is likely that Al3Ti 2DC

298

Z. Fan et al. / Acta Materialia 84 (2015) 292304

(a)

Al
[0-11])

(a)

Al

(111)

(0001)

(0001)

TiB2

[11-20])

2 nm

(b)

111Al
0001TiB2

(c)

200Al

TiB2
[11-20]

1 nm

(b)

Al

-1100TiB2
0.25nm

Al

TiB2

Fig. 4. (a) High resolution TEM image showing the Al/TiB2interface

when the incident electron beam is parallel to both [1 1 2 0] of TiB2
and [0 1 1] of Al; (b) selected area electron diraction (SAED) pattern
taken from a TiB2 particle and the adjacent Al matrix; and (c) the
indexed pattern corresponding to (b). These results suggest the
following well-dened orientation relationship (OR) between TiB2
and the a-Al: (0 0 0 1)[1 1 2 0] TiB2//(1 1 1)[0 1 1]Al.

exists at the solid Al/TiB2 interface. Fig. 7 shows schematically the atomic arrangement in the (1 1 2) plane of
Al3Ti with the [2 0 1] and [2 4 1] directions being
marked. It is shown that the [2 0 1] columns in the
(1 1 2) Al3Ti contain 25 at.% Ti, which is in qualitative
agreement with the Ti-rich conclusion from Fig. 6, where
the brightness of the [2 0 1] columns is uniform and less
bright than that of the Ti columns on the TiB2 surface.
In addition, the spacing of the [2 0 1] columns in the
(1 1 2) Al3Ti (0.25 nm measured from Figs. 5b and 6a)
is also in good agreement with the atomic spacing along
the [2 4 1] direction in the bulk Al3Ti. Based on the
above analysis, it can be concluded that the observed
atomic monolayer at the Al/TiB2 interface is most likely
to be the (1 1 2) Al3Ti 2DC, with the following ORs
between TiB2, Al3Ti 2DC and a-Al:
000111-20TiB2 == 112-201Al3 Ti 2DC == 1110-11Al:

In the following section, we will assume the observed Tirich monolayer at the Al/TiB2 interface is (1 1 2) Al3Ti 2DC
and examine experimentally its stability under dierent
conditions.
3.4. Formation of Al3Ti 2DC on TiB2 particles
The bulk Al3Ti phase (three-dimensional) is only stable
in liquid Al at Ti concentrations greater than 0.15% [3].
However, at lower Ti concentrations (<0.15%), Al3Ti

(0001)

TiB

[11-20]

0.32nm

1 nm

Fig. 5. (a) High resolution TEM image and (b) high angle annular
dark eld (HAADF) STEM image (Z-contrast), showing the existence
of an atomic monolayer on the (0 0 0 1) TiB2 surface. For both cases,
the incident electron beam is parallel to [1 1 2 0] of TiB2, but away
from any low index zone axis of the a-Al. It is noted that (1) from (a)
the atomic positions in the atomic monolayer deviated from that of the
Ti-terminated TiB2 surface; and (2) from (b) the atomic columns of the
monolayer are bright in the Z-contrast image, indicating that the
monolayer might be Ti-rich.

2DC may be stable at the liquid/substrate interface driven

by reduction of interfacial energy [51]. It is understood that
Al3Ti 2DC on TiB2 particles could be formed by adsorption of solute Ti atoms from the melt to the (0 0 0 1) TiB2
surface. Adsorption of Ti at the liquid/substrate interface
is thermodynamically favorable since this reduces interfacial energy. However, it may take a long time for Ti to
reach saturation at the interface if the Ti concentration in
the melt is low. To check the formation of the Al3Ti 2DC
on TiB2 particles during the grain rener addition process,
the Al8TiB2 grain rener and Al10Ti master alloy were
added simultaneously to CPAl at 720 C to achieve a
1013m3 TiB2 number density and 56 ppm excess Ti, which
are equivalent to those associated with the addition of 0.2%
commercial Al5Ti1B grain rener. The resultant TP-1
sample had a fully columnar grain structure (Fig. 2c) similar to that of the TP-1 sample without free Ti (Fig. 2a). This
suggests that no Al3Ti 2DC was formed on the TiB2
particles during isothermal holding at 720 C for 20 min,

Z. Fan et al. / Acta Materialia 84 (2015) 292304

(a)

Al

TiB2
[11-20]

(b)

1 nm

(c)

(d)

299

To check the formation of Al3Ti 2DC on the TiB2 particles at a higher concentration of Ti, a special grain rener,
Al1Ti0.2B, was prepared at 850 C using synthetic TiB2
particles and Al10Ti master alloy under intensive melt
shearing but with dierent shearing times. Intensive melt
shearing was used to enhance mass transport in the melt,
and therefore to accelerate the adsorption of solute Ti at
the liquid Al/TiB2 interface. The obtained Al1Ti0.2B
grain rener was used to grain-rene CPAl at an addition
level equivalent to 0.2% commercialAl5Ti1B grain
rener. The resultant grain structures of the TP-1 samples
are compared in Fig. 8 for addition of grain reners prepared by intensive melt shearing for 2 and 10 min. The
TP-1 sample grain-rened with the grain rener with
2 min shearing exhibited a fully columnar grain structure,
while that with 10 min shearing showed a ne and nearly
equiaxed grain structure. This demonstrates that intensive
melt shearing accelerates the formation of Al3Ti 2DC at
higher Ti concentration in the AlTi liquid. These results
conrm that Al3Ti 2DC is thermodynamically stable at
850 C in concentrated AlTi solution (Al0.56Ti in this
case).
3.5. Dissolution of the Al3Ti 2DC adsorbed on the TiB2
particles

Ti containing column

Ti

It is important to point out that an enhanced kinetic

condition can only shorten the time for the formation of
an equilibrium phase; it should not aect the stability of
a phase. It is expected that the Al3Ti 2DC is only stable
when the Ti concentration is beyond a critical level. This
means that Al3Ti 2DC formed on TiB2 particles at high

Fig. 6. (a) SuperSTEM Z-contrast HAADF image; (b) local Zcontrast HAADF across the Al/TiB2 interface; (c) atomic resolution
EELS map of Ti K-edge (green); and (d) superimposition of the local
Z-contrast image and Ti K-edge map. The atom columns with blue
circles are Ti-rich columns, and those with red circles are Ti columns.
The EELS mapping conrms that the atomic monolayer contains Ti
atoms. (For interpretation of the references to colour in this gure
legend, the reader is referred to the web version of this article.)

Fig. 7. Schematic diagram showing the atomic arrangement of Al

(lime) and Ti (blue) atoms in the (1 1 2) plane of the bulk Al3Ti
intermetallic compound. Also marked here are the [2 0 1] and
[2 4 1] directions of Al3Ti.

possibly due to the low concentration of Ti in the melt

and/or the short duration for the interaction between
TiB2 particles and the solute Ti atoms.

Fig. 8. Macrographs showing the grain structure of CPAl with

addition of the lab-prepared Al-1Ti-0.2B grain rener from synthetic
TiB2 particles (via the Al-8TiB2 grain rener) and free Ti (via the Al10Ti master alloy) to provide the TiB2 particle number density
(1013m3) and free Ti (56 ppm) equivalent to that of addition of 0.2%
commercial Al-5Ti-1B grain rener. The Al-1Ti-0.2B grain rener was
prepared by intensive melt shearing at 850 C during the preparation
for (a) 2 min and (b) 10 min respectively.

Z. Fan et al. / Acta Materialia 84 (2015) 292304

Ti concentration should dissolve in dilute AlTi solutions.

To conrm this, isothermal holding experiments were carried out. 0.2% addition of commercial Al5Ti1B grain
rener was made to CPAl at 800 C for a predetermined
period of time, and stirred using a ceramic rod before casting into a TP-1 mould at 720 C for grain size assessment.
Fig. 9 compares the grain structures of 2 TP-1 samples; one
was cast after isothermal holding for 1 h (Fig. 9a) and the
other one was cast after isothermal holding for 78 h
(Fig. 9b). Isothermal holding for 1 h had little eect on
the Al3Ti 2DC formed on TiB2 particles, and the TP-1 sample showed a ne and fully columnar grain structure, indicating that some solute Ti may have been lost during
isothermal holding. However, isothermal holding for 78 h
removed some of the Al3Ti 2DC formed on TiB2 particles,
resulting in the formation of a much coarser columnar
grain structure. The isothermal holding experiments
(Fig. 10) show that the Al3Ti 2DC formed on TiB2 particles
survives isothermal holding for 48 h at 800 C, but was not
stable in dilute AlTi solution and will dissolve after
suciently long isothermal holding at high temperature.
However, it should be noted that the dissolution of Al3Ti
2DC is a very slow process, and that a few hours isothermal holding in Al with a ppm level of Ti has no eect on the
potency of TiB2 particles covered with Al3Ti 2DC.
In order to further conrm the above nding, extensive
melt shearing was employed to accelerate the dissolution of
the Al3Ti 2DC formed on TiB2 particles in a dilute AlTi
solution. CPAl melt with 0.2% addition of commercial
Al5Ti1B grain rener was intensively sheared at
720 C for 45 min before pouring into the TP-1 mould for
solidication.

240

Grain size, m

300

210

180

150

120
1.0

1.5

2.0

2.5

3.0

3.5

4.0

log(t), min
Fig. 10. Average grain size of CPAl with addition of 0.2% commercial
Al-5Ti-1B grain rener as a function of holding time at 800 C before
being stirred and poured into the TP-1 mould for solidication.

Fig. 11. Grain structure of CPAl with addition of 0.2% commercial

Al-5Ti-1B grain rener, showing the eect of intensive melt shearing
on the eectiveness of commercial Al-5Ti-1B grain rener. The melt
with the grain rener addition was intensively sheared at 720 C for
45 min before pouring into the TP-1 mould for solidication. It is seen
that the commercial grain rener was no longer eective for grain
renement.

The grain structure of the resultant TP-1 sample is

shown in Fig. 11. A simple comparison between Figs. 1b
and 11 reveals that intensive melt shearing for 45 min has
made the commercial Al5Ti1B grain rener ineective
for grain renement. This suggests that the Al3Ti 2DC
formed on TiB2 particles is completely stripped by 45 min
of intensive melt shearing. It is interesting to note that on
the one hand intensive melt shearing accelerates the formation of Al3Ti 2DC on the TiB2 particles in the concentrated
AlTi solution while, on the other hand, it accelerates the
de-adsorption of Al3Ti 2DC on the TiB2 particles in dilute
AlTi solutions.
3.6. Eect of free Ti in relation to Al3Ti 2DC adsorbed on
TiB2 particles

Fig. 9. Grain structures of CPAl with addition of 0.2% commercial Al5Ti-1B grain rener solidied in the TP-1 mould, showing the eect of
isothermal holding time at 800 C on the eectiveness of the commercial Al-5Ti-1B grain rener. The melt with the grain rener addition
was held at 800 C for (a) 1 h and (b) 78 h respectively, before being
stirred and poured into the TP-1 mould for solidication.

It is generally believed that eective grain renement

requires both potent particles as substrates for heterogeneous nucleation and solute elements for eective growth
restriction, which allows for larger undercooling to be
achieved so that more particles have a chance to participate
in nucleation at the solidication front [27,28,31] causing a
columnar-to-equiaxed transition [52]. However, in the case

Z. Fan et al. / Acta Materialia 84 (2015) 292304

Fig. 12. Grain structure of CPAl with addition of TiB2 particles

collected from the commercial Al-5Ti-1B grain rener with very little
free Ti, showing that TiB2 particles with Al3Ti 2DC are eective for
grain renement.

of addition of Al5Ti1B grain rener, the contribution

from the solute Ti to eective grain renement may also
come from the adsorbed Al3Ti 2DC on TiB2 particles, for
which only a small amount of excess Ti is required. This
prompted us to carry out the following experiments to
assess the grain rening eciency of TiB2 particles with
adsorbed Al3Ti 2DC without further free Ti.
5% commercial Al5Ti1B grain rener was added to
CPAl at 720 C to form a 5 kg melt. The melt containing
grain rener was isothermally held for 2 h to allow the settlement of TiB2 particles before furnace cooling in the same
crucible without stirring. The bottom part of the solidied
piece (1 kg) containing the settled TiB2 particles was added
to the fresh CPAl melt to form another 5 kg melt, and the
settling and solidifying experiments was repeated several
times to achieve a grain rener containing only TiB2 particles covered with Al3Ti 2DC but with nominally zero free
Ti. Such a grain rener was then used to grain-rene CPAl
with appropriate addition level to provide a TiB2 particle
number density equivalent to 0.2% addition of commercial
Al5Ti1B grain rener. The resultant TP-1 sample showed
a very ne but columnar grain structure with an average
columnar width of 196 lm (Fig. 12). This result demonstrated that the extracted TiB2 particles with Al3Ti 2DC
can be very potent nucleating substrates, resulting in the
ne columnar grain structure. However, without adequate
solute in the melt a columnar-to-equiaxed transition cannot
occur, leading to a non-grain-rened microstructure.

4. Discussion
4.1. The existence of Al3Ti 2DC adsorbed on the TiB2
particles
In our previous work [36], MD simulation has conrmed that Al3Ti 2DC can exist at the liquid Al/TiB2 interface at temperatures above the Al liquidus. The MD
simulation also revealed that Al3Ti 2DC contains a triangular network of dislocations to accommodate the relatively
large lattice mist between Al3Ti and TiB2, and that formation of Al3Ti 2DC lowers the liquid Al/TiB2 interfacial
energy compared to that without Al3Ti 2DC [36]. In this
paper, we used an experimental approach to conrm the
existence of Al3Ti 2DC.
Our experimental conrmation of the existence of the
Al3Ti 2DC comes from both direct TEM observations

301

and indirect conrmations from the switch-on and

switch-o experiments with the assistance of intensive
melt shearing [47]. HRTEM and HRSTEM observations
have allowed us for the rst time to identify a Ti-rich
atomic monolayer at the Al/TiB2 interface in the
commercial Al5Ti1B grain rener (Figs. 5 and 6). With
the structural analysis (Fig. 7) and the previous MD simulations [36], this atomic monolayer is consistent with (1 1 2)
Al3Ti 2DC, which is most likely formed during the grain
rener production process (characterized by a high concentration of Ti, high temperature and long reaction time).
Our experimental results have also conrmed that TiB2
particles without Al3Ti 2DC are not potent substrates for
heterogeneous nucleation (Fig. 2), and that the nucleation
potency of TiB2 particles can be signicantly improved by
the formation of the Al3Ti 2DC on the TiB2 surface
(Fig. 8). In addition, we have demonstrated experimentally
that Al3Ti 2DC can be made to form on synthetic TiB2
particles in a concentrated AlTi melt by intensive melt
shearing (switch-on, Fig. 8b) and can be either dissolved
in dilute AlTi solutions by prolonged isothermal holding
(switch-o, Figs. 9b and 10) or stripped from the TiB2
particles in dilute AlTi solutions by intensive melt shearing
(switch-o, Fig. 11).These results have conrmed that the
formation of Al3Ti 2DC on the TiB2 surface is crucial for
the eectiveness of AlTiB-based grain reners.
4.2. Formation of Al3Ti 2DC adsorbed on TiB2 surface
Thermodynamically, bulk Al3Ti (three-dimensional) can
only be stable in AlTi alloys with Ti contents greater than
0.15% [3]. However, Al3Ti 2DC is a monolayer formed on
the (0 0 0 1) TiB2 surface through adsorption of Ti atoms
from the AlTi solution. The thermodynamic stability of
Al3Ti 2DC may not follow the AlTi phase diagram; compared with bulk Al3Ti, Al3Ti 2DC may be stable at a lower
concentration of Ti or even at temperatures above the alloy
liquidus. The driving force for the formation of Al3Ti 2DC
is the reduction of interfacial energy at the liquid Al/TiB2
interface. This means that the formation of Al3Ti 2DC does
not violate the second law of thermodynamics if the interfacial energy is taken into consideration for thermodynamic
equilibrium.
The Al3Ti 2DC adsorbed on the (0 0 0 1) TiB2 surface
can only be stable in AlTi solutions with a Ti concentration greater than a critical concentration. This is supported
by the following experimental observations: (i) Al3Ti 2DC
dissolves in dilute AlTi solution (56 ppm Ti) during
isothermal holding (Figs. 9 and 10); (ii) Al3Ti 2DC can
be stripped in dilute AlTi solution by intensive melt
shearing (Fig. 11); (iii) Al3Ti 2DC can form in concentrated
AlTi alloys (e.g., Al0.56Ti in Fig. 8).
However, the kinetics for both formation and dissolution of Al3Ti 2DC are extremely slow. It took 78 h to
achieve some noticeable dissolution of Al3Ti 2DC in an
Al0.01Ti dilute solution during isothermal holding at
800 C (Figs. 9 and 10), and 45 min to strip Al3Ti 2DC
from TiB2 particles in an Al0.01Ti dilute solution at
720 C by intensive melt shearing (Fig. 11). It was also
found that the formation of Al3Ti 2DC took 10 min, even
under intensive melt shearing for a signicantly enhanced
kinetic condition for mass transport (Fig. 8b). These results
suggest that Al3Ti 2DC is not easy to form on the TiB2 surface by adsorption of Ti atoms from the concentrated AlTi
solutions although Al3Ti 2DC is thermodynamically

302

Z. Fan et al. / Acta Materialia 84 (2015) 292304

favorable. Additionally, Al3Ti 2DC is not easy to dissolve

in dilute AlTi solution where Al3Ti 2DC is not thermodynamically stable.
From both the thermodynamic and kinetic points of
view, it can be concluded that Al3Ti 2DC cannot be formed
during the grain rening process. This is because a 0.2%
addition of Al5Ti1B grain rener only provides 56 ppm
extra free Ti in the alloy melt, which is normally isothermally held for a short time (20 min in our case). In addition, the fact that Al3Ti 2DC can be stripped from the
TiB2 surface in dilute AlTi solution by intensive melt
shearing suggests that Al3Ti 2DC is not thermodynamically
stable. Therefore, Al3Ti 2DC on TiB2 particles can only
form during the grain rener production process. AlTi
B-based grain reners are usually produced by in situ chemical reaction in a liquid Al bath containing K2TiF6 and
KBF4 salts at temperatures between 700 and 900 C under
electromagnetic stirring [53]. At the end of the process, the
Al melt contains TiB2 particles, Al3Ti solid phase and some
free Ti. In this process the formation Al3Ti 2DC is favored
by a high concentration of free Ti and a good kinetic condition for mass transport provided by electromagnetic
stirring.
4.3. Grain rening mechanism in the Al/AlTiB system
Eective grain renement requires not only potent
nucleating particles, but also adequate solute elements.
Potent nucleating particles ensure copious heterogeneous
nucleation events while the solute elements provide growth
restriction to the nucleated crystals and constitutional undercooling at the solidication front to allow more particles

(a)

(0001) TiB2 surface

to nucleate and to cause eventually columnar-to-equiaxed

transition. Solidication with only potent particles and
without adequate solute elements produces a fully columnar grain structure with a ne columnar spacing, such as
the one shown in Fig. 12. Conversely, solidication with
a high concentration of solute, but without adequate potent
nucleating particles, will result in a coarse equiaxed grain
structure.
Potency of a nucleating system with given solid particles
and alloy composition can be measured by the lattice mist
between the nucleating substrate and the nucleated solid at
the moment of nucleation, and is therefore a physical property of the nucleating system and is independent of the
solidication conditions [44]. The calculated lattice mist
between TiB2 and the a-Al is 4.22% at 660 C. With the
formation of Al3Ti 2DC at the liquid Al/TiB2 interface,
the lattice mist is reduced to 0.09% by assuming that the
Al3Ti 2DC is a perfect (1 1 2) plane of the bulk Al3Ti. This
means that the adsorbed Al3Ti 2DC on the TiB2 surface
can signicantly alter the potency of TiB2 particles. It
changes the moderately potent TiB2 particles to extremely
potent TiB2 particles covered with Al3Ti 2DC. Our experimental results suggest that Al3Ti 2DC is so rmly attached
to the TiB2 surface that it can be regarded as an integral
part of TiB2.
Ti has the largest growth restriction factor among all
commonly used alloying elements for Al alloys [29,46]. Ti
is therefore very eective for both generating constitutional
undercooling to allow more TiB2 particles to participate in
nucleation and eventually causing the columnar-to-equiaxed
transition. In addition to the above eects, in this work we
have identied another important eect of Ti on grain

(b)

(112) Al3Ti 2DC

(c)

(111) Al

(d)

Al
B

Ti

Fig. 13. Schematic illustration of the mechanism for heterogeneous nucleation of aluminum on (0 0 0 1) surface of a TiB2 particle which has a (1 1 2)
Al3Ti 2DC monolayer. Arrangements of atoms in (a) Ti-terminated (0001) plane of TiB2 surface; (b) (1 1 2) plane of Al3Ti 2DC; and (c) (1 1 1) plane
of Al. (d) Atomic matching at the TiB2/Al3Ti 2DC/Al interfaces.

Z. Fan et al. / Acta Materialia 84 (2015) 292304

renement, i.e., increasing the potency of TiB2 particles by

the formation of Al3Ti 2DC through adsorption of Ti from
the melt.
In summary, the eective grain renement of Al alloys
by the Al5Ti1B grain rener can be attributed to the following factors:
 formation of Al3Ti 2DC on the surface of TiB2 particles
during the grain rener production process, which signicantly increased the potency of TiB2 for nucleation
of the a-Al, as schematically illustrated in Fig. 13;
 excess Ti in the alloy melt after grain rener addition generates eective growth restriction, which increases the
eectiveness of the grain rener by allowing more TiB2
particles to be active for heterogeneous nucleation, which
in turn promotes the columnar-to-equiaxed transition;
 suitable size, size distribution and adequate number density of TiB2 particles in the Al5Ti1B grain rener can
also be contributing factors to eective grain renement.
Although the AlTiB-based grain reners were developed over 60 years, mainly by trial and error, their
degree of optimization is surprisingly high. It is anticipated that further improvement of grain rening eciency will be very dicult, if at all possible.

5. Conclusions
(1) TiB2 particles can nucleate the a-Al, but they have
only a moderate potency.
(2) The nucleation potency of TiB2 particles can be signicantly improved by the formation of (1 1 2)
Al3Ti 2DC on the (0 0 0 1) TiB2 surface.
(3) Al3Ti 2DC is stable in concentrated AlTi solution,
but is unstable and dissolves in dilute AlTi
solution.
(4) The kinetics of both formation and dissolution of
Al3Ti 2DC in liquid Al is extremely sluggish, and
intensive melt shearing can accelerate both the formation and dissolution kinetics.
(5) Excess Ti aects the eectiveness of AlTiB grain
rener by the formation of Al3Ti 2DC to increase
the potency of TiB2 particles and the provision of
free Ti in the inoculated melt to cause columnarto-equiaxed transition.
(6) Eective grain renement of Al alloys by Al5Ti
1B grain rener can be attributed to the increased
potency of TiB2 particles by the formation of Al3Ti
2DC during grain rener production and adequate
Ti solute in the inoculated melt to cause columnarto-equiaxed transition.

[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]

[34]
[35]
[36]

Acknowledgements
[37]
EPSRC-UK is gratefully acknowledged for supporting the
EPSRC Centre LiME under grant EP/H026177/1 and the LATEST2 Programme Grant.

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