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10.1098/ rsta.2002.1147

Grain re¯nement of alloys by

inoculation of melts
By A. L. G r e e r
Department of Materials Science and Metallurgy, University of Cambridge,
Pembroke Street, Cambridge CB2 3QZ, UK

Published online 28 January 2003

Recent progress in understanding the inoculation of aluminium melts is reviewed.

Transmission electron microscopy of inoculant particles in a metallic glass reveals
details of the mechanism of nucleation of aluminium grains. While such studies de­ ne
some of the conditions under which inoculation is e¬ective or not, they do not permit
a prediction of grain size. Unusually for a nucleation-related phenomenon, quantita-
tive prediction is possible. For potent inoculation such as is practised in aluminium
alloys, grain initiation is limited by inoculant particle size, occurring ­ rst on the
largest particles. Simple thermal models can then describe the dependence of grain
re­ nement on alloy content and processing conditions, and enable consideration of
inoculant design.
Keywords: aluminium alloys; grain re¯nement; ino culation;
metallic glass; nucleation; solidi¯ cation

1. Introduction
Inoculation is the addition of solid particles to a metallic melt to act as nucleant
catalysts for the formation of ­ ne equiaxed, rather than columnar, grains. Grain
re­ nement brings many bene­ ts in the solidi­ cation process itself and in the proper-
ties of the as-cast material. Inoculation is almost universally practised in casting of
aluminium and its alloys (McCartney 1989); this is its widest industrial use. Recent
signi­ cant progress in understanding the inoculation of aluminium may also have
relevance for inoculation of melts or solutions in a wide range of systems.
Heterogeneous nucleation on a solid substrate is normally treated using the spheri-
cal cap geometry in the classical theory (this geometry with contact angle ³ is shown
in ­ gure 3, inset (i)). The nucleation kinetics are very dependent on ³ , and cannot
be predicted reliably, as ³ and the underlying interfacial energies are not accurately
measured or calculated. Furthermore, as discussed by Cantor (2003) and earlier by
O’Reilly & Cantor (1995), the classical theory breaks down for potent nucleation
catalysis (small ³ ), which is exactly the case of interest for melt inoculation. Lastly,
heterogeneous nucleation often involves a variety of particles with ill-de­ ned charac-
teristics. The nucleation stage in solidi­ cation modelling has therefore been treated
with adjustable parameters; this paper reviews recent work making quantitative pre-
dictions from independently determined parameters.
One contribution of 15 to a Discussion Meeting `Nucleation control’.

Phil. Trans. R. Soc. Lond. A (2003) 361, 479{495 °

c 2003 The Royal Society
479
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480 A. L. Greer

2000

(iii)

1500
grain size (µm)

zirconium
1000 addition

(ii)

(iv)
500

(i)
0
1 10 100 1000
holding time (min)
Figure 1. Grain diameter of CP-Al inoculated with 1 part per thousand (ppt) Al{5Ti{1B as
a function of holding time before casting. (i) A standard re¯ner shows little fade with hold-
ing time at 800 ¯C. (ii) A poor re¯ner (held at 760 ¯C) converges on the standard behaviour.
(iii) Poisoning of re¯ner action at 800 ¯C after addition of 0.05 wt% zirconium (after 10 min).
(iv) A tantalum-modi¯ ed re¯ner (held at 800 ¯C) is resistant to the poisoning action of added
zirconium. (Data from Bunn (1998).)

Di¬erent types of re­ ner can be more or less e¬ective, and even for one type
there can be better and worse batches. E¬ectiveness may be considered in terms of
suppression of columnar growth or of the degree of re­ nement of equiaxed grains.
The re­ ning action is degraded (poisoned) in the presence of certain solutes in the
melt. The grain size (diameter) in the as-cast product varies with melt chemistry
and processing conditions. For each of these aspects of grain re­ nement by melt
inoculation it would be good to have some predictability.

2. Grain re¯ners for aluminium

The most widely used re­ ners for aluminium are based on the system Al{Ti{B; a
typical composition is Al{5 wt% Ti{1 wt% B (designated Al{5Ti{1B). Measurements
are more easily made in small melt volumes rather than in full-scale castings. The
TP-1 test with a melt volume of ca. 100 cm3 (Boone et al. 1991) is widely used to
assess re­ ners. When the test is modi­ ed to include temperature measurement, the
maximum undercooling ¢Tm ax of an inoculated melt is found to be ca. 0.2 K (Greer
et al . 2000), and even smaller values have been suggested (Johnsson et al . 1993); such
small ¢Tm ax is a sign of potent catalysis. The Al{5Ti{1B re­ ner consists of particles
of Al3 Ti and TiB2 in an ¬ -Al matrix. When added to the melt, the matrix melts and
the dilution of the titanium content leads to rapid dissolution of the Al3 Ti, while the
TiB2 remains stable. It is known that Al3 Ti, when present, is a much better nucleant
than TiB2 , so the potent action of Al{Ti{B re­ ners has been taken to imply that some

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Grain re¯nement of alloys by inoculation of melts 481

Al-based
glassy matrix

TiB2
Al

50 nm
Figure 2. Bright-¯ eld transmission electron micrograph showing ¬ -Al crystallites formed on a
TiB2 particle embedded in a glassy Al85 Y8 Ni5 Co2 (at.%) matrix and annealed. The labelled
crystallite sits on a (0001) ledge on the (10¹10) prismatic face of the hexagonal platelet particle.
(Reproduced with permission from Schumacher et al . (1998).)

Al3 Ti must be stabilized by the TiB2 particles (Schumacher et al. 1998). Indeed, the
re­ ning action of Al{Ti{B re­ ners is potent only when the overall titanium content
of the system is in excess of that needed to combine fully with the boron in the TiB2
particles. With melt stirring to avoid settling of particles, there is no degradation
of re­ ner action with prolonged holding in the melt (­ gure 1, curve (i)). Indeed, a
re­ ner with poor performance can improve with holding (­ gure 1, curve (ii)).
The major problems with Al{Ti{B re­ ners are susceptibility to particle agglomer-
ation and to poisoning; the e¬ect of zirconium is shown in ­ gure 1, curve (iii). Newer
Al{Ti{C re­ ners (with a typical composition Al{3Ti{0.15C) overcome some of these
problems and are becoming more widely used (Schneider et al . 1998). However, the
TiC nucleant particles in these dissolve slowly in the melt, precluding long holding
times (Vandyousse­ et al . 2000).

3. Microscopical studies of nucleation

As-cast microstructures do not readily reveal details of the nucleation stage of solid-
i­ cation, as these can be obscured by subsequent growth. In the case of Al3 Ti acting
as a nucleant for ¬ -Al, the nucleant Al3 Ti may even be removed by peritectic reac-
tion with the melt. These problems would be solved were growth to be stopped at
an early stage; this is possible by using an Al-based metallic glass as an analogue
of the liquid (Schumacher et al . 1998). An Al85 Y8 Ni5 Co2 (at.%) alloy with added
Al{5Ti{1B re­ ner was melt-spun to a glassy ribbon. Figure 2 is a transmission elec-
tron micrograph of one of the TiB2 particles dispersed in the glassy matrix. For this
sample the quench rate (105 to 106 K s¡1 ) was followed by a 30 min anneal at 483 K
before thinning for transmission electron microscopy (TEM). Aluminium crystallites

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482 A. L. Greer

have started to form, but only on the f0001g basal faces of the TiB2 , which is in the
form of hexagonal platelets. The ¬ -Al nucleates even on small f0001g-orientation
ledges on the prismatic faces of the TiB2 . Re-entrant corners are not favoured nucle-
ation sites, as contact with the prismatic faces is avoided. The f0001g-faces of the
TiB2 appear to be coated with a thin layer of Al3 Ti (Cantor 2003; Schumacher et
al . 1998), which is the actual nucleation substrate for ¬ -Al; when in melts of di¬er-
ent chemistry it is absent, there is no nucleation of ¬ -Al, even in the metallic glass,
where the driving force for crystallization is large. Electron di¬raction (Schumacher
et al . 1998) shows that there are well-de­ ned orientation relationships: in all three
phases, the close-packed planes and directions are parallel, and the in-plane repeat
distances match within 6%. The layer of Al3 Ti may be stabilized on the TiB2 by
adsorption e¬ects. The improvement seen in ­ gure 1, curve (ii) can be attributed
to the development of a suitable layer on initially poor nucleant particles. In the
presence of zirconium in the melt, similar TEM studies of the metallic glass show
that the TiB2 particles are converted to ZrB2 ; this has a signi­ cantly larger repeat
distance in the f0001g-plane, is not coated with an aluminide, and does not act as
a nucleation substrate for ¬ -Al (Bunn et al . 1999). TEM studies have also shown
that in the presence of tantalum in the melt a very stable Al3 Ta coating is formed
on TiB2 . A re­ ner exposed to tantalum in the melt is remarkably resistant to zir-
conium poisoning (­ gure 1, curve (iv)). These studies show the importance of both
crystallography and chemistry for e¬ective nucleation.
For commercial re­ ners, at best only 1% of the TiB2 particles succeed in nucleating
grains. The TEM studies o¬er no explanation for this ine¯ ciency, as all the particles
observed in the metallic glass are successful nucleants.

4. Modelling of grain size

(a) The free-growth criterion
The ine¯ ciency suggests that the growth of grains on early nucleation events must
in some way sti®e later nucleation. Maxwell & Hellawell (1975) pointed out that this
happens through latent heat release limiting the undercooling of the melt. This e¬ect
is signi­ cant because typical thermal di¬usion lengths in solidifying inoculated alu-
minium are 102 {103 times the grain diameter. For quantitative predictions of re­ ner
e¯ ciency it is necessary to understand the conditions for grain initiation on nucle-
ant particles. Maxwell & Hellawell assumed classical heterogeneous nucleation on
nucleants with uniform characteristics (most importantly, the contact angle ³ ). The
temperature dependence of the nucleation rate is so strong that there is e¬ectively
instantaneous nucleation at a well-de­ ned undercooling ¢Tn (Hunt 1984). Similarly,
a sharp onset undercooling is predicted by the adsorption model for heterogeneous
nucleation (Cantor 2003). Whether classical nucleation or adsorption is assumed, the
known potency of inoculants implies that ¬ -Al nuclei forming on the nucleants are
thin and ®at. In such a case, nucleation of ¬ -Al may be insu¯ cient to ensure initi-
ation of a grain. For nucleation on the f0001g-faces of TiB2 particles, the sequence
leading to grain initiation is shown in ­ gure 3, inset (ii). Any initial nucleus can
readily grow across the face of the nucleant particle to form a thin coating, but can
then grow further only by reducing the radius of curvature of its interface with the
melt. This radius cannot go below the critical value r ¤ for nucleation at the instan-
taneous temperature. If the diameter d of the particle is such that d < 2r ¤ , then free

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Grain re¯nement of alloys by inoculation of melts 483

1.0
(i) (ii)
minimum-radius
undercooling for grain initiation (ºC) 0.8 q hemispherical cap

0.6
TiB2

0.4 D Tfg TiB2

d
0.2 D Tn

0 2 4 6 8 10
particle diameter (µm)
Figure 3. The bold line indicates the undercooling necessary for grain initiation. The free-growth
undercooling is calculated; the nucleation undercooling is schematic only. Inset (i) shows the
classical spherical-cap model for heterogeneous nucleation. Inset (ii) shows a cap of ¬ -Al growing
on an inoculant particle through the critical hemispherical condition.

growth of the crystal from the particle is not possible. It becomes possible when the
undercooling is increased, thus reducing r ¤ . The critical condition for free growth of
the crystal through the minimum-radius hemispherical shape is when d = 2r ¤ . The
undercooling for free growth ¢Tfg and the nucleant particle diameter d are simply
related by
4¼
¢Tfg = ; (4.1)
¢Sv d
where ¼ is the solid{liquid interfacial energy and ¢Sv is the entropy of fusion per
unit volume. (Equation (4.1) is readily derived from the classical expression for the
critical nucleus radius at small undercooling.) The undercooling ¢Tfg constitutes a
barrier for the e¬ective initiation of a new grain. When a nucleus is formed, it has
an interface with the liquid, but this interface must break free from the inoculant
particle in order to have free growth of the new grain.
Either ¢Tn or ¢Tfg may be the critical undercooling for grain initiation, depending
on which is greater. The ¢Tfg curve in ­ gure 3 shows how this undercooling varies
with particle diameter. As will be seen later, particle diameters in typical re­ ners
vary over a wide range, but many are of the order of 1 m m. This diameter would
correspond to a free-growth undercooling of the order of 0.5 K; since this is similar
to or greater than maximum measured undercoolings, nucleant particles are small
enough for the barrier to free growth to be signi­ cant. Indeed, recent work has taken
the free-growth barrier to be controlling (Bunn 1998; Greer et al . 2000), i.e. it is
assumed that the condition ¢Tfg > ¢Tn applies within the known size range of
inoculant particles, though this could not remain so for inde­ nitely large particles.
In e¬ect, it is assumed that nucleation is so potent (i.e. ¢Tn is so small) that this

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484 A. L. Greer

(a) (b)

temperature

temperature
liquidus
D Tmax D Tz

recalescence

time distance
Figure 4. Schematics of the thermal conditions during solidi¯cation. In case (a), a small, spa-
tially isothermal melt shows recalescence. In case (b), a directionally solidi¯ed melt shows a
quasi-isothermal zone. In each case the undercooling limiting the grain initiation is indicated.

is not the limiting step in initiating grains (schematically illustrated in ­ gure 3). To
test this hypothesis it is necessary to have a quantitative model for the sti®ing of
further grain initiation by latent heat release.
A complete model for melt solidi­ cation would include solute partitioning and
transport, heat transport and ®uid ®ow in addition to crystal nucleation and growth.
Fortunately, simpli­ cations can be made, and two models have been proposed for the
analysis of grain re­ nement: one based on an isothermal melt and one on directional
solidi­ cation. The isothermal-melt model was proposed by Maxwell & Hellawell
(1975). The approximation that the melt is spatially isothermal throughout solid-
i­ cation is based on the large thermal di¬usion length and is good for small melt
volumes as in the TP-1 test. As the melt is cooled below the liquidus temperature,
grains are initiated and grow, releasing latent heat. As more grains grow, the latent
heat release rate increases and eventually exceeds the rate of external heat extrac-
tion, giving recalescence (­ gure 4a). In the solidi­ cation of larger melts there are
clear temperature gradients, but microstructural modelling (Vandyousse­ & Greer
2002) shows that there is a quasi-isothermal zone in which grains grow without sig-
ni­ cant impingement (­ gure 4b). In this zone, the latent heat release balances the
heat extraction. In either case, there is a well-de­ ned maximum undercooling of the
melt, ¢Tm ax or ¢Tz , which limits grain initiation and controls re­ ner e¯ ciency.

(b) Isothermal-melt model

Given the small measured values of ¢Tm ax , the volume fraction crystallized at
recalescence must be small (less than 0.1%). As far as solute is concerned, the grains
can be considered to grow in isolation from each other. It is also reasonable to assume,
and has been veri­ ed numerically (Greer et al . 2000), that the growth of the crystals
at recalescence has not yet become dendritic. Accordingly, solute-di¬usion-limited
growth of spherical grains is assumed. As shown by Maxwell & Hellawell (1975), to

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Grain re¯nement of alloys by inoculation of melts 485

1013

predicted
number of grains (m- 3) 1012
Maxwell & Hellawell

(B)
1011 (A)

measured
1010

1010 1011 1012 1013 1014 1015

number of particles (m- 3)
Figure 5. The number of grains per unit volume as a function of the number of re¯ner particles
per unit volume, showing a general trend to lower e± ciency at higher addition level. Data from
grain diameters measured in TP-1 tests (closed circles) are compared with predictions of the
free-growth model (open circles) (Greer et al . 2000). The predictions are qualitatively di® erent
from those of Maxwell & Hellawell (1975) and are a much better ¯t to the data. (Reproduced
with permission from Greer et al . (2000).)

a good approximation, the growth rate (dr=dt, where r is radius and t is time) at a
given undercooling is proportional to the di¬usivity of the solute in the liquid and
inversely proportional to the growth-restriction parameter, Q, given by
Q = m(k ¡ 1)C0 ; (4.2)
where m is the liquidus slope in the phase diagram of the solute with aluminium,
k is the equilibrium partition coe¯ cient and C0 is the solute content in the alloy
melt. For low-solute contents the Q values for the di¬erent solutes in an alloy are
additive. Cooling curves (­ gure 4a) are calculated by dividing time into a series
of isothermal steps; the number of grains initiated in each step is calculated, as is
the total latent heat release from the incremental growth of all the grains initiated
in earlier steps. This latent heat release, together with the imposed external heat
extraction during the time increment, is used to calculate the cooling rate and thereby
the temperature during the next increment. Once recalescence starts, there are no
more initiation events and the number of grains per unit volume Nv is determined.
In the original application of this numerical model, Maxwell & Hellawell (1975)
assumed classical heterogeneous nucleation on particles of uniform size, with only
one nucleation event permitted per particle. Their prediction for the variation of
Nv with the number of inoculant particles per unit volume for commercial-purity
aluminium (CP-Al) under TP-1 test conditions is shown in ­ gure 5. In regime A,
particles are so sparse that there is time for nucleation to occur on every particle,
i.e. 100% e¯ ciency. In regime B, Nv saturates as more particles are added and the
e¯ ciency falls dramatically. Input parameters to the model are adjusted roughly to
match the experimental data, but the predicted plateau in grain size is not observed.

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486 A. L. Greer

Table 1. Parameters used in the free-growth calculations

(The material parameters are mostly for pure aluminium. The data sources are cited by Greer
et al. (2000).)

quantity symbol units value

solid{liquid interfacial energy ¼ mJ m¡ 2 158

entropy of fusion per unit volume ¢ Sv J K¡ 1 m¡ 3
1:112 £ 106
enthalpy of fusion per unit volume ¢ Hv J m¡ 3 9:5 £ 108
heat capacity of melt per unit volume Cpv J K¡ 1 m¡ 3
2:58 £ 106
di® usivity in melt (Ti in Al) D m 2 s¡ 1 2:52 £ 10¡ 9
cooling rate in TP-1 test dT =dt K s¡ 1 3.5

1.4 0.2

1.2 0

- 0.2
relative number of particles

1.0
± 10% error
- 0.4

error fraction
0.8
- 0.6
fitted log-normal
0.6 - 0.8
distribution

0.4 - 1.0

- 1.2
0.2
- 1.4

0 1 2 3 4 5 6
particle diameter (µm)
Figure 6. The diameter distribution of TiB2 particles in a commercial Al{5Ti{1B re¯ner, ¯tted
to a lognormal distribution with relative error as shown. The black bars show the fraction of
the particles calculated by the free-growth model to be active for an addition level of 1 ppt in
CP-Al cooled at 3.5 K s¡ 1 .

In contrast, Greer et al . (2000) assumed grain initiation was limited by the free-
growth criterion (4.1). Nucleation occurs on every particle, but grain initiation occurs
only when ¢Tfg is exceeded, which on cooling occurs ­ rst on the largest particles. The
number of grains initiated in each undercooling increment depends on the size distri-
bution of the nucleant particles. Fortunately, and in marked contrast to parameters
such as the contact angle needed for a nucleation-based model, the size distribution
is measurable, often by scanning electron microscopy of polished sections of re­ ner
(Bunn 1998; Greer et al. 2000); this for a commercial Al{5Ti{1B re­ ner is shown
in ­ gure 6. When measured distributions are used as input, the free-growth model
gives the predictions shown in ­ gure 5; the spread of particle size eliminates the
division into two regimes predicted by Maxwell & Hellawell. The free-growth pre-
dictions are in remarkably good agreement with experiment, considering that the
input parameters (table 1) are all determined independently and are not adjustable.

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Grain re¯nement of alloys by inoculation of melts 487

Recalescence sets a lower limit to the particle size at which grain initiation occurs.
The black bars in the distribution in ­ gure 6 show the active particles for typical
conditions.
The agreement with experiment gives strong support to the free-growth model,
and further support comes from the close match between predicted and measured
values of ¢Tm ax (Greer et al. 2000). However, the overall shapes of measured cooling
curves are not well matched and suggest a need to consider temperature gradients.
Figure 5 shows that free-growth predictions are better than those based on nucleation
on a uniform set of particles. Predictions from a nucleation-based model could be
­ tted to experiment by, for example, assuming a distribution of contact angle values;
however, the adjustable input parameters would not be susceptible to independent
determination.

(c) Directional-solidi¯cation model

For most castings, an isothermal-melt model cannot be applicable, and there is
no overall undercooling of the melt before grain initiation. Solidi­ cation proceeds
through the casting; locally the solidi­ cation front can be taken to be planar, and its
velocity is antiparallel to the one-dimensional heat ®ow. In the steady state there can
be no recalescence, but rather a temperature pro­ le with distance, of the kind in ­ g-
ure 4b, which migrates into the liquid. As the melt is cooled, grains are initiated and
then grow dendritically. In the quasi-isothermal zone the latent heat release balances
the heat extraction, but after the dendritic envelopes have impinged, the remaining
interdendritic liquid, its composition altered by solute partitioning, solidi­ es more
slowly and cooling resumes. A simple model can be based on the analysis of the
quasi-isothermal zone (Greer et al . 2002). For an assumed ¢Tz , a free-growth analy-
sis as used above gives the number of grains growing in the zone. This undercooling
also sets the dendritic velocity; as for the di¬usion-controlled growth of spheres con-
sidered above, the velocity at a given undercooling is proportional to the di¬usivity
of the solute in the liquid and inversely proportional to Q (equation (4.2)). Assuming
that solute partitioning to and from the growing dendrites involves only the liquid
within the dendritic envelopes, a Scheil analysis can be applied to calculate the
fraction solidi­ ed within the envelopes from ¢Tz . Finally, a Johnson{Mehl{Avrami
analysis is applied to estimate an average rate of transformation within the quasi-
isothermal zone. The rate of latent heat release derived from this solidi­ cation rate
is matched to the external heat extraction. Using these relationships, the under-
cooling in the zone ¢Tz , and thereby the number of grains per unit volume formed
in the solidi­ cation, can be derived from the alloy composition and solidi­ cation
conditions.

(d) Predictions of free-growth modelling

The measured data and the predictions of the isothermal-melt free-growth model
shown in ­ gure 5 are shown again in ­ gure 7, but in terms of the usual measure
of grain size, the mean linear intercept ·l, rather than in terms of Nv (= 0:5=·l 3 )
(Greer et al . 2000). Also included in ­ gure 7 are the predictions of the directional-
solidi­ cation model for the same conditions. The two free-growth models give similar
predictions, not only as shown in ­ gure 7, but over a wide range of conditions; no
distinction is made between the models in the following comparison of prediction

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488 A. L. Greer

600

500
grain size (µm)
400

300

200

100

0 2 4 6 8 10
addition level of refiner (ppt)
Figure 7. Grain diameter (mean linear intercept) for CP-Al inoculated with Al{5Ti{1B at various
levels. The grain diameters measured in TP-1 tests (diamonds) are compared with free-growth
model predictions based on an isothermal melt (circles) or on directional solidi¯ cation (squares).
(Reproduced with permission from Greer et al . (2002).)

and experiment. Figure 7 illustrates that increasing the inoculation level re­ nes the
grain size, which, however, tends to a limiting value. There are very similar trends
of decreasing grain size with increasing cooling rate and with increasing growth-
restriction factor Q. These are not illustrated here, but have been shown by Greer
et al . (2000, 2002). The predicted e¬ect of the cooling rate is consistent with the
sparse data available. In contrast, there are many data available on solute e¬ects,
notably from Spittle & Sadli (1995), who studied various addition levels of Cr, Cu,
Fe, Mg, Mn, Si, Zn and Zr. Their results show that Q is a good universal parameter
for describing solute e¬ects. Furthermore, the free-growth predictions provide a good
match to the measured decrease of grain size with increasing Q.
Overall, the free-growth model agrees with the grain sizes measured in TP-1 tests,
except when the measured sizes exceed 400 m m. Although not always evident from
the standard TP-1 cross-section, such large sizes probably occur when there is direc-
tional columnar growth. The competition between equiaxed and columnar growth is
not accounted for in the simple modelling performed so far. Although it has been
noted that the temperature gradient appears not to be important in controlling the
grain size in the equiaxed regime, high values certainly favour columnar growth (Hunt
1984). Free-growth modelling has also been applied with some success to the predic-
tion of grain size in inoculated aluminium alloys undergoing directional solidi­ cation
in a Bridgman furnace (Greer et al . 2002). It has, however, not yet been applied
to larger-scale commercial castings, in which signi­ cant ®uid ®ow may contribute to
grain initiation by transport of dendrite fragments.

5. Nucleation laws for solidi¯cation modelling

As reviewed, for example, by Stefanescu et al. (1990), comprehensive computer simu-
lation and modelling of solidi­ cation must include, among many factors, macromod-

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Grain re¯nement of alloys by inoculation of melts 489

elling of ®uid ®ow and heat transfer and micromodelling of phase nucleation and
growth. As growth laws are often well established, it is likely that the derivation of
the nucleation law is the greatest outstanding problem in developing a comprehensive
predictive model.
The early observations of Old­ eld (1966) showed that there can be a clear cor-
relation between the population of grains and the maximum undercooling reached
in the melt. In Old­ eld’s case, the population n was proportional to the square of
the undercooling ¢T . This corresponds to a nucleation law for cooling in which the
nucleation rate dn=d¢T is linearly proportional to ¢T . Such simple, empirical laws
predict continuous nucleation rather than the e¬ectively instantaneous nucleation
given by a simple classical nucleation analysis (Hunt 1984). They are easy to apply in
solidi­ cation modelling and have been widely used. In the cellular-automaton{­ nite-
element modelling of Rappaz & Gandin (1993) now used in commercial software, for
example, dn=d¢T has a Gaussian distribution about a maximum as a function of
undercooling. Such laws envisage a spectrum of nucleation sites, each site becoming
active instantaneously when its critical undercooling is reached. This approach is
completely compatible with the free-growth model. With a measured particle size
distribution as in ­ gure 6, the nucleation rate dn=d¢T increases strongly, roughly
exponentially, with increasing ¢T in the undercooling range of interest.
The model that is now known as the free-growth model has been used for many
years in di¬erent contexts. Turnbull (1953) found that small mercury droplets coated
with a potent catalyst for nucleation of the solid exhibited athermal nucleation, in
which the fraction of droplets solidifying on cooling depended only on the under-
cooling and not on time. Turnbull postulated the existence of surface patches, with
a distribution of sizes, on the droplets, and noted that nuclei formed on the patches
would become transformation nuclei on cooling, when the critical nucleation radius
became less than the patch radius. This is equivalent to equation (4.1). Based on
this analysis, Turnbull used the solidi­ cation kinetics to derive the size distribution
of the patches, ­ nding a roughly Gaussian variation of dn=d¢T with ¢T . Grain
initiation controlled by a free-growth condition rather than a true nucleation barrier
had earlier been invoked by Turnbull (1950) to analyse heterogeneous nucleation on
mould walls and similar surfaces. The preservation of the solid phase in cavities in
the mould wall even when the liquid is superheated, and the subsequent free growth
from those cavities at su¯ cient undercooling, can be used to explain the dependence
of the undercoolability of metallic melts on prior superheating.

6. Design of grain re¯ners

In x 4 it was established that a free-growth model with the measured particle size
distribution as input can be used to make quantitative predictions of grain re­ ne-
ment. It is then of interest to use the modelling to design re­ ners with optimized
particle size distributions, for example to give minimum grain size for a given vol-
ume fraction of nucleant phase (i.e. TiB2 for Al{Ti{B re­ ners). Two types of ideal
distribution in diameter have been used: normal (i.e. Gaussian) and lognormal. The
former is mathematically more straightforward, but has the disadvantage of giving
small numbers of particles with unphysical negative diameter; the latter is a better
match to typical size distributions in metallurgical microstructures and ­ ts well in the
present case (­ gure 6). Tronche & Greer (2000) have used normal distributions with

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490 A. L. Greer

250 100

number and volume efficiencies (%)

80
200
grain size (µm)
60
150
40

100
20
.
50 0
0 1 2 3 4 5 6 7 8
mean particle diameter (m m)
Figure 8. Calculations for CP-Al inoculated with a volume fraction of re¯ner particles corre-
sponding to 2 ppt addition of Al{5Ti{1B and cooled at 3.5 K s¡ 1 , showing the grain diameter
(bold line), volume e± ciency (closed squares) and number e± ciency (open squares) as a function
of arithmetic mean particle diameter, for a ¯xed width of size distribution. The mean diameter in
a commercial Al{5Ti{1B re¯ner (¯) is close to the minimum-grain-size optimum. (Reproduced
with permission from Quested et al . (2002).)

the isothermal-melt model; Quested et al . (2002) have used lognormal distributions

with the directional-solidi­ cation model. Qualitatively, the predictions are in agree-
ment for the e¬ects of varying mean diameter and distribution width while holding
constant the volume fraction of nucleant phase. The e¬ects of varying the arithmetic
mean diameter are shown in ­ gure 8, with the width of the lognormal distribution
set to match that in a commercial Al{5Ti{1B re­ ner (geometric standard deviation,
¼ = 0:88). There is a clear minimum in grain size at intermediate values of mean
particle diameter. Large particles (for ­ xed volume fraction) are necessarily few and
give large grain sizes. On the other hand, small particles, though numerous, become
active only at greater undercooling, when the crystal growth rate is greater. The
optimum re­ nement is at intermediate sizes. Interestingly, empirical development
has brought the mean particle diameter in commercial re­ ners very close to this opti-
mum. Figure 8 also con­ rms that, at the optimum re­ nement, the number e± ciency
(i.e. number of grains per added particle) is low. Alternatively, the e¯ ciency can
be evaluated in terms of the volume fraction of nucleant-phase (i.e. TiB2 )-initiating
grains. As the active particles are the largest, this volume e± ciency is substantial
(greater than 60%). While the behaviour in ­ gure 8 has not been quantitatively
tested, it nevertheless indicates that the low number e¯ ciencies usually quoted can
be a misleading guide to re­ ner e¬ectiveness.
In practice it may be more important to have a uniform grain size than a ­ ne grain
size. One reason why grain size might vary across a casting is non-uniformity in the
cooling rate, the e¬ects of which are shown in ­ gure 9. These calculations are for
idealized re­ ners with a Gaussian particle-size distribution of ­ xed width (standard
deviation) 0.5 m m. As the average particle size is increased (again holding the total
volume fraction of the nucleant phase constant), the e¯ ciency (measured as number
or volume fraction) increases and the grain size becomes increasingly insensitive to

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Grain re¯nement of alloys by inoculation of melts 491

600
commercial Al–5Ti–B refiner
500
l = 10.0 m m
grain size (µm) 400

300 l = 1.0 m m
l = 5.0 m m

200

100 l = 2.0 m m
0 2 4 6 8 10 12
cooling rate (K s- 1)
Figure 9. The calculated dependence of grain diameter on cooling rate for CP-Al inoculated with
idealized grain re¯ners (with a Gaussian particle diameter distribution and di® erent average
particle diameters ¶ ) or with a commercial re¯ner (closed circles) with size distribution as in
¯gure 6. (Reproduced with permission from Tronche & Greer (2000).)

cooling rate. As is also shown in ­ gure 9, the calculations suggest that, with the
particle size distribution in a commercial re­ ner, the grain size is rather sensitive to
cooling rate in the range of greatest practical interest: 1{5 K s¡1 .
The calculations yielding the results in ­ gures 8 and 9 also predict that re­ ner
e¯ ciency is greater for narrower particle size distribution. Surprisingly, this is a
rather weak e¬ect. Within the free-growth model, in which larger particles initiate
grains sooner than smaller particles, 100% e¯ ciency would be achieved for mono-
sized particles but the deterministic model would break down in such a case. In an
isothermal melt, for example, all the uniformly sized grains would grow until recales-
cence brought them simultaneously to the critical radius; at that point stochastic
e¬ects would determine which grains would grow and which would re-melt.
The calculations performed so far have all assumed a nucleant particle shape that is
characteristic of a commercial Al{5Ti{1B re­ ner. As seen in TEM, these particles are
hexagonal prisms. In the model these are approximated as discs with a thickness equal
to 35% of their diameter. As the active surfaces are the hexagonal/circular (0001)
faces, the particles would be equally e¬ective if they were thinner. The e¬ectiveness
of re­ ners, measured in terms of the re­ ning achieved for a given volume fraction of
nucleant phase, therefore could be increased if the particles were thinner. For Al{Ti{
B re­ ners, in which the nucleant phase is the hexagonal TiB2 , changing the aspect
ratio of the particles is possible, at least in principle. In contrast, for Al{Ti{C re­ ners
in which the nucleant phase is cubic TiC with octahedral morphology, changing the
particle aspect ratio is not a design option.
Perhaps the most important reason to inoculate melts is the suppression of colum-
nar growth. As noted by Hunt (1984), equiaxed growth is favoured by a larger popu-
lation of nucleant particles and by a smaller undercooling to activate them; the latter
is the more important e¬ect. The free-growth model implies, therefore, that larger
particles would be better for suppressing columnar growth. As yet, however, there

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492 A. L. Greer

has been no quantitative application of the free-growth model that is able to predict
the e¬ects of inoculation on the columnar-to-equiaxed transition in castings.

7. Summary and conclusions

Inoculation of metallic melts can be used to give desirable equiaxed grain structures
on casting. It is most widely practised for aluminium alloys. By embedding them in
a metallic glass, the nucleant action of inoculant particles, relevant for their action in
the melt, can be studied microscopically. The inhibition of growth in the glass per-
mits unambiguous identi­ cation of nucleation sites. The particular case of Al{Ti{B
inoculants used in aluminium alloys shows the importance of chemistry and crys-
tallography for e¬ective nucleation. The nucleant particles are hexagonal platelets
of TiB2 coated with an adsorbed layer of Al3 Ti. Nucleation of ¬ -Al occurs only on
the f0001g-faces of the borides, with the close-packed planes and directions in TiB2 ,
Al3 Ti and ¬ -Al being parallel. The Al3 Ti layer appears to be essential for e¬ective
nucleation. It is promoted by excess titanium in the melt, and its absence explains
the poisoning of re­ ner action in the presence of, for example, zirconium. An under-
standing of layer stability has enabled the modi­ cation of re­ ners to make them
more poison resistant. In successfully inoculated melts, at most 1% of the particles
nucleate grains; this ine¯ ciency is caused by the release of latent heat, limiting the
available melt undercooling, and cannot be directly related to nucleation.
Commercial inoculants for aluminium are so potent that grain initiation is limited
by the barrier to free-growth of nucleated ¬ -Al from the nucleant surface, rather than
by nucleation itself. The undercooling necessary to initiate free growth is inversely
proportional to the diameter of the particle surface, and the particle size distribution
determines re­ ner performance. With measured particle size distributions as the
input, quantitatively correct predictions can be made for grain size as a function of
addition level of Al{Ti{B or Al{Ti{C inoculants, cooling rate and solute level in the
melt. Such modelling allows the design of improved re­ ners. Commercial Al{Ti{B
re­ ners have a characteristic particle size close to that giving a minimum grain size,
and are e¯ cient, as measured by the volume (rather than number) fraction of added
particles which initiate grains.
The quantitative prediction of heterogeneous nucleation kinetics is rare. The suc-
cess of quantitative predictions for inoculation of aluminium alloys relies on grain
initiation being dominated by well-characterized nucleants so potent that grain ini-
tiation is limited only by the free-growth criterion. This condition is likely to be
met in other cases, for example the catalysis of ice nucleation in some living systems
(Franks 2003; Zachariassen & Kristiansen 2000). In such cases of potent nucleation
or seeding, the size distribution of the catalyst substrates may play an important
role in the overall kinetics.
The contributions of past and present members of A.L.G.’ s research group are gratefully acknowl-
edged, in particular those of A. M. Bunn, M. W. Meredith, T. E. Quested, P. Schumacher,
A. Tronche and M. Vandyousse¯. Thanks are due to the EPSRC for ¯nancial support; Alcan
International Ltd (Banbury Laboratory), the London & Scandinavian Metallurgical Co. Ltd
(Rotherham), and Pechiney (Centre de Recherches de Voreppe) for ¯nancial support, access to
research facilities and fruitful interactions; members of the EU Network `Microstructural Engi-
neering by Solidi¯cation Processing’ for useful discussions; and Professor D. J. Fray for the
provision of laboratory facilities.

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Grain re¯nement of alloys by inoculation of melts 493

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Discussion
J. H. Perepezko (Department of Materials Science and Engineering, University of
Wisconsin-Madison, WI, USA). Earlier, Professor Cantor stressed the importance
of adsorption in heterogeneous nucleation. Could you clarify the possible role of
adsorption in your model of grain re­ nement?
A. L. Greer. The point I wanted to make was that, when nucleation on grain-re­ ner
particles is very e¬ective (i.e. when nucleation occurs at very small undercooling),
the nucleation itself ceases to be the controlling factor in initiating grains. In that
case, the undercooling for grain initiation is related only to particle size, accord-
ing to the free-growth model. The mechanism by which such potent heterogeneous
nucleation occurs, however, could well involve adsorption rather than classical nucle-
ation. Indeed, it is clear from Cantor’s work that the classical spherical-cap model
for heterogeneous nucleation could not apply.
F. Franks (BioUpdate Foundation, London, UK ). It was implied that the e¯ ciency
of nucleators is low and depends only on the particle size. In the case of ice nucleation
by AgI, the method of preparation of the catalyst is more important. The most
e¯ cient catalysts are those prepared in situ.
A. L. Greer. You are correct that the condition of the catalyst is important. Only
when the catalyst is very good does the e¬ectiveness of nucleation relate only to par-
ticle size. It is essential that the catalyst is very potent: when it is not, the condition
of the catalyst, rather than particle size, is critical. Your example of AgI has parallels
with what is found for grain-re­ ning catalysts for aluminium. Speci­ cally, the grain
re­ ners work better or worse depending on the chemistry of the re­ ner (i.e. catalyst)
particles’ surfaces. As mentioned in the paper, poor re­ ners can improve with hold-
ing in the melt, an e¬ect explicable in terms of the formation of an aluminide layer
on the boride particles, and not in terms of particle size. Furthermore, the e¬ective-
ness of a re­ ner can be destroyed (`poisoned’) by the action of certain solutes in the
melt. This again is related to the condition of the re­ ner particles. Your point, about
the most e¬ective catalysts being prepared in situ, is also found for grain re­ ners
for aluminium. The titanium diboride particles which act as nucleation catalysts are
most e¬ective when prepared (by reaction of salts) in situ in an aluminium melt.
B. Cantor (University of York, UK ). It seems very surprising that the mean nucle-
ating particle size is much lower than the e¬ective nucleating particle size. I suspect
this comes from assuming a lognormal distribution. A top-hat distribution would per-
haps put the mean nucleating particle size equal to the e¬ective nucleating particle
size.

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Grain re¯nement of alloys by inoculation of melts 495

A. L. Greer. You are correct that the mean particle size is below the typical size
of the particles that are e¬ective. This arises when the particle size distribution
has a tail extending up to large sizes, a feature of the lognormal distribution found
experimentally. We have made calculations of the e¬ects of di¬erent shapes of size
distributions and found that the e¯ ciency of a re­ ner is indeed higher when the size
distribution is narrower. Perhaps surprisingly, this does not seem to be a strong e¬ect.
It should be noted that, as the particle size distribution becomes narrower, in the
extreme, if it were a delta function, our simple model would break down. For a delta-
function distribution, all particles would become active at the same undercooling,
but it would still be the case that only some would initiate grains. Depending on
local thermal ®uctuations rather than particle size, some of the nuclei would grow
and others would re-melt.
R. W. Cahn (Department of Materials Science and Metallurgy, University of Cam-
bridge, UK ). Does the population of inoculant particles frozen into a casting or ingot
cause any problems (e.g. embrittlement)? If so, special e¬orts by the inoculant mak-
ers are needed to eliminate the ine¬ective `tail’ of particles by some process (such as
a cyclone) to separate out a narrow size range.
A. L. Greer. The added particles can indeed cause problems. For cast ingots rolled
into a thin sheet, for example, large particles or aggregates of particles are clearly a
problem if their diameter approaches or exceeds the sheet thickness. The problems
are most likely to occur with the largest particles and, as emphasized, these are
also the most e¬ective nucleants|so compromise may be needed. Embrittlement
induced by the particles is not a problem for aluminium alloys. The addition of hard
particles can even have bene­ cial e¬ects on the mechanical properties. The ine¬ective
particles are the smaller ones and they end up at grain boundaries, swept there by the
growing grains. There, they may play a role (not yet clearly identi­ ed) in in®uencing
the selection of intermetallic phases appearing in the ­ nal stages of solidi­ cation;
these phases may in turn have important e¬ects on the ­ nal product. The use of
a cyclone or suchlike is an intriguing possibility, but it must be remembered that
low-cost production is essential.

Phil. Trans. R. Soc. Lond. A (2003)