REVIEWS

DOI: 10.1002/adem.200700157

A New Analytical Approach

to Reveal the Mechanisms
of Grain Refinement**
By David H. StJohn,* Peng Cao, Ma Qian and Mark A. Easton

his paper presents an overview of a new methodology for investigating the grain refinement performance of alloys and master alloys and then uses this methodology to shed new light on the mechanisms
occurring during superheating and native grain refinement, and the effect of iron and manganese on
grain refinement in magnesium alloys. The methodology also describes changes in grain size upon Zr
grain refinement of Mg and has been used to analyse the potential for the use of SiC to grain refine
Mg-Al alloys. With this new methodology, and the knowledge it generates, the potential for the discovery of new or improved refiners is significantly enhanced.

1. Introduction
Solidification is one of the most important microstructure
formation processes for metallic alloys. The initiation of solidification, namely nucleation, almost always occurs heterogeneously in large masses of liquid metals. The ability to control
such a process lies at the heart of the development of a novel
technology or microstructure.[1] This is because nucleation
controls to a large extent the initial structure type, size scale,
and spatial distribution of the product phases.[2] In the metal
casting industry, it is common practice to control the process
through the introduction of carefully selected nucleating
agents, referred to as inoculation, for the formation of fine,
uniform and equiaxed non-dendritic grain structures.
Achievement of such a grain structure helps reduce the casting defects, improves the mechanical properties and ensures
consistent performance of the cast products.
For magnesium alloys grain refinement has further importance, in that achievement of a fine grain size can fundamentally change their deformation behaviour and improve their
inadequate cold-formability. For instance, grain refinement
below a grain size of about 40 lm (700 grains/mm2) for pure
magnesium can significantly enhance the ductility compared
to coarse grained ( 1100 lm) pure magnesium materials.[3]
Samples of Mg-9Al-1Zn with a grain size of about 1 lm exhibit different deformation mechanisms at room temperature

ADVANCED ENGINEERING MATERIALS 2007, 9, No. 9

[*] Prof. D. H. StJohn

School of Engineering
The University of Queensland
Brisbane, 4072, Australia
E-mail: d.stjohn@cast.org.au
Dr. P. Cao
Department of Engineering
The University of Waikato
Private Bag 3105
Hamilton, New Zealand
Dr. M. Qian
Department of Mechanical and Design Engineering
University of Portsmouth
Portsmouth PO13DJ
UK
Dr. M. A. Easton
Department of Materials Engineering
Monash University
Melbourne, 3800, Australia
[**] The CAST Cooperative Research Centre was established under
and is supported in part by the Australian Governments
Cooperative Research Centres Programme. MQ and DStJ also
acknowledge the support of the Australian Research Council.
MQ acknowledges the support from EPSRC, UK.

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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StJohn et al./A New Analytical Approach to Reveal the Mechanisms of Grain Refinement
without twinning.[4] Further to these established benefits of
grain refinement, recent work[5] has shown that fine and
spherical primary magnesium crystals are directly obtainable
from the liquid state by grain refinement, without the aid of
liquid agitation. This offers a simple alternative to semisolid
processing of magnesium alloys. Another recent development shows that well-controlled grain refinement can lead to
nearly spherical grain structures in magnesium alloys such as
AM-SC1 and ZE41 under different casting conditions.[5] This
provides further opportunities to improve the structural uniformity of a magnesium alloy. In all probability, grain refinement presents itself as an important factor for the further
development of magnesium alloys.
Central to the successful inoculation or grain refinement of
a liquid metal is the identification of a potent nucleating substrate (i.e., those characterised by a small contact angle h[6]). Because of the lack of data on h, crystallographic similarity[7] in
most cases, has been the only measurable criterion that may be
used to assist the selection process. This criterion in general explains most identified effective nucleating substrates as good
crystallographic matching favours the formation of a low energy coherent interface. However, experimental observations
have indicated that the effectiveness of a nucleating substrate
is not just determined by crystallographic matching. Many
other factors such as the substrate geometry and size,[810] the
interactions between the substrate phase and the alloy chemistry including various impurity/minor elements, e.g.[11,12] the
settling of the substrate particles in the melt,[13] etc., could all
come into play. It is desirable and necessary then to develop
an alternative methodology for both the assessment and development of new grain refiners under complex metallurgical circumstances encountered by a commercial alloy.
This paper presents a new methodology for investigating
the grain refinement performance of alloys and master alloys
and then uses this methodology to shed new light on the
mechanisms occurring during superheating and native
refinement, and the effect of iron and manganese on grain
refinement. With this new methodology, and the knowledge
it generates, the potential for the discovery of new or improved refiners is significantly enhanced.
The new methodology for the assessment of grain refinement was developed predominantly from studies of the grain
refinement of aluminium alloys[14] and recently applied to
studies of grain refinement in magnesium alloys.[15] It is
based on using a simple graphical representation of the relationship between grain size and the growth restriction factor
Q to reveal information about the grain refining effectiveness
of alloy systems and master alloys. The following section describes the principles underlying this simple representation.
Section 3 then applies this methodology to analyzing the
results from experiments on Mg alloys to reveal new knowledge about the grain refinement of these alloys. As a result of
applying this analytical method a number of important factors need to be considered if it is going to be possible to reliably compare studies by different researchers on a range of

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alloy systems and master alloys. These factors are considered

in Section 4.

2. A New Analytical Methodology for the Study

of Grain Refinement
Due to the importance of grain refinement to a broad range
of aluminium alloys, considerable work has been carried out
for over half a century to determine the mechanisms by
which grain refinement occurs.[1619] It is now generally accepted that both the potency of the nucleant particles (defined
here as the reciprocal of the undercooling required for nucleation, DTn) and the segregating power of the solute (defined as
the growth restriction factor, Q) are critical in determining
the final grain size.[8,2022] A common method of calculating Q
is to use the formula for the growth restriction factor based
on phase diagram features[21] which is
Q ml c0 k 1 for binary systems and
Xi
Q
m c k 1
1 li 0i i
for alloys with i elements

(1)

It has been found[14] that the grain size can be related to

the factors defined above by an equation of the form
1
b DT
1 n
dp
3
Q
rf

where q is the number density of nucleant particles and f is

the fraction of these particles that are activated, across a wide
range of aluminium alloys and for the existing data on magnesium alloys and b1 is a fitting factor. Hence, the first term of
Equation 1 is related to the availability of nucleant substrates
and the second term is related to the potency of the nucleant
particles and the development of constitutional supercooling
which restricts grain growth and facilitates further nucleation. A theoretical framework for the second term was developed by Easton and StJohn.[20]
One of the most powerful uses of Equation 2 is to analyze
grain size data to determine grain refinement mechanisms.[14]
If the same density of a particular nucleant particle is added
to alloys with a range of Q values and the data is plotted
against 1/Q a relationship of the form
d = a + b/Q

(3)

is found. The gradient, b, is proportional to the undercooling

required for nucleation (DTn in Eq. 2) and the intercept, a, is
related to the number of active particles present. Hence a
more powerful nucleant added with the same number of active particles will have the same intercept but a lower gradient (Fig. 1(a)). However an increase in the nucleant particle
density will decrease the intercept, a, but the gradient, b, will
remain constant (Fig. 1(b)).

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StJohn et al./A New Analytical Approach to Reveal the Mechanisms of Grain Refinement

b
b

Particles giving b have

the highest potency

Grain size

Grain size

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Undertaking experiments to gather grain size data for a

range of Q values allows the grain size data to be plotted
against the inverse of Q. This new methodology for the study
of grain refinement provides information on the potency of
the nucleant particles whether we know what type of particles they are or not. It also provides information on the effectiveness and efficiency of the particles that are deliberately
added or naturally present in the melt. This information is
beneficial in comparing different grain refining systems and
in elucidating the mechanisms of grain refinement responsible for the observed grain refiner performance.
To illustrate the information gained from the new methodology and the relationships proposed in Figure 1. Figure 2(a)
shows the grain size data and their lines of best fit for a range
of aluminium alloys cast under identical conditions but with
controlled additions of TiB2 particles.[14] From these lines it
can be readily observed that once TiB2 particles are added the
slope of the lines, b, becomes lower and then remains constant
while the intercept a decreases as additional TiB2 particles are
added. This follows the expectations described above that the
slope b is controlled by the potency of the particles while the
intercept a is related to the number of active particles added.
Further, Figure 2(b) shows that a decreases according to a
cube root relationship with the number of added particles indicating that a fixed proportion of added TiB2 particles become active nucleants of grains regardless of the amount of
TiB2 added.[14] When no TiB2 particles are added the slope of
the line is steeper and the intercept a is much larger
(Fig. 2(a)). This implies that the natural nucleants are not very
potent and that there are relatively fewer of them. Hence the
need for the addition of grain refining inoculants in aluminium alloys. Also, by comparing the value of the inverse of a
(i.e. the active nucleant particle density) with the particle density of all the particles added through the master alloy, it can
be readily calculated that only about 12 % of the added particles become active nucleants supporting observations reported in the literature.[2]
Although the insights revealed from this analysis of aluminium alloy grain size data are known, the example given
above shows that by plotting grain size data in this manner it
is possible to readily generate useful information by using
this simple analytical approach. Therefore, by applying this

(a)

(b)
Fig. 2. (a) Lines of best fit drawn through grain size data obtained from a range of aluminium alloys with a range of TiB2 additions from no addition to 0.05 % TiB2. (b)
Grain size versus the cube root of TiB2 content. For each alloy, Q was calculated using
Equation 1. A comparison was made with the result of calculations using the thermodynamic modeling package called Thermocalc and this showed reasonable correlation
between the two methods. [23]

methodology to systems where the exact mechanisms occurring, are not known we should be able to reveal new insights
into the grain refinement mechanisms occurring in any alloy
system and, in this instance, magnesium alloys.

3. Application of the New Methodology

This section examines the results of grain refinement experiments using the new methodology as described by Equation 3 to determine whether new light can be shed on the
mechanisms responsible for grain refinement. It will also be
shown that this methodology has a number of limitations
which will be discussed in the final section of this paper.

3.1. Mg-Al Alloys

Minimum
grain size

1/Q

(a)

1/Q

(b)

Fig. 1. (a) shows the effect of changing the nucleant particle potency on the gradient b
while keeping the number of active particles constant and (b) shows the effect of adding
more of the same type of particles on the value of a while the potency, b, remains constant. After [14].

ADVANCED ENGINEERING MATERIALS 2007, 9, No. 9

3.1.1. Effect of Alloy Purity on Grain Size

Recent work[24] concludes that compared to commercial
purity alloys the finer grain size achieved in high purity MgAl alloys (designated as native grain refinement) (Fig. 3), is
due to Al4C3 particles naturally present in the melt. However,
in commercial purity Mg-Al alloys impurity elements such as

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Fe and Mn are likely to combine with Al to form an intermetallic layer on the Al4C3 particles. This lowers the potency of
Al4C3 nucleants, leading to the larger grain sizes observed in
commercial purity alloys. As can be seen from Figure 3, the
intercept, a, for high purity alloys is larger than, or in a similar range to, the value of a for commercial purity alloys. A
larger value of a implies that there are less nucleant particles
in the high purity alloys which is a reasonable expectation.
However, these nucleant particles are more potent (a much
lower value of b) than those existing in the commercial purity
alloys, giving rise to a finer grain size.
For this study high purity aluminium (Fe: 0.001 %, Si:
0.001 %, Cu: 0.0015 0.003 %, Zn: 0.001 % and Ti: 0.001 %) and
high purity magnesium (99.98 %) ingots were used to prepare
high purity Mg-Al alloy melts. To avoid the uptake of iron
and carbon that often accompanies the use of a mild steel crucible, melting of raw materials was conducted in aluminium
titanite (Al2TiO5) crucibles at 730 C. Grain size measurements were done on the central region of conical samples taken from the top of the melt using a BN-coated cone ladle with
the dimensions of j 20 mm j 30 mm 25 mm.
3.1.2. Grain Refinement by Superheating
Commercial purity (99.7 %) magnesium ingots (supplied
by Norsk Hydro) and aluminium ingots were used to prepare
Mg-Al alloy melts (Mg-3Al, Mg-6Al and Mg-9Al). Melting
was conducted in an electrical resistance furnace under SF6
cover gas. Superheating was carried out by raising the temperature of the melt from 730 C to 900 C, holding it for
30 min. and then withdrawing the crucible from the furnace
for rapid cooling (the cooling rate was about 20 C/min) to
the sampling temperature (730 C). Fig. 4 presents the grain
size data obtained from this experiment.[25]
Using the new analytical method the grain size data for
the commercial purity Mg-Al alloys was plotted against 1/Q
before and after superheating. It is clear that superheating
caused significant grain refinement in each of these three alloys. For example, the grain size of Mg-9Al decreased from

Fig. 4. Grain size versus 1/Q for a range of commercial purity Mg-Al alloys before
(data also presented in Fig. 3) and after superheating. Data are from Reference [25].
For each alloy Q was calculated using Equation 1.

180 lm to 100 lm after the superheating treatment. The gradient of the line of best fit for the superheated alloys is nearly
half that for the base alloys (Tab. 1), which suggests that after
superheating the potency of the nucleant particles has increased significantly.
The explanation for native refinement (Section 3.1.1) suggests that superheating of commercial purity alloys causes
grain refinement by removing the impurity coating and exposing fresh Al4C3 surfaces to the melt and hence improving
the potency of these nucleant particles.[26] If cooling is too
slow the impurity layer reforms removing the effect of superheating. By examining Figure 4 it can be concluded that
superheating produces a finer grain size because the particles
have become more potent without increasing the number of
potent particles (i.e. a increases slightly rather than decreases
(Fig. 4), and b decreases in value). This provides support to
the proposed mechanism of impurity layer removal.
The values of a and b for high purity Mg-Al alloys are very
similar to the values for the superheated commercial purity
alloys (Tab. 1). This indicates that the nucleant particles present in the melt are likely to be the same as in the superheated
melt, possibly Al4C3. However, all we can say for certain is
that the potency is the same as the nucleant particles may be
different phases that have the same potency. As the parameter b is proportional to the nucleation undercooling DTn in
Equation 2 it is probable that the term is related to the disreg-

Table 1. The parameters a and b for lines of best fit in Figures 2 to 4.

Line

Fig. 3. Grain size versus 1/Q for a range of commercial purity and high purity Mg-Al
alloys. After Reference [24]. For each alloy Q was calculated using Equation 1.

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R2

L0

8.1

7217

0.924

Lsh

22.9

3933

0.998

Lhp

26.5

4307

0.931

LMn

40.2

1869

0.998

LFe

17.5

3208

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3.1.3. Effect of Fe and Mn Additions on the Grain Size of High

Purity Alloys
In order to understand the role of Fe and Mn in commercial
purity alloys it is useful to study the independent effects of
these two elements when added to high purity Mg-Al alloys.
The results are presented in Figure 5. The surprising result is
that the individual addition of these elements resulted in grain
refinement rather than grain coarsening. It was proposed[27,28]
that new types of nucleants were introduced or formed in the
melt an Fe-Al compound when Fe was added and an e-AlMn
phase when a splatter Al-Mn master alloy was added. It can be
implied from Figure 5 that the Fe-Al nucleant particles have a
very similar potency to the native nucleant particle (Al4C3),
while e-AlMn is more potent than Al4C3. However, there are
only two data points used to plot the Fe addition line and
therefore any conclusions drawn regarding the potency or
type of the particles responsible for the observed grain refinement when Fe is added, are unreliable.

3.2. Grain Refinement by Zr

The addition of Zr to Mg alloys that do not contain Al,
results in very good grain refinement. This is because Zr dissolves such that very high values of Q are generated by only
a fraction of one percent of soluble Zr while leaving high
potency particles of Zr undissolved which have an excellent
orientation relationship with the magnesium matrix.[15]
The interpretation of grain refining mechanisms from
grain size data can be misleading because the soluble Zr and
the number of Zr particles present in the melt are not independent variables.[15] Although the soluble Zr content can be
analyzed, determination of the number of Zr particles
requires detailed metallography to count the number of Zr
particles visible in a cross section.

Despite this limitation useful information can still be

gained by making assumptions based on the requirement that
linear relationships between grain size and 1/Q must exist
along the lines illustrated in Figure 1. To test this idea data
from a set of experiments were analyzed in a recent paper[15]
which provided information on a number of factors affecting
the performance of Zr as a grain refiner and is described to
show how the new methodology can reveal new information,
even when there is unclear information and data with which
to work.
In this example the new methodology is applied to Zr
additions to qualitatively show the effect of stirring, settling
and Zr loss on grain size. Figure 6 is a schematic representing
the changes in grain size that can occur on the addition of Zr
to an alloy designated as A. Alloy A sits on a line of slope b
as the nucleants naturally present in the unrefined alloy have
poor potency and the intercept a has a large value as there are
few particles that activate the nucleation of grains. The
change from A to B occurs when Zr master alloy is added to
the melt but before stirring is applied. The grain size decreases due to the release of a few Zr particles but Q does not
change significantly as little dissolution of Zr has occurred.
However, alloy B sits on a line of slope b due to the addition
of more potent particles. When stirring is applied the Zr particles are distributed throughout the melt causing the grain size
to decrease further to point C. In addition stirring enhances
the dissolution of Zr dramatically causing Q to increase and
the grain size to decrease along C to D. It is likely that these
last two effects occur simultaneously with the grain size following a line between B and D. If further Zr master alloy is
added then the grain size will follow the line between D and
E as the extra grain refiner will add both dissolved Zr and Zr
particles. Further addition from E to F brings the soluble Zr to
the maximum solubility limit according to phase equilibria.
Further additions of master alloy beyond F will decrease the
grains size but Q will not increase further.
If a stirred melt of composition D is left to sit then settling
of Zr particles will occur increasing the grain size to G. Dur-

A
Solubility
limit of Zr

Base alloy
containing
no Zr

b'

Grain size

b''
G

Base alloy with

Zr particles

Settling

D
Zr in solution (0.5%)

E
F

1/Q
Fig. 5. Grain size versus 1/Q for a range of Mg-Al alloys where L0 is for commercial
purity alloys, Lhp for high purity alloys, LFe for high purity alloys with the addition of
Fe and LMn for high purity alloys with the addition of Mn. Data are from References
[27,28]. For each alloy Q was calculated using Equation 1.

ADVANCED ENGINEERING MATERIALS 2007, 9, No. 9

Fig. 6. A schematic representation of the changes in grain size during the addition of
Zr master alloy to a Mg-0.5 %Zn alloy as a function of the value of 1/Q, the potency of
nucleant particles, b, and the number of active nucleant particles. An elaboration of this
model is provided in the text. After [15].

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istry between the nucleant particle and the magnesium phase

and/or the contact angle.

ing settling, the value of Q should remain constant unless Zr

in solution reacts with Fe from the crucible walls or is oxidised. If this occurs then Q decreases due to a loss of soluble
Zr taking the grain size from G to H. These reactions will be
more likely if the melt is held at high temperature for long periods. Assuming no deleterious reactions occur and the melt
is restirred after settling has occurred the grain size will then
decrease from G back to D.
To test the predictions of Figure 6 experiments were carried out on a Mg-0.5 %Zn alloy. The steps from A to B, D, E, F
and G were carried out as described in the caption for
Figure 7. It was found that the grain size changes observed
correspond very well with the predictions of the schematic
representation given in Figure 6. The soluble Zr contents of
the samples were analysed and Figure 7 also plots the measured grain size against 1/Q calculated from the analysed Zr
contents. Good agreement with the model illustrated in
Figure 6 is obtained. Because of the variation in insoluble Zr
content amongst the samples analysed it was not possible to
calculate the value of b for Zr particles. A more extensive set
of experiments is required. To be able to reduce the cost of Zr
addition we need to quantify the relationships to obtain
values for b and a and relate them to actual soluble and insoluble Zr contents. This information will allow calculation of
the exact amount of Zr addition needed to deliver the required grain size and definition of the processing conditions
to prevent wastage due to settling and reaction with the crucible walls and the atmosphere.

3.3. Grain Refinement by the Addition of SiC Particles

The new methodology was also recently applied to SiC
particles[30] and it was found that SiC particles were moderately good nuclei for commercial purity Mg-Al alloys (Fig. 8).
The SiC particles were more effective than the native nuclei
in the alloys and were particularly efficient at grain refining
Mg-1Al where the native grain size was very large. Interestingly, despite the grain size results that indicated stable nucleation behaviour, microstructural analysis showed that the
SiC particles decomposed in the melt. This observation is
supported by other work,[31] which proposes that the SiC particles convert to Al4C3. Further support for this proposition
could have been provided if the grain size measurements
were taken from samples cast under exactly the same conditions as the experiments described in Sections 3.1.1 and 3.1.2.
Because the casting conditions were different the a and b values cannot be compared directly.

4. Discussion

The above examples show that by plotting the grain size

data in the form of a + b/Q information can be gained about
the relative potency of particles and the number of these particles that can act to nucleate grains. This methodology also
shows how sensitive the grain size is to changes in the constitution of the melt as defined by Q. Additionally, it can reveal
the relative effect of changing the value of b (i.e. particles of different potency) or increasing the number
700
A
of particles on the grain size achieved.
Base alloy
600
However, this work shows that to be able to
containing A
no Zr
compare
alloys, alloy systems, master alloys,
500
Solubility
types
of
particle
additions and the amount of parlimit of Zr
400
ticles
added
a
constant
set of casting conditions
G
B
B
300
needs to be used and a consistent or common
200
method of calculating the value of Q. Our early
G
100
work did not do this so we cannot directly comE
D
F
pare the results from aluminium alloys with those
0
F
0.1
0.2
0.3
0.4
0
of the magnesium alloys or between work by dif1/Q
ferent research groups. After considering this diE
D
lemma, the casting conditions that would be suitable as a standard test, are based on the set up
used for thermal analysis developed by Bckerud.[32] This set of casting conditions and experiFig. 7. Experimental assessment of the model presented in Figure 6 on a Mg-0.5 %Zn alloy. Micrograph A corresponds to point A on Figure 6 and has a grain size of 590 lm. Micrograph B with a
mental arrangement also prevents the formation
grain size of 350 lm was obtained after 0.5 %Zr was added to the melt in the absence of stirring.
of chill crystals which are the result of thermal unAfter 2 min. of stirring the grain size further decreased to 110 lm (micrograph D) due to dissolution
of Zr (increasing Q) and a more even distribution of Zr particles. Micrograph E is the result of a
dercooling. However, this casting arrangement
further addition of 0.5 %Zr (total 1 %Zr) that increases Q towards the solubility limit and adds extra
uses a graphite crucible which would not be suitZr particles together reducing the grain size to 54 lm, and micrograph F results from another 1 %Zr
able for magnesium alloys. A possible modificaaddition (total 2 %Zr) which brings Q close to the solubility limit and increases the number of Zr
particles further reducing the grain size to 27 lm. Micrograph G shows the effect of holding the melt
tion would be to use a preheated steel crucible
that produced D for 2 hrs without stirring. The settling of Zr particles causes the grain size to reduce
that delivers a cooling rate of 1 C/s. An addito 200 lm. When the melt is re-stirred for 2 min the grain size returns to 110 lm. The alloys were
melted in an aluminium titanite crucible and the sampling temperature was 730 C. In the centre of
tional advantage of this casting method is that it
the figure the experimentally determined grain sizes plotted against 1/Q calculated from the meacan be used with little modification to determine
sured soluble Zr contents for alloys A, B, D, E, F and G. There is good agreement with the schematic
representation in Figure 6. After [15].
the effect of cooling rate, mould temperature, etc.
Grain Size (microns)

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StJohn et al./A New Analytical Approach to Reveal the Mechanisms of Grain Refinement

Grain Size (m)

700
no addition
SiC1
SiC2

600
500

1Al

400

2Al

300

6Al

200

3Al

9Al

100
0
0

0.05

0.1

0.15

0.2

0.25

1/Q (1/K)
Fig. 8. The grain sizes plotted against 1/Q for the alloys. SiC1 refers to a 0.15 wt%
addition of SiC and SiC2 refers to a 0.3 wt% addition of SiC. After [31]. For each alloy
Q was calculated using Equation 1.

on grain size and whether or not chill crystals are making a

contribution to the measured grain size.
In order to be able to accurately compare grain refinement
performance between different alloy systems it is also important that the method used to calculate Q is standardized or
conversion of data between methods is possible. There are
three methods for calculating Q. One method is to use Equation 1. This method is often suitable for simple binary systems. It can also be used for multiple alloying elements to
gain a good estimate in many dilute multi-component systems. Equation 1 assumes that the liquidus and solidus lines
are linear and that there is no chemical interaction between
the alloying elements and that Q is simply an additive of the
binary values of Q for each element. To overcome this problem it is better to use a thermodynamic modeling package.[23,33] This is particularly important in some less dilute
systems where the additive approach can be inaccurate.[20]
Although there are good thermodynamic databases for aluminium alloys, databases for other alloy systems may be inadequate. Over time these databases will be developed. The
third method can be applied where a thermodynamic database does not exist or where there is doubt about the values
of Q obtained by Equation 1 or a thermodynamic modeling
package. This method requires microprobe analysis to be undertaken to measure the partitioning of the solute elements as
illustrated elsewhere.[34] Ideally, it would be preferable to
standardize on the use of a suitable thermodynamic modeling
package as this would remove the need to undertake microprobe analysis and the use of Equation 1 with its inherent
simplifications.
To be able to have confidence in the values of a and b, at
least five data points are needed over a sufficient range of Q
values. However, as seen from this work useful information
can be obtained from three data points over a broad range of
Q values but any less is unreliable. Sometimes it can be difficult to have a sufficiently broad range of Q values when the
solubility of alloying elements in the melt is low.
There are potential problems that need to be considered
when examining the results which relate to situations where
the particle numbers are not known or they are not stable. For

ADVANCED ENGINEERING MATERIALS 2007, 9, No. 9

example, the added particles may dissolve to some extent

and thus the value of Q may change and also particle numbers may be affected (e.g. Zr as illustrated in Fig. 7, and SiC).
Also, the addition of particles may add impurities that can
poison the potency of particles as is suspected to be the factor
reducing the potency of particles added to commercial purity
Mg-Al alloys. In these cases the analysis can still provide useful insights into the mechanisms occurring even if the actual
values of a and b are not accurate.
If the above points are taken into consideration then the
data obtained from experiment can be compared and conclusions drawn on the nature of the potency of the nucleant particles and the effectiveness and efficiency of master alloys.
Also, comparisons can be made between different alloy systems to determine their potential for grain refinement. For
example, aluminium alloys are generally considered to be alloys that are very responsive to the addition of potent master
alloys. However, it can be noted by comparing the grain size
results of aluminium and magnesium alloys that magnesium
alloys can be refined to much smaller grain sizes (e.g. 40 lm
compared with 100 lm). This is supported by the low values
of a indicating that Mg-Al alloys have a very large number of
nucleant particles naturally present in the melt.
As concluded above, a constant set of casting conditions is
necessary for valid comparisons. However, changes in cooling rate, mould material and casting design are likely to have
a significant effect on the contribution of constitutional supercooling and thermal undercooling to the formation of grains
in the bulk of the melt as well as the formation of chill crystals. These aspects will be investigated in future work.
Despite improvements to the conceptual framework and
analytical skills for examining grain refinement there are still
many questions remaining unanswered. It is likely that the
study of grain refinement of magnesium alloys will continue
for some time as has occurred in the study of grain refinement of aluminium alloys. The methodology presented in this
paper provides a unique tool to maximize the information
arising from further studies.

5. Conclusions
A new grain refinement assessment method is presented
where grain size measurements are plotted against the inverse of the growth restriction factor Q. The examples provided in this paper show that the new analytical methodology provides information on:
the relative potency of naturally occurring and deliberately
added nucleant particles as well as the maximum number
of particles (and the proportion of particles added via master alloys) that can activate the nucleation of grains;
the result and possible mechanisms of poisoning of grain
refinement by alloying or impurity elements;
the mechanisms underlying unexplained phenomena reported in the literature.

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StJohn et al./A New Analytical Approach to Reveal the Mechanisms of Grain Refinement
However, in order to be able to compare the results of experiments undertaken on different alloys, alloy systems and
master alloys, a common set of casting conditions and a common method of calculating Q are required. It is recommended
that the thermal analysis developed by Bckerud be modified
so that a constant cooling rate of 1 C/s is delivered by a preheated or coated steel crucible. Further work needs to be done
to define the exact casting apparatus to ensure that different
alloy systems can be compared. Additionally work needs to
be undertaken to gain an agreed method of calculating the
growth restriction factor Q that is accurate and easily performed.

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