Scripta Materialia, Vol. 41, No. 12, pp.

12551259, 1999
Elsevier Science Ltd
Pergamon Copyright 1999 Acta Metallurgica Inc.
Printed in the USA. All rights reserved.
1359-6462/99/$see front matter
PII S1359-6462(99)00297-3

EQUATIONS FOR NUCLEATION OF HYDROGEN GAS PORES

DURING SOLIDIFICATION OF ALUMINIUM SEVEN WEIGHT
PERCENT SILICON ALLOY
R.C. Atwood, S. Sridhar and P.D. Lee
Department of Materials, Imperial College of Science, Technology and Medicine, London, UK
(Received June 30, 1999)
(Accepted in revised form August 9, 1999)

Keywords: Casting; Alloys, aluminium; Phase transformations, nucleation; Porosity

Introduction

Producing metallic parts for aerospace and automotive industries in as-cast shapes is both less expensive
and faster than many competitive manufacturing techniques. However, the occurrence of casting defects
such as porosity limits the use of cast parts especially in high tolerance applications. Pores are
detrimental to the final properties of the casting, acting as possible initiation points for fatigue cracks.
Although it may not be possible to completely eliminate these defects, the ability to predict the size,
quantity and location of pores allows more accurate prediction of the final properties and the useful
service life of cast parts. Development of solidification models that predict defect formation is vital to
the improvement of cast product quality.
Porosity is usually caused by either volumetric shrinkage (shrinkage porosity) or dissolved gas (gas
porosity) and while the former has been extensively studied [13], there still remains little information
available on gas porosity evolution. The formation of gas porosity is a nucleation-limited process and
the precise mechanism of pore nucleation is not well understood. According to classical nucleation
theory, the required conditions for homogeneous nucleation of pores are quite far from the observed
conditions for pore formation. Heterogeneous nucleation theories require more detailed information
about the features responsible for the nucleation than are usually available. In this work an empirical
approach is followed to produce usable equations that reproduce the behaviour of the material and
which may then aid in predicting the formation of gas porosity within solidification models. The
approach of Charbon and Rappaz [4] for grain nucleation during solidification is used to provide the
form of the equations. Some possible explanations of the observed behaviour are also presented.
One of the authors [5] has previously presented direct observations and analysis of the growth of
hydrogen pores using an X-ray temperature gradient stage (XTGS) during solidification. Al-Cu alloys
were chosen for the high interphase X-ray contrast. The present work uses similar observations from
experiments carried out on aluminium seven-weight-percent silicon (Al7Si) alloy, chosen for its
similarity to an important class of aluminium casting alloys. Statistical analysis of the nucleation
behaviour has been performed in order to determine equations for the prediction of hydrogen pore
nucleation of a similar form to those proposed by Charbon and Rappaz [4] for grain nucleation. The
equations are fitted to in situ radiographic observations and the effect of cooling rate is investigated. The

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1256 RATE EQUATIONS FOR NUCLEATION OF HYDROGEN GAS PORES Vol. 41, No. 12

TABLE 1
Nominal Composition of the A17Si alloy (Tl 618C, Ts 577C [7])
Element Al Si Cu Fe Mn Ti Ni Zn V

wt.% Balance 7.05 0.019 0.16 0.031 0.010 0.012 0.004 0.004
0.2 0.003 0.02 0.004 0.002 0.002 0.001 0.001

empirical parameters thus determined may readily be incorporated into deterministic or probabilistic
computer models for solidification simulations in order to reproduce the observed nucleation and
growth behaviour of hydrogen pores in this material.

Experiment and Analysis

Recently, in situ radiography was used to detect and track pore evolution in AlCu alloys [6]. This same
technique, using an XTGS, was used to track pore evolution in Al-Si alloy of composition listed in
Table 1. Digital video sequences were analysed automatically as described previously [5] to obtain a
nucleation temperature for each pore. The experiments considered were carried out over a range of
thermal gradients from 4.7 to 6.3C/mm and over a range of growth velocities from 0.14 to 0.53 mm/s.
This relatively narrow range of thermal gradients resulted from imprecise control; the intent was to use
a fixed gradient and vary only the growth velocity. The hydrogen level was controlled by bubbling
Ar-H2 mixture through the melt in order to reach a concentration of 25% of the equilibrium solubility
of H in the alloy.
Figure 1 shows the variation of size versus temperature for several individual pores for a typical
experiment using a thermal gradient, G, of 6.3C/mm and a growth velocity, V of 0.51 mm/s. The
temperature at which nucleation of the bubbles occurred was estimated by extrapolating the curve for
each pore to zero radius. For each experiment a statistically significant number of pores (50 150) was
detected and tracked. The projected nucleation temperatures were binned in divisions of 2C and
Gaussian curves were fitted to the nucleation histogram as a function of average cooling rate for each
experiment. The low temperature side of the histograms were clipped before analysis. The clipping was
performed because the diffraction of the X-rays from the advancing eutectic interface were observed to
interfere with the transmitted signals, producing a higher background noise level. This caused some
bubbles to become temporarily undetectable and their reappearance was incorrectly identified by the
analysis software as nucleation events. The final pore density, the mean nucleation temperature, and the

Figure 1. Experimental traces of pore size as a function of temperature for a few of the pores tracked during a typical experiment,
with a temperature gradient G 6.3C/mm and growth velocity V 0.51 mm/s; thus the cooling rate was R 3.2C/s.
Vol. 41, No. 12 RATE EQUATIONS FOR NUCLEATION OF HYDROGEN GAS PORES 1257

TABLE 2
Experimental Conditions and Results
Experiment V G R nmax TN T
Number mm/s C/mm C/s mm3 C C

1 0.30 6.0 1.8 0.85 601 3.4

2 0.14 5.6 0.8 0.06 602 6.6
3 0.27 6.3 1.7 0.94 597 5.5
4 0.53 4.7 2.5 1.21 592 4.7
5 0.15 6.3 0.9 0.17 607 4.3
6 0.50 5.5 2.7 0.91 589 4.2
7 0.28 6.0 1.7 1.06 595 5.1
8 0.49 6.1 3.0 1.42 589 3.1
9 0.14 6.2 0.9 0.38 598 6.1
10 0.29 6.0 1.7 0.38 600 5.2

nucleation temperature deviation for ten experiments using non-grain-refined, unmodified Al7Si alloy
(equilibrium liquidus, Tl 618C; equilibrium solidus, Ts 577C [7]), were used to fit prediction
functions as described below. The data used are summarised in Table 2.

Results and Discussion

Charbon and Rappaz [4] used a normalised Gaussian function to describe grain nucleation during
solidification. A similar approach was applied to pore nucleation with the following function describing
the nucleation of pores:
dn p
dT

n max
T 2
exp
T T N 2
2T 2 (1)

where nmax is the maximum number of nuclei, which could be a function of the total available number
of heterogeneous nucleation sites. T and TN are the deviation and the mean respectively of the Gaussian
temperature distribution function.
The parameters are expected to vary with cooling rate. Figure 2 shows the cooling rate (R)
dependence of the three parameters for non-grain refined samples and the numerical parameters derived
by a least-squares fitting are given below,
n max 0.16 0.51R; R 2 0.74 (2)
T N 0.61 10 3 6.43R; R 2 0.73 (3)
T 6.55 0.98R; R 2 0.47 (4)
where the range of applicability is 0.8 R 3C/s and the significance of fit indicated by the
coefficient of correlation, R2.
Figure 3 shows a histogram of the experimentally observed pore sizes for a typical experiment
compared with a Gaussian distribution fitted to the histogram and a Gaussian distribution derived from
the fitted parameters as shown in Figure 2. There is some noticeable mismatch in Figure 3; this is
expected as the parameters determined by the fitted equations do not exactly match any of the
experimental points. In particular, the spread of the data in Figure 2(b) and (c) is greater for the lower
cooling rate experiments. In these experiments, there were fewer pores available for tracking and hence
1258 RATE EQUATIONS FOR NUCLEATION OF HYDROGEN GAS PORES Vol. 41, No. 12

Figure 2. (a) Maximum pore density, nmax, (b) mean nucleation temperature, Tn, and (c) nucleation temperature distribution
spread, T, as functions of cooling rate R. The parameters of the linear fits shown are given in equations 2 4.

the statistical significance was reduced, as indicated by the low R2 value in Equation 4. It should be
emphasised that while equations (2)-(4) have low regression factors, they are a first attempt to simulate
the experimental trend of the influence of the cooling rate on the statistical parameters that govern the
nucleation equation (1).
The cooling rate R was used as the independent variable as it is inversely proportional to the local
solidification time (ts) for the sample geometry and thermal profile of these experiments. Previous
studies of the Al-Cu system [6] used a range of gradients and velocities and the results were analysed
statistically using multiple linear regression. The statistics showed that ts (and hence R for these
conditions) was a better predictor of the pore nucleation than either the thermal gradient G or the growth
velocity V alone. In the Al7Si experiments presented the thermal gradient is almost invariant hence the

Figure 3. Histogram of nucleation temperatures of pores determined during the experiment as in Figure 1 (bars), fitted with a
Gaussian distribution (thin line) and compared with the Gaussian distribution predicted by the model (thick line).
Vol. 41, No. 12 RATE EQUATIONS FOR NUCLEATION OF HYDROGEN GAS PORES 1259

velocity V and the cooling rate R are almost in a linear relationship, hence either V or R would give an
equally good fit.
Although the Gaussian fit shows reasonable agreement with the experiment, this is not the behaviour
predicted by classical heterogeneous nucleation theory [8]. It is important to emphasise that these curves
are representative of the observed nucleation of the pores, rather than the total number of potential
heterogeneous nucleation sites and their activity. The number of potential nucleation sites as function
of undercooling should rise as the undercooling increases. However, once a few gas pores have
nucleated, the available hydrogen will begin to decrease due to diffusion into the growing pores. This
reduction in available hydrogen causes a decrease in the rate of nucleation as time progresses and the
existing pores grow. The combination of these effects may result in the observed behaviour the rise
due to increased undercooling dominates in the early stage and the drop due to depletion of hydrogen
dominates in the later stage. Hence the empirically derived nucleation functions presented here do not
represent a property of the material, rather they are a combination of the properties of the material and
the applied conditions.
The statistical significance of the measurements was limited at both extremes of the experimental
range. At slow growth velocities and shallow thermal gradients, the number of pores within the
observable sample volume was too low to obtain a good statistical analysis, whereas at high growth
velocities and steep thermal gradients the average size of the pores was too small to be accurately
resolved.

Summary

A statistical prediction model has been applied to the nucleation rate as a function of temperature for
an Al7Si alloy based upon observations of pore formation during solidification in an XTGS. A
normalised Gaussian function was developed (Equations 1 4) which may be used to describe pore
nucleation in mathematical simulations of porosity formation during solidification.

Acknowledgments

The authors would like to thank Alcan Internationals Kingston Research and Development Centre for
supporting the experimental part of this study, and the EPSRC for funding the analysis of this research
under grant GR/L88351 and for funding in part the computational facilities used for the digital video
analysis under grant GR/L86821.

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3. J. Huang and J. G. Conley, in Modeling of Casting Welding and Advanced Solidification Processes VIII, ed. B. G. Thomas,
C. Beckermann, TMS, Warrendale, PA (1998).
4. C. Charbon and M. Rappaz, Mod. Sim. Mater. Sci. Eng. 1, 455 466 (1993).
5. P. D. Lee and J. D. Hunt, Scripta Mater. 36, 399 404 (1997).
6. P. D. Lee and J. D. Hunt, Acta Mater. 45, 4155 4169 (1997).
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