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Directional solidification of metal-gas eutectic and fabrication of regular

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 Vol.2 No.3. Aug. 2005 CHINA FOUNDRY

Directional solidification of metal-gas eutectic

and fabrication of regular porous metals
*Yuan LIU, Huawei ZHANG, Xiang CHEN, Yanxiang LI
(Key Laboratory for Advanced Manufacturing by Materials Processing Technology, Dept. of Mechanical Engineering,
Tsinghua University, Beijing 100084, P. R. China)

Abstract: Directional solidification of metal-gas eutectic (Gasar) is a novel process for making regular porous metals.
This process is based on a solid-gas eutectic reaction involving a gaseous medium and a metal or a ceramic phase, and
allows an easy control of the porosity, such as its pore size, pore orientation and morphology in a wide range by properly
adjusting its melting and solidification conditions. The latest progress and our research work in this field are reviewed in
this paper.

Keywords: metal-gas eutectic; unidirectional solidification; Gasar process; porous metals

CLC number: TG249.9 Document: A Article ID: 1672-6421(2005)03-0184-04

1. Introduction materials manufacturing technologies. This method got its

Porous and foamed metallic materials have become an fame in 1993, after that it was successfully tested and
[3-17]
attractive research field from either the scientific studied in Ukraine, USA, Japan, and China . This
viewpoint or the industrial application prospect, because paper is to introduce our research work in this field.
they exhibit many special combinations of physical and
mechanical properties, such as impact energy absorption 2. Gasar principle
capacity, air and water permeability, unusual acoustic This processing technique utilizes an invariant reaction
energy absorption ability, lower thermal conductivity etc [1]. of the so-called 'metal-gas eutectic transformation' in
Various fabrication methods for porous materials have which the melt is solidified into a solid solution and a gas
been developed. They include the foaming method with phase [18], as shown in Fig.1, which is similar to the
gas bubbling, the vapor deposition or electro-deposition of traditional eutectic transformation (two solid phases
metal onto a polyurethane foam precursor, the powder formed from one liquid phase). Numerous Metal-Hydrogen
sintering method and so on. The spatial distribution of binary systems, including Al-H, Cu-H, Fe-H, Mg-H,
pores in the porous materials fabricated by these methods Mn-H, Ti-H, Co-H, Be-H, Cr-H, and Ni-H, etc, exhibit
is usually random. Just in 1993, a Ukraine scientist this kind of gas-eutectic transformation. Some Metal-Oxyg-
Shapovalov presented a new method in his patent applied en (Ag-O; Fe-C-O; Cu-O), Metal-Nitrogen systems (Fe-N;
in America for producing a new type of porous metals Ni-N; Mn-N) and some kind of ceramic saturated with
whose long cylindrical pores are in an ordered structure [2]. hydrogen, nitrogen or oxygen are also perspective for the
This method was called 'Gasar' process in which an application of the Gasar process.
invariant reaction of the so-called 'metal-gas eutectic
reaction' was utilized to fabricate regular porous structure.
Gasar metals with different porosity and structure may be
synthesized for filters, metal-matrix composites, bearings,
[3]
brakes, damping elements etc . Compared with
traditional fabrication techniques, this process allows an
effective control of porosity, pore morphology and pore
orientation, so it was thought as the revolutionary method
and should be distinguished as a new direction in porous

*Yuan LIU: Ph.D., being mainly engaged in fabrication of porous

materials, alloy materials and solidification technology.
E-mail: yuanliu@tsinghua.edu.cn
Fig.1 Schematic phase diagram for a metal-hydrogen system
[Received date] 2005-02-23; [Accepted date] 2005-05-20
 Vol.2 No.3 Directional solidification of metal-gas eutectic and fabrication of regular porous metals
Like the traditional eutectic transformation, during the
directional solidification process, the gas-eutectic transfo-
rmation may result in the formation of ordered structure
with two phases one of which is gaseous. This method
demands a specific apparatus.
Figure 2 shows a typical apparatus developed by the
authors in the study for making Gasar porous metals. The
main part of the apparatus contains a crucible, a heating
coil and a cylindrical mould with a water cooled copper
plate at the base which are all housed in a high-pressure
vessel.
1.Graphite stopper; 2. High pressure chamber;
3. Heating coil; 4. Molten metal; 5. Graphite crucible;
6. Ceramic mould; 7. Copper chiller; 8. Cooling water
Fig.2 A schematic of the fabrication principle and
apparatus for Gasar metals
The apparatus makes it possible to melt metals in a
crucible and to solidify them in a casting mould under
controllable gas pressure (typically 1-50 atmospheres). By
changing the partial pressure of H2, variable concentrations
of hydrogen in the melt are obtained.
Fig.3 Gasar magnesium (Lotus-type structure) with axial pores distribution ( P H 2 =0.2 MPa, P A r =0.1 MPa, T=1 023 K)
During the following directional solidification process,
as the metal solidifies, the solubility of the hydrogen
dissolved in solid goes through a sharp decrease,
compared with that in liquid, and then the gas bubbles
form as a result of the supersaturated hydrogen isolated
from the solid metal. If the process parameters get
controlled properly, the growth of the bubbles advances
concurrently with the solid and does not leave from the
solidification front, thus the porous structure gets formed.
3. Gasar structure
Depending on variable heat releasing direction, it is
possible to form Gasar structure with axial or radial pore
orientation. As shown in Fig.2, if the bottom plate of the
mould is cooled, the melt poured into the mould is
solidified upward from the bottom and simultaneously the
gas pores grow along the axial direction, too. This kind of
regular porous structure with an axial pore distribution is
also called as lotus-type porous metal or lotus metal
because it looks like lotus roots. Figure 3 shows a typical
lotus-type of porous magnesium sample produced by the
authors. If the lateral surroundings of the mould are
applied by cooling, the melt is solidified inwards and the
pores grow along the radial direction. Figure 4 shows a
typical regular porous magnesium sample with a radial
pore distribution produced by the authors, too.
A few general observations from the Gasar structure
under the study are:
The pore size distribution is non-uniform because of
concurrent growth of small and large pores and
coalescence.
No branching of pores is ever observed to occur.
No pores are nucleated on the mould surface and a non-
porous metal skin in the range of 0.05-5mm thickness
forms first.
Porosity 10%-55% and pore diameters 10-1 500 μm.
Pore shape: cylindrical, spherical, and ellipsoidal.
 CHINA FOUNDRY Aug. 2005

Fig.4 Gasar magnesium with radial pores distribution ( P H 2 =0.2 MPa, PAr =0 MPa, T=1 023 K)

4. Control of porosity and pore size
The average porosity of the entire ingot is measured
through Archimedes' principle. The average pore size is
evaluated by an image analysis system. Generally, for the
Gasar structures with an axial or radial pores distribution,
the porosities at different sites of the ingots produced in
the study are approximately homogeneous and have
insignificant deviation from the measured average
porosity of the entire ingot. In addition, the distribution of
average pore sizes also has less significant fluctuation at
different positions of the produced ingot.
In Gasar solidification, besides the hydrogen, inert gas
such as argon is often added to the Gasar apparatus. The
addition of inert gas can realize the adjustment of the final
porosity, the average pore size as well as the pore size
distribution scope. The gas pressure is a very powerful
technological parameter for the process and it is
adjustable to achieve many different kinds of porosities
and pore sizes, as shown in Figs.5-6. In contrast,
solidification velocity and pouring temperature are less
effective parameters in Gasar process. Figure 5(a) and (b)
show the experimental porosities together with the
predicted ones on the Mg/H2 system. It can also be found
that:
The porosity decreases with increasing partial pressure
of hydrogen when only single hydrogen is used.
The porosity increases with increasing partial pressure
of hydrogen when the total gas pressure keeps constant.
The porosity decreases with increasing partial pressure
of argon when the partial pressure of hydrogen keeps
constant. As shown in Fig.6, the mean diameter Dm of
pores is mainly dependent on the total solidification
pressure Ps under the same pouring temperature and
cooling conditions, namely Dm decreases with the increase
of the solidification pressure.

Fig 5 The experimental porosities (the scattered circle dots) of lotus-type porous magnesium under different partial pressures of
hydrogen and argon. The solid line shows the predicted porosities by the model developed by the present authors in
reference[15]
 Vol. 2 No. 3 Directional solidification of metal-gas eutectic and fabrication of regular porous metals
[2]
[3] V. I. Shapovalov and L.V. Boyko. Gasar- A new class of porous
[4] V. I. Shapovalov. Structure formation behavior of alloys during
Fig.6 The evolution trend of the mean diameter of pores
in lotus-type magnesium with the solidification
pressure Ps (Ps=PH2+PAr), T=1 023 K
5. Summary
Gasar technology is based on a new scientific
knowledge about gas-eutectic reaction in metal-gas
system. Although the researches in this field have been
carried out for 12 years in several countries, unfortunately,
a well understanding on Gasar's manufacturing parameters
as well as its processing control system has not been
established, yet. The current research on the Gasar process
has just been carried out for 3 years by our group. The
Gasar structures with axial and radial pore distribution
have been fabricated successfully with an apparatus
developed by the authors in the study. The experimental
results indicate that the gas pressure is a very powerful
technical parameter that can be applied to achieve various
kinds of porosities and pore sizes. In contrast, the
parameters such as solidification velocity and pouring
temperature are less important and relatively ineffective
for the Gasar process.
Acknowledgments
The present research was supported by the Natural
Science Foundation of China (No.50404002) and
National Program on Key Basic Research Projects (No.
2004CCA05100).
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