Manufacture, characterisation and application of cellular metals and metal foams

1. Introduction

Foams and other highly porous materials with a cellular structure are known to have many interesting
combinations of physical and mechanical properties, such as high stiffness in conjunction with very low
specific weight or high gas permeability combined with high thermal conductivity. For this reason, nature
frequently uses cellular materials for constructional or functional purposes (e.g. wood or bones). Among man-
made cellular materials, polymeric foams are currently the most important ones with widespread applications
in nearly every sector of technology. Even metals and alloys can be produced as cellular materials or foams
and that these materials have such interesting properties that exciting new applications are expected in the
near future.

The term “foam” is not always properly used and shall therefore need to be defined. According to Fig. 1
which lists the designations for all possible dispersions of one phase in a second one (where each phase can be
in one of the three states of matter), foams are uniform dispersions of a gaseous phase in either a liquid or a
solid. The single gas inclusions are separated from each other by portions of the liquid or solid, respectively.
Thus the cells are entirely enclosed by the liquid or solid and are not interconnected. The term “foam” in its
original sense is reserved for a dispersion of gas bubbles in a liquid. The morphology of such foams, however,
can be preserved by letting the liquid solidify, thus obtaining what is called a “solid foam”. When speaking of
“metallic foams” one generally means a solid foam. The liquid metallic foam is merely a stage that occurs
during the fabrication of the material. Solid foams are a special case of what is more commonly called a
“cellular solid”. As in a liquid the minimisation of surface energy only allows for certain foam morphologies,
the solid foam, which is just an image of its liquid counterpart, is restricted in the same way. In contrast,
cellular solids are not necessarily made from the liquid state and can therefore have nearly any morphology,
e.g. the typical open structure of sintered powders. Often such porous structures are also named “foams”
although the term “sponge” is likely more appropriate. In this paper some emphasis is placed on the
production methods and properties of “true” solid foams, but it is felt that the review would be incomplete
without including some methods for producing those cellular metallic structures which are not considered as
foams in the strictest sense.

Fig. 1. Dispersions of one phase into a second one. Each phase can be in one of the three states of matter.
2. Production methods of cellular metallic materials

There are many ways to manufacture cellular metallic materials. The various methods can be classified
according to the state the metal is processed in. This defines four “families” of processes summarised in Fig.
2, each one corresponding to one of the states of matter: one can start

(i) from liquid metal,

(ii) from solid metal in powdered form,
(iii) from metal vapour or gaseous metallic compounds,
(iv) from a metal ion solution.

Fig. 2. Overview of the various “families” of production methods for cellular metallic materials.

2.1. Liquid state processing of cellular metals

A first group of processes creates the cellular structure from the liquid metal. The molten metal is processed
into a porous material either by foaming it directly, by using an indirect method via a polymer foam or,
finally, by casting the liquid metal around solid space holding filler materials which reserve space for what
after further processing becomes the pore space. One further possibility is to melt powder compacts
containing a gas-releasing blowing agent.

2.1.1. Direct foaming of metals

Metallic melts can be foamed directly under certain circumstances by creating gas bubbles in the liquid.
Normally, gas bubbles which are formed in a metallic melt tend to quickly rise to its surface due to the high
buoyancy forces in the high-density liquid, but this rise can be hampered by increasing the viscosity of the
molten metal. This can be done by adding fine ceramic powders or alloying elements which form stabilising
particles in the melt.

Numerous attempts to foam liquid metals in this way — mostly aluminium, magnesium, zinc or alloys based
on one of these metals — have been undertaken in the 1960s and 1970s. Although some quite good metal
foams were produced, the material did not find its way into real industrial application. It is not entirely clear
whether the process control was still inadequate to yield foams of satisfactory and reproducible quality and
price, or whether the need for materials such as aluminium foams was not big enough 30 years ago. In the past
10 years, however, a number of new developments have taken place so that nowadays some improved
production routes are available.
Currently, there are two ways for foaming metallic melts directly: to inject gas into the liquid metal from an
external source, or to cause an in-situ gas formation in the liquid by admixing gas-releasing blowing agents to
the molten metal.

It is interesting to recall that one of the earliest patents written in the 1940s suggested using a second metal as
a blowing agent, e.g. mercury for foaming aluminium. This second metal is vapourised when heating the
aluminium to its melting point and creates pores this way.

[Link]. Foaming by gas injection

The first way for foaming aluminium and aluminium alloys is currently being exploited by Hydro Aluminium
in Norway and by Cymat Aluminium in Canada (the latter’s using methods and patents originally developed
by Alcan International). According to this process as depicted in schematical form in Fig. 3, silicon carbide,
aluminium oxide or magnesium oxide particles are used to enhance the viscosity of the melt. Therefore, the
first step requires the preparation of an aluminium melt containing one of these substances. The problem to be
solved resembles the one encountered in making ordinary metal matrix composites (MMCs), namely the
problem of wetting the particles by the melt and of achieving a homogeneous distribution of the reinforcing
particles. A variety of aluminium alloys is used, e.g. the casting alloy AlSi10Mg (A359) or wrought alloys
such as 1060, 3003, 6016, or 6061.

Fig. 3. Direct foaming of melts by gas injection (MMC foams)

The liquid MMC melt is foamed in a second step by injecting gases (air, nitrogen, argon) into it using
specially designed rotating impellers or vibrating nozzles. The function of the impellers or nozzles is to create
very fine gas bubbles in the melt and distribute them uniformly. This is an important requirement because
only if sufficiently fine bubbles are created, a foam of a satisfactory quality can be obtained. The resultant
viscous mixture of bubbles and metal melt floats up to the surface of the liquid where it turns into a fairly dry
liquid foam as the liquid metal drains out. The foam is relatively stable owing to the presence of ceramic
particles in the melt. It can be pulled off the liquid surface, with a conveyor belt, and is then allowed to cool
down and solidify. Care has to be taken not to damage the pore structure by shearing the foam too much while
it is still semi-solid. Before solidification, the semi-solid foam can be flattened by means of one or more top-
mounted rolls or belts to yield a foam slab with closed and fairly even upper and lower skins. The resulting
solid foam is in principle as long as desired, as wide as the vessel containing the liquid metal allows it, and
typically 10 cm thick.

The volume fraction of the reinforcing particles typically ranges from 10 to 20% and the mean particle size
from 5 to 20 μm. The selection of particle size and content has been carried out empirically. Too high or too
low contents or particle sizes create the problems addressed in Fig. 5. The particles help to stabilise the foam
by mechanisms which are discussed in the literature. It is widely accepted that the accumulation of particles
on the cell walls plays a key role in this stabilisation process. Firstly, the particles increase the surface
viscosity, thus retarding drainage in films. Secondly, the particles are partially wetted by the melt. It has been
derived that the wetting angle has to be in a certain range to ensure that

(i) the bubble/particle interface is stable when the bubble rises through the melt, i.e. the particles are
not stripped off the bubbles,

(ii) that the particles on the interface lower the total energy of a pair of bubbles with particles in
between, i.e. stabilise bubble/particle/bubble interfaces.

For insufficient wetting (high contact angle) as well as for too good wetting (too low contact angle) there is no
stabilisation effect. In principle, from the known wetting angles of ceramic particles with a given melt
particles can be selected which have an optimum stabilisation effect.

Fig. 5. Selection of particle size and content for foaming MMC melts.

The porosities of aluminium foams produced this way range from 80 to 98%, corresponding to densities
between 0.069 and 0.54 g/cm3, average pore sizes from 25 down to 3 mm, and wall thicknesses from 50 to 85
μm. The average cell size is inversely related both to the average cell wall thickness and to the density and can
be influenced by adjusting the gas flow, the impeller speed or nozzle vibration frequency, and other
parameters. In foamed slabs there is usually a gradient in density, pore size and pore elongation which is a
natural consequence of gravitationally induced drainage. Moreover, the shearing forces of the conveyor belt
lead to diagonally distorted cells in the final product. This obviously has a pronounced effect on the
mechanical properties which become anisotropic. The situation could be improved by pulling off the foam
vertically. The foamed material is either used in the state as it comes out of the casting machine, having a
closed outer surface, or is cut into the required shape after foaming. Owing to the high content of ceramic
particles, machining of MMC foams can be a problem.

Advantages of the direct foaming process include the large volume of foam which can be continuously
produced and the low densities which can be achieved. MMC foams are therefore probably less expensive
compared to other cellular metallic materials. The Canadian company Cymat is about to complete a
production line which will deliver 1000 kg of foam per hour in widths up to 1.5 m and thicknesses between
2.5 and 15 cm. Hydro Aluminium produces slabs 70 cm wide, 8–12 cm thick, and up to 2 m long at a rate of
500–600 kg/h. A possible disadvantage of the direct foaming process is the eventual necessity for cutting the
foam, thereby opening the cells. Also, the brittleness of the MMC foam due to the reinforcing particles
contained in the cell walls is in general an unwanted side effect of the foaming technique. Attempts for
making shaped parts by casting the semi-liquid foam into moulds or by shaping the emerging foam with rolls
have been undertaken, thus trying to eliminate one of these disadvantages.
Powder compact melting technique

 The method was developed at Fraunhofer-Institute in Bremen (Germany)

 The method is called “powder metallurgical” because the starting materials are metal
powders but the actual foaming takes place in the liquid state
 The mixing of metal powders — elementary metal powders, alloy powders or metal powder
blends — with a blowing agent
 The mix is compacted to yield a dense, semi-finished product (compaction can be done by
any technique that ensures that the blowing agent is embedded into the metal matrix without
any notable residual open porosity. Examples of such compaction methods are hot uniaxial or
isostatic compression, rod extrusion or powder rolling. Extrusion seems to be the most
economical method).
 Rectangular profiles with various cross-sections are usually made from which thin sheets can
then be obtained by rolling.
 Heat treatment at temperatures near the melting point of the matrix material is carried out.
 The blowing agent, which is homogeneously distributed within the dense metallic matrix,
decomposes.
 The released gas forces the compacted precursor material to expand, thus forming its highly
porous structure.
 The time needed for full expansion depends on temperature and the size of the precursor and
ranges from a few seconds to several minutes.
 Suitable for Al and its alloys: tin, zinc, brass, lead, gold and some other metals and alloys by
choosing appropriate blowing agents and process parameters.
 The most common alloys for foaming – Pure Al or wrought alloys such as 2xxx or 6xxx.
Casting alloys such as AlSi7Mg (A356) and AlSi12 are also frequently used because of their
low melting point and good foaming properties.
Casting methods

Investment casting with polymer foams

 Foams can be manufactured from molten metal without directly foaming the metal.
 According to this process, a polymer foam, e.g. polyurethane foam, is used as a starting point.
If the polymer foam has closed pores, it has to be transformed into an open porous one by a
reticulation treatment.
 The resulting polymer foam with open cells is then filled with a slurry of sufficiently heat
resistant material, e.g. a mixture of mullite, phenolic resin and calcium carbonate or simple
plaster
 After curing the polymer foam is removed by thermal treatment and molten metal is cast into
the resulting open voids which replicate the original polymer foam structure.
 Application of pressure and heating of the mould may be necessary if no filling of the narrow
cavities with the liquid metal can be achieved in simple gravity casting.
 After removal of the mould material (e.g. by pressurised water), a metallic structure is
obtained which is an exact replicate of the original polymer foam.
 Difficulties in this process include achieving a complete filling of the filaments, controlling
the usually directional solidification and removing the mould material without damaging the
fine structure too much.

Casting around space holder materials

 Light-weight porous metals can be produced by casting liquid metal around inorganic or even
organic granules or hollow spheres of low density, or by introducing such materials into a
metallic melt.
 The granules either remain in the metallic product after casting — yielding what is called a
“syntactic foam” — or are removed by leaching in suitable solvents or acids or by thermal
treatment
 This can be done successfully if the content of space holding fillers is so high that all the
granules are interconnected. Vermiculite or fired clay pellets, soluble salts, loose bulks of
expanded clay granules, sand pellets, foamed glass spheres or aluminium oxide hollow
spheres can serve as inorganic filler material.
 Polymer spheres can be used as organic space holders if the solidification of the melt is
sufficiently fast. The latter requires high pressure infiltration, e.g., in a die-casting machin.
 Pre-heating of the bulk of space holders is usually necessary to avoid premature solidification
of the melt, especially when the heat capacity of the bulk is high or infiltration pressure is
low. Owing to the high surface tension of liquid metals, wetting of the granules might cause a
problem, since, in general, the interstices between the granules will not be filled completely.
Creating a vacuum between the granules or pressurising the melt is therefore an important
pre-requisite for infiltration.
 Space-holding salts are removed by leaching in water.
 A wide range of metals can be processed this way, including aluminium, magnesium, zinc,
lead, tin, etc. Parts of a predefined shape can be fabricated by designing a mould of the
desired geometry. In all cases, the morphology of the materials created can be characterised
as “sponge-like”.