Topic 3 - Cellular Materials-Foams (Part 2)

Department of Materials Science and Metallurgy
Lightweight Materials for

Engineering Applications
Topic 3: Cellular materials/foams

Introduction.
The concept of cellular material and basic cellular parameters.
Classification of cellular materials.
Main properties and applications.
Stages in a foaming process.

Cell nucleation.
Foam growth: chemical foaming/physical foaming.
Foam stabilization.
Main foaming processes.

Continuous/semi-continuous foaming processes.
Batch-foaming processes.
Physical properties of cellular materials.

Mechanical properties: flexible/soft and rigid foams impact absorption.
Transport properties: thermal insulation.
Recent developments.
Main industrial
foaming processes
220036 - Lightweight Materials for Engineering Applications
Topic 3

Flexible PUR foams
Polyurethane foams
Rigid PUR foams
Polystyrene foams (EPS, XPS, etc.)

Polymer foams
Polyvinyl chloride foams

Polyolefin foams
Main foaming
processes
Continuous/semi-continuous
foaming processes
Batch foaming processes
Foaming from powder

Metal foams
Chemical foaming
Foaming from the melt

Physical foaming
Replication
Ceramic foams
Direct foaming
Burn-out

Polymer foams: polyurethane foams
Polyurethane (PUR) foams can be classified into two categories: flexible and rigid
foams. The PUR skeleton consists of polyol and polyisocyanate. Polyols can be
considered as the building blocks while polyisocyanates are the jointing agent. All kinds
of PUR foams are prepared by the proper choice of polyol and polyisocyanate in terms
of chemical structure, proportion and functionality.
The essential raw materials for PUR foams are polyisocyanate, polyol, blowing agent,
catalyst(s) and surfactant(s). In the early development, polyisocyanate-based PUR foams
were polyester-based, but after the 1960s polyether polyol-based foams became the most
representative of both flexible and rigid foams.
Mattresses
Automotive
seating
Packaging
Core of sandwich
panels
Thermal insulation
panels for roofs
Some of the possible applications of flexible PUR foams
Possible applications of rigid PUR foams
Ashida, K. Polyurethane and Related Foams: Chemistry and Technology, Taylor & Francis, Florida, USA, 2007.

Polyurethane foaming:
Basic formulation:
(in-situ mixing)
Polyol + isocyanate + H2O
The polyol(s) allow(s) to control the

expansion degree of the foam, as
well as its flexibility.
(+ catalyst(s) + surfactant(s) +
other additives)
Main types of polyols used in PUR foaming: polyether polyol,

polyester polyol and polyol copolymer
Common isocyanates used in the production o

flexible and semi-flexible/rigid PUR foams

Polyurethane foaming:
Polyurethane polymerization:
Urethane group
O
=
OH
N= C = O
Isocyanate
Alcohol (polyol)
R
N
R
O
H
Urethane
Foaming (two-step chemical reaction):

1.
Formation of carbamic acid.
2.
Decomposition of carbamic acid to give away CO2 (blowing agent) and urea.

Polyurethane foam preparation is industrially classified according to the final
characteristics of the foam in flexible and rigid PUR foaming technologies:
- Slabstock foams
Flexible PUR foams (FPF)
Polyurethane
foaming processes
- Molded foams: hot-cure /

cold-cure
- Continuous/discontinuous processes
for producing blocks and panels
Rigid PUR foams
(closed-cell)
- Poured-in-place foams
- Molded foams
- Sprayed foams
Topic 3

Polymer foams: flexible polyurethane foams (FPF)
Slabstock foams
The main difference with molded foams lies in the fact that slabstock PUR foams are
prepared by free-foaming in an open mould.
Slabstock flexible
PUR foam after slicing
As flexible PUR foams prepared by the slabstock process are prepared by freefoaming, they usually require a final cutting step of the upper part, which in some cases
may represent an important amount of disposable material (scrap).
Ashida, K. In: Handbook of Plastic Foams, Landrock, A.H. ed., Noyes, New Jersey, USA, 1994.

Slabstock foams
Basically, the FPF slabstock foaming process consists in the continuous pouring of a
liquid containing the required foaming components on a moving conveyor, which results
in the continuous formation of a free-rising foam commonly known as block or bun foam.
Slabstock
PU foam
Block PU
foam
Block PU
foam cut-off
Polyol(s)
Isocyanate
Inclined conveyor slabstock PUR

foam production line
Mixing
head
Vertical
conveyors
Foam
growth
Slabstock flexible
PUR foam
Vertifoam vertical foaming process to obtain FPF

Molded foams: hot-cure/cold-cure
Direct consequence of equipment requirements such as venting or automatic opening

and closing of the mould or formulation aspects such as faster reacting times, molded
flexible PUR foam production is quite more complex and more expensive than that of
slabstock foams. Depending on the type of curing, two major mold foaming processes are
industrially available: the hot-cure and the cold-cure.
Car seats made of FPF produced

using the hot-cure foaming process
Mattress made of high-resilience (HR)

PUR foam produced using cold-cure
Cold-cure uses low mold temperatures (typically between 60 and 70 C) and higher-reactive
components.

Some applications of flexible PUR foams:
Cushioning and mattresses
Automobile interior
car parts
Transportation and packaging

Polymer foams: rigid polyurethane foams
Rigid PUR foams mainly differentiate from flexible PUR foams by the fact that their
cellular structure is almost fully closed-cell, resulting in foams with low flexibility and
high load bearing capacity, as well as high thermal insulation.
Rigid PUR foams are basically produced
by continuous/discontinuous processes in
the form of blocks and panels, poured-inplace, molded or sprayed.
A: Polyol mix
B: Isocyanate
Poured-in-place rigid PUR

foam mixing pistol
Basic diagram of the equipment

required to prepare rigid PUR foams

Rigid PUR foam

panels for composite
applications
Spray rigid PUR foam

for thermal insulation
FG-reinforced low-density
PUR foam for sound damping
(boat engine rooms, sound
studios, etc.)
Turbine blade made of glass-filled

vinylester resin placed over a rigid
PUR foam core
Molded rigid PUR foams

Some applications of rigid PUR foams:
Thermal insulation
panels for floors
Thermal insulation
panels for roofs
Core of sandwich
panels
Sound absorption
panels (open-cell)
Fibreglass board with rigid PUR foam core
Topic 3

Polymer foams: thermoplastic foams
- Expanded bead moulding (EPS)
- Extrusion physical foaming (XPS)
Polystyrene foams
- Injection-moulding
(structural PS foams)
- Expanded loose-fill
Main thermoplastic
foams and commercial
foaming processes
- Extrusion chemical foaming

Polyvinyl chloride
foams
- Injection-moulding chemical foaming

- Extrusion physical foaming
(microcellular PVC foams)
Polyolefin foams
(polyethylene and polypropylene)
- Continuous/semi-continuous
foaming processes
- Batch foaming processes

Polymer foams: polystyrene (PS) foams
Polystyrene (PS) foams are commercially produced in a wide range of densities for
the most varied applications using five basic foaming processes: expanded bead
moulding (EPS foams), extruded board and extruded sheet (XPS foams), injectionmoulded structural foams and expanded loose-fill packaging foams.
EPS packaging boxes
XPS boards used for thermal

insulation
Klempner, D. and Sendijarevic, V. Polymeric Foams and Foam Technology, Hanser Publishers, Munich, Germany, 2004.

Expanded bead moulding (EPS foams)
Expanded PS foam, commonly known as EPS foam, is produced from expandable PS

beads, prepared by saturating solid PS beads commonly with a hydrocarbon such as
pentane and other additives during suspension polymerization. These expandable beads
are then pre-expanded using steam, aged and stored. The pre-expanded beads are finally
placed in steam-chest moulds, where final expansion and bead fusion takes place,
normally to produce big foamed blocks. These blocks are then cured and cut to the
desired final shape.
Solid unsaturated
PS pellets
Expandable PS
beads
Pre-expanded PS
beads
Final EPS boxes
Typical densities: around 24 kg/m3 for cushioning and about 16 kg/m3 for thermal insulation.

Extrusion physical foaming (XPS foams)
Extruded PS foam, known as XPS, though considerably more expensive than EPS
foam, has the advantage of better moisture resistance and mechanical behaviour. HFC134a or CO2 are commonly used as blowing agents. A single extruder or more recently
a tandem-extruder line is used to soften the solid PS and introduce and mix the blowing
agent with the soften polymer. The polymer-blowing agent mix is then progressively
cooled and allowed to expand by sudden decompression at the end of the die, promoting
the formation of the foam, which is then quickly stabilized by cooling.
XPS tandemextrusion line
Typical densities: 20-40 kg/m3 (boards)

40-160 kg/m3 (sheets)

Injection-moulding (structural PS foams)
Injection-moulded structural PS foam, normally obtained using impact-modified

styrene copolymers as HIPS or ABS, is used in high-density products such as home
appliances, toys and fittings. A chemical blowing agent is used in this process, typically
sodium bicarbonate, azodicarbonamide or mixtures.
Core
Cross-section
Cross-section of a
structural PS foam
Skin
Container made of
structural PS foam
Expanded loose-fill PS foam

Polymer foams: polyvinyl chloride (PVC) foams
Extrusion chemical foaming
Two aspects determine the characteristics and physical properties of extruded PVC
foams: the skin structure and the foamed core. The first is largely influenced by cooling,
while the second one is controlled by the formulation, extrusion conditions and cooling.
Free-foaming process
Free expansion of the melt at the
end of the extruder die.
Integral skin foam (Celuka or inward foaming process)

The surface of the extrudate is cooled immediately after
exiting the die. It is preferred for thicker profiles (> 6
mm), geometrically more complex parts and products
requiring a high quality hard surface.

Integral skin foam (Celuka or inward foaming process)

The surface of the extrudate is cooled immediately after
exiting the die. It is preferred for thicker profiles (> 6
mm), geometrically more complex parts and products
requiring a high quality hard surface.
A third hybrid type, which is the most

common these days, is to co-extrude a
weatherable skin or cap material onto a
Celuka core.
Typical densities: 0.6 g/cm3 (free foaming)
0.4-0.5 g/cm3 (Celuka process)
Main applications: replacement material for
wood-based products and other plastic thin wall
extrusions

Injection-moulding chemical foaming
Rigid and plasticized PVC foams can be prepared by injection-moulding using

exothermic blowing agents such as OBSH (alone or mixed with ADC) or ADC mixed
with ZnO. The obtained structure is of integral-skin type with a dense outer layer and a
foamed core.
Injection-moulded PVC foams
have recently been replaced by
other materials, such as PP in
the case of rigid PVC or EVA
and other soft polymers in the
case of flexible PVC.
Foamed PVC grips
Multi-cavity injection-mould for

producing PVC foamed shoe soles
Typical densities: 0.6-0.9 g/cm3

Extrusion physical foaming (microcellular PVC foams)
Extremely high pressure drop rate at
the exit of the die, followed by quick
cooling
Micrograph of a
microcellular PVC
foam
Schematic representation of an extrusion

foaming
system
used
to
prepare
microcellular PVC foams
Daz, C.A. and Matuana, L.M., J. Vinyl Add. Technol., 15, 211 (2009).
Microcellular
ooze water pipe
Microcellular PVC foam

used for shock isolation
and vibration damping

Polymer foams: polyolefin foams
Though open-cell polyolefin (PO) foams may be obtained, commonly using postmanufacturing operations, the industrially available foaming processes give way to
predominantly closed-cell cellular structures. Also, although PE-based foams are
normally crosslinked prior or during expansion, PP-based foams do not require
crosslinking. Instead, especially melt strengthen PP grades are used.
There are two basic foaming processes used to prepare closed-cell PO-based foams:
continuous and semi-continuous processes for producing foamed sheets and batch
foaming for preparing foamed products with higher thicknesses.
Interior
car parts
Rigid PP foam used as
core in sandwich parts
Low-density PP
foam
Crosslinked PE-based foams
Soft PP foam used as

impact absorbing layer

Continuous/semi-continuous foaming processes
Extrusion
Chemical foaming:
Mixing of polymer and
CBA in the extruder
Extrusion of a solid polymer

sheet containing the CBA
Vertical expansion in
an air oven
Horizontal expansion
in an air oven
Physical foaming:
Mixing of a PBA (SCF, CO2 or hydrocarbons)
with molten polymer in a primary extruder
Gradual cooling of the PBA-polymer

mix in a secondary extruder
Expansion by sudden pressure drop at

the exit of the secondary extruder
Injection-moulding
Chemical foaming:
Mixing of polymer and
CBA in the injection unit
Thermal decomposition of CBA and

mixing of gas(es) with molten polymer
Injection in hot
mould
Expansion inside the hot

mould due to pressure drop
Physical foaming (MuCell process):

Mixing of a SCF (N2 or CO2) with molten
polymer in the injection unit
Injection of the SCF-polymer

mix into the mould
Expansion inside the mould

due to pressure drop
In-situ crosslinking is commonly required for PE-based foams

Antunes, M. and Velasco, J.I. In: Polypropylene: Synthesis, Applications and Environmental Concerns, Silva, L.P. and Barbosa,
E.F. eds., NovaScience Publishers, 2013.

Polymer foams: polyolefin foams Continuous/semi-continuous foaming processes
Extrusion chemical foaming was first introduced in 1958 by Dow Chemical and
developed in Japan by companies such as Sekisui, currently Sekisui Alveo, halfway
through the 1960s for producing crosslinked PE foams. As this foaming process has been
mainly used in the production of crosslinked PE foams, it has normally been classified
according to the type of crosslinking process used: physical by means of high energy
irradiation or chemical by the addition to the extruder of a crosslinking agent.
In the case of polyolefins, the chemical blowing agent (CBA) is normally ADC or
other azo-based compounds, well in its non-activated form (PP-based formulations) or
thermally activated (PE-based formulations).
Typical foams produced using this process:
Flexible foams in the form of sheet rolls (low thickness) - = 20-60
kg/m3
Rigid foams in the form of panels/boards - > 100 kg/m3
Main applications: packaging and protection (low density flexible
foams), structural applications (rigid foams)

The foaming process basically consists in compounding the polymer with the different
additives, mainly the CBA and, in the case of chemical crosslinking, the crosslinking
agent, as well as other processing additives, using an extruder. After exiting the extruder
in the form of a solid sheet, the material is expanded in specially designed air ovens,
Pre-heating
Infrared
normally placed in-line with the extruder.
Another classification considers the way
in which the material is foamed: vertical
expansion, where the solid sheet is foamed
by passing it vertically through a hot air
oven, and horizontal expansion.
heaters
chamber
Compounded
polymer-CBA
solid sheet
Main advantages of vertical foaming:

Thin foamed products (thickness: 0.5-8 mm)
Wide density range: 20-250 kg/m3.
Main advantages of horizontal foaming:
Enables the production of thicker foams (thickness up to 13 mm)
Wide density range: 25-250 kg/m3 (flexible and rigid foams).
Foaming
chamber
Infrared
heaters
Hot air
Foamed
sheet
Scheme of a vertical oven

used to prepare PP foams

Physical foaming by direct extrusion
In this process the foam is directly obtained by the sudden pressure drop generated at
the exit of an extruder die, normally using CO2 or hydrocarbons (iso-butane), although
gases (N2 or CO2) in supercritical conditions may also be used. Normally, the mix of
polymer-PBA is done in a single or twin-screw primary extruder, with the polymer-gas
mix being progressively cooled in a secondary extruder (tandem-extrusion system).
Polymer +
additives
PBA
(SCF, CO2 or
hydrocarbons)

Flexible foams in the form of rolls, film, tube or rod (higher thickness than in
extrusion chemical foaming) - = 20-60 kg/m3
Rigid foams in the form of panels/boards - > 300 kg/m3
Main applications: packaging and protection (low density flexible foams), structural
and automotive applications (rigid foams), thermal and acoustic insulation, etc.
Primary extruder
Foam
Cooling caliper gauge
Mixing stage
Secondary extruder
Cooling stage
Expansion by sudden
pressure drop and foam
stabilization
Scheme of a tandem-extrusion physical foaming process
No solid residues coming from

CBA decomposition are present,
enabling the use of these foams in
direct food contact applications.

Physical foaming by direct extrusion
Low density flexible

foamed roll for packaging

Injection chemical foaming
Chemical foaming typically occurs by the thermal decomposition of a CBA which, at

a given temperature, thermally decomposes releasing one or more gases that act as
foaming agent. The used CBA is typically endothermic, although exothermic or
endothermic/exothermic blends are also used. A mix of citric acid and sodium
bicarbonate is often used as endothermic blowing agent, though exothermic blowing
agents based on ADC or other azo compounds are also commonly used, alone or in
combination with endothermic systems.
Upper part of
the foam
Foam core
Injection-moulded integral PP foam
Lower part of
the foam

Rigid integral foams in the form of panels/boards (thickness up to 20 mm) - > 300 kg/m3
Main applications: transportation, outdoor upholstery and whiteboards, building and construction (intended to
replace plywood and other lightweight composites)

Injection-moulding physical foaming (MuCell process)
This process has the advantage that it does not require the addition of a chemical
additive to the polymer, since it uses a PBA (supercritical N2 or CO2) to foam the
material. Its name derives from the particular microcellular structure of the produced
foams (Mu - micrometer and Cell - cellular).
Foam cross-section
Supercritical
fluid (SCF)
metering system
Clamping
system
Polymer
Injection moulding
chamber
(polymer + SCF)
Injection moulding
machine
Injection
mould
Cell size: 5-50 m

Rigid integral foams with a microcellular structure - >
500 kg/m3
Main applications: business equipment, automotive (rear
door carrier, trunk liners, etc.), electrics, medical
applications and packaging

Batch foaming processes
Compression-moulding chemical foaming
Compounding with CBA and
solid precursor preparation
One-step expansion by compression-moulding

( > 100 kg/m3)
Two-step expansion by compression-moulding
( < 100 kg/m3)
High-pressure gas dissolution physical foaming

Compounding in extruder
and sheet preparation
High-pressure N2
dissolution in autoclave
Low-pressure expansion in
secondary autoclave
Expandable bead foaming process (EPP and EPE)

Compounding in
extruder and pelletizing
Gas dissolution (CO2 or butane) and

foaming in autoclave EPP beads
EPP bead foam preparation in a

steam chest moulding machine
In-situ crosslinking is commonly required for PE-based foams

Polymer foams: polyolefin foams Batch foaming processes
Chemical foaming by means of press moulded foaming is a type of batch-foaming

process, first introduced at the beginning of 1970s by BASF in Germany, in which the
polymer is foamed by the thermal decomposition of a CBA by applying heat and pressure
on a solid precursor previously compounded with the CBA and pre-moulded to a desired
shape, typically by means of extrusion.
One-step expansion
Closing of
the press
Heat
Pressure
Two-step expansion
Solid precursor
(polymer + CBA)
H
H
N-C-N=N-C-N
H
H
Azodicarbonamide (ADC)
Foam
( > 100 kg/m3)
Thermal
decomposition
Heat
Ambient
pressure
Gases:
Solid
+
N2, CO, CO2
residues
Pre-foam
( > 100 kg/m3)
Foam
( < 100 kg/m3)

Closing of
the press
One-step expansion
Heat
Pressure
Two-step expansion
Solid precursor
(polymer + CBA)
H
H
N-C-N=N-C-N
H
H
Azodicarbonamide (ADC)
Foam
( > 100 kg/m3)
Thermal
decomposition
Heat
Ambient
pressure
Gases:
Solid
+
N2, CO, CO2
residues
Pre-foam
( > 100 kg/m3)
Foam
( < 100 kg/m3)

- Closed-cell foams
One-step expansion: medium-high density foams - > 100 kg/m3 (typically 300-700 kg/m3)
Two-step expansion: low density foams (thicknesses up to 120 mm) - < 100 kg/m3 (typically 20-40 kg/m3)
Main applications: protection and packaging (low density foams), construction and automotive applications
(medium-high density foams)

High pressure gas dissolution physical foaming
The high-pressure gas dissolution physical foaming process, developed and

industrially implemented by Zotefoams (UK), is a process where a gas is dissolved into a
polymer, promoting the later formation of the foam by generating a thermodynamic
instability in the polymer-gas mixture through heating. The main difference between this
process and other physical foaming methods lies on the fact that gas dissolution is done
below the melting temperature of the polymer, i.e., in a semisolid-like state.
Typical foams produced using this
process:
Low density isotropic-like foams - <
100 kg/m3
Main applications: protection
transportation, thermal insulation
Antunes, M. and Velasco, J.I. In: Polypropylene: Synthesis, Applications and

Environmental Concerns, Silva, L.P. and Barbosa, E.F. eds., NovaScience Publishers, 2013.
and

Expandable bead foaming process
Expandable bead foaming is a process that can be used to easily obtain PO foams with
densities ranging from as low as 18 kg/m3 to foams with densities around 250-300 kg/m3.
This process allows obtaining a type of PP/PE foam known as Expanded Polypropylene
or Polyethylene (EPP/EPE). EPP/EPE is a closed-cell bead foam in which individual
expanded beads initially impregnated with a blowing agent inside autoclaves and later
expanded are fused together to give the final product by applying hot steam and pressure
inside especially designed moulds, known as steam chest moulds.
- Closed-cell bead foam
Very low density foams - as low as 18 kg/m3
Medium-high density foams (especially EPP) - > 100 kg/m3
Main applications: automotive applications (energy absorbers in bumpers,
seating structures, etc.) (medium-high density foams), packaging
(containers, boxes, etc.), construction materials (drainage, thermal and
sound insulation) and consumer goods

Expandable bead foaming process
Stage 2:
Preparation of the expanded PP/PE beads
Stage 1:
Compounding and pellet preparation by extrusion
PP/PE pellets
Gas
(CO2 or butane)
Water
Heater
Extruder
Extruded
pellets
Stage 3:
EPP/EPE moulding
Autoclave
reactor
Pressure
drop
EPP/EPE bead
foam component
Closing of
the mould
EPP/EPE beads
EPP/EPE steam chest moulding machine
EPP/EPE beads
Superheated
steam

Cellular polymers: other cellular structures
Syntactic foam consisting of hollow
glass microspheres within an epoxy
matrix
Syntactic polymer foams
Honeycomb polymer structures
PLA-based porous scaffold
Porous polymer scaffolds
Cellular polymer-fibre composite

obtained by compression

Metal foams:
As previously explained, metal foams are a special class of cellular metals that
originate from liquid-metal foams and, therefore, have a restricted morphology. The
cells are normally closed, spherical or polyhedral-like and are separated from each
other by thin films.
The manufacture of cellular metals in the most general sense does not always
involve foaming methods. Often, a polymer foam is first opened by a special treatment
and then replicated to yield a metallic structure. Replication can be carried out by
coating with metal vapor, electroplating, or investment casting. The result is a structure
with open porosity (sponge). In this case, the physics of foaming has nothing to do with
the metal, as only the polymer precursor is foamed. Other structures can be used as
templates for creating cellular metals: loose or sintered bulks of inorganic or organic
granular matter, hollow spheres, or even regular polymer structures. In contrast, in true
metal foaming methods the metal is self-forming during foaming.
Banhart, J., J O M, 52, 22 (2000).
Topic 3

Metal foams foaming methods:
Banhart, J., J O M, 52, 22 (2000).
Topic 3

One distinguishing factor between metal foming methods is whether molten metal
or metal powder is used as foaming precursor, though in every case foaming always
takes place in the molten state.
Aluminum foaming precursor prepared

by compaction of aluminum and
titanium hydride powders
Top view of an Al foam-filled

(0.27 g/cm3) Al tube.
Gden, M. and Kavi, H., Thin-Walled Struct., 44, 739 (2006).
Topic 3

Topic 3

Foaming of Powder Compacts (Foaminal/Alulight)
The production process begins with the mixing of metal powders (elementary metal
powders, alloy powders, or metal powder blends) with a blowing agent (also in powder
form, commonly TiH2), after which the mix is compacted to yield a dense, semifinished product (foaming precursor).
Compaction of the powder mixture can be done by uniaxial or

isostatic compression, rod extrusion or powder rolling.
Baumgrtner, F., Duarte, I. and Banhart, J., Adv. Eng. Mater., 2, 168 (2000).
Duarte, I. and Banhart, J., Acta Mater., 48, 2349 (2000).
Photo of Al-TiH2 foaming

precursors and aluminum foams

After the preparation of the foaming precursor, the next step is heat treatment at
temperatures near the melting point of the matrix material. The blowing agent, which is
homogeneously distributed within the dense metallic matrix, decomposes and the
released gas forces the melting precursor material to expand.
Metal foam
The time needed for full expansion depends on the temperature and size of the
precursor and ranges from a few seconds to several minutes. The method is not
restricted to aluminum and its alloys. Tin, zinc, brass, lead, gold and some other metals
and alloys can also be foamed with appropriate blowing agents and process parameters.
Baumgrtner, F., Duarte, I. and Banhart, J., Adv. Eng. Mater., 2, 168 (2000).
Duarte, I. and Banhart, J., Acta Mater., 48, 2349 (2000).

Foaming is done by heating the foaming precursors inside a hollow mold, creating
foams with a solid outer skin and a highly porous cellular core.
Example of an aluminum foam prepared

Quite complicated parts can be manufactured by
by powder compactation (Alulight)
injecting the still expanding foam into suitable moulds.
Banhart, J., Prog. Mater. Sci., 46, 559 (2001).
Topic 3

Sandwich panels consisting of a foamed metal core and two metal face sheets can be
fairly easily obtained by bonding the face sheets to a piece of foam with adhesives.
Alternatively, if pure metallic bonding is required, conventional sheets of metal
(aluminum or steel) are roll-clad to a sheet of foamable precursor material. The
resulting composite can be deformed in an optional step, e.g., deep drawing. The final
heat treatment leads to sandwich-like structures.
Sandwich-like panel formed by an Al

foam core and two steel face sheets
Al/Al foam sandwich-like panel

Topic 3

A second difference is the gas source used for foaming: an external source can be
used or dissolved gas can be forced to precipitate (physical foaming) or a blowing
agent can be thermally decomposed in-situ (chemical foaming). Third, foaming can be
instantaneous (i.e., addition of gas leads to immediate foaming), or an intermediate
product is created that can be foamed in a later stage (delayed foaming). Finally, the
mechanism of foam stabilization may be different depending of the foaming method.
- Alporas process
Chemical foaming
Foaming from
the melt
Physical foaming
- Foaming of ingots containing blowing

agents (Formgrip/Foamcast)
- Physical foaming using gas injection
(Hydro/Alcan)
- Solid-gas eutectic solidification (Gasar)

Chemical foaming using the Alporas process
In the Alporas chemical foaming process a foam is prepared by adding a blowing

agent directly to a molten metal. Heat causes the blowing agent to decompose and
release gas, which then propels the foaming process.
TiH2
Thermal
decomposition
Onset: 450 C
End: 700 C
Ti + H2
Blowing
agent
Typical densities after slicing: 0.18-0.24 g/cm3

Average cell size: 2-10 mm.

Chemical foaming of ingots containing blowing agents (Formgrip/Foamcast)
The powder-compact melting process has been recently modified by incorporating

TiH2 particles directly into an aluminum melt instead of using powders to prepare a
foaming precursor. To avoid premature H2 evolution the melt has to be either quickly
cooled down below its melting point after mixing or the blowing agent has to be
passivated to prevent it from releasing gas before solidification. The former technique,
is known as Foamcast. One inconvenient of this technique lies in achieving a
homogeneous distribution of TiH2 particles.
Melts containing silicon carbide are used to obtain
stable foams. The foaming process can be influenced by
varying heating rates and final foaming temperatures,
thus allowing the production of a great variety of
different pore structures. This process has been named
Formgrip, which is an acronym of foaming of
reinforced metals by gas release in precursors.
Aluminum/silicon-carbide
foams (Formgrip)

Physical foaming using gas injection (Hydro/Alcan)
The idea of injecting gas directly on the molten metal was patented just after
chemical foaming, considering even the addition of foam stabilizing particles
(commonly silicon carbide and aluminum or magnesium oxide particles - 10-20 vol.%).
Air, N2 or
argon
Foam slabs of two different

densities and cell sizes produced
using the gas injection method
Scheme of physical foaming using gas injection.

sholt, P., Metal Foams and Porous Metal Structures, ed. Banhart, J., Ashby, M.F.
and Fleck, N.A., MIT-Verlag, Bremen, Germany, p. 133 (1999).
Typical densities: 0.069-0.54 g/cm3

Average cell size: 3-25 mm.

Physical foaming using solid-gas eutectic solidification (Gasar)
The solid-gas eutectic solidification method exploits the fact that some liquid metals
form an eutectic system with H2. If one of these metals is melted in an H2 atmosphere at
high pressure (up to 50 atm), the result is a homogeneous melt filled with H2. If the
temperature is lowered, the melt will eventually undergo an eutectic transition to a
heterogeneous two-phase system. If the composition of the system is sufficiently close
to the eutectic concentration, a segregation reaction will occur at one temperature. As
the melt is solidified, gas pores precipitate and are entrapped in the metal.
Typical porosities: 5-75%

Cell size: 10 m to 10 mm
Metal foam obtained by the Gasar

Micrograph of a Gasar foam
method, showing largely elongated pores (surface normal to pore direction)

Cellular metals: other cellular structures
Alongside the several available foaming processes (cellular metals that originate from
liquid metals), other methods can be used to prepare cellular metals, owing to the
sintering activity of metals or the fact that they can be electrically deposited:
Sintering of hollow spheres
Gas entrapment
Slurry foaming
Starting from a solid metal in powdered form
Pressing around fillers

Sintering of powders or fillers
Extrusion of polymer/metal mixtures
Reaction sintering
Starting from a metal vapor or gaseous metallic compounds

Starting from a metal ion solution
Vapor deposition
Electrochemical deposition

Cellular metals: other cellular structures
Cellular Al made by investment

casting with polymer foam
Syntactic hollow
sphere structure
Cellular aluminum made by

sintering of fillers
Nickel foam prepared by

electrochemical deposition
Stainless steel cellular

metal made from sintering
of hollow spheres

Ceramic foams:
Typical materials used for manufacturing cellular ceramics include crystalline
inorganic materials such as silicon carbide (SiC), alumina (Al2O3), zirconia, cordierite,
mullite, but also silicate glass and carbon as well as concrete.
Three different approaches can be followed in order
to produce a ceramic foam:
Replication of a sacrificial foam template
Direct foaming of a liquid slurry
Burn-out of fugitive pore formers
Open-cell ceramic
foams used in filtration
Activated
carbon foam
Colombo, P., Phil. Trans. R. Soc. A, 364, 109 (2006).

Ceramic foams:
The great majority of ceramic foams are currently fabricated industrially using this
technique, that produces the so-called reticulated ceramics, which present an open-cell
structure.
The process consists in the impregnation of a flexible open-cell polymer foam
(commonly made out of polyurethane, PU) with a ceramic slurry, the removal of excess
slip by squeezing or centrifuging, followed by drying, a burn-out step to eliminate the
polymer template and high-temperature sintering.
Micrograph of a PU foam template

Micrograph of an Al2O3
reticulated foam
Photo of an open-cell ceramic

foam prepared by replication

Ceramic foams:
The ceramic slurry, which can be

based on a variety of oxides and nonoxides, often contains various additives
to act as binders, rheological agents or
setting compounds to facilitate the
coating process and increase the
adherence to the template.
Cellular structure: only open-cell
Relative densities: 5-30%
Cell size: 150 m to a few milimeters
Graded structures in which the cell size
varies along one axis can be obtained either by
stacking templates with different morphologies
or by compressing a wedge-shaped template.
Faure, R. et al. J. Eur. Ceram. Soc., 31, 303 (2011).
Al2O3 foam with discontinuous

radial porosity gradient

Ceramic foams:
A variation of the replication technique described previously is a process where the

polymeric template is not burned out but pyrolyzed to yield a pyrolitic carbon skeleton
that can then be coated by a ceramic material, generally using chemical vapor deposition
(CVD).
Topic 3

Ceramic foams:
Direct foaming consists in the generation of bubbles inside a liquid slurry containing
ceramic powders or inside a ceramic precursor solution to create a foam which then
needs to be set in order to maintain its porous morphology, before heating to high
temperature for sintering.
The blowing agent can be a low boiling- Micrographs of ceramic foams prepared by
point liquid or solid (such as CaCO3 powder, direct foaming of liquid slurries using starch:
which decomposes upon heating), or gas can be
developed in situ by chemical reactions (for
instance, cross-linking reactions in silicone
resins leading to the formation of water, or
oxidation of a solid C or SiC filler forming
CO2 gas) or can be added to the liquid mixture
by mechanical stirring or bubbling (gas Yin, L., Peng, H.X., Dhara, S., Yang, L. and Su, B., Compos.
Part B: Eng., 40, 638 (2009).
injection).

Ceramic foams:
In order to avoid the collapsing of the liquid foam and for retaining the cellular
morphology, special additives need to be added to the liquid in order to harden the
foamed structure once it is stabilized.
Gel casting employs in situ polymerization to stabilize
foams produced from aqueous ceramic powder suspensions
Use of clot-forming proteins or ovalbumin as binders
Liquid slurry
setting strategies
Use of enzymes, starch, cellulose derivatives or alginates

that lead to gelling
Addition of crosslinking PU precursors to the slurry
Freezing
Topic 3

Ceramic foams:
Ceramic foams obtained by direct foaming are usually dried and sintered by
conventional means; an initial slow pyrolysis step for carefully eliminating the organic
setting agents needs to be applied when necessary.
Cellular structure: closed-cell (typically interconnected) or
open-cell
Relative densities: wider range than replication
Cell size: wider range than replication but with limitations for
obtaining large cells
Micrograph of a hydroxyapatite
ceramic foam obtained by direct
foaming (gel casting)
Due to ceramic struts that are

more dense and with limited defects,
these
foams
have
improved
mechanical strength - compression
strength can reach 30 MPa for a
relative density of 0.3.
Dense strut in a ceramic foam
obtained by direct foaming

Ceramic foams:
With direct foaming it is easy to produce foams with a graded porosity along one
direction and variable shapes, as the solution can be cast in any mould.
Conversely, it is more difficult to produce a material with a narrow distribution of cell
sizes, and occasionally both closed and open cells are present in the material. Also, some
unwanted anisotropy may sometimes be found.
Micro-cellular SiOC foam obtained by direct foaming
using a blowing agent and pre-ceramic polymer:
Foam growth
direction
Graded porosity ceramic foam

obtained by direct foaming
Sharafat, S. et al. Fus.

Eng. Des., 81, 455 (2006).

Ceramic foams:
Glass foams are generally produced by mixing solid foaming agents, such as
hydroxides, carbonates, sulphates, carbides or carbon powders, with glass powder. Upon
heating, the glass becomes a viscous liquid and the decomposition or oxidation of the
foaming agent lead to the formation of bubbles, which remain trapped within the melt.
The glass is then cooled before collapsing of the cells can occur.
Owing to the high

viscosity of glass melts,
glass
foams
are
generally closed-cell.
Micrograph of a borosilicate
glass foam
Wang, B. et al. High Strength Borosilicate Foams by Expansion of Ar-Filled Pores and Release of Dissolved Ar Gas, AZo J. Mater.
Online (2011).

Ceramic foams:
Burn-out of fugitive pore formers
In this method, hollow cells are produced when the solid material that occupies that
space within the volume of the component disappears during heating at high
temperature. Starch, wax, polymeric beads (PMMA, PS, PVC), carbon black, sawdust
have all been used with various degrees of success.
Cellular structure: closed-cell or interconnected/
partially open-cell
Relative densities: low relative densities require high
amounts of blowing agent and thus careful control during
foaming to avoid the formation of cracks
Cell size: controlled by the characteristics of the
sacrificial filler
Microcellular SiOC foam obtained by

the burn-out of polymeric microbeads
Graded structures can be obtained by layering using

fillers with varying dimensions.

Ceramic foams:
Reticulated vitreous carbon foams
They are produced by carbonizing organic polymer foams (e.g. phenolic resin or PU
foams, usually open-cell) through a high-temperature heat treatment.
Carbon foams
They are obtained by foaming petroleum pitch with blowing
agents or coal pitch using volatiles that form upon heating in an
autoclave, followed by heat treatment at 2400-2600 C.
Cellular concrete
It is obtained at low temperature by adding surfactants to
a Portland cement-based slurry and introducing air during
mixing. This mixture is then cast into place and cured at
ambient temperature. Alternatively, the slurry can be
precast, pre-cured and then processed at higher temperature
in an autoclave (so-called autoclaved aerated concrete).
Activated
carbon foam
Autoclaved
aerated concrete

Ceramic foams: other cellular structures
Micrographs of a cross-section of two
cordierite honeycombs:
Micrograph of a hydroxyapatite
latticework:
Cellular ceramic obtained by

sintering of hollow spheres:
Micrograph of a Si-SiC cellular ceramic

obtained by liquid Si infiltration of fir:

Topic 3 - Cellular Materials-Foams (Part 2)

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