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www.rsc.org/databases
ISSN 1463-9262
Jacobs et al.
Sustainable polymer foaming using
carbon dioxide
Bhaskar et al.
Debromination of flame retardant
plastics with microwave irradiation
1463-9262(2008)10:7;1-B
CRITICAL REVIEW
1.
Introduction
2.
heating. The state below T g is called the glassy state and the state
above T g is called the rubbery state. Above T g , polymers are
capable of plastic deformation without fracture.19 Furthermore,
the polymer matrix will swell and the viscosity of the polymer
decreases, allowing processing of the polymerCO2 mixture at
lower temperatures. The diffusivity inside the polymer is also
enhanced, enabling the use of CO2 as a medium to add additives
to the polymer matrix. The type of polymer, together with the
applied pressure and temperature determine to a large extent the
amount of CO2 that can be dissolved in the polymer.
Once the polymer is saturated, a rapid decrease in pressure
will induce a shift in the thermodynamic equilibrium, leading to
an oversaturation of CO2 in the polymer. However, this does not
necessarily lead to nucleation and cell growth. If the temperature
at which the polymer has been saturated is relatively low, the
polymer can still be in the glassy state, because T g has not been
sufciently depressed by the sorption of CO2 . Therefore, phase
separation and nucleation will only occur once the saturated
sample is heated to a temperature above the glass transition
temperature. This will lead to cell growth and the nal formation
of the polymeric foam. Below the glass transition temperature,
foaming cannot occur, because the polymer matrix is too rigid.
If the saturation temperature is high enough and the polymer
CO2 mixture is in the rubbery state due to sufcient depression of
T g , phase separation and nucleation will occur instantaneously
upon depressurization. Cell growth will stop once the polymer
matrix returns to the glassy state, either due to a decrease
in temperature or a decrease in the CO2 concentration in the
polymer and the polymer is no longer plasticized.
The gas phase can separate from the polymer phase by
two mechanisms. If the pressure drop results in a metastable
state, nucleation will be the dominant mechanism for foam
formation. In the unstable state, spinodal decomposition will
be the dominant mechanism.20 This is schematically depicted
in Fig. 3. Both mechanisms are diffusion driven, although the
direction of diffusion is opposite. In spinodal decomposition,
diffusion moves from low concentration to high concentration,
due to a high driving force. This review, however, will focus
on nucleation as the mechanism for polymer foaming since it is
usually suggested as the dominant phase separation mechanism.
Fig. 3 Schematic phase diagram of the composition vs. the gas pressure.
4.
matrix into the cells, which results in larger cells. Fig. 7 clearly
illustrates the effect of a decreasing depressurization rate on
the cell size. If depressurization occurs in two steps, a foam
with a bimodal cell size distribution will be produced. The rst
step will induce nucleation and some cell growth. The second
depressurization step results in secondary nucleation and further
growth of the primary nucleated cells. The secondary nuclei have
less time to grow and will therefore be smaller. An example of
such a foam is given in Fig. 8.
Nanocomposite foams
6. Bioscaffolds
Porous biodegradable polymer matrices have received increasing
attention because of their potential application within the eld
of tissue engineering and guided tissue regeneration. These
materials can act as a temporary support for in vitro cell growth
and can encourage cellular growth in vivo. As the cells grow, the
support of the matrix is no longer needed and over time, the
polymer matrix degrades into chemically benign components,
which are not harmful to the surrounding cells. One of the most
commonly used biopolymers is poly(lactic-co-glycolic) acid
(PLGA), because it biodegrades into lactic and glycolic acid,
which are relatively harmless to the growing cells. Furthermore,
its use in other in vivo applications, such as resorbable sutures,
has been approved by the Food and Drug Administration.80
Also, the degradation rate of PLGA can be controlled by
varying the ratio of its co-monomers, lactic acid and glycolic
Green Chem., 2008, 10, 731738 | 735
Fig. 9 Micro-CT image of scaffolds processed at (a) rapid depressurization; and (b) very slow depressurization. This gure is taken from
Barry et al.89 and has been reproduced with kind permission of Springer
Science and Business Media.
Teng et al.90 have combined the CO2 -foaming process with salt
leaching in order to increase the porosity and interconnectivity
of poly(D,L)lactic acid PDLLA)/hydroxyapatite (HA) scaffolds.
PDLLA/HA composite and NaCl have been mixed in a heated
mold after which the mixture is foamed with CO2 and the salt is
washed out.
Next to the previously described polymers, PEMA/
THFMA,91,92 poly(isoprene-co-styrene)/THFMA91 and polycaprolactone (PCL)62 also have also been successfully foamed
using CO2 and have a high potential to be used as bioscaffolds.
7.
Polymer blends
8.
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