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Development of PLA foam products through three different foam processing

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Conference Paper · October 2015

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 5th International Conference on Biofoams
Sorrento, October 13-16th 2015

DEVELOPMENT OF PLA FOAM PRODUCTS THROUGH THREE

DIFFERENT FOAM PROCESSING ROUTES

Mohammadreza Nofar1 and Chul B. Park2

1
Research Center for High Performance Polymer and Composite Systems (CREPEC), Department of
Chemical Engineering, McGill University, Montreal, Quebec, Canada H3A 2B2,
Email: [email protected]
2
Microcellular Plastics Manufacturing Laboratory, Department of Mechanical and Industrial Engineering,
University of Toronto, 5 King’s College Road, Toronto, Ontario, Canada M5S 3G8
Email: [email protected]

ABSTRACT
In this work, we investigated the foaming mechanisms of PLA, specifically effects of
crystallization and additives on PLA’s foaming behaviors through such technologies as
extrusion foaming, foam injection molding, and bead foaming. We verified that compounding
the PLA with nanoparticles as well as enhancing PLA’s slow crystallization kinetics can
significantly improve the PLA’s foaming behavior in all three foam processing methods. The
presence of nanoparticles and the enhanced crystallization compensated for PLA’s low melt
strength during foam processing, and thereby improved PLA’s foam-ability with minimized
gas loss and improved expansion ratio. Moreover, they acted as heterogeneous cell nucleating
sites and significantly promoted the foamed samples’ cell density with uniform cell
morphology. In PLA bead foaming in which we developed bead foams with double crystal
melting peak structure, the generated high-melting temperature crystals during gas-saturation
significantly affected the expansion ratio and cell density of the PLA bead foams by
enhancing the PLA’s melt strength and promoting cell nucleation around the crystals.

Keywords: Polylactide, foaming, crystallization, nanoparticles

1. INTRODUCTION
Poly (lactic acid) or polylactide (PLA) is a thermoplastic polyester produced from
renewable resources such as cornstarch and sugarcane, and is compostable in the environment
[1]. Due to the said features and its competitive material and processing costs, and
comparable mechanical properties, PLA is considered as a promising replacement for
polystyrene (PS) products [2]. PS foams are of the PS products that are broadly being used in
a wide range of applications such as packaging, cushioning, construction, thermal and sound
insulation and plastics utensils. Therefore, producing PLA foams can be a suitable substitute
for these products [3].
Currently, the mass production of low-density PLA foams with a uniform cell morphology
using supercritical carbon dioxide and nitrogen as the physical blowing agent is still quite
challenging. This is mainly due to PLA’s low melt strength [4]. Introducing a chain extender
to create a branched structure [5]; modifying the L/D ratio configuration of the PLA
molecules [6]; varying the PLA’s molecular weight [5-6]; and compounding the PLA with
different types of additives [7] have been recognized as efficient methods to improve PLA’s
poor melt strength, and consequently, its foamability. Also, enhancing the PLA’s slow
 First A. Author, Second B. Author and Third C. Author

crystallization kinetics has proven to be a significant parameter for improving its inherently
low melt strength and for extending its applications [8]. The enhanced crystallization
compensates for the PLA’s low melt strength during processing and thereby its foam-ability
[9]. The enhanced crystallization can further improve the final product’s mechanical
properties and the PLA’s low heat deflection temperature (i.e., service temperature) [10].
This paper discusses the cell nucleation and expansion mechanisms in PLA foaming
through various foaming processing technologies, i.e., bead foaming, extrusion foaming, and
foam injection molding. We discuss the influence of additives and crystallization on the cell
nucleation and expansion behaviors of PLA foams through the said foaming processing
technologies.

2. BEAD FOAMING PROCESS

In our recent studies [11-12], we developed expanded PLA (EPLA) bead foams with a
double-crystal melting peak structure. In this technique, the high-temperature melting peak
crystals that form during the isothermal saturation step in a batch-based bead foaming process
maintain the bead geometry. The formation of this high melting temperature crystal is due to
the crystal perfection during which the saturation occurs. The gas saturation occurs around the
melting temperature of the PLA at which the unmelted crystals become more perfect with a
higher melting temperature [13]. These induced high-melting temperature crystals can
significantly affect cell nucleation and the expansion behaviors of PLA bead foams during the
cooling/foaming step. In other words, cell nucleation can be promoted around the formed
crystals [14]. On the other hand, the low-melt strength PLA molecules become high-melt
strength material. This increases the PLA’s ability to expand by minimizing both gas loss and
cell coalescence [3, 9]. But too high a crystallinity will depress the foam’s expansion ability
due to the increased stiffness of the matrix [3].
A small autoclave foaming chamber and a lab-scale bead foaming chamber were used to
produce PLA bead foams with double crystal melting peak structure [11-12]. The PLA was a
long-chain branched PLA with D-lactide content of 4.6 mole% and melting temperature of
150oC from NatureWorks. This branched PLA was derived from the melt extrusion of a linear
PLA (Ingeo™ 8051D from NatureWorks® LLC) with 0.7 wt% of an epoxy-based multi-
functional chain extender (BASF Joncryl™ ADR 4368C).
The ratio of the induced crystal melting peaks could be controlled by varying the saturation
temperature, time, and pressure [11-12]. As the saturation temperature (Ts) increased, a less
amount of crystals was encountered to crystal perfection during the annealing and thereby a
smaller area was generated as the second peak at high temperatures. However, the generated
second peak appeared at higher temperatures due to the increased molecular mobility and
easier molecular retraction (i.e., better perfection) [11-12]. In contrast, the samples annealed
at higher temperatures revealed a larger area as the low melting peak crystals due to the
increased amount of melt available for crystallization during cooling. Moreover, the samples,
which were annealed for a longer time, showed a larger amount of perfect crystals due to the
longer diffusion time for molecular rearrangement. Compared to the lower saturation
pressures, the double peak structure was generated at a lower range of Ts when the CO2
pressure was increased. This was due to the plasticization effect of the dissolved CO2, which
suppressed the required Ts range [11-13].
Figure 1 shows the DSC heating thermograms of the expanded PLA bead foams produced
under various saturation pressures and temperatures at a given saturation time of 60 min.
Figures 2 and 3 also show the expansion ratio and the cell morphology of the expanded PLA
bead foams obtained using various saturation pressures and temperatures.
 5th International Conference on Biofoams
Sorrento, October 13-16th 2015

Figure 1: DSC heating thermograms of the PLA bead samples achieved at various saturation conditions.

As seen, after saturation at 870 psi and 2500 psi, with the increased saturation temperature,
bead foams with expansion ratios of 3 to 25 times and 3 to 30 times, respectively, were
obtained. The corresponding average cell sizes were also observed between 500 nm-500 µm
and 700 nm-15 µm, respectively. As Figure 1 shows, after saturation at 870 psi and 2500 psi
at the lowest corresponding saturation temperatures, 25-30% of crystallinity was induced
during the saturation. These large amounts of crystals were involved in promoting the cell
nucleating toward nano-sized cells.

Figure 2: Expansion ratio of the foamed PLA beads after saturation at various CO2 pressures
and temperatures.
After saturation at CO2 pressures of 870 psi and 2500 psi, as the saturation temperature
increased, the expansion ratio of the PLA bead foams were enhanced up to 25 times and 30
times, respectively. This was due to the reduced stiffness of the PLA matrix which facilitated
the cell growth. In other words, with the increased saturation temperatures, the amount of
induced perfect crystals (i.e., the second peak crystals) started to decrease from around 25-
30% to less than 15%. Therefore, due to the reduced crystallinity of the matrix, the
heterogeneous cell nucleation rate was also suppressed and cell growth governed the foaming
mechanism.
As Figure 3 shows, after saturation at 870 psi and 2500 psi, the obtained cell density was
decreased with the increased saturation temperature. According to the DSC analyses, after
saturation at 137.5°C (870 psi) and 110°C (2500 psi), 27% and 25% of crystallinity was
induced during the saturation, respectively. The large amount of induced crystallinity
 First A. Author, Second B. Author and Third C. Author

significantly promoted the heterogeneous cell nucleation rate through the local pressure
variations around the crystals [14]. However, the cell growth was noticeably hindered due to
the increased stiffness of the PLA matrix. On the other hand, after saturation at higher
temperatures, although the reduced amount of perfect crystals facilitated the cell growth, it
also reduced the cell nucleation density because of the reduced heterogeneous cell nucleation
sites (i.e., perfect crystals induced during the saturation).

Figure 3: SEM images of the PLA foamed samples saturated for 60 min at CO2 pressures of 870-psi and
2,500-psi and at various saturation temperatures.

3. EXTRUSION FOAMING
Several researchers have investigated the effect of crystallization on the foaming behavior
of PLA during the foam extrusion process [3]. It is well known that isothermal melt
crystallization occurs at temperature ranges between the PLA’s Tm and Tg [15]. As explained
earlier, during extrusion foaming, where the PLA/gas mixture can encounter isothermal melt
crystallization, a certain amount of nucleated crystals can affect the PLA’s foaming behavior
by enhancing the cell density and the expansion ratio.
In our recent study, extrusion foaming of PLA- nanoclay (CN) was extensively conducted
on a tandem extrusion system, as shown in Figure 4. Using this tandem extrusion system we
investigated the induction of isothermal melt crystallization along the second extruder in a
tandem line on the PLA foaming behavior with and without presence of CN [9]. A
commercial linear PLA (Ingeo 2002D) with a D-lactide content of 4.5% was supplied by
NatureWorks LLC, USA. The nanoclay (Cloisite 30B: alkyl quaternary ammonium bentonite)
was provided by Southern Clay Products Texas, USA. The PLA-CN master-batch was
prepared using a counter-rotating twin-screw extruder. CO2 was used as the physical foaming
 5th International Conference on Biofoams
Sorrento, October 13-16th 2015

agent. During the foaming of PLA nanocomposites, we varied the tandem line’s temperature
profile, and therefore, controlled the extruded PLA foam properties by varying the amount of
induced crystallization along the tandem line.

Figure 4. Schematic of the tandem extrusion line

Figures 5 and 6 shows the cell morphology of the PLA-CN foamed samples as well as their
expansion ratio follow by the temperature profile variations of the second extruder, which are
controlled by the induced crystallinity from varying the 2nd extruder’s temperature profile.
First of all, in the presence of dissolved CO2, clay, and shear action, the PLA crystallization
kinetics was significantly enhanced. The foamed results showed that both the cell density and
the expansion ratio were greatly promoted with increased clay content and the dissolved CO2,
as well as by the possibly nucleated crystals. On the other hand, Figures 5 and 6 shows that
reducing the temperature profile along the second extruder, with a constant residence time,
significantly enhanced the cell density and expansion ratio of the foamed samples. This was
most likely due to the accelerated isothermal crystallization of PLA and PLACN along the
extruder. Therefore, by choosing a lower temperature profile, we could expect a greater
degree of crystals and thereby enhanced cell nucleation rate through promoted heterogeneous
cell nucleation around the crystals and increased expansion ratio via improved melt strength.

Figure 5: Cell morphology of the PLA foams while varying the temperature profile of the second extruder.
 First A. Author, Second B. Author and Third C. Author

45
9 wt% CO2
PLACN5
40 PLACN1
PLA0

Expansion ratio
Zone 1 Zone 2 Zone 3 Heat e Die
Profile1 180°C 140°C 130°C 130°C 120°C
35 Profile2 180°C 135°C 125°C 125°C 120°C
Profile 3 180°C 130°C 120°C 120°C 120°C

30

25
Profile 1 Profile 2 Profile 3

Figure 6: Expansion ratios of the PLA foams while varying the temperature profile of the second extruder.

4. FOAM INJECTION MOLDING

We also investigated the PLA foam injection molding by incorporating talc and nanoclay to
enhance the cell density and to improve the cell uniformity along the foam injected molded
samples. It has been shown that not only the talc and more significantly nanoclay particles but
also the expedited crystallization through the additives increased the cell density and
enhanced the cell uniformity of the injected molded PLA foams.
The commercially available injection grade linear PLA, Ingeo™ 3001D, NatureWorks_
LLC was used. Talc and Cloisite 30B nanoclay were also used as the additives and N2 was
used as the physical blowing agent during the foam injection molding. A 50-ton Arburg
Allrounder 270/320 C injection molding machine (Lossburg, Germany) was used with
MuCell® technology. For samples with a void fraction of 30%, regular foam injection
molding (RFIM) was used, while the samples with 55% void fraction were fabricated using
foam injection molding with mold opening (FIM+MO).
Figure 7a shows the cellular morphology in the transition and core regions of PLA,
PLA/talc and PLA/clay foams with 30% void fraction made using RFIM. Compared to the
PLA composites, the more severe cell elongation was observed in neat PLA. In the PLA/talc
samples, the addition of 5 wt.% talc improved the PLA’s foam structure, specifically in the
core region. In the RFIM samples, the presence of talc improved the PLA’s cell nucleating
power and melt strength. In the PLA/clay samples, the addition of 5 wt.% nanoclay further
improved the cell morphology and yielded the highest cell density and the lowest cell size
compared to the other cases. The larger number of the uniformly dispersed nanoclay particles
together with the larger number of the crystals nucleated through the nanoparticles [16]
further improved the cell nucleation rate as well as the melt strength of the PLA/gas mixture.
Figure 7b shows the cellular morphology in the transition and core regions of the PLA and
PLA composite foams with 55% void fractions fabricated using FIM+MO method. In
FIM+MO, foaming was introduced after a noticeable time delay (9 s), which should have
decreased the melt temperature significantly. This cooling of the melt provided a chance for
PLA to further crystallize, especially with dissolved gas [15, 16-18], before foaming, and thus
to enhance the melt strength and cell nucleating power.
On the other hand, the fillers also played an important role for the cell morphology of the
foams made using FIM+MO. In PLA, the large cells in the bimodal structure were in the
range of hundred microns and the small cells in the range of tens of micron, an order of
magnitude smaller. The addition of 5 wt.% talc slightly improved the bimodal structure and
increased the number of smaller cells. On the other hand, the addition of 5 wt.% nanoclay
yielded a uniformly distributed cellular structure with the highest cell density and the lowest
 5th International Conference on Biofoams
Sorrento, October 13-16th 2015

cell size compared to the other cases in its bimodal structure. PLA/clay foams possessed cells
with relatively uniform spherical shape, with average cell sizes of less than 50 µm and cell
densities of more than 2×107 cells.cm-3. The average cell density and cell size of PLA,
PLA/talc and PLA/clay samples made using RFIM and FIM+MO are given in Figure 8. The
quality of foams based on the smaller cell size and higher cell density can thus be ordered as
PLA/clay > PLA/talc > PLA. In PLA, the average cell size increased from 94 µm to 224 µm
when the void fraction was increased from 30% to 55%. However, when the nanoclay was
used, the small cell size could be maintained with an increase in the void fraction.

Figure 7: (a) Representative SEM micrographs of PLA, PLA/talc and PLA/clay foams with 30% void fraction
and (b) with 55% void fraction. Lower micrographs show the cell morphologies of the transition and core
regions. Magnification is the same for each row.

Figure 8: (a) Average cell size and (b) average cell density of PLA, PLA/talc and PLA/clay foams of RFIM and
FIM+MO, measured in the core region. Error bars show ± one standard deviation.

5. CONCLUSIONS
Investigations of PLA foaming behaviors showed that adding micro-sized additives and
more effectively nanoparticles improved the PLA foams cell nucleation rate and the final cell
density by enhancing the heterogeneous cell nucleation power through the local pressure
variations around these additives. Moreover, the introduced additives can also expedite the
crystal nucleation rate, which could further improve the cell density through the similar path
that the additives affect. In general, the enhanced crystallization kinetics can significantly
increase the expansion ratio and the cell density of the PLA foamed samples. The crystal
nuclei that are induced during foam processing can increase the PLA’s inherently low melt
strength through the crystal-to-crystal network. Simultaneously, the crystal nuclei act as
heterogeneous cell nucleating agents and can promote cell density.
 First A. Author, Second B. Author and Third C. Author

It should be noted that although the cell density of the PLA foams can be promoted by
introducing micro-/nano-sized additives and crystallinity, too high an additive content and/or
crystallinity can hinder the expansion ratio of the PLA foams due to the PLA’s increased
stiffness.

REFERENCES
[1] D.W. Grijpma, and A.J. Pennings, (Co)polymers of L-lactide, 2. Mechanical properties.
Macromolecular Chemistry and Physics, 195, 1994, pp. 1649-1663
[2] D. Garlotta, A literature review of poly(lactic acid), Journal of Polymers and the Environment, 9
(2), 2001, pp. 63-84.
[3] M. Nofar, and C.B. Park, Poly (lactic acid) foaming, Progress in Polymer Science, 39 (10),
2014, pp. 1721-1741.
[4] L.T. Lim, R. Auras, and M. Rubino, Processing technologies for poly (lactic acid), Progress in
Polymer Science, 33, 2008, pp. 820-852.
[5] J. Dorgan, and J. Williams, Melt rheology of poly(lactic acid): Entanglement and chain
architecture effects, Journal of Rheology, 43, 1999, pp. 1141-1155.
[6] J. Dorgan, J. Janzen, M. Clayton, S. Hait, and D. Knauss, Melt rheology of variable L-content
poly(lactic acid), Journal of Rheology, 45, 2005, pp. 607-619.
[7] S.S. Ray, P. Maiti, M. Okamoto, K. Yamada, and K. Ueda, New polylactide/layered silicate
nanocomposites. 1. preparation, characterization, and properties, Macromolecules, 35, 2002, pp.
3104-3110.
[8] R.M. Rasal, A.V. Janorkar, and D.E. Hirt, Poly(lactic acid) modifications, Progress in Polymer
Science, 35, 2010, pp. 338-356.
[9] M. Keshtkar, M. Nofar, C.B. Park, and P. Carreau, Extruded PLA/clay nanocomposite foams
blown with supercritical CO2, Polymer, 55 (16), 2014, pp. 4077-4090
[10] Y. Srithep, P. Nealey, and L.S. Turng, Effects of annealing time and temperature on the
crystallinity, heat resistance behavior, and mechanical properties of injection molded poly(lactic
acid) (PLA), Polymer Engineering Science, 53, 2013, pp. 580-588.
[11] M. Nofar, A. Ameli, and C.B. Park, Development of Polylactide bead foam with double crystal
melting peak structure, Polymer, 2015, 69C, 83-94, DOI: 10.1016/j.polymer.2015.05.048
[12] M. Nofar, A. Ameli, and C.B. Park, A Novel Technology to Manufacture Biodegradable
Polylactide Bead Foam Products, Materials and Design, In Press, Accepted Manuscript, DOI:
10.1016/j.matdes.2015.06.052
[13] M. Nofar, Y. Guo, and C.B. Park, Double crystal melting peak generation for expanded
polypropylene bead foam manufacturing, Industrial Engineering Chemistry Research, 52, 2013,
pp. 2297−2303
[14] A. Wong, Y. Guo, and C.B. Park, Fundamental mechanisms of cell nucleation in polypropylene
foaming with supercritical carbon dioxide - effects of extensional stresses and crystals. Journal
of Supercritical Fluids, 79, 2013, pp. 142–151.
[15] M. Nofar, W. Zhu, and C.B. Park, Effect of dissolved CO2 on the crystallization behavior of
linear and branched PLA, Polymer, 53, 2012, pp. 3341-3353.
[15] A. Ameli, M. Nofar, D. Jahani, C.B. Park, Development of high void fraction polylactide
composite foams using injection molding: crystallization and foaming behaviors, Chemical
Engineering Journal, 262, 2015, pp. 78-87
[16] M. Nofar, A. Tabatabaei, C.B. Park, Effects of nano-/micro-sized additives on the
crystallization behaviors of PLA and PLA/CO2 mixtures, Polymer, 54, 2013, pp. 2382-2391
[17] M. Nofar, A. Ameli, C.B. Park, The thermal behavior of polylactide with different D-lactide
content in the presence of dissolved CO2, Macromolecular Materials and Engineering, 299 (10),
2014, pp. 1232–1239
[18] M. Nofar, A. Tabatabaei, A. Ameli, C.B. Park, Comparison of melting and crystallization
behaviors of polylactide under high-pressure CO2, N2, and He, Polymer, 54, 2013, pp. 6471-
6478

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