Chemical Engineering Science 75 (2012) 49–62

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

The effects of extensional stresses on the foamability of polystyrene–talc

composites blown with carbon dioxide
Anson Wong, Chul B. Park n
Department of Mechanical & Industrial Engineering, University of Toronto, Toronto, Ontario, Canada M5S 3G8

a r t i c l e i n f o abstract

Article history: This study investigated the effects of extensional strain and strain rates on the foamability of PS–talc
Received 3 December 2011 composite. Foaming processes were observed in situ for PS–talc composites with different surface
Received in revised form treatment, size, and weight content of talc under extensional stress. Talc with the largest particle size
8 February 2012
produced the highest cell densities despite its lower talc particle density for heterogeneous nucleation.
Accepted 13 February 2012
Available online 3 March 2012
Meanwhile, the surface treatment seemed to slightly improve the talc’s dispersion, but it did not cause
significant differences in their foaming characteristics. The enhanced cell nucleation that took place
Keywords: with the larger talc was due to the higher tensile stresses generated around them in the presence of
Plastic foam other growing bubble as compared to those around smaller talc particles. As the level of the applied
Polystyrene
extensional strain and/or the strain rate increased, the cell density increased significantly in all cases,
Talc
and the cell density differences became smaller, especially when the talc content was high. The
Extensional stress
Visualization extensional stress caused the decrease of local pressure needed to induce nucleation around the smaller
Nucleation talc particles, so the effects of talc size became less apparent.
& 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Nucleating agents are often needed in plastic foaming processes
to produce foams with high cell densities, small cell sizes, and
narrow cell size distributions. Microcellular plastic foams, which
are defined as foams with cell densities of 109–1015 cells/cm3
and an average cell diameter of 0.1–10 mm (Park et al., 1995),
possess these characteristics. Compared with conventional foams
or their unfoamed counterparts, microcellular foams exhibit
improved mechanical properties such as impact strength
(Collias and Baird, 1995; Doroudiani et al., 1998; Matuana et al.,
1997; Michaeli et al., 2009; Shimbo et al., 2007) and fatigue life
(Seeler and Kumar, 1993), thermal stability (Shimbo et al., 1992)
and insulation (Suh et al., 2000), acoustical insulation (Suh et al.,
2000), and optical properties (Kabumoto et al., 1998). Dating as
early as Hansen and Martin’s work in the 1960s (Hansen and
Martin, 1964), several studies have investigated the effectiveness
of various nucleating agents in plastic foaming processes. For
example, Yang and Han (1984) compared the foamability of low
density polyethylene (LDPE) blends using 9 different nucleating
agents (aluminum stearate, calcium carbonate, calcium hydro-
xide, calcium stearate, Celogen CB, sodium bicarbonate, sodium
bicarbonate/citric acid mixture, talc, and zinc stearate). Colton
and Suh (1987a, b) carried out theoretical and experimental
studies on heterogeneous cell nucleation phenomena using
n
Corresponding author. Tel.: þ1 416 978 3053; fax: þ1 416 978 0947.
E-mail address: park@mie.utoronto.ca (C.B. Park).
polystyrene (PS) filled with zinc stearate, stearate acid, and
carbon black. In a subsequent study by Colton (1989), the
microcellular foams of semi-crystalline polymers (polypropylene)
were produced using talc and sodium benzoate as nucleating
agents. Chen et al. (2002) investigated the effects of the filler size
of calcium carbonate, talc, and titanium oxide on the foamability
of high density polyethylene (HDPE). They found that a smaller
additive size led to a higher cell density when the gas saturation
pressure was high. Ramesh et al. (1994a, b) developed a cell
nucleation model based on the survival of microvoids generated
in the rubber particles and experimentally verified this concept
with PS–rubber composites. Kim et al. (2011) found that rubber
particles need to have a critical size in the foaming of thermo-
plastic olefin (TPO) to achieve the maximum cell density. In
theory, a smaller nucleating agent has higher number density-
and surface area-to-weight ratio. Hence, the number of nucleating
sites and the total area for heterogeneous nucleation are also
higher than for larger particles of the same weight content.
Consequently, a number of researchers have also investigated
the feasibility of nano-particles such as nanoclay (Jiang et al.,
2009; Lee et al., 2005; Pilla et al., 2010), nanosilica (Lee et al.,
2011; Saiz-Arroyo et al., 2011; Zhai et al., 2006), nanocellulose
(Kuboki et al., 2009), carbon nanofiber (Shen et al., 2006), and
carbon nanotubes (Pilla et al., 2007) as nucleating agents.
In addition to promoting cell nucleation, it has also been sug-
gested that nano-particles could also suppress cell coalescence
and coarsening, which are the two major cell deterioration
mechanisms that lead to non-uniform cell morphology and foam
shrinkage (Okamoto et al., 2001).

0009-2509/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2012.02.040
50 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62
Of the nucleating agents mentioned above, talc is one of the
most widely used due to its effectiveness in promoting cell
nucleation, the ease with which it disperses in polymer, and its
low cost. Many research studies have been conducted to identify
the optimal talc content and processing conditions for the foam-
ing of various polymer–talc composites, such as LDPE (Han et al.,
1976; Yang and Han, 1984), HDPE (Chen et al., 2002; Lee and Park,
2006), PP (Colton, 1989; Naguib et al., 2003; Park et al., 1998), PS
(Xu et al., 2003), and PLA (Pilla et al., 2009). Our previous study
(Leung et al., 2012) investigated the foaming processes of PS–talc
composites (three types of talcs with different sizes and surface
treatment) by direct in situ observation of the foaming processes
under static conditions. It was observed that the growth of
existing cells triggered additional cell nucleation in the surround-
ing regions, where the cells nucleated in clusters and rapidly
propagated (see Fig. 1). This result verified the cell nucleation
mechanism first described by Albalak et al. (1990) in their
polymer devolatization study. They found that the growth of
adjacent cells caused tensile stresses that decreased the local
system pressure, which subsequently increased the degree of
supersaturation and hence cell nucleation rate in these regions
(Albalak et al., 1990). On the other hand, under the processing
conditions investigated in our previous study (Leung et al., 2012),
the clustering cell nucleating phenomena that induced simulta-
neous cell nucleation in multiple layers caused a significant light
scattering around the nucleated cells, hence making the charac-
terization of the numbers and sizes of cells from the foaming
images extremely difficult and prone to error. Consequently, the
effects of talc size and surface treatment could not be evaluated
accurately.
In industrial plastic foaming processes, molten polymers often
flow through a sequence of converging sections, notably within
the die of an extrusion foaming line or the injection nozzle of a
structural foam molding system. Due to the viscoelastic nature of
polymers, extensional stress is retained near the die exit where
foaming occurs. Therefore, to evaluate their effectiveness, it is
imperative to study the foamability of the PS–talc composites
under an extensional flow. We have demonstrated previously that
an applied extensional strain significantly improved the effec-
tiveness of talc in enhancing cell nucleation in PS–talc composites
(Wong et al., 2011). Specifically, when a PS sample blended with
5 wt% talc was stretched uniaxially, the foaming process occurred
faster, and the maximum cell density increased more than two-
orders of magnitude, as compared with the static case. However,
since only one type of talc was used, the effects of surface
treatment and particle size remained unclear. Using the same
talc that we used in our previous study (Leung et al., 2012), our
current study has been expanded to investigate the foamability of
PS blended with various weight content of talc particles that have
different particle sizes and surface treatments under extensional
flow. To allow us to analyze the cell nucleation and growth
processes in situ at different levels of extensional strain and
extensional strain rates, this study was conducted using the batch
foaming visualization system developed in our previous work
(Wong et al., 2011).
Fig. 1. Schematics of the bubble formation phenomena of PS/CO2 system with talc
(Leung et al., 2012).
2. Theoretical background
According to the classical nucleation theory (Blander and Katz,
1975; Gibbs, 1961), the critical radius (Rcr) dictates the growth or
collapse of a nucleated cell: one that is bigger than Rcr grows
spontaneously, and the one that is smaller than Rcr collapses. For
both homogeneous and heterogeneous nucleation, Rcr is given as
follows:
2glg
Rcr ¼ ð1Þ
P bub,cr P sys
where Pbub,cr is the pressure inside a bubble at the critical size; Psys
is the local system pressure around the bubble; and glg is the
surface tension at the liquid–gas interface. Blander and Katz
(1975) suggested that the nucleation rate is equal to the rate at
which bubbles at the critical size gain molecules and grow. Based
on this analysis, they derived the homogeneous nucleation rate
(Jhom) and heterogeneous nucleation rate (Jhet) as follows:
sffiffiffiffiffiffiffiffiffi !
2glg 16pg3lg
Jhom ¼ N exp  ð2Þ
pm 3kb T sys ðP bub,cr P sys Þ2
sffiffiffiffiffiffiffiffiffiffi !
2=3 2glg 16pg3lg F
Jhet ¼ N Q exp  ð3Þ
pmF 3kb T sys ðP bub,cr Psys Þ2
where N is the number of gas molecules per unit volume; m is the
molecular mass of the dissolved gas molecules; kb is Boltzmann’s
constant; Tsys is the local system temperature around the bubble;
F is the ratio of the volume of the heterogeneously nucleated
bubble on the nucleating site to the volume of a spherical bubble
with the same radius of curvature; and Q is the ratio of the liquid–
gas surface area of the heterogeneously nucleated bubble to
the surface area of a spherical bubble with the same radius of
curvature. Both F and Q depend on the surface geometry of the
nucleating agent and the contact angle (yc) between the bubble
surface and the nucleating agent surface measured in the polymer
phase. Their expressions for various geometries have been
derived previously. Specifically, Fisher (1948) considered the case
where a bubble nucleates on a smooth and rigid planar surface,
such as glass. Fletcher (1958) and Wilt (1986) studied bubble
nucleation on a rigid spherical surface. Alternatively, if the
spherical dispersed phase is softer than the polymer matrix
(e.g., rubber in a PS matrix at a low temperature), cell nucleation
could occur in the spherical cavity. This scenario was examined
by Wilt (1986) and Cole (1974). Meanwhile, Apfel (1971) studied
the case where deformation occurred to both the bulk and
dispersed phases. This happened if the stiffnesses of the dispersed
and the bulk phases were similar as in polymer blends. Further-
more, Wilt (1986) and Cole (1974) also studied nucleation in
conical cavities, which can be used to model the irregular surface
roughness and geometry of many nucleation agents and their
agglomerates, such as talc. Using their expressions of F and Q
factors for a conical cavity, Leung et al. (2006) proposed a modified
heterogeneous nucleation theory whereby nucleating sites con-
sisted of conical cavities of various semi-conical angles (b) to
simulate the random and rough surface geometry of nucleating
agents. The expression for F and Q and the resulting formula for the
heterogeneous nucleation rate are given in the following formula
(Cole, 1974; Leung et al., 2006; Wilt, 1986):
 
1 cos yc cos2 ðyc bÞ
Fðyc , bÞ ¼ 22 sinðyc bÞ þ
4 sin b
1sinðyc bÞ
Q ðyc , bÞ ¼ ð4Þ
2
 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62 51

sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi !
Z 16pg3lg Fðyc , bÞ nucleation and growth processes with various distributions of b,
2=3 2glg
Jhet ¼ rb ðbÞN Q ðyc , bÞ exp  db ð5Þ which demonstrated that cell nucleation rates and cell densities
b pmFðyc , bÞ 3kb T sys ðP bub,cr Psys Þ2

were significantly affected by rb(b) (Leung et al., 2008). In general,

where rb(b) is the probability density function of b. Based on this a small b led to a higher cell density since the values of both F and
theory, Leung et al. numerically simulated simultaneous cell Q were also lower. Meanwhile, Wang et al. (2010) simulated the
pressure profile around a solid particle near the presence of a
Table 1 growing cell under the following three constraints for the solid
Summary of talc characteristics. particle: static; simple rotation; and a combination of translation
and rotation. It was demonstrated that tensile stresses exist in local
Name Median particle Surface
regions around a particle in each case. This result supported the
size (mm) treatment
extensional stress-induced cell nucleation theory proposed by
Stellar 410 10 No Albalak et al. (1990) and confirmed in our previous work (Leung
Cimpact CB7 1.8 Yes et al., 2012).
Cimpact 710 1.7 No The stresses around particles result in a local pressure varia-
tion (DPlocal). Therefore, the local system pressure can deviate
from the overall system pressure (Psys), and can be represented as
(Psys þ DPlocal). Consequently, the stress effect can be incorporated
into the expression for Rcr and J by modifying the Psys terms in
Eqs. (1) and (4), respectively, as follows (Leung et al., 2012; Wong
et al., 2011):
2glg
Rcr ¼ ð6Þ
P bub,cr ðP sys þ DP local Þ
sffiffiffiffiffiffiffiffiffi !
2glg 16pg3lg
Jhom ¼ N exp  ð7Þ
pm 3kb T sys ðP bub,cr ðP sys þ DP local ÞÞ2
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi !
Z 16pg3lg Fðyc , bÞ
2glg
J het ¼ rb ðbÞN2=3 Q ðyc , bÞ exp  db
b pmFðyc , bÞ 3kb T sys ðP bub,cr ðP sys þ DP local ÞÞ 2

ð8Þ
When a polymer/gas solution is subjected to a compressive stress,
the DPlocal will be positive, so the overall degree of supersatura-
tion (i.e., Pbub,cr  (Psys þ DPlocal)) will be lowered. This leads to a
Fig. 2. Batch foaming visualization system with extensional stress-inducing decrease in the cell nucleation rate. On the other hand, if the
ability (Wong et al., 2011). polymer/gas solution is subjected to an extensional stress, the

Table 2
Summary of experimental cases.

Exp. # Tsys (1C) Psat (MPa)  dP/dt9avg (MPa/s) Talc wt% (%) e de/dt (s  1)

1 100 3.45 (500 psi) 6 0.5 0 2

2 100 3.45 (500 psi) 6 0.5 0.55 2
3 100 3.45 (500 psi) 6 0.5 1.1 2
4 100 3.45 (500 psi) 6 2.0 0 2
5 100 3.45 (500 psi) 6 2.0 0.55 2
6 100 3.45 (500 psi) 6 2.0 1.1 2
7 100 3.45 (500 psi) 6 5.0 0 2
8 100 3.45 (500 psi) 6 5.0 0.55 2
9 100 3.45 (500 psi) 6 5.0 1.1 2
10 100 3.45 (500 psi) 6 5.0 1.1 0.1

Fig. 3. Sample SEM pictures of PS–talc composites. (a) Cimpact CB7, talc wt% ¼ 5; (b) Stellar 410, talc wt%¼ 5.
52 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62
DPlocal will be negative, which will cause an increased overall
degree of supersaturation. Hence, the cell nucleation rate will
increase. In relation to the overall cell density, the unfoamed
volume (Nunfoam) at time t is determined by integrating the total
cell nucleation rate with respect to time from time¼0 to t, as
follows:
Z t
Nunf oam ðtÞ ¼ ðJhom ðt 0 Þ þ Ahet J het ðt 0 ÞÞdt 0 ð9Þ
0
where Ahet is the surface area of the nucleating agents per unit
volume of the polymer/gas solution. In this study, the talc size,
Fig. 4. Talc particle density and size distribution for talc wt%¼0.5. (a) Cimpact 710;
(b) Cimpact CB7; (c) Stellar 410.
surface treatment, and weight content of the PS–talc composites
were varied. Based on the assumption that the different talcs used
in this study were similarly shaped, the surface area-to-weight
content ratio was expected to decrease as the talc size increased
due to the decreased talc particle density. Therefore, when the
same talc content was used, the surface area available for
heterogeneous nucleation was expected to decrease as the talc
size increased. According to Eq. (9) this might have led to a
decreased nucleation rate. On the other hand, the disruption of
flow and hence the pressure variation (DPlocal) around a larger
Fig. 5. Talc particle density and size distribution for talc wt%¼ 2.0. (a) Cimpact 710;
(b) Cimpact CB7; (c) Stellar 410.
 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62 53

particle might also be higher than it would be for a smaller higher affinity between the PS and the talc would lead to a lower
particle. In regions where there exist higher tensile stresses, cell yc which, based on Eq. (4), would increase F and Q, and hence,
nucleation would be enhanced based on Eqs. (7) and (8). Mean- decrease tendency for cell nucleation. Further, the application
while, a surface treatment might lead to a change in the affinity of of extensional strain could lead to a negative DPlocal, and, there-
the talc particles for a polymer. If the affinity was increased by the fore, both the homogeneous and heterogeneous nucleation rates
surface treatment, a better dispersion of talc particles could be
expected during the polymer–talc compounding process, which
could lead to a higher talc particle density and lower average talc
particle size, hence favorable for cell nucleation. Meanwhile, the

Fig. 6. Talc particle density and size distribution for talc wt%¼5.0. (a) Cimpact 710; Fig. 7. Summary of particle density, size distribution, and surface area vs. talc wt%.
(b) Cimpact CB7; (c) Stellar 410. (a) Ntalc,avg; (b) savg; (c) Ahet,avg.
54 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62
would increase. This effect could vary depending on the level of
extensional strain and the strain rate, as well as the geometry,
surface characteristics, weight content, and size of the talc
particles. In this context, we investigated the effects of exten-
sional strain and the strain rate on cell nucleation behavior as the
talc size, surface treatment, and content were varied.
3. Methodology
3.1. Experimental materials and sample preparation
The plastic material used for the foaming experiments was
PS (Styron PS685D, Dow Chemical Ltd.). The PS melt flow index
and density were 1.5 g/10 min and 1.04 g/cm3, respectively. The
blowing agent used was CO2 (99% pure, Linde Gas Canada). Three
types of talc from Luzenac were used: Cimpact 710 (median talc
size¼ 1.7 mm, untreated), Cimpact CB7 (median talc size¼ 1.8 mm,
surface treated) and Stellar 410 (median talc size ¼10 mm,
untreated). Cimpact CB7 uses the same base talc particles as
Cimpact 710 but with the addition of a surface treatment.
Consequently they have a very similar talc size distribution and
median talc sizes. The surface treatment was proprietary, hence
the chemical characteristics were not disclosed. Nevertheless,
based on the dispersion of these talc particles in the PS matrix,
Fig. 8. Foaming sequences for talc wt%¼0.5. (a) e ¼ 0; (b) e ¼1.1 at de/dt¼ 2.
the relative affinity of these talcs on PS could be estimated. These
results could be used to analyze the effect of this surface
treatment on the foaming behavior of PS while keeping the
particle size distributions the same. Meanwhile, the surface
characteristics of Cimpact 710 and Stellar 410 are the same, so
a comparative study between these two PS-composites would
reveal the effects of talc sizes on plastic foaming processes.
Table 1 summarizes the talc properties. PS resins and talc
particles in powder form were first compounded to 20% PS–talc
in three master batches using a C.W. Brabender 3-piece batch
mixer with twin, counter-rotating roller blades and a 60 cm3
capacity. For all cases, the mixer was operated at 50 rpm and
180 1C for 10 min. Following this, these master batches were
compounded with different amounts of PS resins via the same
process to produce PS–talc composite samples with 0.5, 2.0, and
5.0 wt% of talc. Consequently a total of nine different PS–talc
composites were examined in this study. With a hot press
maintained at 180 1C, the PS–talc samples were then compression
molded to films 400 mm thick. Upon pressure release, the molded
films were quenched with a large reservoir of water at approxi-
mately 13 1C. The films were then cut into the shape of tensile test
samples (ASTM D638 Type V) using the standard mold used to
form the study’s test samples. During the cutting processes, the
mold was preheated to 100 1C to prevent the brittle test samples
from fracturing.
 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62
3.2. Experimental methods
Foaming experiments were carried out under the foaming
visualization system with extensional stress-inducing ability
(see Fig. 2). A plastic sample was first saturated with pressurized
CO2 at an elevated temperature within the chamber for 30 min.
A specific amount of one-dimensional extensional strain at a
controlled strain rate was subsequently applied to the sample by
the rotational motion of two counter-rotating rollers on which the
two ends of the samples were fixed. Immediately after the
application of strain, a computer system triggered the release of
gas via a solenoid valve, thus inducing a thermodynamic instabil-
ity that caused foaming to occur within the PS–talc samples. At
the same time, a high-speed camera with a high magnification
lens captured the foaming processes in situ. A desirable pressure
drop rate can be achieved by adjusting the size of the opening of a
metered valve along the gas release path. Our previous study
provided a detailed description of the design and operation
procedure of this system (Wong et al., 2011).
Since our goal was to study the effect of talc size and surface
treatment on the foaming behavior of PS–talc composites in an
extensional flow, the system temperature, saturation pressure, and
average pressure drop rate were kept constant at 100 1C, 3.45 MPa
(500 psi) and 6 MPa/s, respectively. Based on Li et al.’s PS/CO2
solubility data, the dissolved CO2 content in PS under these conditions
was 1.27 wt% (Li et al., 2004). The actual dissolved gas content might
have varied to a small degree due to the addition of talc, but the
Fig. 9. Foaming sequences for talc wt%¼ 2.0. (a) e ¼ 0; (b) e ¼1.1 at de/dt ¼2.
55
differences were expected to be negligible as a low gas content was
used. The levels of Psat and  dP/dt9avg were selected at low levels so
that the gas content and pressure drop effect would not dominate the
extensional strain effect in the foaming processes. Also, a low
temperature of 100 1C was chosen so that a higher level of exten-
sional stress would be induced in the sample with an applied strain
due to the higher viscosity and elasticity at that temperature. Stress
relaxation and gas loss via diffusion would also be slower at this low
temperature. Each of the PS–talc composites was first foamed under
static conditions (i.e., e ¼0). Subsequent foaming experiments were
conducted with strain e ¼0.55 and 1.1 while keeping de/dt constant
at 2 s  1. It is noted that the strain and strain rate values used in this
study were engineering strain and strain rates (i.e., e ¼ DL/L
and de/dt¼ d(DL/L)/dt). To investigate the effect of de/dt, additional
experiments using the samples with 5 wt% talc were conducted
with e ¼1.1 but at de/dt¼0.1 s  1. Each experiment referred to above
have been done three times to ensure the repeatability of the test
data. Table 2 summarizes the experimental cases for each of the
three talcs.
4. Results and discussion
4.1. Characterization of talc distribution in PS samples
Due to Cimpact 710 and Cimpact CB7 smaller sized talc
particles, we expected that larger numbers of these would be
56 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62

dispersed into the PS polymer matrix than would Stellar 410
when the same weight content of talc was used. But the actual
talc particle density and size distribution would also strongly
depend on the quality of the distributive and dispersive mixing in
the compounding stage. The talc particles would also be re-
oriented during the compression molding process. Therefore, to
obtain accurate information about talc distribution within the
plastic samples, three pieces of unfoamed samples were randomly
selected from each PS–talc composite, and scanning electronic
microscope (SEM) images were taken along a fractured surface of
each sample that was frozen with liquid nitrogen. In the SEM
images, the talc particles appeared to be white platelets of
different lengths. Fig. 3 shows sample SEM images of a PS-talc
composite with 5.0 wt% Cimpact CB7 and one with 5.0 wt% Stellar
410. The length of each talc platelet was carefully measured
within a known area (At). The measured data was then grouped

Fig. 10. Foaming sequences for talc wt%¼ 5.0. (a) e ¼ 0; (b) e ¼ 1.1 at de/dt¼2; (c) e ¼1.1 at de/dt¼ 0.1.
 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62
according to length, and frequency tables of talc size vs. length
were generated from the resulting data. Subsequently, the parti-
cle density of each length group (N italc ) was determined using the
following equation:
 3=2
ni
Nitalc ¼
At
where i¼1 to k (k equals the total number of length groups) and
ni represents the frequency of talc particles in the i-th length
group. This procedure was repeated three times for each PS–talc
composite to obtain the talc particle density vs. the length
distribution information. The average talc density vs. size dis-
tribution information is shown in a matrix of talc particle density
vs. length graphs in Figs. 4–6 for talc wt%¼0.5, 2.0 and 5.0,
respectively, where the error bars denote the standard deviations
of the three sets of test data. A similar technique was used in our
previous study (Leung et al., 2012). The total particle density
(Ntalc) of each sample was then determined as follows:
X
k difference between the savg of Cimpact 710 and Cimpact CB7 was
Ntalc ¼ N italc
i¼1
Finally, the average value of Ntalc, denoted as Ntalc,avg, of each
PS–talc composite was calculated (refer to Fig. 7a).
Figs. 4–6 show that the average particle densities for Stellar
410 were significantly lower than for the other two talcs. In
particular, Fig. 7a specifically demonstrates that the Ntalc,avg of
Fig. 11. Nunfoam vs. time and maximum Nunfoam for talc wt%¼ 0.5. (a) e ¼0; (b) e ¼ 0.55 at de/dt¼ 2; (c) e ¼1.1 at de/dt¼ 2; (d) maximum Nunfoam.
57
Stellar 410 was close to one order of magnitude lower than
Cimpact 710 and Cimpact CB7 for all three talc wt%. Meanwhile,
surface treatment seemed to help disperse the talc, as seen in the
higher Ntalc,avg of Cimpact CB7 compared with Cimpact 710 at a
higher talc content of 2% and 5%. This behavior was also observed
in our previous work (Leung et al., 2012). In this study, however,
ð10Þ
the effect was not as clear because there were significant varia-
tions in Ntalc for the PS–talc composites, as shown by the errors in
Ntalc,avg, which denoted the standard deviation of the Ntalc data
shown in Fig. 7a. The range of talc sizes for Stellar 410 were much
wider than for the other two talcs. A Gaussian distribution was
applied as a fitting curve to each of the three runs of the particle
density data, and the mean value of the Gaussian distributions
were obtained. The average value of s for each PS–talc composite
was then taken as the average talc size (savg) in each case, as
Fig. 7b shows. The errors represent the standard deviation of the s
data. We observed that the savg for Stellar 410 is significantly
larger than for the other two types of talc, which is reasonable
due to the larger median talc size of Stellar 410. Meanwhile, the
ð11Þ insignificant. To estimate the differences in Ahet for each case, we
assumed that each talc platelet had a circular disk shape with
diameter equal to savg. We also disregarded the surface area along
the thickness direction; hence, the total surface area of a talc
platelet was equal to twice the area of the circular disk. Therefore,
by taking the Ntalc,avg and savg data shown in Fig. 7a and b, the
average Ahet, denoted as Ahet,avg for each case, was determined
58 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62

through the following equation: calculated at each time instant using the following three equations:
hp i  
Ahet,avg ¼ Ntalc,avg s2avg ð12Þ NðtÞ 3=2
2 Nf oam ðtÞ ¼ ð14Þ
Ac
The results are summarized in Fig. 7c, which demonstrates that
Cimpact CB7 has the highest Ahet, followed by Cimpact 710, and Nunf oam ðtÞ ¼ Nf oam ðtÞ  VERðtÞ ð15Þ
finally Stellar 410, at all talc wt%. The errors of Ahet,avg, denoted as " ! #
DAhet,avg, were determined by error analysis using the following 4 X 10
R3i ðtÞ
VERðtÞ ¼ 1 þ p N f oam ðtÞ ð16Þ
equation: 3 i ¼ 1 10
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
DNtalc,avg 2 where VER(t) is an estimated volume expansion ratio at time t.
DðAhet,avg Þ ¼ Ahet,avg þ ð2Dsavg Þ2 ð13Þ Figs. 11–13 show the Nunfoam vs. time graphs for each PS–talc
N talc,avg
composite at different applied e levels (while keeping de/dt con-
where DNtalc,avg and Dsavg denote the errors in Ntalc,avg and savg, stant at 2 s  1) for talc wt%¼0.5, 2.0, and 5.0, respectively. The
respectively. maximum Nunfoam data is also summarized in Figs. 11d, 12d,
and 13d. The three different talc types that had the same talc
concentration and processing conditions were plotted on the same
4.2. Foaming results
graph so that their performance could be compared directly and
clearly. For all PS-composites, the cell nucleating rate and maximum
Samples of the foaming visualization data for selected experi-
cell density increased significantly as the applied e increased. In
mental conditions are shown in Figs. 8–10 for talc wt%¼0.5, 2.0,
most cases, the maximum cell densities at e ¼2 increased over two
and 5.0, respectively. The cell density with respect to the unfoamed
orders of magnitude as compared to the static cases. This phenom-
volume (Nunfoam) for each case was characterized based on the
enon was especially apparent for Cimpact 710 and CB7. Further,
method detailed in our previous study (Wong et al., 2007). A brief
Figs. 10b and c and 14 show that the cell density also increased
description of that is given here as follows: First, N(t), the number
significantly with the applied de/dt. To explain this behavior, we can
of cells within a superimposed circular boundary with an area of Ac
consider the PS–talc composites as viscoelastic materials whose
at time t was counted at each time instant until cell nucleation
stress–strain relationship conforms to the Kelvin–Voigt model as
ceased. The radii of 10 randomly selected bubbles at time t (i.e.,
follows:
Ri(t), where i¼1y10) were also measured. Subsequently, the cell
density with respect to the foamed volume, Nfoam(t), and the cell deðtÞ
sðtÞ ¼ EeðtÞ þ Z ð17Þ
density with respect to the unfoamed volume, Nunfoam(t), were dt

Fig. 12. Nunfoam vs. time and maximum Nunfoam for talc wt%¼ 2.0. (a) e ¼0; (b) e ¼ 0.55 at de/dt¼ 2; (c) e ¼1.1 at de/dt¼ 2; (d) maximum Nunfoam.
 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62
Fig. 13. Nunfoam vs. time and maximum Nunfoam for talc wt%¼ 5.0. (a) e ¼0; (b) e ¼ 0.55 at de/dt¼ 2; (c) e ¼1.1 at de/dt¼ 2; (d) maximum Nunfoam.
where the Ee(t) and the Zde/dt terms are the elastic and viscous
terms, respectively. From this model, it is clear that as e and/or
de/dt increased, the tensile stress, s(t), also increased, which
ultimately led to a decrease in the local system pressure due to an
increasingly negative DPlocal generated by the applied e. Therefore,
the cell nucleation rates increased according to Eqs. (7) and (8),
which eventually led to the increased cell densities based on Eq. (9).
Meanwhile, as DPlocal became more negative, the Rcr also decreased
(Eq. (6)). If the Rcr decreased below the radius of curvature in some
microvoids that originally reside in cavities on the surface of talc
particles due to incomplete wetting, these microvoids would have
grown spontaneously into nucleated cells.
It was found that, despite the lower Ntalc,avg and Ahet,avg of
Stellar 410 within the PS polymer, the PS–stellar 410 composites
had the earliest onset of cell nucleation and the highest maximum
cell densities in all cases. Since Stellar 410 has the highest savg,
this finding is inline with our hypothesis that larger particles can
be favorable for cell nucleation due to high pressure variations
around these particles. In the local regions where tensile stress is
present, Rcr decreased and Jhet increased according to Eqs. (6)
and (8), respectively. Therefore, earlier onset times for nucleation
and higher cell densities were observed in the Stellar 410 cases.
This effect was most dominant in the static cases. As the level of
applied e increased, the differences in the maximum cell densities
between each PS-composite at the same talc concentration were
also reduced. This was caused by the increased tensile stress that
was applied to the polymer as the level of the applied e or de/dt
59
increased. This action effectively lowered the local Psys. Hence,
more cell nucleation could occur around smaller talc particles,
such as those of Cimpact CB7 and Cimpact 710, despite their
lower ability to cause pressure variations in their surrounding
regions. Also, due to the lowered local Psys, smaller microvoids
would be activated to grow. Consequently, the talc size effects
became less dominant. Nevertheless, this study demonstrates
that larger nucleating agents might be superior to smaller ones
in enhancing cell nucleation despite their lower particle density
and surface area for heterogeneous nucleation. In addition to the
larger particle sizes, it is further noted that Stellar 410 exhibited
broader ranges of talc-size distribution when compared to the
other two talcs. This demonstrates that nucleating agents with
broad particle size distribution might be beneficial for foaming
due to the existence of large particles that helped to initiate
foaming.
The surface treatment used in this study did not result in a
conclusive trend in the foaming behavior. Since the Ahet of the
surface-treated talc (Cimpact CB7) was higher for all talc weight
contents, the surface treatment might have increased the affinity
between the PS and the talc particles. Hence, yc would be
decreased and cell nucleation would become less favorable on
these surfaces. Due to the competing phenomena of increased Ahet
and decreased yc, the surface treatment used in this study has no
significant effects on cell nucleation rate and density.
Importantly, while we observed that the increase of Ahet led to
a higher cell nucleation rate and cell density, the maximum
60 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62

Fig. 14. Effect of de/dt on Nunfoam vs. time and maximum Nunfoam for talc wt%¼5.0.
(a) Nunfoam vs. time; (b) maximum Nunfoam.

Nunfoam remained at low levels below 106 cells/cm3 in the static

condition for all PS–talc composites (see Fig. 15). To generate
a high cell density, in addition to including a large number of talc
particles, it is important to use a high e and de/dt to induce a high
level of extensional stress. These results suggest that in extrusion
foaming processes, the dies must be designed to induce sufficient
extensional stress to enhance the effectiveness of the cell nuclea-
tion agents.

5. Conclusion

Through in-situ observation of the plastic foaming processes of

PS–talc composites, the effects of extensional strain and strain rate
have been demonstrated. Nine different PS–talc composites have
been studied to elucidate the effects of surface treatment, size, and
the weight content of talc on the foamability of PS under extensional
stress. It has been demonstrated that the Stellar 410 talc, which has
the largest particle size, yielded the earliest onset of cell nucleation
and the highest cell densities at each talc content (i.e., 0.5%, 2.0%, Fig. 15. Maximum Nunfoam vs. Ntalc,avg. (a) e ¼ 0; (b) e ¼ 0.55 at de/dt¼2; (c) e ¼1.1 at
and 5.0%) despite its lower talc particle density and total surface de/dt¼0.1 and 2.
area than the Cimpact 710 and Cimpact CB7 talcs. The surface
treatment seemed to result in a better talc particle dispersion in the place with the larger talc particles was due to the higher tensile
PS–talc composites, but it did not cause noticeable differences in stresses generated around the larger particles when compared to the
their foaming behaviors. The enhanced cell nucleation that took smaller particles with other growing bubbles present. As the applied
 A. Wong, C.B. Park / Chemical Engineering Science 75 (2012) 49–62 61

extensional strain and/or the strain rate increased, the foaming
processes took less time to complete, and the cell density increased
significantly in all cases. Also, the differences in cell densities among
the different talc types became smaller, especially when the talc
content was high at 2.0% and 5.0%. As extensional strain and the
strain rate increased, the local tensile stresses in the polymer matrix
also increased. This caused a decrease of local pressure needed to
induce nucleation around the smaller talc particles. As a result, the
effect of talc size became less pronounced.
Acknowledgments
The authors are grateful to the Consortium of Cellular and
Micro-Cellular Plastics (CCMCP), the Ontario Research Foundation
(ORF), and the Natural Sciences and Engineering Research Council
of Canada (NSERC) for their financial support of this project.
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