Foams and Wood Composite Foams Produced by Rotomolding

Smithers Rapra Technology, 2013
199 Cellular Polymers, Vol. 32, No. 4, 2013

Foams and Wood Composite Foams Produced by Rotomolding
Foams and Wood Composite Foams
Produced by Rotomolding
Alexandre Raymond and Denis Rodrigue*
Universit Laval, Department of Chemical Engineering, 1065 Avenue de la Mdecine,
Quebec City, Quebec, Canada, G1V 0A6
SUMMARY
In this work, a simple method is presented to produce foams and wood
composite foams by rotational molding. As a special case, wood our (maple) /
linear low density polyethylene (LLDPE) was used to study the effect of chemical
blowing agent (CBA) concentration (0-0.6%wt.) and wood content (0-20%wt.).
From the samples produced, a complete characterization was performed
including density, morphology, and mechanical properties in tension and exion.
The results show that tensile and exural moduli increased with wood content,
while tensile strength and elongation at break decreased. The optimum wood
content was found to be around 20%wt. for the composites and around 0.4%
wt. CBA for the range of conditions studied.
Keywords: Polyethylene, Foams, Composites, Rotomolding
INTRODUCTION
Rotational molding (rotomolding, rotational casting, rotocasting) is a low
shear process used to produce almost stress free, one-piece hollow products
without weld lines [1]. With this process, a very wide range of part dimensions
can be produced; i.e. from very small (few grams) to very large (100,000 L
reservoirs) [2]. Rotational molding has signicant advantages over other
processing methods like injection molding and blow molding: easier to get
complex shapes (less design constraints), lower capital investment and
greater exibility with respect to material or color change from part to part.
These features are well recognized in all production sectors and this is why
rotomolding is still today one of the fastest growing process of the plastic
industry over the last few years.
*Denis.Rodrigue@gch.ulaval.ca
Alexandre Raymond and Denis Rodrigue
Even if different resins can be used for rotomolding, polyethylene has more
than 85% of the market today [1-2]. But for each resin, there is always the
possibility to improve on the properties (mechanical, thermal) via structural
modications. Two well-known modications are: adding reinforcement to
produce composites (higher mechanical properties) [3-4], and adding a blowing
agent to foam the material (lower density and higher insulation) [5-7]. Although
some literature can be found on composites and foams as separate materials,
almost nothing is available on composite foams (combining both into one).
One of the most used reinforcement over the last 10 years has been natural
(cellulosic) bres. This material was introduced into different resins to improve
mechanical properties, reduce raw material costs and give a natural look
(aesthetics) [8]. One major drawback of natural bres, is their hydrophilic
nature leading to poor adhesion to hydrophobic matrices and their tendency
to absorb moisture (humidity) from the atmosphere. Recently, Ward-Perron
and Rodrigue [9] showed that under most rotomolding conditions (biaxially
rotating mold heated at 10
o
C/min), wood bres can lose most of their humidity
(total content less than 1%wt.) in less than 5 min. This time is believed to
be enough so the material can be considered dried before the polymer resin
starts to melt and no prior wood treatment is needed (drying), thus simplifying
greatly processing in comparison with extrusion and injection molding of
typical wood-plastics composites (WPC). Furthermore, since all the materials
are in a powder/particle form (polymer, wood, chemical blowing agent), simple
dry-blending can be used to mix all the components which is again less time
and energy consuming than standard melt blending (extrusion + pelletizing/
pulverizing).
The main objective of this work was to produce foams and composite foams
by rotational molding using the single step process. In particular, the effect
of chemical blowing agent (0-0.6%wt.) and wood content (0-20%wt.) was
investigated using linear low density polyethylene as the matrix. To produce the
rotomolded parts, all the materials were dry-blended before being introduced
into the mold (no drying). As a rst step, no surface treatment of the wood
particles was done to improve adhesion with the polymer matrix.
EXPERIMENTAL
Materials
The polymer used was a grade of linear low density polyethylene (LLDPE):
EXXONMOBIL LL 8460.29. This polymer (ExxonMobil Chemical Canada) has
a melt ow index of 3.3 g/10 min (2.16 kg, 190
o
C) and a density of 938 kg/
m
3
. As reinforcement, maple wood our was purchased from PWI Industries
(St-Hyacinthe, Quebec, Canada). The material received was only sieved
and no surface treatment was performed. Only particles between 125 and
250 microns were used as they correspond to the average LLDPE particle
size as similar particle size will limit powder segregation in the dry-blending
and initial rotomolding steps. For foaming, the chemical blowing agent (CBA)
used was Celogen 754A (Chempoint, USA). Figure 1 presents typical images
of the materials used in a powder form.
Figure 1. Scanning electron micrographs of the raw materials: (a) LLDPE, (b) Maple
our, and (c) Celogen 754A
Sample Preparation
First, all the materials were dry-blended using an anchor-type mixer for 3
to 4 minutes. To simplify the process, the wood our was not dried before
processing as most of the volatiles inside the wood particles are believed to
be removed in the rst minutes of the rotational molding cycle as discussed
previously [9]. Figure 2 shows typical drying curves of the wood powder using
different amounts of material to simulate different powder bed thicknesses
Figure 2. Drying curves for the maple wood our used at a temperature ramp of
8.3C/min and different powder bed thickness
(4, 9 and 14 mm). The initial humidity was around 5.9%wt. for standard room
conditions (23
o
C, 50% RH). The measurements were performed at a heating
ramp of 8.3
o
C/min (from 50 to 150
o
C) to simulate typical rotomolding conditions
inside the mold. The tests were done on a MX-50 moisture analyzer (A&D
Company, Tokyo, Japan). The results indicated that up to 9 mm, less than 1%
humidity (material considered dried) is left in the wood particles for times higher
than 10 min (typical value before the polymer starts to melt and sticks to the
mold walls). Even for a 14 mm powder bed, the humidity is around 2.5% for
this time. Nevertheless, these drying results can be considered as worse-case
scenario for two reasons. First, wood content in the composite bed (blend
of wood our and LLDPE) was kept low (20% maximum here) so the total
humidity is directly proportional to wood content as polyethylene humidity
can be considered negligible (about 0.2%) [9]. Second, the measurements in
the humidity balance were performed under static conditions. In a biaxially
rotating mold, it is believed that heat and mass transfer is highly improved
due to convection, thus decreasing substantially the time to remove humidity
in the wood particles. Based on this analysis, humidity in the wood our can
be assumed to be almost zero under standard rotomolding conditions and
no prior drying step is needed before molding.
To produce rotomolded samples, a conventional shuttle-type rotomolding
machine with two-arms was used at WES Industries (Princeville, Quebec,
Canada). The aluminum mold selected had the shape of a two-level rectangular
box with total dimensions of 35 x 21 x 12 cm
3
. One vent on the side of the
mold (see Figure 3a), 12.5 mm in diameter, was lled with glass wool to
prevent powder losses. Typical examples of the molded parts are presented
in Figure 3. After preliminary runs, the optimum processing conditions for
the foams were: a 4:1 speed ratio, a heating time of 21 minutes with an oven
(natural gas heated) temperature of 280
o
C and a cooling time of 28 minutes
with forced air (blowing fans) during summer time (May-August 2012). For
the composite foams, the oven temperature was decreased to 270
o
C with
a cooling time of 24 min. Lower oven temperature is probably related to the
nucleating effect of the wood particles (less energy needed to decompose the
CBA and nucleate bubbles) and lower cooling time can be associated with
lower density reduction (less insulation effect leading to faster heat transfer) as
described in the Results section. In all cases, a demolding agent was applied
to help part removal. Finally, to eliminate shrinkage and warpage, the parts
were internally blown with compressed air. Characterization samples were
cut directly inside the at surfaces of the molded parts.
The rst series of samples was performed by changing the CBA content
(0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6%wt.) to produce the foams Then, a second
series of samples was produced using 0.1%wt. of CBA and changing wood
our content (0, 5, 10, 15, 20%wt.). For the composite foams, 0.1% CBA
was selected as this concentration was found to give a good compromise
Figure 3. Typical images of the rotomolded parts produced. a) Neat LLDPE (side
view), b) neat LLDPE (top view), c) foam (0.1%wt. CBA), and d) composite foam
(0.1%wt. CBA + 5%wt. maple our)
between density reduction and keeping mechanical strength. More results
and information can be found in another recent publication on the properties
of the wood composites alone [10].
Density
Density of LLDPE powder, maple our and molded composites/foams was
determined using a gas (nitrogen) pycnometer Ultrapyc 1200
e
(Quantachrome
Instruments, USA). The results reported are the average and standard deviation
of a minimum of 5 samples.
Morphology
The morphology of the molded parts was examined via scanning electron
microscopy (SEM) on a JEOL model JSM-840A. Each sample was cryogenically
fractured in liquid nitrogen to expose the internal structure and the surfaces
were coated with a thin layer of Au/Pd. Micrographs were taken at different
magnications to get a complete quantitative morphological analysis.
Foam morphology was characterized via two parameters: cell diameter (D)
and cell density (N
f
). Cell diameter was determined using Image-Pro Plus 4.5
(Media Cybernetics) on SEM images. The software calculates the average
of 90 diameters taken every 2 degree from the geometric center of each cell
area. Cell density, dened as the number of cell (N) per cubic centimeter of
foam is obtained by [11]:

N
f
=
N
A
3 2
(1)
where A is the area of the micrograph in cm
2
.
Mechanical Properties
Flexural modulus was measured on a model 5565 (Instron, USA) universal
tester in a three-point bending geometry (ASTM D790) using a 50 N load cell.
Five samples having cross-sections of about 14 x 5 mm
2
were tested. The
span (distance between supports) was set at 100 mm to limit internal shear
in the samples and the travel speed was set at 10 mm/min.
Youngs modulus, tensile strength and elongation at break were determined
using a model 5565 (Instron, USA) universal tester with a 500 N load cell.
Type V dog bone samples were cut from the molded parts according to ASTM
D638. The tests were performed at room temperature at a deformation rate
of 10 mm/min. A minimum of ve samples was used to get an average and
standard deviation.
RESULTS AND DISCUSSION
Figure 4 present typical morphologies for the foams and composites foams
produced. Even for the neat polymer (0, 0), some porosity can be observed
Figure 4. Typical morphologies of the rotomolded parts. The numbers in parenthesis
represent (CBA content, wood our content) in wt.%
as rotomolded parts are usually slightly undercooked to limit polymer (and
wood here) degradation. Based on the density results of Figure 5, porosity is
estimated at 1% (0.925 vs. 0.938 g/cm
3
) which can modify the nal mechanical
properties of the parts (as discussed later). Then, it is clear that increasing
blowing agent content increased the number of bubble (cell density), thus
decreasing density (Figure 4) as more gas is generated and trapped inside the
molten polymer matrix. In our case, an optimum CBA content was obtained
around 0.5% as higher values did not decreased density further. Actually,
density was higher at 0.6% CBA as possible gas loss and cell collapse (broken
cell walls) can be seen in sample (0.6, 0) in Figure 4. Nevertheless, a wide
range of part density (0.449-0.722 g/cm
3
) was achieved (Figure 4) with good
and uniform cell structure, especially for CBA content between 0.3 and 0.6%.
To analyze further the foam morphology, Table 1 presents the results obtained
for average cell diameter and cell density. It is clear again that an optimum is
Figure 5. Density of the rotomolded foams (top) and composite foams (bottom)
obtained here, but closer to 0.3% CBA where minimum cell size and maximum
cell density are obtained simultaneously.
Table 1. Morphological parameters of the foams
produced
CBA content
(%wt.)
D
(mm)
N
f
(10
3
cells/cm
3
)
0.1 471 155 2.66
0.2 445 126 9.54
0.3 401 134 16.4
0.4 458 143 12.6
0.5 482 150 11.0
0.6 513 127 10.0
For the composite foams, the morphology does not seem to be as homogeneous
as the neat foams. In this case, cell size distribution is very large due to the
presence of wood particles which are known to act as nucleating agents [12]
and also limit gas diffusion [13], thus creating possible gas pockets in the
polymer melts. Also, the morphology of composite foams is always difcult
to quantify as most of the big voids seen in the micrographs are coming from
bre pull-out. Nevertheless, based on the results of Figure 5, density did
not changed substantially with wood content up to 15% since the blowing
agent content was constant, and increased slightly at 20% wood as wood
density (1.480 g/cm
3
) is higher than LLDPE (0.938 g/cm
3
). Again, this will
affect mechanical properties as discussed next.
For the exural modulus, Figure 6 shows that decreasing foam density led to
substantial decrease: up to 83% lower at 0.6% CBA. This is expected as less
material is available to sustain the stresses when density decreases [14-15]. On
the other hand, keeping the density almost constant (constant CBA content),
adding wood particles led to substantial increase in exural modulus. In our
case, an increase of 62% (from 408 to 655 MPa) was obtained by adding
20%wt. of maple our. This results clearly shows that composites foam can
be made by rotomolding and can have similar exural modulus as the neat
polymer (655 vs. 680 MPa), but at lower density (0.884 vs. 0.925 g/cm
3
).
Finally, Figures 7-9 present the tensile properties of the foams and composite
foams in terms of modulus (Figure 7), strength (Figure 8) and elongation at
break (Figure 9). As for exural modulus results, tensile modulus is decreasing
with increasing CBA content. In this case, the decrease is 86% (from 184 to
26 MPa) which is higher than the 62% in exion. On the other hand, adding
wood particles led again to a slight modulus increase (24%) compared to the
Figure 6. Flexural modulus of the rotomolded foams (top) and composite foams (bottom)
Figure 7. Tensile modulus of the rotomolded foams (top) and composite foams (bottom)
foam without wood our. This can be related to possible orthotropic particle
orientation inside the sample due to the biaxial rotation of the molding in
processing. Small variation in modulus trend can be related to inhomogeneities
in the composite foam morphology as presented in Figure 4. This would need
more work to improve processing and get optimized results.
For tensile strength, Figure 8 shows that the value decreases with increasing
CBA content. Nevertheless, the values for the composite foams are lower than
for the neat foam, but almost constant indicating that good contact occurs at
the wood-polymer interface. Actually, there was no clear evidence that bad
contact (voids, cracks, gas cells) occurred in our samples as presented in
Figure 10, even if rotomolding is a low pressure process. Nevertheless, good
contact (physical) does not mean good adhesion (chemical). This aspect will
also need more work as surface treatment of the wood particles can be made
before dry-blending and rotomolding. This aspect is currently being studied.
Finally, Figure 9 presents the results for the elongation at break. Again, the values
are decreasing with increasing CBA content as most polymer foams become
Figure 8. Tensile strength of the rotomolded foams (top) and composite foams (bottom)
more brittle than their polymer matrix counterpart [16-17]. For the composite
foams, elongation at break is decreasing even more with increasing wood
content as the particles have lower elasticity compared to the polymer matrix.
CONCLUSIONS
In this work, foams and composites foams were produced via rotomolding.
In particular, the chemical blowing agent concentration range studied was
0-0.6%wt., while the maple our content was varied between 0 and 20%wt.
From the results obtained, several conclusions can be obtained:
Rotomolded parts can be produced by the simple dry-blending technique
since all the raw materials are in a powder form. But careful control of the
particle size distribution must be made to limit possible segregation related
to material handling and biaxial rotation of the mold.
Figure 9. Tensile elongation at break of the rotomolded foams (top) and composite
foams (bottom)
Wood-polymer composites can be produced without the necessity of
wood drying before processing. Based on dynamic drying curves and SEM
micrographs of the wood-polymer interface in the nal parts, no clear voids
or gas cells were observed indicating good physical contact between both
phases.
The optimum blowing agent content for the processing conditions selected
should be around 0.4%. This value represents a compromise between 0.5%
giving the lowest density (0.449 g/cm
3
) and 0.3% giving the most uniform
cell structure (lowest cell size of 401 microns and highest cell density of
16.4x10
3
cells/cm
3
). For the composite foams, 20%wt. wood our gave the
highest mechanical properties (modulus) in tension and exion.
Although the wood composites have good aesthetic properties (natural look),
more work needs to be done in order to improve the homogeneity of the
molded parts, to increase the stress transfer at the wood-polymer interface
and to increase even more wood content for enhanced material properties.
These investigations are currently under way and the results will be reported
in a future communication.
ACKNOWLEDGEMENTS
Financial support from the National Science and Engineering Research
Council of Canada (NSERC) was appreciated. Technical support from the
Research Centre on Advanced Materials (CERMA) was also highly useful.
LLDPE samples from ExxonMobil Chemical Canada (Ron Cooke) are highly
appreciated. Finally, WES industries inc. is highly thanked for machine time
allowing to perform the experimental work related to sample preparation (dry
blending) and rotomolding samples. Thanks also to Q. Hatte for the humidity
measurements and Y. Giroux for the density measurements.
REFERENCES
1. Crawford R.J. and Throne J.L., Rotational Molding Technology, William
Andrew Publishing and Plastics Design Library, USA (2002).
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4. Ward-Perron N. and Rodrigue D., Proc. of SPE ANTEC, paper 00467 (2012).
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Smithers Rapra Technology, 2013

199 Cellular Polymers, Vol. 32, No. 4, 2013

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