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Processing Enhancers for Rotational Molding of Polyethylene

Article  in  Polymer Engineering and Science · April 2004

DOI: 10.1002/pen.10870

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 Processing Enhancers for
Rotational Molding of Polyethylene
BHARAT INDU CHAUDHARY*

The Doto Chemical company

2301 N. Brazosport Blvd
Freeport, lX 77541

ELIZABETH TAKk2S

Department of Chemical Engineering

McMaster University
Hamilton, Ontario, Canada L8S 4L7

JOHN VLACHOPOULOS

Department of Chemical Engineering

McMaster University
Hamilton, Ontario, Canada L8S 4L7

Rotational molding is a zero shear process used to manufacture hollow plastic

parts. One disadvantage of this process is long cycle times, which are significantly
affected by the sintering rates of thermoplastic powder. The objective of this work
was to evaluate low molecular weght additives as sintering enhancers for polyethyl-
ene and to validate the results in rotational molding. The following additives were
blended with linear low-density polyethylene: mineral oil, glycerol monostearate and
pentaerythntol monooleate. The additives resulted in decreased melt viscosity and/or
elasticity at low shear rate. The reduction in melt elasticity was particularly signifi-
cant. Sintering studies confirmed that the additives resulted in sigdcantly faster co-
alescence. In uniaxial rotational molding, the decreased melt viscosity and elasticity
obtained with mineral oil were observed to result in much faster densification and
bubble removal. Part thickness was uniform and there was no warpage. Adding
mineral oil to polyethylene reduced the cycle time in uniaxial rotational molding
and the peak impact strength was identical to that obtained without any additive.
Biaxial rotational molding experiments confirmed that the use of mineral oil re-
sulted in shorter cycle time without sacrificing peak impact strength.

INTRODUCTION stages in the rotational molding cycle are the powder

melting and sintering (5).During the tumbling process,
R otational molding, also known as rotomolding,
is a shear and pressure free process used to
manufacture hollow plastic parts such as toys, con-
the fmer powder particles get sieved down closer to
the wall and the larger particles form layers on top (6).
As the temperature rises in the mold, the powder soft-
tainers, tanks, kayaks, and playground equipment
ens and melts, adhering to the mold wall (6) and
with relatively low investment (1). It involves the tum-
forming a homogenous, bubble free melt pool along
bling, heating and melting of thermoplastic powder,
the entire inside surface of the mold. Biaxial rotation
typically of 35 mesh particle size, in a biaxially rotat-
ensures that the powder is evenly distributed in the
ing mold, followed by coalescence, fusion or sintering
mold. After the heating cycle is completed, the mold is
and cooling (1-4), The fundamental and controlling
cooled resulting in solidification of the polymer. The
amount of powder determines the wall thickness of
'Corresponding author. E-mail: bchaudhary@dow.com the rotomolded part.

POLYMER ENGINEERING AND SCIENCE, OCTOBER 2001, Vol. 41, NO. 10 1731
 Bharat Indu Chaudhary, Elizabeth T a k k s , and John vlachop~ulos
A number of researchers (3,5-2 1) have studied var-
ious aspects of rotational molding, such as heat
transfer, fluid flow phenomena, mechanical properties
of the molded parts, sintering, computer simulation of
the process, bubble formation and removal, and the
use of micropellets in rotational molding. Polyethylene
accounts for more than 85% of the volume in roto-
molding ( 1, 5) because of its acceptable processability,
good thermal stability (4) and good mechanical prop-
erties. Hence, many of the studies have focused on
the rotational molding of linear low-density polyethyl-
ene, but a considerable amount of research has also
been done on other materials (4, 22-24), including the
polyolefms made using single site metallocene catalyst
systems (25-27).
Cycle times in rotational molding are long (about
25-30 minutes) and the maximum air temperature in-
side the mold can be as high as 200-3OO0C, depend-
ing on the type of polymer. Conventionally, cycle
times have been reduced by using polyethylene of re-
duced molecular weight or melt viscosity. However,
this can result in inferior impact strength. This paper
describes novel polymer compositions that result in
reduced cycle times and which do not adversely affect
impact strength. This has been achieved by blending
small amounts of low molecular weight additives with
polyethylene resulting in reduced melt viscosity and/
or elasticity at zero or low shear rate, particularly the
melt elasticity, which in turn yields faster sintering
and enhanced bubble removal during rotational mold-
ing.
EXPERIMENTAL
Various low molecular weight additives were blended
with linear low-density polyethylene (LLDPE) using a
30-mm twin-screw extruder. A relatively high loading
of the additives, 3 weight percent (Yo), was used in
order to significantly affect melt viscosity and elas-
ticity. The characteristics of the LLDPE are given in
Table 1. The additives used were mineral oil (MO), glyc-
erol monostearate (GMS) and pentaerythritol mono-
oleate (PEMO). The grades of GMS and PEMO used
were Atmer (Trademark of ICI) 129 and Emerest
(Trademark of Henkel) 2427, respectively.
Mineral oil and PEMO were liquids at room temper-
ature whereas GMS was in the form of solid pellets
with a melting point of about 70°C. The additives were
first tumble blended with LLDPE pellets and then
melt blended on the twin-screw extruder. The LLDPE
Table 1. Properties Before Pulverization
Density (g/cm3)
Melt Index (dl0min)
ESCR (hours)
Notched lzod Impact Strensth (J/m) at 40°C
1732
was also extruded to make a control formulation with-
out the additives. Melt temperatures ranged from
203°C to 210°C.
The extruded formulations were pelletized and the
following properties were measured: density in accor-
dance with ASTM D-792; melt index (2.16 kg, 190°C)
in accordance with ASTM D- 1238; environmental
stress crack resistance (ESCR), in accordance with
ASTM D-1693, measured by immersing 10 notched
specimens of each sample in a 10% lgepal solution
and observing the time taken for 50% of the speci-
mens to break; and notched Izod impact strength of
compression molded specimens in accordance with
ASTM D-256.
After melt blending and extrusion, pellets were
made that were subsequently pulverized (at identical
grinding conditions) and characterized. Bulk density
was measured in accordance with ASTM D-1895. The
bulk density of a powder is the mass of powder that is
held in a given volume without being packed. Sieve
analysis was conducted in accordance with ASTM D
1921-89. A set of sieves ranging in opening size from
35 mesh (500 microns) to 100 mesh (149 microns)
was used. The average particle size for each sieve was
defined as the nominal opening size of that sieve plus
the nominal opening size of the next larger sieve in
the stack divided by two. The mean particle diameter
was calculated by the following equation:
Dm= Z(P, x Di)/lOO
Where: D, = mean particle diameter in microns
Pi = percent of material retained on sieves
(or pan)
Di = average particle size in microns of
material on sieve
The relationship between sieve-opening size in mesh
and microns (pm) is given in the published literature
(28) for selected sieve sizes. By plotting the literature
values, and non-linear regression, the following equa-
tion was obtained:
Opening Size,pm = 28887 X (SieveSize,
R 2 =1 (2)
Equation 2 was used to compute sieve-opening size in
pm for those mesh sizes not disclosed in the literature
(28).The values of sieve-opening size in pm were used
to calculate the following average particle sizes: 559
Fm for 30 mesh (559 Fm) sieve: 530 p m for 35 mesh
~ ~~ ~~ ~~~
Additive Blended with LLDPE
none 3 wt% MO 3 wt?h GMS 3 wt % PEMO
0.9399 0.9380 0.9425 0.9407
4.1 4.6 4.6 4.6
534 503 >5000 -
66 65 66 63
POLYMER ENGINEERINGAND SCIENCE, OCTOBER 2001, Vol. 41, No. 10
 Processing Enhancersfor Rotational Molding of Polyethylene
(500 pm) sieve; 450 pm for 40 mesh (401 pm) sieve;
349 pm for 50 mesh (297 Fm) sieve; 237 pm for 80
mesh (177 pm) sieve; 163 pm for 100 mesh (149 pm)
sieve; and 149 pm for the pan.
For the sintering experiments, polymer cylinders
were prepared by compression molding pellets using a
plate with holes of diameter 0 . 3 2 mm and height of
0.3 mm. The cylinders were cut off from the compres-
sion-molded sheet.
The apparatus used for the sintering experiments
consisted of a heat chamber and a n optical micro-
scope equipped with a video camera. The camera was
connected to a videocassette recorder and television,
which in turn was connected to a personal computer
with a frame grabber board where the images were
stored.
The two polymer cylinders were positioned at the
center of a small glass cup to make point contact be-
tween themselves. The glass cup was placed in the
center of the heat chamber, which had glass windows
on top and bottom for inspection and for taping of the
process.
The temperature of the oven was controlled by the
thermocouple sitting in the wall of the heat chamber
and was set at 230°C. The temperature in the glass
cup was also measured. The conditions were kept
identical for all samples and the recording of the sin-
tering experiments started when the temperature in
the sample holder (glasscup) reached 90°C.
To simulate the rotational molding temperature pro-
file, the sintering experiments on the different sam-
ples were performed under non-isothermal conditions
and the neck formation between the two cylindrical
particles was recorded as a function of time. A typical
temperature 0 profie for the sintering experiments is
shown in Rg. 1.
After the completion of the sintering process (approxi-
mately 400 sec), the taped images were grabbed at in-
tervals of 15 sec in the initial stages and less frequently
300
200
100
0
0 5 10
Time (min)
Fig. 1 . ll~picaltemperature pro^ in sintering experiments and in rotational molding.
POLYMER ENGINEERING AND SCIENCE, OCTOBER 2001, Vol. 41, No. 10
in the advanced stages. Neck growth between the
two particles and the particle radius were measured
using an image analyzer software program called
SigmaScanTM Pro (Jandel Scientific Software, 1992).
The neck diameter was measured directly, while the
particle diameter was calculated from the measure-
ment of the surface area of the particles. Sintering
rate was determined from the measurements of the
neck radius between the particles and the particle ra-
dius. The sintering time (time required for 99% com-
pletion of neck growth) was calculated based on the
sintering rate curves and using an empirical model
(see Theoreticat section below).
Two of the pulverized samples ("no additive" and '3
wtYo MO") were selected for rotational molding experi-
ments. They were initially studied on a lab scale uni-
axial rotational molding machine. In this machine, the
mold rotated only on the horizontal axis. The experi-
mental setup consisted of an electrically heated oven,
an aluminum mold and a control panel. A table fan
provided the cooling. The oven was made of two in-
frared heating panels. A 9.5 X 9.5 x 10 cm3 cube-
shaped aluminum mold was used for the experi-
ments. The outside surface of the mold was painted
black and the inside surface of the mold was coated
with a water based mold release. A Pyrex glass win-
dow was in the front of the mold for visual observa-
tion. The air temperature inside the mold was mea-
sured by a thermocouple, which was connected to the
control panel through a slip ring. A shot weight (poly-
mer sample) of lOOg was used to produce molded
parts of about 3-mm thiclmess. The speed of rotation
was set to 4 revolutions per minute (rpm),which is a
commonly used major axis speed in biaxial rotational
molding. The oven controller temperature was preset
at 427°C.
During the molding experiments, the preweighed
powder was loaded into the mold and the rotation was
started. After the oven was placed over the mold, the
15 20 25 30
1733
 Bharat Indu Chaudhary. Elizabeth Takbcs, and John Vlachopoubs
inside air temperature was recorded every 30 seconds.
The heating was stopped when the inside air tempera-
ture reached a maximum of 190, 210, 220, 225, 230
and/or 245°C.Stopping the heating at different maxi-
mum inside air temperatures &=) varied the heating
cycle time. After the oven was removed, a fan was
used to cool the mold. The molded parts were un-
loaded when the temperature in the mold reached
mom temperature.
Biaxial rotational molding experiments were also
performed using the two powder samples (“no addi-
tive” and “3 wtYo MO”) studied in uniaxial rotomold-
ing. The mold was attached to the end of the arm via
a plate, but not rigidly, such that the assembly could
move. The arm rotated in two axes. The speed and/or
ratio of the arm and plate determined the speed
and/or ratio of the rotation. The outer axis speed (pri-
mary axis) corresponded to the speed of the arm while
the inner axis speed (secondaryaxis) corresponded to
the speed of plate. The arm rotated vertically (outer or
main axis) and the plate rotated horizontally. The
mold was made from steel and had a box shape of di-
mensions 30 cm X 30 cm X 20.5 cm.The oven was
heated by forced air circulation, the air being heated
by natural gas. The oven temperature was set to
315.6”C.The rotation speed was set on the control
panel as follows: Outer axis (armspeed): 8 rpm; Inner
axis (plate speed): 10 rpm. The test resin (1.4 kgl was
placed in the mold and after closing the mold, the arm
was transported to the oven. At the completion of the
preset oven heating time (which varied from 1260 to
1440 seconds), the a n n was moved to a cooling cham-
ber where the mold was precooled by the surrounding
air for 300 seconds. More intensive cooling then fol-
lowed (using a fan for 1800 seconds).
The molded parts were inspected, cut and prepared
for impact tests. A dart drop tester was used to per-
form low temperature dart impact tests (Associationof
Rotational Molders Method) in order to characterize
the mechanical properties of the rotomolded parts.
The technique used is commonly called the Bruceton
Staircase Method or Up-and-Down Method. This test
determines the energy required to cause a failure in
the rotomolded part by a free falling dart (weight of
the dart was 4.53 kgl. The maximum possible drop
height was limited to 3.05 meters (m). For the impact
tests, 8.3 cm X 8.3 cm square samples were cut from
the molded parts. Before the tests, the specimens
were conditioned in a freezer for 8 hours at -40°C.
The mean failure energy, MFE, (in m kg) was calcu-
lated as follows:
MFE= h x w (3)
where, h: mean failure height, m
w: dart weight in kg.
Bubble content in the molded parts was studied
using a n optical microscope (Olympus SZ 4045)
equipped with video camera. Samples of approxi-
mately 1-mm thickness were cut from the cross sec-
tion parallel to the surface of the molded parts.
1734 POLYMER ENGINEERING AND SCIENCE, OCTOBER2001, Vol. 41, No. 10
The thickness distribution of the molded parts was
measured with a digital micrometer. The average
thickness and standard deviation were calculated for
each sample. The standard deviation is a measure of
thickness uniformity.
The density of the molded parts was measured
using MD-200s high precision electronic densimeter.
The method is based on Archimedes’ Principle. The
equipment contains a precision balance, which sup-
ports a water tank and sample-testing stand. The
specimens (4 cm x 4 cm square) for this measure-
ment were cut from the molded parts. First, the mass
of the dry sample was measured on the top of the test
stand. Then the sample was immersed in the water
and measured again on the test stands submerged
plafform, and the specific gravity was calculated.
THEORETICAL
The novel blend compositions described in this
paper were designed to enhance sintering during rota-
tional molding. The concept was to blend small
amounts of low molecular weight additives with poly-
ethylene to result in significant reductions in rheologi-
cal properties such as viscosity and/or elasticity in
the molten state. However, upon cooling and solid&
cation of the polymer, these additives would be solu-
ble only in the amorphous fraction of the polyethylene
and therefore would not affect the crystalline regions.
That way, the mechanical properties of polyethylene
would not be affected at low loadings of the additives.
Sintering or coalescence of polymer particles is one
of the most important stages of the rotational molding
process. It plays a significant role in the hating cycle
and affects the properties of the molded parts. There-
fore, the sintering behavior of polymers provides useful
information about their rotomoldability. Sintering is
defined as the formation of a homogeneous melt from
the coalescence of powder particles. During sintering
there is a thermodynamic driving force for the particles
to lower their surface energy by reducing their surface
area (29).In polymers, the sintering is governed by vis-
cous flow (30).The driving force is the surface tension
and the viscosity offers resistance. The sintering mech-
anism (31, 32) is illustrated in Rg. 2.
As the sintering of the two spherical particles pro-
gresses, material transport occurs resulting in growth
of the contact neck between the particles. The sintering
rate can be expressed by the rate of the neck growth.
The quantitative characterization of the process can
be described by the following expression (33).which is
valid at the initial stages only (32,34):
y/a = (3rt/2qa)i’z (4)
where r, q, y, a and t are the surface tension of the
polymer, viscosity, neck radius, particle radius, and
sintering time, respectively. The growth of the neck
between the two particles is proportional to the
square root of time. The coalescence of the two parti-
cles is completed when the two particles have adhered
together to form a single particle (y/a = 1).
 Processing Enhancersfor Rotational Molding of Polyethylene
Fig. 2. Schematic sketch of the sintering sequencefor two particles.
In rotational molding the overall cycle time depends
not only on the rate of oven heating, but also on the
rate of sintering of the polymers. Sintering time (ts) is
defined as the time required for 99% completion of
neck growth and can be calculated using the following
empirical model:
y/a = 1 - A.e-(t/ts) (5)
The model can fit the measured rate of neck growth.
The same curve fitting and non linear regression can
be used to calculate neck growth at various intervals
(say, 330 seconds).
RESULTS AND DISCUSSION
Table I describes the properties of LLDPE and
blends with low molecular weight additives (before
pulverization).The use of GMS resulted in the w e s t
density and significantly improved environmental
stress crack resistance (ESCR).The notched Izod im-
pact strength of compression molded samples, condi-
tioned at 40°C,was not adversely affected by the ad-
ditives.
The melt index data in Table 1 show that blending
of low molecular weight additives with LLDPE resulted
in reduced viscosity at moderate shear rate.
However, for rotational molding, the more relevant
rheological properties are melt viscosity and elasticity
measured at zero shear rate. These properties were
measured at a very low shear rate of 0.1 s-l (to ap-
proximate zero shear conditions) by increasing the
temperature from 150°C to 250°C in increments of
10°C,allowing the samples to equilibrate at all tem-
peratures. The melt elasticity was determined from
measurements of Tan 6 (lossmodulus divided by stor-
age modulus). The results are plotted in Figs. 3 and 4.
Blending 3 wtYo of PEMO and GMS with LLDPE re-
sulted in decreased viscosity. Although the blend
comprising 3 wt% MO had higher viscosity than
the control LLDPE up to a temperature of 190°C,the
POLYMER ENGINEERINGAND SCIENCE, OCTOBER 2001, Vol. 41, No. 10
Where:
a -particle radius
a, -initial particle radius
af -final particle radius
y -neck radius
L -length of the sintering
particles
W -width of the sintering
particles
sensitivity of viscosity to temperature was greater for
the blend comprising MO than for the control sample,
and this strongly affects the rate of sintering. Melt
elasticity at all temperatures was sigmkantly reduced
with all three additives (MO, PEMO and GMS). I t is ex-
pected that the decreased melt elasticity and viscosity
(or, in the case of the blend comprising MO, greater
sensitivity of melt viscosity to temperature) will result
in enhanced particle coalescence and/or bubble re-
moval during rotational molding. That is, blending
small amounts of low molecular weight additives with
polyethylene should result in faster sintering, reduced
mold temperatures and consequently shorter cycle
times.
The properties of the materials, after pulverization,
are shown in Fig. 5. The si@icant powder properties
affecting rotational molding are bulk density and par-
ticle size distribution. Bulk density gives information
about the packability of the resin. If the bulk density
is hgh, the resin packs well during rotational mold-
ing, resulting in fewer bubbles. The bulk densities of
three of the materials were similar (approximately
0.30 g/cm3), which suggests that there were not large
differences in the amount of entrapped air in these
materials. However, the pulverized blend comprising
GMS exhibited significantly lower packing density,
which might result in comparatively more bubbles
during rotational molding.
The powder quality can also be quanwied by mea-
suring the particle size distribution. This property
characterizes the quality of the powder and its behav-
ior in the rotational molding process. Coarse particles
lead to increase in the cycle time and surface defect.
Fine particles result in good surface finish and en-
hance heat transfer (35).However, too many fine par-
ticles can result in flow and melting problems. For
example, fine particles can melt before the rest of the
powder and prevent other particles from entering sec-
tions of the mold such as comers, channels and ribs.
1735
 Bharat lndu Chaudhay, Elizabeth Takbcs, and John Vlachopoulos

r(
I
4500

4000
- LLDPE
-8- LLDPE with 3% MO
% -e- LLDPE with 3% GMS
3500
0
c,
*LLDPE with 3% PEMO
I
3000
2
2500
h
-s
VJ

g 2000
$
1500

1000
150 160 170 180 190 200 210 220 230 240 250

Temperature ("C)
Fig. 3. Effect of additives on melt viscosity at low shear rate.

Also, fine particles cause agglomeration due to buildup
of static. Therefore, in rotational molding, it is gener-
ally accepted that the powder size should range from
nominal 35 to 1 0 0 mesh size (36). From Flg. 5, it can
be seen that the LLDPE and blend comprising mineral
oil had similar particle size distributions, while the
other two resins were slightly different.
The results of the sintering measurements are
shown in Flgs. 6 and 7.The latter shows the sintering
sequences for the different samples. At t=O sec. below
the melting point of the polymer, the particles were
solid. Sintering commenced when the temperature
reached the melting temperature of the polymer. The
contact-zone between the two cylindrical particles in-
creased and neck-formation started. As sintering pro-
gressed, neck growth increased until the two particles
fused together. The coalescence of the particles was
completed when the neck radius became equal to the

90 I -- -
80
70
60
. : 50 1 --

40 I A
30
20
10
r
i

0 I 1 I I t I I I

1736 POLYMER ENGINEERING AND SCIENCE, OCTOBER 2001, Vol. 41, No. 10
 Processing Enhancers for Rotational Molding of Polyethylene

Powder Retained on Sieves or Pan (%I

50

45
-15- LLDPE with 3% MO
40
-0-LLDPE with 3%GMS
35

30

25

20

15

10

0
559 or greater 530 450 349 23 7 163 149 or less

Average Particle Size (pm)

Fig. 5. Particle size distributions of the puluerized resins.

particle radius. All three additives (MO, GMS and
PEMO) resulted in significantly faster sintering and
coalescence, with only slight differences between addi-
tives. The test is conducted in static mode (with no ro-
tation), but the results are applicable to rotational
molding since sintering occurs after the particles have
adhered to the wall and centrifugal force is not a sig-
nificant factor during rotational molding.
Because of the air trapped between powder particles,
bubbles are formed at the later stages of sintering in

1.o I
n
Eh 0.9
v
v)

.
a
I
0.8

3 0.7
none 3Wl% 3wt% 3wtW
ti
5
.I
0.6 MO GMS PEMO
6
Onset of Sintering 95 90 90 90
9 0.5
%
.s 0.4
(seconds)

sza
zd 0.3
Calculated Sintcriog

Time (xconds)
850 584 634

5 yla at 330 seconds - 0.84 0.95 0.94 0.93

g 0.2

0.1
100 150 200 250
-from Curve Fitting

300
I

3 50 400

Time (seconds)
Fig. 6. Effit of additives on rate of neck growth-

POLYMER ENGllVEERNVG AND SCIENCE, OCTOBER 2007, Yo/. 47, No. 70 1737
 Bharat lndu Chaudhary, Elizabeth T a k k s , and John Vlachopoulos
t=O sec e l 3 5 sec t=270 sec t=390 sec Observation
no
additive
3yo
MO
3yo
GMS
3%
PEMO
Fig. 7. Effectof aiiditiues on s i n k i n g sequence.
rotational molding. The rheology, thermal properties
and powder properties of the resin influence the num-
ber and initial size of the bubbles (37).The amount of
entrapped air and initial bubble size, along with the
surface tension, further affect the bubble dissolution
or bubble removal process in the polymer melt (38).
The bulk density and particle size distributions of the
pulverized LLDPE and blend comprising mineral oil
were similar, while the bulk density and/or particle
size distributions of the blends comprising GMS and
PEMO were different. Hence, only the pulverized
LLDPE and blend comprising mineral oil were com-
pared in rotational molding experiments.
A crucial process parameter influencing the proper-
ties of rotomolded parts is the air temperature inside
the mold (2, 39-41). A typical temperature profile
recorded in the center of the mold is shown in Fig. 8.
The air temperature profile inside the mold is charac-
teristic of the resins used in the process. The inside
air temperature rises to a peak temperature (maxi-
mum inside air temperature (T-)) in the heating
cycle and decreases in the cooling cycle until it reaches
mom temperature. The temperature rise (the slope of
the curve) in the heating cycle is different along the
curve depending on the properties of the polymer and
on the stage of the process. Four major stages can be
identified: induction stage (up to A), adherence (from
1738
Transparent
Transparent
Transparent
Transparent
A to B), rnelting-sinterhg(from B to C) and fusion or
densification (C to D). Bubble removal occurs during
the second part of the densBcation process. At point
D, when the melt pool becomes homogeneous and
bubble free, the heating cycle finishes and the cooling
process starts. The temperature in the mold starts to
decrease steadily up to point E where crystallization
takes place and the polymer starts to solid$. These
stages, which have been described elsewhere (2, 22),
are significantly aected by material properties (rheo-
logical, particle size distribution, thermal transitions) as
well as process parameters (such as the oven heating
time and the maximum air temperature inside the
mold). For example, if the time is not long enough for
bubble removal, it can result in under-fused parts.
The air temperature profiles in the center of the mold
recorded as a function of time during uniaxial rota-
tional molding of LLDPE and the blend comprising
mineral oil were similar (Fg.8).The sample contain-
ing MO exhibited similar duration at each stage (in-
duction, adherence, sinter-melting and fusion) as the
reference LLDPE ('no additive").
In rotational molding, as the layers of polymer build
up, some air is trapped in the melt and bubbles are
formed. The presence of bubbles in molded parts
depends not only on material properties, but also
on process conditions. If the cycle time is not long
POLYMER ENGINEERING AND SCIENCE, OCTOBER 2001, Vol. 41, No. 10
 Processing Enhancers for Rotational Molding of Polyethylene

250
D no additive

3
e
200

0
00
150

100

50

0 I 1 I I I I

0 5 10 15 20 25 30 35

Time (min)
Rg. 8. Air ternpemture pro& in the center of the mold (T- = 210°C).

enough, the molded part will have lots of bubbles.
Therefore, inspection of the part for bubble content
can provide good information on the progress of the
process. Agure 9 shows photographs of the cross sec-
tions parallel to the surface of rotomolded parts made
by uniaxial rotational molding of the two selected sam-
3 wt?! mineral oil") at a maxi-
ples ("no additive: and '
mum inside air temperature (T-) of 210°C.The parts
made from the sample containing mineral oil were al-
most bubble free, indicating that the densification

No additive 3 wt YOmineral oil

Fig. 9. Cross section parallel to s@me of rotomolded parts made at T
, = 21 0°C.

POLYMER ENGINEERING AND SCIENCE, OCTOBER2001, Vol. 41, No. 10 1739

 Bharat Indu Chaudhary, Elizabeth Takhcs, and John Vlachopoulos

process was completed. The large number of bubbles
in the reference LLDPE (Yno additive") suggests that
the densification process was still at an early stage.
That is, the use of mineral oil resulted in much faster
bubble removal, as predicted earlier from the viscosity
and Tan 6 measurements on the blends.
The properties of the rotomolded boxes obtained
from uniaxial rotomolding of the various samples are
shown in Table 2. Measurement of the thickness dis-
tribution is a good test to check the quality of the
molded parts. The thickness of parts is affected by
surface leveling in the adherence stage. The degree of
smoothness is measured by the standard deviation of
the thickness, and depends not only on the properties
of the polymer, but also on the process parameters.
The heating time is one of the most important control-
ling factors in surface leveling. For example, if the
heating time is not long enough, the surface of the
molded part will be uneven. From Table 2, it can be
seen that the parts molded from the reference sample
("no additive") exhibited slightly larger standard devia-
tion than those made from the sample containing
mineral oil. That is, the sample containing mineral oil
resulted in a more uniform thickness profile. There
was no warpage in any of the parts. Increasing the
maximum inside air temperature tended to improve
thickness uniformity.
Densification is one of the most important aspects
of the rotational molding process and significantly af-
fects the part properties. The degree of densification is
characterized by measuring the density of the part.
The density of the molded parts made a t different
maximum air temperatures was measured and is re-
ported in Table 2. The sample containing mineral oil
started densifying earlier than the reference sample.
This observation is consistent with the enhancement
in bubble removal and thickness uniformity obtained
with the blend comprising mineral oil.
Impact strength is one of the most sensitive proper-
ties of the molded part, and it can be correlated to

Table 2. Results From Uniaxial Rotational Molding

T
, ("C) No additive 3% mineral oil
Mean Failure Energy, MFE (m kg)
190 - 5.2
210 7.2 8.9
220 - 9.3
225 9.2 -
230 9.5 0.0
245 2.4 -
Type of Failure
190 - ductile
21 0 brittle ductile
220 - ductile
225 ductile -
230 ductile brittle
245 brittle -
Thickness (mm)
190 - 3.14
21 0 3.15 3.12
220 - 3.08
225 3.05 -
230 3.08 3.05
245 3.10 -
Standard Deviation of Thickness (mm)
7 90 - 0.27
21 0 0.32 0.24
220 - 0.20
225 0.25 -
230 0.25 0.21
245 0.27 -
Density (g/cm3)
190 - 0.9275
21 0 0.9288 0.9390
220 - 0.9398
225 0.9408 -
230 0.9408 0.9390
245 0.9433 -

1740 POLYMER ENGINEERING AND SCIENCE, OCTOBER 2001, Vol. 41, No. 10
 Processing Enhancers for Rotational Molding of Polyethylene

the process conditions. Any small change in the heat-
ing cycle can significantly affect the impact strength,
especially that at low temperature (41). Therefore, this
parameter can be used to determine the processing
windows of the different samples. Table 2 shows the
mean failure energy (MFE) and type of failure of the
parts molded at different maximum inside air temper-
atures in uniaxial rotation. The mean failure energy,
which represents the impact strength of the material,
varied with the maximum inside air temperature. As
the,,T increased, the MFE increased to a maximum
value and then dropped. The sample containing 3
wtYo mineral oil exhibited peak MFE virtually identical
to that obtained without any additive, but at lower
values of T-. This finding was also consistent with
the results of the sintering studies.
Biaxial rotational molding was also used to fabricate
parts from LLDPE and the blend with mineral oil. The
properties of the molded parts are tabulated in Table
3. Both samples resulted in similar values of peak
MFE (about 9 m kg), but at different cycle times. The
MFE of the part fabricated from the control LLDPE
("no additive") tended to increase with increasing oven
time and reached its peak (with ductile failure) at
1440 seconds. Conversely, with 3 WF!! mineral oil, the
MFE reached its peak (with ductile failure) at 1260
seconds. After 1260 seconds, the MFE of the sample
comprising mineral oil decreased continuously and
brittle failure occurred at longer cycle times, indicat-
ing that the parts were over-cooked (resulting in ox-
idative degradation). This c o n f i i s that the operating
window for this resin had shifted to shorter oven
times, possibly even less than 1260 seconds. These
results correlate well with those obtained from the
sintering and uniaxial rotomolding experiments.
CONCLUSIONS
Blending 3 +o! of MO, GMS and PEMO with LLDPE
resulted in significantly decreased melt elasticity at
low shear rate. Furthermore, melt viscosity was de-
creased by the addition of GMS and PEMO. Although
the blend comprising MO had higher viscosity than
the control LLDPE up to a temperature of 190°C, the
sensitivity of viscosity to temperature was greater with
MO. The use of GMS resulted in increased density
and sigmiicantly improved environmental stress crack
resistance (ESCR).The additives did not adversely af-
fect the notched Izod impact strength of compression
molded samples conditioned at -40°C.
Sintering studies confirmed that the additives re-
sulted in significantly faster coalescence. In uniaxial
rotational molding, the greater sensitivity of melt vis-
cosity to temperature and decreased melt elasticity
obtained with mineral oil were observed to result in
much faster densifkation and bubble removal. Part
thickness was uniform and there was no warpage.
Adding mineral oil to polyethylene significantly re-
duced the cycle time, and the peak impact strength of
samples conditioned at -40°C was identical to that
obtained without any additive. Biaxial rotational mold-
ing experiments confirmed that the use of 3 wt??o min-
eral oil resulted in shorter cycle time without sacrifc-
ing peak impact strength.
In summary, blending small amounts of low molecu-
lar weight additives with polyethylene has been shown
to enhance particle coalescence and bubble removal

Table 3. Results From Biaxial Rotational Molding

Time (seconds) No additive 3% mineral oil
Mean Failure Energy, MFE (m kg)
~

1260 - 8.7
1320 8.3 7.6
1380 7.8 6.1
1440 8.9 0
Type of Failure
1260 - ductile
1320 some ductile, some brittle ductile
1380 ductile brittle
1440 ductile brittle
Thickness (mm)
1260 - 2.74
1320 2.70 2.70
1380 2.75 2.79
1440 2.76 2.71
Standard Deviation of Thickness (mm)
1260 - 0.24
1320 0.21 0.22
1380 0.27 0.18
1440 0.21 0.19

POLYMER ENGINEERING AND SCIENCE, OCTOBER 2001, Vol. 41, No. 10 1741
 Bharat Indu Chaudhay, Elizabeth T a k k s , and John Vlachopoulos
during rotational molding, resulting in shorter cycle
times, without adversely affecting impact strength.
However, it may be necessary to optimize the types
and amounts (possibly less than 3 &Yo) of additives
such that other mechanical properties are also not
adversely affected.
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