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Novel Processing Additives for Rotational Molding of Polyethylene

Article  in  International Polymer Processing Journal of the Polymer Processing Society · November 2009
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 REGULAR CONTRIBUTED ARTICLES
O. Kulikov1,*, K. Hornung1, M. Wagner2
Not for use in internet or intranet sites. Not for electronic distribution.
1
LRT-7, University of the Federal Armed Forces, Munich, Germany
2
Polymerphysik, Technical University Berlin, Germany
Novel Processing Additives for Rotational Molding
of Polyethylene
Over 85 % of the articles manufactured via rotational molding
employ Polyethylene (PE) resins. PE resins used for rotomold-
ing have usually particle sizes less than about 0.8 mm and used
as powders or micro-pellets. During heating in a rotating
mold, these particles get fused and merge into one piece. A dis-
advantage of the rotomolding process is long cycle times that
affect not only the production rate but also increase thermal
degradation of the polymer due to its long exposure to heat.
One of the problems in rotomolding is bubbles of gasses
trapped during sintering of the PE powders which reduce me-
chanical strength of the article produced. We propose to use
reacting mixtures of Polyethylene Glycol with citric acid as
an additive to rotomolding grades of PE. The additive acceler-
ates sintering of the PE particulates and greatly reduces num-
ber of bubbles in the melt but at high concentrations (> 0.4
wt.%) it impedes flow of the particles. Fine powders with parti-
www.polymer-process.com
cles of irregular shape and wide distribution of sizes are char-
acterized by low flowability while micro-pellets of oval shape
with smooth surface have too high flowability for rotomolding.
To improve cost-efficiency and quality of the rotomolding pro-
cess we propose to use micro-pellets instead of powders and to
fabricate micro-pellets by extrusion at reduced temperatures
and cutting the produced strands in conditions of air-cooling.
Amazingly, the same processing additives improve extrusion
of PE resins and rotomolding of the PE micro-pellets. The ad-
ditives also adjust flowability of micro-pellets in the direction
to optimum. Silica fume, vinyl-silanes and stearates can be in-
gredients of the additive package. Mechanisms of the observed
W 2009 Carl Hanser Verlag, Munich, Germany
improvements are discussed.
1 Introduction
Rotational molding, also referred to as rotomolding or rota-
tional casting, is a plastics processing technology for producing
hollow seamless articles and it comprises four steps: charging
of polymer as solids (free-flowing powder or pellets) or liquids
(melt) into the mold; heating of the mold in an oven to proces-
sing temperatures with simultaneous rotation in two axes
(Bruins, 1971; Beall, 1998; Crawford and Throne, 2002; Craw-
ford and Kearns, 2003; Dodge, 2004). While heated, the poly-
* Mail address: Oleg Kulikov, LRT-7, UniBw Munich, 85577 Neu-
biberg, Germany.
E-mail: oleg@kulikow.de
452
Carl Hanser Verlag, Munich Intern. Polymer Processing XXIV (2009) 5
mer adheres to the mold and gets fused completely. Next steps
are cooling of the mold by air or a water spray, and unloading
of a produced item from the mold. In contrast to other polymer
forming processes like extrusion or injection molding, fusing
of the particles occurs at conditions of nearly “zero-shear”
stress, because only forces of surface tension govern the flow
of the melt. Advantages of the rotational molding in compari-
son with other techniques are the following: larger size of
molded parts; lower cost of tooling and easer prototyping;
thicker outer corners of the parts that impart higher strength
and structural stability to the molded items; an opportunity to
produce large and small parts of complicated shapes as one
piece. Examples of the items produced by rotational molding
include road barriers and buffers; traffic signal cones; plastic
containers, tanks and barrels; automotive parts; hobby and
sporting equipment; playground equipment and toys; furniture.
One of the problems in rotomolding is bubbles of gasses
trapped during sintering of the PE powders. Pick and Harkin-
Jones (2004) report a correlation between the number of voids
(bubbles) in a rotomolded article and its impact performance,
with a higher number of voids resulting in lower impact perfor-
mance. According to Spence and Crawford (1996a) the particle
size distribution affects the porosity of the product while over-
heating of the polymer melt for bubble removal results in low-
ering of mechanical properties of the product. Greco and Maf-
fezzoli (2004) predicted existence of an optimum sintering
temperature at which the density of the sintered product gets
to its maximum for a good quality rotationally-molded product
having limited number of voids. Kontopoulou et al. (1999) as
well as Kontopoulou and Vlachopoulos (1999) investigated
the formation and dissolution of bubbles during sintering of
PE powders to evaluate how it is affected by powder proper-
ties, chemical structure, thermal properties and rheology. Bel-
lehumeur and Tiang (2000) conclude that the polymer rheolo-
gical properties seem to dominate the initial size of the
bubbles formed. Many efforts have been done to decrease the
number of bubbles by changing the internal mold pressure.
While application of vacuum has shown some improvement
in decreasing the bubbles content (Evans, 1998), the use of po-
sitive pressures appears to be more efficient according to Xu
and Crawford (1993). Gogos (1999) investigated bubble disso-
lution in typical polymer melts encountered in rotational mold-
ing. He writes that a sharp pressure increase leads to a steep
concentration gradient in the vicinity of the bubble/melt inter-
face that can lead to extremely fast bubble shrinkage due to in-
creased rate of the gas dissolution. The presence of water has
 O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
also been recognized as a possible cause of bubbles (Foster,
1970; Conway, 1973), but according to Spence and Crawford
Not for use in internet or intranet sites. Not for electronic distribution.
(1996b) preheating of PE powders to remove moisture have
shown no effect on their content.
In production of the PE powders for rotomolding with particle
sizes less than 0.5 mm (35 mesh) a raw resin powder from the
polymerization reactor is blended with pigments and additives
in an extruder, mixed and extruded through a set of dies and pel-
letized in conditions of water cooling. The produced pellets are
ground and classified to proper particle size. The pelletizing
and grinding operations are costly because of high energy con-
sumption. An attempt was made to produce PE powders for ro-
tomoding without pelletizing and grinding (Kallio et al., 2001),
but from a practical view point it is more convenient to manu-
facture micro-pellets for rotomolding. With the use of micro-
pellets the number of post-processing steps is reduced thereby
reducing the cost of the material (Nugent, 2006). Opposite to
micro-pellets for rotomolding with regular oval shapes and aver-
aged sizes from about 0.5 to 0.8 mm, PE powders for rotomold-
ing have smaller averaged size of the particles (from 0.3 to
0.4 mm) and wide particle size distribution as well as irregular
shapes. Potentially, powders can be compacted so that fine parti-
cles would fill the voids between the larger ones. Wang and
Kontopoulou (2007) observed fewer bubbles in the melt and bet-
ter mechanical properties of the rotomolded articles when pow-
ders were used in comparison to the use of micro-pellets. Never-
theless, last ten years the use of micro-pellets is considered as a
step forward for the rotomolding technology with following
benefits: uniform melting; improved handling; elimination of
dusting; faster sintering times (10 to 12 % reduction); more uni-
form wall thickness; and improved surface finish.
www.polymer-process.com
Free-flow behavior of the PE particulates is important to get
even thickness of the walls of the rotomolded articles. The
fluidity of PE powder is influenced by various properties, such
as particle sizes, shapes and surface roughness of the particles.
As a general tendency fine powders show less fluidity (Yo-
koyama, 1997). Fine powders of PE often demonstrate low
fluidity because of elongated shapes of the particles, sharp
edges as well as such features like “fibers” and “tails” at the
surface of the particles. With low fluidity of the particulate
matter, an inner surface of the rotomolded parts gets wavy ap-
pearance with high variations of the wall thickness. With PE
powders a bridging often occurs and air gets trapped in the cor-
W 2009 Carl Hanser Verlag, Munich, Germany
ners of the mold so that the produced parts are not suitable for
use (Beall, 1998). Large pellets (> 2 mm) have too high fluid-
ity, they are bouncing inside the mold and do not stick easily
to flat surfaces but accumulate in the corners of the mold. Also
sintering of such pellets creates a lot of bubbles that do not dis-
solve in polymeric melt. Optimization of flow and fewer voids
can be achieved by downgaugeing of the pellets to sizes from
0.3 to 0.8 mm (micro-pellets).
Fine mineral powders, e. g. talcum, silica fume, micronized
silica and fly ash, are often used in industry as free-flow agents.
For example, micronized silica was used as a flow agent for
polymeric powders by Uminski and Saija (1998). However a
temptation to improve flow behavior of fine PE powders by
mixing them with fine mineral powders is dangerous because
these hydrophilic powders impact mechanical properties of
the rotomolded articles. The use of dry mixing of mineral pig-
ments (usually < 0.4 % by weight) with powder of PE is used
Intern. Polymer Processing XXIV (2009) 5
widely in such countries like India as a most economical and
flexible way of coloring of the rotomolded articles. However,
it reduces the toughness and impact strength of the rotomolded
articles by well over 50 % in most cases (Nagy and White,
2004; Henwood, 2006). The drop of mechanical performances
can be tentatively explained by following mechanism: The
mineral particles separate PE grains and delay a sintering of
them. Thermal degradation of the polymer caused by longer
exposures to heat reduces its mechanical properties. Addition-
ally, the particles with hydrophilic surface are not wetted by
the hydrophobic polymer melt and therefore such particles cre-
ate local discontinuities of adhesion of one grain of the poly-
mer to another. Small particles with hydrophilic surfaces are
prone to agglomeration because of hydrogen forces between
them. The hydrogen forces are weak and if such agglomerates
are embedded into polymer they create weak zones inside the
polymer matrix that concentrate mechanical stresses.
Polyolefin composition containing wax and metal salts of
long-chain fat acids were proposed long ago to improve pro-
cessability of PE resins (Happoldt et al., 1945). Chaudhary
et al. (2001) used low Molecular Weight (MW) additives like
wax, mineral oil and glycerol monostearate as sintering enhan-
cers in rotational molding. With this, melt viscosity and elasti-
city were reduced while much faster densification and bubble
removal were observed. Suitable sintering enhancers include
aromatic or aliphatic hydrocarbon oils, esters, amides, al-
cohols, acids, and their organic or inorganic salts as well as
silicone oils, polyether polyols such as Polyethylene Glycol
(PEG), glycerol monostearate (GMS), pentaerytritol monoole-
ate, erucamide, stearamides, adipic acid, sebacic acid, styrene-
alpha-methyl-styrene, calcium stearate, zinc stearate, phtha-
lates and blends thereof. The sintering enhancers allow a re-
duction in sintering time, cycle time and/or maximum mold
temperature but problems in the use of the additives are follow-
ing: The sintering enhancers that are dissolvable in polyolefins
work as plasticizers and reduce toughness of the rotomolded
articles. The low-viscous sintering enhancers that are immisci-
ble with polyolefins, e. g. silicone oils and PEG, coalesce inside
the melt into large beads. The macroscopic discontinuities in
the polymer matrix concentrate mechanical stresses and cer-
tainly reduce impact strength of the rotomolded parts.
Our proposal is related in part to fumed silica with sizes of
particles about 10 nm. For manufacturing of fumed silica, in-
dustry is commonly using a continuous flame hydrolysis tech-
nique. It involves conversion of silicon tetra chloride (SiCl4)
to the gas phase using an oxy-hydrogen flame. It then reacts
with water to yield silica (SiO2) and hydrochloric acid (HCl).
The hydrochloric acid is easily separated as it remains in the
gas phase, while the fumed silica is solid. The primary silicone
oxide particles with hydrophilic surface form aggregates with
sizes which much exceed the optimum size desired for the pur-
pose of our proposal. A method for reducing the aggregate
sizes is proposed by Kratel et al. (1976). It includes reaction
of pyrogenically obtained silica with organo-silicon or orna-
no-silane compounds and water vapors in a ball mill. Such
treatment of silica fume makes surface of the nano-particles
hydrophobic. An organo-silane cross-linking process is used
widely in industry in manufacturing of cable isolations and
pipes of small diameter from polyolefins (Penfold et al.,
2000). We can expect therefore that with proper selection of or-
453
 O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
gano-silanes, e. g. vinyltrimethoxysilane (VTMOS) and vinyl-
triethoxysilane (VTEOS), the silica particles with modified
Not for use in internet or intranet sites. Not for electronic distribution.
surface would do not agglomerate and can reinforce the poly-
mer matrix by chemical bonding between the silica surface
and PE molecules.
A considerable number of patents are dedicated to removing
of bubbles and reinforcement of the molded shapes. We can ca-
tegorize them roughly into three groups:
1. Sizing of a particulates to improve densification of melt:
Maziers (2005) mentioned that micro-pellets exhibit a bet-
ter bubble removal as a function of temperature than do
powders. Swain (2004) proposed to use resin pellets and
from 20 to 40 % by weight of ground resin powder to yield
rotomolded objects having enhanced impact strength, En-
vironmental Stress Crack Resistance (ESCR) and other
strength characteristics.
2. Processing and nucleating additives: Rotational molding
compositions normally contain heat and/or light and/or UV
stabilizers for the olefin polymers. Whereas an unstabilized
resin-based system provides a molded object having inferior
physical properties but which is free of surface pinholes, the
stabilized system provides a molded object which has vastly
improved physical properties, but which has surface pin-
holes and volume voids. It was proposed by Sowa (1976) to
use about from 0.01 to 0.04 per cent by weight of the fatty
acid salt such as calcium stearate and lithium stearate per
100 parts by weight of olefin polymer-based rotational
molding compositions to provide rotational moldings with
pinhole-free surfaces and void-free product. Needham
(1987) proposed addition of zinc stearate into rotational
molding compositions containing cross-linking agents to
www.polymer-process.com
prevent the formation of voids in the final rotationally
molded article. He also proposed (Needham, 1996) to use
nucleating agents, like calcium carbonate; zinc oxide; pig-
ments such as carbon black and titanium dioxide to improve
resistance of rotomolded articles such as rotomolded con-
tainers to puncture. The supposed nucleating agents should
have a particle size in the range of from about 0.05 to 20 mi-
crons, preferably from about 0.1 to 10 microns and they have
to be homogeneously distributed in the melt of PE, e. g. by a
compounding extruder.
3. Densification aids: Densification aids were proposed re-
cently by Maziers (2008a, 2008b). One densification aid
W 2009 Carl Hanser Verlag, Munich, Germany
comprises fluoropolymer as a major component and a min-
or component selected from the group consisting of a poly-
ether-block copolymide, a thermoplastic polyurethane, a
polyetherester and PEG. Other densification aid comprises
a polyetherester, optionally consisting essentially of a mix-
ture of a polyetherester as major component with a minor
component selected from the group consisting of poly-
ether-block co-polyamide, thermoplastic polyurethane,
PEG and fluoropolymer. As for the polyetheresters, these
are copolymers having polyester blocks and polyether
blocks. They generally made of soft polyether blocks,
which are the residues of polyetherdiols, and of hard seg-
ments (polyester blocks), which usually result from the re-
action of at least one dicarboxylic acid with at least one
chain-extending short diol unit. The PEGs in two referred
inventions are preferably selected with an average MW
from 150 to 700 Da.
454
We propose here novel formulations of a hydrophilic densifica-
tion aid, blending of the densification aid with PE resins in an
extruder and manufacturing of micro-pellets for rotomolding.
Pelletizing with water cooling is used in industry nowadays to
produce micro-pellets. Instead of the pelletizing with water
cooling we propose extrusion at reduced temperatures and pellet-
izing with cooling in air or gas atmosphere. Amazingly, the
same formulations of the densification aid work as Polymer Pro-
cessing Additives (PPA) for extrusion. Micro-pellets produced
with novel PPA manifest better flow than industrial grades of
PE powders for rotomolding. The idea of such improvement
did not come to mind at once and the experiments described be-
low show steps in development of the proposal.
2 Experiments
In series of experiments on sintering of PE particulates we used
coarse powder of LLDPE (LL6301RQ, melting point 125 8C,
MI = 5.0 g/10 min) from ExxonMobil Chemical and a grade of
LMDPE (M9001RW, MI = 3.2 g/10 min) for rotomolding from
the SCG Chemicals. A fraction of fine particles with sizes below
350 lm was separated from the LL6301 grade for some experi-
ments by sieving. To mix PE powders with additives we used
as a blender a meat grinder equipped with a heater and a thermo-
stat to keep the metal body of the grinder at temperatures in
range from 80 to 90 8C. We used as additives vinyl-
silane “Geniosil X10” (VTMOS) from Wacker Chemie, glycer-
ol mono-stearate (GMS) and following grades of PEG:
PEG 200, PEG 400, PEG 2000, PEG 6000. We also used citric
acid from Aestar and fumed silica “Aerosil 300” from Degussa
as components of the additive batch. Fumed silica is character-
ized by extremely small sizes of silica particles (10 nm) while
the particles are agglomerated in larger clusters. To facilitate
mixing of the additives with the PE powders we added some
amount of methanol to the blender. In the process of mixing the
methanol was evaporated. To sinter particulates we used a sim-
ple mold that was assembled from a 3 mm steel plate and a thick
(about 15 mm) steel ring at the plate with an inner diameter of
50 mm. Samples in the amount of 5 g were loaded to the mold
and gently compacted by a disk from PMMA to ensure equal
thickness of the polymer material in the mold. A digital camera
equipped with a magnifying objective lens was arranged at the
top side of the mold to record process of sintering of PE particu-
lates under magnification. Some of the recorded photos are pre-
sented in figures (Fig. 1 to 4) and arranged in vertical rows for
comparison. Width of the photos corresponds to about 6.8 mm
of the mold inside in its central area.
In experiments on extrusion of PE resins to demonstrate an
opportunity to produce micro-pellets with novel PPA we used
a screw-extruder from Extrudex. A barrel of the extruder is
made with 4 shallow grooves in its feeding zone. The grooves
are 8 mm width and the depth of them is made with gradual
slope from 2 mm to zero in the direction of a conveying of
polymer material. It is well known that extruders with axial
grooves in the feeding zone of the barrel provide stable con-
veying of pellets and powders (Gruenschloss, 2003; Rauwen-
daal, 1986). A feeding zone of the extruder is cooled by water
to room temperature. All parts of the extruder that are in con-
tact with molten polymer are produced from a steel alloy
Intern. Polymer Processing XXIV (2009) 5
 O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
(34CrAlNi7) and nitrided, that is saturated by Nitrogen to hard-
en a thin (about 0.1 mm) surface layer of the parts. The die for
Not for use in internet or intranet sites. Not for electronic distribution.
extrusion is made with diameter 2 mm and length 60 mm also
from this nitrided steel. The 2 mm hole of the die is conjugated
with a 508 cone having 8 mm diameter at the entrance of the
die. To produce some amount of micro-pellets we used the
same screw extruder but the die was replaced.
Narrow Molecular Weight Distribution (MWD) of PE resin
is important for rotomolding and therefore we used for our ex-
trusion experiments the grades of LLDPE from ExxonMobil
Chemicals with such MWD: LL1201 XV (density 0.925 g per
cm3, melting point 123 8C and MI = 0.7 g/10 min) and LL
1001 XV (0.918 g per cm3, melting point 120 8C and
MI = 1 g/10 min). We also used for comparison LDPE with
wide MWD from the ExxonMobil Chemicals: LL166 BA
(0.923 g per cm3, melting point 110 8C and MI = 0.2 g/10 min).
An induction oven with maximum electrical power of 1.8 kW
was used to heat the steel mold to controlled temperature in open
air. Heating was going in two stages: first, preheating of the
mold to 70 8C for 5 min and, second, a main sintering period
with the temperature of the bottom plate of the mold rising up
to 230 8C. The steel ring was coated by a thin layer of silicone
rubber to ensure easy separation of polymer from the mold.
The same ring was used after cooling to room temperature in
next experiments. The bottom plate in our experiments was not
coated and therefore we replaced the used plate by an identical
one for every experiment. The used plates were cleaned from
molten polyethylene and heated overnight in an electrical oven
to temperatures up to 400 8C to burn out organic residues.
www.polymer-process.com
W 2009 Carl Hanser Verlag, Munich, Germany
Intern. Polymer Processing XXIV (2009) 5
First, we made experiments on sintering of LLDPE
(LL6301RQ) powders from ExxonMobil Chemicals. In sinter-
ing of coarse LLDPE powder a lot of bubbles of various sizes
are trapped inside the melt. While small bubbles dissolve and
disappear, a number of larger bubbles stay inside the melt after
20 min of heating and longer. In contrast to the coarse powder,
in melting of fine powders of LLDPE with particles of sizes be-
low 350 lm even a greater number of bubbles is present soon
after merging of the PE particles but the bubbles mostly dis-
solve and disappear in about 15 min of heating to high tem-
peratures, see Fig. 1A. In further experiments we used only
fine powders.
Glycerol Mono-Stearate (GMS) is known as a densification
and processing aid to accelerate fusion of LLDPE powder. In
our experiments, additives of GMS indeed show some im-
provement in sintering of the blend of LLDPE powders with
0.2 wt.% of GMS. In 9 min of heating of the LLDPE particu-
late we observe approximately two times fewer bubbles
trapped inside the melt, see Fig. 1B. Surprisingly, additives of
polyethylene glycol (PEG 400) at the same concentration
0.2 wt.% show a sharp reduction in the number of bubbles as
well as a shortening in a sintering time about 30 %, compare
photos in Fig. 1A and 1C. The observed reduction of amount
of bubbles in the melt can be explained by very high perme-
ability of PEG to water vapors and Oxygen. So, these gasses
may escape from the melt along the boundaries coated by
PEG. Sintering of PE powder is accelerated further at higher
concentrations of PEG. The optical refraction index of PEG is
higher in comparison with LLDPE and therefore we can distin-
Fig. 1. Sequence of photos showing sintering
of fine LLDPE-powder (A), sequence of photos
showing sintering of fine LLDPE-powder with
additives of glycerol mono-stearate (0.2 wt.%),
sequence of photos showing sintering of fine
LLDPE-powder with additives of 0.2 wt.%
PEG 400 (C)
455
 O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
guish in photos of high resolution macroscopic beads of PEG
inside the melt, see Fig. 1C. It seems so that the PEG evenly
Not for use in internet or intranet sites. Not for electronic distribution.
distributed among the LLDPE powder coalesces under heating
to a few large beads inside the melt. In Fig. 1C a white circle
shows location of one large inclusion of PEG inside the melt.
Macroscopic inclusions of foreign material inside the polymer
matrix are not desirable. It was also detected that PEG ser-
iously impedes flowability of the PE powder if it is used in con-
centrations above 0.2 wt.%.
A sintering of fine particles of polyethylene with additives
of hydrophilic fumed silica in concentrations from 100 to
1000 ppm occurs in a distinctively different manner from the
sintering of pure LLDPE-powder, see Fig. 2A. In addition to
bubbles of trapped gasses we observe a dense network of chan-
nels (gaps between the PE grains) inside the melt. Both the bub-
bles and channels disappear in time and leave macroscopically
large clusters of silica fume inside the melt. In general, additives
of hydrophilic silica fume delay sintering of the PE powder and
the higher the concentrations of silica fume the further is the de-
lay. If mineral particles of submicron and micron sizes, e. g. a fly
ash or bentonite, are blended with PE powder we observe long
delays in fusion of the PE-grains. The powder of silica fume
can be used together with PEG to improve free-flow of the
blend. With the use of such combination sintering times are
short and we do not observe large beads of PEG inside the melt.
Yet, silica fume is present inside the melt as large clusters, see
also about the use of combination of PEG and silica fume below.
It is known that nano-particles of hydrophilic silica fume at-
tract each other by hydrogen forces and agglomerate to macro-
www.polymer-process.com
W 2009 Carl Hanser Verlag, Munich, Germany
456
scopic clusters but if fumed silica is treated by organo-silanes it
gets a hydrophobic surface and the particles are less prone to ag-
glomeration. We can expect that with the use of the treated silica
fume the gaps between merging grains of LLDPE would be nar-
rower, while nano-particles themselves are better embedded into
the molten polyethylene. In Fig. 2B we see a time sequence of
sintering of the LLDPE powder with additives of silica fume
and vinyl-silane (VTMOS, GenioSil XL10). The additives were
blended with powder of LLDPE at about 100 8C in a ball mill to
reduce the aggregate sizes of silica fume while sizes of PE grains
are not changed. In this case, we observe that after 9 min of heat-
ing the number of bubbles of trapped gasses in the melt is con-
siderably fewer in comparison with reference experiments with-
out additives. So, we can speculate that the fumed silica
separates PE grains and delays fusion of them so that trapped
gasses can escape from the melt through the gaps between the
PE grains. With the use of silica fume treated by VTMOS the
gaps are thinner than with not treated silica fume and the delay
times are negligible. In fact, we observe acceleration in sintering
of PE grains if they are blended in a ball mill with vinyl-silane
and silica fume. Combination of three components: fumed sili-
ca, VTMOS and PEG shows short sintering times as well as a
quick removal of trapped gasses from the melt. In contrast to
GMS and PEG, a sole addition of organo-silane (VTMOS) at
the same concentration shows neither fewer bubbles nor shorter
sintering times, see Fig. 2C.
In experiments on sintering of LMDPE grade (M9001RW)
for rotomolding from SCG Chemicals we observe a large num-
ber of bubbles trapped inside the melt, see Fig. 3A. These bub-
Fig. 2. Sequence of photos showing sintering
of fine LLDPE-powder with additives of
400 ppm silica fume (A), sequence of photos
showing sintering of fine LLDPE-powder with
additives of 132 ppm silica fume and of
250 ppm VTMOS GenioSil XL10 (B), sequence
of photos showing sintering of fine LLDPE-
powder with additives of 0.2 wt.% VTMOS
GenioSil XL10 (C)
Intern. Polymer Processing XXIV (2009) 5
 O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
bles are larger in size in comparison with the case of fine pow-
ders of LLDPE powder from ExxonMobil and they do not disap-
Not for use in internet or intranet sites. Not for electronic distribution.
pear after long heating of the melt. Fine powders of amorphous
silica are known in industry as a flow-improving agent. Flow of
LMDPE powders can be improved by additives of fumed silica:
The angle of free repose of the LMDPE powder without any ad-
ditives is 458 and it is reduced to 42.58 by the additives of silica
fume (800 ppm). The angle of repose was measured by pouring
hot powders onto a horizontal surface so that they formed a con-
ical pile. The angle between the surface of the pile and the hori-
zontal surface is the angle of repose. In our experiments it was
measured from photos of the piles. When hydrophilic silica
fume is added to the LMDPE powder it visually reduces an
amount of bubbles in the melt after 7 min of heating but the gaps
between PE grains collapse slowly. So, after 10 min of heating
the amount of the trapped gasses seems to be unchanged in com-
parison with the reference experiment, see Fig. 3B. We can
clearly see in Fig. 3C that additives of PEG 6000 to the LMDPE
powder in the concentration 0.4 wt.% shorten duration of sinter-
ing and nearly eliminate bubbles inside the melt similar to addi-
tives of PEG to fine LLDPE powders. Similar to the experiments
with LLDPE we can distinguish at photos in Fig. 3C macro-
scopic beads of PEG trapped inside the melt. White circles in
Fig. 3C show positions some of them. Viscosity of PEG 6000 is
higher and these inclusions are of smaller size in comparison
with the use of PEG 400.
Particles of LMDPE are characterized by elongated shape and
jagged surface and therefore they resist to flow. Additives of
PEG impede flow of LMDPE powders further. Flow of LMDPE
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W 2009 Carl Hanser Verlag, Munich, Germany
Intern. Polymer Processing XXIV (2009) 5
powder with additives of PEG can be improved by silica fume.
For example, the angle of free repose of the LMDPE powder
with 0.4 wt.% of PEG is reduced from 72 to 608 by the additives
of silica fume (800 ppm). Such amount of silica fume delays
slightly sintering of PE powder as we can see from comparison
of Fig. 3C and Fig. 4A but opposite to the use of PEG alone we
do not observe macroscopic inclusions of PEG inside the melt.
We used a mixture of PEG 6000 with citric acid (ca,
0.64 wt.%) as densification aid. We see from Fig. 4B that sinter-
ing of the LMDPE powder with additives of the reacting mixture
of PEG + ca goes virtually without bubbles. Opposite to the use
of PEG 6000 alone we cannot distinguish macroscopic beads of
PEG inside the melt. Silica fume can be used as a component
of the additive package to improve flowability of the LMDPE
powder with the additives of the mixture PEG + ca. As it is men-
tioned above, silica particles delay merging of PE grains but,
surprisingly, in Fig. 4C we can see that for the powder with the
reacting mixture PEG + ca the delay is negligible even at rela-
tively high concentrations of fumed silica (800 pm).
In extrusion experiments at first we compared extrusion of
LLDPE with and without PPA at various temperatures: 130,
135, 145, 165, 185, 205, 225, 235 8C. Characteristic curves that
are the curves of Pressure at the extrusion die versus Extrusion
Rate (linear velocity of the extrudate derived from volumetric
extrusion rate) for extrusion trials of LL1201 XV without
PPA are presented in Fig. 5A for two temperatures: 145 (a solid
line) and 225 8C (a dashed line). The best-fit curves connect ex-
perimental data: symbols of open circles (145 8C) and open
squares (225 8C). At the characteristic curve for extrusion at
Fig. 3. Sequence of photos showing sintering
of fine MDPE-powder without any additives
(A), sequence of photos showing sintering of
fine MDPE-powder with additives of 800 ppm
silica fume (B), sequence of photos showing
sintering of fine MDPE-powder with additives
of 0.4 wt.% PEG 6000 (C)
457
 O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
145 8C an onset of sharkskin (at 2 mm/s) and stick-slip (at
27 mm/s) instabilities are marked by arrows. For extrusion at
Not for use in internet or intranet sites. Not for electronic distribution.
higher temperatures onsets of surface instabilities are delayed.
However, for LLDPE with narrow MWD the sharkskin in-
stability appears at low rate of extrusion (below 6 mm/s for
LL1201 XV) even at temperatures as high as 225 8C. The
sharkskin instability greatly disturbs surface of the extrudate
and therefore manufacturing of pellets for rotomolding with
smooth surface from LLDPE with narrow MWD is hardly pos-
sible. The instabilities can be eliminated by the use of recently
proposed PPA made from a blend of PEG with silica fume (Ku-
likov et al., 2009). For extrusion experiments with such PPA
we mixed under heating PEG 2000 with silica fume (1 wt.%)
and added 5 g of this PPA per 1 kg of the LLDPE pellets. Ex-
trusion trials were made at various temperatures, see above. In
the range of extrusion rates from 2 to 45 mm/s and for tempera-
tures below 185 8C the measured pressures manifested little
variations versus temperature. Surprisingly, we observed an in-
crease of the extrusion pressures at temperatures from 185 to
235 8C. Characteristic curves of extrusion of LLDPE with
PPA for two temperatures: 145 (a solid line) and 225 8C (a
dashed line) are presented in Fig. 5A. The best-fit curves con-
nect experimental data: symbols of solid circles (145 8C) and
solid squares (225 8C). We can see from comparison of the
curves that pressures at the extrusion die can be considerably
less for reduced temperatures of extrusion than for elevated
temperatures if LLDPE is blended with PPA. This result is very
opposite to extrusion of neat LLDPE where apparent viscosity
drops at elevated temperatures.
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W 2009 Carl Hanser Verlag, Munich, Germany
458
To compare an impact of PPA on extrusion of PE with wide
and narrow MWD we used a blend of PEG 2000 with 1 wt.% of
silica fume as PPA for extrusion of LDPE (LD 166BA) and
LLDPE (LL 1001 XV) in concentration 0.5 wt.% at the tem-
perature 165 8C and for extrusion rates from about 4 to
100 mm/s. For comparison we extruded these PE resins also
without PPA. Characteristic flow curves that are the curves of
Pressure at the extrusion die versus Extrusion Rate are pre-
sented in Fig. 5B. The best-fit curves connect experimental
points for extrusion of PE resins without PPA: a solid line with
symbols of open circles for LLDPE and a dashed line with
open squares for LDPE. For extrusion of PE resins with PPA
the best fit curves connect experimental points: a solid line
with symbols of solid circles for LLDPE and a dashed line with
solid squares for LDPE. Opposite to extrusion of neat LLDPE,
extrusion of LLDPE with PPA goes stable at extrusion rates up
to 80 mm/s where so called elastic instability or “gross melt
fracture” occurs. While extrusion of LLDPE is greatly im-
proved by the PPA and pressures at the extrusion die are re-
duced 4 to 5 times in comparison with extrusion of LLDPE
without PPA there is only marginal pressure reduction for ex-
trusion of LDPE with PPA.
In one set of experiments we used a reacting mixture of PEG
2000 with 2 wt.% of citric acid as PPA in the concentration
0.2 wt.% for extrusion of LLDPE (LL1201 XV) and compared
it with other processing additives. For comparison we used also
PEG 6000, PEG 2000, and Viton that is a standard Processing
Additive in industry to improve extrusion of LLDPE with nar-
row MWD. First, we extruded 1 kg of PE pellets with every
Fig. 4. Sequence of photos showing sintering
of fine MDPE-powder with additives of
0.4 wt.% PEG 6000 and 800 ppm silica fume
(A), sequence of photos showing sintering of
fine MDPE-powder with additives of 0.4 wt.%
PEG 6000 and 26 ppm citric acid (B), se-
quence of photos showing sintering of fine
MDPE-powder with additives of 0.4 wt.%
PEG 6000 (0.4 wt.%), 800 ppm silica fume
and 26 ppm citric acid (C)
Intern. Polymer Processing XXIV (2009) 5
Not for use in internet or intranet sites. Not for electronic distribution. O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
A)
Fig. 5A. Characteristic flow curves (pressure vs. extrusion rate that is
averaged extrudate velocity) for extrusion of LLDPE (LL1201 XV) with
(0.5 wt.%) and without polymer processing additives (PPA, PEG
2000 + 1 wt.% of silica fume) at two temperatures: 145 and 225 8C.
Onsets of sharkskin and stick-slip instabilities are marked by arrows
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C)
Fig. 5C. Curves of pressure reduction vs. extrusion time for extrusion
of LLDPE (LL1201 XV) at 165 8C and extrusion rate about 40 mm/s
with various polymer processing additives: Viton, PEG 6000, PEG
2000, PEG 2000 + 1 wt.% of citric acid. A vertical line separates a
stage of conditioning of the die and a stage of purging by neat LLDPE
one of the additives and then purged the extruder by neat
W 2009 Carl Hanser Verlag, Munich, Germany
LLDPE to see how quick it can be cleaned from the additives.
The curves of pressure reduction vs. extrusion time are pre-
sented in Fig. 5C for extrusion at 165 8C and at extrusion rate
(averaged extrudate velocity) about 40 mm/s. We start the time
counting at the moment when LLDPE with PPA is loaded to
the hopper of the extruder. A vertical line separates a stage of
conditioning of the die and a stage of purging by neat LLDPE
when it is loaded to the extruder. We observed suppression of
sharkskin when Pressure Reduction gets above 20 %. Dead
time in Fig. 5C corresponds to the time to convey the polymer
material through the extruder. The conditioning time by defini-
tion is the time duration that is necessary to suppress sharkskin
since the PE resin with PPA starts to flow through the die. In
Fig. 5C we can see that a composition of the additive compris-
ing PEG 2000 and citric acid (PEG2K+ca) shows best pressure
reduction at the extrusion die as well as a shortest conditioning
time in comparison with other additives. It seems so that cata-
Intern. Polymer Processing XXIV (2009) 5
B)
Fig. 5B. Characteristic flow curves for extrusion of LLDPE
(LL1001 XV) and LDPE (LD166 BA) with (0.5 wt.%) and without poly-
mer processing additives (PEG 2000 + 1 wt.% of silica fume) at
165 8C. Onsets of sharkskin and stick-slip instabilities are marked by
arrows
D)
Fig. 5D. Micro-pellets produced by extrusion at 132 8C of LLDPE
with melting point 125 8C in conditions of air-cooling
lytic properties of the extrusion die are important and we ob-
served much longer conditioning times for extrusion with the
die made from stainless steel. It appears also that silica fume
in amount about 1 wt.% in the composition of PPA helps to
shorten conditioning times and to get good lubrication at the
die. We observed a reduction in these performances if no silica
fume or concentrations of silica fume different from 1 wt.%
were used to prepare the PPA. Without silica fume in the com-
position of PPA curling of the extrudate of small diameters,
e. g. 0.5 mm, may happen so that it leaves the die shaped like
a helix. Details of our extrusion experiments and manufactur-
ing of micro-pellets we are going to publish elsewhere.
Pelletizing of LLDPE material in air without PEG additives
is hardly possible at low temperature of extrudate, e. g.
138 8C, not only because of high pressures at the die but also
because of pronounced die drool and accumulation of molten
PE resin at the die exit. PE melt does not stick to the metal sur-
face wetted by PEG while the low viscous PEG lubricates a ro-
459
 O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
tating knife. If pellets are cut by the rotating knife at higher
temperatures, e. g. 165 8C, they stick together. Therefore pelle-
Not for use in internet or intranet sites. Not for electronic distribution.
tizing with air cooling would be not possible at such tempera-
tures. Extrusion of LLDPE with additives of low viscous
PEG, e. g. PEG 2000, at temperatures below 130 8C cannot be
recommended too as the extrudate surface gets rough, friction
losses at the die oscillate in time while the averaged pressure
is increasing. With the use of PEG 8000 extrusion goes stable
down to temperatures as low as 128 8C but at higher pressures
at the die as compared to the use of PEG 2000.
To demonstrate an opportunity to fabricate micro-pellets by
extrusion at reduced temperatures and pelletizing in open air
we used as a die set a pack of 7 injection needles with inner
diameter about 0.5 mm and 20 mm length soldered by silver al-
loy inside a steel housing. We used no additional cooling in the
process but convection of air. LLDPE (LL1201 XV) was
blended inside a screw extruder with additives (0.5 wt.%) of a
reacting blend of PEG 8000 and 1.6 wt.% of citric acid. We
started extrusion at 165 8C and after a conditioning time about
one hour that is necessary to get stable lubrication at the die
we reduced gradually a temperature of the die. We used a rotat-
ing knife from a meat grinder to cut strands to pieces at aver-
aged melt velocity about 22 mm/s. The produced micro-pellets
do not stick to each other at temperatures of extrusion from 130
to 135 8C. With this simple appliance it is possible to cut micro-
pellets as cylinders or disk-like pellets of oval shape with thick-
ness about half of the diameter by varying the rotation speeds
of the knife. Appearance of the micro-pellets is presented in
Fig. 5D. The produced micro-pellets demonstrate good flow
properties (an angle of free repose is about 408) and obviously
can be used for rotomolding or flood feeding of an extruder.
www.polymer-process.com
We also fabricated some amount of micro-pellets by stretching
and cutting thin strands of LLDPE by a rotating knife of a
wood planer. The strands of LLDPE with PA were extruded at
reduced temperatures (about 132 8C) from the die set with
small holes and stretched by rollers in conditions of air cooling
to diameters about 0.3 mm before they were cut. Extrusion of
PE resins with narrow MWD at reduced temperatures without
PPA produces strands with deep sharkskin defects. Stretching
of the strands with sharkskin makes surface roughness and re-
lative thickness variations even deeper. So, fabrication of mi-
cro-pellets from PE resins with narrow MWD at reduced tem-
peratures would be not possible without PPA.
W 2009 Carl Hanser Verlag, Munich, Germany
3 Discussion
PEGs are slightly dissolvable in PE resins at high temperatures.
They reduce surface tension and viscosity of molten PE and the
additives of PEG are already known in industry as an agent to
improve cohesive strength of a weld joint in hot sealing of PE
films. So, it is no wonder that additives of PEG accelerate sin-
tering of the PE powders but mechanism of the PE melt densi-
fication with additives of PEG is not yet understood. We can
tentatively explain the observed improvements by high perme-
ability of PEG to Oxygen and water vapors. To our knowledge
a systematic research on gas permeability of PEG and PEG-
based esters is missing but from the data in literature (Metz,
2003; Massey, 2003; Lin and Freeman, 2004) we can derive
that diffusion of water vapors, Carbon dioxide and Oxygen
460
through PEG is much better in comparison to PE resins. Zhang
and Cloud (2006) proposed a qualitative mechanism of gas per-
meability of silicon rubber: thermal motion of long and flexible
siloxane molecules provides “openings” in silicones for the gas
molecules which permit diffusion of gasses. Chemical struc-
ture of PEG molecules resembles molecules of siloxanes and
gasses can diffuse through the PEG and PEG-based esters in a
similar way. In fact, hydrophilic properties of PEG make diffu-
sion of water vapors through the bulk of PEG and PEG-based
esters much easier in comparison with silicone rubbers.
PEGs with molecular weights from 200 to 10 000 Dalton can
react under heating with carboxylic acids and anhydrides of the
carboxylic acids, e. g.: stearic acid, oxalic acid, adipic acid, ci-
tric acid, maleic anhydride, phthalic anhydride, etc. (Bauer
et al., 2000). Reactivity is higher with lower MW PEGs, stron-
ger acids and with anhydrides. If weights of the curing agents
are selected close to stoichiometry or above it and the mixture
has in average more than two reacting groups per molecule,
the ester-condensate can be a thermoset. It is clear that such re-
acting mixtures of PEG with carboxylic acids and anhydrides
gain higher viscosity in time of heating and if they are used as
an additive package for rotomolding the additive is less prone
to coalescence to large beads inside the melt in comparison
with neat PEG. PEG reacts readily with citric acid under heat-
ing above 140 8C with release of water vapors. Additionally, ci-
tric acid is decomposing at temperatures above 175 8C to water
and Carbon dioxide. In our experiments the amount of citric
acid (MW = 192.1) was below stoichiometry and we cannot
count on sharp increase in viscosity of the reacting mixture.
Therefore another tentative explanation can be proposed: flow
of the reacting mixture under forces of surface tension is dis-
turbed by tiny bubbles of water vapors that appear in the reac-
tion of condensation and gases from decomposition of citric
acid. Additionally, it seems to be advantageous, if fusing grains
of PE are purged by water vapors released from the condensa-
tion reaction while water molecules can escape from the voids
between PE grains due to very high permeability of PEG.
From our experimental observations we can conclude that
blends of PEG with silica fume as well as a reacting mixture
PEG + ca does not coalesce into a few large beads like neat
PEG does but stay trapped inside the melt as small-size inclu-
sions. We used citric acid as a reactant but special mixtures
can be used to facilitate formation of the inclusions of smaller
sizes and with core-shell structure. For example, stearic acid
and stearates, e. g. glycerol monostearate, can be added to the
reacting mixture of PEG and citric acid as a surface-active re-
agent to facilitate formation of the inclusions with core-shell
structure where the core is from hydrophilic visco-elastic mate-
rial with low modulus while the shell is hydrophobic and em-
bedded into PE. Nano- and micro-sized particles with core-
shell structures are well known for the use as impact modifiers.
So, opposite to large beads of PEG in PE matrix the small-size
inclusions of these reacting mixtures can even enlarge tough-
ness and impact resistance of the rotomolded articles.
Polyethylene is exposed during grinding to extreme shear
stresses and to temperatures close to its melting point in pre-
sence of oxygen. If PE powders with high surface area are
stored in an air atmosphere for prolonged periods, oxidative
degradation of PE molecules would continue. Additionally,
surface of grains of the PE powder is enriched by chemical
Intern. Polymer Processing XXIV (2009) 5
 O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
components of low MW that migrate from the bulk of PE
grains. Presence of low MW PE and waxes significantly re-
Not for use in internet or intranet sites. Not for electronic distribution.
duces entanglement of long PE molecules at the boundaries of
the sintered PE grains and causes local weakness of cohesive
strength of the polymer. We believe that the cohesive strength
can be enlarged by cross-linking of PE molecules across the
grain boundaries and by anchoring nano-particles of silica
fume in both contacting grains of PE during the fusion process.
In our experiments we added vinyl-silane to the blend of the PE
powder with silica fume in hope to get reinforcement of the
boundaries between the merging grains of PE. The additives
of vinyl-silane do not improve sintering of the PE grains if they
are used alone. Therefore we believe that shorter time of sinter-
ing of the blend comprising vinyl-silane VTMOS and silica
fume in comparison with neat PE powder can be an indication
that the nano-particles of silica with surface modified by vi-
nyl-silane indeed get embedded into molten PE. During roto-
molding process the molecules of vinyl-silane that are grafted
to the surface of silica particles may create chemical bounding
between the modified silica particles and molecules of PE as
well as cross-linking of the PE molecules in a boundary layer
of the merged grains of PE. Yet, direct measurements of impact
strength to confirm integration of silica particles to polymer
matrix are missing and have to be done in future.
Flow performances of the PE particulates are important to
get uniform thickness of the walls and to avoid “bridging” in-
side the mold between opposite walls and in the corners of the
rotomoded article. The use of PEG and reacting mixtures of
PEG with carboxylic acids as PPA impede flow of PE powders.
Additionally, blending of the PE powders with such additives
is costly. We propose that blending of PPA with PE resins has
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to be done inside an extruder for manufacturing of micro-pel-
lets. Micro-pellets of oval shape with sizes from 0.3 to
0.8 mm provide superior handling and processing perfor-
mances in rotomolding (Beall, 1998; Whatcott, 2008; Craw-
ford and Kearns, 2003). Our experiments demonstrate that mi-
cro-pellets can be produced by extrusion of PE resins at
reduced temperatures. High fluidity of micro-pellets is consid-
ered sometimes as a disadvantage of the material while flow-
ability of PE powders is below optimum. The proposed PPA
adjusts flowability of micro-pellets in proper direction, i. e. re-
duce it. Yet micro-pellets with PPA show better flowability
than fine PE powder without PPA.
W 2009 Carl Hanser Verlag, Munich, Germany
It is amazing that the same composition and concentration of
additives used as a densification aid in sintering of PE particu-
lates helps to improve extrusion of the PE melt: to suppress
sharkskin and to reduce extrusion pressure. As a tentative mech-
anism of the observed lubrication we can propose following:
Commercially available LLDPE grades comprise low MW or-
gano-phosphites as antioxidant additives. The antioxidants de-
plete Oxygen from the PE melt and get converted to organo-
phosphates that are low MW esters of alcohols and phosphoric
acid. PEG reacts with these esters at the surface of the die so
that high MW esters appear in the reaction of trans-esterifica-
tion. Reaction rates depend on presence of catalysts. We used
in our experiments the die that is made from a steel alloy com-
prising Aluminum and Vanadium. These metals are good cata-
lysts for a poly-condensation and trans-esterification reactions.
The high MW esters of PEG and phosphoric acid have high af-
finity to metal surface and therefore they accumulate at the die
Intern. Polymer Processing XXIV (2009) 5
surface and form a layer of a plastic lubricant. With the use of
the catalytic die we observe relatively short conditioning times
while with the dies having low catalytic properties, e. g. a
Chromium coated die, the conditioning times are much longer.
The use of carboxylic acids in the composition of PPA for ex-
trusion of PE resins with narrow MWD allows to shorten condi-
tioning times and to get better lubrication at reduced tempera-
tures of extrusion. Actually, inside an extruder the temperatures
can be higher (185 to 195 8C in our experiments) while the die
is at the reduced temperatures. Extrusion can go at temperatures
of the die so close to the melting point of the PE resin that the ex-
trudate with cold surface can be pelletized with a rotating knife
at the die exit in conditions of air cooling. Otherwise, a rotary
knife can be used for cutting of PE strands of small diameters
after stretching of them. We observe that at reduced tempera-
tures of extrusion the additives are ejected from the extrudate
to its surface. We have some indirect indications from our ex-
perimental observations that if silica fume is suspended in PEG
it moves to the extrudate surface together with PEG. If pelletiz-
ing goes in air or gas atmosphere, these additives would stay at
the surface of the micro-pellets and therefore they can be reused
as densification and sintering enhancers for rotomolding.
4 Conclusions
We present here first experimental results on the use of react-
ing mixtures of PEG with citric acid as sintering and densifica-
tion enhancers for rotational molding of PE particulates. Sin-
tering of PE grains with these additives goes virtually without
bubbles of trapped gasses and duration of heating of the mold
in rotomolding can be 20 to 30 % shorter. Therefore, higher
productivity and better mechanical properties of the roto-
molded articles can be achieved. From our observations we
can conclude that reacting mixtures PEG + ca do not coalesce
into a few large beads like neat PEG does but stay trapped in-
side the melt as small-size inclusions.
We demonstrated here that reacting mixtures of PEG with
citric acid improve sintering of PE powders but impede flow
of them. So, it is not advisable to use them with PE powders.
Surprisingly, the same mixtures that are helpful to reduce
sintering time of PE particulates do work as Polymer Process-
ing Additive (PPA) for extrusion of PE resins with narrow Mo-
lecular Weight Distribution (MWD). The proposed PPA sup-
presses extrusion instabilities, reduces extrusion pressure 2 to
5 times and allows extrusion at temperatures close to solidifi-
cation points of the PE resins. Therefore micro-pellets can be
produced from PE resins with narrow MWD in conditions of
air-cooling. Flow of the produced micro-pellets is better than
flow of the industrially available powder from PE resin. Roto-
molding experiments with such micro-pellets we reserve for
next publications.
Fabrication of micro-pellets for rotational molding with
water cooling is already cost efficient in comparison to PE
powders. It seems so that fabrication cost of micro-pellets can
be reduced by pelletizing in air with proposed PPA while the
rotomolded articles can be produced in shorter times and of
better quality. More experimental and analytical investigations
are required to prove better Impact Strength and Environmen-
tal Stress Crack Resistance of the rotomolded articles made
461
 O. Kulikov et al.: Novel Processing Additives for Rotational Molding of PE
from micro-pellets and novel PPA as well as to get deeper in-
sight in the mechanisms of the observed improvement of sin-
Not for use in internet or intranet sites. Not for electronic distribution.
tering and extrusion of PE resins. However, we believe that
manufacturing of micro-pellets with proposed PPA from PE re-
sins with narrow MWD in conditions of air cooling and the use
of these micro-pellets for rotomolding can be a quantum leap in
technology of rotomolding. Patent pending.
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Acknowledgements
We would like to thank Dr. Winyu Tanthapanichakoon and
Dr. Chris Rauwendaal for stimulating discussions. We thank
gratefully ExxonMobil Chemicals and SCG Chemicals for pre-
senting us Polyethylene resins for our experiments. Financial
support by the German Science Foundation (Deutsche For-
schungsgemeinschaft) is gratefully acknowledged.
Date received: May 28, 2009
Date accepted: August 24, 2009
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DOI 10.3139/217.2296
Intern. Polymer Processing
XXIV (2009) 5; page 452 – 462
ª Carl Hanser Verlag GmbH & Co. KG
ISSN 0930-777X
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Intern. Polymer Processing XXIV (2009) 5