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of the articles manufactured via this technology employ polyethylene (PE) resins. PE
resins used for rotomolding have usually particle sizes less than 0.8 mm and used as
powders or micro-pellets. A disadvantage of the rotational molding 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. Chaudhary et al. [1] used
low Molecular Weight (MW) additives like wax, mineral oil and glycerol monostearate
as sintering enhancers in rotational molding. With this, melt viscosity and elasticity
were reduced while much faster densification and bubble removal were observed.
Surface of grains of the PE powder is enriched by chemical components of low MW
particles of silica fume with modified surface in both contacting grains of PE during
the fusion process.
One of the problems in rotational molding is bubbles of gasses trapped during
Experiments were done with MDPE from the SCG Chemicals (M9001RW, MI=3.2
g/10 min) and LLDPE from ExxonMobil Chemicals. PE powder was blended with
various additives at temperatures about 80°C. Methanol was used as a solvent and
adjuvant to improve dispersion of the additives among the particles. Samples in the
amount of 5 g were loaded into a mould 50 mm in diameter and gently compacted by
a disk from PMMA to ensure equal thickness of the polymer material in the mould.
Sintering was going at controlled temperatures of the mould up to 230°C. A digital
camera was used to record process of sintering of the PE particulates under
magnification. Some of the recorded photos are presented below and arranged in
vertical rows for comparison. Width of a single photo corresponds to about 6.8 mm of
the mould inside in its central area.
Surprisingly, additives of PEG with Molecular Weights (MW) from 400 to 8,000 Da
greatly reduce number of bubbles inside the melt and accelerate fusion of PE grains
but coalesce to a few beads inside the melt. Such inclusions can reduce mechanical
strength of PE. From results of our experiments we propose to use reacting mixtures
of PEG with citric acid as Processing Additive (PA) for rotational molding. PEG reacts
with citric acid (CA) at temperatures above 160°C with release of water. Additionally,
citric acid is decomposing at temperatures above 175°C to water and Carbon dioxide.
PEG is characterized by very high permeability to these gasses. We believe that
"purging" of the merging PE grains with water vapors combined with easy diffusion of
water through the foamed mixture of PEG+CA can be a mechanism that reduces
amount of trapped gasses inside the melt. It seems so that foaming of the PA
impedes its flow under capillary forces and we do not observe any large beads of
PEG+CA inside the melt. It is important to use optimal amounts of CA in the PA. Too
much of CA would foam the melt and too low amounts of CA would not stop merging
of PEG into a few large beads.
In our experiments we added vinyl-silane (VTMOS, 250 ppm) to the blend of the
LLDPE powder with silica fume (Aerosil 300, 132 ppm) in hope to get reinforcement
of the boundaries between the merging grains of PE. The additives of vinyl-silane as
well as of silica fume with hydrophilic surface do not improve sintering of the PE
grains if they are used alone. Therefore we believe that shorter time of sintering of
the blend comprising vinyl-silane and silica fume in comparison with neat PE powder
that we observed can be an indication that the nano-particles of silica with surface
modified by vinyl-silane indeed get embedded into molten PE. During rotomolding
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
walls of the molded parts. Fine powders of PE with particles of irregular shape and
wide distribution of sizes are characterized by flowability below optimum while micro-
pellets of oval shape with smooth surface have too high flowability for rotational
molding. To improve quality of the rotational molding we propose the use of micro-
pellets and coarse powders of PE with our PA instead of fine powders. To
demonstrate an industrial potential, micro-pellets were manufactured by extrusion of
molten PE at temperatures from 7°C to 10°C above melting point of LLDPE resin
through a set of holes 0.5 mm in diameter and by cutting the strand by a rotating knife
at the die hot face in conditions of air-cooling. Amazingly, the same PA used for
rotational molding improves extrusion and essentially reduces pressure at the die so
that extrusion of LLDPE can be done at reduced temperatures. Without the PA
extrusion at such temperatures is hardly possible because of 'sharkskin' and 'stick-
micro-pellets with as much as 0.5 wt. % of our additives is less than the angle of free
repose for MDPE powder without additives. The proposed compositions of PA are
cheap and not harmful, see foe details [2]. They would easily comply with the
Figure A: Sintering of fine MDPE-powder without any additives in time from top to
bottom. Bubbles are trapped inside the melt. Figure B: MDPE-powder with
additives of PEG 6000 (0.4 %). Number of bubbles is reduced but PEG is
coalesced to a few beads inside the melt. The beads are shown by circles. Figure
C: MDPE-powder with additives of PEG 6000 (0.4 %) and citric acid (26 ppm).
Sintering of PE powder goes virtually without any bubbles or beads of PEG.