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Bubble dissolution in molten polymers and its role in rotational molding

Article  in  Polymer Engineering and Science · July 1999

DOI: 10.1002/pen.11505

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 Bubble Dissolution in Molten Polymers
and Its Role in Rotational Molding
M.KONTOPOULOU and J. VLACHOPOULOS'

Centrefor Advanced Polymer Processing and Design (CAPPA-D)

Department of Chemical Engineering, McMaster University
Hamilton, Ontario, Canada LBS 4L7

The presence of bubbles is inherent in the rotational molding process and can
often cause poor quality in rotomolded parts. In an effort to gain a fundamental un-
derstanding of bubble removal in polymer melts, a model that includes diffusion,
surface tension, and viscosity effects has been implemented. This work has been
complemented with experiments performed in a heated chamber, which enabled
the visualization of the bubble formation and removal process. It was concluded
that bubble removal is mainly dBusion controlled and is not influenced sic-
cantly by melt viscosity when the latter lies within ranges typical for rotational
molding resins. Air concentration in the bulk of the p o w e r melt and initial bubble
size were found to be of great importance. The application of pressure after the
polymer has melted accelerates the dissolution rate, owing to an increased driving
force for diffusion.

IlpTRODUCTIOlll the material properties. An attempt has been made to

R otational molding, also known as rotocasting or
otomolding is a method for producing hollow
plastic articles. It involves tumbling a thermoplastic
powder in a bnxially rotating, heated metal mold, until
all the plastic melts and forms a uniform coating on
the inside surface. Polyethylene in powder form is ex-
tensively used in rotomolding.
Considering the fact that rotational molding is virtu-
ally a shear and pressure free process, viscosity (more
specifically zero shear viscosity) is the most important
parameter used to assess whether a resin is suitable
for this process (1).The use of low viscosity resins fa-
vors powder coalescence (sintering) (2).allows the
molten polymer to flow efficiently inside the mold, and
ensures good surface finish. High viscosities result in
poor surface finish and excessive amounts of bubbles
(3).
The presence of bubbles in rotomolded parts is a se-
rious problem, because it can potentially sect the
mechanical properties of the parts. Moreover, the
presence of bubbles and pitholes (bubbles on the
outer surface of the part, that is adjacent to the mold)
poses a problem to the part appearance and aesthet-
ics. The objective of the current research is to present
a fundamental study on the formation and removal of
bubbles from polymer melts and its dependence on
T o whom correspondence should be addressed
develop a rigorous model, which includes the parame-
ters relevant to the bubble formation process, such as
surface tension, viscosity and diffusion.
LITEIlATuRE REVIEW
The presence of bubbles in viscous materials has
been encountered in metal and glass processing, and
there is a great deal of literature addressing this as-
pect. Greene and G&ey (4) used a specially designed
apparatus to study oxygen dissolution in molten glass.
They modeled the process by solving a Fickian type
equation a n d treated the moving boundary as a
Stefan type problem. Doremus (5).through a compari-
son of theory with experiment computed diffusion co-
efficients of oxygen in molten glass and commented
on the possible mechanisms for the diffusion process.
The models concerning bubble growth and dissolution
in glass melts have been reviewed by Kramer (6).
The diffusion controlled dissolution of air bubbles in
water has been studied by Epstein and Plesset (7).
They discussed the effect of surface tension and were
able to derive an analytical solution by neglecting it.
Readey and Cooper (8) and Cable and Evans (9) have
treated the problem of molecular diffusion of gas bub-
bles with the inclusion of moving boundary and radial
convective transport effects.
Other studies (10-14) have covered the aspect of
bubble growth and collapse in viscous or viscoelastic
fluids. These papers are mostly concerned with the
formation and removal of cavitation bubbles in poly-

POLYMER ENGINEERING AND SCIENCE, JULY 1999, Vol. 39, No. 7

 M.Kontopoulou and J. Vhchopoulos
meric solutions of relatively low viscosities and at rela-
tively high Reynolds numbers. In these cases, bubble
dynamics are mainly controlled by pressure differ-
ences and fluid velocities. The bubble growth or col-
lapse mechanism is modeled by solving the coupled
continuity and momentum equations, without taking
diffusion into account.
Bubble formation and removal is not a situation en-
countered frequently in common polymer processing
methods, so there is very limited literature covering
the aspect of bubble removal from polymer melts. A
great deal of work has been done, though, on the for-
mation of bubbles in polymer melts during the foam-
ing process. Han and Yo0 (15) and Arefmanesh and
Advani (16, 17) in their work on bubble growth in poly-
meric foams showed that the important phenomena
occurring during bubble growth are mass, momen-
tum, and energy transfer between the bubble and the
fluid surrounding it. The transfer of mass in foam
processing is due to the diffusion of dissolved gas
from the fluid into the bubble. Ramesh et al. (18)veri-
fied Arefmanesh and Advani's theoretical predictions,
by comparing them with experimental data.
Bubble# in R o t a t i d Molding
In an initial attempt to describe the bubble forma-
tion problem relevant to rotational molding, Rao and
Throne (19) drew extensively from the theories of
metal sintering and densfication. According to them
the formation of a homogeneous melt from powder
particles is a two-step process. During the first stage,
which is denoted as sintering,the powder particles
stick, or fuse, together at their points of contact.
Interfaces and bridges develop between adjacent par-
ticles, until the mass becomes a porous three-dimen-
sional network. During this stage there is little change
in the density of the mass.The next step is the densi-
j b f b n ,where the network begins to collapse into the
void spaces, which become bubbles. The bubbles are
either pushed ahead of the coalescing front to the free
surface, if the melting is sufficiently slow, or become
encapsulated and remain in the polymer after it is
quenched, which is the usual case for rotomolding.
Other researchers (20,211 distinguished three dis-
crete mechanisms: a sintering type of mechanism,
bubble formation. and removal and surface leveling.
Progelhof et aL (21) observed two phenomena: forma-
tion of voids in the molded part and surface leveling.
They reported a slow movement of the voids towards
the f k e surface. Kelly (22)suggested that bubbles re-
main stationary and that the oxygen in the air bubble
begins to physically dissolve in the polymer, as the
temperature of the melt increases. The oxygen is the
first gas to dissolve, because it has twice the solubility
of nitrogen in polyethylene. The depletion of oxygen
results in the reduction of the bubble diameter, which
in turn results in the increase of the pressure inside
the bubble, as dictated by the laws of surface tension.
The increase in pressure forces nitrogen to dissolve in
the polymer, further reducing the bubble diameter.
iim
Crawford and Scott (20).in a detailed study of the
phenomena occurring during the bubble formation
and removal, confirmed Kelly's suggestion that bub-
bles remain virtually stationary in the melt, because
of the high viscosity of the melt. They described the
melting and collapse of the powder as the combina-
tion of two bulk movements: first the progression of
the melt front through the powder mass to the free
surface and then the collapsing of powder particles
into the melt. Air is trapped during the latter process.
Spence and Crawford (23-25) presented an exten-
sive study on the processing variables affecting the
formation and removal of bubbles. They studied the
effects of viscosity, powder characteristics, processing
conditions, moisture, mold material, and mold release
agents. They also found that mold pressurization dur-
ing the rotomolding cycle is an efRcient method to re-
move bubbles from rotomolded parts.
Crawford and his co-workers (24. 26) proposed a
model for the removal of bubbles from rotomolded
parts, which is based on the concept that the mecha-
nism for bubble removal is governed by the diffusion
of gas through the polymer melt. The approach to-
wards the development of the W s i o n based model
follows the approach by Greene and Gaffney (4).
Although these models seem to describe qualitatively
the removal of bubbles from polyethyelme melts, they
rely on the estimation of constants by curve fitting.
THEORY
Dyaamiaa of Bubble M..drrtion
Although in reality the polymer melt during rota-
tional molding contains many bubbles, a simplified
approach will be implemented, which treats the disso-
lution of a single spherical gas bubble in an inAnite
polymer melt (Flg. 1). The problem is assumed to be
isothermal.
The kinematics of the problem are satisfied by the
continuity equation, which for spherical geometry,
uni-directional flow in the r direction, constant den-
sity, p and using the boundary condition that the
bubble wall velocity, at r = R is U,= dR/dt, is simpli-
fied to (27):
R2R
u, = y-r
The dynamics of the system are governed by the con-
servation of momentum in the radial direction
ap
p
(-+ ur-
ar
aur)
= - - +ar @..Ir
Since the fluid is highly viscous, the inertia terms can
be neglected and Equation 2 becomes
ap + -
-- a (r2Tm) - Tee +
1 - =
(3)
ar P ar r
POLYMER ENGINEERING AND SCIENCE, JULY 1990, Vol. 39, No. 7
 Bubble Dissolution in Molten Polymers

ng.1 . Geometry of a single spher-

ical bubble ~Urrounded
by M in^-
nite amount ofjzuid

Taking into account spherical symmetry ( T =~ T,J, an The components of the rate of deformation tensor for
integration from the bubble wall to infinity allows us uniaxial elongational flow are:
to relate the stresses within the fluid to the gas pres-
sure inside the bubble and the ambient pressure (14):

P(R) - P(W) + 7 , (W) - T,(R) +

&=O (4)
k o m Equation I , we have
A force balance at the bubble-liquid interface gives:
au, - --~ R ~ R
_
ar r3
2rRu + a R 2(P(R) - T,(R)]L= P@ [P,+ T,,]G (5)
Substitution of J3q 10 into Eq 9 gives
Since the normal stress due to a low viscosity gas can
be neglected, T ~ = 0.
, Equation
~ 5 becomes: 4PR
A r r = --
r3
2a
P(R) = T J R ) + Pg - (6) 2PR
A,, = A, =-
r3
where the pressure Pg is the average gas pressure
within the bubble. The n o d stresses can now be calculated by using
Substitution of Eq 6 into Eq 4 and assuming that at the Newtonian constitutive Eq 8 and the rate of defor-
r = m, T , = 0 mation components, given by Eq 1 1 . The result can be
substituted in Eq 7 and after rearranging and naming
2u 44 = PJ
Pg - P(w) - - + 2 dr= 0 (7)

For a Newtonian liquid, the stress components de-

pend on the rate of deformation:
Equation 12 relates the pressure inside the bubble to
the rate of dissolution of the bubble.

POLYMER ENGINEERING AND SCIENCE, JULY 1990, Vol. 39, No. 7 1191
 M. Kontopoulou and J . Vlachopoulos
Dstermlnrtion of the Remsure Inaide the Bubhle
In order to determine the rate of dissolution of the
bubble from Eq 12,we must have a relation for the
gas pressure inside the bubble. This can be found by
applying the conservation of mass principle for gas in-
side the bubble (28).If the buildup of adsorbed gas on
the bubble wall is assumed to be negligible, the rate of
decrease of gas within the bubble equals the rate of
diffusion of gas from the bubble across the wall, to-
wards the liquid. The mass balance can be written
(28):
(13)
r= R
Assuming that the gas inside the bubble is ideal, the
concentration of gas within the bubble can be related
to the pressure inside the bubble: cg = Pg/(RJ)
Y-
The pressure inside the gas bubble can be also related
to the gas concentration at the bubble-liquid interface
through Henry's law:
where Kh is Henry's law constant. This equation is valid
for dilute solutions.
To solve Equation 14 it is necessary to know the
Concentration profile in the liquid. This can be deter-
mined by solving the complete diffusion equation for
the liquid surrounding the bubble, which for spherical
coordinates can be simplified by neglecting the terms
involving convective transport (29):
Equation 16 can be solved subject to the following
boundary and initial conditions:
c fr, 0)= q,r >R
Zimcfr,t ) = q. t
r-m
>0
CfRt ) = G,t >0
The concentration of gas dissolved initially in the bulk
of the polymer melt can be determined from Henry's
law, if the melt is saturated with air:
In reality it is impossible to know the degree of satura-
tion of the polymer melt, so when comparing model
predictions to experimental data, it is necessary to as-
sume that c, will be a fraction x of (
4:,
1192
Table 1. Numerical Values of Physical Properties at 1W'C.
Physical Property Value Reference
~~
Diffusion coefficient, m2/s 8.57 X lWg (30,31)
Henry's law constant, mol/(m3Pa) 3.75 x lW5 (30, 31)
Surface tension, N/m 0.026 (32)
~~
By comparison with several experimental data, as will
be shown in the Experimental section, it has been
found that x lies between 0.9 and 1.
NamerICrl Soldon &heme md Model
xmplammtation
The rate of bubble dissolution can be determined by
solving simultaneously Equations 12, 14,and 16 with
the aid of JZqtdbm 15 and 1 7.A numerical method,
using a finite Werence discretization and a forward
Eulerian scheme is implemented. A quasi-steady state
approximation (solution of the steady-state equation
for every time step) is used for solving the dffision
equation, following the steps shown below:
hitially, as the powder melts and the pockets of
air form, the system pressure is equal to the a m -
bient pressure. Once the bubble is formed, the
pressure inside the bubble increases slightly due
to curvature, through the action of surface ten-
sion [Equation s). The initial pressure Pg inside
the bubble can be determined from Equation 6,
by neglecting T~ (assumingthere is no movement
of the melt due to bubble shrinbage yet) and set-
ting P(R) equal to the ambient pressure. In order
for the solution to begin. the initial bubble radius
is substituted for R in E q d b n 6,at the first time
increment.
By using the initially estimated pressure Pg in-
side the bubble, the air concentration at the air
bubble interface, ,c can be determined from
Henry's law, Eq 15. The initial concentration of
air dissolved in the bulk of the polymer, q,is also
determined from Henry's law, Eq 17,using the
ambient pressure.
The concentration gradient ac/& can be deter-
mined for the first time increment by solving
Equation 16.
Equations 12 and 14 are solved simultaneously,
to give the new values of Pg and R at the end of
the time increment.
Using the most recent value of Pg,the new air
concentration, c,can be determined from J3q 15.
By using this ,c and the new bubble radius, the
concentration gradient W a r can be determined
for the second time increment Eq 16 and the pro-
cedure is repeated.
In order to implement the model the initial bubble
diameter, ambient pressure and physical constants of
POLYMER ENGINEERING AND SCIENCE, JULY 1990, Vol. 39, No. 7
 Bubble Dissolution in Molten Polymers

0.30 1.036
--Bubble Diameter
0.25
1.031
-5
E
E 0.20 -I

0)
P
-f 0.15 1.026 $
0 X
0
nm
2 0.10
m' 1.021
0.05

1.016
0 2 4 6 8 10 12 0 2 4 6 8 10 12
Time (min) Time (min)

Flg. 2. Diameter and air pressure inside the bubble versus Flg. 4. Relative magnitude of surface tension and n o d
time for the dissolution of a typical gas bubble [d,= 0.25 stress terms as afunction of time in a PE melt [d,= 0.25 nun.
nunJ in a PE melt [k = 3000 Pas,c, = 0.995 at 190°C. fi = 3000 Pas, 19O"C,c, = 0.995 [c,),).

0.30
__ p= loo00 P a s
RESULTS-MODEL PREDICTIONS
0.25 - p = so00 Pas
......... = 500 Pas Bubble Diudution Mechadmm
-EE
L
0.20
The application of the proposed model gives an in-
E
5 0.15
s e t to the mechanism of bubble dissolution. As the
.-
0 bubble forms, the air pressure, Pg.inside the bubble
;
a
0.10 is slightly kugher than the ambient pressure, because
of the action of surface tension (Equation 6). Through
m
0.05 the application of Henry's law it can be seen that
higher air pressure inside the bubble results in a
0.00 1 higher concentration of air, c,, in the polymer/air in-
0 2 4 6 8 10 12 terface (bubble walls) compared with the concentra-
Time (min)
tion ciin the rest of the polymer melt, which is ex-
Flg. 3. Effectof melt viscosity on bubble dissolution curues in posed to ambient pressure (see also Rg. I).
a PE melt [d,= 0.25 mm, 190°C.c, = 0.995 [ c , ) ~ ) .
The concentration difference gives rise to a dnving
force, which results in the diffusion of air from the bub-
ble to the surroundings. As gas is removed from the
bubble, the diameter decreases and the air pressure in-
side the bubble inu-eases further. Flgwe 2 shows the
change in Pg as the bubble diameter decreases, for the
the system, such as viscosity, surface tension, diffusion dissolution of a typical gas bubble of initial diameter
coefficient, and Henry's law constant are required. The equal to 0.25mm in a PE melt, which is close to satu-
concentration of air in the polymer melt is determined rated conditions (q = 0.995( ~ 3 , ~ )and has a viscosity
by curve fitting, since it is impossible to determine of 3000 Pa% at 190°C.At long times, Pg increases
either theoretically or experimentally, as explained in dramatically as R --f 0 (Equation6), and this causes
the Theory section (Equations17aand 1 7b). an acceleration in the bubble dissolution rate. This
happens because the increase in Pg inside the bubble
Emtimation of Physical Conmtants results to an increase in q,,, as predicted by Henry's
law and subsequently to an even larger concentration
The diffusion coefficients and Henry's law constants difference between the bubble/& interface and the
for air into polyethylene melt were estimated by us- polymer melt, thus acceleratmg diffusion.
ing data and charts published by Griskey (30).The
Lennard-Jones parameters for air, needed for using Effect of Vi.cOrity
Griskey's charts, were obtained from Bird et aL (29).
The temperature dependence of these parameters can It has been reported that melt viscosity affects bub-
be estimated by applying an Arrhenius type equation ble dissolution rate, because as melt viscosity de-
(31).Surface tension values for PE melts were ob- creases, polymer chains become shorter and diffusion
tained from Wu (32). of air through the melt is facilitated (23).However, it
A summary of the physical constants used in this has been shown that both in the case of the diffusion
work is shown in Table 1. of gases in solid polymers (33)and in molten polymers

POLYMER ENGINEERING AND SCIENCE, JULY 1999, Vol. 39, No. 7 1193
 M. Kontopdou and J. Vlachopoulos
0.30
-0.S98 Caat
0.00
0 5 10 15
Time (min)
m.5. mxt of bulk concentrationof air on bubble dissolu-
tion curves (d,= 0.25 nun,+ = 3000P a s , 190°C).
(30)diffusMty does not depend on the viscosity of the
polymer but rather on the size of the gas molecule
and on the monomer type and structure.
The effect of viscosity in the bubble dissolution
process can be understood better by inspecting the
force balance at the bubble-liquid interface (Equatdon
6).As the bubble shrinks. a normal force is generated
in the polymer melt, which acts on the opposite direc-
tion, that is, it opposes the movement of the bubble
boundary. For a Newtonian liquid. the normal stress
increases when viscosity increases (EQuatlon 8). Thus
for higher viscosity values, the normal force opposing
the movement of the bubble boundary is larger.
Bubble dissolution rates, for viscosity values rang-
ing from 500 to 10,OOO Pa-s at 190°C. are shown in
Ng. 3.This range of viscosities was chosen because it
is typical for PE rotomolding grade resins. From Rg. 3
it can be seen that the effect of viscosity is marginal
and is more prominent at longer times, when bubble
diameter becomes small. This can be understood by
examining the relative magnitude of contribution of
the terms in Equation 6. The relative magnitudes of
the surface tension and normal stress terms for the
typical bubble dissolution case shown in Q. 2, are
plotted in Ng. 4. In the beginning the surface tension
0.05 DoS0.2S
D30.20
0.00
0 5 10 I5 20 25
Time (mln)
Fig. 6. E f f x t of initial bubble diameter on bubble dissdutlon
m s (c, = 0.995 (4-)I = 3000&*s, 190°C).
1194
rn o Experimental [24]
- Simulation
0.15 9
20 0 10 20 30 40 50
Time (min)
m. 7. Comparison of o d e 1 predictions with
datafrom Spence (24).
term is around 150 times larger than the normal
stress term (which depends on viscosity). This means
that at the early stages the magnitude of the normal
stresses is insignificant and does not affect the result.
At much longer times. as the dissolution of bubble
proceeds, the surface tension term becomes only
around three to four times larger, meaning that now
the normal stress term (and thus the viscosity contri-
bution) becomes significant. As the bubble diameter
tends towards zero. both terms increase abruptly.
E!feat of BuIk Coaaemtration o# Air ln the
Polymer Melt
Another very important parameter is the bulk con-
centration of air in the polymer melt. Polyolefin melts,
in equilibrium with the atmospheric air, will always
contain dissolved air. The solubility of air depends on
pressure and the amount of dissolved air when the
polymer melt is saturated can be determined from
Henry’s law (30, 31). The exact amount of air con-
tained in the polymer melt in typical rotomolding con-
ditions cannot be determined exactly, but our results
show that the melt is close to the saturation condi-
tions. However, even when the melt is slightly below
the saturation point, the dissolution rate is signifi-
cantly accelerated, because of an increased concen-
tration gradient: this is demonstrated in Ng.5.
E f k t of Initial Bubble Size
The initial bubble diameter greatly affects the rate of
bubble dissolution. as can be seen in Fgg. 6.From this
it can be concluded that the initial size of the bubbles
formed is very important for the subsequent dissolu-
tion, and there is a critical initial bubble diameter
above which a bubble cannot be completely dissolved
for usual rotomolding cycles of up to 2 M O minutes.
Compui.onw*--
30
A comparison of the model predictions with data
published in the literature (24) is shown in Fgg. 7. The
published data refer to the diffusion of air in a medium
POLYMER ENGINEERING AND SCIENCE, JULY I-, Yo/. 39, No. 7
 Bubble &solution in Molten Polymers

50000 observation and recording of bubbles as they formed

c
E
: and disappeared. Details of this technique can be
i- moo0
L
found in the literature (20,23,24).
The model predictions, obtained by using q = 0.996
5 (3, are in reasonably good agreement with the ex-
9
1
30000
perimental data, as seen in Rg. 7.
0
a
g 20000 meet of Presaarc
.-
g
*
Increasing pressure after the melt has formed has
p
m
10000
been reported to increase bubble dissolution rates
E
significantly, if the pressure is introduced after the
O O
polymer has melted (24,25).The effect of pressure in
101.33 126.66 151.99 177.32 202.65 227.98
Pressure (kPa)
bubble dissolution can be explained as follows: First,
when the ambient pressure increases from Po to P,,
Q. 8. Effect of pressure on initial concentration gradient
(4= 0.25 mm p = 3000 Pas. 190°C). the pressure inside the bubble increases as well. This
causes an immediate shrinkage of the bubble, which
can be predicted by using Boyle's law (24,34):
0.30
-126.66 kPa
P,V, = POVO
- -151.99 kPa
-..171.32 kPa
-
- 202.65 kPa

where 0 and 1 denote initial and final conditions re-

spectively. For a spherical bubble:

0.05 ' ', \ v=--4TR3

1%
1
.: \
3
0.00
0 10 20 30 40 50 Substitution of Eq 19 into Eq I 8 gives:
Time (6)

Rg. 9. E f f x t of pressure on bubble dissolution curves (d,=

0.25 nun. p = 3000 P a s , 190°C).

The second effect is associated to the dependence of

density polyethylene melt (NCPE 8017 by Neste Chem-
icals with hWl = 3.2).at a temperature of 190°C. under
atmospheric pressure. The experiments had been con-
ducted using the hot plate technique, during which a
50 g sample of powder was placed on a base plate en-
closed by a cylindrical ring, complete with a glass
viewing port. The glass viewing port permitted the
0.5 1 I
C sure line and sealed hot plate rig, which incorporated
0 10 20 30
Time ( 5 )
the driving force for dissolution on pressure. Before
increasing the pressure, the already formed melt is
close to saturation conditions, corresponding to Po.
When the pressure inside the bubble increases sud-
denly to P I , the concentration of air, G,at the bubble
walls increases, according to Henry's law, while the
concentration of air, ci,inside the polymer melt re-
mains practically unaffected. Therefore the gradient
ac/ar, which is the driving force for diffusion increases
sigruficanty. as shown in RJ. 8. The respective disso-
lution curves are shown in Rg. 9. m e 10 shows a
comparison of model predictions with experimental
o Experimental1241
- Simulation data provided by Spence (24).under an absolute pres-
sure of 200 kPa (2bar).The experimental results pre-
sented were obtained by using pressurized hot plate
tests under isothermal conditions, at 190°C using a
polyethylene with MFI = 3.2 (NCPE 8017 by Neste
Chemicals). The setup consisted of a controlled pres-
a pressure connection, thermocouple probes and a
viewing window. Details of the technique can be found
elsewhere (24,25,34).
40 50 60 70
In light of the above, the fact that the polymer must
be completely molten before pressure is introduced
(25)can be readily explained. If the pressure were in-
troduced prior to the melting of the polymer, the melt

POLYMER ENGINEERING AND SCIENCE, JULY 199#, Vol. 3#,No. 7 1195

 M. Kontopoulou and J. Vzach~p~Ulo~

Table 2. Material Properties.

Material MFR (@I0 min) Zero Shear Viscosity (Pa-8) Density (kg/m3) Melting Point ("C)

LL-8461 3.3 2658 938 128

LL-8361 5.2 1830 932 128
LL-8556 6.5 1413 935 127
All resins supplied by Imperial Oil (Exxon Chemical Canada).
'
Zero shearviscos'itymeasured at 1 W C .

0.30 0.30
- model predktions Bubble interactions 1

\ C, = 0.974 (CJ.,

0.05 1
"."" r -
0 2 4 6 8 10
0 0.5 1 1.5 2 2.5 3
Time (min) Time (min)

R g . 1 1 . llJpical bubble dissolution curves for D P E with Rg. 13. Regbns obserued during the dissolution of a typical
MFI=5at190°C. air bubble in LLDPEfir high bubble concentmtions.

would become saturated with air upon melting, so ness of the powder bed inside the cup was around
there would be no increased gradient to facilitate the 5 mm. The process of powder melting and air entrap-
bubble dissolution. ment inside the melt was observed through an Olym-
pus optical microscope and recorded with a Pana-
EXPERXHENTAL sonic video camera. Several bubbles were observed as
they subsequently dissolved and image analysis was
Bubble dissolution experiments were conducted by performed to determine the dissolution rate. All the
using a heated chamber, which consisted of a cylin- experiments were done isothermally at 190"C,under
drical oven with a diameter of 16 cm and a height of atmospheric pressure and the duration of the experi-
11 cm.A sample cup holder, made of glass (D = 2.5 ments was 30 min. Table 2 shows a listing of the
cm. H = 1 cm) was loaded with a predetermined resins used and their properties.
amount of powder and placed in the center of the Thermo-Gravimetric analysis OGA) was performed
heating chamber, which was kept at a constant tem- in the polymer samples using a Netzsch STA-409
perature with the aid of a temperature controller. The Simultaneous Thermal Analyzer, at 190°C under at-
temperature of the polymer melt was constantly moni- mospheric air. The purpose of this test was to exam-
tored,through a K-typethermocouple. The initial thick- ine the possibility of degradation, existence of residual

0.30
0 low bubble content

0.25
l o A A A A A MFh5
.-O--LLDPE

0.20 -.
0
A
0.15 -~
0
A
0.10 --

0.05 ~-

0.00- ' ' ' 2 - .

0 0.5 1 1.5 2 2.5 3 3.5 4
Time (min)
Rg. 12. Bubble dissdutron
' curvesforlowandhighbubble Rg. 14. llJpica2 dissdution curvesfor LulpEs with cliiffent
-oc ' nsinLLDpEwithMFI=5at190°C. viscostties.

1196 POLYMER ENGINEERING AND SCIEWCE, JULY I-, Vol. 39, No. 7
 Bubble Dissolufion in Molten Polymers
monomer vapors in the polymers or gas generation
when the polymer is exposed to conditions similar to
the experimental conditions. These tests showed that
there was no degradation or generation of vapors of
any kind for the time period applicable to the bubble
removal experiments.
Rem~ltaand Cornparimon With Model predictlop.
From the experimental results it was seen that there
is a great variability in the behavior of the bubbles, de-
pending on their size, their proximity to other bubbles
and the overall bubble content in the polymer melt.
Some typical dissolution curves for an LLDPE with
MFI = 5, along with the model predictions, are shown
in Rg. 11. In Rg. 11, time zero is considered as the
time when the bubbles have formed and have as-
sumed a spherical shape. The bubbles shown have
been carefully chosen so that they are relatively iso-
lated inside the polymer melt, to eliminate' any inter-
action effects. The model predictions, obtained by
using ci = O.95(cJMt.are in reasonably good agree-
ment with the experimental data.
Bubble dissolution is considerably slower in regions
of high bubble content. Figure 12 compares the be-
havior of one of the isolated bubbles shown in Rg. 1I,
with that of a bubble in a region of high bubble con-
tent. It appears that in the latter case, after the bubble
forms, there is an induction period where there is very
little dissolution, followed by a period during which
considerable dissolution takes place. The possibility
that this behavior might be due to degradation oc-
curring during the course of the experiments was
excluded by performing TGA analysis in the polymers.
The existence of two periods is illustrated in Rg. 13,
for the same bubble shown in Rg. 12. It is speculated
that the initial period is associated with interaction
between neighboring bubbles, which can result to the
transfer of air from one bubble to another. Owing to
the presence of many bubbles diffusing simultane-
ously, the melt becomes almost saturated, thus reduc-
ing the concentration difference and the drivhg force
for dissolution. From an inspection of the dissolution
process of all the bubbles, it was seen that the change
in slope observed in F@. 13 was associated with the
disappearance of the smaller surroundmg bubbles, so
that the bubble under consideration remained even-
tually relatively isolated. I n this case, the model can
be applied successfully only for the second region,
which coincides with the disappearance of the sur-
rounding bubbles. A value q = 0.974 (c,),~ is used in
this case.
From the above it becomes clear that the higher the
overall bubble content in the melt, the slower the bub-
ble dissolution.
Polymer viscosity does not seem to have a s i w c a n t
effect on the rate of bubble removal. This confirms the
model predictions and was observed by using three
LLDPE resins with Merent MFIs (Table2). Some typi-
cal dissolution curves of relalively isolated bubbles for
the three LLDPE resins are shown in Rg. 14.
POLYMER ENGINEERING AND SCENCE, JULY 7 9 9 9 , V d . 39, No. 7
This result seems to be somewhat contradictory to
the general belief that increased viscosity results in
slower bubble dissolution. It has been observed in our
experiments, though, that when the melt viscosity is
higher, more and larger bubbles form initially upon
melting and densification of the powder. This may be
the cause for the longer times needed for complete
dissolution of bubbles observed in practice.
Initial bubble size is very important. Small bubbles
tend to dissolve quickly, while big ones may not dis-
solve at all during the experiment. This effect can be
clearly seen in Rg. 11, and it is consistent with model
predictions.
CONCLUSIONS
A model that includes diffusion, surface tension,
and viscosity effects has been applied, in an effort to
describe bubble dissolution in polymer melts. It was
concluded that the process is controlled by the W-
sion of air from the bubbles to the melt. Bubble disso-
lution depends sgnifhntly on initial bubble size,sur-
face tension, and air concentration in the polymer
melt, but it is not influenced considerably by melt vis-
cosity when the latter lies within ranges typical for ro-
tational molding resins.
The application of pressure after the polymer has
melted leads to a sigdicant acceleration of the disso-
lution rate, owing to an increased driving force for dif-
fusion.
Bubble removal experiments confirmed model pre-
dictions for relatively isolated bubbles. In the case of
high initial bubble contents in the polymer melt, dis-
solution was delayed considerably and two distinct re-
gions were observed: an initial period, where dissolu-
tion is very slow as a result of interactions between
bubbles, followed by a fast dissolution period, associ-
ated with the disappearance of surrounding bubbles.
These results reveal that one of the most important
factors governing the bubble dissolution process is
the bubble content initially present in the polymer
melt.
ACKNOWLEDGMENTS
This work has been supported financially by the
N a t u d Sciences and Engineering Research Council
of Canada (NSERC), the Ontario Government, and
Imperial Oil Canada. The authors would also like to
thank Imperial Oil Canada (Exxon Chemical Canada)
and Mr. Blair Graham for their help and for supplying
the resins used in this work and Ms. E. T&cs for
performing the resin characterization.
NOHENCLATURE
Concentration (moi/m3)
Concentration of gas inside bubble (m01/m3)
Concentration of gas in bulk of polymer
melt (moi/m3)
Saturation concentration of gas in bulk of
polymer melt (m0l/m3)
1197
 M.Kbntopdou and J. Vlachopoulos

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1198 POLYMER ENGINEERING AND SCIENCE, JULY 1990, Vol. 39, No. 7

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