Polymer International Polym Int 54:946–955 (2005)

DOI: 10.1002/pi.1794

Effects of injection-molding processing

parameters on acetaldehyde generation and
degradation of poly(ethylene terephthalate)
Shunahshep R Shukla† , Elizabeth A Lofgren and Saleh A Jabarin∗
Polymer Institute, College of Engineering, University of Toledo, Ohio 43606, USA

Abstract: The acetaldehyde (AA) generation behavior of poly(ethylene terephthalate) (PET) has been
investigated in terms of its relationship to changes in various processing conditions. A single-cavity
injection-molding machine was used to prepare preforms in order to relate changes in barrel temperature,
screw shear rate, back pressure, cooling time and total residence time to levels of AA generated during
processing. Within the temperature range 280–300 ◦ C, a 10 ◦ C rise in processing temperature causes AA
production to double. Shear rate increases from 20 to 40 m min−1 result in 13–21 % increases in AA
generation at temperatures from 300 to 280 ◦ C. Increased back pressures from 0 to 200 bar result in AA
concentration increases of about 1.2 ppm for each 50 bar pressure increase. The majority of this change
is caused by increased polymer residence time. Longer cooling times also increase overall cycle times
and result in higher levels of AA generation, at the rate of almost 7 ppm per additional minute at 290 ◦ C
processing conditions. Apparent activation energies of 167 kJ mol−1 were calculated for samples prepared
at various shear rates. These results are in agreement with literature values obtained under conditions of
static mixing and indicate that shear rate and plastication do not significantly affect reaction mechanisms
for AA generation.
 2005 Society of Chemical Industry

Keywords: poly(ethylene terephthalate); processing; acetaldehyde; injection molding; degradation

INTRODUCTION EXPERIMENTAL
Thermal and thermal oxidative degradation of Drying
poly(ethylene terephthalate) (PET) have been the sub- All evaluations were performed using Eastman PET
jects of many research papers.1 – 12 The specific effects homopolymer resin with an intrinsic viscosity (IV)
of various processing conditions, however, have not of 0.73 dL g−1 . PET is known to undergo hydrolytic
yet been satisfactorily investigated, since most previ- degradation at temperatures exceeding 110 ◦ C. To
ous research topics have not included extrusion and avoid this, all resin was dried to moisture levels
injection molding. The current work establishes rela- below 50 ppm13 before exposure to other processing
tionships among several important processing condi- conditions. A Conair dryer, with desiccant in the
tions during extrusion and injection molding and their circulating air loop, was used for this purpose. Drying
relative effects on acetaldehyde (AA) generation and was carried out in two steps. A low-temperature drying
the degradation behavior of PET. Material changes step at 102 ◦ C for 18 h was followed by a high-
resulting from processing temperature, screw shear temperature drying step at 150 ◦ C for 4 h. The final
rate, melt residence time, back pressure and cooling moisture content was found to be less than 30 ppm, as
time variations have been included in these evalua- measured with a DuPont moisture analyzer.
tions. The primary objective of this work has been
to utilize a single-cavity injection-molding machine Processing
to provide a methodology for and investigations of The dried PET pellets were introduced into the
the various parameters affecting the production of injection-molding machine with a K-loader automatic
AA during injection molding of PET. These inves- loading system supplied with the drying unit. All
tigations can then be extended to provide a the- preforms were prepared with a 55 ton, single-
oretical background for establishing simulation and cavity, reciprocating-screw Arburg injection-molding
prediction models for multi-cavity injection-molding machine. For all runs the injection pressure was set at
systems. a constant value of 1900 bar, with a holding pressure

∗ Correspondence to: Saleh A Jabarin, Polymer Institute, College of Engineering, University of Toledo, Ohio 43606, USA
E-mail: [email protected]
† Current affiliation: Ohio State University, Columbus, Ohio, USA

Contract/grant sponsor: PET Industrial Consortium

(Received 27 September 2004; revised version received 2 December 2004; accepted 15 December 2004)
Published online 28 February 2005
 2005 Society of Chemical Industry. Polym Int 0959–8103/2005/$30.00 946
 AA generation during PET injection molding

of 1700 bar. The melt flow rate for all shots was set at AA concentration in preforms
40 cm3 s−1 . The mold temperature was controlled by Preforms prepared under a variety of processing
circulating cooling water (10–21 ◦ C) flowing through conditions were evaluated in terms of residual AA
the drilled channels in the mold cavity and core plates. concentration. The preforms were prepared for gas
The mold cooling time for all except the residence chromatography analyses by submersion in liquid
time runs was set at 25 s. Extruder barrel temperatures nitrogen, followed by coarse manual crushing. The
were controlled by heater bands in the various zones resulting preform pieces were then finely ground
and monitored with temperature sensors. All extruder under liquid nitrogen using a stainless steel Ika-
zones were set to the same temperature to give a Werk mill. The cold powder was immediately
consistent temperature profile, for ease of analysis separated using sieves to obtain particles in the
and interpretation of experimental data. Tables 1 to 3 range 20–40 mesh for analyses. Cold particles of
summarize the various processing conditions utilized ground preform materials were weighed and loaded
for preform production. into ATD-400 sample tubes for measurement of
AA concentration. These sample tubes were sealed
Table 1. Shear rate and temperature variations after loading. Care was taken to maintain ambient
temperatures of less than 18 ◦ C during grinding
Screw rotation rate and sample preparation, in order to minimize
Back pressure Cooling
loss of residual AA from the ground preform
Temperature (◦ C) (bar) (m min−1 ) (rpm) time (s) materials.
Preform residual AA concentrations were measured
280, 290 and 300 0 20 183 25 with a Perkin-Elmer Auto System XL gas chro-
280, 290 and 300 50 20 183 25 matograph (GC), equipped with a flame ionization
280, 290 and 300 50 25 229 25
detector (FID) and utilizing a 30 mm × 0.32 mm ID
280, 290 and 300 50 30 275 25
Stabilwax DA (carbowax) capillary column. The
280, 290 and 300 50 35 320 25
280, 290 and 300 50 40 366 25 GC oven was maintained at 60 ◦ C and the FID at
280, 290 and 300 50 50 366 25 300 ◦ C. Residual AA was volatilized from ground pre-
form material with a Perkin-Elmer ATD-400. Samples
were held in the ATD oven at 150 ◦ C for 45 min, in
Table 2. Back pressure variations a constant helium purge. Released AA was held in
the ATD cold trap (−30 ◦ C), packed with Tenax
Screw rotation rate
GR (60/80) and Carbosphere (80/100), throughout
Temperature Back pressure Cooling the sample heating cycle. After completion of sample
(◦ C) (bar) (m min−1 ) (rpm) time (s) heating, trapped AA was injected into the GC col-
umn as a result of rapid heating (300 ◦ C) of the cold
290 0 30 275 25
trap. The areas of the AA peaks, with retention times
290 50 30 275 25
290 100 30 275 25
of about 2.3 min, were measured using Perkin-Elmer
290 150 30 275 25 Turbochrom software. The GC was calibrated with
290 200 30 275 25 known amounts of AA treated in a manner similar
290 250 30 275 25 to that of the ground preform materials, but held
290 300 30 275 25 at 250 ◦ C for 10 min. Concentrations of AA were
calculated as µg AA (g PET)−1 or ppm.

Table 3. Cooling time variations

Melt viscosity studies
Screw rotation rate
Melt viscosity studies were conducted in order to
Temperature Back pressure Cooling evaluate the degradation of PET as a result of
(◦ C) (bar) (m min−1 ) (rpm) time (s) processing through the injection-molding machine.
All melt viscosity measurements were performed with
290 50 30 275 40
a Rheometrics cone-and-plate type viscoelastic tester
290 50 30 275 35
290 50 30 275 30 at oscillation frequencies from 0.1 to 100 rad s−1 and
290 50 30 275 25 at a constant oscillation amplitude and temperature.
290 50 30 275 24 The gap between the cone and plate was maintained
290 50 30 275 23 at 0.05 mm throughout all rheological evaluations,
290 50 30 275 22 which were performed at 280 ◦ C under a nitrogen
290 50 30 275 21 atmosphere. Preform pieces were vacuum-dried for
290 50 30 275 20 24 h at 140 ◦ C before evaluation. Results have been
290 50 30 275 19 reported in terms of equivalent solution IV values,
290 50 30 275 18
obtained with a calibration curve relating melt viscosity
290 50 30 275 17
corresponding to zero shear viscosity to known IV
290 50 30 275 16
values.

Polym Int 54:946–955 (2005) 947

SR Shukla, EA Lofgren, SA Jabarin

Time–temperature measurements 60

Preform acetaldehyde concentration (ppm)

The time–temperature profile of the PET polymer
melt was monitored using an Omega fiber-optic 50
y = 0.285x + 36.6
infrared sensor, following the procedure of Campbell 300 °C
et al.14 The infrared sensor was installed in the nozzle 40
of the injection-molding machine and was placed flush
to the surface so as not to disturb the flow of the 30
polymer melt through the nozzle. This sensor is a non- y = 0.173x + 16.8
contact temperature measuring device with a standard 20 290 °C
response time of 50 ms. The fiber-optic lens collects
the infrared heat radiation emitted by the polymer 10 y = 0.122x + 9.06 280 °C
melt, and the radiation is then directed to a detector
cell. The detector emits a signal corresponding to the 0
15 20 25 30 35 40 45
intensity of the incident radiation, which is amplified Screw speed (m min−1)
and linearized and then output to the cable connector.
Figure 1. Effect of screw speed on preform AA concentration at 280,
290 and 300 ◦ C.

RESULTS AND DISCUSSION

Preforms prepared under the conditions described in where S is the shear rate in reciprocal seconds, D is the
Tables 1 to 3 were evaluated in terms of the AA that screw diameter, h is the screw channel depth and N is
was generated during processing. This generated AA the screw rpm. Using this relationship, the maximum
remained in the injection-molded preforms and this shear rates experienced by the PET melt in the barrel
was analyzed to obtain residual AA concentrations. of the injection-molding machine were found to range
The following discussions include the effects of various from 264 s−1 at 40 m min−1 to 132 s−1 at 20 m min−1 .
processing conditions on AA concentrations in the Since these values fall within the shear rate range
preforms and also the state of degradation in terms specified by Gregory and Watson,15 the PET melt can
of preform IV. The effects of shear rate changes were be assumed to have Newtonian behavior under the
monitored at temperatures from 280 to 300 ◦ C, with experimental conditions.
back pressure and cooling time held constant. Back The flow of the PET melt between the screw of the
pressure and cooling time influences were monitored injection-molding machine and the inner barrel surface
at 290 ◦ C and constant 30 m min−1 screw rotation can be approximated by the flow of an incompressible
speeds. Back pressure was changed from 50 to 300 bar Newtonian fluid between two coaxial cylinders. The
with 25 s cooling times held constant. Cooling times following expression from Bird et al 16 can then be
were varied in the range from 16 to 40 s with applied for the volume heat source Sv resulting from
constant back pressure values of 50 bar. The changes the viscous dissipation:
in the cooling times were utilized for investigation of
2
dvz
residence time effects on AA generation. Sv = µ (2)
dx
Shear rate and temperature where µ is the viscosity of the fluid (which in the
Preforms were prepared at screw speeds from 20 case of a Newtonian fluid, does not depend on the
to 40 m min−1 using extruder barrel temperatures shear rate), vz is the velocity of the fluid and x is the
of 280, 290 and 300 ◦ C. Figure 1 illustrates the direction perpendicular to the screw or barrel surface.
dependence of preform AA concentration on shear rate Equation (2) neglects curvature effects.
at each processing temperature. Specific experimental For the steady-state velocity of a fluid, with constant
conditions are outlined in Table 1. It can be seen velocity in a slit, the velocity profile is linear and can
that AA generation at all three temperatures appears be represented by the relation:
to increase linearly with the rate of screw rotation.
Gregory and Watson15 have estimated the steady- x
vz = V (3)
state flow properties of PET melts as a function of h
temperature, shear rate and IV over a temperature
range of 265 to 295 ◦ C and an IV range of 0.35 to where V is the velocity of the screw. The rate of viscous
0.82 dL g−1 . They found that over the shear rate range heat production per unit volume is:
of 50 to 1000 s−1 the flow behavior of PET was nearly
2
V
Newtonian. Sv = µ (4)
The following relationship can be utilized for h
calculation of shear rate at any single point along
an extruder screw. where h is the distance between the screw and the
barrel wall for any single point along the screw and
DN hence is a constant. Now let µ/h2 be designated by K ,
S= (1) a constant. Therefore, Sv ∝ V 2 . In this case, the heat
19.1h

948 Polym Int 54:946–955 (2005)

 AA generation during PET injection molding

generation due to viscous heat dissipation will increase

Preform acetaldehyde concentration (ppm)

60
with the square of the velocity. This implies that 20 m min−1
25 m min−1
the temperature rise due to viscous heat dissipation 50 30 m min−1
for the 40 m min−1 case,
T40 , will be roughly four 35 m min−1
40 m min−1
times the temperature rise due to viscous dissipation 40
for the 20 m min−1 case,
T20 , for the same screw
rotation time. Since the total screw rotation time for 30
the 40 m min−1 case was only half as much as the total
screw rotation time for the 20 m min−1 case, for this 20
system, we can write:
10

T20 ≈ 0.5(
T40 ) (5)

0
275 280 285 290 295 300 305
The temperature rise due to viscous dissipation for the Temperature (°C)
20 m min−1 case was only half as much as that for the
40 m min−1 case. In a similar way, we can argue for the Figure 2. Effect of temperature on preform AA concentration at screw
speeds of 20–40 m min−1 (At 30 m min−1 , y = 4 × 10−7 e0.0617x ).
observed temperature rise with shear rate for all data
points. Table 4 summarizes the predicted temperature
rise per unit volume due to shear heating alone. In this
case,
T = T − T0 , where T is the final temperature increase exponentially with shear rate. In this case, data
after shear and T0 is the initial temperature before was refitted to an exponential curve to obtain a very
shear. Note that in Table 4, t1 is the screw retraction slightly better fit. However, for any curve, over small
time or plasticating time for the 20 m min−1 screw enough increments, the behavior can be approximated
rotation rate, Q is the energy generated due to the as linear. For these analyses and within the domain
viscous dissipation in J m−3 , m is the mass of the of the experimental conditions, changes in shear rate
polymer undergoing shearing in kg, and Cp is the and induced temperature rise are small enough for all
specific heat of the material in J kg−1 K−1 . trends to approximate linearity. Since it makes very
The most important fact that emerges from Table 4 little difference whether the linear fit or exponential
is that the temperature rise shows a linear dependence one is utilized, most of the data have been fit linearly,
on the shear rate. In order to further interpret the with the knowledge that this treatment is not as
data of Fig 1, the AA generation values must be rigorous as one based on exponential dependence.
plotted versus barrel temperature with shear rate as Figures 1 and 2 show clearly that, at all shear
the constant parameter, and Fig 2 presents the data rates, more AA is generated at higher temperatures.
in this form. The first important observation that The effects of shear rate on this AA generation are,
can be made from this plot is that for every 10 ◦ C however, not as obvious. As shear rates increase from
rise in temperature, the AA generation rate nearly 20 to 40 m min−1 , absolute amounts of AA generated
doubles. Secondly, the effect of barrel temperature increase by 2.4, 3.4 and 5.7 ppm at 280, 290, and
on AA generation is far greater than the effect of 300 ◦ C, respectively. These changes seem to indicate
screw shear rate. These values for AA generation at that, at higher temperatures, total AA generation is
each shear rate can be seen to vary exponentially increasingly dependent on shear rate.
with extruder temperature. Curves for all shear rates The viscous dissipation expression, given in
give excellent exponential fits with R2 values of Eqn (4), predicts that for the same velocity or screw
0.98 or greater. In the case of data obtained at circumferential speed, for two different temperature
30 m min−1 , y = 4 × 10−7 e0.0617x . levels, the viscous dissipation should be greater when
Table 4 shows that the temperature rise increases the viscosity is higher. The viscosity of a polymer
linearly with shear rate and Fig 2 shows that AA melt decreases with an increase in temperature. Thus,
concentration increases exponentially with barrel µ290 < µ280 and, for the same velocity and geometry,
temperature. This suggests that AA generation should the viscous dissipation at 280 ◦ C should be greater

Table 4. Predicted temperature rise at various shear rates

Screw
T/unit volume =

Sv = KV 2 Sv = Kf(V1 )2 retraction time t Q = Sv tρ Q/(mCp )

K × 20 × 20 K × 1.000 × 20 × 20 1.000 × t1 1.00 × K1 1.00 × K2

K × 25 × 25 K × 1.563 × 20 × 20 0.800 × t1 1.25 × K1 1.25 × K2
K × 30 × 30 K × 2.250 × 20 × 20 0.667 × t1 1.50 × K1 1.50 × K2
K × 35 × 35 K × 3.063 × 20 × 20 0.571 × t1 1.75 × K1 1.75 × K2
K × 40 × 40 K × 4.000 × 20 × 20 0.500 × t1 2.00 × K1 2.00 × K2

K1 = K × 20 × 20 × t1 ; K2 = K1 /(mCp ); V1 = screw speed at 20 m min−1 ; f = a factor relating (V1 )2 to other screw speeds or values of (V)2 ;
ρ = density (kg m−3 ).

Polym Int 54:946–955 (2005) 949

SR Shukla, EA Lofgren, SA Jabarin

than that at 290 ◦ C. As the change in total AA gen- cause shear heating of the polymer melt and produc-
erated at each temperature level depends directly on tion of AA. The total quantities of AA measured in
the change in temperature, we would expect that the preforms produced under the various experimental
dependence of total generated AA on the screw shear conditions all include AA produced as a result of the
rate should be higher at the lower temperature value. shear heating through the gate. Values obtained at dif-
This is because the contribution of viscous dissipa- ferent temperatures and as a result of changing screw
tion should be greater than at the higher temperature, speed, back pressure and residence time would all be
where the contribution of viscous heat dissipation reduced if AA generated by shear heating through the
would be comparatively lower. The absolute increases gate could be excluded.
in AA values thus appear contrary to what one might The volume of polymer melt experiencing the very
expect from first principles. In reality, this discrep- high shear through the gate is relatively small, since it
ancy does not exist. On close inspection of the data, includes only the layer flowing closest to the wall. A
it is found that the percentage increase in AA gener- cross section of the polymer melt would thus exhibit
ation at 280, 290 and 300 ◦ C is 21.2 %, 16.9 % and a distribution of temperatures and AA concentrations.
13.4 %, respectively, over the shear rate range from These values would tend to be higher near the outer
20 to 40 m min−1 . Thus, the relative dependence of polymer surface. Shear rate calculations have been
AA generation at higher temperatures becomes more based on assumptions that have not taken into account
in accordance with first principles. The slopes of the any distributions of shear rates or temperatures.
plots given in Fig 1 include the effects of temperature AA generation results include overall increases with
as well as shear rate. At higher temperature levels, contributions from various sources. Future work is
the effects of changes in all processing parameters anticipated to model and analyze the flow behavior in
on the absolute values of AA generated and on the cases of single-cavity and multi-cavity molds during
AA generation rates are magnified. Thus, for proper injection molding of PET preforms. This work should
interpretation, the data should be analyzed using per- also relate the generation of AA to differences in shear
centage changes in AA generation. While at higher heating and polymer flow.
temperatures absolute amounts of generated AA are
higher with increased shear rates, the overall percent- Back pressure
age changes are lower. The effects of injection-molding machine back
In addition to shear resulting from screw rotation, pressure variations were investigated at an extruder
the PET melt is exposed to another source of shear. temperature of 290 ◦ C,with a screw rotation rate of
As the polymer melt flows into the mold cavity, it 30 m min−1 (275 rpm) and a cooling time of 25 s, as
passes through a narrow gate, where it encounters given in Table 2. The levels of AA generated, as a
very high rates of shear. Under current experimental result of back pressure variations from 0 to 200 bar,
conditions, the gate diameter is 4 mm. The expression are shown in Fig 3. It can be seen that residual AA
for wall shear rate γw can be utilized, assuming simple concentrations increase linearly with increasing back
Poiseuille flow, to obtain:17 pressure, to give an overall increase of about 20 %


 within the evaluated pressure range. Several different
3n + 1 8V  mechanisms may contribute to this increase. These
γw = (6)
4n D contributing factors include: (a) a temperature rise
due to adiabatic compression of the melt; (b) increased
where V  is the average velocity of the fluid and D is screw shear; and (c) increased residence time of the
the diameter of the capillary. Assuming that n ≈ 1, we PET in the injection-molding machine.
may write:
32Q
γw = (7) 35
π D3
Preform acetaldehyde concentration (ppm)

where Q is the volumetric flow rate.

For a typical shot, 48 cm3 of material is injected into 30
the mold cavity in 1.2 s, and the volumetric flow rate
Q is thus 40 cm3 s−1 . The wall shear rate γw can then
be computed from the expression: 25
y = 0.0232x + 24.2
32 × 40
γw = = 6366 s−1 20
π × 0.403

This shear rate, through the gate of the injection-

molding machine, is much higher than rates encoun- 15
0 50 100 150 200 250
tered by the melt in the screw. Screw shear rates at
Back pressure (bar)
30 m min−1 are 198 s−1 . As the polymer melt passes
through the gate, it experiences shear rates 32 times Figure 3. Effect of back pressure on preform AA concentration at
higher than those in the screw. These high shear rates 290 ◦ C.

950 Polym Int 54:946–955 (2005)

 AA generation during PET injection molding

An approximation for the adiabatic temperature rise 3.0

in the PET melt can be calculated using the specific
volume data for a PET melt given by Zoller and

Screw rotation time (s)

Bolli,18 the specific heat data for melted PET given by 2.5
Smith and Dole,19 and the expression:

2.0 y = 0.00196x + 2.04

P
V = Cp
T (8)

At 290 ◦ C and, for example, 200 bar back pressure, 1.5

V = 0.0144 cm3 g−1 from Zoller and Bolli18 and
Cp = 2.04 J g−1 K−1 from Smith and Dole.19 After
substituting the values with appropriate units into 1.0
Eqn (8), the rise in temperature
T is found to 0 50 100 150 200 250
be of the order of 0.14 ◦ C. This value can then be Back pressure (bar)

utilized in the expression given in Fig 2, relating AA Figure 4. Effect of back pressure on screw rotation time at 290 ◦ C.
concentration to temperature. The resultant increase
in AA concentration, from the 0.14 ◦ C higher exposure
It has been shown that adiabatic compression at
temperature, was found to be about 0.2 ppm of total
50 bar does not contribute significantly to AA
increase. In the case of samples prepared at 290 ◦ C
generation during extrusion. Temperature changes in
and 50 bar back pressure,
V = 0.00332 cm3 g−1 and
the melt are also very small under these experimental
the
T is found to be 0.008 ◦ C. In this example,
conditions. Increased residence time in the melt state,
the resultant increase in AA concentration is only
therefore, appears to be the major factor contributing
0.01 ppm, which is not a significant source of AA
to additional AA generated under conditions of
during extrusion.
increased back pressure. Residence time increases
The screw rotation time increases by nearly 0.1 s
include increased screw rotation times, resulting
per shot for every 50 bar increase in back pressure.
from increased back pressure. The total rise in AA
Normally, while the machine is running, there are
concentration resulting from a 50 bar increase in
about 6.5 shots in the injection-molding machine at
back pressure is 1.16 ppm. This value of 1.16 ppm
any given time. A 50 bar rise in back pressure can,
minus the 0.24 ppm resulting from screw shear leaves
therefore, increase the residence time of the PET in
0.92 ppm AA generated primarily as a result of
the screw by 0.65 s. The residence time experiments
increased time in the melt. This value includes the
are described in the next section and from those we
0.1 ppm AA generated within the screw during the
can infer that for every 50 bar increase in back pressure
increased time of rotation.
an AA concentration increase of about 0.1 ppm can
be attributed to increased time of heating within the
screw. Residence time
The effects of screw shear rate at 290 ◦ C can be Total polymer residence times were calculated using
assessed from the slope of the AA versus screw speed the flight-volume data for the screw section of the
given in Fig 1. At a screw shear rate of 30 m min−1 , extruder, the volume of the melt reservoir, the volume
the AA generation resulting from screw rotation alone of the mold cavity, and the cycle time. These values
is estimated to be 5.18 ppm. The relationship between comprise the total residence time from the entrance of
screw rotation time and back pressure is given in Fig 4. the pellets to the feed section through the hopper,
It can be seen that screw rotation time increases by until the time when the preform is ejected from
about 0.1 s per shot for every 50 bar increase in back the mold cavity. As cooling times are increased
pressure. The screw rotation time at a 30 m min−1 from 16 to 40 seconds, these changes result in
screw rotation rate and 50 bar back pressure is 2.14 s. cumulative additions to all of the shots remaining
As a result, the total AA value of 5.18 ppm generated in the injection-molding system. Each cooling time,
by shear alone must be divided by the screw rotation therefore, increases polymer residence time by more
time of 2.14 s to obtain about 2.4 ppm of AA per than the time required for one injection cycle. Figure 5
second of screw rotation. For 0.1 s of screw rotation, gives an overall schematic drawing showing the various
therefore, the AA generated by screw shear alone is processes included in a complete injection-molding
0.24 ppm. From the slope in Fig 3, the total increase cycle. This complete cycle is the total residence time
in AA generation resulting from a 50 bar rise in back under evaluation.
pressure is found to be 1.16 ppm. The 0.24 ppm of Changes in AA generation as a result of varying
AA generated by shear can now be subtracted from cooling times (ranging from 16 to 40 s) were monitored
the total AA generated, to obtain AA generation that at a processing temperature of 290 ◦ C. Back pressure
cannot be attributed to screw shear: was set at 50 bar and screw speed held at a constant
30 m min−1 . Figure 6 shows the linear dependence
1.16 ppm (total) − 0.24 ppm 0.92 ppm AA (other of this relationship, with increased cooling times
= resulting in longer overall residence times and higher
(screw shear) than screw shear)

Polym Int 54:946–955 (2005) 951

SR Shukla, EA Lofgren, SA Jabarin

Machine cycle 50

Preform acetaldehyde concentration (ppm)

start

40

30 y = 0.1143x − 5.872
Plastication
Mold
unit moves
closes
forward
20

10

Screw rams
forward / shot 0
injection 0 100 200 300 400
Total residence time (s)

Figure 6. Effect of total residence time on preform AA concentration.

Packing

the total flight volume. The total flight volume can

accommodate about 5.63 shots of polymer, therefore,
the volume of the material present in the feed zone
Plastication
will comprise at least 3.9 shots.
It is difficult to estimate the exact solids volume
Screw rotation fraction in the barrel of an injection-molding machine.
The 51 s induction time, illustrated in Fig 6, results
in part from the volume fraction of unmelted solids
Backward present in the feed and transition zones of the machine.
Cooling movement of
the mold the plasticating This induction time also includes cooling time during
unit
which the injection-molded part remains in the mold
after it has been cooled to a temperature below which
AA is no longer generated. The time required for
complete ejection of the preform from the mold also
Mold opens
contributes to this induction time. It represents all the
time during which AA generation is not significant,
Ejector even though polymer material is present within the
advancement injection-molding machine.
Ejector retraction
Melt viscosity
End of cycle
Samples prepared under various experimental condi-
tions were evaluated in terms of melt viscosity using a
Figure 5. Processes involved in a complete injection-molding cycle. viscoelastic tester. The results corresponding to zero
shear viscosity were then converted to equivalent IV
values in order to monitor changes resulting from pro-
levels of generated AA. The linear relationship of cessing variations. Measurements were performed on
AA generation to total residence time has a negative preform materials prepared from 280 to 300 ◦ C at
intercept, which corresponds to an apparent induction screw speeds of 20 to 40 m min−1 . The results show
time of about 51 s before measurable AA is generated that the IV has very little dependence on shear rate
during this total residence time. Possible explanations when samples are processed at 280 or 290 ◦ C. Samples
for this induction time are discussed below. processed at 300 ◦ C show a slight decrease in IV with
Pellets do not melt immediately as they enter increasing shear rate, as illustrated in Fig 7. Overall IV
the feed zone of an injection-molding machine. values are slightly lower for samples exposed to higher
Conventional models for most screws in extrusion temperatures, with samples processed at higher shear
and injection molding assume that in the feed zone rates exhibiting the greatest temperature dependence.
there is a well-defined solid bed present in the screw Viscosity measurements were also taken to study
channels adjoining the melt pool. This solid bed the effects of back pressure and cooling time during
continues to diminish as it progresses towards the injection molding. Figures 8 and 9 show that no
metering zone, along the screw axis. In the case of the appreciable changes in IV occur as a result of back
equipment used for these experiments, the feed section pressure changes from 0 to 200 bar or for cooling
comprises about 60 % of the total screw length. If a times from 15 to 25 s. During evaluations of back
uniform gradient is assumed in the transition section, pressure, the barrel temperatures were maintained
the feed section could constitute more than 70 % of at 290 ◦ C, the screw rotation rate at 30 m min−1

952 Polym Int 54:946–955 (2005)

 AA generation during PET injection molding

0.80
0.74

0.72 0.75
Intrinsic viscosity

Intrinsic viscosity
0.70 0.70
0.68
0.65
0.66
0.60
0.64

0.62 0.55

0.60 0.50
15 20 25 30 35 40 45 10 15 20 25 30
Screw speed (m min−1) Cooling time (s)

Figure 7. Effect of screw speed on melt IV values at 300 ◦ C. Figure 9. Effect of cooling time on melt IV values at 290 ◦ C.

0.80
time–temperature profile of the polymer melt was
0.75
recorded in real time as tables, using Quattro Pro soft-
ware. These tables were then transferred to an Excel
Intrinsic viscosity

0.70 program for graphical analyses. Figure 10 gives an

example of data obtained using this method. Similar
0.65 measurements were performed as barrel temperature
setting were changed within the range 280–300 ◦ C.
0.60 For all runs the injection pressure was set constant at
1900 bar, the holding pressure at 1700 bar, the cool-
0.55 ing time at 25 s, the mold cooling water was 15.6 ◦ C,
the screw speed was set at 40 m min−1 , and the back
0.50
0 50 100 150 200 250 pressure was 100 bar.
Back pressure (bar) The data represented by trendline 1 in Fig 10 were
collected as soon as all setpoint values on the injection-
Figure 8. Effect of back pressure on melt IV values at 290 ◦ C. molding machine read 285 ◦ C, after temperature
settings had been reduced from 290 ◦ C. Trendlines
and the cooling time at 25 s. Cooling time effects 2 and 3 were, respectively, obtained after 10 and
were monitored at the same temperature and screw 21 additional shots had been made after the shot
rotation conditions and a constant back pressure of represented by trendline 1. These trendlines illustrate
50 bar. Under these experimental conditions, samples measured changes in melt temperature during various
exhibit minimal changes in IV, while at the same time stages of the injection-molding process, as well as
showing increased AA generation. These results can times required for temperature stabilization in each
be explained according to Goodings’s2 mechanism process. It can be seen from these data that the melt
of thermal degradation, which indicates that as temperature of the polymer stabilizes at a far slower
long as sufficient available free hydroxyl end-groups rate then the barrel temperature of the extruder. These
are present, broken polymer links resulting from results indicate that attainment of stable dynamic
degradation can repolymerize with the production conditions requires a considerable amount of time,
of equivalent amounts of AA and carboxyl end- once setpoints are changed or after extruder start-up.
groups. In this manner, changes resulting from thermal Changes in the three trendlines of Fig 10 represent
degradation are offset by the repolymerization process, various stages of the injection-molding cycle. The
with very little net loss in molecular weight or IV. recorded melt temperature rises and falls very sharply
Only after the available hydroxyl end-groups have at stages in the cycle that correspond to screw injection
been consumed (as a result of prolonged heat history), induced compression and screw retraction induced
will significant loss in IV be recorded. It can thus be decompression of the polymer melt. About 1.2 s after
seen that changes in levels of generated AA are more initiation of injection, the temperature reaches its peak
sensitive indicators of polymer degradation state than value due to adiabatic compression of the polymer
are changes in IV values. melt. The temperature falls slightly, during the holding
stage in the machine cycle. It then falls to the baseline
Time–temperature measurements of polymer value within 1 s. In the holding stage, the temperature
melt of the polymer melt shows a steady decline as a
Measurements of polymer melt temperatures were result of dissipation of frictional heat generated during
obtained with a fiber-optic infrared sensor in the injection stage, as the material flows past the
the nozzle of the injection-molding machine. The nozzle and gate and into the mold cavity. This heat

Polym Int 54:946–955 (2005) 953

SR Shukla, EA Lofgren, SA Jabarin

284
1
3 2
282

280
Temperature (°C)

278

276

274

272

270
0 50 100 150 200 250 300
Time

Figure 10. Temperature profiles measured in real time with an infrared sensor in the nozzle of the injection-molding machine (300 divisions in
x-axis = 60 s).

is slowly dissipated to the surroundings, during the value. It is therefore appropriate to use the total
holding stage. The decline also occurs because the amount of AA generated during the production of
melt shot is thermally inhomogeneous, with the rear an injection-molded part, rather than the rate of
of the shot, in the vicinity of the screw head, at the AA generation, for calculating apparent activation
lowest temperature.20 In addition to the temperature energies. Total levels of AA (AT ) generated at
changes from compression and decompression, a crest various processing conditions were thus used for these
in the temperature profile is observed immediately calculations. Figures 1 and 2 show total AA values
after screw retraction. This crest corresponds to shear obtained for samples processed with screw speeds
heating caused by the rotation of the screw. The from 20 to 40 m min−1 , at temperatures from 280 to
duration of the observed crest is very small compared 300 ◦ C, with 50 bar of back pressure, and 25 s cooling
with the total cycle time since the screw rotates for only times. Sample sets processed at each screw speed but
a small fraction of the cycle time. The temperature rise at three different temperatures would have equivalent
from shear heating is seen to be less significant than processing exposure times. Since AA generation is a
the temperature rise from adiabatic compression of zero-order reaction,8 values for total generated AA at
the polymer melt. each screw speed were plotted as functions of their
The results obtained after establishment of stable processing temperatures to prepare Arrhenius plots
dynamic extrusion conditions at temperatures from according to:
280 to 300 ◦ C indicate that measured temperatures
were generally lower than set temperatures. The AT ∝ k = Ae−E/RT (9)
peak temperatures corresponding to screw injection
induced compression were usually 5–6 ◦ C lower or
than the set temperatures. Baseline temperatures ln AT = ln A − E/RT (10)
representing polymer in the melt reservoir were
where E is the activation energy and k is the rate
about 12–14 ◦ C lower than set temperatures. These
constant for AA generation during injection molding.
differences may have occurred because the screw
The gas content R is 8.314 J K−1 mol−1 and T is
rotates for less than 10 % of the total cycle time.
the absolute temperature (K). Figure 11 shows the
In commercial melt cavity machines, the screw rotates
Arrhenius plots prepared with the AA generation
for 70–80 % of the total cycle time. For commercial
data. The slopes of lines through these data were
extruders, levels of shear heating are higher and melt
used according to slope = E/R to obtain the apparent
temperatures are much closer to barrel temperatures.
activation energy values shown in Table 5.
The results given in the table indicate that these
Activation energy for AA generation changes in screw rotation rate have little effect on
The process of melting and injection molding a the values of activation energy for AA generation.
polymer material in an extruder usually involves a The average apparent activation energy value of
distribution of residence times rather than a single 167 kJ mol−1 is in agreement with those given by

954 Polym Int 54:946–955 (2005)

 AA generation during PET injection molding

4.0 4 Longer cooling times increase overall cycle time

3.8 and thus result in higher levels of AA generation, at
the rate of almost 7 ppm per additional minute at
290 ◦ C processing conditions.
3.6

3.4 5 Apparent activation energies of 167 kJ mol−1 were

3.2 calculated for samples prepared at various shear
20 m min−1
ln k

3.0
rates. These results are in agreement with literature
25 m min−1
values obtained under conditions of static mixing
2.8
30 m min−1 and indicate that shear rate and plastication do
2.6 35 m min−1 not significantly affect reaction mechanisms for AA
2.4 40 m min−1 generation.
6 Measurements obtained with an infrared sensor in
2.2
0.00174 0.00175 0.00176 0.00177 0.00178 0.00179 0.00180 0.00181 0.00182 the injection-molding machine nozzle indicate that
1/T (K−1) the measured baseline melt temperature is generally
lower than the set barrel temperature and that
Figure 11. Arrhenius plot of total generated AA present in
attainment of stable dynamic conditions requires
injection-molded preforms (ln k) versus reciprocal processing
temperature (1/T).
a considerable amount of time.
7 No appreciable changes in material IV values were
Table 5. Activation energy values for AA generation
recorded at 290 ◦ C processing temperatures in
response to variations of shear rate, back pressure
Screw rotation rate (m min−1 ) Activation energy (kJ mol−1 ) or cooling time. An explanation for this behavior
20 175
is that as long as excess hydroxyl end-groups are
25 164 present, broken polymer links can be reformed with
30 163 the production of equivalent amounts of AA and
35 173 carboxyl end-groups.
40 159

Goodings (149 kJ mol−1 ),2 Jabarin (159 kJ mol−1 )13 ACKNOWLEDGEMENTS

and Halek (157 kJ mol−1 ).8 The similarity of these The authors gratefully acknowledge the members of
results indicates that shear rates, present in the screw the PET Industrial Consortium for their support of
section of the injection molding machine, do not have this research.
a significant influence on the basic mechanism of
AA generation reactions previously investigated under
conditions of static mixing. Data from the current REFERENCES
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