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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 Thermal and thermal oxidative degradation of poly(ethylene terephthalate) (PET) have been the subjects of many research papers.1 – 12 The specific effects of various processing conditions, however, have not yet been satisfactorily investigated, since most previous research topics have not included extrusion and injection molding. The current work establishes relationships among several important processing conditions during extrusion and injection molding and their relative effects on acetaldehyde (AA) generation and the degradation behavior of PET. Material changes resulting from processing temperature, screw shear rate, melt residence time, back pressure and cooling time variations have been included in these evaluations. The primary objective of this work has been to utilize a single-cavity injection-molding machine to provide a methodology for and investigations of the various parameters affecting the production of AA during injection molding of PET. These investigations can then be extended to provide a theoretical background for establishing simulation and prediction models for multi-cavity injection-molding systems.

EXPERIMENTAL Drying All evaluations were performed using Eastman PET homopolymer resin with an intrinsic viscosity (IV) of 0.73 dL g−1 . PET is known to undergo hydrolytic degradation at temperatures exceeding 110 ◦ C. To avoid this, all resin was dried to moisture levels below 50 ppm13 before exposure to other processing conditions. A Conair dryer, with desiccant in the circulating air loop, was used for this purpose. Drying was carried out in two steps. A low-temperature drying step at 102 ◦ C for 18 h was followed by a hightemperature drying step at 150 ◦ C for 4 h. The final moisture content was found to be less than 30 ppm, as measured with a DuPont moisture analyzer. Processing The dried PET pellets were introduced into the injection-molding machine with a K-loader automatic loading system supplied with the drying unit. All preforms were prepared with a 55 ton, singlecavity, reciprocating-screw Arburg injection-molding machine. For all runs the injection pressure was set at 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: sjabari@utnet.utoledo.edu † 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

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Care was taken to maintain ambient temperatures of less than 18 ◦ C during grinding and sample preparation. but held at 250 ◦ C for 10 min.05 mm throughout all rheological evaluations. followed by coarse manual crushing. The cold powder was immediately separated using sieves to obtain particles in the range 20–40 mesh for analyses. 290 and 300 280.3 min. The resulting preform pieces were then finely ground under liquid nitrogen using a stainless steel IkaWerk mill. Released AA was held in the ATD cold trap (−30 ◦ C). for ease of analysis and interpretation of experimental data. The melt flow rate for all shots was set at 40 cm3 s−1 . These sample tubes were sealed after loading. Back pressure variations Screw rotation rate Temperature (◦ C) 290 290 290 290 290 290 290 Back pressure (bar) 0 50 100 150 200 250 300 (m min−1 ) 30 30 30 30 30 30 30 Cooling time (s) 25 25 25 25 25 25 25 (rpm) 275 275 275 275 275 275 275 AA concentration in preforms Preforms prepared under a variety of processing conditions were evaluated in terms of residual AA concentration. Residual AA was volatilized from ground preform material with a Perkin-Elmer ATD-400. All melt viscosity measurements were performed with a Rheometrics cone-and-plate type viscoelastic tester at oscillation frequencies from 0. After completion of sample heating. with retention times of about 2.1 to 100 rad s−1 and at a constant oscillation amplitude and temperature. equipped with a flame ionization detector (FID) and utilizing a 30 mm × 0. Preform pieces were vacuum-dried for 24 h at 140 ◦ C before evaluation. Melt viscosity studies Melt viscosity studies were conducted in order to evaluate the degradation of PET as a result of processing through the injection-molding machine. obtained with a calibration curve relating melt viscosity corresponding to zero shear viscosity to known IV values. All extruder zones were set to the same temperature to give a consistent temperature profile. Cold particles of ground preform materials were weighed and loaded into ATD-400 sample tubes for measurement of AA concentration. Table 1. 290 and 300 280. The areas of the AA peaks. 290 and 300 280. 290 and 300 280.32 mm ID Stabilwax® DA (carbowax) capillary column. Concentrations of AA were calculated as µg AA (g PET)−1 or ppm. The GC was calibrated with known amounts of AA treated in a manner similar to that of the ground preform materials. 290 and 300 280. Preform residual AA concentrations were measured with a Perkin-Elmer Auto System XL gas chromatograph (GC). The preforms were prepared for gas chromatography analyses by submersion in liquid nitrogen. The GC oven was maintained at 60 ◦ C and the FID at 300 ◦ C. Results have been reported in terms of equivalent solution IV values. The mold temperature was controlled by circulating cooling water (10–21 ◦ C) flowing through the drilled channels in the mold cavity and core plates. Shear rate and temperature variations Screw rotation rate Temperature (◦ C) 280. Cooling time variations Screw rotation rate Temperature (◦ C) 290 290 290 290 290 290 290 290 290 290 290 290 290 Back pressure (bar) 50 50 50 50 50 50 50 50 50 50 50 50 50 (m min−1 ) 30 30 30 30 30 30 30 30 30 30 30 30 30 Cooling time (s) 40 35 30 25 24 23 22 21 20 19 18 17 16 (rpm) 275 275 275 275 275 275 275 275 275 275 275 275 275 Polym Int 54:946–955 (2005) . 290 and 300 280. which were performed at 280 ◦ C under a nitrogen atmosphere. packed with Tenax GR (60/80) and Carbosphere (80/100).AA generation during PET injection molding of 1700 bar. throughout the sample heating cycle. trapped AA was injected into the GC column as a result of rapid heating (300 ◦ C) of the cold trap. 290 and 300 Back pressure Cooling (bar) (m min−1 ) (rpm) time (s) 0 50 50 50 50 50 50 20 20 25 30 35 40 50 183 183 229 275 320 366 366 25 25 25 25 25 25 25 Table 2. in a constant helium purge. Samples were held in the ATD oven at 150 ◦ C for 45 min. in order to minimize loss of residual AA from the ground preform materials. 947 Table 3. were measured using Perkin-Elmer Turbochrom software. The gap between the cone and plate was maintained at 0. Tables 1 to 3 summarize the various processing conditions utilized for preform production. Extruder barrel temperatures were controlled by heater bands in the various zones and monitored with temperature sensors. The mold cooling time for all except the residence time runs was set at 25 s.

the maximum shear rates experienced by the PET melt in the barrel of the injection-molding machine were found to range from 264 s−1 at 40 m min−1 to 132 s−1 at 20 m min−1 . They found that over the shear rate range of 50 to 1000 s−1 the flow behavior of PET was nearly Newtonian.82 dL g−1 . Therefore. following the procedure of Campbell et al . EA Lofgren. The following relationship can be utilized for calculation of shear rate at any single point along an extruder screw.122x + 9. The flow of the PET melt between the screw of the injection-molding machine and the inner barrel surface can be approximated by the flow of an incompressible Newtonian fluid between two coaxial cylinders. It can be seen that AA generation at all three temperatures appears to increase linearly with the rate of screw rotation. SA Jabarin Time–temperature measurements The time–temperature profile of the PET polymer melt was monitored using an Omega fiber-optic infrared sensor.1h (1 ) where h is the distance between the screw and the barrel wall for any single point along the screw and hence is a constant. Back pressure was changed from 50 to 300 bar with 25 s cooling times held constant. Figure 1 illustrates the dependence of preform AA concentration on shear rate at each processing temperature. The following expression from Bird et al 16 can then be applied for the volume heat source Sv resulting from the viscous dissipation: Sv = µ dvz dx 2 (2 ) where µ is the viscosity of the fluid (which in the case of a Newtonian fluid. the heat Polym Int 54:946–955 (2005) . Preform acetaldehyde concentration (ppm) 60 50 40 30 y = 0. The rate of viscous heat production per unit volume is: Sv = µ V h 2 (4 ) DN 19. The detector emits a signal corresponding to the intensity of the incident radiation. the velocity profile is linear and can be represented by the relation: vz = x V h (3 ) where V is the velocity of the screw. Equation (2) neglects curvature effects. does not depend on the shear rate). The following discussions include the effects of various processing conditions on AA concentrations in the preforms and also the state of degradation in terms of preform IV. 290 and 300 ◦ C. Since these values fall within the shear rate range specified by Gregory and Watson.15 the PET melt can be assumed to have Newtonian behavior under the experimental conditions. Cooling times were varied in the range from 16 to 40 s with constant back pressure values of 50 bar.173x + 16.14 The infrared sensor was installed in the nozzle of the injection-molding machine and was placed flush to the surface so as not to disturb the flow of the polymer melt through the nozzle. This generated AA remained in the injection-molded preforms and this was analyzed to obtain residual AA concentrations. vz is the velocity of the fluid and x is the direction perpendicular to the screw or barrel surface.06 280 °C Figure 1. and the radiation is then directed to a detector cell. Back pressure and cooling time influences were monitored at 290 ◦ C and constant 30 m min−1 screw rotation speeds. Sv ∝ V 2 . with constant velocity in a slit. which is amplified and linearized and then output to the cable connector.35 to 0. RESULTS AND DISCUSSION Preforms prepared under the conditions described in Tables 1 to 3 were evaluated in terms of the AA that was generated during processing. D is the screw diameter.6 300 °C y = 0. For the steady-state velocity of a fluid. a constant. Gregory and Watson15 have estimated the steadystate flow properties of PET melts as a function of temperature. S= 948 where S is the shear rate in reciprocal seconds. The effects of shear rate changes were monitored at temperatures from 280 to 300 ◦ C.SR Shukla. Shear rate and temperature Preforms were prepared at screw speeds from 20 to 40 m min−1 using extruder barrel temperatures of 280. The changes in the cooling times were utilized for investigation of residence time effects on AA generation. Effect of screw speed on preform AA concentration at 280. The fiber-optic lens collects the infrared heat radiation emitted by the polymer melt. Using this relationship.8 20 10 0 15 20 25 30 35 Screw speed (m min−1) 40 45 290 °C y = 0. In this case. Specific experimental conditions are outlined in Table 1. This sensor is a noncontact temperature measuring device with a standard response time of 50 ms. with back pressure and cooling time held constant. shear rate and IV over a temperature range of 265 to 295 ◦ C and an IV range of 0. Now let µ/h2 be designated by K . 290 and 300 ◦ C. h is the screw channel depth and N is the screw rpm.285x + 36.

the AA generation rate nearly doubles. Table 4 shows that the temperature rise increases linearly with shear rate and Fig 2 shows that AA concentration increases exponentially with barrel temperature.75 × K2 2. In order to further interpret the data of Fig 1. and Cp is the specific heat of the material in J kg−1 K−1 . for the same velocity and geometry.25 × K2 1.50 × K1 1. K2 = K1 /(mCp ). µ290 < µ280 and. The effects of shear rate on this AA generation are. over small enough increments. Curves for all shear rates give excellent exponential fits with R2 values of 0. Table 4 summarizes the predicted temperature rise per unit volume due to shear heating alone. These values for AA generation at each shear rate can be seen to vary exponentially with extruder temperature. at higher temperatures. Q is the energy generated due to the viscous dissipation in J m−3 .800 × t1 0.063 × 20 × 20 K × 4. For these analyses and within the domain of the experimental conditions. given in Eqn (4). Effect of temperature on preform AA concentration at screw speeds of 20–40 m min−1 (At 30 m min−1 .000 × 20 × 20 K × 1. the effect of barrel temperature on AA generation is far greater than the effect of screw shear rate. changes in shear rate and induced temperature rise are small enough for all trends to approximate linearity. for two different temperature levels. Figures 1 and 2 show clearly that. not as obvious.5( T40 ) (5 ) 60 50 40 30 20 10 0 275 20 m min−1 25 m min−1 30 m min−1 35 m min−1 40 m min−1 280 The temperature rise due to viscous dissipation for the 20 m min−1 case was only half as much as that for the 40 m min−1 case.571 × t1 0.00 × K1 T /unit volume = Q/(mCp ) 1. respectively. The most important fact that emerges from Table 4 is that the temperature rise shows a linear dependence on the shear rate. we can argue for the observed temperature rise with shear rate for all data points. 290.25 × K1 1. the AA generation values must be plotted versus barrel temperature with shear rate as the constant parameter. data was refitted to an exponential curve to obtain a very slightly better fit.0617x ).75 × K1 2.00 × K2 1.500 × t1 Q = Sv t ρ 1. f = a factor relating (V1 )2 to other screw speeds or values of (V )2 . V1 = screw speed at 20 m min−1 . more AA is generated at higher temperatures. ρ = density (kg m−3 ). the viscous dissipation at 280 ◦ C should be greater Sv = KV 2 K × 20 × 20 K × 25 × 25 K × 30 × 30 K × 35 × 35 K × 40 × 40 Sv = Kf (V1 )2 K × 1. As shear rates increase from 20 to 40 m min−1 . Polym Int 54:946–955 (2005) 949 . Secondly. m is the mass of the polymer undergoing shearing in kg. T40 . The viscous dissipation expression. In this case. Predicted temperature rise at various shear rates 285 290 295 Temperature (°C) 300 305 Figure 2. predicts that for the same velocity or screw circumferential speed.00 × K1 1. at all shear rates. however. In a similar way. T = T − T0 . for any curve.563 × 20 × 20 K × 2. total AA generation is increasingly dependent on shear rate. for the same screw rotation time. the behavior can be approximated as linear.50 × K2 1.667 × t1 0.98 or greater. 3.7 ppm at 280. the viscous dissipation should be greater when the viscosity is higher. with the knowledge that this treatment is not as rigorous as one based on exponential dependence. T20 . Note that in Table 4.000 × 20 × 20 Screw retraction time t 1. Since the total screw rotation time for the 40 m min−1 case was only half as much as the total screw rotation time for the 20 m min−1 case. In the case of data obtained at 30 m min−1 . The first important observation that can be made from this plot is that for every 10 ◦ C rise in temperature.00 × K2 K1 = K × 20 × 20 × t1 . This implies that the temperature rise due to viscous heat dissipation for the 40 m min−1 case.4 and 5. The viscosity of a polymer melt decreases with an increase in temperature. and Fig 2 presents the data in this form. This suggests that AA generation should Table 4.000 × t1 0.4. y = 4 × 10−7 e0. increase exponentially with shear rate. absolute amounts of AA generated increase by 2. Since it makes very little difference whether the linear fit or exponential one is utilized. t1 is the screw retraction time or plasticating time for the 20 m min−1 screw rotation rate. will be roughly four times the temperature rise due to viscous dissipation for the 20 m min−1 case. These changes seem to indicate that. However. we can write: T20 ≈ 0. where T is the final temperature after shear and T0 is the initial temperature before shear. most of the data have been fit linearly. for this system.AA generation during PET injection molding Preform acetaldehyde concentration (ppm) generation due to viscous heat dissipation will increase with the square of the velocity. y = 4 × 10−7 e0. Thus. and 300 ◦ C.250 × 20 × 20 K × 3. In this case.0617x .

with a screw rotation rate of 30 m min−1 (275 rpm) and a cooling time of 25 s. we would expect that the dependence of total generated AA on the screw shear rate should be higher at the lower temperature value. Future work is anticipated to model and analyze the flow behavior in cases of single-cavity and multi-cavity molds during injection molding of PET preforms. since it includes only the layer flowing closest to the wall. 16. The expression for wall shear rate γw can be utilized. 48 cm3 of material is injected into the mold cavity in 1. AA generation results include overall increases with contributions from various sources. Thus. the relative dependence of AA generation at higher temperatures becomes more in accordance with first principles.4 %. the PET melt is exposed to another source of shear. As the polymer melt flows into the mold cavity. and the volumetric flow rate Q is thus 40 cm3 s−1 . It can be seen that residual AA concentrations increase linearly with increasing back pressure.SR Shukla. respectively. Shear rate calculations have been based on assumptions that have not taken into account any distributions of shear rates or temperatures. where it encounters very high rates of shear.9 % and 13. it experiences shear rates 32 times higher than those in the screw. over the shear rate range from 20 to 40 m min−1 . the gate diameter is 4 mm. This work should also relate the generation of AA to differences in shear heating and polymer flow. 290 and 300 ◦ C is 21. the overall percentage changes are lower. In reality. The wall shear rate γw can then be computed from the expression: 32 × 40 γw = = 6366 s−1 π × 0. At higher temperature levels. On close inspection of the data.2 s. EA Lofgren. through the gate of the injectionmolding machine. The slopes of the plots given in Fig 1 include the effects of temperature as well as shear rate. are shown in Fig 3. to give an overall increase of about 20 % within the evaluated pressure range. Back pressure The effects of injection-molding machine back pressure variations were investigated at an extruder temperature of 290 ◦ C.2 %. back pressure and residence time would all be reduced if AA generated by shear heating through the gate could be excluded.2 20 15 0 50 100 150 200 250 Back pressure (bar) Figure 3. as a result of back pressure variations from 0 to 200 bar. is much higher than rates encountered by the melt in the screw. this discrepancy does not exist. Several different mechanisms may contribute to this increase. As the change in total AA generated at each temperature level depends directly on the change in temperature. The absolute increases in AA values thus appear contrary to what one might expect from first principles. for proper interpretation. Assuming that n ≈ 1. These values would tend to be higher near the outer polymer surface.403 This shear rate.0232x + 24. where the contribution of viscous heat dissipation would be comparatively lower. to obtain:17 γw = 3n + 1 4n 8V D (6 ) cause shear heating of the polymer melt and production of AA. While at higher temperatures absolute amounts of generated AA are higher with increased shear rates. it is found that the percentage increase in AA generation at 280. In addition to shear resulting from screw rotation. and (c) increased residence time of the PET in the injection-molding machine. These high shear rates 950 30 25 y = 0. The volume of polymer melt experiencing the very high shear through the gate is relatively small. (b) increased screw shear. the effects of changes in all processing parameters on the absolute values of AA generated and on the AA generation rates are magnified. SA Jabarin than that at 290 ◦ C. Screw shear rates at 30 m min−1 are 198 s−1 . as given in Table 2. the data should be analyzed using percentage changes in AA generation. Preform acetaldehyde concentration (ppm) 35 where V is the average velocity of the fluid and D is the diameter of the capillary. we may write: 32Q (7 ) γw = π D3 where Q is the volumetric flow rate. Effect of back pressure on preform AA concentration at 290 ◦ C. Polym Int 54:946–955 (2005) . The levels of AA generated. Under current experimental conditions. A cross section of the polymer melt would thus exhibit a distribution of temperatures and AA concentrations. Values obtained at different temperatures and as a result of changing screw speed. assuming simple Poiseuille flow. The total quantities of AA measured in preforms produced under the various experimental conditions all include AA produced as a result of the shear heating through the gate. Thus. it passes through a narrow gate. These contributing factors include: (a) a temperature rise due to adiabatic compression of the melt. As the polymer melt passes through the gate. For a typical shot. This is because the contribution of viscous dissipation should be greater than at the higher temperature.

0 0 50 100 150 Back pressure (bar) 200 250 Figure 4. the total AA value of 5. It can be seen that screw rotation time increases by about 0. Residence time increases include increased screw rotation times. In the case of samples prepared at 290 ◦ C and 50 bar back pressure. A 50 bar rise in back pressure can. This value can then be utilized in the expression given in Fig 2. therefore. Each cooling time.2 ppm of total increase. the rise in temperature T is found to be of the order of 0. The total rise in AA concentration resulting from a 50 bar increase in back pressure is 1.1 ppm can be attributed to increased time of heating within the screw.008 ◦ C. therefore. The residence time experiments are described in the next section and from those we can infer that for every 50 bar increase in back pressure an AA concentration increase of about 0. 200 bar back pressure. The resultant increase in AA concentration. which is not a significant source of AA during extrusion. and the cycle time. From the slope in Fig 3. The effects of screw shear rate at 290 ◦ C can be assessed from the slope of the AA versus screw speed given in Fig 1. there are about 6. In this example.16 ppm (total) − 0. V = 0. increases polymer residence time by more than the time required for one injection cycle. V = 0. to obtain AA generation that cannot be attributed to screw shear: 1.16 ppm. Figure 5 gives an overall schematic drawing showing the various processes included in a complete injection-molding cycle.5 2. Back pressure was set at 50 bar and screw speed held at a constant 30 m min−1 . This value includes the 0.24 ppm of AA generated by shear can now be subtracted from the total AA generated.24 ppm 0.65 s.01 ppm. Figure 6 shows the linear dependence of this relationship. For 0.19 After substituting the values with appropriate units into Eqn (8).92 ppm AA (other = (screw shear) than screw shear) Polym Int 54:946–955 (2005) 1.18 ppm.00332 cm3 g−1 and the T is found to be 0.18 ppm generated by shear alone must be divided by the screw rotation time of 2. Effect of back pressure on screw rotation time at 290 ◦ C.19 and the expression: P V = Cp T (8 ) 3.18 the specific heat data for melted PET given by Smith and Dole.04 J g−1 K−1 from Smith and Dole. These values comprise the total residence time from the entrance of the pellets to the feed section through the hopper.AA generation during PET injection molding Screw rotation time (s) An approximation for the adiabatic temperature rise in the PET melt can be calculated using the specific volume data for a PET melt given by Zoller and Bolli. these changes result in cumulative additions to all of the shots remaining in the injection-molding system. therefore.92 ppm AA generated primarily as a result of increased time in the melt. Increased residence time in the melt state.1 s per shot for every 50 bar increase in back pressure.04 At 290 ◦ C and. The 0. increase the residence time of the PET in the screw by 0. resulting from increased back pressure. therefore. for example. The screw rotation time increases by nearly 0.1 ppm AA generated within the screw during the increased time of rotation.1 s of screw rotation. As cooling times are increased from 16 to 40 seconds.14 s to obtain about 2. Temperature changes in the melt are also very small under these experimental conditions. until the time when the preform is ejected from the mold cavity.4 ppm of AA per second of screw rotation.00196x + 2. As a result. relating AA concentration to temperature. Residence time Total polymer residence times were calculated using the flight-volume data for the screw section of the extruder. the AA generated by screw shear alone is 0. Normally. This value of 1.24 ppm resulting from screw shear leaves 0.14 ◦ C.0144 cm3 g−1 from Zoller and Bolli18 and Cp = 2.16 ppm minus the 0. The screw rotation time at a 30 m min−1 screw rotation rate and 50 bar back pressure is 2. This complete cycle is the total residence time under evaluation. Changes in AA generation as a result of varying cooling times (ranging from 16 to 40 s) were monitored at a processing temperature of 290 ◦ C. the AA generation resulting from screw rotation alone is estimated to be 5. from the 0.5 1. The relationship between screw rotation time and back pressure is given in Fig 4.16 ppm. the total increase in AA generation resulting from a 50 bar rise in back pressure is found to be 1. the volume of the mold cavity.5 shots in the injection-molding machine at any given time. It has been shown that adiabatic compression at 50 bar does not contribute significantly to AA generation during extrusion. appears to be the major factor contributing to additional AA generated under conditions of increased back pressure. the resultant increase in AA concentration is only 0.0 2. the volume of the melt reservoir. At a screw shear rate of 30 m min−1 . with increased cooling times resulting in longer overall residence times and higher 951 .24 ppm. was found to be about 0.14 ◦ C higher exposure temperature.1 s per shot for every 50 bar increase in back pressure. while the machine is running.0 y = 0.14 s.

872 20 10 Screw rams forward / shot injection 0 0 100 200 Total residence time (s) 300 400 Packing Figure 6. results in part from the volume fraction of unmelted solids present in the feed and transition zones of the machine. Measurements were performed on preform materials prepared from 280 to 300 ◦ C at screw speeds of 20 to 40 m min−1 . even though polymer material is present within the injection-molding machine. If a uniform gradient is assumed in the transition section. as illustrated in Fig 7. which corresponds to an apparent induction time of about 51 s before measurable AA is generated during this total residence time. This solid bed continues to diminish as it progresses towards the metering zone. Conventional models for most screws in extrusion and injection molding assume that in the feed zone there is a well-defined solid bed present in the screw channels adjoining the melt pool. This induction time also includes cooling time during 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 linear relationship of AA generation to total residence time has a negative intercept. therefore. Overall IV values are slightly lower for samples exposed to higher temperatures. The results corresponding to zero shear viscosity were then converted to equivalent IV values in order to monitor changes resulting from processing variations. Melt viscosity Samples prepared under various experimental conditions were evaluated in terms of melt viscosity using a viscoelastic tester. the feed section comprises about 60 % of the total screw length.63 shots of polymer. Plastication Screw rotation Cooling the mold Backward movement of the plasticating unit Mold opens Ejector advancement the total flight volume. Viscosity measurements were also taken to study the effects of back pressure and cooling time during injection molding.SR Shukla. During evaluations of back pressure. Figures 8 and 9 show that no appreciable changes in IV occur as a result of back pressure changes from 0 to 200 bar or for cooling times from 15 to 25 s.1143x − 5. the screw rotation rate at 30 m min−1 Polym Int 54:946–955 (2005) Ejector retraction End of cycle Figure 5. The results show that the IV has very little dependence on shear rate when samples are processed at 280 or 290 ◦ C. along the screw axis.9 shots. It represents all the time during which AA generation is not significant. illustrated in Fig 6. Possible explanations for this induction time are discussed below. In the case of the equipment used for these experiments. The total flight volume can accommodate about 5. It is difficult to estimate the exact solids volume fraction in the barrel of an injection-molding machine. Effect of total residence time on preform AA concentration. The time required for complete ejection of the preform from the mold also contributes to this induction time. Samples processed at 300 ◦ C show a slight decrease in IV with increasing shear rate. the feed section could constitute more than 70 % of 952 . levels of generated AA. The 51 s induction time. the barrel temperatures were maintained at 290 ◦ C. Processes involved in a complete injection-molding cycle. SA Jabarin Preform acetaldehyde concentration (ppm) Machine cycle start 50 40 Mold closes Plastication unit moves forward 30 y = 0. EA Lofgren. Pellets do not melt immediately as they enter the feed zone of an injection-molding machine. the volume of the material present in the feed zone will comprise at least 3. with samples processed at higher shear rates exhibiting the greatest temperature dependence.

68 0. using Quattro Pro software. 0.70 0. The temperature falls slightly.55 0. Time–temperature measurements of polymer melt Measurements of polymer melt temperatures were obtained with a fiber-optic infrared sensor in the nozzle of the injection-molding machine.70 0.55 0.6 ◦ C. Cooling time effects were monitored at the same temperature and screw rotation conditions and a constant back pressure of 50 bar. changes resulting from thermal degradation are offset by the repolymerization process. For all runs the injection pressure was set constant at 1900 bar.50 0 50 100 150 Back pressure (bar) 200 250 Figure 8.80 0. which indicates that as long as sufficient available free hydroxyl end-groups are present. the temperature reaches its peak value due to adiabatic compression of the polymer melt. the screw speed was set at 40 m min−1 .74 0. broken polymer links resulting from degradation can repolymerize with the production of equivalent amounts of AA and carboxyl endgroups. Figure 9. Trendlines 2 and 3 were. and the cooling time at 25 s.60 0.60 0. In the holding stage.72 Intrinsic viscosity 0.65 0. The Polym Int 54:946–955 (2005) time–temperature profile of the polymer melt was recorded in real time as tables. the temperature of the polymer melt shows a steady decline as a result of dissipation of frictional heat generated during the injection stage.80 0. the mold cooling water was 15. respectively. Changes in the three trendlines of Fig 10 represent various stages of the injection-molding cycle. obtained after 10 and 21 additional shots had been made after the shot represented by trendline 1. These tables were then transferred to an Excel program for graphical analyses. after temperature settings had been reduced from 290 ◦ C.70 0. Under these experimental conditions. Effect of back pressure on melt IV values at 290 ◦ C. The recorded melt temperature rises and falls very sharply at stages in the cycle that correspond to screw injection induced compression and screw retraction induced decompression of the polymer melt. will significant loss in IV be recorded.50 0. with very little net loss in molecular weight or IV. In this manner.65 0. The data represented by trendline 1 in Fig 10 were collected as soon as all setpoint values on the injectionmolding machine read 285 ◦ C. samples exhibit minimal changes in IV. while at the same time showing increased AA generation. during the holding stage in the machine cycle. This heat 953 . as well as times required for temperature stabilization in each process. Only after the available hydroxyl end-groups have been consumed (as a result of prolonged heat history). the holding pressure at 1700 bar. Effect of screw speed on melt IV values at 300 ◦ C.75 Intrinsic viscosity 20 25 30 35 Screw speed (m min−1) 40 45 0.64 0.75 Intrinsic viscosity 0. It then falls to the baseline value within 1 s. It can be seen from these data that the melt temperature of the polymer stabilizes at a far slower rate then the barrel temperature of the extruder. and the back pressure was 100 bar.60 15 10 15 20 Cooling time (s) 25 30 Figure 7. These results can be explained according to Goodings’s2 mechanism of thermal degradation. These trendlines illustrate measured changes in melt temperature during various stages of the injection-molding process.2 s after initiation of injection. Effect of cooling time on melt IV values at 290 ◦ C. These results indicate that attainment of stable dynamic conditions requires a considerable amount of time.62 0.66 0. Similar measurements were performed as barrel temperature setting were changed within the range 280–300 ◦ C. Figure 10 gives an example of data obtained using this method. the cooling time at 25 s. About 1. once setpoints are changed or after extruder start-up. It can thus be seen that changes in levels of generated AA are more sensitive indicators of polymer degradation state than are changes in IV values.AA generation during PET injection molding 0. as the material flows past the nozzle and gate and into the mold cavity.

rather than the rate of AA generation. 200 250 300 is slowly dissipated to the surroundings. The duration of the observed crest is very small compared with the total cycle time since the screw rotates for only a small fraction of the cycle time. It is therefore appropriate to use the total amount of AA generated during the production of an injection-molded part. The peak temperatures corresponding to screw injection induced compression were usually 5–6 ◦ C lower than the set temperatures.314 J K−1 mol−1 and T is the absolute temperature (K). The results obtained after establishment of stable dynamic extrusion conditions at temperatures from 280 to 300 ◦ C indicate that measured temperatures were generally lower than set temperatures. For commercial extruders. Figures 1 and 2 show total AA values obtained for samples processed with screw speeds from 20 to 40 m min−1 . Baseline temperatures representing polymer in the melt reservoir were about 12–14 ◦ C lower than set temperatures. EA Lofgren. in the vicinity of the screw head. 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). and 25 s cooling times. with 50 bar of back pressure. The decline also occurs because the melt shot is thermally inhomogeneous. at the lowest temperature. Activation energy for AA generation The process of melting and injection molding a polymer material in an extruder usually involves a distribution of residence times rather than a single 954 value. a crest in the temperature profile is observed immediately after screw retraction. the screw rotates for 70–80 % of the total cycle time. The results given in the table indicate that these changes in screw rotation rate have little effect on the values of activation energy for AA generation. The average apparent activation energy value of 167 kJ mol−1 is in agreement with those given by Polym Int 54:946–955 (2005) . The gas content R is 8. levels of shear heating are higher and melt temperatures are much closer to barrel temperatures.8 values for total generated AA at each screw speed were plotted as functions of their processing temperatures to prepare Arrhenius plots according to: AT ∝ k = Ae−E/RT or ln AT = ln A − E /RT (10) (9 ) where E is the activation energy and k is the rate constant for AA generation during injection molding. These differences may have occurred because the screw rotates for less than 10 % of the total cycle time. The slopes of lines through these data were used according to slope = E /R to obtain the apparent activation energy values shown in Table 5. Sample sets processed at each screw speed but at three different temperatures would have equivalent processing exposure times. at temperatures from 280 to 300 ◦ C. for calculating apparent activation energies. during the holding stage. Total levels of AA (AT ) generated at various processing conditions were thus used for these calculations. Figure 11 shows the Arrhenius plots prepared with the AA generation data. In commercial melt cavity machines. SA Jabarin 284 1 282 3 2 280 Temperature (°C) 278 276 274 272 270 0 50 100 150 Time Figure 10. This crest corresponds to shear heating caused by the rotation of the screw. The temperature rise from shear heating is seen to be less significant than the temperature rise from adiabatic compression of the polymer melt. with the rear of the shot.20 In addition to the temperature changes from compression and decompression.SR Shukla. Since AA generation is a zero-order reaction.

2 0. An explanation for this behavior is that as long as excess hydroxyl end-groups are present.00182 1/T (K−1) Figure 11. vol 8.00175 0. back pressure or cooling time. CONCLUSION AA generation behavior of PET has been investigated in terms of its relationship to changes in various processing conditions during injection molding. Part C 30:399 (1970). ed by Salamone JC. Toledo (2000). New York. Polym Eng Sci 24:1056 (1984). 2 Shear rate increases from 20 to 40 m min−1 result in 12–21 % more generation of AA at temperatures from 300 to 280 ◦ C. Soc Chem Ind (London) Monograph 13:107 (1961).8 The similarity of these results indicates that shear rates. Polym Degrad Stab 43:431 (1994). 3 Ritchie PD.00178 0. Data from the current experiments fit the zero-order kinetics proposed by Halek.8 2.2 ppm for each 50 bar pressure increase. 5 Apparent activation energies of 167 kJ mol−1 were calculated for samples prepared at various shear rates. Soc Chem Ind (London) Monograph 13:211 (1961). 14 Campbell GA. New York (1968). 6 Measurements obtained with an infrared sensor in the injection-molding machine nozzle indicate that the measured baseline melt temperature is generally lower than the set barrel temperature and that attainment of stable dynamic conditions requires a considerable amount of time. Levels of AA in preforms were found to increase with increasing processing temperature. Activation energy values for AA generation Screw rotation rate (m min−1 ) 20 25 30 35 40 Activation energy (kJ mol−1 ) 175 164 163 173 159 4 Longer cooling times increase overall cycle time and thus result in higher levels of AA generation.2 3. broken polymer links can be reformed with the production of equivalent amounts of AA and carboxyl end-groups. J Polym Sci. Goodings (149 kJ mol−1 ). 10 Jabarin SA.8 3. 8 Halek GW.2 Jabarin (159 kJ mol−1 )13 and Halek (157 kJ mol−1 ). 3 Back pressure increases from 0 to 200 bar result in AA concentration increases of about 1. ACKNOWLEDGEMENTS The authors gratefully acknowledge the members of the PET Industrial Consortium for their support of this research.00177 0.0 3. J Polym Sci 20:37 (1956). 20 Amano O and Utsugi S. back pressure and overall residence time. Interscience. A Course on PET Technology. The Flow of High Polymers.00181 0. University of Toledo. 11 Dzieciol M and Trzeszczynski J.00176 0. a 10 ◦ C rise in processing temperature doubles the AA concentration in an injection-molded preform. J Macromol Sci Phys 18:555 (1980).00180 0. J Appl Polym Sci 69:2377 (1998). Arrhenius plot of total generated AA present in injection-molded preforms (ln k ) versus reciprocal processing temperature (1/T ). Angew Chem Int Ed 7:182 (1968). 19 Smith CW and Dole M. p 6114 (1996).6 3. Dontula N. 15 Gregory DR and Watson MT. REFERENCES 1 Marshall I and Todd A. 17 Middleman S.00174 0. 13 Jabarin SA. CRC Press Inc. Coudane J and Vert M.0 2. Dev Polym Degrad 5:9 (1984). 6 Jabarin SA and Lofgren EA. 12 Dzieciol M and Trzeszczynski J. Table 5. Trans Faraday Soc 49:67 (1953). do not have a significant influence on the basic mechanism of AA generation reactions previously investigated under conditions of static mixing. Sukanek PC and Devanathan H. present in the screw section of the injection molding machine.4 20 m min−1 25 m min−1 30 m min−1 35 m min−1 40 m min−1 2.4 ln k 3. 7 No appreciable changes in material IV values were recorded at 290 ◦ C processing temperatures in response to variations of shear rate. Polym Eng Sci 20:680 (1980). Transport Phenomena 277 (1960).00179 0. Polym Int 54:946–955 (2005) 955 . 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. Polym Eng Sci 30:385 (1990). at the rate of almost 7 ppm per additional minute at 290 ◦ C processing conditions. 34. Polym Eng Sci 31:1674 (1991). 2 Goodings EP. 4 Buxbaum LH.6 2. 7 Zimmerman H. Specific conclusions are given below: 1 Within the temperature range from 280 to 300 ◦ C. shear rate. J Appl Polym Sci 77:1894 (2000). Polym Sci: Polym Symp 74:3 (1986).. 9 Villain F. 16 Bird BR. in Polymeric Materials Encyclopaedia.8 with the enhanced mixing provided by variations in shear rate and plastication causing no appreciable changes in reaction mechanisms. The majority of this change occurs because of increased residence time. 5 Zimmerman H and Kim NT. Stewart WE and Lightfoot EN.AA generation during PET injection molding 4. 18 Zoller P and Bolli P.