Key Engineering Materials Vols 611-612 (2014) pp 922-927 Online: 2014-05-23

© (2014) Trans Tech Publications, Switzerland

doi:10.4028/www.scientific.net/KEM.611-612.922

Acetaldehyde generation in processing PET by means of hot runner

systems
G. Lucchetta1, a*, S. Chirico1
1
DII, University of Padova, via Venezia 1, 35131 Padova, Italy
a
giovanni.lucchetta@unipd.it

Keywords: acetaldehyde, polyethylene terephthalate, hot-runners, extrusion.

Abstract. Polyethylene terephthalate (PET) is a polyester widely used as packaging material in

drink-bottling application. PET is rather sensitive to heat and oxidation and during processing it
may undergo degradation reaction with generation of acetaldehyde. In this work the generation of
acetaldehyde in a hot runner system has been measured. A special test apparatus was developed to
separate the contributions due to the action of the extruder screw from those due to the melt
residence at high temperature. Results showed that the acetaldehyde content non-linearly increases
with temperature and residence time. A model has been proposed to provide for the generation of
acetaldehyde as a function of temperature and residence time regardless of the geometry and other
specific conditions of the process.

Introduction
Polyethylene terephthalate (PET) is a polyester widely used as packaging material in food
industry especially in drink-bottling application. The chemical inertness of PET, the good barrier
properties towards moisture and oxygen, the impact resistance and the very low weight of PET
bottles compared to glass ones of the same filling volume are the reason of the rapid growing up of
the consumption of PET. However, PET is rather sensitive to heat and oxidation and during
production and processing it may undergo degradation reactions, which generate by-products [1].
These substances can evaporate if they are volatile or diffuse into the liquid content after bottling
[2]. Among the various by-products acetaldehyde is particularly critical because it possesses a
distinct odor and taste, which affects the organoleptic properties of non-carbonated mineral waters,
being detectable in low concentration in mineral water [3].
Several attempts have been made to investigate the factors influencing the formation of
acetaldehyde during PET production and processing as well as the responsible mechanisms [4].
Hydrolytic, thermal and thermal oxidative degradation of PET have been the subjects of many
research papers [5]. Hydrolytic chain scission seems to represent the fastest and most dangerous
process, causing relevant molecular weight loss and mechanical property deterioration [6]. This
type of degradation is usually limited drying PET before melt processing. Villain et al. investigated
the effect of stabilizers on PET degradation, evaluating the amount of pollutants generated in
injection-moulded preforms with PET stabilizers. They observed that thermal degradation of fibre
grade PET caused the production of a larger amount of acetaldehyde [2]. Marshall and Todd used
melt viscosity of PET to estimate the kinetics of thermal degradation for long residence times (up to
30 hours) at melting temperature [7]. They observed that the rate of degradation increased as
oxygen concentration increased during melting. Goodings used acetaldehyde generation, inherent
viscosity and changes in carboxyl end group concentration to monitor PET behaviour during
polymerization and degradation [8]. He noted that stirring PET during melting liberates
acetaldehyde and results in a smaller reduction of inherent viscosity. Jabarin and Lofgren measured
the rates of thermal degradation in terms of melt temperature, melt residence time, melt
environment and drying environment, observing that they had all influence on the degradation of
PET [9]. Khemani investigated thermal degradation of polyester and copolyester over an extended
period of time and he estimated the rate of acetaldehyde generation by mid chain scission
mechanism [10]. Shukla el al. investigated acetaldehyde generation in terms of its relationship to
changes in various processing conditions during injection moulding [11].

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications, www.ttp.net. (ID: 128.210.126.199, Purdue University Libraries, West Lafayette, USA-03/06/15,21:37:47)
 Key Engineering Materials Vols. 611-612 923

The problem of acetaldehyde generation is particularly critical when using longer hot runner
systems, which maintain PET at high temperature for long residence times. The technology of
stretch blow moulding is nowadays evolving following this trend due to the increasing requirements
in terms of productivity. Therefore a model able to predict the generation of acetaldehyde as a
function of processing conditions is needed to support the development of new and larger blow
moulding machines. To this aim, the objective of this work is to evaluate the production of
acetaldehyde in a laboratory extruder equipped with a hot runner channel.

Experimental
Materials. All evaluation was performed using Artenius Global PET in pellets, with an intrinsic
viscosity (IV) of 0.82 dl/g. The resin was kindly supplied by SIPA S.p.A (Vittorio Veneto, Italy)
and it was dried in a drier (Piovan, DS605) at 105°C for 16 hours before processing.

Processing apparatus and sampling. PET was extruded in a Thermo Scientific Haake Polylab
Rheomex OS, (D=25 mm and L/D=25) equipped with a modular hot runner system (D=10 mm).
Two length values of hot runner were adopted, namely L=913 mm and L=519 mm (Figure 1). The
temperature regulations were performed by means of a Thermodyne controller. Both the modular
hot runner system and the temperature controller were supplied by SIPA S.p.A. Tests were
performed at different temperatures and screw rotation (Table 1). A flat temperature profile, either
for the four different zones of the extruder and for two different hot runners (four temperature zone
for shorter channel, and eight zones for longer ones) was adopted. The screw speed was changed
between 50 and 150 rpm, and the residence time, required for PET samples to go through the hot
runners, was varied between 20 s and 120 s. The hot runner is provided with a valve that allowed
sampling of PET immediately after the extruder exit. This special test apparatus was developed to
separate the contributions due to the action of the extruder screw from those due to the melt
residence at high temperature.

Fig. 1 Modular hot runner system used in the experiments

Table 1 Experimental condition
Hot runner length [mm] Extruder and hot runner zones Screw rotation speed [rpm]
temperature [°C]
519 280, 290 and 300 50, 75,100,150
913 280, 290 50, 75, 100,150
913 270, 275, 280, 285, 290, 295 and 300 150
For each test two samples were collected respectively at the extruder exit (opened valve) and at the
end of the hot runner (closed valve). To avoid the generation of acetaldehyde during cooling, all
samples were collected and cooled for one minute in a water-jacketed sampler. Each test was
replicated 3 times.
924 Material Forming ESAFORM 2014

Determination of acetaldehyde content. PET samples were analysed to evaluate the content of
acetaldehyde generated during processing and entrapped in the specimens. The samples were
prepared for head space gas chromatography analysis by immersion in liquid nitrogen, followed by
coarse milling using a blade mill with a 5 mm sieve. The resulting sample pieces were then finally
ground under liquid nitrogen by ultra centrifugal mill with 0.5 mm sieve. Using nitrogen liquid is
mandatory to prevent further generation of acetaldehyde due to overheating of the samples. Then
the cold powdered PET samples were weighed, placed in a septum capped vials for acetaldehyde
content measurement. Because acetaldehyde is a volatile compound at room temperature particular
care was taken to operate the grinding and the vials preparation at an ambient temperature less than
18°C
Residual acetaldehyde concentration was measured by a head space auto sampler (Dani
Instruments, HSS-3950) connected to a gas chromatograph equipped with a flame ionization
detector (FID) and using a packed column filled with Porapack QS (80-100 mesh). Operative
conditions are summarized in Table 2.
Table 2 Operational condition of gas chromatograph and auto sampler
Auto sampler
Bath temperature 120°C
Manifold temperature 125°C
Preconditioning 30 min
Gas chromatograph
Column Packed (Porapack QS (80-100 mesh)
Oven temperature 140°C
Detector FID ( fed with air and hydrogen)
Rata Gas carrier Nitrogen (30 cc/min)

Results and discussion

The following discussion includes the effects of temperature and residence time on acetaldehyde
concentrations measured in PET samples. Extruded PET was prepared under the conditions
described in Table 1 and then evaluated in terms of the acetaldehyde generated during processing.
The generated acetaldehyde that remained inside the specimens was analysed to obtain residual
acetaldehyde concentrations. By subtraction of acetaldehyde generated in samples collected at the
end of the hot runner and at the extruder exit, it has been possible to evaluate the acetaldehyde
generated in the hot runner, therefore neglecting the contribution of the extruder. To the best of our
knowledge no such data are available in literature.
In Figure 2 the effects of the temperature changes on residual acetaldehyde (generated in the hot
runners) are shown in a temperature range from 270 to 300 °C, for both short and long hot runners
and for a screw speed of 150 rpm. For all the tests reference temperature values were consistently
measured by thermocouples placed in the hot runner system. The effect of the shear induced self-
heating process was neglected. As it can be noticed the acetaldehyde content increases with
temperature up to 6 times. Similarly, the increase in the residence time results in an increase of the
generation of acetaldehyde.
Furthermore, despite the lack of data for shorter runner configuration, it appears as the effect of
residence time on acetaldehyde generation is less important, as it can be expected, but not
negligible, as it yields a sensitive increasing in acetaldehyde contents for the highest temperature.
In Figure 3 the effects of the residence time (in the hot runner) on residual acetaldehyde for two
different temperature values is showed. The residence times were calculated using only the volume
data of the hot runner. The temperature increase for each residence time results in an increase in the
generation of acetaldehyde. This result was expected as for dried polymers with low moisture
content the generation of acetaldehyde is mainly related to effects of thermal degradation rather
than hydrolysis [7]. The residual acetaldehyde data exhibits a non-linear behavior with respect to
the residence time, for each temperature. An appropriate non-linear model dependence of
 Key Engineering Materials Vols. 611-612 925

acetaldehyde contents with residence time was then proposed (Equation 1). This result is not in
accordance with the cited literature [11]. This discrepancy is probably due to the fact that the
amount of residual acetaldehyde considered is referred only to the hot runner, neglecting the
contribution of the extruder. The proposed model is the following:

 Ea 
 Ct R − 
 RT 
AA = A0 ⋅ e (1)

where Ea is the activation energy, T is the absolute temperature [K], R is the gas constant [J K-
1
mol-1], tR [s] is the residence time, and A0 [ppm] is the acetaldehyde content at tR = 0 and C [s-1] is
an optimization constant. The model was the fitted to the experimental data. The identified
parameters are reported in Table 3.
Table 3 Model parameters

A0 [ppm] 2.36e+10
C [s-1] 1.86e-2
Ea [kJ mol-1] 115.3
R [J K-1 mol-1] 8.314

This model, which expresses the generation of acetaldehyde as a function of temperature and
residence time, regardless of the geometry and other specific conditions of the process (e.g. the flow
rate or screw rotation speed), adequately fits the experimental points data for each processing
conditions investigated.
The proposed model is able to provide for the generation of acetaldehyde as a function of
temperature and residence time. In fact it is sufficient to change only the process temperature for
evaluate the generation of acetaldehyde to vary the residence time, as confirmed by the
experimental data.
265 270 275 280 285 290 295 300 305
7 7
Hot runner acetaldehyde concentration [ppm]

Hot Runner Lenght 913 [mm]

6 6
Hot Runner Lenght 519 [mm]

5 5

4 4

3 3

2 2

1 1

0 0
265 270 275 280 285 290 295 300 305
Temperature [°C]

Fig. 2 Effect of temperature and hot runner geometry on acetaldehyde generation.

926 Material Forming ESAFORM 2014

10 20 30 40 50 60 70 80 90 100 110 120

5,0 5,0

Hot runner acetaldehyde concentration [ppm]

4,5 4,5
280°C
4,0
280°C 4,0
290°C
3,5 290°C 3,5
300°C
3,0 300°C 3,0

2,5 2,5

2,0 2,0

1,5 1,5

1,0 1,0

0,5 0,5

10 20 30 40 50 60 70 80 90 100 110 120

Residence time [s]

Fig. 3 Effect of residence time on acetaldehyde generation.

Conclusion
In this work the generation of acetaldehyde in a hot runner system has been measured. A special
test apparatus was developed to separate the contributions due to the action of the extruder screw
from those due to the melt residence at high temperature. PET samples were analysed to evaluate
the content of acetaldehyde generated during processing and entrapped in specimens, which were
prepared by immersion in liquid nitrogen to prevent further generation of acetaldehyde due to
overheating of the samples. Residual acetaldehyde concentrations was then measured by a head
space auto sampler connected to a gas chromatograph.
The acetaldehyde contents (generated only in the hot runner) in PET samples were found to
increase with increasing processing temperature and residence time. A non linear dependence of
acetaldehyde contents with residence time was found and a model able to predict the acetaldehyde
generation to vary temperature and residence time was proposed. To the best of our knowledge no
data and models are available in literature to predict the amount of generated acetaldehyde during
melt extrusion process, and furthermore able to eliminate the contribution of the extruder.

References
[1] Dzieciol, M., Trzeszczynski, J., 1998. Studies of temperature influence on volatile thermal
degradation products of poly(ethylene terephthalate), Journal of Applied Polymer Science, vol.
69/12, pp. 2377-2381.
[2] Villain, F., Coudane, J., Vert, M., 1995. Thermal degradation of polyethylene terephthalate:
study of polymer stabilization, Polymer degradation and stability, vol. 49/3, pp. 393-397.
[3] Mutsuga, M., Kawamura, Y., Sugita-Konishi, Y., Hara-Kudo, Y., Takatori, K., Tanamoto, K.,
2006. Migration of formaldehyde and acetaldehyde into mineral water in polyethylene terephthalate
(PET) bottles, Food Additives and Contaminants, vol. 23/2, pp. 212-218.
[4] Zimmerman, H., Kim, N.T., 1980. Investigations on thermal and hydrolytic degradation of
poly(ethylene terephthalate), Polymer Engineering and Science, vol. 20/10, pp. 680-683.
[5] Ewender, J., Franz, R., Mauer, A., Welle, F., 2003. Determination of the migration of
acetaldehyde from PET bottles into non-carbonated and carbonated mineral water, Deutsche
Lebensmittel Rundschau, vol. 99/6, pp. 215-221.
 Key Engineering Materials Vols. 611-612 927

[6] Paci, M., La Mantia, F.P., 1998. Competition between degradation and chain extension during
processing of reclaimed poly(ethylene terephthalate), Polymer Degradation and Stability, vol. 61/3,
pp. 417-420.
[7] Marshall, I., Todd, A., 1953. The thermal degradation of polyethylene terephthalate,
Transactions of the Faraday Society, vol. 49, pp. 67-78.
[8] Goodings, E.P., 1961. Thermal degradation of poly(ethylene terephthalate), Soc Chem Ind
(London) Monograph 13: 211
[9] Jabarin, S.A., Lofgren, A.A., 1984. Thermal Stability of Polyethylene Terephthalate, Polymer
engineering and Science, vol. 24/13, pp. 1056-1063.
[10] Khemani, K.C., 2000. A novel approach for studying the thermal degradation, and for
estimating the rate of acetaldehyde generation by the chain scission mechanism in ethylene glycol
based polyesters and copolyesters, Polymer Degradation and Stability, vol. 67/1, pp. 91–99.
[11] Shukla, S.R., Lofgren, E.A., Jabarin, S.A., 2005. Effects of injection-molding processing
parameters on acetaldehyde generation and degradation of poly(ethylene terephthalate), Polymer
International, vol. 54/6, pp. 946–955.
Material Forming ESAFORM 2014
10.4028/www.scientific.net/KEM.611-612

Acetaldehyde Generation in Processing PET by Means of Hot Runner Systems

10.4028/www.scientific.net/KEM.611-612.922