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Polymer Degradation and Stability 82 (2003) 3746 www.elsevier.


Degradation of post-consumer polypropylene materials exposed to simulated recyclingmechanical properties

Anna Jansson*, Kenneth Moller, Thomas Gevert
SP Swedish National Testing and Research Institute, Department of Chemistry and Materials Technology, s, PO Box 857, SE-501 15 Bora Sweden Received 6 March 2003; received in revised form 11 April 2003; accepted 12 April 2003

Abstract Two post-consumer polypropylene (PP) materials have been examined and compared using a simulated recycling test procedure consisting of repeated cycles of alternating extrusion and accelerated thermo-oxidative ageing. The materials were also subjected to repeated extrusion and thermo-oxidative ageing separately. The materials were characterized by mechanical and chemical properties, such as elongation-at-break, oxidative induction temperature, carbonyl index and changes in molecular weight distributions. The dierent batches of recycled PP diered substantially in terms of durability and recycling potential. This illustrates one of the problems involved in handling recycled materials i.e. dierent batches and material streams may dier quite a lot. Interestingly, the elongation-at-break was signicantly dierent for samples taken after ageing and extrusion, respectively. The elongation decreased upon each ageing step, and increased as a result of the subsequent extrusion. Furthermore, the combination of extrusion and ageing tended to degrade the materials faster compared to ageing or repeated extrusion performed separately. # 2003 Elsevier Ltd. All rights reserved.
Keywords: Polypropylene; Recycling; Degradation; Tensile testing; DSC; FTIR; SEC

1. Introduction The large amount of waste produced by society is a growing environmental problem that has to be managed in order to achieve a more sustainable society. One way to reduce waste is to recycle materials such as paper, glass, metals and polymers in closed loop systems, where the same materials are used several times. In these types of systems, the materials are repeatedly collected, reprocessed, and then shaped into new products i.e. mechanical recycling. Whereas paper, glass and metals are today extensively recycled by mechanical recycling in Sweden, according to the packaging collection service, only a small percentage of polymeric packaging materials are recycled by re-melting and shaping into new products according to the APME, Association of Plastics Manufacturers in Europe [1]. This is together with economical and logistic reasons, due to lack of knowledge about quality and durability of recycled
* Corresponding author. Tel.: +46-33-165329; fax: +46-33-103388. E-mail address: (A. Jansson). 0141-3910/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0141-3910(03)00160-5

polymeric materials. The fact that polymeric materials are organic matter that degrade through oxidation during use and when the material is subjected to high temperature and shear forces when processed, can also explain the limited recyling of these materials. Although some polymeric products are today recycled by mechanical recycling, the majority is still put in a landll, incinerated or otherwise disposed of. Furthermore, products made from recycled polymers are often cheap, of only moderate quality and of very simple design. Since extraction of raw material is the most environmentally aecting part of polymer production, it would be benecial for the environment if recycled polymeric material to a greater extent could replace virgin material [2]. However, further knowledge about the properties of recycled polymeric materials is needed in order to nd appropriate and useful applications and increase the use of these materials. One appropriate investigation procedure for polymer materials would be the simulated recycling method, developed at our institute (Fig. 1). In this method, the material is exposed to both processing, simulating manufacturing of a product, and accelerated thermo-oxidative ageing, simulating the


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Fig. 1. The simulated recycling model. Samples are taken after each ageing step as well as after each processing i.e. extrusion step.

usage phase. We have in previous studies used the simulated recycling method to investigate High- and Low Density Polyethylene [3, 4], as well as an ABS (Acrylonitrile Butadiene Styrene) material [5]. For the investigated stabilised Low Density Polyethylene (LDPE) material, the combination of processing and accelerated ageing seemed to degrade the material faster than processing or accelerated ageing performed separately. The material could withstand at least twice as many separate extrusion or ageing steps compared to the number of simulated recycling steps before the elongation at break reached a value below 100%, and the material was considered degraded [3]. On the other hand, the High Density Polyethylene (HDPE) material was not signicantly aected even after 10 simulated recycling steps [4]. Accelerated thermo-oxidative ageing is a common method for estimating the service lifetime of polymeric materials. Repeated extrusion or injection moulding, on the other hand, are most often used to estimate their recycling potential [611]. In this study, two post-consumer polypropylene (PP) materials have been investigated by combined processing and ageing, as well as ageing and repeated extrusion. Since PP contains tertiary hydrogen bonds, the material is more vulnerable to thermo-oxidative degradation than polyethylene.

The PP-1 material has been in service as storage boxes for approximately 5 years, and was originally manufactured by Borealis. It is a MC1312M grade co-polymer, containing small amounts of ethylene units to improve the impact strength of the material. The Melt Mass Flow Rate (ISO 1133) was 12-13 g/10 min (230  C, 2.16 N) according to the supplier. Two antioxidants, Tinuvin 770 (Hindered Amine Light Stabliliser, HALS) and Irgafos 168 (phosphite co-stabiliser) were found in the PP-1 material using Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) analysis. No quantication of the antioxidant content was done. The PP-2 material has been in service for approximately 10 years, was originally produced Borealis and had a Melt Mass Flow Rate of 1213 g/10 min at 230  C and 2.16 N, according to the supplier. The PP-2 material was also co-polymerised with a few percent of ethylene to achieve better ductility. This PP batch contained dierently coloured akes, which turned out to be a contamination of approximately 1.2% by weight HDPE. Fourier Transform Infrared (FTIR) spectroscopy was used to identify the contaminant material, which probably originated from the milling process. Antioxidants used in the PP-2 material, were identied by extraction and Time of Flight Matrix Assisted Laser Desorption Ionisation Mass Spectrometry (TOFMALDI-MS) analysis. Irganox 1010 (hindered phenol) and Irgafos 168 (phosphite co-stabiliser) were detected, but no quantications of the antioxidants were done. 2.2. Processing and ageing Both PP materials were processed in a Brabender Plasti-Corder PLE 651 Extrusiograph, single screw extruder. Screw dimensions were 19 mm diameter and 500 mm length. A slit die with the dimensions 20.00.8 mm was mounted on the extruder. The temperature prole was 150175200220230  C and the screw rotation speed was 30 rpm for both materials. The extruded lms were cooled in air and gently stretched on a conveyor belt. The thickness of the extrudates was approximately 0.2 mm. In order to extrude the materials several times and simulate closed loop recycling, the lms were ground into akes in a Rapid granulator 1540 after each ageing step. Accelerated ageing was performed in Salvis draft air ovens at 130  C. The lm samples were neither in contact with the oven walls nor each other during the ageing. For PP-1, each ageing step was 48 h at 130  C, which corresponds to at least 10 years of indoor use. The estimation is based on the assumption that the thermooxidative ageing corresponds roughly to a doubling of the ageing rate for each increase of 10  C. Dixon recommends the use of a relatively low activation energy when calculating the accelerating factor in order not to overestimate the service life [12]. For PP-2, each ageing cycle was 24 h at 130  C.

2. Experimental 2.1. Material Two dierent PP materials were recollected from real waste streams and investigated. Both materials contained organic blue pigment (Cu-phtalocyanine according to the supplier) and had been used as storage boxes prior to re-collection and granulation into akes. The re-collection was done by Strandplast, Perstorp, Sweden. The materials were chosen because they were quite well dened regarding age and origin. Both materials were received as ground akes with an approximate size of 331 mm. The materials will from now on be designated PP-1 and PP-2.

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The rst PP material, PP-1, was subjected to three dierent series of processing and/or ageing. In the simulated recycling series (series SR1), PP-1 was subjected to alternating extrusions and ageing steps (48 h at 130  C). Ten extrusions and nine ageing steps were performed. In the second series (series EA1), ten extrusions were performed, and then the material was aged for 480 h. Finally, in the third series (series AE1), the material was aged for 480 h prior to 10 repeated extrusions. Note that step one in the AE series is an extrusion step to form the strips from which samples are taken. The purpose of these investigations was to verify if alternating extrusion and ageing degrade polymer materials faster than either procedure performed separately. Therefore, the PP-1 material was subjected to the same numbers of extrusions and ageing steps in all three series, but in dierent combinations. Also the PP-2 material was exposed to three dierent series of processing and/or ageing. In the rst series (series A2), an extruded PP lm was exposed to oven ageing at 130  C for totally 480 h and samples were taken out for analyses every 24 h. Note that step one in the A2-series is an extrusion step. In the second series (series E2), the PP material was extruded 14 consecutive times. After each extrusion, samples were taken out for analyses. The third series (series SR2), was a combination of alternating extrusion steps and ageing steps (24 h at 130  C), i.e. simulated recycling. Six extrusions were performed, and samples were taken out after each extrusion as well as after each ageing step. 2.3. Testing Mechanical properties, i.e. elongation-at-break, were studied by tensile testing according to the ISO-527 standard. An Instron tensile tester 5566, equipped with an Instron 2663-302 video extensiometer was used. Dumb-bell shaped test specimens (SIS 162202) were punched out from the extruded lms and conditioned at 23  C and 50% relative humidity for 12 h before testing. Each reported result is an average of ve to 12 tensile tests. Oxidative induction temperature (Tox) was measured using either a Mettler Dierential Scanning Calorimeter, DSC type 30 - TA 8000 or a TA Instruments DSC 2920. For all measurements, a temperature scan from 50 to 250  C and a heating rate of 10  C per minute were used. Samples weighing approximately 5 mg were punched out of the lms and put in aluminium crucibles. Tox was measured in oxygen atmosphere with a gas ow of 50 ml/min. Nitrogen was used as purge gas when measuring the degree of crystallinity. For all PP-1 samples, the equipment from TA Instruments was used. The Mettler equipment was used for the PP-2 material, except for the last measurements in the repeated extrusion series (extrusion step no. 1114). Furthermore,

some comparing tests were made on PP-2 to make sure that the results from the two dierent instruments corresponded. Carbonyl content in the degraded material was measured with a Cygnus 100 Mattson FTIR-spectrophotometer. The ratio between the absorbance of the intensity of the carbonyl peaks absorbing at 1712 cm1 (carboxylic acid) and at 1720 cm1 (ketonic carbonyl group) and that of a reference peak (absorbing at 1892 cm1) was calculated. The ratio was used as a measure of the carbonyl content in the sample, here designated Carbonyl Index (CI). Changes in molecular weight and molecular weight distributions (Mw, Mn, and Mw/Mn) were measured by Size Exclusion Chromatography (SEC). The samples were dissolved in 1,2,4-trichlorobenzene before injection. The instrument, a Waters C+V operated at 135  C, was calibrated with polystyrene standards for polyethylene via the universal calibration curve. To transfer to polypropylene calibration the data were corrected according to the two Mark Houwink relations giving a correction factor of 1.3 [13]. TOF-SIMS analysis was used to determine the type of antioxidant in the PP-1 material. The TOF-SIMS data was recorded on a TOF-SIMS IV instrument (IONTOF GmbH, Munster, Germany) using a pulsed pri mary ion beam of 25 keV Ga+ at a current of 0.55 pA. The analysis area was between 200200 and 300300 mm2 and the analysis time was 200 s. Positive spectra from both the sample surface and a freshly microtomed cross section surface were recorded. The antioxidants in the PP-2 material were extracted in chloroform and analysed by TOF-MALDI-MS. A Bruker Biex III instrument with a detection limit of 1091015 moles was used for the analysis. Extract (50 ml) was mixed with 50 ml 0.15 M matrix solution i.e. Dithranol (1,8,9-Trihydroxynaphtalene) in Chloroform and 1 ml 0.15 M ChloroformSodium Chloride-solution. The accelerating current was 19 kV, and 25 scans were run in order to achieve the spectra.

3. Results and discussion 3.1. The rst polypropylene material, PP-1 3.1.1. Elongation-at break , PP-1 Fig. 2 shows how the elongation-at-break varies during simulated recycling (series SR1). One step in Fig. 2 corresponds to either an extrusion or an ageing step (48 h at 130  C). After each ageing step the elongation-atbreak dropped considerably, but returned more or less to the initial value after extrusion. However, after the last extrusion, the material was highly degraded and strips could no longer be formed from the now waxlike material. Therefore, the elongation value was set to zero


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Fig. 2. Elongation-at-break values for PP-1 subjected to simulated recycling, series SR1. Step 1 is the rst extrusion, step 2 the rst ageing, step 3 the second extrusion, and so forth. After each extrusion step the elongation values are in the range 600700% and after each ageing step the elongation drops, and a zig-zag shaped curve is formed.

Fig. 3. Comparison of elongation-at-break for samples (PP-1, simulated recycling SR1) aged at 130  C in air and nitrogen respectively. The broken line represents the material thermally treated in nitrogen. For both types of ageing, the elongation-at-break drops after ageing (step 2 and 4) and increases after the subsequent extrusion (step 3 and 5), indicating that oxidative degradation alone does not cause the elongation drop.

for step 19 (Fig. 2). This type of zig-zag shaped curve has been observed before, in a LDPE material subjected to simulated recycling [3]. The behaviour of the elongation data is still not fully understood but possible explanations are:  Re-organisation of the lamellar structure; lamellar thickening during ageing at high temperature (130  C) leads to a decrease of the elongation-atbreak [14]. Re-extrusion and melting of the material include forming of new crystallites, with initial size and structure.  Surface degradation; predominantly the surface layer is degraded upon ageing. The degradation products act as stress raisers and lower the elongation-at-break values. In the subsequent reextrusion a new surface layer is formed and the elongation values increase. Ageing of thin lms in 18 O2 labelled oxygen, followed by TOF-SIMS analysis has shown that the oxygen concentration is higher in a very thin surface layer, probably well below 1 mm down to a few nm, compared to the bulk material [15].  Dilution of degraded polymer chains; the oxidative degradation takes place in the amorphous part of the material, since the oxygen diusion into the crystallites is very limited. As the investigated material is PP, the degradation will give chain scission in the amorphous part. During reprocessing, non-degraded material from the crystalline phase is melted and blends with the degraded polymer chains. Hereby, the degraded polymer chains from the amorphous part are

diluted and more high molecular weight polymer chains become available to form tie molecules between the crystallites. This may explain the improvement of the elongation-at-break after the extrusions. When the melt is cooled and re-crystallisation occurs, both degraded and nondegraded polymer chains form crystallites. In order to investigate the inuence of the high ageing temperature on the elongation-at-break, while avoiding oxidation, some PP-1 strips were treated thermally in a nitrogen atmosphere at 130  C for 48 h. Fig. 3 shows that the thermal treatment in nitrogen had almost the same eect on the elongation-at-break as ageing in circulating air. Furthermore, DSC measurements show an increase in degree of crystallinity after ageing steps, and this indicates that some re-crystallisation occurs during the ageing steps. A subsequent extrusion of the material, thermally treated in nitrogen, caused a recovery of the elongation-at-break value. A second thermal treatment in nitrogen atmosphere again decreased the elongationat-break value (Fig. 3). For comparison, reprocessing by compression moulding was studied. Only a few percent improvement of the elongation-at-break could be observed after compression moulding. The mixing process in the extruder seems to be important for the recovery. In the AE1 series, nine ageing steps were followed by ten extrusion steps. Samples were taken out every 48 h during ageing and after each extrusion. The rst 10 steps in Fig. 4 show how the elongation-at-break decreases continuously during the ageing, from 700 to approximately 50%. These data indicated a severe

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Fig. 4. Elongation-at-break for PP-1, series AE1, ageing followed by repeated extrusion. The ageing causes a decrease in the elongation-atbreak and the following extrusion improves the elongation. Step 11 represents the rst extrusion step.

degradation of the material. However, upon grinding and re-extrusion of the aged material the elongation-atbreak value increased to almost the initial value. This is the same type of increase in elongation-at-break that was observed upon each extrusion step in the simulated recycling experiments (Fig. 2). Interestingly, PP-1 exhibited a nal elongation-at-break value of 550% and could therefore not be regarded as degraded even after nine steps of ageing followed by 10 extrusions (Fig. 4). In comparison, PP-1 was highly degraded after 19 steps of simulated recycling. Evidently, the simulated recycling degrades the material faster. Fig. 5 shows the EA1 series where PP-1 was rst extruded ten times, and then aged for a longer period of time. The elongation decreased slightly as a result of each extrusion. After the rst ageing step, the elongation

Fig. 5. Elongation-at-break for PP-1, series EA1, repeated extrusion followed by ageing. The elongation slowly decreased upon extrusion. On the subsequent ageing, step 11, the elongation dropped considerably. After step 19 the elongation-at-break was only 5%.

dropped to approximately 150% and remained at that level until step 14, upon which it dropped to less than 100%. After having been subjected to all 19 steps, the material was extruded once again to investigate if the initial elongation-at-break value could be recovered. However, both the surface and the bulk material were so degraded that the elongation could not be improved. Both extrusion and ageing degrades polymeric materials. The present investigation clearly shows that the order in which extrusion and accelerated ageing are performed is important. Simulated recycling and extrusion followed by ageing degraded the material faster compared to ageing followed by extrusion. One explanation to the faster degradation in the SR and EA series is hydroperoxide formation and decomposition. Hydroperoxides (ROOH) are intermediate degradation products formed upon polymer oxidation. They are relatively stable at temperatures below 150  C, but decompose to form two highly reactive radicals at high processing temperatures. These radicals, i.e. alkoxy (RO.) and hydroxy (.OH) radicals, can then abstract hydrogen atoms from the polymer chains. Alkyl radicals are thereby formed, and the auto-oxidation continues. The formation of the alkoxy and hydroxy radicals accelerates the oxidation process considerably, since two additional radicals are formed out of one in each oxidation step, according to the polyolen autooxidation mechanism [16]. In series SR1 hydroperoxide formation and decomposition in every cycle may explain the faster degradation. Since we have investigated a post-consumer material, hydroperoxides are most likely present in the starting material and they may decompose already in the rst extusion step. Moreover, in series EA1 imperfections caused by the extrusions may accelerate the degradation during the subsequent ageing. When all the ageing steps were performed rst, series AE1, the material could withstand nine steps of ageing followed by 10 extrusion steps. Probably, the lm surface was slightly oxidised during the ageing whereas the bulk material was substantially less degraded than would be expected for such a thin lm (0.20.3 mm). The following extrusion steps should further degrade the material, but due to the presence of residual stabiliser, the material recovered after mixing in the extruder. In Fig. 6 all three series (SR1, AE1 and EA1) are plotted in the same graph. The lled circles represent the samples analysed after extrusion steps and the open circles represent the samples analysed after ageing. The straight lines are obtained by least square linear ts for lled and open circles respectively. The elongation-atbreak values decrease continuously in both data series. The decrease in elongation-at-break noticed for the samples analysed after ageing (open circles) represents a more or less reversible deterioration of physical nature, since the material recovers after a subsequent extrusion


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at-break for samples taken after ageing and after thermal treatment in nitrogen are compared. It seems like ageing in circulating air causes a larger drop in elongation-at-break and the recovery after the subsequent ageing is not as high as for the samples taken after thermal treatment in nitrogen. Beside the re-crystallisation some degradation also seems to occur if oxygen is present during the ageing. 3.1.3. Oxidative induction temperature (Tox), PP-1 Both ageing and extrusion cause antioxidant deactivation, which gives decreased Tox values. In Fig. 7, Tox values obtained during simulated recycling, series SR1, are compared to those measured upon 10 ageing steps and then after repeated extrusions and those in opposite order, series AE1 and EA1, respectively. From step one up to step nine the Tox values are quite similar for all three series. From step 10 up to step 18 the three series dier more, probably due to in-homogeneous degradation. In step 18 the Tox values are almost the same for all three series, but in step 19, Tox for the SR1 sample decreases considerably, whereas the other two samples remain on the same level. Tox for unstabilised polypropylene has been measured to approximately 180  C on soxhlet extracted PP material. In series AE1 the Tox value drops approximately 8  C after the rst extrusion, step 11, Fig. 7. This can be explained by hydroperoxide formation during the thermooxidative ageing. At the high extrusion temperature these hydroperoxides decompose forming highly active radicals which rapidly deactivates the antioxidants. Karlsson and Camacho have observed rapid initial decrase in oxidation induction time (OIT) for PP upon repeated extrusion [17]. 3.1.4. Carbonyl Index (CI) , PP-1 The Carbonyl Index was measured for some of the data points in the PP-1 material. A small carbonyl peak was observed already in the starting material, probably

Fig. 6. The elongation-at-break for all three PP-1 series shown in the same graph. The lled circles represent samples taken after the extrusion steps and the open circles, samples taken after ageing steps.

step. However, the slope of the bottom straight line may indicate a superimposed irreversible deterioration of chemical nature. When the antioxidants are deactivated no recovery of the material could be observed and the material fails, step 18 and 19 in cycles SR1 and EA1. 3.1.2. Degree of crystallinity, PP-1 The degree of crystallinity was measured by DSC for PP-1, series SR1, after a few extrusions and ageing steps, respectively. Since the thermal history of the samples, i.e. extrusion and cooling in air, compared to oven ageing at 130  C was of interest, the crystallinity was analysed without pre-heating. Table 1 shows the degree of crystallinity for samples taken after extrusion (step 1, 3 and 15) and after ageing (step 2, 4 and 16) in series SR1. The degree of crystallinity increased by 4 8% or 1020% in a relative sense, after each ageing step. The results were the same for the samples treated thermally in nitrogen atmosphere. For these samples, surface oxidation should not play an important role for the elongation-at-break results. These results indicate that re-crystallisation could, at least partly, explain the zig-zag shaped elongation-at-break curve obtained from the simulated recycling experiments. In Fig. 3, elongationTable 1 Degree of crystallinity after extrusion and ageing respectively in series SR1 Sample Step 1 (after extrusion) Step 2 (after ageing) Step 3 (after extrusion) Step 4 (after ageing) Step 15 (after extrusion) Step 16 (after ageing) Degree of crystallinity (%) 39 47 41 46 41 45

Fig. 7. Tox for PP-1, series SR1 (*), series AE1 (&) and series EA1 (~). Note that not all samples are measured in series AE1.

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originating from additives or contaminants in the material. The carbonyl absorbance was in the same range as the absorbance of the reference peak at 1891 cm1, resulting in a CI value of approximately 1, for the starting material. A pronounced increase in the CI value was not detected until the material was very degraded, i.e. when the elongation-at-break was close to zero and the Tox value had decreased to approximately 180  C. Fig. 8 shows how the CI increases in step 19 in series SR1. Also the Tox value decreases at this point. In the AE1 series no increase in CI was detected in the last step i.e. nine ageing steps followed by eleven consecutive extrusions. However after the last ageing, step 9, (18 days of ageing) degraded brittle spots were observed on the lms. CI for a sample taken from a degraded area was 1.7 and CI for the sample taken from a non-degraded part of the strip was 1, similar as for the starting material. This observation favours the dilution theory, where the degraded parts of the material are mixed with non-degraded material in the extruder. This observation also illustrates the inhomogeneous nature of degradation in polymer materials. Ten consecutive extrusions in the EA1 series did not aect the CI value. In step 19, after both extrusions and ageing the extruded strips were partly degraded. The CI values diered depending on where the samples were taken. The sample from a brittle part of the strip had a CI value of 2.5 while the CI for a non-degraded sample was 1. The same phenomenon was observed for the Tox analysis, the results depended on where the sample was taken. Where the strip was degraded the Tox value was only 183  C. The corresponding Tox value for a nondegraded part it was 198  C, as showed in Fig. 7. 3.2. The second polypropylene material, PP-2 For comparison a second PP material, PP-2, was investigated. PP-2 was dierently stabilised, had been in

service for a longer period of time and was also contaminated by HDPE. Three dierent test series were performed; simulated recycling (series SR2), repeated extrusion only (E2) and ageing only (A2). 3.2.1. Elongation-at-break, PP-2 Fig. 9 shows that the elongation-at-break for PP-2 was not considerably aected by 20 consecutive days of ageing at 130  C (series A2). The material could also withstand 14 repeated extrusions with a drop in elongation-at-break from 800 to 400% (series E2). The PP-2 material showed an opposite elongation-at-break behaviour, compared to the PP-1 material. Ageing did not cause any signicant drop in elongation-at-break for the PP-2, whereas repeated extrusion decreased elongationat-break somewhat. One explanation for this opposite behaviour could be the dierent stabilisation systems in the two materials. The PP-1 material is stabilised with a hindered amine (Tinuvin 770) and the PP-2 material contains phenolic antioxidant (Irganox 1010). Both materials also contain organic phosphite (Irgafos 168) as co-stabiliser. Moreover, HDPE akes were found in the PP-2 material and this impurity may explain the dierence in elongation-at-break between the two materials. The results from the simulated recycling are not as straightforward as for the separate ageing or extrusion. Series SR2 shows a large spread in elongation-at-break. Each data point represents an average of at least ve and most often more measurements. Even though the highest and lowest values are excluded from the calculations the standard deviations are still higher than 100%. Large drops in elongation-at-break were

Fig. 8. Tox (&) and Carbonyl Index (*) for the PP-1 material plotted in the same graph.

Fig. 9. Elongation-at-break for the PP-2 material; SR2 (*), A2 (&) and E2 (~). A pronounced drop in elongation-at-break is observed after step 6 and 9 in the SR2 series. After these drops the material recovers again. Interestingly, the material can withstand 14 repeated extrusions (E2) and 20 ageing steps (A2) with maintained elongation at break values. In the simulated recycling series (SR2) the material had an elongation-at-break value close to 0 and could not be recovered by extrusion after step 12.


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observed after step six and nine. After each of these extremes, the material recovered and the elongation increased to almost the initial value, and thereafter decreased again. It is remarakble that the elongation-atbreak drop observed in step nine occured after an extrusion step. In previous observations elongation-atbreak drops have been observed after accelerated ageing steps. One explanation is that this sample was taken from a more contaminated part of the material. The observed large spread in the results is probably due to an in-homogeneously degraded starting material. Several studies by staining as well as chemiluminescence techniques have shown that oxidation of polyolens is a heterogeneous process [1824]. In addition, the contamination by HDPE contributes to the heterogeneous nature of PP-2. The results in Fig. 9 suggest that the investigated polypropylene material should not be recycled more than twice (two closed loops, or four steps in Fig. 9), to guarantee the quality of the material in terms of elongation-at-break. After step 12, i.e. six extrusions with intermediate ageing, the material was highly degraded and could not be extruded into strips. Therefore, the elongation-at-break value was set to zero at this point. Interestingly, the material seemed to degrade faster when subjected to simulated recycling, i.e. the material in the extrusion and ageing series consistently withstood more steps without decreased elongation-atbreak values. Importantly, if PP-2 had been evaluated by repeated extrusion only, the material would have seemed to be able to withstand ten recycling steps. 3.2.2. Oxidative induction temperature (Tox) and Carbonyl Index (CI), PP-2 Fig. 10 shows the results from the Tox measurements. When exposed to ageing at elevated temperature the material lasted for 14 days without any drop in Tox value. Repeated extrusion, on the other hand, lead to

rapid deactivation of antioxidant, i.e. Tox decreased substantially already upon the ve rst extrusions, which was not the case for the simulated recycling series (series SR2). In order to investigate whether this was an eect of in-homogeneity of the material, 10 lms extruded once, but at dierent occations, were analysed. The mean value of Tox based on the measurements on these 10 lms was 190.7  C, with a standard deviation of 2.9. The highest and lowest values were 194.7 and 185.6  C, respectively, giving a temperature range of 9.1  C. This clearly shows that the material is heterogeneous which might explain the Tox results in Fig. 10. Hence, the anomalies in the results are due to a below average concentration of stabiliser in the particular sample studied. This is a quite common problem in degraded and recycled materials [25, 20]. No signicant change in degree of crystallinity could be detected by DSC measurements after six simulated recycling steps. When the antioxidants are deactivated, oxygen reacts with the polymer chain and forms carbonyl groups, mainly ketones and carboxylic acids. Carbonyl peaks were observed at $ 1712 cm1 (carboxylic acid) and $ 1720 cm1 (ketonic carbonyl group) for PP-2 when exposed to simulated closed-loop recycling. The two peaks are overlapping, but as the material degrades the maximum peak shifts towards the carboxylic acid band. In the PP-2 samples subjected to either ageing (series A2) or repeated extrusion (series E2), only very low carbonyl absorption could be detected by FTIR measurements. Hence, the CI value did not change during the oxidation of the polymer. When the Tox decreases, the carbonyl IR-absorbance increases in the subsequent cycle in the SR2 series (Fig. 11). In other words, when all antioxidants had been deactivated, carbonyl groups were rapidly formed by auto-oxidation, both through chain propagation and termination reactions. At this stage of degradation the

Fig. 10. Tox for the three PP-2 test series, SR2 (*), A2 (&) and E2 (~). In the A2 and E2 series not all samples are analysed.

Fig. 11. Tox (&) and Carbonyl Index (*) for the PP-2 material are plotted in the same graph. The drop in Tox is detected one cycle before the corresponding increase in Carbonyl Index.

A. Jansson et al. / Polymer Degradation and Stability 82 (2003) 3746 Table 2 Molecular weight for PP-2 samples extruded once (step 1), and after four extrusions and three ageing steps (step 7) Material PP-2 step 1 PP-2 step 7 Mn103 35 34 Mw103 140 129 Mw/Mn 4.0 3.9


The values are means of two measurements.

mechanical strength of the material was very poor. Since only small amounts of carbonyl groups could be detected in either the extrusion or the ageing series, the antioxidants in these materials were probably not fully deactivated. However, the Tox measurements showed a decreased antioxidant activity for both the extrusion and the ageing series, after the 9th and the 13th steps, respectively (Fig. 10). In accordance with the CI results, the elongation-at-break for series E2 and A2 were at a level of 400800% for the last cycles, which indicates that these samples still have acceptable mechanical properties. 3.2.3. Molecular weight distributions PP-2 After the fourth extrusion step in the simulated recycling series, the weight average of the molecular weight, Mw, of PP-2 had decreased somewhat (Table 2). The polydispersity (Mw/Mn) had decreased as well and the elongation-at-break values had started to drop and thereafter recover, which indicates that some parts of the samples had started to degrade. This indicates that molecular chain breakage has taken place in the high molecular weight fraction. Long molecules are known to be important for high elongation-at-break values [26,27]. Similar results, i.e. decreased Mw and Mw/Mn, have also been reported from studies of repeated extrusion of commercial polypropylene grades [9,28,29].

 Combining extrusion and ageing denitely aects the degradation behaviour of the material. So does the order in which extrusion and accelerated ageing are performed. Simulated recycling or repeated extrusion followed by accelerated ageing more severely aects the material degradation than ageing followed by repeated extrusion.  Mechanical testing and elongation-at-break should be used with care, since the results may give dierent indications of the status of the material, depending on the sample preparation. Re-extrusion most often tend to improve the mechanical properties of a material, as was the case for the PP-1 material.  Mechanical recycling with the ambition to produce high quality products is not an easy task. This investigation shows some of the diculties, for example variation between dierent batches in terms of stabilisation, contamination etc.

Acknowledgements Mistra (Foundation for Strategic Environmental Research), Swedish Environmental protection Agency and Formas (The Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning) are gratefully acknowledged for nancial support. Strandplast is acknowledged for supplying the PP materials, Ulrika Carlander (SP) for TOF-MALDI experiments, Peter Sjovall (SP) for TOF-SIMS experiments and Anders Martensson at the Department of Polymer Technology at Chalmers for SEC measurements. Soa Kallquist and Mariann Pettersson for their assistance with laboratory work at SP. Dr Arne Holmstrom (SP) and Professor Thomas Hjertberg (Chalmers) is acknowledged for reviewing and discussing the results presented in this paper.

4. Conclusions

 During simulated recycling of PP-1, a zig-zag shaped elongation-at-break curve was observed. The elongation-at-break dropped upon each ageing step and increased again upon each extrusion step. We suggest three explanations to this behaviour: (1) changes in degree of crystallinity, (2) surface degradation, and (3) dilution of degraded polymer chains after re-extrusion. The elongation behaviour is probably explained by a combination of all three mechanisms.  In conclusion, simulated recycling degraded the polypropylene materials faster than repeated extrusion or ageing, and better mimics reality and should therefore be a valuable tool for recycling investigations.

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